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REINHOLD PLASTICS
APPLICATIONS SERIES
^POLYPROPYLENE
by
THEODORE O. J.^^KRESSER
Spencer Chemical Gompany
Orange, Texas
REINHOLD PUBLISHING CORPORATION

NEW YORK
CHAPMAN & HALL, LTD., LONDON
Copyright © 1960 by
REINHOLD PUBLISHING CORPORATION
All rights reserved
Library of Congress Catalog Card Number 60-53435
Printed in the United States of America

Reinhold Plastics
Applications Series
This series, which started in 1957, has now grown to greater

proportions than at first planned. The present volume on
"Polypropylene" is the nineteenth to be published, and five
or six more are in prospect. The series, which started with the
theme, "guidance in application," was designed to devote one
book to each of the more important plastics materials, de-
scribing the physical and chemical properties for each material
and its optimum end-product use. Now, however, stimulated
by the industry's wide and cordial acceptance, the series has
been broadened to include books on production processes.
Despite the introduction of volumes on production proc-
esses the general character of the books will remain the same.
They will be semi-technical and addressed primarily to engi-
neers, designers, students, and in fact to all practical people
in plastics. The new plastics materials, of course, will continue
to be covered. Books on Alkyd Resins and Polycarbonates
are now in preparation.
The process books will include volumes on Premix Mold-
ing, Blow Molding, Plastics in Tooling, and on Modern
Methods of Plastics Extrusion.
Production curves in the plastics field continue to rise at
an astonishing rate, and so it is with considerable confidence
that this volume in the expanded applications series is pre-
sented.
Herbert R. Simonds
Editor
TITLES PUBLISHED
Acrylic Resins, Milton B. Horn

Amino Resins, John F. Blais
Cellulosics, Walter Paist
Epoxy Resins, Irving Skeist
Fluorocarbons, Merritt A. Rudner
Gum Plastics, M. Stafford Thompson

Laminated Plastics, D. J. Duffin
Metallizing of Plastics, Harold Narcus
Phenolic Resins, David F. Gould
Plastic Sheet Forming, Robert L. Butzko
Poly amide Resins, Don E. Floyd

Polyester Resins, John R. Lawrence
Polyethylene, Theodore O. J. Kresser
Polystyrene, William C. Teach and George C. Kiessling
Polyurethanes, Bernard A Dombrow

.
Runnerless Molding, Ernest P. Moslo
SiUcones, Robert N. Meals and Frederick M. Lewis

Vinyl Resins, W. Mayo Smith
PREFACE
In this day when scientific advances are looked upon with

some suspicion, and people quite rightly wonder, sometimes,
if a new miracle really is all for the good, it is a great pleasure
to be able to write on a subject where no one can deny that
the scientific progress made is for the greater good of mankind.
Writing a book about a material during the period when it
is just starting to come into volume production is a difficult
but challenging job. The technical journals each month bring
out more news of growth and change, and the temptation to
wait and see what the next development will be is almost
irresistible.
As time
goes on, however, it becomes obvious that the main
development are following very closely those laid out
lines of
by Professor Natta and the publications of the Montecatini
Company several years ago.
This book could not have been written without their as-
sistance. The chapter on the chemistry of polypropylene is
taken almost entirely from Professor Natta's pubhcations,

and he has been kind enough to read it before pubhcation and
make necessary corrections.
Both the chapter on properties and that on processing owe
a great deal to publications of Drs. RanaUi and Crespi of the
Montecatini organization, and permission to reproduce many
of the excellent illustrationsfrom these publications is grate-
fully acknowledged. The Montecatini Company was also very
helpful concerning applications in Europe.
vii
viii Preface
The Hercules Powder Company was very kind in making

available much of their wealth of experience on applications
in the United States, and the assistance of the AviSun Corp.,
Spencer Chemical Co., Enjay Corp., Eastman Chemical Co.,
Dow Chemical Co., and many others was also most valuable.
The early years in the development of any product are full
of problems and difficulties, and polypropylene is certainly
no exception. Some of the current problems have led a few
people to doubt that polypropylene will grow in the manner
predicted by its advocates. These problems may be very seri-
ous in some fields and may, indeed, change the order and
direction of development; however, they are similar to prob-
lems that have been solved with other materials, and they
will not long delay the development of this one.
The only real possibility that polypropylene may fail to
fulfill present expectations is that closely related polyolefin

materials, made by similar methods from olefins other than
propylene, may be developed so rapidly that they will take
away some of the markets this book predicts for polypropylene.
Even this can hardly change the picture very radically. It will
not be a serious miscalculation on the part of people planning
to produce polypropylene, because the change in base material
will not involve extensive plant revisions, and the chemical
and physical research on polypropylene is equally applicable
to other polyolefins. At the present time there is no reason to
believe that polypropylene will not perform as expected; there
is much reason to believe that it will be the most spectacularly
successful thermoplastic ever produced.
The opinions expressed in this book are those of the author
and do not necessarily reflect the conclusions of the Spencer
Chemical Company in certain respects.
The greatest part of the information in this book is from
technical publications here and abroad. Whenever a section
leans very heavily on a single source it has been mentioned
Preface ix
in the text; however, in many cases the information has been

collected from various sources which are not separately ac-
knowledged. In such a new subject, pubhshed information
must necessarily be supplemented by information drawn from
private conversations and private communications. If any
material which the originator considered confidential has
inadvertently been used, the author asks that consideration
be given to the fact that this book has been written mainly as
a service to the polypropylene industry. It should be a benefit
to all companies in the field to have a "polypropylene primer"
available to assist in orienting the public and any newcomers
in the business.
Publications which have been consulted in the preparation
of thisbook include Modern Plastics, publications of the
American Chemical Society, Journal of the Society of Plastics
Engineers, Plastics Technology, Plastics World, British Plas-
tics, Chemical Processing, Chemical Week, Chemical Engi-
neering, Modern Packaging, the transactions of the Plastics
Institute (Britain) and many others.
Particular thanks are due to the Spencer Chemical Com-
pany for permission to undertake this work, and especially to
S. P. Horkowitz, manager of the Spencer Technical Labora-
tory at Orange, Texas, and Dr. G. Ham, Technical Director

of the Spencer Plastics Division, for their help in the project.
Theodore Kresser
Orange, Texas
November, 1960
CONTENTS
Preface vii
1. Introduction 1
2. Properties of Polypropylene ^
3. Chemistry of Polypropylene 65
4. Production of Polypropylene 94
5. Processing of Polypropylene 107
6. Packaging Applications 163
7. Applications of Polypropylene in the

Durable-Goods Industries 192
8. Applications in Soft-Goods Industries 221
9. Future Developments 246
Index 265
1, INTRODUCTION
Polypropylene is a thermoplastic resin, and in this sense its
history starts with the first thermoplastics discussed in the

first volume of this series.
Some understanding of the major developments that oc-

curred after the great commercial success of polyethylene is
necessary to appreciate the position of polypropylene.

Introduced in 1941, high-pressure polyethylene has be-
come the most widely used plastic, and continues to grow at
a tremendous pace. Linear polyethylene, developed in 1955,
has made tremendous progress but has so far hardly come up
to its initial promise. At a 1959 consumption of 83 million
pounds, perhaps a quarter of the production capacity is used.
Polypropylene is tied in very closely, both technically and
commercially, with linear polyethylene. The Ziegler catalysts,
which were originally developed to make linear polyethylene,
were the first catalysts to make polypropylenes of the types
we are discussing, and the now in use for commercial
catalysts
manufacture of polypropylene are direct developments from
the original Ziegler catalysts. The entire technology of poly-
propylene manufacture is based on work originally done to
make linear polyethylene.
The tremendous penetration of polyethylene into fields
long held by traditional materials such as paper, metals, etc.,
has caused people to be much more open minded regarding

the use of plastics in many fields. The general consumer satis-
1
2 Polypropylene
faction with polyethylene articles has done much to erase the

stigma of "cheap and fragile" that had been associated with
plastics for many years. Plastics are now seriously considered
as components of relatively expensive appliances and house-
hold goods.
Linear polyethylene manufacturers did a tremendous job
of market development for their material. This created a
great demand for higher heat resistance, greater strength and
stiffness, greater resistance to gas and water transmission,
and all the other excellent properties of linear polyethylene.
Experience has shown, however, that Unear polyethylene also
has serious limitations which, in many cases, restrict its useful-
ness, and that there has not been sufficient improvement in
properties to reach some large markets.
Polypropylene is, therefore, falling heir to a great deal of
the interest built up in linear polyethylene. It has many of
the good properties of linear polyethylene, but to a greater
degree, often carrying them on to a point where the improve-
ment becomes really significant. Polypropylene also lacks
some of the serious faults of linear polyethylene. This will be
discussed in detail in Chapter 2.
Polypropylene, however, is of greatest historical interest,
not as the latest member of a fast-growing thermoplastic
family but as the first member of an enormously promising
group of sterically regulated polymers.

When Professor Natta of the Instituto di Chimica Indus-
triale del Politecnico first explained his discovery of isotactic
polypropylene to the scientific world in 1954 it was greeted
with a degree of excitement out of all proportion to the
announcement of a new plastic material. Even though it was
evident that the material had valuable properties and was
potentially inexpensive, this seemed insufficient to justify the
furor stirred up by the papers. We heard all kinds of en-
thusiasm about a major breakthrough in polymer technology,
Introduction 3
and duplicating processes heretofore impossible except within

the living cell.
Subsequent events, however, have shown that the most

exuberant enthusiasts were conservative. Natta's work sparked
a volume of research on polymerization never before ap-
proached. Within a short time thescientific literature was full
of endless examples of stereospecific polymerization. The

patent literature all over the world also soon showed the
effect of this tremendous growth of scientific effort.
Curiously enough, some of the most startling and perhaps,

in the long run, most valuable consequences of this work
resulted not in polypropylene but in improved synthetic
rubbers. The use of synthetic rubber had always been limited
because the molecules produced in the factory had a random
or helter-skelter structure. Natural rubber, on the other hand,
has a very regular structure. This fact had beenknown for a
great many and there has been much speculation as to
years,
the means whereby the living cell was able to direct the
growth of the rubber molecule into this regular pattern.
Professor Natta's work included some sterically ordered
dienes. Thousands of researchers all over the world imme-
diately saw that this might be the clue to the long-sought
synthetic rubber that would really duphcate natural rubber.
Without going into detail at this point, subsequent research
proved this to be true. Several pilot plants have made quanti-
ties of new types of synthetic rubbers that come up to all
expectations, and large-scale capacity has begun to come on

stream. In addition to the types of sterically ordered rubbers
known in Nature, there are now several new ones that can
be produced synthetically.
Like all great breakthroughs in knowledge, it immediately
became necessary to compare this achievement with the entire
previously known art, each specialist working in his own
field. It was soon proved that every unsaturated monomer
4 Polypropylene
that was known to produce a useful addition polymer by any

other means of catalysis, produced a different kind of polymer
with a stereospecific catalyst, or sometimes several kinds of
polymers with different catalysts or under varying conditions.
At this time we have no idea as to what impact these new
polymers will have on the plastics industry, but it is safe to
say that it will be very great.
It is also quite clear that the stereospecific catalysts will
strongly affect another great use of synthetic polymers in

our economy, that of The high strength required
textile fibers.
by a textile fiber had heretofore been possible only with the
use of rather expensive monomers. Strongly polar groups
were needed in the molecule to give the intermolecular forces
necessary for high strength, and monomers containing such
groups are expensive. Stereospecific polymerization showed
that relatively simple and inexpensive starting materials, such
as propylene, could make fibers that were as strong as the
more complex and expensive fiber-forming materials now on
the market. It is not the purpose of this book to explore the
complicated problems that separate the laboratory discovery
of a fiber-forming polymer from the general adoption of the
fiber, but in economic facts are so evident that
this case the
it is quite impossible for problems of technology or custom
long to delay widespread use.

Montecatini in Italy has made a great deal of progress in
this field; it has spun yams as fine as 1.5 denier, finer
than natural silk, and has produced blankets and robes that
feel very much like wool. By a different technology, cotton-
like fabrics can also be produced from polypropylene.
It is quite impossible to dye polypropylene fiber in conven-
tional ways, but Montecatini has shown polypropylene fibers

dyed in bright colors. Its 10-million-pound-a-year fiber plant
near Rome should soon be in production, and the position
this fiber takes in the textile market should soon be seen.
Introduction 5
In this country there has been a great deal of interest in

polypropylene fiber; definite plans that have been announced
will be discussed in Chapter 9. A small amount of coarse
polypropylene fiber has been made for industrial uses and
monofilament weaving, such as car-seat covers, but a domestic
textile fiber seems yet a few years distant.
The entrance of American Viscose Corporation into the
polypropylene field in 1959, through its subsidiary AviSun,
put a strong textile-fiber organization into the field. Its
commercial product was polypropylene film for packaging

first
purposes, but it can hardly be doubted that it will also go

into the fiber market. The domestic delay in the fiber field is
undoubtedly due to the overcapacity in the synthetic-fiber

field which makes the major companies reluctant to introduce
a new material. In 1958 the synthetic-fiber industry operated

at something like 70 per cent of capacity, and a considerable
amount of new capacity has come into operation since.
The commercial development of polypropylene resin is
also closely linked with that of low-pressure polyethylene.

The tremendous success of polyethylene plastic, which started
right after World War II and continues to the present time,
made American industry very receptive to the idea that an
improved polyethylene would have an even more striking
success. When Ziegler in Germany, in 1954, and the PhilHps
Petroleum Co. in this country, in 1955, announced processes
for producing a higher-density polyethylene, stronger and
stiffer than the polyethylene then known, there was a tre-
mendous rush to obtain licenses to make the material. By
1958, installed capacity for producing high-density poly-
ethylene exceeded 350 million pounds per year. In that year
sales probably did not reach 50 million pounds. Although
increased consumption of low-pressure-process polyethylene
continues, it is now evident that a major miscalculation had
been made as to its growth and near-term market. As a
6 Polypropylene
matter of fact it now appears that the major use of low-pres-

sure polyethylene may be as a blending agent to upgrade the
properties of the high-pressure materials.
The actual commercial history of polypropylene resin is
quite brief. Montecatini was the first commercial producer;

it began to export polypropylene resin into this country in
1957.
Interest in the materialwas very active in Europe, and a
number European firms obtained Montecatini licenses.
of
For the first two years it appeared, from announced plans,
that the polypropylene industry would grow more rapidly in
Europe than in the United States.
The first domestic producer of polypropylene was the Her-
cules Powder Company, which started a 25-million-pound-
per-year plant in 1957. The reception of the resin was very
favorable, and it has announced the building of a 100-million-
pound plant.
The next domestic producer was AviSun, which put facili-
ties, converted from linear polyethylene production, on stream
in the fall of 1959. This plant was leased from Koppers. At

the same time it also started the production of polypropylene
film for packaging purposes. A small number of producers
had previously made polypropylene film from Hercules or
Montecatini resin. Neither the production nor the marketing
facilities of enough to put any great
these firms were large
volume on the market. With a captive source of resin, and
the tremendous marketing organization that American Vis-
cose has built up for cellophane at its disposal, it can be
expected that AviSun will be able to produce and sell a great
deal of polypropylene film very shortly.
The remarkable achievement of the AviSun Corporation in
having resin on the market a year after they started in busi-
ness was made Both of
possible by a combination of factors.
the parent companies, American Viscose and the Sun Oil
Introduction 1
Company, had been doing extensive polypropylene research

for several years. They had both built up a considerable staff
of polypropylene experts and a good volume of technical
information. After the parent-company managements had
decided that it would be more advantageous to work together
than for each to set up separate polypropylene facilities, it
was discovered that the work done by the two companies
fitted together remarkably well. The Sun Oil Company had
concentrated research on monomer and polymer production

up to the finished resin, whereas Viscose had worked mainly
on the processes for making the resin into film and fiber. In
this way AviSun, at its inception, had all the background work
already done. The next important factor was the opportunity

to lease part of the Koppers linear polyethylene facihties for
conversion to polypropylene. Since the processes are quite
similar, it took only a short time to make the conversion, and
AviSun was operating a plant in advance of other firms who
had announced plans before AviSun was even formed.
The Standard Oil Company of New Jersey announced its
plans to enter the polypropylene field on August 22, 1958,
and its Humble Oil subsidiary started construction on a
40-miUion-pound plant in that year. This facihty went into
production early in 1960. Part of the production of this plant
will be marketed by the Spencer Chemical Company on a

4-year contract.
The Dow Chemical Company announced in 1959 that
it would construct polypropylene production facilities at
Bay City, Michigan, and at Torrance, California; the latter
facility is expected on stream in 1961. No announcement of
capacity or timing of the Bay City facility is now available.

At about the same time, Eastman Chemical Products Co.
announced that it would be supplying polypropylene, but
without any statement of time or capacity. Later it an-

nounced a capacity of 25 million pounds in Longview, Texas.
8 Polypropylene
It had been known throughout the industry that this company
had been market testing considerable tonnage of polypro-

pylene in 1959, but without any indication as to source. It
has since been announced that this had been produced in a

small-capacity plant which wiU continue to produce develop-
mental quantities until the main plant is completed.
Firestone has announced that it will build a polypropylene
plant at Hopewell, Virginia.
The Industrial Rayon Corporation had a small pilot plant
in operation in 1959 and was actively entering the fiber field.
Since it specializes in fabrics for heavy-duty industrial uses,
it is not as much concerned with the dyeing and finishing
as are other producers, and it may have entered the field
without such specialized knowledge.

2. PROPERTIES OF POLYPROPYLENE
Since polypropylene has yet to find its place in the plastics

market, we must reach our understanding of its major ap-
plications by considering its properties. A large number of
physical and mechanical properties have been used for many
years as guides to the usefulness of plastic materials for
various apphcations. Many of these standard properties have
been determined for polypropylene.
Since polypropylene is by no means a standardized material
it would be somewhat misleading to give single values to
represent the material, and merely stating ranges is not very

informative. We will therefore start this chapter with a look
at the physical properties of some commercially available
polypropylene as reported by the manufacturer.
These tables are reproduced as received, without any at-
tempt to correlate them or draw direct comparisons, because

methods of sample preparation and test methods differ
enough to make direct comparison meaningless. These do not,
of course, represent all possible polypropylenes, and later
discussion will include references to still other resins. They
do, however, give us a convenient starting point because they
represent actual materials now available on the market. The
trade names of the materials and designations are included
where given.
For the sake of simplicity we shall not hereafter refer to
any of these specific materials but will consider a representa-
tive polypropylene, keeping in mind that it may be possible
that some polypropylenes may differ appreciably from this.
9
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Properties of Polypropylene 13
Table 2.3. Properties of "Escon'
Various grades of Escon will be offered to permit the processor to

choose the grade best suited for his needs. For this reason, a range
of data is shown for several of the typical Escon properties. As the
density (crystallinity) of polypropylene increases, the tensile stiffness
and surface hardness of the material also increase. Values for all of
these properties will vary, depending upon how the sample is molded
and what, if any, treatment is given to the sample after molding.
Property Data Method

General Properties
Density (73°F) (g/cc) 0.897-0.910 ASTM D1505-57T
Melt index (250°C)
(g/10 min) 1-10 ASTM 1238-57T
(load, 2,160 g)
Environmental stress
cracking (100% "Ige-
pal CD-630") None Bell Labs.
Burning rate Slow ASTM D635
Machining qualities Excellent
Mold shrinkage (in./in.) 0.015-0.030
Water absorption (%) 0.01 ASTM D570-57T
Mechanical Properties
Yield strength, psi
(2"/min) 3,800-5,100 ASTM D638-58T
Tensile strength, psi
(2'7min) 2,500-4,900 ASTM D412-51T
Yield elongation, %
(2"/min) 13-18 ASTM D638-58T
Ultimate elongation, %
(2"/min) 22-315 ASTM D4 12-5 IT
Impact strength
(ft-lb/in.)
Izod notched 1
Izod unnotched 16
Hardness
Rockwell R 80-90 ASTM D785-51
Shore D 70-75 ASTM D675-55
Elastic modulus, psi
(2'7min) 45,000-60,000 ASTM D638-58T
14 Polypropylene
Table 2.3 (cont.)

Flexural modulus of
elasticity, psi (2"/min) 111,000-176,000 ASTM D790-58T
Flexural modulus of rup-
ture
(Flexural strength), psi
(O.OS'Vmin) (no
break-max load) 65,000-81,000 ASTM D790-58T
Compressive yield stress,
psi (O.OS'Vmin) 5,300-6,400 ASTM D695-54
Compressive strain @
yield, %
(O.OS'Vmin) 15 ASTM D695-54
Compressive elastic
modulus, psi (0.05'V
min) 53,000-63,000 ASTM D695-54
Stiffness in flexure, psi 95,000-150,000 ASTM D747-58T
Modulus of elasticity, psi 100,000-128,000 ASTM D1043-51
Taber abrasion (mg.
loss/ 1000 cycles)
(CS-17 wheel, 1,000 g
load) 29-32
Thermal Properties
Melting point (°F) 335 polarizing micro-
scope
Vicat softening point (1
kg) (°F) 266-293 ASTM 1525-58T
Deflection temperature ASTM D648-56
°F @264 psi fiber
stress 131
°F @66 psi fiber stress 188
Coefficient of thermal
conductivity
(cal/cm/cm/sec/°C) 2.80x10
(Btu/in./ft/hr/°F) 1.13
Coefficient of linear
thermal expansion
(in./in./°C) 0.00020 ASTM 696-44
Specific heat @73 °F
(cal/g) 0.46
I
Table 2.3 {cont.)
lectrical Properties
Volume resistivity (ohm-
cm) 6.5x10 ASTM D257-54T
Dielectric strength
(volts/mil)
short time, V&" thick-
ness 660 ASTM D149-55T
step by step, V&" thick-
ness 650
Dielectric constant (10
cycles) 2.0 ASTM D150-54T
Dissipation (power)
factor (10 cycles) 0.0002-0.0003 ASTM D150-54T
In comparing polypropylene with other plastics, one of its
striking properties is its low density. This is important from a

cost standpoint, because it means that more units of any given
size can be made from a pound of polypropylene than from
a pound of other thermoplastics. In many applications the
light weight will be an advantage, quite regardless of cost.
Figure 2.1 is a bar graph which represents the cubic inches
of material in a pound of plastic.
Tensile strength extreme importance. Figure 2.2
is also of
shows how polypropylene compares with other common
themoplastics. In this case it is not so outstanding, but it is
still superior to many others.

If these data are compared with Figure 2.3, which shows
per cent elongation at break, it will be seen that polypro-
pylene has a very favorable combination of relatively high
strength with great elongation. Of all the materials compared,
only expensive nylon is better when the combination of
strength and elongation is considered.
Stiffness will often determine the plastic to be used for any
particular application. It is not always the stillest material
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183 Polypropylene
CELLULOSE ACETATE 1
ACETATE - BUTYRATE
AND PRO PI NAT E 1
NYLON 1
POLYSTYRENE 1
POLYET H YLENE
LINEAR 1
LOW DENS ITY 1
POLY PROPYLENE 1
22 26 30
CUBIC INCHES PER POUND
Figure 2.1. Volume per pound of common thermoplastics.
LOW DENSITY
POLYETHYLENE
IMPACT STYRENE
HIGH DENSITY
POLYETHYLENE
CELLULOSE
ACETATE-BUTYRATE
POLYPROPYLENE
CELLULOSE ACETATE
STYRENE
NYLON
2 4 6 8 10
TENSILE STRENGTH 1000 PS I
Figure 2.2. Tensile strength of common thermoplastics.

Properties of Polypropylene
ST Y RENE
IMPACT STYRENE
CELL ULOSE
ACETATE-BUTYRATE
LINEAR
POLYETHYLENE
POLYPROPYLENE
NYLON
LOW DENS ITY
POLYETHYLENE
200 400
PERCENT ELONGATION
Figure 2.3. Ultimate elongation of common thermoplastics.
that is best for every application. Figure 2.4 shows that poly-
propylene is a material of intermediate stiffness.
As with tensile strength and elongation, it is necessary to
consider flexural strength with stiffness. Some of the com-
parison materials, such as nylon and low-density polyethylene,
cannot be broken in flexure on standard test specimens. The
flexural strength of the others is compared in Figure 2.5.
LOW DENS ITY

~1
POLYETHYL ENE
LINEAR
POLYETHYLENE 1
POLYPROPYLENE 1
IMPACT STYRENE
CELLULOSE
ACETATE 1
CELLULOSE
ACETATE- BUT Y RATE 1
STYREN E 1
NYLON 1
200 400
FLEXURAL MODULUS lOOOPS 1
Figure 2.4. Stiffness of common thermoplastics.

I
20 Polypropylene
HIGH DENSITY
POLYETHYLENE 1
GEL LULOSE
ACETATE 1
IMPACT STYRENE 1
POLYPROPYLENE 1
POL YSTYRE NE 1
2 4 6 8 10 12
FLEXURAL STRENGTH I000P5
Figure 2.5. Strength in flexure of common thermoplastics.
Surface hardness is very important in many applications.

Figure 2.6 shows polypropylene to be one of the harder of
the common thermoplastics.
Polypropylene has the highest heat-distortion point of any
of the less-expensive plastics; among familiar materials, only
nylon is higher. It is very significant that the heat-distortion
point of polypropylene is high enough not merely to allow
exposure to boiling water but even to permit autoclaving at
moderate pressures. This opens a wide field previously closed
LOW DENSITY
POLYETHYLEN E
HIGH DENSITY
POLYETHYLENE
CELLULOSE
ACETATE-BUTYRATE
POLYPROPYLENE
STYRENE AND
IMPACT STYRENE
NYLON
40 80 120
ROCKWELL HARDNESS (R)
Figure 2.6. Rockwell hardness of common thermoplastics R scale.

to thermoplastic materials. Figure 2.7 shows the heat-distor-

tion point of several familiar plastics.
Anyone who has had much experience with plastics has
found that these standard properties can give only a very
rough idea of how well a particular plastic will be adapted to
a given application. There are many new techniques for eval-
LOW DENS ITY

POLYETHYLENE
HIGH DENSITY
POLYETHYLEN E
CELLULOSE
ACETATE -BUTYRATE
IMPACT STYRENE
STYRENE
CELLULOSE
AC ETATE
POL YPROPYLENE
NYLON
100 200 300
HEAT DISTORTION TEMP °F
Figure 2.7. Heat-distortion temperature of common thermoplastics.
uating resins that give a great deal more information than do

these properties, and there are specific properties which relate
to definite applications. The following pages wiU discuss some
of the special properties that must be considered, as well as
the range of properties that can be obtained from poly-
propylene.
This more detailed study will be carried on in two stages.
First, the general physical properties of polypropylene, as
they are determined in the laboratory, will be discussed to
22 Polypropylene
give an understanding of what kind of material it really is

and how it under conditions of processing and use.
will react
The second part will describe processing methods and ap-
plications, and will explain the special properties of poly-
propylene. In all phases, comparison with more familiar
plastics will be used to maintain perspective.
STRENGTH CHANGE WITH TEMPERATURE
Since polypropylene is a thermoplastic material, one of

the most important aspects of its behavior relates to its
change in properties with regard to temperature.

In common with all thermoplastics, polypropylene is an
extremely hard, stiff, but brittle material at very low tempera-
tures, gradually becoming softer, more flexible, and tougher
as the temperature increases, and finally reaching a stage
where it softens beyond the range of usefulness. Figure 2.8
shows how the stilSness of isotactic polypropylene varies with
temperature. In order to give some standard of comparison,
a similar curve is given for high-density polyethylene.
Although high-density polyethylene is not, to most people, a
very familiar material, its properties are sufficiently similar
which to use must
to polypropylene so that the question as to
often arise. For this reason seems a useful comparison to
it
make. It will be seen in Figure 2.8 that just below room

temperature the two materials have the same stiffness. Upon
warming, polypropylene softens a little more rapidly than
polyethylene, so that through most of the range of ordinary
use polypropylene is the more ffexible. As the temperature
approaches the boiling point of water, however, the two
materials again reverse positions, polyethylene dropping off
rapidly to a negligible strength while polypropylene retains
at least a little stiffness until somewhat above 212°F.
It should be pointed out that a wide range is possible in

the properties of polypropylene, and the particular sample
used to obtain these data is not as stiff as most polypropylene
o NCA
w30 LI R
POLYETHYLENE
20
POLYPROP YLENE
°IOF
-300 -150 150

TEMPt RATURE
Figure 2.8. Comparison of polypropylene and linear polyethylene at
various temperatures.
now on the market. Typically, polypropylene is appreciably

stiffer than linear polyethylene in the room temperature
range, even though Figure 2.8 shows it to be less stiff.
Below room temperature the difference between the two

materials is more marked; polypropylene becomes stiff much
24 Polypropylene
more rapidly than polyethylene and remains the stiffer of the

two materials until, at a very low temperature, the materials
again reverse positions. This means that, for applications
requiring flexibility at low temperatures, polypropylene is
probably not to be recommended.

The fact that a very rapid change in stiffness, such as is
exhibited by polypropylene around the freezing point, is
referred to as a "glass transition," coupled with the fact that
certain arbitrary brittleness tests will cause the failure of
polypropylene samples at about this temperature has led
many people to believe that the material is entirely useless at
low temperature. This is by no means true, because, even
below its glass-transition temperature, polypropylene is still a
good deal more flexible and tougher than some widely used
materials, such as polystyrene, at room temperature. At
extremely low temperature polyethylene undergoes transition
and becomes much stiffer than polypropylene, whereas in
this region polypropylene retains a much more useful degree
of flexibility. Polypropylene varies a good deal, but the gen-
eral picture shown in Figure 2.8 is valid.
The problem of properties versus temperature can also be
studied from the point of view of impact strength, i.e., the
abiUty to withstand a sudden blow. Figure 2.9 shows the
impact strength versus temperature relationship of high-
density polyethylene, polypropylene, and polystyrene. Poly-
propylene is much tougher above room temperature, but it
will be noted that at low temperature it does not completely

lose strength but remains at a relatively low but still useful
its
level between polystyrene and high-density polyethylene.

High-impact polystyrene is widely used in refrigerators be-
cause of low-temperature toughness. These data do not ex-
tend to the extremely low temperatures shown in the previous
figure, but it seems likely, from the data shown there, that if
U.7
o
•o5 POLYPROP Y LENE
1-2
o
<
LINEAR POLYETHYLENE
POLYSTYRENE
200 100 100
TEMPERATURE "F
Figure 2.9. The change of impact strength with temperature for three
thermoplastic materials.
they were so extended the polyethylene line would ultimately

dip below the polypropylene line.
From this we can see that, although temperature makes
considerable difference, polypropylene retains a useful degree
of strength over a wider temperature range than do most
thermoplastics, being particularly outstanding at high tem-
peratures and adequate for many applications at low
temperatures.
26 Polypropylene
THE EFFECT OF RATE OF LOADING ON STRENGTH
Another important factor in the physical properties of a

material is the effect of the rate of application of stress. Any
material can hold, for a short time, a load that will eventually
break and a sharp quick blow may shatter a material that
it,
We have
could easily withstand a similar load, slowly applied.
already mentioned the resistance of polypropylene to quickly
applied loads. We shall now consider how it withstands loads
of long duration. Much of the following refers to work done
by Bryce Maxwell at the Princeton University Plastics Labo-
ratory. This is concerned primarily with the phenomenon
known as creep, but is approached by loading the material
with a force, the frequency of application of which can be
varied. It might be supposed that a material that was strong
and stiff to short-term loads would show less creep on long-
time loading than a material that deformed more from fast
loads, but this is by no means true. The properties of poly-
ethylene are a case in point. The relatively soft low-density
polyethylene deforms easily under short-term loads, whereas
the high-density material is a good deal more resistant to
them. It turns out, however, that when a load is applied over
a long time, the positions are reversed, and the low-density
material can withstand a greater load than the high-density
material for the same deformation.
This means that it is essential to understand the time-
dependent properties of a material before using it in any
application. Although long-term creep tests are essential for a
final determination of the suitability of a material for applica-
tions involving long-term stresses, a great deal can be learned
in a short time by applying a dynamic stress to the material.
These dynamic data can be manipulated to determine actual
creep resistance or stress relaxation; however, what we shall
present here is in terms of loss factor, which measures the heat
lost in the material because of the dynamic loading. A high

loss factor gives the material vibration-absorbing qualities,
but this also means that its resilience, or ability to recover
from deformation, is poor. Of special interest is the change
in loss factor with the change in frequency of the dynamic
load. At a high frequency of load application, most materials
0.01 0.1 1.0 10

CYCLES PER SECOND
Figure 2.10. The change of loss factor with frequency of load

application for polypropylene and linear polyethylene.
have a low loss factor, but with many materials this increases
rapidly as the frequency drops oif. This indicates that the
structure of the plastic is being permanently deformed by the
load, and long-term tests would show that it has poor creep
characteristics.
High-density polyethylene is a familiar case of this sort.
Early workers were highly impressed by the strength and

rigidity of this material and confidently predicted excellent
long-term strength on the basis of these characteristics. Long-
term testing proved quite the opposite; the strong, hard,
28 Polypropylene
high-density polyethylene really had less long-term load-

carrying ability than the soft, weak, low-density material.
This fact could readily have been predicted from dynamic test
data. Figure 2.10 shows the change in loss factor with fre-
quency at — 10°C.
30 50 120
TEMP OQ
Figure 2.11. The change in loss factor at 100 cps with temperature
for polypropylene and linear polyethylene.
The sharp rise shown by linear polyethylene at the low-

frequency end is is different, as can
obvious. Polypropylene
be seen in Figure 2.10, lower curve, which shows a very
moderate increase in loss factor between 100 and 0.01 cycles.
This indicates that polypropylene will resist long-term loads
well.
Similar curves can be drawn up to and somewhat above
room temperature, where the increase in loss factor for linear
polyethylene is even more marked. At about 40° or 50°C
the loss factor of linear polyethylene, even at high frequency,

increases very rapidly, and the material loses its resiliency.
This is which
illustrated in Figure 2.11, the top curve of
shows 100 cps against
loss factor for linear polyethylene at
temperature. The lower curve gives the same data for poly-
propylene.
POLYPROPYLENE
2 LINEAR POLYETHYLENE
UJ200
0.1 1.0 10 100

CYCLES PER SECOND
Figure 2.12. The change of in phase modulus with frequency of load

application for polypropylene and linear polyethylene.
It is surprising how moderate the change in loss factor with

temperature is A rapid rise between the
for polypropylene.
— 10°C and room temperature concurs with our pre-
figure
vious knowledge that polypropylene changes rapidly in this
temperature range. The effect of frequency, however, remains
very small. At room temperature the high frequency loss
factor of polypropylene is greater than that of linear poly-
ethylene, but, unlike the polyethylene, there is no rise as
frequency decreases.
30 Polypropylene
Even more remarkable is the fact that as we increase the

temperature above room temperature the loss factor of poly-
propylene again decreases and remains quite low up to
120°C. This means that polypropylene remains resilient and
retains its ability to recover from loads even up to high tem-
2000-
1500-
POLYPROPYLENE
60O0 - 20.5 GPS
0.1000-
500-
3 4 5 6
STRAIN 0.001 IN PER IN
Figure 2.13. Stress-strain curve for polypropylene at 60 °C and

20.5 cps load application.
peratures, whereas the Unear polyethylene loses its resilience

above room temperature.
at only a little
The modulus of elasticity in phase with the loading, when
an intermittent load is applied, varies with the frequency of
application. Here, again, a small variation with frequency
gives promise of good long-term strength, whereas a larger
one indicates a tendency to creep. Figure 2.12 gives a plot
of in-phase modulus versus frequency for polyethylene and
polypropylene showing that polypropylene is less time-
dependent. At the lower frequencies the modulus of poly-
ethylene drops off sharply, but polypropylene changes very

little.
This ability to carry loads for long periods and over a

wide temperature range is one of the properties that will make
polypropylene very valuable in engineering and other applica-
tions. More than almost any other plastic, it can be considered
for applications that require long life under severe conditions

of stress and environment.
For engineering purposes there is a very important point
on the stress-strain curve known as the limit of linear re-
sponse. Figure 2.13 shows the beginning of a stress-strain
curve for polypropylene at 60°C and 20.5 cps. Even at this
high temperature polypropylene will take a stress up to about
1,000 psi perfectly linearly. Within this range there should
be no permanent deformation.
EFFECT OF ENVIRONMENT ON STRENGTH
Environment includes factors other than those so far con-

sidered, one of the most important of these being the effect of
various materials with which the plastic is in contact. Almost
every application involves contact with materials that may
weaken the plastic, and in many applications its ability to
contain some other substance is critical.
It is well known that polyethylene exhibits a property
called environmental stress cracking, which is characterized
by failure at relatively low but complex stresses in the pres-
ence of certain stress-crack-inducing agents. This has been
an important limitation of polyethylene in many applications,
and it is only in recent years, after nearly 20 years of inten-
sive work on the problem, that some polyethylene manufac-
turers have succeeded in making polyethylene that is substan-
tially free from this weakness.
Polypropylene has shown no sign of this defect, either with

32 Polypropylene
agents that induce stress cracking in polyethylene or with a

wide variety of other materials.
The problems of chemical resistance and permeability of
polypropylene cannot be answered in such an easy and cate-
gorical manner. The polyolefins all have excellent resistance
to water and to water solutions of many materials, especially
salt and acid solutions that are very destructive to metals.
Table 2.5. Change in Tensile Strength of Polypropylene and

Polyethylene on Immersion in Selected Liquids (3 to 6 Weeks)
Polypropylene
Polyethylene
(per cent crystallinity)
Liquid
Low density Linear 63 56
Xylene -30.7 -12.8 -5.3 -1.0

Turpentine -37.7 -15.6 6.0 -16.3
Chloroform -100% 7.9 0.8 2.0
Hexane 9.3 23.5 -6.3 -14.8
Commercial bleach -22.8 -18.2 -24.2 -20.9
1% hydrogen peroxide -13.9 -32.7 8.6 -7.2
The use of polyolefins in structures which must be in con-

tact with such agents is a growing application which should
receive added stimulus from the availability of polypropylene
with its superior physical propetries. In many cases the actual
chemical resistance of polypropylene is superior to that of
other polyolefins, but this cannot be taken as a general rule.
The data in Tables 2.5 and 2.6 represent results of a series
of tests with high- and low-density polyethylene and poly-
propylene. It must be remembered that
it is dangerous to
generalize Other grades and

too broadly on these data.
sources of both polyethylene and polypropylene might give
better or worse results; however, the samples used were
representative of some of the most widely used materials.
The contact liquids used were ones that were known or
expected to have particularly drastic effects on poly olefin

materials. The most active materials in Table 2.5 were tested
for a shorter time than those in Table 2.6.
Examination of the tables shows that linear polyethylene
has by far the poorest resistance to the materials tested. As a
Table 2.6. Change in Tensile Strength of Polypropylene and

Polyethylene on Long Immersion in Selected Liquids
(4 Months or More)
Polypropylene
Polyethylene
(per cent crystallinity)
Liquid
Low density Linear 63 56
Water 1.8 -1.1 -8.6

Isopropyl alcohol 1.1 -7.1 -7.1 -11.3
Primol D -8.1 -78.0 10.1 -20.0
Silicone oil -1.5 -11.0 13.8 -7.1
Methylethylketone -5.2 -42.7 -6.0
10% sodium hydroxide -1.6 -14.0 3.2 -4.5
10% common salt 2.6 -6.5 -9.1
10% acetic acid -8.1 9.8 13.2 -4.7
Dioctyl phthalate -6.5 -2.3 5.9 -3.6
Linseed oil -5.6 -60.5 1.1 -3.4
Corn oil -50.5 16.0 -19.8
Methanol 2.2 2.5 2.3 -7.2
"Igepal" * -100 -100 9.8 -1.8
* A surface-active agent used as detergent.
matter of fact, it is the only sample, in most cases, which is
weakened to a point that clearly precludes its use. The low-

density polyethylene and the polypropylene rank differently
with the various reagents, sometimes one, sometimes the
other being best. It should be remembered that the tables
give per cent tensile change. Since the polypropylene starts
out considerably stronger than the low-density polyethylene,
it may still be stronger even when it has lost 10 per cent of
34 Polypropylene
its and therefore may be preferable even where its

strength,
rating in the tableis poorer. In general, for any application
where prolonged contact with any substance is an important

part of the requirement, tests should be made under condi-
tions approximating those of actual use.
RESISTANCE TO LIQUID PERMEATION
The situation as regards permeability is even more com-

plex. Most published literature leads one to believe that the
Figure 2.14. Water permeability of polyethylene and polypropylene.
permeability of the available polyolefins is about that shown

in Figure 2.14, which shows the water permeability of low-
density polyethylene to be quite high, that of the linear con-
siderably lower, and that of polypropylene a little lower still.
This relationship does not hold at all when we consider other
permeants.
First, there is a group of materials that have stress-crack-

inducing When these are used as permeants, hnear
activity.
polyethylene shows high permeability, probably because

microscopic cracks are opened up in it. Permeability to three
such materials is shown in Figures 2.15 through 2.19.
/
LI NEAR /pOLYETHVLENE
:2oo
/ LESS CRYSTALLINE
/ POLY PROP YLJ^WT
/ ^^ 9QViy^VtHZ
100
/ ^^^^.^-^^^^^^HIGHLY CRYSTALLINE
Z^ ^^^^^^^
80
DAYS
POLYPROPYLENE
120
Figure 2.15. Methylethylketone permeability of polyethylene and

polypropylene.
As can be seen in the graphs, low-density polyethylene and

polypropylene resist these materials much better than does
the high-density polyethylene. Silicone oil, a common polish
ingredient, was very well resisted by low-density polyethylene
and polypropylene but not by linear polyethylene. Methyl-
ethylketone, a lacquer solvent, and methyl alcohol permeate
the low-density polyethylene and polypropylene to a lesser
extent than they do the linear material. The two polypro-
pylene samples tend to bracket the low-density polyethylene
in some cases. Rather surprisingly, methyl alcohol permeates
36 Polypropylene
300-
:200
tflOO-
Figure 2.16. Methyl alcohol permeability of polyethylene and

polypropylene.
600-
LIN EAR/POL YETHYL ENE
= 200-
POLY PROPYLENE
LOW DENSITY POLYETHYLENE
Figure 2.17. Silicone oil permeability of polyethylene and

polypropylene.
DAYS
Pigure 2.18. Chloroform permeability of polyethylene and
polypropylene.
400-
:200
Figure 2.19. Isopropyl alcohol permeability of polyethylene and

polypropylene.
38 Polypropylene
higher crystallinity polypropylene more readily than lower

crystallinity. With substances of this sort, polypropylene is
the preferable polyolefin, quite regardless of permeability,

because even low-density polyethylene shows some tendency
toward stress cracking, and the polypropylene article would
have the longer service life.
S300
=200
I*'
100
10 20
DAYS
Figure 2.20. Hexane permeability of polyethylene and
polypropylene.
In the case of chloroform (Figure 2.18), low-density poly-

ethylene shows the greatest permeability and high-density
polyethylene the least, with polypropylene falling between,
but nearer the high density.
There are also substances to which low-density poly-
ethyleneis the most resistant. Isopropyl alcohol (Figure 2.19)
is an example. In such a case the low-density polyethylene
would be the preferred material from a permeability stand-

point.
There is also a group of solvents that permeate polypro-

pylene more readily than they do other poly olefins. The most
striking of these is hexane (Figure 2.20). Turpentine shows
the same behavior to a lesser extent. Where permeability is
an important factor, polypropylene should not be used with

these materials.
^300
150-
20 30 40
DAYS
Figure 2.21. Hydrogen peroxide permeability of polyethylene and
polypropylene.
Other materials that must be considered very carefully are

those that give oS highly reactive gases. Hydrogen peroxide,
for instance (Figure 2.21), shows more rapid permeation of
polypropylene than of other poly olefins.
Similarly, "Clorox" (a chlorine-containing bleach) per-
meates one of the polypropylene samples quite readily
(Figure 2.22).
It should be observed that the two polypropylene samples
differ widely in their resistance to those reagents, and that it
40 Polypropylene
is the low-crystallinity sample which has the better resistance.

In most other cases the highest-crystaUinity sample is better.
This shows that no one type of polypropylene will have the
best resistance to all materials, but that a choice will have to
be made in each individual case.
300
:200.
100-
Figure 2.22. "Clorox" permeability of polyethylene and

polypropylene.
In Chapter 3 the relationship between crystallinity and

permeability is discussed. Permeation is mainly through the
amorphous fraction.
The percent crystallinity of the materials in this study was
as shown in Table 2.7.
Table 2.7.
Material 7o crystallinity at 25°C

Low-crystallinity polypropylene 56
High-crystallinity polypropylene 63
Low-density polyethyelne 61
Linear polyethylene 91
It is possible to make polypropylene with a crystallinity

both above and below that of these samples, and it will then
differ from them in permeability. In the current state of
knowledge, it wiU be necessary to make simulated service
tests in any case where permeability to some specific liquid is
critical.
OTHER ENVIRONMENTAL FACTORS
In common with other poly olefins and most other plastics,

polypropylene is adversely affected by ultraviolet irradiation.
This is important only where the material will be subjected
to direct sunlight or other sources of ultraviolet light.
Very effective stabilizers are available which can protect
polypropylene from such damage. Figure 2.23 shows the
effect of 0.5 per cent of a good ultraviolet-light stabilizer on
80
/
tn
o
-1
POLYPROPYLENE
/
I WITHOUT /
STABI LI ZER /
UJ
E20
1 WITH
STABtLI ZER^/^
50 100 150
HOU RS EX PCS U RE
Figure 2.23. Light stabilizers protect polypropylene against strength

loss from light exposure.
42 Polypropylene
the loss of strength of polypropylene fibers when they are

exposed to concentrated ultraviolet light in an exposure
cabinet. The exposure times shown correspond to a long
service life under any natural environment. Where a black
color is not objectionable, excellent resistance to ultraviolet
can also be imparted by the use of carbon black.
POLY PROPYLENE
250
oc
UJ
a.
40
o
o
z
230
1-
o
^20
<
z
iii
LINEAR ^/
POLYETHYLENE^^"^
5 100 150 250

HOURS AT 200»F
Figure 2.24. Polypropylene oxidizes rapidly compared to linear

polyethylene.
OXIDATION OF POLYPROPYLENE
A great deal of attention has been paid to the susceptibility

of polypropylene to oxidation. In fact, polypropylene is a
useful thermoplastic only because means have been found for
stabilizing it against oxidative attack. Unstabilized polypro-
pylene oxidizes rapidly at relatively low temperature. Fig-
ure 2.24 compares oxygen uptake at 200°F for unstabilized
polypropylene with that of linear polyethylene.
This is not really a matter for concern, because commercial
products will all be stabilized. Figure 2.25 shows how greatly
an antioxidant can lengthen the time before any appreciable

oxidation starts. There is a 64-hr period before any oxygen
uptake starts, even at this relatively high temperature. This
gives polypropylene an oxidation stability comparable to that
of other thermoplastic materials.
50-
40-
UNSTABI LI ZED
STA Bl L IZE D
20
20 40 60
HOURS AT30 0OF
Figure 2.25. Antioxidant reduces oxidation of polypropylene at
elevated temperatures.
In service, polypropylene is really much more heat-stable

than some polymers which are generally considered quite
satisfactory in this respect.
Table 2.8 shows the change in tensile properties of two
representative commercial polypropylene resins at 110°C,
compared to a medium-density polyethylene and a linear
polyethylene resin.
It will be seen that 30 days at 110°C the linear poly-
after
ethylene has lost all and elongation; the medium-
strength
density polyethylene, while retaining its strength, no longer
44 Polypropylene
elongates; and the two polypropylene samples are, if any-

thing, strongerand more flexible than at the outset.
One very important fact about the oxidative breakdown
of polypropylene is that it becomes more fluid as oxidation
progresses. This can be shown in a variety of ways. Fig-
ure 2.26 shows the effect on melt index and of increased time
Table 2.8. Tensile Strength (psi)
Polyethylene Polypropylene
Time (days)
at 110°C Medium Linear 1 2
density
2,330 4,550 4,630 4,990

7 2,830 4,840 4,870 5,070
14 2,890 4,890 4,750 5,090
30 2,220 180 4,870 5,000
Elongation (%)
275 110 45 105
7 155 90 190 85
14 150 75 110 75
30 75 65
of preheat at the comparatively low temperature of 190°C.-

Polyethylene tends to stiffen and become less fluid under
the influence of heat and oxidation. This causes a crust of
decomposed polymer to form on the surface of equipment in
contact with the molten polymer. This crust carbonizes and
flakes off in a molding machine, or builds up and disrupts
the flow in an extrusion die. Problems related to this char-
acteristic constitute a fairly large item of cost in polyethylene
processing.
Polypropylene, by becoming more fluid as it decomposes,
willbe squeezed out before it has a chance to carbonize; thus
equipment will be kept clean much more easily. Polystyrene
is similar to polypropylene in this respect,becoming more

fluid as it who has had experi-
breaks down. Every processor
ence with both polystyrene and polyethylene is well aware of
the increased carbonization problems encountered with the
0.57
MELT INDEX RISE

0.56 I90OC
0.55
0.64
0.53
0.52
5 10 15 20 25
HEATI N& Tl ME - Ml N
Figure 2.26. The melt index of polypropylene increases with time

at 190°C.
latter material. This effect is discussed in more detail under

"Injection Molding and Extrusion of Polypropylene," in
Chapter 4.
CHARACTERIZATION OF POLYPROPYLENE RESINS
Up to this point we have considered polypropylene in gen-

eral, as compared to other plastics, and the behavior of
particular polypropylene resins which seem to be reasonably
representative of the material.
46 Polypropylene
It has been mentioned that polypropylene is an extremely
versatile material that can be made in many modifications.

It is essential to the understanding of the material that a few
simple standard tests should be made to show what can be

expected from a particular sample. Chapter 3 will discuss
the relationships between molecular configuration and phys-
ical properties, but here we are concerned only with simple
physical tests which reflect these molecular configurations.
The earliest and most comprehensive method of charac-
terizing polypropylene was worked out in the Montecatini
laboratories. The following pages reflect various publications
of G. Crespi and F. Ranalli of that organization, which give
the best information currently available regarding the range
of properties of polypropylene.
Isotactic Index
What this term means in regard to molecular configuration
will be considered later. For the present it will represent
the percentage of the resin that is insoluble in boiling n-

heptane. This is a very important value for polypropylene,
in many ways resembling the effect of density on the physical
properties of polyethylene.
Melt Index of Polypropylene

Much caused by the use of the term grade or
confusion is
melt index to characterize the flow properties of polypro-

pylene, because it is natural to expect that this is the same
value used to characterize polyethylene.
When the usual commercial grades of polypropylene are
run in a melt indexer in the manner used for polyethylene, a
very low value results. Flow is so little under these conditions
that it cannot be accurately measured. For this reason it is
common practice to modify the conditions in order to get a
measurable value. At this time there is no industry-wide
.
standardization of the conditions to be used, so that data

sometimes refer to different modifications.
In this book the term grade or melt index will refer to
determinations run on the standard melt indexer at 190°C
under a load of 22 lb. This is about 10 times the load used
for polyethylene. The other most common modification is to
use the standard load at 230°C. These methods give values
in the same general order of magnitude, but they are by no
means directly comparable.
5000
1
•
J
1/
y
'h
'
/
J
1\ 7
1
7S
h 4000
In 7
/
2
>-
/ n
Ten // 1 3500
)0 90 100
Isotactic index (%)
Figure 2.27. Variation of tensile yield stress with isotactic index

and melt index. (Left: grade over 5; right: grade below 1.) {Courtesy
Montecatini)
48 Polypropylene
Yield Strength
Perhaps the most striking effect of changing the isotactic

index is that increased isotactic index increases the yield
strength of the resin very sharply. Figure 2.27 shows this.
The four lines represent differences in melt index from below
1 on the right, to above 5 on the left. Note that at any given
110
/
/
/
100
/
/ /
/' /
90
/'
/
80
//
90 100
Isotactic index (%)
Figure 2.28. Variation of surface hardness (Rockwell R) with

isotactic index and melt index. (Top: grade over 5; bottom: grade
below 1.) {Courtesy Montecatini)
level of isotactic index, the higher melt index, that is the

easier-flowing resin, has the higher yield point. This is directly
contrary to experience with cellulosics and plasticized vinyls,
where easier flow means a more yielding resin. The reasons
for this rather unexpected behavior will be found in Chapter 3.
Hardness
Rockwell hardness also increases with increased isotactic
index and increased melt index, as shown in Figure 2.28.
Again, the easier flowing material is the harder.
Stiffness
The stiffness of polypropylene is greatly affected by isotac-

tic index and melt index, in much the same way as are yield
point and surface hardness; that is, the higher isotactic index
and the higher melt index give the stiff er resin. The data on
220,000
180,000 ^
•160,000 £
140,000
120.000
100,000
90 100
Isotactic index (%)
Figure 2.29. Variation in stiffness (flexural elastic modulus) with

isotactic index and melt index. {Courtesy Montecatini)
this relationship cannot adequately be expressed in a few

lines. They by the area shown in Fig-
are best expressed
ure 2.29 which bounded on the top by the high-melt-index
is
material and on the bottom by the low-melt-index material.

At very high isotactic index, melt index has no influence,
50 Polypropylene
whereas at lower isotactic-index levels, the high-melt index

material is stiffer.
Tensile Strength and Elongation
These factors are strongly influenced by melt index. If the

melt indexis over 10, elongation is below 100 per cent; as the
sample does not extend enough to orient it, failure occurs at

comparatively low values. If the melt index is low, elongation
may go up to 900 per cent, and the resulting orientation gives
a high breaking point. Lower isotactic index also gives higher
elongation, but in this case orientation is less and the break
strength lower. The rate of straui also greatly influences the
strength and elongation; at a low rate there is a great deal
of elongation, and the break strength is high. At high rates
of elongation the yield point will be higher, but the sample
will elongate less and will break well below the yield point.
Shear Stress
In polypropylenes of high isotactic index, shear stress falls
off with increasing melt index, as shown in Figure 2.30.
400
^ 5000
^
^ 360
E \^ 5500
p
\^ S
4500 J^
280
-0.4 0.4 0.8 1 2 og grade
O.i 2 4 6 1 20 grade
Mel inde X
Figure 2.30. Variation of shear stress with melt index, isotactic index
95 to 96 per cent. (Courtesy Montecatini)
Impact Strength
The relationship of isotactic index and melt index to im-
pact strength is somewhat complex, as shown in Figure 2.31.
Material with a low melt index has a uniformly high impact
strength, quite regardless of the isotactic index. Material with
a higher melt index, however, has high impact strength only
when the isotactic index is relatively low.
^100 50
I 80
00
^ 60 \
\V ^^
I 40
^^ — 20 S
_E
20
I 10
80 90 100
Isotactic index (%)
Figure 2.31. Variation of impact strength with isotactic index and

melt index. (Top: grade below 1; bottom: grade above 5.) {Courtesy
Montecatini)
Softening Temperatures
The vicat softening point shows a relationship to isotactic

index and melt index with which we are by now quite familiar.
The higher isotactic index and the higher melt index give the
highest vicat point (see Figure 2.32). It is perhaps a little
difficult to accept at first, but the material which flows most
easily is the hardest in almost all respects. It must be kept in

mind, however, that it is not the strongest or toughest.
,
52 Polypropylene
100 /
// 7
y^y^ y'/
^^
^
^
80 90 100
Isotactic index (%)
Figure 2.32. Variation of softening point (vicat) with isotactic

index and melt index. (Top: grade above 5; bottom: grade below 1.)
{Courtesy Montecatini)
Low-Temperature Brittleness
One of the much-discussed properties of polypropylene is
its low-temperature brittleness. This has been mentioned in

comparison with other plastics, but it is by no means the
same for all polypropylene, varying a great deal with melt
index and to a lesser extent with isotactic index. Figure 2.33
shows that the brittle point (as defined by ASTM D746)
rises very rapidly as the melt index goes up, especially when
the isotactic index is high (left curve) . A lower isotactic index
makes it possible to go to a higher melt index before the
brittle point is reached. This fact will limit the use of highly
isotactic materials with a high melt index in many applica-
tions, in spite of the many good qualities of this combination.
The previous discussion should give a reasonable idea of
what kind of material polypropylene is. It has a few prop-
20 \
^,0
/,'
/
/ 1
i
y ^ ,/
I 2 4 6 810 100
Grade
Figure 2.33. Variation of brittle point (ASTM:D 746) with melt

index and isotactic index. (Left: isotactic index 80 to 90 per cent;
right: isotactic index 70 to 80 per cent.) {Courtesy Montecatini)
erties that relate especially to particular applications, and

these are discussed in the following pages.
POLYPROPYLENE-FILM PROPERTIES
The polypropylene-film industry is so new that it cannot

be assumed that the film now available represents the ultimate
properties attainable; however, the currently available films
are our best guide to an understanding of what kind of film
can be made from polypropylene.
Biaxial orientation greatly improves the strength of poly-
propylene film, and many authorities believe that the future
of polypropylene film lies in a product so oriented. However,
polypropylene film made by the simple chill-roll extrusion
54 Polypropylene
method, which gives very little orientation across the sheet,

has properties that appear to be good enough to ensure a
wide market.
It has been the experience in the plastic-film industry, so
far, that the only resins to appear only as biaxially oriented
film are those whose properties, when not so oriented, are
not adequate to assure substantial markets. Polystyrene and
polyester resins are such materials. Other resins, such as
polyethylene, are improved considerably by biaxial orienta-
most of the polyethylene film on the market is made
tion, yet
by methods that do not take advantage of this fact. This is
because polyethylene film has adequate properties for most
uses, even when not fully oriented. This is also true of cellu-
losics and vinyl which are generally not oriented.
films
It is initially, this will also be true
probable that, at least
of polypropylene film. For this reason two types of unoriented
polypropylene film, both made on chill-roll equipment of
conventional design, were selected for description here.
These films differ in that the resin used to make type 1
has a low melt index and a high isotactic index, whereas the
resin used for type 2 has a high melt index and a low isotactic
index.
The properties of these films are shown in Table 2.9 in
comparison with properties of polyethylene and cellophane
films.
Certain factors not included in the table are worth discus-
sion. The lower-melt-index film retains its strength at much
lower temperatures than does the higher-melt-index film.
Poor low-temperature properties are often cited as a weak-

ness of polypropylene film, and the higher-melt-index film
should not be recommended for applications such as frozen-
food wrapping where low-temperature resistance is needed.
The lower-melt-index film, however, is entirely adequate for
such purposes.
c
18-20
4,400-18,000
15-45 4,400-8,100 1-3 3.5-6.8 0.05
150-200
0.4
10-300 5-10
29-30 3,400-3,600 100-125 1,000-2,000 0.25 125 580
a
'o
Ph
75-225 5-10
0.7 280 990
11 29-30 2,800-3,100 50-70 1,500-3,500
97
a 29-31 2,400-2,600 300-375 45-50 1,500-2,000 2-3 0.65 280
1a
29-31 2,800-4,400 200-250 350-450 2-3 0.65

97 280
100-115
sq
°F)
(g/100 75
100°F)
10^) at
psi) cc/100
X
(psi
°F, permeability
(NTP hr/mil
at
(psi)
(75
103
hr/mil
X (%)
modulus
impact
permeability
strength
vapor
factor
(%) in./atm./24
in./24
Elongation
Spencer
Tensile Tensile CO,
Area Haze
Water
sq o.,
Gas
56 Polypropylene
The other important difference between the two types of

polypropylene film is that the stiffness, indicated in the table
by the tensilemodulus, is much greater in the type-1 mate-
rial. It can be seen in the table that the type-2 polypropylene
film is in the same stiffness range as medium-density poly-
ethylene film, whereas the type-1 polypropylene is more
nearly on a par with high-density polyethylene or cellophane.
Present markets show that both stiffness ranges have wide
areas of usefulness. This is one example of the great versatility
of polypropylene resins, which will make it possible to adapt
them to almost any application.
Although the main reason why these films differ is the
difference in isotactic index between the two base resins, this
does not completely determine the properties of the film.
The physical properties of the film are determined over a

considerable range by conditions of extrusion. The stiff cello-
phane-like film or the flexible polyethylene-like film can be
made from the same resin under different extrusion conditions.
In general, the stiff have poor tear strength and
film will
poor impact strength, whereas the flexible film will be excel-
lent in these properties. This means that most of the many
property compromises, which require dozens of different
resins to achieve with polyethylene, will be possible with one,
or at most a few, polypropylene resins.
The area factor is the number of square inches of 1-mil
film that can be made from a pound of resin. Polypropylene
film has the highest area factor of any plastic film now avail-
able. This means that at any given price per pound the poly-
propylene film will be cheaper, for the same area, than any
other film at the same pound price. The advantage over
polyethylene film is small, but over cellophane it is very
significant.
The tensile-strength figures are rather low compared to
some that have been quoted for polypropylene film, but, even
so, the type-1 material exceeds polyethylene by a consider-

able margin, and approaches that of cellophane. The rela-
tively high elongation that accompanies this tensile strength
shows that the polypropylene film is much tougher than the

competitive films, even though it is stiffer than most of them.
This combination of stiffness and toughness is very valuable
and should open many markets.
The stiffness enables the polypropylene film to be processed
easily on high-speed wrapping machinery, and the high
elongation makes the resulting package very durable.
Polypropylene film is readily heat-sealable by the same
equipment used for polyethylene film. It requires about 50°
higher sealing temperature but is not any more critical as to
control and requires no longer time to seal. Although this
may mean that some sealing equipment will have inadequate
heating capacity to maintain maximum rates, relatively minor
machine modification should make it possible to obtain ade-
quate speed.
Water and gas permeability of these films was in the
same range as that of polyethylene, which we know is
adequate for many purposes. Cellophane is a better gas
barrier, but in the uncoated form it has a much higher mois-
ture-vapor transmission. To equal polypropylene in this
respect, the relatively expensive coated cellophane would be

needed.
Although no data appear in the table, polypropylene film
has outstanding grease resistance.
Biaxially Oriented Film

The following data represent the properties of some experi-
mental biaxially oriented polypropylene film. The great im-
provement in tensile strength over the unoriented film is
evident by comparison of Table 2.10 with Table 2.9. It
should be noted that this increase in strength is accomplished
58 Polypropylene
without any drastic reduction in elongation. Although this
film is biaxially oriented, can be seen that orientation in

it
both directions is not the same, because properties differ

so much in the two directions.
Table 2.10. Properties of i/i-MiL Oriented Polypropylene

Film
Tensile strength Along sheet Across sheet
Room temperature 15,000 psi 60,000 psi
300°F 4,000 psi 8,800 psi
Elongation at break (room tempera-
ture) 200% 35%
Elmendorf tear strength 12g 13g
Mullen burst strength 37 psi
Moisture-vapor transmission (25 °C) 0.28g/10C sq in./24 hr
Gas permeability
Oxygen, 25 °C, 1 atm 200 cc/100 sq in./24 hr
Carbon dioxide 25 °C, 1 atm 730 cc/100 sq in./24 hr
Yield 61,000 sq in./lb
Shrinkage Along sheet Across sheet

200°F None None
250°F 5% 8%
300°F 12% 28%
Much depends on the relative costs of oriented and un-

oriented films.It was about ten years from the time biaxially
oriented polystyrene film was first introduced until it could be

produced at a price that could attract a large market. By now,
the techniques for making such film are highly developed, and
it may be possible to produce it at prices competitive with the
large-volume films such as polyethylene and cellophane. On
the other hand, it may for some time compete only with
special high-strength films such as nylon and polyester. At
present, no valid judgment is possible.
The differences in moisture-vapor transmission and in
gas transmission (Tables 2.9 and 2.10) are in part due to
the various temperatures used and in part probably to resin

variations. It is not likely that orientation would influence
them greatly. Note also that Table 2.10 refers to Vi-mil film,
Table 2.9 to 1-mil film.

Table 2.11 gives data furnished by a commercial producer
and concerns the properties of the polypropylene film he
had available. The strength of this film is much better than
Table 2.1 I.
Film properties Values
Specific gravity 0.885-0.895

Yield (theoretical) sq in./lb/l mil 30,900-31,300
Water-vapor transmission rate g/100
sq in./24 hr/1 mil 0.45-1.10
Maximum use temperature before
softening 300°F
Types of heat seal Impulse and radiant bar
Heat-seal range 3 50-425 °F
Tensile strength (average) (psi)
Machine direction 7,600
Transverse direction 4,600
Elongation (average) (%)
Machine direction 741
Transverse direction 730
Tear strength (average-mod. Elmen-
dorf)
Machine direction 82
Transverse direction 426
O2 transmission (cc/100 sq in./l mil/
atm) 180-260
CO2 transmission (cc/100 sq in./l
mil/atm) 586-870
Clarity, haze, gloss Excellent optical properties
Dimensional stability Excellent up to max. use
temp.
Printability Equivalent to polyethylene
Resistance to acids Excellent
Resistance to alkalies Excellent
Resistance to organics Variable
60 Polypropylene
that shown in Table 2.9 but nowhere near that of the oriented
film in Table 2.10. not stated whether this is oriented
It is
or not. The improvement could come from a slight

strength
degree of orientation or simply from differences in resin and
processing. This probably reflects more nearly what may be
expected of good commercial film than does the information
in Table 2.9.
ELECTRICAL PROPERTIES OF POLYPROPYLENE
Like all the hydrocarbon polymers, polypropylene has

excellent electrical resistivity. Some are better than those of
polyethylene or polystyrene; for instance, polypropylene has
the lowest dielectric constant by a small margin. Power factor
is also very low but is strongly influenced by the preparation
of the resin. Power factors similar to the best electrical-grade
polyethylene could be obtained only at additional processing
costs.
Resistivity, both volume and surface, are excellent, and
dielectric strength is extremely high. The following data were
obtained on Vi-mil biaxially oriented film.
Table 2.12. Electrical Properties of Polypropylene Film .
AT 90% Relative Humidity

30°C 150°C
Power factor 0.0011 0.0063
Dielectric constant (60 cps) 2.11 1.86
Volume resistivity (ohm-cm) 4.9 X IQi* 3.6 X 10^2
Surface resistivity (25 °C) 1.4 X 10i5 ohms
Dielectric strength (25 °C) 740 volts/mil
It can readily be seen that the high dielectric strength,
accompanied by the heat resistance, makes it an excellent

material for insulation of motor windings.
The low dielectric constant recommends it for communica-
tion-wire insulation. Many people now believe that its rela-

tively low brittleness temperature is a serious obstacle in
this field. For thin coatings, however, it is quite possible that
it will have sufficient flexibility at low temperatures. The
extraordinary low brittleness temperature of polyethylene has

set a standard for this property that may, in fact, have no
valid relation to performance in service.
These figures are rather different when molded slabs are
used instead of thin film. Table 2.13 gives values determined
on Vs-in. molded slabs.
Table 2.13.
Property ASTM method Value
Dielectric strength (short time) D149 770-820 volts/mil

Dielectric constant (106 cps) D150 2.0-2.1
Dissipation factor D150 0.0002-0.0003
Volume resistivity D257 1016 ohm-cm
The differences in dielectric strength and volume resistivity

are probably due to the different physical form of the sample.
From either table, however, it is evident that polypropylene
has electrical properties equal to the best of other dielectric
materials.
PHYSICAL PROPERTIES OF POLYPROPYLENE PIPE
The first criterion of a pipe is its burst strength. Since one

of the main advantages polypropylene has over other plastic
materials is its temperature resistance, it is helpful to compare
the change in burst strength of polypropylene pipe, over a
range of temperatures, with that of other plastic pipe.
Figure 2.34 shows four lines, the upper line giving the
performance of rigid PVC pipe. At room temperature and
below, this pipe is extremely strong, but its rate of decrease
in strength with temperature is very rapid. The line is shown
62 Polypropylene
7100
2840 i 200
20 40 60 80 100 120
Temperature (°C)
Figure 2.34. Change of burst strength with temperature for several

types of plastic pipe. (Courtesy Montecatini)
as dotted above about 60°C, as it is not considered practical

to use this material at higher temperatures.
Lines B and C represent polypropylene pipe, line B having
the higher isotactic content. Although strength at low tem-
peratures is considerably less than PVC, the decrease of
strength with temperature is also considerably less. In par-
ticular, the strength-temperature slope becomes quite mod-
erate above about 60°C, which makes its use practical even
up to 100°C. This may make it suitable for domestic hot-
water systems.
The bottom line refers to low-density polyethylene. This
not only starts much lower than polypropylene but its loss of
strength is so great that it has little use above about 60°C.
Although polypropylene has not been in existence long

enough for long-time strength to have been established,
preliminary testing shows that the embrittlement that sets in
so rapidly when linear polyethylene is held for extended
periods at high temperatures does not seem to be a factor
with polypropylene. Spherulite growth under laboratory con-
ditions can be carried to the point where the material loses
its strength. This may prevent the use of the most highly
isotactic polypropylenes for services requiring protracted ex-
posure to high temperatures. The presence of stereo blocks
in the molecule prevents crystallization beyond a certain
point and limits spherulite growth. The use of very high-
molecular-weight material can also solve this problem, as it
does with high-density polyethylene, but this introduces

processing problems that may be more costly than the im-
provement is worth.
Polypropylene pipe for hot water would have the addi-
tional advantage (besides those of corrosion resistance, lack
of taste and odor, etc.) that it has in any service: the
thermal conductivity of polypropylene is much less than that
of metal, so heat loss from the water would be reduced.
Since piping is expected to last for a long time under con-
tinuous stress, it is important to consider the long-term life
of polypropylene pipe. Figure 2.35 shows the hoop stress

required to burst plastic pipe as a function of time. One of
the samples is polypropylene and one is a special linear poly-
ethylene pipe material. At 120°F the polypropylene pipe
withstands considerably higher stresses than special linear
—
64 Polypropylene
i 1 1
3000 Polypropylene -
_ 120°F
2000 ~^
Special linear Polyethylene
1000
900
__^
— '
Polypropylene
iq4°F
-^
__
800 — ~" — . __
700 ^..^ Special 1
inear Polyethylene ^..^.,_^
6 00 - ^
194° F -
500 - ~^ - —
400 -
300 - -
200
100 L 1 1
HOURS TO FAILURE
Figure 2.35. Hoop stress required to burst plastic pipe as a function

of time and temperature.
material; however, at 194°F the decrease of strength with

time becomes considerably more severe for polypropylene.
This means that this particular polypropylene pipe is not
recommended for continuous service at temperatures as high
as 194°F. It has previously been mentioned that polypro-
pylene can be modified greatly, and other samples might be
better.
3. CHEMISTRY OF POLYPROPYLENE
NEW WORDS FOR NEW POLYMERS

No discussion of the molecular structure of polypropylene
is possible without a clear understanding of a number of new
terms, which were introduced by G. Natta of the Instituto di
Chimica Industriale del Politecnicio, Milan, Italy, and first
publicly discussed at a meeting of the Geselleschaft Deutscher

Chemiker at Bad Nauheim, Germany, on April 25, 1956.
These terms describe the order of the molecular configuration
of a high polymer.
Tacticity
The first and most general of these terms is the adjective

"tactic" with its corresponding noun "tacticity."
A tactic polymer is a polymer consisting of molecules
whose monomeric, or basic structural, units follow one an-
other in the chain with their respective spatial configurations
in some particular order. This order may be very simple or
quite complex, partial or complete. All that is essential is
that the arrangement is not random or accidental. It is also

possible to have progressive arrangements of tacticities along
the molecule. Evidently, the kinds and varieties of tacticity
possible in a largeand complex molecule are very great, and
a considerable literature has grown up describing them. This
is, however, beyond the scope of this chapter. We shall
discuss only the two kinds of tacticity needed to understand
polypropylene, and mention a few others very briefly.
65
66 Polypropylene
Before going into the various kinds of tacticity, however,

we must define one other word that gets into all these discus-
sions, and this is the adjective "steric" which also appears
as a prefix "stereo-."
This is used by the chemist to designate the position of
molecules in space. "Spatial" is a fairly good but more
general synonym. A steric configuration therefore a con- is
figuration in space. A steric regularity a regularity of posi-

is
tion in space, and a molecule with steric regularity can be

said to be stereoregulated.
Atactic Polymer
To return to tacticity, the easiest term to define is "atactic."

This means having no tacticity, or no steric order, the parts
of the molecule being randomly disposed in space relative to _
each other. I
Isotactie Polymer
The really important term as regards polypropylene is
"isotactie." In simplest terms an isotactie polymer

one is
whose basic building blocks are unsymmetrical, and in which

the building blocks are so arranged that, if one passes along
the chain from one block to the next, it will be found to be
in the same relative position in space.
To explain this definition we shall have to go back to some
of the fundamentals of stereochemistry. The basic fact of the
stereochemistry of organic molecules is that the 4 bonds of
a carbon atom will, if possible, arrange themselves as if they
came out of the apexes of an equilateral tetrahedron, with the
carbon atom in the center of the tetrahedron. In Figure 3. -la,
if we imagine that we are looking directly at a face of a
tetrahedron, then there is one line which goes straight away
from us. The other three apexes are on the plane we are look-
ing at. A line from the center of the tetrahedron through the
Chemistry of Polypropylene 67
apexes, however, does not he in this plane but each line

slants upward toward us shghtly.
It is very convenient, when trying to represent this three-
dimensional figure on a sheet of paper, to have two of these
bond lines on the plane of the sheet of paper. When we shift
our point of view to look directly at the plane of two

of thebond lines, we find that they form an angle of about
130 deg, and that of the other two bonds one comes up away
ABC
Figure 3.1. Bond directions in the carbon atom.
from the paper at a certain angle, and the other goes down
away from the paper at the same angle. If we look directly
at the plane now, the bonds above and below the paper
would be directly over each other, so, to get a projection
that we can visualize, we can shift our point of view down to
get Figure 3.1b.
If we now discard the tetrahedron, leaving only the bond
lines through its apexes, we from
get Figure 3.1c. The lines
the center to and 3 are in the plane of the paper. The line
1
from the center to 2 comes up toward us from the paper, and

the line from the center to 4 goes down away from us at the
same angle. Figure 3.1c is a very convenient way of represent-
ing how a carbon atom in a long molecule is arranged in
space. If we take the bonds represented by 1 and 3 in Fig-
ure 3.1c to be the ones that go to the main chain of the
molecule, we can then represent this chain by a zigzag line
68 Polypropylene
across the paper, with the bottom pomts of the zigzag rep-
resenting another carbon atom in the same way but upside
down.
Figure 3.2. Schematic representation of part of the main carbon chain

of a long hydrocarbon molecule, showing bond directions.
We now have a means of putting down on paper a rep-

resentation of what isotactic means. The first part of the
definition is that the molecular building block must be un-
symmetrical. Now, the main chain bonds are necessarily the
same. Therefore, to get an unsymmetrical building block it is
necessary for the atoms attached to the other two bonds of
our carbon atom to be different.
Keeping to the simplest case and avoiding, for the present,
any discussion of the many fascinating ways in which giant
molecules may be built up from smaller ones, an unsym-
metrical building block can be discussed.
H H
Figure 3.3. Diagram showing ethylene entering a long-chain molecule.
The simplest way for a polymer to form is by the direct

polymerization or joining together of small molecules con-
taining a double bond. The simplest such molecules are the
olefins, and the simplest of these is ethylene. If we make a
diagram for ethylene, we see that, to get a double bond,

steric
the bond angles
of the carbon atoms must be bent or strained,
perhaps as in Figure 3.3a.
When the double bond opens up and joins this molecule
with others to make a polymer, as in Figure 3.3b, it can be
seen that the chain building block is entirely symmetrical.
This means that ethylene cannot make an isotactic polymer.
The simplest monomer that can make an isotactic polymer
^"3
H H
Figure. 3.4. Diagram showing propylene entering a long-chain

molecule.
is propylene. If we represent propylene as we did ethylene in

the previous figure, we find that one of the carbons attached
to the double bond is attached to a methyl group by one of
its other bonds and to a hydrogen by the other (Figure 3.4a),
while the second carbon is attached to two hydrogens.
When becomes part of the chain, one of the carbon

this
atoms in the chain is now unsymmetrical, i.e., it is bonded
to a hydrogen on one side and to a methyl on the other.
The next part of our definition is that, if we go from one
building block to another along the chain, it will be found
in the same relative position in space. If we draw a few
more propylene molecules similar to the first one we
drew (see Figure 3.5), we have represented an isotactic
portion of a polypropylene molecule. If the unsymmetrical
chain carbon is examined it will be seen that the attached
methyl is always on the bond coming up from the paper
70 Polypropylene
toward the viewer, while the hydrogen is on the bond

extending down. Therefore, they always have the same rela-
tive position in space.
If we had a similar portion of the molecule, but with the
methyls sometimes up and sometimes down in random
fashion, this condition would be called atactic.
k^1^ H 1
H
>^^^
1 H
^
T^
. 1 1
1
1
H " H H H
T 1
«"3 ""3 '»z '"z '»z

Figure 3.5. Diagram of part of an isotactic polypropylene molecule.
Syndiotactic Polymer
Another term that is of interest, although less important

to us, can very readily be explained now. "Syndiotactic" is
the term used to describe the polymer where methyls (or in
general the unsymmetrical groups) alternate up and down
regularly —
one up, the next down.
This method of representing the main polymer chain on
the plane of the sheet of paper, and the groups bonded to the
chain carbons above and below the plane, is a very convenient
way to show what these various tacticities mean. It is, how-
ever, misleading if we think of this as representing the experi-
mental work that Natta announced at that historic meeting at
Bad Nauheim.
We have been working backwards toward a point
really
where we can understand what the experiments showed and
how an isotactic polymer molecule is disposed in space.
If we take one of our plane diagrams, say Figure 3.5, and
visualize now that the atoms on this skeleton are so large

that they really crowd each other, and that the main chain,
while it resists distortion of the bond angles and rotation

about a bond, does have a certain flexibility, it will be seen
that an isotactic polymer would not stay in this stretched-out
position by itself. In particular, those methyl groups sticking
up all along one side, because of their mutual repulsion,
would tend to take positions as far from each other as pos-
sible. In the case of isotactic polypropylene, the equilibrium
position has the methyls arranged around the main chain in
spiral fashion, completing one spiral in three propylene units.
It is this three-group-length spiral that first drew Natta's
attention to the fact that he was examining an unusual mate-

rial. It is this spiral molecule that interlocks with other spiral
molecules to form the crystals which are so important in the
behavior of polypropylene.
Figure 3.6 shows a diagram of the two possible spiral
arrangements for a polypropylene molecule, one right-handed
and one left-handed.
In the crystals, the two enantiomorphous spirals are
present in equal quantities. There are two possible orienta-
tions for each of them, one with the CH-CH bond in the
up and the other with the CH-CH bond in the
direction,
down direction. Isomorphous spirals differing in the orienta-
tion of the CH-CH bond occupy about the same space and
can substitute for each other in a crystal.
The upper part of the figure represents a side view of a
short segment of polymer chain. The numbers to the right
refer to the monomer units. Each monomer unit consists of
3 carbon atoms, 2 in the chain and 1 outside. Each monomer
unit is rotated 120 deg from the next one, so that the fourth
one is placed identically with the first. This sequence will
continue indefinitely until the tacticity of the molecule is
changed, or something else interferes.

The lower part of the figure represents an end view of the
same segment of molecule, showing very clearly how the
72 Polypropylene
unsymmetrical carbon atoms have been located to give the

The manner in which the right- and left-
least interference.
handed helices tend to fit together is apparent. They always
crystallize in pairs, as shown in the illustration.
Figure 3.6. Diagram of the position of the carbon atoms of isotactic

polypropylene in space, when crystallized.
Stereoblock Polymers
In addition to isotactic, syndiotactic, and atactic polymers,

it is also possible to make polymers that start off being isotac-
tic and then, after maintaining this condition for a while,
and continue again being isotactic, but
reverse their position
Such polymers are called
in the opposite position in space.
stereoblock polymers, and they differ in properties from
the previously discussed types. Stereoblock polymers can, of
course, differ from each other greatly, because the length of
the blocks can vary from very short to very long.
Depending on how often the order of a stereoblock polymer

reverses along the chain, the polymer shows more or less
elastomeric properties.
Generally, infrequent inversion in a long chain causes
only a slight lowering of the melting point and a slight in-
crease in elastic elongation. Tensile strength and yield point
will be about the same. The properties of these polymers are
essentially the same as high-molecular-weight isotactic
polymers.
In the same way, small isotactic blocks in an atactic chain
do not alter the properties appreciably.
When there are isotactic blocks long enough to produce
partial crystallization of the polymer, some new and interest-
ing characteristics appear. The material remains elastomeric
but begins to have some of the properties of vulcanized elas-
tomers. The crystallized portions act similarly to the cross
links in a vulcanized elastomer and prevent the cold-flow
characteristics of unvulcanized elastomers. Such polymers can
be partially stretched to produce crystallization, and will then
have a reversible elongation of 50 to 100 per cent or more.
These materials have tensile strengths higher than most vul-
canized rubbers.
This vulcanization-like effect of crystallinity, of course, dis-
appears when the material is heated above the melting point
of the crystals.
The revolutionary technical possibilities of an elastomer
that can be injection molded, or handled by any other thermo-
plastic technique, to yield a product with the properties
of a vulcanized rubber, without any kind of cure or after-
treatment, almost stagger the imagination.
Polymers of this type are of particular interest as they are
more readily made by direct polymerization than pure isotac-
tic polypropylene. Although certain catalysts under some
conditions can produce mostly isotactic polymers, the usual
74 Polypropylene
catalysts, under operating conditions most suitable for eco-

nomic production, produce mixtures of isotactic, atactic, and
stereoblock polymers.
It is not difficult to keep the purely atactic portions low,
thus producing a raw polymer consisting of a mixture of
isotactic and stereoblock chains. This raw polymer would
evidently be cheaper than a pure isotactic polymer produced
by the solvent fractionation of the raw polymer.
It also appears that for many applications the presence of
these stereoblock fractions will have many advantages. When
olefins more complex than propylene are polymerized there
are many more types of possible polymers, but a full discus-
sion of these is beyond the scope of this book.
Optical Activity
Although it is not a new term, the general problem of

steric configurations leads to the question of optical activity.
It is well known that some organic compounds have the prop-
erty of rotating the plane of polarization of a beam of
polarized light passed through a solution of the compound.
These are called optically active substances.
The science of stereochemistry is based upon this prop-
erty. When a steric model of optically active compounds
was developed it turned out that two models, differing only

in steric configuration, could be made.
It was then determined that the substance having one of
these steric configurations rotated a beam of light to the

right, and the other rotated it to the left. These are called
dextrorotary and levorotary, respectively, and in chemical
literature are indicated by writing d- and L- in front of the
name of the substance, as D-glucose.
Because of the close connection between stereochemistry
and optical activity, the optical activity of these sterically
ordered polymers was investigated. It was found that most
of them are not optically active in solution, although crystal-

lized forms affect polarized light, as will be discussed later.
Some optically active substances, however, are capable of

forming polymers. Ordinary atactic polymers of these mate-
rials show little or no optical activity, but it was found that
properly ordered polymers of these materials were optically
active. In some cases the polymer is a hundred times as
optically active as the monomer.
THE EFFECT OF STEREOREGULARITY ON

POLYMER PROPERTIES
Crystallinity and Tacticity

It was mentioned in the discussion of isotactic poly-
propylene that the regular location of the methyl group on
the polymer chain gave it a spiral configuration. There are
really four possible spiral configurations, two right hand and
two left hand. One of each was shown in Figure 3.6. Such
a regular chain can evidently interlock closely with other
chains to form a crystal, whereas any lack of regularity inter-
feres with crystal formation.
This means that an isotactic polymer will be highly crystal-
line, and an atactic polymer will not. The percentage of
isotactic polymers in any given sample will be reflected in
its degree of crystallinity, but this is not intended to mean that
there is a simple numerical relationship between the two.
Crystallinity is affected by many factors other than the
percentage of isotactic material. For instance, the heat history
of the sample is very important. If a sample is cooled rapidly
from a melt, the chains do not have time to align themselves

into the proper position for crystal formation before the
viscosity of the melt becomes so high that they "are frozen
into place. In this way a highly isotactic sample could have
a low crystallinity percentage.
76 Polypropylene
Also, a relatively short chain makes it easier for the

molecules to assume a crystalline position than does a long
chain. Therefore, a lower-molecular-weight sample might
show a higher degree of crystallinity than a higher-molecular-
weight sample, even though the percentage of isotactic
polymer were the same.
This discussion is necessary because the properties of
polypropylene samples are sometimes described with refer-
ence to percentage of isotactic polymer and sometimes with
reference to per cent crystallinity.
Natta and other European sources prefer to use per cent
isotactic. They ordinarily determine this by extraction with
boiling n-heptane, assuming the insoluble portion to be a
pure isotactic polymer. This is not, of course, the definition
of an isotactic polymer, but repeated tests on material so
extracted have shown that this reagent makes a quite reliable
separation between isotactic and atactic polypropylene. The
analysis is a classic gravimetric procedure requiring only rela-
tively simple laboratory equipment, and the results depend
entirely on the properties of the basic polymer, not on the
physical history of the sample. It is, however, quite time con-
suming, and requires considerable skill in its execution.
American sources prefer to use percentage crystallinity, as
it involves an instrumental procedure which requires little
time and can generally be carried out by laboratory tech-

nicians. The instrument is complex and expensive, generally
an X-ray spectrograph, although the value can also be deter-
mined by infrared. American laboratories generally have such
instruments available, and their use saves much time. If care
is taken in sample preparation to assure maximum possible
crystallinity, and if samples that differ little in factors other
than percentage of isotactic polymer are compared, then the
percentage crystallinity can be taken, at least relatively, as a
measure of percentage of isotactic polymer.
Since the data which will be discussed are only qualitative

and represent polymers that are by no means absolutely rep-
resentative of any polymer that may be encountered com-
mercially, the terms percentage crystallinity and percentage
of isotactic polymer will be considered essentially as different
measures of the same thing. For the present purpose, no
confusion should result if the foregoing discussion is kept in
mind.
The Effect of Stereoregularity on Permeability
The degree of crystallinity of a sample of polypropylene is
also very important in determining its permeability to liquids.

As with other partly crystalline materials, solvent penetration
is almost entirely through the amorphous areas. The relation-
Figure 3.7. Effect of degree of crystallinity of polypropylene on

n-heptane permeability.
78 Polypropylene
30C

toluene permeability.

carbon tetrachloride permeability.
ship between solvent penetration and crystallinity is shown

very clearly in Figures 3.7, 3.8, and 3.9. The solvents used
are materials which penetrate polypropylene very rapidly.
The degree of crystallinity for the samples of polypropylene
is ^, 66 per cent; B, 64 per cent; and C, 63 per cent. It can
be seen that this rather small range of crystallinity may

produce a three- or fourfold change in permeability charac-
teristics, although the results are not quite the same with the
various materials. With n-heptane, for instance, the differ-
ence between A and B is greater than the difference between
B and C, whereas with toluene the opposite is true. The
solvent action of the test liquid appears to be an important
factor in permeability. Many solvents actually extract soluble
fractions from the plastic, and this facilitates passage of the
liquid. Although crystallinity is the main influence in these
tests, it cannot be inferred that other samples having the
same crystallinity will quantitatively reproduce these results.
Other Properties Related to Crystallinity

As we have seen before, solubility is a function of molecu-
lar configuration and can be related to per cent crystallinity,
as shown in Figure 3.10.
This graph represents the results of extracting 10-mil film
for 22 hr at 75°F with toluene. The soluble fraction of
polymers in the most useful crystallinity range is quite small.
Practically all other physical properties also are profoundly
influenced by crystallinity. The crystalline polymer is stiff,
strong, and resistant to heat, but the amorphous polymer is
soft, weak, and rapidly softened by heating.
Any practical polymer which is a mixture of the two has
properties intermediate between them, depending on the per-
centage of each present.
The polymer of greatest commercial interest at present is a
80 Polypropylene
highly crystalline one, but this is not necessarily the best one
for all purposes.
The physical properties of commercial polymers, discussed
in Chapter 2, reflect, among other things, the judgment of the
producers in balancing properties by controlling steric con-
figuration and crystallinity.
<6
50 60
PERCENT C RYSTALLI NUT
Figure 3.10. Effect of degree of crystallinity on toluene extractables

in polypropylene.
STEREOSPECIFIC CATALYSTS
The basic discovery that made possible isotactic polypro-

pylene, and the whole group of sterically controlled polymers,
was the fact that certain catalysts have the ability to add a
monomer unit to a growing polymer chain in a particular
position relative to the previously added group. These are
called stereospecific catalysts.
The tremendous volume of research sparked by Natta's
original announcement of ordered polymers has disclosed a
vast number of catalysts which have this property. Both

patent and technical literature in this field have been full of
and catalyst combinations.
descriptions of different catalysts
Many had been studied previously in
of these catalysts
relation to their usefulness for making polyethylene by the
low-pressure process. Because of its symmetry, ethylene can-
not polymerize in a sterically ordered manner, but the fact
that the same catalysts that made linear polymers with
ethylene also made isotactic polymers with unsymmetrical
olefins in some cases has led to much confusion in this matter.
It should be understood that the catalysts discussed here are
stereospecific because of the ordered polymers they can make
with unsymmetrical olefins. They may also make linear poly-
ethylene, but this has nothing to do with their stereospecificity.
Natta's original work had been done with catalysts rather
similar to the Ziegler type, e.g., an aluminum alkyl (triethyl
aluminum or triisobutyl aluminum) and have been widely
used in conjunction with titanium IV chloride. Although
titanium is one of the most effective metals in such catalysts,
almost any of the elements of the fourth, fifth, and sixth
groups in the periodic table are useful, and have been men-
tioned in the literature or patented. The metal is essential,
since diethyl aluminum chloride has no practical catalytic
activity in these reactions. For stereospecific activity it was
found that titanium in the trivalent state was more effective.
Organometallic compounds other than the aluminum alkyls
are also effective; for instance, dimethyl magnesium, propyl
magnesium chloride, diethyl zinc, phenyl magnesium bro-
mide, and tetrabutyl orthotitanate have been described. A
number of substituted aluminum hydrides are also effective.
All the above materials belong to the class generally called
Ziegler catalysts, although some differ a great deal from those
originally used by Ziegler. There are two other broad classes
of catalysts that have stereospecific properties and were orig-
82 Polypropylene
inally discoveredby their ability to make linear polyethylene.

These are usually designated by the names of the companies
The Phillips catalysts consist of
holding the original patents.
calcined chromium III oxide catalysts supported on silica
alumina. Numerous promoters modify the action of these
catalysts.Typical are nickel, thorium, iron, manganese,
uranium, vanadium, molybdenum, tungsten, and zirconium.
In contrast to this relatively simple group of substances, the
Standard Oil Co. of Indiana has a series of patents that in-
clude many materials, for instance, combinations of an alkali
metal and an oxide of Periodic Group VIA, an alkali metal
hyride with the same group of oxides, nickel-cobalt alloy
supported on activated carbon, partially reduced nickel and
cobalt oxides, lithium (or sodium) aluminum hydride and
an oxide of Group VA, and many other combinations.
The purpose of this listing is to show the complexity of
this subjectand to illustrate the tremendous amount of work
that has been done on the stereospecific catalysts.
It must not be thought that practically anything will work
in this manner; quite the contrary is true, for only very spe-
cific combinations show any activity, and frequently small
traces of other materials will completely inactivate the cata-

lyst. For instance, small amounts of nickel, cobalt, and other
metals in Ziegler catalysts will cause them to form dimers
or other very low polymers instead of high polymers.
It is much too early in the development of this field for
there to be a very good theory as to how these catalysts work.
One suggestion is as follows: Visualize an olefin molecule
approaching the aluminum triethyl as
C2H5 C2H5
= CHR —
+ -f
C2H5--Al CH2 > C2H5--Al -c = CHR

1
C2H5
The presence aluminum activates the olefin as in-

of the
dicated, and the is then complexed with the alkyl. This
olefin
complex is stabilized by the shift of an ethyl with its electron
pair, and the process can start over. If the olefin is unsym-
metrical, it is easy to see that the position of the molecules
during the complexing might be such that the olefin would
always have to present itself in a certain specific orientation
in order to react.
It is interesting that there are a number of Ziegler-type
catalysts that are hydrocarbon-soluble. This makes it possible
to produce polymers with no solid catalyst phase present.
This has obvious advantages in the separation of catalyst and
polymer. It has been found, however, that these catalysts are
not stereospecific, so the polymer produced is atactic.
Evidently a solid phase is essential to the formation of

ordered polymers. Therefore, it may be that it is not a single
catalyst molecule that forces the olefin to present itself in a
specific orientation, but a crystal structure consisting of a
relatively large number of molecules.
Natta has shown that there are catalytic complexes con-
taining transition metals and metal organic groups which
alone do not polymerize the alpha olefins and are not stereo-
specific catalysts when adsorbed on amorphous substances,
but become highly stereospecific on certain crystalline
supports.
He reported polymerization carried out with triethyl
aluminum and various titanium compounds at 70° to 80°C
with n-heptane as solvent and the percentage of polypro-
pylene produced which was not extractable in boiling n-hep-
tane. This is the usual way of determining the isotactic fraction.
Ti(OC3H7)4 alone or adsorbed on silica alumina gave less
than 10 per cent isotactic polymer. CoCL support raised
this to 35 to 45 per cent.
When TiCls was used, the yield of isotactic polymer de-
84 Polypropylene
pended upon the crystal structure of the TiCls. This com-

pound exists in three crystalline forms. The two that are of
interest here are the alpha, or violet form, and the beta, or
brown form. When the violet form was used as catalyst sup-
port, the polymer was 80 to 90 per cent isotactic. With the
brown form the polymer was only 40 to 50 per cent isotactic.
STEREOREGULATED DIOLEFIN POLYMERS
These two forms of TiCls are also very interesting in that

they order diolefins in a very remarkable way. Although this
concerns only the synthetic-rubber industry and is only in-
cidental to the polypropylene problem, it is of great theoret-
ical interest and illustrates clearly the potentialities of stereo-
specific catalysts. When diolefins polymerize, the second
double bond may be positioned in several ways, the best-
known of which are cis and trans. These are represented by
plane diagrams, shown in Figure 3.11, and differ only in the
way the double bonds are located relative to each other in
the chains. The double bonds are in the chain in both cases,
the butadiene being attached by its end carbons or in the
1,4 position.
The interesting point relative to the TiCls crystal form is
that when polybutadiene is made using catalysts containing
the alpha form of TiCls the polymer is 1,4-trans, and when
the beta form is used, 1,4-cis results.
Diolefins can also polymerize in the 1,2 position with only
two carbons actually attached to the double bond joining the
chain, while the other double bond remains out as a side
chain. This is called the vinyl configuration. This type of
polymer was not known before the discovery of the stereo-
specific catalysts. Figure 3.11 also shows vinyl polybutadiene.
This kind of butadiene can be formed in isotactic configura-
tion, and the syndiotactic form is also possible. The atactic

form is not represented but can also be made.
The importance of this discovery can only be understood

if we remember that natural rubber is almost pure c/5-poly-
isoprene, and that the failure of synthetic rubber to match
^C=C /C=-
CIS c = c
TRANS
— CHj H H CHj— CH2
H H H H
1 1 1
1
VINYL
ISOTACTIC "2
"2 Sh, "2 i„^ «2 U^ OH,
H en* ij Sh
VINYL
S YN DIOTACTI
"2 "2 "2 "2

Sh, l„^
Figure 3.11. Four-ordered polybutadienes.
the low heat build-up and high resihence of the natural prod-
uct was due to the inability of the polymer chemist to
duplicate this natural structure. The use of stereospecific
catalysts has resulted in the synthesis of practically pure cis-
polyisoprene. High-cis polybutadiene has a tendency to

low temperature, but this can be prevented by
crystallize at
reducing the cis content to 80 per cent without serious loss
of other properties. The vinyl dienes are still too new to deter-
mine their uses. They produce rubbers of interesting but not
outstanding properties and offer a possible variation for the
86 Polypropylene
production of new high-polymer types for specific appHcations.

The many unsaturated side chains offer obvious sites either
for reaction with inorganic substituents or for the grafting
of other polymers. Much work
is being done on exploring
the many by the structural features of

possibilities indicated
these polymers. Although no commercial products have yet
been announced as a result of these studies, it can hardly be
doubted that the results will eventually have a major influence
not only on the synthetic-elastomer industry but quite possibly
on the plastic and fiber industries as well.
CHEMICAL REACTIONS
The polypropylene molecule differs from the polyethylene

molecule in that there is a methyl group attached to every
other carbon atom in the polypropylene chain, whereas linear
polyethylene has practically no branches on the chain, and
low-density polyethylene has perhaps two or three side chains
per hundred chain carbon atoms.
Oxidation
It is well known hydrogen atom which is attached

that a
to a tertiary carbon atom (one which is connected to three
other carbons, as it would be at a branch in the chain) is
more reactive than hydrogen attached to carbon atoms which
are connected with only one or two other carbons.
One of the results of this is that the oxygen uptake of
polypropylene is much greater than that of polyethylene.
At 200°F unstabilized polypropylene will absorb oxygen at
0.117 cc/g/min after an induction period of 11 hr, whereas
linear polyethylene has a 164-hr induction period and then
only absorbs at 0.0031 cc/g/min. This requires the use of
antioxidants in polypropylene. This subject is discussed
further in later chapters.
Sulfochlorination
High-molecular-weight polypropylene can be made vul-

canizable by sulfochlorination and then vulcanized with
polyvalent bases. These rubbers have highly reversible de-
formation values, or good rebound. In many respects their
technical properties are far superior to those of sulfochlorin-
ated polyethylene, which has some industrial applications.
Unlike polyethylene, which requires considerable (25 to 40
per cent) chlorination in order to break up the crystal struc-
ture and form an elastomer, polypropylene can be made sub-
stantiallyamorphous to begin with, if atactic polymer is used.
This means that a small amount of sulfur (less than 1 per
cent) and only enough chlorine to produce the equivalent
sulfochlorination are needed to make the polymer vulcaniz-
able. The vulcanized product has better elastic properties
than sulfochlorinated polyethylene, and, because of the small
amount of chlorine introduced, it is much lighter.
Sulfochlorinated polypropylene represents a class of sat-

urated elastomers which have better properties than other
known saturated rubbers and should have wide applications.
MOLECULAR WEIGHT OF POLYPROPYLENE
Polypropylene is an early stage of development

in such
that techniques are largely borrowed from studies of
still
more famiUar materials. Routine determinations of the

molecular weight of polyethylene usually have been accom-
plished by means of solution- viscosity measurements. One of
the commonest means of calculation was the Harris equa-
tion [Harris, /. Polymer Sci., 8, 353 (1952)].
When work on polypropylene started, it was natural to
attempt to use the same type of equation, with coefficients
changed to fit the new material. Several experimenters have
88 Polypropylene
reported results which agree quite closely [R. E. Hughes and

J.B. Kansinger, ACS Meeting, New York, September, 1957;
R. Chiang, /. Polymer ScL, 28, 235 (1958)].
These equations relate the intrinsic viscosity (?y) to the

weight average molecular weight Mw, as follows, using the
average of the two references.
(^)= 1.04 X 10-4 MwO.80

135°C, "Decalin"
Determining Mw from an equation of this sort is rather

difficult, so a graph of the form shown in Figure 3.12 is
usually used for its solution.

Determining the intrinsic viscosity of a material requires
the extrapolation of several viscosity determinations made at
different concentrations. As this is time consuming, it is
common practice to use the inherent viscosity i-yr-] in
place of the intrinsic viscosity in this equation; f]r is the rela-

^y solution
tive viscosity jj^^ inherent viscosity requires only
fj solvent
one determination made on a solution of a very low concen-
used is low enough, there is no
tration. If the concentration
substantial difference between inherent and intrinsic viscosity.
In calculation of concentrations for use in these equations,
concentration is in grams per deciliter at the temperature of
the test. If solutions are made up at room temperature, the
volume measured must be corrected for thermal expansion.
Polypropylene presents a problem not found in poly-
ethylene because of its rapid oxidation at relatively moderate
temperatures. It is necessary to protect the solution from
oxidation, or results will be erratic and the viscosity deter-
mined will be low. The easiest way to do this is to add a little
antioxidant to the solution. If the entire preparation is carried
on in an atmosphere of nitrogen, similar results can be

obtained.
It must be kept in mind that viscosity is, at best, a second-
ary method of determining molecular weight and must be
0.2 0.3 0.6 1.0 2.0 3.0

INTRINSIC VISCOSITY
Figure 3.12. The relationship between molecular weight and intrinsic

viscosity in polypropylene.
calibrated by reference to some primary method such as

osmotic pressure changes, boiling-point raising, or freezing-
point lowering.
As in other high polymers, average molecular weight, even
if accurately determined, has only limited value for charac-
terizing the polymer.
90 Polypropylene
Molecular-Weight Distribution
Any sample of a high polymer consists of chains of many

different lengths. The average size of the chain means little
if the sizes that make up the average are not known. A mate-
rial with a given average molecular weight, made up entirely
of molecules very nearly aUke, will be very different from a
material of the same average molecular weight but made up
of very short and very long molecules. The details of the
molecular-weight distribution are very important in determin-
ing the properties of the polymer.
The fractionation of polypropylene is more complex than
that of polyethylene because the solubility of a polypropylene
molecule depends not only upon its length but also on its
tacticity.
Natta reports that the percentage of isotactic polypropylene

is nearly the percentage which is not extracted by boiling
heptane. Further extraction of the residue with more active
solvents produces a series of fractions differing in molecular
weight but not appreciably in tacticity. This means that both
the atactic fraction and the isotactic fraction will have a
molecular-weight distribution as well as an average molecular
weight, and quite probably all these figures will be required
in order to characterize a sample.
It is not possible at this time to explain specifically how
these factors affect the important properties of the plastic,
but, judging from experience with other polymers, it is quite
certain that close control of polymer properties will neces-
sitate a better understanding of these effects.
It may be that this will be less important with polypro-

pylene than it has been with other polymers, because the
proportion of isotactic to atactic polymer may have an over-
riding effect on many properties. It appears, even at this
stage of development, however, that low-temperature prop-
erties are to a considerable extent influenced by molecular

weight, the higher-molecular-weight materials having the
better properties.
CRYSTALLITE SIZE OF POLYPROPYLENE
Crystallite size as well as percentage of crystallinity influ-

ence the properties of a plastic material. In general, small and
uniform crystalhtes are preferable to larger or varied ones,
because the large crystallite tends to produce points of stress
concentration which cause premature failure. The control of
crystaUite size has been a major source of improved physical
properties in polyethylene.
Polypropylene has a crystallite which is roughly a circular
disc about 150 A in diameter and 50 to 60 A thick. The
polypropylene molecule (c-axis) runs in the direction of the
thickness.
This size is shghtly smaller than the value of 190 A gen-
erally accepted for low-density polyethylene, and much
smaller than values of 360 to 390 A reported for various
linear polyethylenes, showing that polypropylene should be
quite free from the stress-raising effects of large crystallites
which are the source of premature failure, especially in hnear
polyethylene. This appears to be due to the numerous methyl
side chains on the polypropylene molecule, which restrict
crystallite size.
Rapidly cooled polypropylene has smaller crystallites than
slowly cooled samples. The figures given refer to maximum
size found after relatively long annealing. Typical film
samples may have crystallite diameters from 110 to 120 A,
which will grow with age, depending on conditions of storage.
Certain treatments, such as gamma radiation, tend to ac-
celerate the growth of crystaUites, and this is particularly
92 Polypropylene
marked in the case of oriented film. This could cause deterio-

ration of properties in such environments.
Spherulites in Polypropylene
Like other poly crystalline plastics, polypropylene crystals

form relatively large aggregates spherulites. These
called
are readily studied by means of polarized Ught because they
exhibit birefringence. Unlike the other poly crystalline plastics,
polypropylene forms at least four distinct types of spherulites
which differ not only in amount but even in the sign of their
birefringence. There are also many mixed types which show
birefringence differences within the same spherulite.
A great deal of work has been done on this problem by
Natta, and more recently by Keith, Padden, Walter, and
Wycoff of American Viscose. The main significance of this
work is achieving an understanding of the formation of the
spherulite.
Two of the kinds of spherulites found consist of crystals of
the most common type, which were described by Natta early
in polypropylene development. The other two seem to con-
sist of quite a different crystalline form. When this form
occurs, it generally applies to an entire spherulite, even
though all surrounding crystallites are normal. It is not
known what causes these two forms; apparently it is mostly
due to an accident of starting, although the temperature at
which the spherulite is grown appears to have some influence.
Under certain conditions spherulites can be grown to quite
large sizes.When this is done, cracks begin to appear be-
tween the spherulites, and also within them. The dark areas
between spherulites were first believed to be amorphous
polymer, but it has now been found that they are mostly
voids, and very large spherulites can be separated from one
another with little effort. This clearly shows the great impor-
tance of controlling spherulite growth if strength is to be

maintained.
If a sample of polypropylene is partially crystallized and
then rapidly quenched, a feathery growth of crystals is ob-
tained, among which is a considerable amount of amorphous
material. As the structure of this feathery crystallization is
extremely fine, it does not interfere greatly with light trans-
mission, and a clear film can be obtained.
Once the material has been cooled to the point where it is
solid, further crystal growth is quite slow, and, although it
will continue to progress, it may take sufficient time to permit

a reasonable lifetime for the plastic.
If individual spheruhtes are separated out and their density
is it will be found to be as high as 0.919 from a
measured,
polymer originally 0.905. The same polymer rapidly quenched
from +300° to -77°C will have a density of only 0.897
g/mil.
4. PRODUCTION OF POLYPROPYLENE
PROPYLENE PRODUCTION
The first step in the production of polypropylene is to
obtain a supply of monomer, propylene.
its
Over 90 per cent of the propylene consumed today is

polymerized to high-octane gasoline. This demand is satisfied
by propane-propylene mixtures easily separated from refinery
off-gases. Polypropylene requires substantially pure pro-
pylene, and this requires extra processing steps.
It is estimated that 20 billion pounds of propylene are
produced, 80 to 85 per cent of which are recovered from
refinery off-gases; the rest are by-products of ethylene
production.
In addition to aviation gasoline, propylene is used in a
wide variety of chemicals; however, it does not appear that
there is likely to be any shortage in the near future. Certainly
the amounts needed for even a large polymer production
should be no strain on the available resources.
PROPANE-PROPYLENE SEPARATION
A Cs fraction can be isolated rather easily by fractional

distillation. Adsorption and absorption techniques have been
described but are not currently of very great importance.
Usually two distillations in series, each having 30-40 stages,
94
Production of Polypropylene 95
will isolate a mixture with less than 2 per cent outside the
C3 range.
Separating propane from propylene is rather more difficult
than most commercial distillation separations. Relative-

volatility data given in Figure 4.1 indicate that at 300
psi the relative volatility is very low. It is convenient to op-
erate at this pressure to permit condensation of reflux with
cooling water.
.10 1.20 1.30

RELATIVE VOLATILITY PROPYLENE TO PROPANE
Figure 4.1. Relative volatility of propylene-propane mixtures.

96 Polypropylene
The use of an extractive distillation agent to improve the

relative volatility is possible, but the extra expense of han-
dling and separating the extracting agent is more, generally,
than the cost of the increased height of column required to
make the separation without the agent. The fact that the
propane ratio in the feed may vary appreciably adds to the
problem of designing a system for propylene purification.
For polypropylene manufacture, particular care must be
taken to remove all traces of water, which will destroy the
catalyst. Methyl acetylene must also be completely removed,
as it is a cross-linking agent which will produce infusible
polymers.
If the distillation column is operated at 300 psi, the re-
covery of 99 per cent plus propylene requires a column height

of about 140 ft, so it is generally more convenient to have
two shorter columns operated in series.
A vapor-recompression cycle makes it possible to operate
in the 100 to 200 psi pressure range with a single column.
Overhead vapor is compressed and then condensed as heat-
ing medium for the column reboiler. In a large refinery it is
often possible to use a refrigeration unit, which also serves
other processes, to provide condensation at lower pressures
where the relative volatility is more favorable.
All things taken into consideration, it appears that neither
technical nor economic problems are likely to limit the supply
of propylene to the expanding polypropylene industry.
POLYMERIZATION OF PROPYLENE
The manufacture of polypropylene is so new that each

manufacturer is still very secretive about his particular proc-
ess, and there is no standardization of production procedures.
Certain basic methods of operation, however, are apparent
from the literature.
The first step in the manufacture of polypropylene is the

purification of the monomer discussed previously. In order
to avoid variation in product properties and possible poison-
ing of the catalyst, it is necessary to refine the propylene to a
high purity. Some plants perform their own purification, others
depend on the monomer supplier. Purification is carried out
in a rectifying column with, in some cases, selective absorp-
tion of specific impurities. Special care must be taken to be
sure the gas is dry.
When the gas is obtained, present processes are of two
distinct classes, depending on the type of catalyst employed.
These differences are similar to those in linear polyethylene
production, although the catalysts may not be the same.
The first class, which covers all current production facili-
ties, is similar to the Ziegler process for polyethylene, in that
the catalyst used is produced in situ by the reaction of its
constituents. In a minor modification of this the catalyst is
formed in a separate vessel just before entering the reaction
vessel. It may be subject to some aging before use or to some
degree of grinding for the control of certain properties, but
basically it is made as required, and cannot be stored or
transported between manufacture and use.
These catalysts are generally formed from transition metal
saltsand organometallic compounds. One such composition
that is particularly suitable for the production of isotactic
polypropylene is titanium trichloride and aluminum triiso-
butyl. Catalysts of this type were discussed in detail in

Chapter 3.
The second class uses catalysts generally referred to as

preformed catalysts because they are made outside the reac-
tion vessel at some earlier time. These are the Phillips-type
(chromium oxide on silica alumina) and the Standard Oil
catalysts (molybdenum oxide, cobalt molybdate, and other
molybdates on a variety of refractory bases). The activity of
98 Polypropylene
these catalysts can be modified by promoters such as sodium

calcium hydride, etc. This is more detail
also discussed in
in Chapter 3. Catalysts of this sort are not now being used
commercially, but some of them can polymerize propylene to
form largely isotactic polymer.
All the catalyst types used for linear polyethylene can,
with some modification, be used for polypropylene, with the
exception of the soluble complex types. For stereospecific
polymerization a solid phase appears to be essential.
The process of making polypropylene consists essentially
of three steps — the polymerization proper, the separation of
the catalysts and solvents from the polymer, and the pelletiz-
ing of the polymer to make granules suitable for use in plastic
conversion equipment.
Linear polyethylene can be made in two ways. The tem-
perature of the reaction can be kept high enough to keep the
polymer as formed in solution, or it can be low enough
it is
to cause the polymer to precipitate out as a suspension.

For polypropylene the suspension process is generally
indicated because, unlike linear polyethylene, the properties
of the polymer are greatly influenced by the temperature, and
high temperatures produce soft, rubbery atactic polymers
rather than the desired isotactic form.
Catalyst composition, however, is also very important in
determining tacticity, so it is possible that a catalyst may be
developed that will permit the more convenient solution-type
operation. It is also possible that applications may develop
which can use atactic polymers or polymers with appreciable
atactic content.
All the factors involved in the control of polypropylene
polymerization are not known at this time. In addition to
catalyst composition, the physical form of the catalyst is very
important. Molecular-weight distribution, in particular, may
be influenced quite markedly by grinding the catalyst after it
is formed. Aging before use may also have an influence on

this property. This means that catalyst production must be
very closely keyed to plant operation so that the age and
condition of the catalyst is always the same at the moment
of use.
Gas composition is also on polymer
a strong influence
properties. It is must be quite pure, but
true that the gas
controlled amounts of other gases may be deliberately added
to change polymer properties. Hydrogen, for instance, is
added to reduce molecular weight, and thus improve the flow
properties. Other unsaturated gases may also be added to
propylene to produce copolymers of many types.
In the suspension-type operation, monomer at a pressure
of about 100 atm is added to a well-agitated reactor contain-
ing a dispersion of catalyst in a liquid hydrocarbon. The
reaction temperature is well below the softening point of the
polymer. Polymer granules form around the catalyst par-
ticles and are kept in suspension by the agitator. This can be
continued until the polymer content reaches about 40 per
cent,which is the maximum that can be conveniently pumped.
Although early processes were batchwise, most current pro-
duction is on a continuous basis.
The solvent-polymer-catalyst slurry is then pumped to a
flash drum where a reduction in pressure removes the un-
reacted monomer, which is then recycled. A purification step
may be required in the recycle system to prevent build-up of
impurities.
From here the slurry is run into a centrifuge or filter to
remove the diluent. Proper choice of diluent and temperature
at this point will leave the majority of the atactic polymer in
the solvent phase, and the solid matter wiU be mostly isotac-
tic. The solvent is then distilled to separate it from the atactic
and low-molecular-weight material, which is removed from
the system as a by-product.
100 Polypropylene
The polymer is then reslurried with an extractant, for

instance weak HCl in methanol, to decompose the catalyst.
This must be done before the mixture is exposed to air, hence
any previous operations must be carried out in a completely
closed system. The extractant is then removed in another
centrifuge or filter.
The polymer is then washed with water to remove the HCl,

steam-distilled to remove final traces of solvent, dried, ex-
truded, and formed into pellets.
The complete removal of HCl and chlorine containing
reaction by-products of the catalyst decomposition reaction
is essential to keep the polymer from corroding processing
equipment.
For some end uses, such as most injection-molding appUca-
tions, it is more convenient to add a corrosion inhibitor
which absorbs the corrosive materials rather than attempting
to remove the very last traces.
Electrical gradeswhich demand the best electrical prop-
erties require complete removal of all residues, and film
grades which must have the greatest possible clarity must

be free from all extraneous material. This method of catalyst
removal is evidently effective only in the case of Ziegler-type
catalysts, whose residues are entirely acid-soluble. When
catalysts on a refractory-type substrate are used, it is neces-
sary to dissolve the polymer in a solvent at elevated tempera-
ture (xylene at 130°C, for instance) and centrifuge or filter
the hot solution to remove catalyst residues.
In order to obtain a colorless polymer, this solution may
be decolorized by treatment with suitable clays, silica gel, or
other decolorizing agents. It is also necessary to add anti-
oxidants to the polymer before it is exposed to the air.
Although a rough separation of isotactic from atactic

polymer may have been made earlier, it is generally at this
point that final separation is made. The hot, filtered, and
antioxidant-protected solution is cooled to room temperature

which precipitates out the isotactic fraction, leaving the atac-
tic in solution.
Another filtration or centrifuging separates out the isotactic
material which is, however, saturated with xylene, a rather
difficult solvent to remove.
The xylene wet cake may be extracted with a series of
more volatile solvents to remove xylene. Final solvent re-
moval may be by steam distillation, or devolatilizing
extruders may be used to remove solvent and form the pellets
at the same time. Figure 4.2 is a flow sheet of this process
showing the essential These vary a great deal in
steps.
detail —
often some may be combined, and in other cases
the steps may be split up into more subdivisions. As the
discussion indicates, the final dissolving and filtration steps
may not be necessary when the catalyst is of such a nature as
to be completely extractable in the earlier steps.
It is evident that this is a complex process involving the
interrelation of numerous steps, each of which can cause loss

of product or of quality. In spite of this complexity, it is a
straightforward process that does not involve a great deal of
labor cost. Once the design and method of operation are
settled, the plant will run automatically and economically.
Unlike the high-pressure polyethylene process which uses
special high-pressure pumps, valves, piping, autoclaves, etc.,
this process uses equipment familiar to every chemical
engineer.
The reactor is a closed tank with an agitator. It will differ
in detail, depending on operating pressure, but this is usually
below 100 atm, so that no unfamiliar construction is required.
The same is true of all other items of equipment; centrifuges
may be substituted for the filters shown. Except for the need
for maintaining a dry and inert atmosphere in the first one,
no unusual problems are involved.
102 Polypropylene
The first solvent recovery must have special provision for

removing all traces of water, since water destroys the effec-
tiveness of the catalyst.
MONOMER CATALYST
MONOMER REACTO R -
I
STORAGE
RECYCLE
SOLV ENT
FLASH DRUM RECYCLE
I
FILTER -
H STILL AÂ CTTC
I
AND LOW POLYMER

AGITATOR EXTRACTANT
FILTER
I
RECOVERY CAT ALYST
I
RESIDUE
AGITATOR WATER
Fl LTER WATER AND

TaTALYST RESIDUE
STEAM STILL ÂTER
ANTI 0X1 DANX
DECOLORIZER DISSOLVER ]—• 1
ST0RA6E~|
RECOVERY FILTER SOLVENT

CL
T
CATAL YST
E
COOLER
RESI DUE
FILTER I ^RECOVErTIaTAC TIC
I
POLYMER
EXTRACTION I
RECOVERY I
SOLVENT
STO RAGE
SHI PPING
Figure 4.2. Flow sheet of polypropylene manufacture.
The devolatiUzing extruders used in the final operation

may not be famiUar to These consist of long screw ex-
all.
truders, similar to the machines used in extruding plastic

film or pipe, except that they are longer. At one or several
places along the barrel length, there are openings or vents.
The screw is modified at these points to assure a low pressure
on the polymer. The polymer is heated and melted as it
progresses forward in the barrel, which heats and volatihzes

the solvent. When comes to one of the vents,
the polymer
The evaporation of solvent
the solvent flashes out of the vent.
is generally assisted by drawing a vacuum on the vent. These
machines have been improved until they can remove a great

deal of solvent, but their best function is to remove the last
traces. When film-grade polymer is being produced, it may
be necessary to provide inert-gas blanketing to exclude all
oxygen from the process.

The product leaves the extruder through a die, forming a
number of small rods; on cooling, these are cut with rotary
knives or more often with a flying knife at the die face. The
whole operation may be performed under water. This method
produces a pellet that ranges from lentil-shaped to nearly
spherical, and has excellent flow properties in the processing
equipment used to put the resin into its final form. Round
pellets are also much better suited to the pneumatic transfer
systems being installed in most modern processing plants.
Unlike low-density polyethylene, which is useful for many
purposes as essentially pure polymer, the usefulness of poly-
propylene is dependent upon its being stabilized against heat
and oxidation. Although the art of stabilizing polypropylene
is quite new, it has a highly developed tradition to draw from.
The fact that for some purposes, polyethylene must be
stabilized — the linear variety for almost all purposes —has
led to the development of stabilizers particularly suitable for
poly olefins. Many of the stabilizers used for vinyl chlorides
are also effective in polypropylene, despite the fact that the
nature of the degradation is so different in the two cases.
Many of the materials used in the protection of rubber
against oxidation are also useful in polypropylene. The years
of experience with antioxidants in this industry have been
very helpful in developing similar materials for polypro-
104 Polypropylene
pylene. In some cases where rubber antidoxidants had serious

drawbacks, related materials were found to be suitable.
In spite of its novelty, much has been found out about
stabilizing polypropylene, and this is an important part of
polypropylene technology. In the process, some stabilizer
must be added to the resin before it is subjected to any
elevated temperature. Additional stabilizer, or special stabi-
Uzer for some specific purpose, may also be added in a subse-
quent operation.
COLORING OF POLYPROPYLENE
Colors can be incorporated into polypropylene by any of

the methods used for polyethylene and thermoplastics the —
two-roll mill, Banbury mixer, or compounding extruder.
These types of equipment are generally used ( 1 ) for applica-

tions where color dispersion is critical, for instance where
carbon black is to be incorporated to improve the resistance
to light exposure; (2) where a particularly even color or an
accurate color match is needed; (3) for reworking scrap and
off-grade material, with the incorporation of color.
Economic factors, however, cause a large proportion of the
colored polypropylene to be dry colored. In this process the
various colors and pigments are blended with the resin in a
tumbling barrel or other dry mixer. This dry blend is then
used as feed for the processing equipment, depending on the
turbulence of flow in the processing step to complete the
mixing. This method of coloring is particularly useful in the
injection-molding industry. Some difficulty has been encoun-
tered with the dry coloring of polypropylene.
It has been common practice in the injection-molding
industry to insert a wide variety of dispersion aids into the
nozzle of the molding machine. The nozzles vary in design
but all serve the same general purpose of increasing the
turbulence of flow, and so improving the dispersion of color.

Many of these devices have been quite successful in produc-
ing excellent color dispersions in polystyrene and in poly-
ethylene, but have been markedly less successful in the case
of polypropylene. The previous discussion of the flow prop-

erties of polypropylene makes it easy to understand why this
would be the case. The sharp break in the viscosity of poly-
propylene with increased temperature means that when the
resin is heated in the molding machine the portion near the
walls, which gets hot first, becomes fluid, and the mass moves
easily through the cylinder without any great degree of tum-
bling or turbulence. The sensitivity of the viscosity to rate of
shear aggravates this tendency. The first-melted portions flow
first, are subjected to the greatest shear, and become even
more and the material away from the walls has no
fluid,
tendency whatsoever to mix in with the material near the

walls. This flow pattern persists to a considerable degree even
through the rather complicated and tortuous passages of the
various dispersion devices in the injection machine.
In order to get color dispersion in polypropylene melts,
it is necessary to force the wall and center layers of the melt
to mix together, regardless of their natural tendency to remain
apart.One successful device for doing this was developed
by the Plastic Color Division of the Ferro Corp. This is
called a spherical Venturi, and its operating principle is just
the opposite of that of an ordinary Venturi tube. Instead of
changing fluid velocity efficiently and without turbulence, the
spherical Venturi deliberately uses the energy produced by a
change in velocity to shatter the laminar flow of the plastic
and create turbulence.
This is accomplished by forcing the plastic through a small
hole 0.030 to 0.050 in. in diameter into a sphere about V2 in.
in diameter and then immediately forcing it through another

small hole. These two successive, rapid-velocity changes
106 Polypropylene
create a great deal of turbulence. Figure 4.3 shows a typical

spherical Venturi. Exact dimensions will, of course, vary with
the type and size of machine. With dispersion aids of this sort
^-plEce TO BE
^ IKI
secTioMs- HALVED
THIS t
TU;o
OKI
^ DIA.SPHEI2.E
-N^ 63(.029D1A )
DRILU THRU
Figure 4.3. Spherical Venturi plate for dispersing color in

polypropylene. (Courtesy Ferro Corp.)
it is possible to get entirely satisfactory dry-blended color

with polypropylene.
It must be kept in mind that polypropylene will mold at
higher temperatures than many other plastics; thus extremely

heat-stable colors are required. In general, however, colors
that have been successful in polystyrene and polyethylene will
also be satisfactory in polypropylene.
5. PROCESSING OF POLYPROPYLENE
The processing of polypropylene closely resembles the

processing of polyethylene and other thermoplastics, but it
has certain special characteristics that modify its processing

requirements somewhat, and it responds particularly favora-
bly to certain modifications of conventional methods. These
special processing characteristics will be discussed in detail
in this chapter, with only such mention of the basic process
as is essential to the understanding of the modifications.
Where reference is made to equipment used to process poly-
ethylene, further details of this equipment may be obtained
from the first book in this series.
EXTRUSION OF POLYPROPYLENE
Although the greatest present use of polypropylene is in

injection molding, market research and the history of other
thermoplastic materials make it very clear that the largest
ultimate market will be for extrusion purposes.
General Considerations
Polypropylene is a relatively easy material to extrude and
will perform reasonably well in any machine designed to
extrude polyethylene.
As with the other poly olefins, a relatively long extruder
produces better-quality melt. An L/D ratio of 20:1 is good
107
1 08 Polypropylene
practice, although satisfactory resuhs can be obtained from

ratios ranging from 16:1 to 24:1.
Relatively high compression screws are also recommended,
with a 4:1 compression (preferably produced by increase of
root diameter) being a minimum. A relatively long (4 turns
or more) metering section is desirable.
Double-screw as well as single-screw machines have been
used successfully on polypropylene.
Screen packs and valving in the melt channel are generally
less effective with polypropylene than with polyethylene be-
cause of the great sensitivity of the viscosity of polypropylene
melts to rate of shear. Back pressure built into the die by
increased land length appears to be the preferred way to
control the extrusion. An increase of land length restricts
flow without increasing the rate of shear as does a valve or
a screen pack. In many cases this will require a consider-
able change in die design from that used for other plastics.
A land length 50 times part thickness is not unusual, and

approach to the land should be long and shallow. It is easy
to understand that if the flow is a little more rapid in one
area, the rate of shear wiU be higher, and hence the viscosity
will be lower in this area, resulting in uncontrolled flow.
Streamlining of the die is very important because of the de-
crease in melt viscosity that results from too long exposure
of the polypropylene to heat. Material delayed in relatively
stagnant areas will soften and behave very differently when
it leaves the die.
The above discussion should not discourage the use of the
same dies for polyethylene as for polypropylene, since per-
fectly satisfactory results can often be obtained from them;
however, if a new die is to be built, the considerations men-
tioned should improve quality and output. If the proper die
is used, really remarkable extrusion rates can often be ob-
tained with polypropylene. It appears likely that familiar ex-
Processing of Polypropylene 109
trusion economics will be completely upset when the abihty

of polypropylene to extrude rapidly is thoroughly understood.
Polypropylene does not absorb moisture, so, except for
compounds containing carbon black or other hygroscopic
fillers, no drying is needed. The quahty and output of an ex-
truder, however, can frequently be improved by the use of a

hopper dryer which will deliver material to the feed section
of the extruder at a uniform temperature around 190°F.
The susceptibility of polypropylene to oxidation is still great
enough, in spite of advances in stabilization, that the extru-
sion of the highest-quality film, or other critical products,
benefits from the exclusion of oxygen from the process. This
is conveniently done by displacing the air between the granules
being fed to the extruder with an inert gas.
POLYPROPYLENE-FILM PRODUCTION
The greatest volume of extruded polyproplene is expected

to go into thin film for packaging. Polypropylene can be
made into film by any of the processes used to produce film
from other thermoplastics.
A new material is inevitably tried out first on equipment
originally designed for other materials, and polypropylene has

been no exception. When the polypropylene resins now avail-
able are run on the kind of equipment used to make poly-
ethylene blown tubing, it is not difficult to obtain film, but it
is not very attractive in appearance. It does not have gloss
or clarity equal to polyethylene blown tubing, except at thick-
nesses below 0.3 mil (0.0003 in.), and its physical properties
are not much better than those of polyethylene film. Although
the development of resins that are better for this method of
processing is not impossible, at present the main promise of
polypropylene as a film material lies in its adaptability to the
chill-roll extrusion method.
110 Polypropylene
Chill-roll Extrusion of Polypropylene Film
In this method the hot plastic is extruded through a long

slit die, and the resulting web is brought into contact with a
polished steel roll that is water-cooled. Chill-roll equipment
falls into two general classes which are adaptations of equip-
ment originally designed for other purposes. The first of these
is the equipment used for coating paper with polyethylene. In
STRIPPER ROLL
TO
01 E
Wl NDER
A( R
KNIFE
igure 5.1 Chill-roll casting, vertical-extrusion method.

(Courtesy F. W. Egan Co.)
this, the web is extruded straight down and makes contact

with the chill roll while traveling almost vertically downward.
The coating equipment is modified either by moving the die
nearer the chill roll, so that film falls upon it, or by removing
or drawing back the rubber pressure roller. After following
the chill roller through 180 deg or more, the cooled film
can be taken off onto a stripping roll, from which it goes to a
trimmer, and then through tensioning rolls, to a windup. The
chill rolls used in this equipment may be quite large, up to
3 or 4 ft in diameter, and are usually polished to a mirror

finish. Figure 5.1 is a diagram of this arrangement. For
thin polypropylene film the mirror finish is not essential, as
the film makes no real contact with the roll but rides on an
air film, giving excellent gloss and clarity, even from a dull
chill roll. The transition from roll contact conditions, where
the film takes on the imprint of the roll surface, to air film
condition, where the roll surface is immaterial if it has no

gross imperfections, depends mostly on linear speed and film
thickness, although other factors also influence it. Thicknesses
below 2 or 3 mils generally run on an air film at speeds
above 100 fpm. High extrusion temperature and high roll
temperature are influences favoring contact, whereas thin film
and high linear speeds favor air-film conditions. Commercial
operations will probably be under air-film conditions, in most
cases, to obtain economical production rates. A single chill
roll is commonly used in this arrangement. The stripper roll
may be a siHcone-rubber roll which runs in contact with the
chill roll, or a steel roll spaced out a httle. Test runs have
been made employing the rubber pressure roll used in coat-
ing. It is necessary to adjust the point of contact between chill
roll and film so that the film has been on the chill roll about
a foot before the pressure roll hits it. It is also necessary to
have positive cooling on the pressure roll, or it will become
hot and stick to the film. Some coating equipment provides
for wetting the pressure roll as it leaves the chill roll, and
then squeegeeing it dry before it contacts the product. A
film of water can also be provided by means of a furnishing
roll, as in printing. These methods can keep the pressure
roller cool. In any event, the pressure roller does some dam-
age to the high gloss of the polypropylene film, but it
stabilizes operation, and

improves uniformity of the film,
allows considerably higher operating speeds. Depending on

the film and use, it may sometimes be advantageous. As
shown in Figure 5.1, an air knife may also be used to assure
contact of film and roll.
On a chill-roll casting unit, when the web emerges from
the die it is desirable to bring it into contact with the chill
roll as soon as possible. The distance between die lips and roll
surface is determined by the construction of the equipment;
if possible it should be less than an inch, and one-half inch

112 Polypropylene
or less is even better. The film will not generally make contact
with the roll at the nearest point, except for heavy film, at low
speeds. Thin film run at high speed will not really contact the
roll at all, except at the edges, but will ride all the way on
an air film, as previously mentioned. One reason why a short
distance between die and roll is necessary is to prevent the
edges of the film from drawing in excessively, reducing the
usable width and building up a heavy "bead" at the edges.
This effect more severe with polypropylene than with poly-
is
ethylene, because of its low melt viscosity. Not only does the
film narrow excessively, but, under some conditions, the width

is extremely unstable. Short gap and high take-up speed favor
stability.
The most important reason why is essential to have a

it
very narrow gap between the die and chill roll is that the
lip
clarity and gloss of the film are dependent upon extremely

rapid chilling of the melt from extrusion temperature to some
temperature below the crystaUization point. If the film is
drawn through the air for any considerable distance before
contacting the roll, it cools too gradually, and large crystals
form which make it dull and cloudy.
The film take-up speeds attainable with polypropylene film
are very high. The best film resins, run at recommended tem-
peratures, can be drawn down to 0.1 mil without tearing off,
at speeds as high as 500 fpm. Most of the factors that limit
the speed of polyethylene-film casting units do not appear to
affect polypropylene film until speeds are much higher. Poly-
propylene permits the use of very low chill-roll temperatures
which give more rapid chilling of the film, and this pushes
the limitation on speed up to higher levels as well. The lower
heat content of polypropylene also serves to reduce the time
required to chill the film to handling consistency.
Horizontal Extrusion. The other general type of equip-
ment used for chill-roll extrusion is a development from
equipment designed for other thermoplastic film or sheeting,

such as polyethylene, cellulose acetate, butyrate, or styrene.
In this equipment the film is extruded horizontally, or just
a little less. It contacts the top of the chill roll and follows it
down around 180 deg or more, where it is picked up by

another pohshed roll similar to the first. Equipment of this
type is shown There may be as many as four
in Figure 5.2.
chill rolls in succession, and then the film goes on to trimming
KNIFE
DIE
CASTING^
ROLLS >-< r^ —^TO
Wi NDER
Figure 5.2. Chill-roll casting, horizontal-extrusion method.

{Courtesy F. W. Egan Co.)
and roll up, as shown. Increasing the number of rolls assures
a cool film at the take-up and prevents troubles caused by

thermal contraction of the film after it is rolled up.
Rolls in this equipment are generally smaller than in the
previous type, 18 diameter being common, and
in. to 1 ft in
8 in. not unusual. This equipment often has a polished roller

above the first chill roll, which can be brought down on the
film. When extruding heavy sheeting this serves to improve
the top surface, but it cannot be used for thin film; 10 mils is
probably the thinnest sheet benefited by the top roller. This
equipment may not be capable of as high speeds as the
previous type because of the smaller chill-roll diameter, but
it may make better film.
It appears very likely that many of the high-speed chill-
roll plants set up for the extrusion of polyethylene film will
114 Polypropylene
attain the high web speeds for which they were designed only
if they are converted to the manufacture of polypropylene
film.
Die Design
Although slot or manifold dies of conventional design are
usable for making polypropylene film by the chill-cast method,
there are certain design features that are very important for
successful operation. Figure 5.3, which is adapted from a
drawing of a die cross section furnished by F. W. Egan and
Figure 5.3. Cross section of die for extrusion of polypropylene flat
film. (Courtesy F. W. Egan Co.)

Co., shows one way in which most of these features can be

obtained.
( 1 ) Die hps tapered to permit very close approach to roll
surface.
(2) Long land and gradual approach to land.
(3) Solid jaw on roll side to make leaks on this side
impossible.
(4) Die passages streamlined and well finished.
(5) Adjustment perpendicular to land to prevent one jaw
projecting out ahead of the other.
In addition to these features, it should be kept in mind
that, provided it has the essential features, the simpler a die
is, the better. Every joint is a potential leak and a potential
source of hang-up. Every unnecessary bolt or screw is a source
of extra maintenance work and down time.
An extrusion die must be made of high-grade tool steel,
heat-treated to relieve strains at well above the highest ex-
pected operating temperature.
All surfaces in contact with the plastic should be well
finished and chrome-plated. It is not necessary to poHsh the
surfaces highly; a smooth but dull surface appears to be
easier to keep clean. The plating must be free from porosity
or pinholes which will catch and hold polymer.
Control of Web by Air Flow

With either type of equipment it is desirable to provide a
stream of air to force the film against the chill roll shortly
after it must be rather low in

leaves the die. This air stream
velocity and accurately controlled, or it will cause flutter in
the web and will cool the die lips. A well-controlled low-
velocity air stream will, however, stabilize operations and
permit higher speeds in most cases.
The "air-knife" technique is even more effective than the
low-velocity air stream. In this method an air duct is fitted
116 Polypropylene
with a set of adjustable lips which are the same length as the
used and have a narrow opening between them, of
chill roll
the order of 0.050 in. Air is passed through this duct at

considerable pressure, 5 to 10 psi being common. The narrow
jet or "knife" of air which emerges presses the molten poly-
Figure 5.4. Commercial chill-roll casting unit with air knife in place.
Die not shown. (Courtesy F. W. Egan Co.)
mer against the chill roll. Since the volume of air is small,
no considerable chilling of the die lips results, and, if the
knife is directed properly, flutter of the web will not result.
Much skill is involved in the use of the air knife, and many
have become discouraged because of poor initial results. The
knife must be well constructed of rigid material, and means
for adjusting the position and direction must be accurate and
positive.
The knife should be directed at the roll surface, and should I

contact the web as soon as practical after the film leaves the
die. Figure 5.4 shows a chill-roll unit with air knife in
place. It is quite possible to cut the hot film off entirely
with the air knife if it blows against unsupported film, and
this is perhaps what has discouraged more users than any
other difficulty; however,if the jet blows directly at the roll
and narrow enough to avoid setting up air currents at a dis-

is
tance, no trouble should be encountered. For greatest effect,

the lips of the air knife should be quite close to the film
surface.
One advantage of the air knife is that it can prevent the
development of an air film between the chill roll and the web
up to considerably higher web speeds and down to thinner

film thicknesses than is possible without it. If the roll is highly
polished, a smoother surface and higher gloss are obtained
on the side of the web that contacts the roll.
Puckering of Film
Good contact with the chill roll also is effective in pre-

venting the very common defect of chill-cast film known as
puckering or seersuckering.
In extreme cases the appearance closely resembles that of
seersucker cloth. There will be longitudinal strips in the film
which are perfectly flat, and between these lines the film will
be puckered or wavy. This effect appears to be due to differ-
ences in cooling rate caused by imperfect contact with the

Although the air knife will not prevent the forma-
chill roll.
tion of these marks under all conditions, it does appreciably

extend the range of operating conditions over which flat film
can be made.
It should be noted that the linear speeds at which these
defects appear are considerably higher for polypropylene

than they are for polyethylene. Early work indicated that
118 Polypropylene
there would be no puckers in polypropylene film, but this was

before the possibility of extremely high linear speeds was dis-
covered.
One of the reasons for the better performance of poly-
propylene in this respect is that the formation of the puckers
is made much more serious by the build-up of oxidized mate-
rial on the die lips, which causes gauge variations at very
short intervals. These gauge variations contribute greatly to
uneven roll contact of the film. With polyethylene these
deposits build up very rapidly and are apparent even after
only a few hours of operation. If the extrusion is uninter-
rupted and at a rapid rate, the amount of oxidation de-
and a reasonable period
posit tends to stabilize after a while,
of operation is do con-
possible. Nevertheless, the deposits
tinue to grow, and it is necessary to stop the machine every
few days, at best, in order to remove the accumulation. The
tendency of polypropylene to break down to a less viscous,
rather than a more viscous, material prevents the formation
of these oxidized deposits. Polypropylene-film dies may be
operated for months without shutdown caused by die deposits.
This not only reduces down time and maintenance costs on
the machine but eliminates the progressive deterioration of
film quality between cleanings.
Gel Streaks in Film
The same reaction of polypropylene to heat also eliminates

another source of defective film that can be very serious in
the case of polyethylene. If die passages are not perfectly
streamlined, or if the inner die surface is roughened in any
manner, polyethylene may build up oxidized material within
the die or in polymer passages elsewhere in the machine. This
build-up periodically peels off, causing streaks in the film.
Polypropylene has no tendency to do this.
Gels in Film
It is not possible at this time to form a firm conclusion

regarding the problem of gels in polyproplene film. Gels are
a serious source of trouble in polyethylene film, and they
have generally been attributed to an oxidation cross-linking
phenomenon similar to the one which causes the annoying
surface deposits referred to above. On the basis of the fact
that polypropylene does not cross-link in such a manner, it
has been assumed that the gel problem would be eliminated.

From time to time remarkably gel-free polypropylene film has
been exhibited, but current production resins do not appear
to be uniformly gel-free. There apparently is some other
mechanism of gel formation in polypropylene, and it cannot
be certain at present how completely these gels can be elimi-
nated.
Flat Film by the Water-Bath Method

Polyethylene film has long been made by extruding molten
material out of a narrow slit die into a water bath. This
method has recently been considered obsolescent, and several
of the largest plants using it have closed down; however,
some such equipment is still in operation.
The first attempts to apply this process to polypropylene
film gave rather poor results, especially as to appearance.
Further work on the process, however, has shown that, if the
water tank is carefully baffled and rigidly supported to pre-
vent the formation of surface wavelets, the water level can
then be brought up very close to the die opening, and this will
produce clear film. The distance between die lip and water
surface required to get this effect is about Va in. Figure 5.5
shows a water bath with necessary baffles in place.
The water carry-over problem that limits the speed of
water-bath polyethylene film appears to be easily controUed
120 Polypropylene
in the case of polypropylene, and web speeds as high as those

obtainable in cast film are possible.
Figure 5.5. Small water-bath film unit showing baffles on water bath
to prevent waves in water. (Courtesy F. W. Egan Co.)
It should be kept in mind that these speeds are higher than
any obtainable with polyethylene. Generally available ma-

chine speeds are the limiting factor, and machines have not
yet been built that will exceed the ability of the resin to ex-
trude and draw down.
General Considerations in Film Extrusion

Contrary to experience with other thermoplastics, poly-
propylene extrudes better at the highest screw speed and out-
put Also contrary to other experience, the use of a

rates.
restricted screenpack or other method of producing back
pressure on the screw does not improve the appearance of
polypropylene film, nor does it steady the operation of the
extruder.
A long extruder barrel is a greater advantage in poly-
propylene extrusion than in that of any other thermoplastic.
In general, an extruder with a 15:1 ratio of screw length to
diameter will extrude less polypropylene at any given speed
than it will, say, polyethylene. If the ratio of length to diam-
eter above 20:1, however, quite often the output of poly-
is
propylene will be greater than that of polyethylene.

The reason for this is that polypropylene shows a sharper
drop in viscosity as it heats up than do most other thermo-
plastics. This means that the frictional heat build-up is smaller,
so a larger part of the heat required to reach extrusion tem-

peratures must be provided by thermal conductivity from
the cylinder walls. This is partly, but not entirely, compen-
sated for by the fact that polypropylene requires rather less
heat per pound to reach a given temperature than do most
plastics. This situation was discussed more fully in Chap-
ter 2. Extrusion temperature for polypropylene film is usually
from 525° to 575 °F. Below this the film is not clear, and
above 600 °F the resin degrades. Table 5.1 shows typical
conditions. One of the most common problems encountered
in polypropylene-film extrusion is generally described as
surge. This appears as variations in film thickness and can
usually also be observed as variation in film width as it is
extruded. The normal reaction of those familiar with ex-

truders is to slow down or to put in a heavier screen pack.
These expedients usually make the situation worse, since this
variation does not appear to originate in the screw, as such
fluctuations do with other plastics, but in the die itself, due
to the low melt viscosity of the material, which does not allow
122 Polypropylene
build-up of enough pressure in the die to estabHsh a positive

flow pattern.
Corrective action is to increase extruder speed, lengthen
the die land,and decrease the die opening. Die lands of 1 in.
or more are recommended, and lengths below V4 in. are
almost inoperable. A die opening from 15 to 25 mils is gen-
erally satisfactory with a reasonably long land. In addition to
Table 5.1. Recommended Processing Conditions for

Two Polypropylene Film Resins
Low melt index High melt index
Cylinder temperature 450°-550°F 450°-550°F

Die temperature 525°-550°F 500°-550°F
Stock temperature 550°-575°F 525°-550°F
Chill-roll temperature 40°-100°F 40°-100°F
Screen pack None finer than None finer than
100 mesh 100 mesh
Extruder L/D ratio 20/1 min 20/1 min
Die gap (mils) 15-25 15-25
Die land V2 to 1 in. V2 to 1 in.
Air gap (in.) 1/4 to 1/2 Va to 1/2
promoting surge, wider die openings also tend to increase the

unidirectional orientation of the film and aggravate its tend-
ency to tear easily in the direction of extrusion.
Biaxial Orientation
A great deal has been said about biaxial orientation of

polypropylene film. This consists of drawing the film out
sidewise as well as in the direction of extrusion. Extremely
high film strengths can be developed in this way. Table 5.2
shows how stretching increases the strength of polypropylene
film.
The strength of polypropylene film made by the chill-roll

method is probably adequate for the principal uses it will
have. Chill-roll film may receive a small amount of stretch
across the web, because, while the film as a whole makes no

firm contact with the chill roll, the edges do, and they will
usually stick to the roll when they touch it if the chill-roll
temperature is above 160°F. As the film cools, the edges
remain in place, and the film between is stretched. The high
linear-expansion coefficient of polypropylene makes this
stretch appreciable. It can also be extended somewhat in
Table 5.2. Effect of Stretching on Strength of

Polypropylene Film
Ultimate tensile
stretching (%) strength (psi) Elongation (%)
None 5,600 500
200 8,400 250
400 14,000 115
600 22,400 40
900 23,800 40
the longitudinal direction by increasing web tension. If the

chill-roll temperature below 160°F, there will generally be
is
no sticking of the edges and no transverse stretch. Numerous

devices have been suggested for the biaxial orientation of
polypropylene film but only one will be mentioned here as a
guide.
A textile tenter is a device long used in that industry to
control the width of cloth, especially after washing or dyeing
operations. It consists of a series of clips, not unlike those
found at the top of the common "clip board" used to hold
papers, arranged on two endless chains which run on two
tracks. These tracks are horizontal and can be arranged so
that the clips grasp the edge of the plastic film as it emerges
from the die or comes from a cooling roll. The tracks diverge
slightly so that the clips pull the film sideways. The angle of
the tracks can be regulated to produce any desired amount
of stretch, and the whole tenter can be mounted in an oven
124 Polypropylene
to control the temperature at which the stretch occurs. This

device is used to orient other plastic films and should prove
suitable for polypropylene.
SHEET EXTRUSION
Polypropylene can be made into heavy sheet by means of

the equipment commonly used to make impact styrene sheet.
Extrusion temperature will vary with the kind of poly-
propylene, but most current resins would require 420° to
550°F stock temperatures. Die temperature is preferably 10°
to 20 °F below stock temperature, and small temperature dif-
ferences across the die may be used to obtain even flow across
the die, as with other thermoplastics.
Die lip settings should be approximately the same as the
desired sheet thickness; a drawdown not above 10 per cent is
permissible.
This equipment generally has three rolls set vertically
above one another, with the sheet passing between the top
two. The upper roll, which is adjustable, should be set to
maintain contact with the sheet, without, however, causing an
excess of material to build up in the nip. A build-up in the
nip will cause surface defects in the sheet.
The polypropylene will generally take the same finish as
the roll surface. Its ability to reproduce roll surface is con-
siderably greater than that of polyethylene. Roll-surface tem-
peratures are generally 180° to 190°F, or just cool enough
to prevent sticking. Cooler rolls will reduce the effect of roll
surface; i.e., if is glossy the sheet wifl be
the roll surface
duller if the roll and vice versa. The cold roll may
is cool,
also cause mottUng of the surface and may stiffen the sheet
so that it wrinkles. Various surface finishes or embossed de-
signs are easily produced by modifying the roll surface in an
appropriate way.
PIPE AND MISCELLANEOUS EXTRUSION

The equipment used for polyethylene pipe can generally be
used for polypropylene pipe, although the sizes produced on
a die may not be identical for the two materials because
of the difference in flow properties. The equipment most com-
monly used for this purpose consists of a die which permits
the passage of plastic through the annular space between a
central core or pin and an outer bushing. These dies differ
only in the manner in which the core is supported, which, of

course, determines the flow path of the plastic material.
Two general methods are used. In the first, the core is sup-
ported on two or more radial members at which are its base,
rigidly fastened to the die body. In recent years it has been
more usual to use an offset die in which the pin goes right
through the die body, while the plastic enters on the side,
and turns at right angles. The most important practical dif-
ference between the two dies is that the offset die is particu-
larly well adapted to the use of the "internal-mandrel" method
of sizing and supports the pipe as it leaves the die.
Polypropylene, like any other plastic, is soft when it leaves
the extrusion die, and it is quite incapable of sustaining its
own weight or maintaining its shape. The major problem in

pipe extrusion is to support and cool the pipe at this point.
In the internal-mandrel method the die pin holds in
front of it a water-cooled mandrel which supports and cools
the pipe, and at the same time finally fixes its internal diam-
eter. Thisis most easily done with the offset-type die, because
this permits water lines to be run through the die core to
the mandrel, without excessive difficulty. This method is very

difficult to operate with heavy-walled polypropylene pipe and
should generally be used only for thin-walled tube.

The other currently popular method is the vacuum sizing
chamber. This method was brought to a high state of de-
126 Polypropylene
velopment in Europe and is becoming popular here. In this
method the hot pipe taken from the die into a water-cooled
is
metal cylinder, which has a perforated section in its center

which communicates with a passage that can be evacuated.
By drawing a vacuum on this center section, the soft pipe is
drawn up close to the walls of the cylinder. This method fixes

the outer diameter of the pipe while cooling it to the point
where it can be handled. Many other methods of supporting
and sizing pipe are also in use, but these two are the most
common.
Polypropylene resin makes satisfactory pipe by either
method. After the initial sizing, the pipe is carried under
streams of water and immersed in a water tank to cool it
completely.
In small sizes, polypropylene pipe can be coiled the way
polyethylene pipe is, but for larger sizes it must be cut into
lengths for transportation.
Extruder cylinder temperatures should be regulated to give
a stock temperature from 375° to 500°F, depending on resin
and equipment. Die temperature may be the same as stock
temperature or slightly above or below. Which gives the
best results must be determined in each individual case.
A vacuum of 3 to 4 in. of water is adequate for maintain-
ing proper contact with a vacuum die.
The cooling water in the internal mandrel may be run

slightly warmer than is generally done with polyethylene, to
prevent premature cooling and seizing. A given mandrel will
probably produce slightly smaller polypropylene pipe than
polyethylene, because the polypropylene sets at a higher tem-
perature and therefore shrinks more on cooling to room
temperature.
Most shapes can be made from polypropylene without
much modification of current practices, but it is generally
preferable to use longer land lengths, and the approach to

the land must be very gradual.
It must be remembered that polypropylene is a consider-
ably stiff er material and sets up more rapidly than poly-
X
•
y
X
X
150
/
Polyethylene /
High density / Polyethylene
^^^/ Low density^,''
100
/l yAv
,'' / X Polypropylene
50
'^'^''^\
1 1 I
TEMPERATURE
Figure 5.6. Specific heat v^'. temperature curves of leading polyolefins

compared.
ethylene. This means that the outer skin of a heavy-walled

shape can become so rigid by rapid cooling that it will not
give when the interior cools and shrinks. Those who have
extruded styrene or acrylic will understand that shrinkage
causes voids to form in the body of the plastic. In order
to prevent this, the extrusion must be cooled more gradually.
128 Polypropylene
Starting out with a hot-water bath and gradually moving into

cooler water is one good method. For some shapes, air flow
or contact with cooled metal guides or plates is adequate.
Polypropylene requires considerably less cooling than poly-
ethylene because its heat content (specific enthalpy) is lower
in the critical cooling regions. This means that cooling from
a given extrusion temperature to a lower temperature requires
the removal of considerably fewer calories of heat. As cooling
capacity is frequently the limiting factor in extrusion, outputs
are generally higher with polypropylene — in some cases,
much higher. Figure 5.6 shows specific-heat-content (en-
thalpy) curves for polypropylene and other poly olefins. Note
particularly that the linear polyethylene has a very much
greater change in heat content during the critical cooling
period when it is changing from the molten state to a rigid
solid. Low-density polyethylene does not change as much,
but it still requires a great deal of cooling to bring it to the
point where it becomes self-supporting.
EXTRUSION COATING
The excellent barrier properties of polypropylene recom-

mend it an extrusion coating material.
as
When polypropylene is used in equipment designed for ex-
trusion coating polyethylene, it is generally possible to have a
good coating operation without excessive trouble; however,
the two polymers are, for all practical purposes, incompatible.
When polypropylene follows polythylene in the extruder,
the transition will be better at slow screw speed and low
pressure. The opposite transition is easier at high speeds and
high pressure.
The use of an extended die jaw which reduces the gap
between the die lips and the point of contact with the sub-
strate appears to have even more importance with poly-
propylene than with polyethylene. Provision for heating the

extension is essential, because otherwise its temperature will
drop below die temperature, and the main purpose of the ex-
tension, which is to maintain melt temperature, is lost.
The thermal sensitivity of polypropylene makes tempera-
ture regulation somewhat more critical. The usual relation
of improved adhesion with increased stock temperature is ob-
served with polypropylene. If stock temperatures in the region
of 625° 650°F, which are not unsual with polyethylene,
to
are used with polypropylene, a blistery coatingwiU be ob-
tained, which has excellent adhesion but no value. This
means that the speed, adhesion, thickness, and temperature
balance must be achieved at a somewhat lower temperature
with polypropylene. Since the type of resin, residence time at
melt temperature, etc., all influence the decomposition rate,
no top temperature can be quoted, but, ordinarily, tempera-
tures of from 575° to 600°F will give adequate adhesion
without excessive loss of polymer properties.
Any of the famihar techniques for keeping the plastic hot
until it passes through the nip are helpful. These comprise
heating the an: gap, heating the paper, and the afore-men-
tioned extended die Hps. In some cases, merely speeding up
the machine will improve adhesion. As processors gain ex-
perience with polypropylene, it appears probable that very
economical operation at high speed will be possible. The rec-
ommendations as to machine design for fihn making apply
equally well to coating operations.
MONOFILAMENT PRODUCTION
Extruded polypropylene monofilament comprises the sec-

ond largest market for the material in this country at the pres-
ent time. Nevertheless, the number of producers is not large,
and information about the process is meager. Most of the
130 Polypropylene
following information from experimental work reported by

is
Mclntyre, Craven, and Heumann

of the Enjay Corp.
The general plan of monofilament extrusion equipment is
shown in Figure 5.7. The extruder used is essentially the same
Figure 5.7. Diagram of Monofilament production unit
A Extrusion die D Orientation oven

B Quench tank E Second Godet
C First Godet F Spooling unit
as that used for other polypropylene extrusion, except that

the machines are generally smaller.
The die is a straight manifold type, generally similar to the
tee-type die used in flat film extrusion, except that the die
opening is not a continuous slit but a series of small round
openings. The die openings commonly face downward.
After the filament leaves the die, it is run through a quench
tank containing water. It then passes over a set of driven
rollerswhich determine its initial speed. These are termed
"godets," and it is customary to take several laps around
them to assure that there will be no slippage. From here the
filament enters an orientation oven where its temperature can

be accurately controlled, then to another set of drawing rolls
going faster than the first set.
This means that the filament has been elongated several
hundred per cent under accurately controlled temperature con-
ditions. This elongation is the most critical part of the process,
as it produces the orientation essential to good strength.
After leaving the second set of pull rolls, the filament may
be annealed by raising its temperature somewhat, either while
maintaining a constant length or while permitting a slight
retraction. This stabilizes it against shrinkage, at least up to
annealing temperature, without any great loss of strength.
This step is omitted in the figure for simplicity, and it may not
be used in some cases. The filament is then cooled and wound
up. Generally, each filament is wound on a separate spool.
Monofilaments are relatively coarse fibers with a diameter
of from 0.003 to 0.012 in. In textile terms this is 40 to 1000
denier. The denier is a unit which represents the weight, in
grams, of 9,000 m of fiber. Textile fibers have a denier of
from 1 to 15.
In a typical commercial monofilament setup, a P/i-in. ex-
truder may carry a die with 18 orifices. Die orifice may vary
somewhat with the size of fiber, but a hole diameter of about
0.050 in. will do for all but the finest fiber. This setup will
produce about 1 5 lb of fiber /hr.
The strongest fibers are made from resins of high molecular
weight and high isotactic index, or density. Although the com-
mercial resins now good fiber, which is
available produce
very successful in monofilament uses, experimental resins
all
with higher molecular weight and higher tacticity than those

available commercially have shown that, when special resins
for this purpose become available, considerable improvement
can be expected. To get the greatest strength, extrusion tem-
perature should be as low as practicable with the available
132 Polypropylene
resin.With a resin of high isotactic index, this will be around

425°F.
The quench-bath temperature should be as high as possible
without boiling where the filament enters the water. This is
generally around 120°F. Some benefit can be obtained by
adding glycols or other materials to increase the boiling point
of this bath, but this introduces carry-over problems.
The orientation-oven temperature should be as high as
possible without melting the fibers. This will be about 350°F
with the most suitable resins.
The speed ratio between the two godets is set by the
amount of elongation necessary to obtain full draw of the
fiber. This will vary with resin and processing conditions and
must be determined experimentally. At a given speed on the

first godet, the speed of the second godet is increased until
the fibers start to turn white or break; it is then slowed down
until the fibers are clear again. This gives the point of maxi-
mum orientation and strength.
The air gap between the die and the surface of the water
in the quench tank appears to have Kttle effect on the fiber
properties.
Polypropylene monofilaments, made as recommended
above, show very sharp spots in an X-ray diffraction pat-
tern, which means they have a high degree of axial orientation.
They show a low elongation and little shrinkage below the
temperature at which they were oriented.
POLYPROPYLENE MULTIFILAMENT YARN PRODUCTION
The difference between monofilament and multifilament

yarn is only in the diameter of the individual filaments. The
multifilament is so much finer, 1.5 to 6 denier against 40 to
1 ,000 denier for the monofilament, that the entire technology
is different. The number of holes necessary to make a die that
would take the capacity of even a small extruder would be

entirely impractical to handle. The dies used are called spin-
nerets and usually consist of a number of very fine holes ar-
ranged in a circular pattern. The hole diameter bears about
the same relation to filament diameter as it does in monofila-
ment, which means it may be as small as 0.005 in. for fine
fiber. The small diameter of these holes requires the resin
to be much hotter for multifilament production than for

monofilament production and places a great strain on the
stability of the polymer. A temperature of 650° to 700°F is
required, which is well above the point where polypropylene
breaks down rapidly. The complete exclusion of oxygen by
means of inert-gas blanketing is essential, and special stabili-
zation of the polymer is also needed.
The temperature required to reduce the viscosity to the
point where the plastic will extrude through such a small
orifice can be reduced by the use of a solvent, and the means
used for its removal profoundly affect the nature of the fila-
ment. This is one of the ways in which widely different poly-

propylene filaments can be provided. The solvent may be
removed by evaporation, merely by passing the hot filament
through heated air. It may also be removed by extraction,
by extruding the filament into a bath which dissolves out
the solvent but does not weaken the polypropylene, and then
drying out the filament. In either case, orientation of the fiber
to produce maximum strength must be carried out after
solvent removal.
Linear speeds in these operations are very high, generally
above 1,500 fpm for economical operation.
In spite of these high speeds the amount of material pass-
ing through one spinneret is quite small, and it is not prac-
tical to produce the pressure in a screw extruder. This is

134 Polypropylene
particularly so since a screw extruder does not operate well

at such low viscosity. Pressure can be produced by the use of
inert gas at high pressure or by a small gear pump.
Unlike the monofilament, not practical to wind up the
it is
individual fibers, but the whole group produced from a single

spinneret is assembled together. They are usually given a
twist so that the group of fibers makes a single thread, hence
the name multifilament.
Multifilament may be crimped in different patterns to
change its and may be cut into lengths to pro-
characteristics
duce staple which can be handled by the techniques used for
natural fiber. It may, also, be given coatings of different kinds
to vary its handling characteristics.
INJECTION MOLDING OF POLYPROPYLENE
Since the largest present use of polypropylene is for injec-

tion molding, this one field where there is plenty of
is
production experience, and techniques have been developed

to a considerable extent.
Physical Properties Related to Injection Molding
The physical properties of polypropylene have been dis-

cussed in a general way
Chapter 2. It is worth while, how-
in
ever, to consider specificallywhere polypropylene fits among
injection-molding materials, so that it can be determined what
kinds of articles should be molded from it.
All molded parts require some degree of stiffness, and the
gradation from rigid to flexible is a useful way to classify a
plastic. Polypropylene is a relatively rigid plastic, with flex-
ural strength near that of cellulose acetate plastics. General-
purpose polystyrene is much more rigid, whereas impact
polystyrene is slightly more rigid. This is a very useful area
in the stiffness gradation, being now occupied mainly by the
relatively expensive acetate plastics. The stiffness of poly-

propylene will permit it to replace impact styrene of the same
wall thickness and retain practically the same stiffness. It
should be noted that polypropylene is much stiffer than high-

density polyethylene, with which it is frequently compared,
over most of its usable temperature range.
Tensile strength, as such, is more rarely a major considera-
tion in the selection of a molding resin, but polypropylene
falls in the same range in this property as in the previous one.
Surface hardness of polypropylene is similar to or slightly
more than that of cellulose acetate or butyrate. The poly-
styrenes, both straight and impact, have a higher surface
hardness. This is one property where the difference between
polypropylene and high-density polyethylene is particularly
striking. The surface hardness of polypropylene is more than
twice that of high-density polyethylene on the Rockwell "R"
scale. This should greatly improve the resistance of the sur-
face to accidental marring and denting. In some cases this
hardness range appears to provide more durability than
either the harder or softer surfaces. The slight resiUence of
the surface protects from Ught scratching that so easily
it
mars the surface of harder plastics, and it does not show in-
dentation from pressure as easily as softer ones. This prop-
erty has long been understood as an advantage of acetate and
butyrate resins, as against their cheaper harder and softer
competitors. In polypropylene we have the same advantage
at more moderate cost. This must be qualified somewhat be-
cause the polypropylene part is often so much more glossy
that very small scratches are more visible.
One property where polypropylene clearly exceeds all
other moderately priced plastics is heat-distortion tempera-

tures. Only nylon is better. It is quite significant that the
66-psi heat-distortion temperature of polypropylene is very
near the boiling point of water. This means that polypropy-
136 Polypropylene
lene not only does not soften appreciably at boiling tempera-

tures but even retains a useful amount of stiffness. This is in
marked contrast to "boilable" polyethylenes which retain
form but have little useful stiffness at the boiling point.
Once the decision has been made that polypropylene would
make a useful part, the cost must be considered. In addition
to a relatively low initial price, polypropylene has such a low
density that it is appreciably cheaper per part than the per-
pound price would indicate.
Polypropylene has one property that is of special impor-
tance to the molder, so it is mentioned again even though it

was discussed earlier in this chapter. This is the fact that its
specific-heat content does not increase with temperature as

rapidly as that of other polyolefins (see Figure 5.6).
To explain what this means in a practical way, all molders,
when going from polystyrene to polyethylene, made the dis-
covery that it is necessary to put more heat into a given
weight of polyethylene to get it to some particular molding
temperature, and, conversely, to take more heat out in order
to cool it down again. This, of course, puts greater demands
on the heating and cooling systems of the machine and re-
duces speed and capacity.
When high-density polyethylene was introduced, it had been
hoped that, because of its greater stiffness and temperature

resistance, which allows it to be taken out of the mold hotter,
this capacity loss could be reduced. Of course, quite the con-
trary was observed, and was found that the high-density
it
material was even harder to heat and cool rapidly. This was
due to the fact that, when it was heated through its melting
range, a very sharp increase in specific-heat content occurred.
Therefore, a relatively great amount of heat has to be
put into it to raise it a few degrees in this range.
It might be expected that polypropylene with its very regu-
lar structure would exhibit a similar need for a great amount
of heat in its melting range. This is not at all true. Poly-

propylene, because of its lower increase in specific-heat con-
tent with increasing temperature, can be heated to a higher
temperature with less heat input than can polyethylene. Since
its molding temperature is higher than that of low-density
polyethylene, it does not have a practical advantage over this
material in the heat-input requirement, but it does have a

very valuable superiority over the high-density material. It
has the advantage in cooling that might be expected. Since

it can be removed from the mold hotter than can low-density
polyethylene, it requires appreciably less cooling.
In estimating the effect of these differences on machine
capacity, it should be kept in mind that, because of the higher
molding temperatures needed and the low density of poly-
propylene, no advantage in shot capacity or even hourly plas-
tifying capacity can be expected. A
very appreciable reduction
in cycle, however, is possible because of the faster setting-up
time.Both the lower heat capacity, which decreases the
amount of cooling needed to get to a given temperature, and
the higher heat resistance, which permits ejection at a higher
temperature, work together to cause rapid setting up. It is
often possible to mold an article from polypropylene in half
the time it takes for a high-density polyethylene. This makes
it a much more profitable material to mold.
The viscosity of a polypropylene melt drops sharply be-

tween 450° and 525 °F, so it is best to aim at a molding tem-
perature in this range. Figure 5.8 shows that at 450°F the
linear polyethylenesample was softer than the harder of the
two polypropylene samples, but at 550°F this was reversed.
The softer polypropylene and the low-density polyethylene
show a similar relationship. This rather sharp viscosity gradi-
ent in the narrow temperature range may be somewhat dis-
concerting to those who are not used to it. It is actually very
useful when the temperature is just right. The main flow
138 Polypropylene
should occur while the material is still in the low-viscosity

range and should be timed so that the temperature has
dropped out of that range just as the mold fills. Under these
temperature conditions, a polypropylene molding shows very
httle tendency to flash, but fills the mold easily and reliably.
450 500
CYLINDER TEMPERATURE "F
Figure 5.8. Flow vs. temperature curves for polyolefins.
This also makes polypropylene very responsive to tempera-

ture changes in this region; however, it is not excessively
sensitive, so normal control fluctuations cause no more
trouble than with other plastics.
can readily be seen that the polypropylene flow curve
It
is a point where the product wifl fiU much more

rising to
rapidly than polyethylene, and long flows in thin sections can
easily be made. Generally, cylinder temperatures above
600 °F are not recommended for polypropylene, because the
material begins to decompose; however, the very easy flow
characteristics of the resin make higher temperatures un-

necessary.
Another feature of the flow properties of polypropylene
that is very helpful, when understood and properly manipu-
lated, is the fact that its melt viscosity drops very sharply
when it is caused to flow, and the faster it flows, the lower its
viscosity becomes.
Most plastics have this property to some extent, and per-
haps it merits a little description. If a true fluid like water
gives a certain flow at a certain pressure, it will flow twice as
fast under twice the pressure. It has long been known that
plasticsrespond to increases in pressure with more than pro-
portional flow increases. It has also been well understood
that this more than proportional flow increase is a very useful
property for obtaining short cycles. Acetate formulations
have been modified to increase this property, and such in-
crease has been a major goal in the development of poly-
ethylene resins.
It is often represented in the form of shear-rate versus
shear-stress curves. In these curves the rate of flow (shear
rate) is plotted against the pressure required to produce the
flow (shear stress). Figure 5.9 shows such a curve for poly-
propylene and high-density polyethylene. It is clear that the
slope of the polypropylene curves is much greater. The prac-
tical effect of this phenomenon is that, when a polypropylene
melt leaves the sprue and runners, where it is moving rapidly,
and enters the mold cavity, where its speed slows down, the
melt tends to stiffen up even before it cools at all. Also, it
tends to be more fluid in restricted areas of the mold where

the fluidity is most needed, and less fluid in wider openings.
Although this should not be taken as an excuse for poor
mold design, it does make the material flow more evenly
through a mold, with less tendency to spurt ahead irregu-
larly where there are variations in the path available to it.
140 Polypropylene
PRESSURE
Figure 5.9. Shear-rate-shear-stress curves for polyolefins.
This also means that polypropylene is ideally suited to get

the maximum benefit from the new techniques which are de-
signed to obtain maximum effective pressure in the mold.
Melt-Compression Techniques
These techniques are called by various names such as
precompression molding, sequential-impact molding, and
others.
The essential feature of these molding methods is that a
valve is placed either in the nozzle or in the gates of the
mold itself. The valves are closed when the plunger starts
forward and remain closed until full ram pressure has built
up on the plastic behind the valve. The valve is then opened,
allowing the plastic to spurt into the mold under full pressure.
In the form called valve gating, the valve is in the mold

itself. In the form called sequential-impact molding, there
are two or more valved nozzles that are opened in sequence
by mechanisms located in the machine itself, each being
opened long enough after the previous one for the plastic
pressure to have reached a maximum again.
Plunger
10,000 psi
10 cu in/sec
Granular Region Melt Region

408, 11.7 cu in. 50 Cu in
AVp = AVg + AVm + AVs
Figure 5.10. Schematic diagram of injection-molding process.
These techniques were, of course, developed for use on

plastics otherthan polypropylene; however, the steep slope
of the shear-rate-shear-stress curve of polypropylene makes
them so valuable, specifically for this material, that it is worth
while to discuss the principles involved. To understand what
happens during the injection stroke of an ordinary injection-
molding machine. Figure 5.10 should be referred to. Con-
sider a plunger which can produce 10,000 psi at a speed of
10 cu in./sec. Pushing the loose plastic granules in the
feed section of the machine forces them ahead to create
pressure on melted material farther forward, which then flows
through the nozzle and into the die. The loosely packed ma-
terial has to be compressed from its loose bulk density to the
final density of the plastic. This will require a displacement
of the piston about equal to one full shot, just to remove the
air. In addition to this, the melted plastic in the cylinder is
142 Polypropylene
quite compressible so that much plunger motion is used

merely to compress the plastic.
It is possible to calculate all these factors exactly, but
such calculations are beyond the scope of this book. Suffice

it to say that, to inject 5 cu in. of material, the plunger may
have to displace 12 cu in. or more. During all this time,

material is flowing into the mold under a pressure well below
the 10,000 psi which the plunger can produce. As we have
seen, this will make very inefficient use of the pressure, be-
cause, at the relatively slow injection rate, the response of
the melt to pressure is very poor.
If, instead of following the above sequence, we move the
plunger forward with a closed valve in the nozzle, the granules
will be fully compressed and, as pressure builds up, the melt
will also be compressed up to the capacity of the plunger.
When at this point the valve is opened, material starts to
flow through the nozzle at its maximum pressure. If flow
through the nozzle exceeds the speed of plunger travel, de-
compression of the melt will add its surge of flow, resulting
in extremely fast flow at maximum pressure, taking the great-
est possible advantage of the pressure sensitivity of the melt
viscosity.
This gives very rapidfilling. In one test reported, the effec-
was six times as fast from the precompressed

tive filling rate
melt as it was from the same machine used in the conven-
tional manner. This makes possible the filling of thin-wall
sections that would be impossible by older techniques, be-
cause the melt would set up before filling was complete. Core
shifting is reduced because the melt viscosity remains so low
that no pressure gradients develop around the core, and weld
lines are eliminated.
Of course by the use of
similar results could be obtained
very much larger pumps, producing more rapid plunger
travel, but the cost of this would be very much greater than
the cost of the valving arrangement.
A typical valve for this purpose is activated by a small
high-speed hydraulic cylinder. Total movement of the valve
from full shut to full open is very small and takes something
on the order of 2 milliseconds (msec). The time of opening
can be very accurately controlled, and this gives very precise
control of the amount of material entering the mold.
When using such a system
it is generally unnecessary to
have temperature variation within the mold to control the

flow; maximum coohng can be used to give minimum cycles.
In this respect also, polypropylene is especially suited to
take fullest advantage of the technique, because good surface
finish is obtained even with a very cold mold. If melt tempera-
ture is and pressure is high
in the range previously indicated
enough to ensure smooth filling, a good surface can be ob-
tained with the mold as cold as 60° to 8Q°F. With precom-
pression molding it may be possible to use a mold as cold
as 40 °F with even faster cycles.
Shrinkage of Moldings
The average shrinkage of polypropylene is 1 or 2 per cent

(0.01 to 0.02 in./in.). This is less than half that of either
linear or low-density polyethylene, but still two or three
times that of polystyrene. The relatively wide molding range

of polypropylene permits quite a considerable control of
shrinkage by changing conditions. In most molds there is
one injection temperature which gives minimum shrinkage,

the shrinkage increasing above or below this. Low mold
temperature and efficient cooling of the mold, high injection
pressure, and longer ram-forward time all reduce shrinkage.
Polypropylene is remarkably versatile in this respect, and
pieces can often be made of it on molds designed for other
144 Polypropylene
plastics, maintaining dimensional tolerances merely by con-

trolled cooling.
Moldability Area
A very informative way of comparing the relative mold-

ability of various plastics is the moldability-area method. The
following data were furnished by Montecatini.
Cycles (sec)
40 50 60 70 30 40 50 60 70 30 40 50 60
High impart polystyrene Polypropylene Low-density polythene
Figure 5.11. Moldability areas of thermoplastics. (Cowrê^y

Montecatini)
Figure 5.11 shows the moldability areas of high-impact

styrene, polypropylene,and low-density polyethylene, using
the same machine and the same mold in each case. The
shaded area represents the range of time-temperature condi-
tions over which satisfactory moldings can be made. The
upper line represents the maximum temperature which can
be used without overheating and decomposing the plastic.
The lower line is the lowest temperature at which the mold
is completely filled. The left-hand point of the area is the

shortest cycle at which a satisfactory molding is possible, and
the area is arbitrarily ended at the right side at a cycle twice
the shortest cycle.
The shape and size of the shaded area give a clear idea of
the relative ease of molding the materials. It can be seen
not only that polypropylene gives shorter cycles than high-
impact polystyrene but that the temperature range over which
reasonably short cycles are possible is much wider for poly-
propylene.
The low-density polyethylene shows up more favorably in
this comparison, but it must be kept in mind that the low-
temperature molding range of this material is of little prac-
tical use because of warpage and other defects that appear
when itmolded cold. When the molding conditions that
is
from a production point of view are considered,

are practical
polypropylene compares quite favorably with polyethylene.
Mold Design
Good mold design is worth while in polypropylene, as with
all other plastics, but it is not at all critical as to type of
mold. Polypropylene molds well in all conventional kinds of
mold —two and three plate, hot runner, runnerless, or valve-
gated.
In multiple-cavity molding it is particularly important to
balance runner lengths to each cavity, and to have equal
cavities per runner. This goes back to the same pressure
sensitivity of the flow properties. If the mold is unbalanced,
the parts affording the freest flow will receive a dispropor-
tionate share of the flow, even more so than is the case with
most other plastics.
Relatively large runners {V4- to %-in. diam) stepped
down each branch are desirable, and the cross section
at
should be as nearly round as practicable. Fine-machined
146 Polypropylene
surfaces on the runners are better than polished ones, as the

surface of the molding may be marred if cooled material slips
off a polished runner surface into the mold.
In small multiple-cavity work 0.040- to 0.060-in. gates
are generally adequate, but large pieces should be given large
gates.Gate land lengths should be kept small, preferably
below 0.040 in.
Jump gates, tab gates, or gates in the center of the bottom
of the piece, which are commonly used to prevent jettingby
impingement of the entering plastic on a mold wall, should
also be used for polypropylene, but this practice does not
differ from that used with other plastics.
Large parts should be multiple-gated, as with other mate-

rials, with careful selection of gate locations to minimize
jetting, sinks, weld marks, etc.
Warpage caused by differential shrinkage in large flat

pieces is a problem with polypropylene, but by no means to
the same extent as with polyethylene, and the commonly
known techniques for minimizing it are usually quite suc-
cessful.
It should be kept in mind that it is most advantageous to
mold polypropylene at the highest pressure possible. This

means that mold construction should be very solid to with-
stand the pressure without distortion.
Polypropylene an excellent injection-molding material.
is
Generally, when a molder tries anew material he will for

some time be rather doubtful about its molding characteris-
tics. Practically every molder who tries a suitable grade of
polypropylene is very pleased with its performance almost

from the first shot. This does not mean that any of the factors
of good molding practice, described in the previous para-
graphs, can be neglected, but it does mean that special prob-
lems that come up with many other materials do not arise
with polypropylene.
Fluidization on Heating
There is no moisture problem such as that which is en-

countered in nylon or acetate. One fact that has often been
considered a problem with polypropylene is its tendency to
increase in melt index when subjected to heat. This must be
POLYSTYRENE
MINUTES IN INJECTION CYLINDER
Figure 5.12. Change in flow with increased holding time in injection

cylinder.
kept in mind when molding polypropylene. It does, for in-

stance, somewhat it is by no
limit the reuse of scrap, but
means the new or special problem that people have implied.
The ability of polyethylene to withstand prolonged heating
without increase of fluidity is seldom required and it is, at
best, a doubtful advantage. Polypropylene behaves in this
respect much like polystyrene or acetate. Figure 5.12 shows
the change in spiral-flow distance with cylinder residence
time at 550°F. It is apparent that the polypropylene samples
148 Polypropylene
are very similar to polystyrene in increasing flow with longer

residence time. Far from being a problem, this tendency to
fluidizeon prolonged heating is a great advantage. When
molding polyethylene, the material against the cylinder walls
and heaters (that material which has had the longest heat
history) is the least fluid; therefore it tends to stay there and
decompose until it forms a black crust which flakes off and
causes black spots in the moldings. When molding polypro-
pylene, that material with the longest heat history is much
more fluid, hence it is rapidly forced out and replaced by
fresh material. This prevents its further decomposition, keeps
heat-transfer surfaces clean and efficient, and makes the
plastic slip more easily through the machine.
Good shutdown practice is still desirable, but the penalty
for shuttingdown a machine hot is half a dozen sloppy pale-
yellow shots when you start up again which is much better —
than a whole day of carbonized moldings.
Resin variables as well as machine variables affect the
molding of polypropylene and the properties of the resulting
pieces. Table 5.3 summarizes some of these variables. These
effects are, of course, modified to some extent by the par-
ticular machine and mold used, but they should give some
guidance.
Machines for Molding Polypropylene

Injection-molding machines are made by numerous com-
panies and in many models and sizes. The choice of a ma-
chine for molding polypropylene is based on the same prin-
ciples as for any other plastic. The size of the machine de-
pends on the size of the shot to be molded. It must be kept
in mind that, because of the low density of polypropylene,
a molding machine will not be able to produce as heavy a
shot as it would of a denser plastic.
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150 Polypropylene
The special advantage gained by fast injection makes it
very desirable to use a machine with a fast injection speed

and capable of producing a high injection pressure. This also
means that a high clamping pressure is desirable.
Sequence of the Molding Operation

The flow of material through the press is as follows: The
resin is placed in a feed hopper at the upper right. From
this it feeds through a volumetric feed-measuring mechanism
into the throat of the cylinder below. A plunger, which travels
from right to left under hydrauHc pressure produced by a
pump in the base of the machine, pushes the resin granules
into the heater. The heater is encircled by electrical band
heaters which provide the heat necessary for melting the
granules. The interior of this heater contains a torpedo or
spreader which distributes the polymer mass into relatively
thin layers for uniform heat penetration.
After being melted in the heater, the plastic is forced
through the nozzle, which is located to the left of the heater,
into the mold.
A powerful, hydraulically operated toggle clamp holds the
mold together while the plastic is injected into it. When the
molding has cooled sufficiently, the mold is opened and
the piece is removed.
The duration of each element of this cycle is controlled by
automatic timers, and the temperature of the heater is con-
trolled by means of a thermoregulator. In many installations,
positive means for removing the piece from the mold can be
provided. In this case the operation can be completely auto-
matic, requiring the services of an operator only to fill the
feed hopper and remove finished pieces. In large plants, even
these operations are taken over by conveyors, and the plant
requires labor only for adjustment and repairs.
THERMOFORMING OF POLYPROPYLENE
This is the oldest of plastic processing methods; the cellu-

loid doll was thermoformed from plastic sheet in the very
infancy of the plastics industry. Thermoforming was super-
seded by injection molding 25 years ago, and has only re-
cently resumed an important position among plastic process-
ing techniques.
Thermoforming is a broad term used to describe any proc-
ess wherein a plastic sheet is heated and then forced into
contact with a mold to produce a shaped article. It is dis-
tinguished from blow molding by having cold sheet as a

starting material, whereas blow molding starts with a tube
which is usually hot.
As might be expected from its age, thermoforming is a
complex of a tremendous number of special techniques for
special purposes. It is not our intention to go into any con-
siderable number of these here. We will concentrate on a few
that offer the greatest potential for polypropylene.
Vacuum Forming
Most important of these is the complex of related tech-
niques calledvacuum forming, where the heated sheet is
forced into conformity with a die by vacuum. These tech-
niques include straight vacuum forming, where the sheet is
drawn into a female mold of the proper size. This is perhaps
the simplest method, and is satisfactory where the depth of
draw does not exceed one half the opening. When deeper
draws are desired, it is where
better to use drape forming,
the sheet drawn over a male form of the proper shape,
is
final shaping being assured by vacuum. A hybrid of these is

called drape-assist or plug-assist vacuum forming, in which
the sheet is first stretched into approximate shape by a male
152 Polypropylene
form and then drawn from the male form into contact with
a female dieby vacuum.
This group of techniques is extremely versatile and can
make a wide variety of thin-walled shapes. Rapid improve-
ments in equipment for vacuum forming have shortened the
cycles and allowed automatic operation to the point where
this method is now often the cheapest way of making a given
piece.
The current resurgence of vacuum forming is based mainly
on impact styrene sheet, although acrylics, cellulosics,
and vinyls are also used. Polyolefins have heretofore had little
application in this field. The principal virtue of this process
is its ability to make thin-walled articles. Since this puts a
premium on stiffness of the material, low-density polyethylene
fails on the first count; articles drawn from it simply are not
stiff enough. It was expected that high-density polyethylene
would eliminate this objection because it is so much stiffer.

It was found, however, that this material required excessive
heating cycles. The reason for this can easily be seen in the
heat-content curve of Figure 5.6. Stated simply, it takes too
much heat to raise linear polyethylene to softening tem-
perature.
Polypropylene, as can be seen from Figure 5.6, is a great
improvement in this respect. The practical value of this heat-
content difference can be seen in Table 5.4.
Table 5.4.
Heating time (sec /mil)

Heater temp Polyethylene Polyethylene
(°F) (60 mil) Polypropylene (125 mil) Polypropylene
1200-1125 0.30 0.25 0.32 0.27

1100-1025 0.40 0.33 0.40 0.32
Polypropylene takes 1 5 to 20 per cent less time to heat to

forming temperature than does linear polyethylene. A similar
time saving will also be made in the cooling cycle. This im-
provement does not make polypropylene competitive with
impact styrene in this respect, but it does narrow the gap.
Figure 5.13. Modern thermoforming machine. (Courtesy

Auto-Vac Co.)
Pressure Forming
Another development in the thermoforming field, which

is by no means new but has only recently been incorporated
into high-speed automatic equipment, is pressure forming,
where compressed air is used to force the plastic sheet against
the die. Vacuum forming is, by its nature, limited by atmos-
154 Polypropylene
pheric pressure, and no vacuum can exert more than 1 atm of

pressure on the plastic. In pressure forming, this limitation
is removed, and any desired pressure can be obtained. Cur-
rent practice indicates that pressures above 125 psi have no
particular advantage, but up to this pressure faster cycles, and
in some cases, better parts can be obtained.
The use of pressure substantially eliminates one very
critical problem usually found in vacuum forming; this is the
sagging of the heated sheet. In order to soften a sheet for

forming by vacuum alone, it is sometimes necessary to heat
it to the point where it no longer can support its own weight.
This sag may cause folds or wrinkles or merely thickness
variations. The use makes it possible to form the
of pressure
sheet when it is and easier to control. This, of
slightly stiffer
course, also shortens both heating and cooling cycles.
Heavy sheeting is necessarily fed into a forming machine
one sheet at a time, but modern machines are now equipped
to roll-feed the lighter gauges.
Polypropylene sheets can be economically thermoformed
in modern high-speed forming equipment. Figure 5.13 shows
a modern automatically controlled forming machine with dual
heaters.
Skin Packaging
Another thermoforming technique having even greater po-

tentialities for polypropylene application is skin packaging.
In this process, articles to be packaged are arranged on a
sheet of cardboard, which may be printed for brand identifica-
tion and other information. This assembly is then placed on
a perforated plate which can be evacuated from underneath.
A softened plastic sheet is placed over the assembly, and
vacuum drawn. This forces the hot plastic against the
is
articles tobe packaged and against the cardboard backing.

In the case of polypropylene, the hot plastic will adhere to
cardboard and similar materials quite adequately, without

special treatment of the board or other special techniques.
Since this method usually requires film thinner than 5 mils,
heating time is not very long and over-all cycles can be rapid
enough for economical production.
BLOW MOLDING
Development of Blovs^ Molding
The blow-molded squeeze bottle is the application many
people consider most characteristic of polyethylene, in spite
of the fact that the volume used never approached the amount
employed in other ways.
Linear polyethylene quickly showed itself to be well
adapted to blow molding, even though it lacks the resilience
or snapback characteristic needed for a squeeze bottle. Poly-
propylene is also very easily blown, and, because of better
resilience and stress-crack resistance, it will probably replace
linear polyethylene in many applications.
For a long time the development of a blow-molding indus-
try in this countrywas hampered by a patent condition which
gave a very few relatively large firms an almost monopolistic
control of the industry. These firms were interested only in
making containers and so prevented recognition of the fact
that blow molding is an excellent and economical method
of producing hollow articles of all kinds.
Influence of European Equipment

Blow-molding equipment imported from Europe has estab-
lished a thrivingblow-molding industry in this country, and
recent cross-licensing agreements have freed the industry
from the patent difficulties that have heretofore hampered it.
It appears, therefore, that blow molding will account for
much more material in the coming years than previously.

156 Polypropylene
Polypropylene in Blow Molding
Polypropylene is very well adapted to blow molding. It

has an excellent chance of benefiting from the success of
linear polyethylene in this field. The thermal properties of
polypropylene permit considerably shorter cycles than linear
polyethylene allows, and the physical properties are also gen-
erally better.
How Blow Molding Works

AU blow-molding machines operate on the same principle.
A heavy-waUed tube is produced, and, while it is still hot, it
is closed at one end and then inflated with compressed air to
conform to the inside of a hollow mold. The most common

way to produce the original tube, called a parison, a term
derived from glass-blowing practice, is to extrude it, although
some firms utilize injection molding.
Main DiflFerences Between Blow-Molding Machines

The basic problem in using an extruded parison is that
extrusion is a continuous process, whereas blow molding is
an intermittent one. The multitude of variations in blow-

molding machines results from the different approaches used
to correlate the continuous extrusion with the intermittent
blowing.
The most used techniques are as foUows: Some companies
stop and start the extruder for each parison, but most
use a continuously operating extruder. The first, and still
very popular, means was a direct adaptation of conven-

tional glass-bottle blowing.A series of split molds is carried
around on a circular table which indexes them successively
under the extruder nozzle, where the parison is being formed.
When the parison reaches the right length, the mold closes,
cutting off the parison but holding it in position inside the
mold. It then indexes to the next position where the parison
isblown into conformity with the mold, and at the same time
an empty open mold is placed under the extruder nozzle. At
successive locations the part is cooled and ejected from the
mold.
A minor modification of this method uses only two molds
which are reciprocated between the loading position and a
cooling and ejection position. While a parison is being ex-
truded into one mold, the other one is being cooled, and the
piece is ejected just in time for the mold to receive the next
parison.
In another common method the extruder feeds a mani-
fold leading to a number of dies, usually four. A valving
arrangement directs the flow to each of the dies in turn,
forming a parison at one station, and, when it is done, start-
ing another at the next station. Each mold goes through its
cycle of closing, inflation, cooling, opening, and ejecting in

the same place underneath the die which forms the parison.
In the older machines the parison was pinched shut at the
lower end by the closing of the mold and inflated either
through an air hole in the extrusion die or by a needle thrust
through an excess amount of material above the bottle proper,
which had been pinched enough to collapse the hole of the
parison. Inflation through the die, of course, is only possible
in those machines which stop plastic flow through the die,
either by stopping the extruder or by valving the flow.

These methods closely resemble the glass-blowing opera-
tion, making the bottle right side up, and result in a bottle
neck that has to go through some sort of finishing operation

before use.
More recent machines blow the bottle upside down. The
open end of the parison slips over a pin in the base of the
mold, which is the same size as the desired inside of the
bottle neck. This pin is hollow and is used to inflate the bottle.
158 Polypropylene
When the mold closes, the material which has slipped over
the pin is caught between the pin and the closing mold, which
forms it into the exact finished size and shape of the bottle
neck. At the same time the parison is cut off by the part of
the mold forming the bottom of the bottle, and this end is
pinched shut by the mold. In this way a bottle is made that is
completely finished at the end of the cycle and requires no
further operations.
The need for pinching the parison in the mold
conflicting
and having the cut end open to slip over the pin in the bottom
of the next mold requires parisons to be cut twice, leaving a
little piece of scrap which is usually left joined to the bottle
by a thin web of plastic. The machine operator has to pull

this piece of scrap free of the bottle, but this is the only
finishing operation required.
Special Considerations in BIov^ Molding Polypropylene
Any machines blow polyethylene bottles will

that will
perform on polypropylene bottles. The polypro-
just as well
pylene will require somewhat higher temperatures. It will be
necessary to adjust cycles to obtain the right parison length,
and, of course, a given extrusion die will not give quite the
same weight and thickness to the parison.
The superior strength of polypropylene will make it pos-
sible to use thinner walls and less material per piece. Even
though polypropylene is more expensive per pound, it should
make cheaper bottles than polyethylene. This means not only
that polypropylene may be substituted for polyethylene but
that it should expand markets into fields now held by metal
cans or glass bottles.
Blow Molding Articles Other Than Containers

Recent expansion in the blow-molding field has resulted
from the recognition that blow molding is by no means limited
to bottlemaking but is a versatile method for making hollow

articles of many kinds. Many articles now made by injection
molding two halves and fastening them together to make a
hollow part can be blow-molded more conveniently. Toys, in
particular, are very suitable for blow molding; for instance,
doll parts, or the bodies of toy automobiles, blocks, balls,
and a variety of other articles.
A blow-molded article must have some sort of opening
to admit the blowing air, but it need be only large enough
to admit a hollow needle, and can easily be closed up later.
MISCELLANEOUS PROCESSING METHODS
Hot Gas Welding

The best way to make tanks and relatively large structures
out of polypropylene, particularly if only one or a few of
one kind are to be made, is hot gas welding. This technique

has been widely used on rigid vinyl, polyethylene, and other
rigid thermoplastics.
Relatively heavy sheeting Vs in. and up is cut and welded
together by techniques closely resembling those used in

metal-plate fabrication.
Pieces are bent by placing an oven just warm
them in
enough to make enough to make
the sheet easily bent, but not
it lose its shape entirely. With polypropylene this is about
310°F, which is considerably hotter than for any other

thermoplastic. This creates a problem where ovens are heated
with low-pressure steam, because they cannot maintain such
a high temperature. Gas or high-pressure steam, however,
easily reaches this temperature.
After the pieces are cut and bent to the proper size and
shape, they are clamped in jigs to hold the edges together
firmly, and then welded.
The welding "torch" consists of a device which heats a
1 60 Polypropylene
stream of inert gas to about 700 °F. It may be either elec-

trically or gas heated; in the latter case the flame does not
contact the plastic. A welding rod made of polypropylene
about Vs in. in diameter is both the
laid into the joint while
rod and the edges of the joint are being heated by the torch.
A butt weld can also be made by heating the two edges of
the joint by pressing them against a heated metal bar until
they are soft and sticky. The bar is then removed, and the
edges are pressed together. Either method makes joints that
are quite adequate for sound structural fabrication. Table 5.5
Table 5.5. Weld Values for Butt-Welded "Agile-Prolene"

(per cent of parent material strength)
Material
thickness (in.) Type weld Weld value (%)
1/8 Double-V 5 beads 95-100
V4 Double-V 5 beads 95-100
1/8 Double-V 2 beads 85-96
l^ Double-V 2 beads 70-85
l^ Heated-tool butt 80-100
shows results reported by the American Agile Co. on their

brand of polypropylene sheet.
Machining Polypropylene
Polypropylene machined by regular metalworking
is easily
equipment. Tools must be very sharp, and overheating must
be avoided, but, in general, the problems are less severe than
with other thermoplastics. This is a very convenient way of
fabricating models, prototypes, or parts where only a small
number will be required.
Pov^der Techniques
There are several ways in which articles can be made out

of powdered polypropylene: flame spraying, fluidized powder
dipping, and the "Engel" process. The first two are methods
of coating metals with a corrosion-resistant layer of poly-

propylene.
Flame Spraying. In this technique powdered polypro-
pylene is sprayed through a gas flame onto the surface to be
coated. Careful regulation of flame temperature is needed to
melt the powder to the point where it will flow into a solid
coating without degrading it. Generally, one or more base
coats are necessary to bond the polypropylene to the metal.
Atactic polypropylene, or a mixture of atactic polypropylene
with a little of the isotactic material, may be used as the base
coat. It is also advantageous to have the base metal heated,
and it must be free of oil, dirt, or other materials that interfere
with bonding.
Fluidized Powder Dip. In this process powdered poly-
propylene is placed in a box, and an inert gas is blown up
through the powder until mobile or fluidized state.
it is in a
Hot metal parts are then dipped into the fluidized powder.
The metal must be hot enough to melt the polypropylene
particles that come into contact with it. The metal tempera-
ture and the length of time it is left in the powder determine
the thickness of the coating. After the part has been removed
from the bath, it may be reheated in an oven to smooth the
outer surface of the coating.
"Engel" Process. This is a very versatile method for mak-
ing large polypropylene articles, particularly those whose
shape is not well adapted for welding, for instance, pleasure-
boat hulls, bathtubs, etc.
The powder used in this process does not have to be as fine

as in the two previous methods, a fine pourable granule being
suitable. A light metal mold is filled with powdered poly-
propylene, covered with an insulating cover, and placed in a
heated oven. It is heated long enough to cause the desired
thickness of polypropylene to melt and adhere to the inside
of the mold.
162 Polypropylene
The mold is then removed from the oven, the excess poly-
propylene powder is dumped
out, and the mold is returned
to the oven, with the top open to smooth out the inside
surface. An oven temperature around 700°F is required for
this process. After the inside has flowed smooth, the mold is
removed from the oven and cooled, and the piece is stripped
out of the mold.
It appears likely that the highly isotactic polypropylene
which is most other purposes will not be very
desirable for
useful in these powder techniques. The relatively severe tem-
perature treatment causes a breakdown of the polypropylene
which increases its crystallinity to the point where it becomes
quite brittle. Material with a lower isotactic index is more
successful, and improvements in stabilization will probably
be made before long.
6. PACKAGING APPLICATIONS
POLYPROPYLENE-FILM APPLICATIONS
Although polypropylene-film applications are still in their
infancy, people who are familiar with the material are con-
vinced that this market is due for a tremendous growth in
the very near future.
Film clarity (which has always been a critical problem
with polyethylene film, in many cases determining equip-
ment construction, operating conditions, and choice of resin)
is no problem at all with polypropylene. Before polypropylene
had been commercially available a year, film resins were on

the market that could not only match cellophane in clarity
but even exceed it.
Polypropylene embraces a wide variety of materials which

differ much more than, say, polyethylene, and this means that
very different films for a wide variety of applications can be
made. The kind that has shown the greatest promise so
far is the clear, stiff film made from the most nearly atactic
grades of polypropylene. When made by the chill-roll process,
these films are as clear or clearer than cellophane and show
greatly superior physical properties.
Although polyethylene film has often been discussed as a
competitor to cellophane, it has never really been that, and
the great volume of polyethylene film has been used in

applications for which cellophane could never be considered.
163
1 64 Polypropylene
A breakdown of the packaging market for polyethylene film

is shown in Table 6.1.
It can be seen that fresh produce is the largest category,
and not a field where cellophane is a possible
this certainly is
factor. Many of the other large categories are also essentially
noncompetitive with cellophane.
Table 6.1. Consumption of Polyethylene Film in Packaging

(Millions of Pounds)
End use
Tobacco 0.5
Candy 4.5
Baked goods 3.0
Meat and poultry 5.5
Snacks 1.5
Frozen foods 6.5
Dairy products 5.5
Fresh produce 68.0
Other foods 5.0
Textiles 12.0
Drugs 1.0
Garment and shirt bags 30.0
All others 37.0
180.0
The rapid growth of polyethylene has had a tendency to

make people forget that, of the 600 million pounds of trans-
parent film used in 1958, 400 million were cellophane. It is
this two thirds of the market that is the natural target for
polypropylene film. Unless polypropylene takes a substantial
part of this, it cannot obtain any real market. What chance
does it have of doing so?
Cellophane users are characterized by a surprising willing-
ness to pay extra money for a better package. A large propor-
tion of the cellophane market is in special premium grades,
which cost more than ordinary cellophane but have better
Packaging Applications 165
properties. It is therefore a great oversimplification to say

that because polypropylene film can be made cheaper than
cellophane it will replace it.
Cellophane holds its present position because of the ability

of the cellophane producers to adapt and modify their mate-
rial for each application. The number of kinds and grades is
truly bewildering, and each one represents a cooperative

effort between the producer and some consuming industry.
Machinery has been designed in a similar manner, so that
the entire equipment and packaging concept of many indus-
tries is tied in directly to this one material. The idea that a
saving of a few cents a pound will penetrate this structure is

naive.
On the other hand, polypropylene film has advantages
other than price. Its tear resistance is far superior to that of
cellophane, and —
what may prove its greatest advantage in
articles where turnover is not rapid — the aging characteristics
are much better.
Polypropylene film is a better barrier material than many
grades of cellophane; moisture resistance, for instance is
much greater.
The advantage cellophane holds in having had high-speed
packaging machinery specifically designed for it is rapidly
being lost by the appearance of new machinery which can
handle polypropylene film just as rapidly.
As already stated, a few cents a pound premium will not
displace cellophane from its firmly entrenched position in the
packaging field, be assumed that the packag-
but neither can it
pay 30 to 100 per cent more

ing industry will long prefer to
for a packaging material that offers no advantages either in
package quality or in operational economy. This is not in-
tended to mean that these markets will either inevitably or
rapidly fall to the first person astute enough to make poly-
propylene film. Penetration will be slow and irregular, and
1 66 Polypropylene
undoubtedly many polypropylene-film manufacturers will be

sadder and wiser before any great volume develops.
The facts of physical properties and economies seem to
point inevitably, however, to a polypropylene-film market as
large or larger than the present cellophane market, and, un-
like the polyethylene-film market, it will be largely carved
out of the present cellophane market. Certain fringe areas
of the polyethylene-film market, where clarity and stiffness
are primary considerations, will also fall to polypropylene.
In addition to the above markets, about 50 million pounds
a year of specialty films such as "Pliofilm," vinyl, saran, etc.,
enter the packaging These hold their position because of

field.
certain special properties, most of which would probably not

be satisfied by the cellophane-replacement type of polypro-
pylene film under discussion. The versatility of polypropylene
is so great, however, that, as production experience grows, it
seems highly probable that these markets, which are generally

characterized by very high material costs, will also be pene-
trated in large part by it. Polypropylene film will also open
up many new markets on the basis of its own special
properties.
Let us now consider in a little more detail exactly where
polypropylene film will penetrate most readily. In order to
do this, a brief review of the advantages which it holds over
cellophane is in order.
Dried Products
Perhaps the greatest weakness of cellophane is its moisture
sensitivity.Although moisture proofing improves its moisture
resistance, it is still true that cellophane must have a moisture
content within narrow limits for optimum properties. A wide
variety of dried products tend to draw the moisture out of
cellophane, causing it to embrittle and break in use. Such
:
products are more suitably packaged in polypropylene, for

example
Dried milk Cake, biscuit, roll mix

Flour products Rice
Dessert powders Noodles
Powdered starch Spaghetti
Cellophane is also limited, by its tendency toward break-

age, to packages weighing less than 3 lb. Materials ordinarily
packaged in larger units are better off in polypropylene.
Specific applications for polypropylene film will be dis-
cussed as regards packaging ten major categories of materials,

in the following order:
Baked goods Dairy products

Fresh produce Miscellaneous food items
Frozen foods Textile products
Meat and poultry Tobacco products
Confectionery Paper products
In considering these applications we shall assume that

significantimprovements will be made in the handling of
polypropylene film on medium- and high-speed automatic
wrapping machinery. The progress already made in the use
of polyethylene film in such equipment should lead to its
rapid adaptation to polypropylene. This is particularly true
of direct-wrap and carton-overwrap machinery where the
superior stiffness of polypropylene film, as compared to poly-
ethylene film, shouldmake the conversion of cellophane-
handling equipment much less of a problem.
It also seems that the problem involved in sealing poly-
propylene film at high speeds, especially through several
layers as is necessary for sealing an overwrap, will be solved
for many packaging applications.
The problem of opening a polypropylene overwrap easily
168 Polypropylene
and conveniently is also well on its way to solution. It is quite

easy to make polypropylene film in such a way as to offer
the "built-in tear tape" feature that has been highly publicized
as an advantage of linear polyethylene film. In polypropylene
film,however, it is a real practical advantage, since it can be
controlled to any degree, or even be eliminated, rather than
being an inherent feature of the film, as it is in linear poly-
ethylene. In general, much more practical solutions to the
problem are found in embedded tear tapes or strings, per-
forations, peelable seals, or extruded beads.
It is also assumed that present problems involving Food
and Drug Administration approval for the use of Polypro-

pylene film in contact with food will be solved.
Many of the markets we shall discuss have already been
penetrated to a considerable degree by cast medium- or high-
density polyethylene film and may be shared for a consider-
able time with these materials. From the long-range point of
view, however, many of them will ultimately fall largely to
polypropylene films because of their inherently superior
properties.
Baked Goods
The baking industry is the largest single market for trans-
parent flexible packaging materials. In the past year about
150 million pounds of flexible packaging materials were used
by this industry. Despite a phenomenal growth in the use of
polyethylene film in this field, and a minor amount of poly-
propylene film, 85 per cent of this was cellophane.
Bread Wrap. Approximately half this amount was used to
wrap bread. Out of 8 or 9 miflion loaves of white bread, only
IVi to 2 million loaves were wrapped in cellophane; the
remainder are still waxed-paper wrapped.
Since it has been found that %-mil polypropylene will
handle in bread-wrapping equipment just about as weU as
1-mil polyethylene or cellophane, polypropylene should be

price-competitive not merely with the premium wraps but
with waxed paper as well. Under these circumstances it
should be just a matter of time before the approximately

7 5 -million-pound cellophane market, plus three or four times
this amount as a replacement for waxed paper, should be
available for polypropylene film.
It should be understood that price is by no means the
primary consideration which will force this revolution. The
main consideration is the superiority of the polyolefin
wrapper, and price will merely determine which polyolefin
is used. The advantages of the polyolefin wrappers are:
(1) Longer preservation of freshness. This means not
only that the consumer receives a superior product but that
the product has a longer shelflife before it becomes unsalable,
and the producer has much more flexibility in scheduUng

production, as he is no longer held to such a brief inventory
period. By extending the production day the output of a
bakery can be substantially increased without added invest-
ment; equipment which now stands idle a substantial part of
each day can be operated practically continuously, if desired.
(2) A package which has an inherently "fresh" feel.
Although polypropylene film is stiffer than polyethylene film,
the thinner film that can be used still results in a soft-feeling
package, and the consumer associates this with freshness.
(3) A package which resists accidental tearing.
(4) A package that can be reclosed by twisting or folding
the film, thus preserving the freshness of opened loaves.
(5) Equal to any other wrapping in preserving flavor and
retarding mold.
(6) Can be stored under refrigeration without becoming
brittle. In regard to this, much has been said about the low-
temperature brittleness of polypropylene. It is true that thick
sections of molded polypropylene become brittle at low tem-
1 70 Polypropylene
peratures, but film made of selected resins by the chill-roll

technique retains strength and flexibility even at deep-freeze
temperatures.
Wrapping machines, and attachments for modifying older
machines, are now available to use polypropylene film at
v^rapping speeds equal to those possible with any other
material.
At present it appears that the Food and Drug Administra-
tion is polypropylene film used in wrapping
satisfied that
bread does not transfer anything whatsoever to the bread,
and hence does not come under the food-additive provisions
of the law. Further study will be required to determine if the
same fact holds for other bakery products which contain
more sugar, fats, oils, etc., which might extract material from
the wrapper. If any degree of extraction is found, it will be
necessary to identify the material extracted and prove con-
clusively that it has no potentially harmful effects. This is a
difficult task which could delay the use of polypropylene film
in such applications for a long time.
Other Baked Goods. Although bread wrapping is the larg-
est single use of film forwrapping baked goods, more than
half of the cellophane now used in this industry goes for the
packaging of cake, rolls, crackers, biscuits, and miscellaneous
items. The importance of impulse buying in these items has
made the transparent package especially valuable. This
market is largely served by the polymer-coated grades of
cellophane which are 30 to 90 per cent more expensive than
ordinary cellophane. This means that the price advantage of
polypropylene film is even more important.
To date, there no penetration of polyolefin
is practically
films in due
this field. This
in large part to the wide variety
is
of equipment used for the purpose, and the lack of any single
large target, such as bread wrap. It has not, as yet, been
found worth while to produce the machines, or adaptations
of machines, to use polypropylene film in these packages.

The problems are no more complex than those involved in
bread wrap; as a matter of fact, because of lower packaging
speeds, and the common use of cardboard boxes or trays
under the wrapper, the problems are really much simpler,
and their solution is merely a matter of time.
The advantages are just as great, and, because of the gen-
erally slower and less accurately predictable -turnover of such
products, the advantages of longer shelf life are even more
important. Polyethylene has not been able to penetrate this
field because the oils, fats, and sugars that are present create
a greaseproofness problem. Polypropylene film has inherently
superior greaseproofness which should obviate this difficulty.
The fact that polyethylene film lacks the gloss and clarity of
cellophane has also hampered its acceptance. Polypropylene
film has no such problem.
The cost advantage of polypropylene film is particularly
important in the baking industry because it operates on a
very low profit margin, and because the cost of packaging is a
much greater part of the sales price than most is true in
industries. A recent survey by Modern Packaging magazine
showed that, among the bakers surveyed, packaging costs
ranged from IV2 to 32 per cent of factory selling price. It
also showed that companies packaging the same kind of
goods had very nearly the same cost ratios. These conditions
should make this industry move very quickly into a packag-
ing material showing a cost advantage.
In summary, the baked-goods industry should offer a
market which, even at the present size of the industry, should
take up to about 400 million pounds of transparent films.
There seems to be little reason why the largest part of this
should not eventually be polypropylene film.
It will require a great deal of time, effort, and money,
however, to develop this market. Cooperative programs be-
172 Polypropylene
tween film producers and consumers will be needed to match

the efforts that will be made by waxed-paper and cellophane
producers to retain this market. The list below gives a partial
enumeration of baked goods that could advantageously be

packaged in polypropylene film.
Bread Cracker meal and crumbs Poultry stuffing
Bread crumbs Fruit cake Pretzels
Iced cakes Icecream cones Rolls and buns
Cookies Marshmallow-topped biscuits Muffins
Saltines, soda crackers Sugar wafers Doughnuts
Zweiback Melba toast
Fresh Produce
Fresh produce is currently the largest market for poly-
ethylene film. It consumes about 75 miUion pounds a year,

and this total is growing rapidly. In certain applications such
as the potato or carrot bag, polyethylene is firmly entrenched.
Industry practice is well established for the use of a bag for
these commodities, and this is a convenient process. The
comparative difficulty of blowing polypropylene film puts it
at a disadvantage in bag production. This disadvantage, how-

ever, may be a temporary one, as high-speed machinery is
being developed which will make

a bag out of flat film
almost as economically as one can now be made out of
tubing. Under these circumstances it seems probable that
the superior clarity and high strength of polypropylene film
will make it possible to replace a considerable part of the
polyethylene now used.
There are also many fresh-produce items that do not lend
themselves very conveniently to bagging and which are not
now very generally packaged. A partial list follows.
Asparagus Chicory Cabbage Escarole

Broccoli Cherries Cauliflower Sweet corn
Green beans Grapes Kale
Green peas Celery Mustard greens
Several of these items require packaging rather different

from the usual bag. Irregular shape and size, for instance, is
much more easily compensated for by an overwrap package.
For overwrap, the superior stiffness of polypropylene film will
have a great advantage. Cellophane is hardly a contender in
this field because of its moisture sensitivity.
Table 6.2.
Average Estimated
annual Estimated Estimated potential for
supply per cent per cent polypropylene
thousands pkg pkg thousands
Crop of lbs 1960 1965 of pounds
Apples 3,379 35 35 4.5

Beans, snap 542 5 50 2.6
Beets 137 20 50 0.4
Carrots 1,250 90 50 3.9
Celery 1,435 20 40 5.0

Corn 1,339 10 25 2.4
Grapefruit 1,732 20 20 1.3
Grapes 846 5 20 1.3
Lemons 589 20 20 0.4

Lettuce 3,280 5 50 10.0
Limes 26 15 20 0.2
Onions, dry 1,785 35 35 2.5
Oranges 4,796 20 20 3.5
parsnips 65 35 35 0.1
Peas, green 66 5 25 0.8
Potatoes, white 17,158 55 25 7.8
Potatoes, sweet 1,306 5 30 1.2
Radishes 236 75 30 0.8

Tangerines 337 5 20 0.5
Turnips 393 50 30 0.5
Total 49.5
Retail level packaging and items not listed 5.0
Liners 5.0
Estimated total potential for polypropylene 59^5

174 Polypropylene
Another trend in fresh-produce packaging that should

favor polypropylene film is the tendency to do the packaging
at larger distribution centers rather than at the retail level.

The bag is a natural package for retail use, since labor
costs are less important than the ability to perform the
operation with a minimum of special equipment. As the
operation increases in scale, the labor assumes greater sig-
and high-speed equipment requiring a minimum of

nificance,
labor becomes more attractive. A bag is not, in general, a
good choice for high-speed automatic packaging; overwrap
is usually more practicable. This gives polypropylene film a
distinct advantage because it has superior handling qualities
in such equipment.
In order to make a reasonable estimate of the market
available for polypropylene film, detailed estimates of the
1958 polyethylene film consumption for produce packaging
made by D. R. Stokes, United States Department of Agricul-
ture, were studied. Considering the over-all tendency to in-
crease the percentage of produce packaged, and the com-
petitive positions of the various packaging materials, the
estimates in Table 6.2 seem to be reasonable. In view of these
figures, and the fact that the volume of produce shipped is
constantly increasing, it does not seem overoptimistic to
predict a fresh-produce market for polypropylene film in
excess of 50 million pounds within the next 5 years.
Frozen Foods
Before discussing frozen-food markets for polypropylene
film, it is worth repeating that the often-discussed low-
temperature brittleness of polypropylene does not occur in
thin film, which retains a great deal of its flexibility and
toughness down to deep-freeze temperatures, if the proper
resin is used and proper processing methods are employed.
The frozen-food market today includes about 1 ,000 differ-
: :
ent items with a yearly volume of 6 or 7 billion packages.
If we exclude frozen juices, the packaging of which in poly-

propylene film would require very considerable technological
changes which are not in the immediate offing, the frozen-
food retail-packaging market will shape up approximately as
follows
Billions of
Produce packages annually
Vegetables and fruits 1.5

Precooked foods and specialties 1.5
Seafood 0.5
Meat, meat products, poultry 2.0
Frozen foods at present are generally packaged in a paper-

board carton covered with a printed, waxed-paper wrap. This
is an attractive package, well adapted to stimulating impulse
buying, but it is relatively expensive, wastes space, and does
not offer very good protection to the contents.
The protest against the deficiencies of this package has
already started a movement toward a polyethylene-bag pack,
especially for the so-called "free running" vegetables such as
peas, corn, carrots, lima beans, and mixed vegetables.
Unlike the polyethylene bag for fresh produce, many of
these bags are made in continuous sealing and filling ma-
chines which start with flat film. Machines of this type are
capable of very rapid, completely automatic operation suit-
able for the large-scale freezing plant. With equipment of
this sort the superior clarity and gloss of polypropylene film
should make it a strong contender.
Although this method of packing frozen foods has not yet
achieved any very great volume, it is increasing rapidly. It has
the following strong advantages over present packs
(1) It costs considerably less.
(2) Its lighter weight saves shipping costs.

176 Polypropylene
( 3) The rolls of film take up much less space in the plant

than do the cartons and overwrap.
(4) The consumer can use part packages and reseal for
further storage.
In addition to the frozen foods now common, others are
being investigated that should be very suitable for packaging
in a polypropylene bag or pouch. Baby foods are one such
item. The possibility of using just the amount desired, reseal-
ing, and storing in the freezing compartment with full reten-
tion of flavor and quality is the big feature here. The savings
over glass jars or cans will be considerable.
The boilable pouch which can serve both as package and
as container for preparation of the food has had many advo-
cates for some time. Its use has been retarded because of its
questionable strength retention at boiling-water temperature.

This has, in general, resulted in the use of very expensive
films such as polyester resins. Polypropylene film has ample
strength at the temperature of boiling water for this applica-
tion, and it is very likely that the availability of polypropylene
film will spark a big expansion in this line.
Two other frozen-food items are of interest. One is the
packaging of frozen baked goods, such as rolls. This is already
being done, to some extent, with polyethylene film, but poly-
propylene film would be better.
There is development work going on in the freezing of
candies to retain freshness. Polypropylene film has particular
advantages here because of its superior resistance to greases.
A completely moistureproof package is essential to prevent
condensation of moisture on the candy during thawing.
The current polyethylene consumption for frozen foods is
only 7 or 8 million pounds a year, and polypropylene can

hardly be expected to displace polyethylene entirely. Develop-
ments now in progress, however, should raise the total to 25
or 30 million within 4 years, half of which could go to

polypropylene.
Meat and Poultry

Commercial meat production is at present about 26 billion
pounds yearly, about 16 billion of which is sold as fresh red
meat.
At the present time about half of all fresh meats sold are
prepackaged, mostly from self-selection meat cases, and the
trend is to increase prepackaging. Cellophane dominates the
prepackaged meat by virtue of special coated grades
field
which give the meat packer the proper relationship between

moisture control and oxygen transmission. Polyethylene film
is used to some extent, very thin films having desirable pro-
tective characteristics but lacking the needed strength. "Plio-
film" is also used to a considerable extent in fresh-meat pack-
aging, in spite of its high cost and low oxygen transmission.
It is difficult to evaluate the position of polypropylene film
in this industry because any large penetration of the market
depends on the development of films with the desired trans-
mission properties at practicable thicknesses, and also of
better wrapping and sealing techniques. The great versatility
of polypropylene leads to the hope that such developments
might be forthcoming, but in its present form it does not
appear that polypropylene film would be a strong contender.
The potential market is probably above 50 million pounds a
year.
Poultry packaging consumes a good deal of transparent
film, especially some relatively expensive products such as
"Pliofilm," saran, and "Cry-o-vac." These films have a par-
ticularly good ability to conform to the contour of the poultry,
making a very neat and attractive package. Polyethylene film
is used only to a small extent in spite of its lower price, be-
178 Polypropylene
cause it does not have this form-fitting property to the same

extent. Polypropylene film can be made with considerably
higher elongation than polyethylene film, and it seems likely
that a suitable film for this purpose could be developed
without much trouble.
Present successful applications of polyethylene film, such
as with sausage, bacon, ham, and processed meats, are fully
open to market penetration by polypropylene film because of
its superior appearance and strength.
Confectionery
Almost 3 pounds of confectionery products were

billion
produced in the last year. About 5 miUion
United States
pounds of polyethylene film were used for packaging it. Poly-
ethylene film has almost ideal protective characteristics for
confectionery packaging, but its appearance generally leaves
something to be desired. Confectionery depends to a great
extent on impulse buying, and even a little haze in the film
can be an obstacle.
The superior gloss and clarity of polypropylene film
should be an important factor in this market, and should
make it possible not only to take over present polyethylene-
film uses but to double or triple this amount in a short time.
Paper and cellophane have a large market in the direct
wrapping of hard candies, caramels, and chewing gum. This
apphcation depends on the use of extremely high-speed ma-
chinery, some of which can wrap 1,200 pieces a minute. Such
equipment is generally limited to the type of film for which it
is designed, so no rapid replacement is possible. Work to
date, however, shows that polypropylene film has excellent

characteristics for handling on high-speed machinery, so it
should be possible to develop suitable equipment. This will

require close cooperation between film producers and machine
manufacturers. A market now using 35 million pounds of

cellophane a year is involved. A list of products wrapped in
this manner is shown below.

Caramels Lozenges Hygroscopic types
Chewing gum Marshmallows (butter mints, etc.)
Chocolates Mints Candy-coated nuts
Hard candy Jellies Peanut brittle
Lollipops Gum drops Candy-coated popcorn
Candy sticks and canes
Dairy Products
In this industry, plastic film is used mainly for the com-

mercial shipment of dry powdered milk and liquid cream.
Polyethylene is generally used. Polypropylene film should be
a strong competitor because of its superior strength. This
should permit a reduction of film thickness, which is generally
in the 3- to 4-mil range with polyethylene, to 2 mils, result-
ing in a cheaper package with superior handling and sealing
characteristics and equivalent product protection.
The only other major use for plastic film in this industry
is in window tops for containers of cottage cheese, ice cream,
prepared salads, and other refrigerated specialty foods. This
use is now by polyvinylidine chloride film, used
largely filled
because of its high gloss, clarity, and toughness. Polypro-
pylene should provide equally good properties at considerably
lower cost.
The use in this industry should be up to 10
total film
millionpounds within 5 years, and polypropylene film may
be taking half by that time, with greater percentages later.
Miscellaneous Food Items

A wide variety of food items not falling into the previous
classes should be excellent candidates for polypropylene film
180 Polypropylene
packaging. Without going into detail on each one, the follow-

ing partial list is presented for consideration.
Bouillon cubes (prewrapped) Dried fruits (apples, apricots,

Cereals [candy or honey coated, dates, figs, pears, peaches,
flakes, puffed rice and wheat, prunes, and raisins)
and uncooked (oatmeal, etc.)] Dried vegetables (beans, peas.
Chocolate (cooking) and rice)
Cocoa Flour (wheat, corn, etc.)
Coffee (beans) Noodles and macaroni
Dehydrated foods (eggs, fruits, Nuts (unshelled)
soup mixes, and vegetables) Popcorn (popped, unpopped)
Dessert and drink powders (fruit Sandwiches
drinks, gelatin, ice-cream Sugar
mixes, malted milk, and pud- Tea
dings) Yeast (wet and dry)
Dog food (dry biscuits and
pellets)
In all must be remembered that the use

food packaging it
of polypropylene film will be contingent upon proving either

that the food extracts nothing from the film or that the sub-
stances extracted are harmless. This may delay development
of these fields. The following applications have no such
limitations.
Textile Products
The use of transparent-film wrap in the textile field has

grown very rapidly in the last few years, and the future looks
very promising. Some of the manyadvantages are: (1) pro-
tecting the item from soiling, (2) allowing inspection of the
article to help selection, (3) promoting impulse buying,
(4) low cost, and (5) giving the package an appealing
appearance.
Until a few years ago cellophane dominated this market,
but it has lost good deal of ground recently, mainly because

of its poor aging characteristics, which give the package a
short shelf life. Polyethylene and vinyl film have moved into
this field in volume, and polystyrene film has had some

success.
Polyethylene film is a major factor in packaging blankets,
sheets, pillowcases, shirts, sweaters, infants' wear, children's
wear, women's gloves, pillows, and draperies. It is also used
in packaging yard goods, men's hosiery, napkins, tablecloths,
pajamas, underwear, and household furnishings.
The use of polyethylene film in these applications has been
hampered by just those characteristics that polypropylene
will improve. These are: (1) gloss and clarity; (2) strength,
especially on heavier articles; (3) stiffness; and (4) the
ability to handle on high-speed machinery.
The film with the above-mentioned characteristics, that
textilemanufacturers have been trying unsuccessfully to get
from polyethylene-film manufacturers, is almost a perfect
description of polypropylene film, and it seems inevitable that
the greatest part of this market will go to polypropylene as
rapidly as suitable film is available.
Vinyl film holds much of the sheet- and pillowcase-pack-
aging market because of acceptance a good many years ago,
when no other suitable film was available. Present users are
aware of. the changes occurring in transparent films, and it
seems likely that polypropylene can easily be a replacement,

because, on an area basis, vinyl film is almost twice as expen-
sive as polypropylene film should be when it is available in
volume. There will also have to be some modification of
wrapping machinery.
Considering the advantages of polypropylene film in this
market, and the rapid rate of growth of the market, 25 million
pounds should be consumed within 5 years. The following list
182 Polypropylene
gives some textile products suitable for packaging in poly-

propylene film:
Bandages Hosiery Shirts

Blankets Infants' wear Shoelaces
Bolt goods Linens Sweaters
Children's wear Napkins Tablecloths
Draperies Pajamas Towels
Gauze Pillowcases Underwear
Gloves Pillows Washcloths
Handkerchiefs Sheets Yarns
Tobacco Products
Cigarettes are by far the most important tobacco product,
and the 40 million pounds of cellophane used yearly to
package cigarettes is a natural market for any new film.
At this time, cellophane is firmly entrenched in this market,
largely because the extremely high-speed wrapping machines
used are geared to this film.
Polypropylene film appears to have the characteristics
necessary to take over this market eventually. Its excellent
machine-handling characteristics should make it easy to

develop the necessary equipment. The protective characteris-
tics of polypropylene film are superior to those of cello-
phane, and the price should be appreciably lower.
Several million pounds of cellophane are also used as
cigar wrappers and as over wrappers on five-packs and larger
boxes. The problem of replacing this with polypropylene film
should be less difficult than that of penetrating the cigarette
field, because the mechanization of the packaging lines is not
so extreme. There is market for pouch
also a small potential
material for pipe tobacco. At present, laminates of paper and
polyethylene are used. Polypropylene film should be strong
enough to use without the paper reinforcement, and also
moisture-resistant enough to make other barrier materials,
such as aluminum foil, unnecessary.
These markets might grow to 3 or 4 milUon pounds in

5 years.
Paper Products
The number of packages or units of paper products sold
annually totals many billions. The major item, which amounts
to perhaps half the market, is toilet tissue. In general, these
products are paper wrapped, but certain premium grades are
packaged in cellophane. Polypropylene film should easily re-
place the cellophane and, because of its lower cost, should be
able to extend the market to replace a good part of the paper
wrapping.
Polyethylene film is used to wrap quite a few paper nap-
kins. Annual sales of paper napkins amount to about 500
milUon packages. About a third of these are premium grades
for which polypropylene-film wrapping should be immedi-
ately adaptable. The remainder of the market is in low-cost
grades which will probably continue to be paper-wrapped
for some time, purely on a cost basis.
A potential market up 20 million pounds should not be
to
unrealistic in 5 years. The
following list gives some paper
products that could well be wrapped in polypropylene film.
Confetti Napkins Tissues

Cups Plates Toilet tissue
Doilies Sandwich bags Towels
Envelopes Sanitary napkins Typing paper
Garbage bags Shelf paper Writing tablets
Gift wraps Stationery
Miscellaneous Items
In addition to the categories discussed above, there are

almost innumerable other items that are regularly sold in
quantity at retail and would therefore be advantageously
wrapped in polypropylene film. Many of these are now cello-
184 Polypropylene
phane wrapped, and many are packaged in paperboard

cartons, with or without a film overwrap. In these cases a
better package can be made at lower cost with polypropylene
film. Some of these products are
still sold in bulk or pack-
aged in paper. These products should benefit greatly from

the use of polypropylene-film wrapping. A few of these prod-
ucts are listed below.
Bottle wraps Friction tape Rubber goods

Candles Games and puzzles Sanitary items
Clay (modeling) Glassware Slide fasteners
Decalcomanias Golf balls Soap
Deodorants Leather goods Sponges
(unscented) Matches String and twine
Dyes (egg and house- Moth repellents Thread
hold) Plastic articles Tire patches
Flowers, bulbs Play balls Tire wrapping
Flowers, cut blooms Powder puffs Wood products
Flower seeds Razor and blades
Polypropylene-film applications today are very small in

volume and must be considered experimental, so present con-
sumption figures would be meaningless even if they were
available. Our estimates, therefore, are based on potential
markets and the known properties of polypropylene film,
compared to competitive materials. The timing of the de-
velopment of these markets depends, to a great extent, on
factors that cannot be assessed accurately at this time. Merely
to give an idea of the magnitude of the market that can rea-
sonably be expected, however, a summary of the previous
discussion is presented in Table 6.3.
POLYPROPYLENE BOTTLES
When linear polyethylene was first introduced, it was ex-

pected that it would compete with low-density polyethylene
for the squeeze-bottle business. The stiff er resin should make

a strong enough bottle with considerably less material, thus
reducing the cost. It turned out that linear polyethylene
does not have the resilience necessary for a squeeze bottle.
It may be stiff enough, but it does not recover when squeezed.
Table 6.3. Estimated Consumption of Polypropylene

Film in Packaging Uses
Millions of pounds
1965 1970
Baked goods 80 250

Fresh produce 50 200
Frozen foods 20 80
Meat and poultry 20 60
Confectionery 10 30
Dairy products 5 30
Textile products 20 80
Tobacco 5 40
Paper products 15 50
Other 40 200
Total 265 1,020
We have seen in our study of polypropylene properties that

polypropylene has considerably better resilience than has
linear polyethylene. Since it also processes well by the blowing
method, a good quantity of polypropylene should find its way
into squeeze bottles. There is no considerable commercial
output of these bottles in this country yet, but many have
been produced experimentally, and there is some commercial
production in Europe.
The plastic bottle has found many uses where the squeeze
feature is not essential. The fact that it is both light and
unbreakable gives it an advantage over glass. Polypropylene
has a strength superiority that should give it many of these
applications. Where cost is a factor, a polypropylene bottle
186 Polypropylene
can be made enough thinner and will process enough faster

to make it the least expensive plastic bottle available. Fig-
ure 6.1 shows a polypropylene bottle.
Where strength is a factor, the amount of polypropylene
needed is enough less than most other plastics to give it an
advantage.
:^^-^
Figure 6.1. A typical polypropylene bottle. (Courtesy Hercules

Powder Co. )
POLYPROPYLENE AEROSOL CONTAINERS
One of the most recent polypropylene applications has

been in aerosol containers. This field has been dominated by
metal cans, and strength considerations have prevented the
use of plastics. The wall thickness required to get adequate
strength in a polypropylene aerosol bottle generally makes it
as expensive as the metal can. In some applications, however,

where style and appearance are dominant factors, the design
freedom that is possible in the polypropylene container out-
weighs economic factors. This is particularly true in small-
sized containers, where the material cost is not a great factor,
and in applications where a relatively low pressure gives ade-
quate dispersion of the aerosol.
These considerations have led to the first use of poly-
propylene arerosol bottles in the perfume Only 7 years
field.
ago, aerosol colognesand perfumes were nonexistent, but in

1959 they accounted for 77 per cent of the entire fragrance
market. In terms of the aerosol market, colognes and per-
fumes accounted for only about 8 to 9 per cent of the total
aerosol containers produced, but, because of the luxury na-
ture of the trade, they constitute about 20 per cent of the
industry's dollar volume.
One of the drawbacks to the use of aerosol containers in
this field is that the traditionally fancy perfume bottle is
more can be done to an aerosol

attractive than anything that
can. This is why polypropylene has been able to invade the
field successfully. There are many problems in this field re-
lated to the compatibility of perfume components with the

polypropylene container, and long test periods are required
to be certain that the scent does not deteriorate on storage;
however, considerable success has been already achieved.
It is probable that the invasion of the perfume field by
polypropylene will be slow and gradual rather than spectacu-
188 Polypropylene
lar, but, as experience is built up, it should be possible to

reduce the cost and displace the metal can in many aerosol
applications.
POLYPROPYLENE BOTTLES AND CLOSURES

Polypropylene is already well established in the closure
field. It has a very valuable combination of characteristics.
This is a highly competitive where the price is hmited
field,
by the stamped metal closures and

availability of inexpensive
phenolic caps. Unlike most compression moldings, bottle
caps are manufactured on automatic machinery that is almost
as economical to operate as is injection molding. The very
lowest price range is, at present, not open to polypropylene.
Many consumer items are, however, packaged in ornamental
containers that require a light-colored and attractive closure.
Here polypropylene competes with the more expensive urea
and melamine resins among the thermosets, and with a num-
ber of other thermoplastics.
The thermoplastics have a great advantage in the specialty
closure field, because the thermosets are limited by the com-
pression-molding technique to relatively plain and simple
shapes. The injection-molding technique gives the designer
complete freedom to make the closure any shape he wants,
and to ornament it in any way. Injection molding is also a
very economical method of molding, and polypropylene re-
inforces this advantage by molding in exceptionally short
cycles.
The light weight and high strength of polypropylene make
it possible to compete very favorably on a price basis. It
is so tough and impact resistant that it is superior to poly-

styrene,and it is enough stiff er than polyethylene to give it
an advantage here, too. The surface gloss and abrasion re-
sistance are also superior to polyethylene, and it has enough

resilience so that it shares with polyethylene the advantage
of requiring, at most, a minimum of gasketing.
Polypropylene is superior to both of the other widely used
thermoplastics in its resistance to solvents and other envi-
ronmental factors that are likely to cause crazing, stress
cracking, and other premature failure.
INJECTION-MOLDED CONTAINERS
The fast molding cycles possible with polypropylene and

the thin wall sections made possible by its strength and stiff-
ness make it a very attractive material for injection-molded
containers.
It has already had some success in this field. An injection-
molded ointment or cosmetic jar is currently in production.

This is molded with double walls, so that it closely resembles
the heavy milk-glass jar that has been standard in this field
for many years. It weighs only a small fraction of what the
glass jar weighs, thus saving shipping costs. Its light weight
and impact resistance mean that it can be shipped with much
less protective packing than can the glass jar. Its wide base
makes it very stable in use.
The main jar with its double walls is molded in one piece,
with the hollow wall open at the bottom. A separately molded,
flat, bottom plate snaps into the bottom to close it off.
A wide variety of injection-molded boxes, cases, etc., now

molded in polystyrene will probably gradually be taken over
by polypropylene because of its improved impact resistance.
The main limitation will be in those cases where clear poly-
styrene is used in order to display the contents. Because of
its crystalline nature, molded polypropylene pieces are not
entirely clear, so that some color or pigment will be necessary

190 Polypropylene
for an attractive appearance. Since a large part of the boxes

and cases now made in other resins are colored, this limita-
tion should not be serious.
VACUUM-FORMED TRAYS AND BOXES
Inexpensive, thin-walled yet rigid, vacuum-formed trays

and boxes have been increasing in popularity for some years.
They are used for food packaging, especially of meats, and
for small packages of jams, jellies, catsup, and the like. In
more complex shapes they are used to assemble "sets" of
toys, paints, and the like, to increase the size of the sales
unit. This is especially true in the craft and hobby field where
a wide variety of materials is now offered in "set" form, many
on vacuum-formed plastic trays.
The main materials of construction are impact styrene and
rigid vinyl. These materials give some dissatisfaction, espe-
cially breakage in those applications where the package must
support considerable weight.
There is a great deal of interest shown in polypropylene by
manufacturers in this field, and tests indicate that it may in-
crease the usefulness of these packaging forms.
SKIN AND BUBBLE PACKS
The plastic skin and bubble packs have been growing

rapidly. They make a very attractive package, with excellent
display of contents, and at the same time protect the mer-
chandise completely against atmosphere and handling.
It is difficult, at present, to make polypropylene films en-
tirely clear, except in the thinnest gauges. This is a serious
drawback in the bubble pack, where the merchandise lies an
appreciable distance below the film, and where the film has to
be thick enough to be self-supporting.
In the skin pack the situation more favorable; thinner

is
films can be used, and, as the film on the item

lies directly
displayed, a slight haze is not visible. The polypropylene

film is quite glossy, so the package has an attractive appear-
ance. The fact that uncoated board can be used as a base for
polypropylene skin packs gives it some advantage.
APPLICATIONS OF POLYPROPYLENE
IN THE DURABLE-GOODS
INDUSTRIES
The fact that we can even talk about the use of a plastic
material in the durable-goods industries is, in itself, evidence
of the significant strides plastic materials have made
toward greater acceptability in the past decade. A wide vari-
ety of plastics has shown in recent years that with the
proper part and design, and under the right conditions, plas-
tics can be more reliable and longer lasting than a part made
of any other material. A study of the properties of poly-
propylene leads to the conclusion that this material can ben-
efitfrom the experience with older plastics, and build a large
market in the durable-goods industries.
Durable goods are divided into two categories producer —
durables and consumer durables.
The producer durables consist of industrial-plant machin-
ery and equipment. They present some of the severest re-
quirements on a material found in any application, and the
standards of reliability and permanence are the highest.
Nevertheless polypropylene has already had a very consider-
able amount of acceptance in just this field.
POLYPROPYLENE IN CORROSIVE-CHEMICAL SERVICE
The strength, rigidity, temperature resistance, and chemi-

cal resistance of polypropylene naturally recommend it as a
192
Applications in the Durable-Goods Industries 193
material for the production of chemical-process equipment

that must be resistant to corrosive chemicals or biological
attack.
The use of vinyl chloride resins for such purposes received
great impetus in Germany during World War II, and this
experience has been widely adapted elsewhere since that time.

In the United States polyethylene has been widely used for
such purposes, and the linear polyethylenes extended the
range of usefulness. This long history of successful use of
thermoplastics in process equipment is both an advantage
and a disadvantage to polypropylene.
The disadvantage is that it is a new material seeking to
replace other materials which already have a history of suc-
cess. The advantage is that techniques for the production of
the parts have been worked out, and many designs adapted
to the efficient use of thermoplastics are available. Perhaps
even more important is the fact that engineers and designers
have started to think about thermoplastic components. Until
very recently, the idea that a durable piece of equipment
could bemade out of plastics would not even be considered
by most designers, but excellent service in a variety of very
adverse environments has changed their thinking in this
respect.
One of the main limitations of thermoplastic processing
equipment is the low softening temperature of the material.
Polypropylene extends the usefulness of thermoplastic parts
quite appreciably in this respect. The difference is really a
very significant one, because it withstands service tem-
peratures well above the boiling point, which makes it use-
ful for containing boiling-water solutions of many corrosive
chemicals. The superior strength, stiffness, temperature re-
sistance,and resistance to stress cracking often make it pos-
sible to produce a vessel for some particular service with
considerably less polypropylene than any of the competitive
194 Polypropylene
plastics. For this reason the polypropylene piece may be ap-

preciably cheaper.
A considerable line of standard sizes of tanks made of
polypropylene is available. Figure 7.1 shows two typical
tanks. These have had wide success in the electroplating in-
dustry as containers for acid and corrosive solutions, and
Figure 7.1. Polypropylene tanks for corrosive chemical service.

(Courtesy American Agile Corp.)
in the manufacture of chemical specialties. In addition to

tanks, a wide variety of fabricated parts, such as fume hoods
and ducts, pipe fittings, etc., is available.
A very interesting piece of chemical equipment that has
been successfully made of polypropylene is a plating tank
complete with an attached fume hood. Electrolytic cells
24 in. ID, 48 in. deep, with a 50-in. over-all height, have
been made, using V^-in material for the shell and a 2-in.
bottom. These cells are reinforced at top, middle, and bottom
and have an outlet welded into the side near the bottom.
The use of plastic liners in steel tanks has been common

practice for some years, in kinds of service where the metal
would be corroded rapidly. A serious problem in installations
subjected to temperature changes is the fact that the thermal
expansion of the plastic is much greater than that of the steel,
leading to buckling and even breaking after many tempera-
Figure 7.2. A polypropylene liner in a steel tank, showing open-

end construction to allow for expansion. {Courtesy American Agile
Corp.)
ture cycles. A very ingenious solution to this problem was

found by the American Agile Co. The tank involved was
for use in handling sulfuric acid. It was 15 ft long, but
narrow and relatively shallow. Calculations showed that dif-
ferential expansion in the 15-ft length would lead to varia-
tions up to % or 1 in. The high strength of the polypropylene
liner made it entirely practical to omit one of the small sides
of the steel tank, thereby accommodating the expansion with-
out trouble. This is shown in Figure 7.2.
196 Polypropylene
POLYPROPYLENE VALVES, PIPES, AND FITTINGS
The use of polypropylene tanks and industrial containers

carries with it a demand for valves and fittings to
go with
them. A considerable variety of these is available, and the
supply is growing. This is another case where the rapid de-
Figure 7.3. A valve made of polypropylene, showing internal con-

struction. (Courtesy Montecatini)
velopment of a polypropylene item was made possible by

previous success with rigid polyvinyl chloride. The two ma-
terials are similar enough in properties so that valve designs
could be readily adapted, the polypropylene has as its main
advantage much better heat resistance, and throughout most
of the temperature range better impact resistance as well.
Styrene copolymers have also been used for this service, but
their heat resistance is no better than that of polyvinyl
chloride.
Polypropylene should replace these materials even in ap-

plications where temperature is not a factor, simply because
a better valve can be made at a lower price. The vinyl has
some advantage in cost per pound, but its specific gravity
is so high that the cost per piece is higher. It is also an
expensive material to fabricate because of the thermal in-
stability of the melt and the fact that its decomposition re-
leases hydrochloric acid. This means that molding conditions
are determined mainly by the temperature the resin will stand,
and not by the requirements of economical operation. It also
means that all equipment must either be corrosion-resistant
or be subject to high maintenance costs. The styrene copoly-
mers are more satisfactory molding materials but are high
in cost.
Polypropylene, on the other hand, is very easy to mold
into complex shapes on fast cycles, and, considering its low
density, is relatively inexpensive to begin with.
Figure 7.3 shows a typical polypropylene valve for indus-
trial use.
Polypropylene Pipe
The industrial use of polypropylene pipe for corrosive-

liquid service is starting, and it appears likely that it will
gradually replace rigid polyvinyl chloride and styrene co-
polymers in this service, on the basis of superior properties
and lower cost.
The largest volume of thermoplastic pipe, however, is
polyethylene. This is used in irrigation and farm-water

supplies, water-well piping, and similar applications where
chemical resistance is not a factor. In these applications
its low cost and ease of installation are important factors. Its
particular advantage, as far as installation goes, is the fact
that it can be readily coiled, so that long continuous lengths
can be transported and laid into position without the use of
198 Polypropylene
couplings. Polypropylene pipe is at something of a disad-

vantage in this respect, because it is a good deal stiffer and
cannot be coiled except in the smallest sizes. It is also difi&-
cult to join polypropylene pipe with the simple clamp-type
fittings used for polyethylene pipe.
Polypropylene has entered intothis field in one respect,
in the molded used for joining polyethylene pipe.
fittings
These have generally been made of high-impact polystyrene,

but polypropylene fittings are stronger and cost about the
same. Figure 7.4 shows such fittings.
Inexpensive and very satisfactory welding techniques are

available for joining polypropylene pipe and it is likely that
it main use joined in this manner.
will find its
The largest amount of pipe is for domestic water and gas
pipe. Plastic pipe has had no great popularity m these fields,
partly because of the mass of regulations that necessarily
limit such uses, but mainly because all previous plastic piping
was really marginal in its properties for this service.
Although long-term service proving tests will be required,
it seems that polypropylene pipe will be entirely satis-
factory. For one thing, the heat resistance of polypropylene
pipe is good enough so that it can be used for hot water as
well as for cold. It can also easily be made strong enough to
withstand normal city water pressures.
Since it will not rust or corrode, maintenance should be
a much less serious problem. As far as can be determined at
this time, polypropylene is completely free of the pinhoUng

or stress cracking, which has been a serious problem with
polyethylene pipe.
It must be kept in mind that the problem is not so much
with the resin as with the pipe industry itself. Devotion to
price competition has caused it to adopt the practice of
adulterating the product with a large amount of scrap and
off-grade resin. This has resulted in poor pipe which has given
i
Figure 7.4.. Polypropylene fittings for polyethylene pipe. {Courtesy

Spencer Chemical Co.)
polyethylene pipe a bad name. Similar lack of foresight could

damage the polypropylene-pipe industry just as seriously.
The fire underwriters have a logical objection to the use
of any thermoplastic pipe in domestic gas service. Obviously,
in case of fire a pipe that would melt through and aUow gas
to feed the flames would be very bad. They do not, how-
ever, object to the use of a thermoplastic pipe in the under-
200 Polypropylene
ground portions of gas lines, and cellulose acetate butyrate

pipe has been used in this manner. Polypropylene pipe should
be cheaper and just as satisfactory in this application.
Polypropylene pipe can be threaded and assembled in
the same way as metal pipe, unlike polyethylene pipe;
however, this does not use its strength in the most efficient
manner, and it is doubtful that any great volume will be used
in this way.
The industrial use of polypropylene pipe for corrosive
service has startedand should continue to grow. Apphcations
in domestic service will depend upon the development of
new techniques and methods of installation, as well as revi-
sion of building codes. These facts, as well as the interests
of metal-plumbing producers and trade unions in maintaining
the present high-labor-cost methods of installing plumbing
5^ will delay the adoption of polypropylene piping and fittings
2|
for a long time.
>5K There is, however, increasing discontent with the backward
nature of the housing industry, and this will eventually result
in an industrialized house where items such as plumbing will
be preassembled by production-line techniques. When this
happens, polypropylene is the most likely known candidate

for many of the components.
POLYPROPYLENE IN AIR CONDITIONING AND

REFRIGERATION
The growth of air conditioning and industrial refrigeration

of all sorts has overtaxed available sources of cooUng water
in almost all parts of the country. This has made it necessary
to reuse cooling water by dissipating the heat to the atmos-
phere. Some sort of cooling tower is the most economical
method for this purpose. Cooling towers today must take
larger and larger cooling loads, and the economics of their
operation are constantly being subjected to closer scrutiny.

The cooling process is complicated by the variability of
the weather, and the fact that the warm water being recircu-
Figure 7.5. Plastic cooling-tower grid packing. {Courtesy Fluor

Products Co. )
lated through the system is an ideal medium for the develop-

ment of microorganisms, algae, bacteria, etc.
The conventional material for a large industrial cooling

tower has been redwood. Being a natural organic material, it
contributed to the inherent troubles of the cooling tower by

202 -
Polypropylene
adding nutrients for the microflora of the water, and was

itself deteriorated by the cooUng-tower environment.
This has led to a continuing search for a superior material
for cooling- tower construction. The problem of the outside
of the tower is not too complicated, but the packing is very
critical, because this really is what determines the perform-
ance of the tower.
The Fluor Products Co. has developed a packing which
consists of injection-molded grids, which have shown better
efficiency than conventional packings. They are currently
molded of polystyrene, but experimental quantities have
been molded of polypropylene, demonstrating that such
a large and complex molding can be made of polypropylene
without difficulty. Figure 7.5 shows a stack of these grids.
be expected that the polypropylene grids will be
It is to
better than the polystyrene in serviceswhere the cooling

water may be contaminated with materials that attack poly-
styrene. This is particularly the case of refinery service where
traces of aromatic hydrocarbons may soften and eventually
destroy the polystyrene packing.The polypropylene packing
also hasan advantage in cases where the water entering the
tower approaches the boiling point under some conditions.
This will warp polystyrene grids but will not affect poly-
propylene.
As long as polypropylene is appreciably more expensive
than polystyrene it will probably be used only in those cases
where the service is too severe for polystyrene.
POLYPROPYLENE IN TEXTILE MACHINERY
Polypropylene is wide variety of

also being adopted for a
industrial uses where its not the major
chemical resistance is
factor. Typical of these is textile machinery. The high humid-

ity required for successful spinning and weaving is very de-
structive to metal parts, and many dyeing and finishing

solutions are corrosive in nature. Polypropylene is entirely
unaffected by these adverse conditions. Textile processing is
also very dependent upon having smooth hard surfaces in

contact with thread and fabric, so that they do not drag or
snag in any way. The low frictional coefficient and abrasion
Figure 7.6. Textile machinery parts made of polypropylene.

resistance of polypropylene surfaces make them ideal both

from the operational point of view and for freedom from
maintenance problems. In addition, many complex shapes
can be injection molded at much lower cost than they can be
produced by other means.
Some typical examples of polypropylene textile machinery
parts are shown in Figure 7.6. The items pictured are bob-
bins, spools, separators, spindles, and containers.
204 Polypropylene
ELECTRICAL USES OF POLYPROPYLENE
The material used in the electrical insulation of wire gen-

erally represents so small a proportion of the total cost of
an installation that its cost is a rather minor factor in selec-
tion. Electrical installations also are expected to last a long
time without failure, which requires any new insulation ma-
terial to go through long testing periods before being ap-
proved. These factors have delayed rapid acceptance in this
field, in spite of the fact that polypropylene is for many pur-
poses the best electrical insulating material available.

Polyethylene owed its original development entirely to its
exceptional electrical characteristics. Polypropylene shares
these characteristics, and in addition has superior strength^
abrasion resistance, and heat resistance.
Because polypropylene ordinarily retains minute traces of
be needed
catalyst residues, a specially purified grade will
for high-frequency applications such as coaxial cable, and
these grades are not yet available. For most purposes, how-
ever, the slight increase in loss factor, which is the principal
penalty of these residues, is of no consequence.
Insulated wire used for two main purposes the trans-
is —
mission of electricity for light and power, and for commu-
nications.
Light-duty Pevsner Wire
The light-and-power category is still quite varied, and,

for purposes of discussion, can be divided into light and
heavy duty. Light-duty wiring includes all domestic wiring
and those circuits in commercial and industrial installations
which feed electric light and small loads such as for office
machinery. Such wire is now largely insulated with poly-
vinyl chloride-based insulations. Voltage used is small, gen-
erally 220 volts or less, and the frequency is low, usually

60 cps. Circuits are rarely loaded enough to operate very
much above room temperature. In these applications poly-
propylene would permit very considerable economies. In the
first place, the simple substitution of polypropylene for poly-
vinyl chloride at the same wall thickness would reduce the
weight of insulating material enough to make it cheaper.
The wall thickness, however, is not determined by electrical
requirements but by purely mechanical ones. A half mil of
polypropylene would adequately insulate against 220 volts.
Two principal mechanical problems require much heavier

coatings. The first is abrasion resistance. In the larger in-
stallations such wires are pulled through conduits. This pull-
ing abrades them heavily against the conduit walls, especially
at corners. Polypropylene insulation has a harder surface
and better abrasion resistance, and slips over metal more
easily than polyvinyl chloride insulation. This should make
it possible to reduce coating thickness when using poly-
propylene.
The other mechanical problem is the tendency of the wire
to cut through the insulation at corners and in other situa-
tions where it is under strain. Wire can never be perfectly
centered in the insulation; however, the main problem is that
when the wire is held firmly against a hard object it gradually
pushes through the insulation. This is a combination of simple
creep, and softening as the temperature rises. Polypropylene
is resistant to considerably higher temperatures than polyvinyl
chloride. This factor also permits the use of thinner insula-
tions with polypropylene, without increased danger of failure.
Polypropylene is somewhat more stiff than polyvinyl chlo-
ride of the type used for insulation. Thus, if the same thick-
ness of polypropylene were used, the wire would be stiffer
and less easy to handle; however, thinning the wall would

206 Polypropylene
The thinner wall would have the added

restore the flexibility.
advantage of reducing wire diameter and permitting more
wires to be placed in the same conduit. It is even possible
that the better heat resistance of the polypropylene insulation
would permit heavier loading of the circuits without danger,
and so reduce the amount of wire needed.
These things are all, of course, subject to the strictest regu-
lation, and the changes suggested can be made only after
long and careful testing has shown them to be safe.
Appliance Cord
A closely related type of wiring is the appliance cord, the
wire used to connect a lamp or appliance to the house wiring.
This is now generally insulated with polyvinyl chloride, but
some rubber is also used. Equal durability could be obtained
with considerably less polypropylene; however, the cord
would still be stiffer. Since flexibility is a major requirement
in this type of wire, it is doubtful that present types of poly-
propylene would be suitable.
Heavy light-and-power wiring is an entirely different mat-
ter. This is the wiring used for heavy machinery and for
main lines. These lines are not insulated with thermoplastics
but with rubber or neoprene, because they are generally more
highly loaded and operate at higher temperatures. It is pos-
sible that the improved thermal resistance of polypropylene
will allow polypropylene-insulated wire to be used in certain
marginal applications of this type, but it is doubtful that any
thermoplastic will take it over altogether.
Communications Wire
Communications wire is the other large use of insulated
wire. This also falls intotwo general classes the coaxial —
cable used for radar, television, and other high-frequency
work, and telephone and telegraph cable. The situation re-
garding the high-frequency applications has already been

discussed.
Telephone and Telegraph Wire

Thermoplastics are used in two different kinds of applica-
tions in the telephone and telegraph industries — cable sheath-
ing and primary insulation. The sheathing used is, at present,
polyethylene. It serves as a protection for the cable against
both abrasion and moisture penetration. Because of this,
wall thicknesses are and the diameter is

rather heavy,
large. Polypropylene would undoubtedly afford the same pro-
tection with less material, but, even with reduced wall thick-
ness, it would make a stiff cable which would be very difficult
to handle. It could, of course, be made as flexible as poly-
ethylene, but at this stage of development it appears doubtful
that it would have any advantage over polyethylene in this
form.
Primary insulation of communications wire is, at present,
divided between vinyl and polyethylene. The advantage of
polyethylene, which is gradually replacing the vinyl, is that
its dielectric constant is lower, thus permitting the use of
a thinner insulation. The insulation thickness is not deter-
mined either by its electrical resistance or by its mechanical
strength. A thousandth of an inch would give enough in-
sulation as far as current flow is concerned, and primary
insulation is protected by a cable sheath, so it is not subject
to any mechanical damage. Insulation is made as thick as it

is simply to hold the wires apart far enough to reduce their
mutual capacitance and prevent "cross talk" in the cable. A

low dielectric constant reduces the distance required for this
purpose, so the insulation can be thinner, and a cable of any
given number of conductors can be smaller.
Polypropylene has a lower dielectric constant than poly-
ethylene, and should have an advantage in this respect. The
208 Polypropylene
advantage is small, however, and it may be difficult to justify

a change for this purpose alone. The next major change in
the primary insulation of communications wire will probably
be to the use of foamed insulation. This reduces the dielec-
tric constant a great deal more than any solid insulation.
Polypropylene foam should be a strong competitor in this
field, because of its superior physical strength. Present tech-
niques do not permit the production of foamed insulation
in the thicknesses required to make this an actuality, but
much development work is going on.
Molded polypropylene parts also have a great potential
in electrical applications. A start in this direction has been
made with a trouble lamp which has a polypropylene handle.
The thermosetting plastics are well entrenched in the elec-
trical field, and for applications where temperatures may be
high, they will certainly retain their places. Polystyrene is
used for a number of electrical applications where tempera-

ture is not a problem, such as switch plates, appUance plugs,
etc. Polypropylene is much tougher and more heat resistant,
but the difference in price will at first limit the polypropylene
to those applications where a special point is being made of
quality, and price is of secondary importance.
Polypropylene for Components of

Electronic Equipment
Polypropylene is an excellent material for coil forms, tube
sockets, and many other electronic components. It is com-

pletely immune to the effects of dampness which damage
fabric- or fiber-based insulation materials, and its heat resist-
ance is superior to other thermoplastics. The injection-mold-
ing process can make these complex shapes very accurately
and economically. A coil form is shown on the far right of
Figure 7.6,
I
Electrical Applications of Polypropylene Film
Both polyethylene and polystyrene found their earliest
applications in the electrical field. In this field, superior prop-

erties will justfy the relatively high prices required for the
initial small-scale production. Polypropylene is no exception
to this tendency, and a considerable amount of polypropy-

lene film has been used, mostly in the form of tapes, for a
variety of electrical applications. These include capacitor di-
electrics, cable-barrier tape, layer insulation, and the taping
of coils and foil-wound transformers. The high dielectric

strength of thin films, excellent heat resistance, low dissipa-
tion factor, and good winding characteristics have made it
quite successful in this field.
The volume involved in such applications is small com-
pared to that in the packaging field, but it does represent a
growing market for relatively small amounts of the highest-
quality film.
CONSUMER DURABLES
The consumer durables constitute a great part of what
people term the American way of life. They are that part of
our possessions that we expect to last a long time, that we
take particular pride in — They are the
the "big ticket" items.
products of some of our largest and most dynamic industries,
and the envy of the whole world.
The growing importance of plastics in this field is not only
a source of pride for the industry but a real promise of grow-
ing markets. Polypropylene is already making a contribution
in such products, and there is every reason to believe that it

will soon be one of the most important plastics for such
applications.
210 Polypropylene
Polypropylene Applications in Appliance Parts

Despite its origin in the metal and mechanical trades the
appliance industry is already a heavy user of plastics, and
this use growing every day. Impact styrene, vinyls, and
is
various copolymers are now most heavily used. Polypropy-

lene should add much impetus to this trend, because it will
provide better parts at lower prices.
Figure 7.7. Household appliances with polypropylene parts.

(Courtesy Montecatini)
Typical apphances using polypropylene parts are shown in

Figure 7.7. These are: top left, a coffee grinder; center, a
sterilizer; right, and lower left, a cleaner. All
a hair dryer;
these have major components made of polypropylene.
The items pictured are European in origin, but similar ones
have been made in this country. For instance, a coffee maker
with a polypropylene pouring lip has been produced. This
replaces a metal lip. The polypropylene lip is more attractive,
immune to tarnish and corrosion, and costs less than the
metal. The ability to stand repeated contact with boiling

coffee makes polypropylene the best plastic for this use.
Similar considerations resulted in the use of polypropylene
for the silverware container of a new line of dishwashers. A
one-piece polypropylene molding replaced a wire basket
covered with vinyl plastisol. Not only is this less expensive;
it is more durable, because there is no coating to be cut or
scraped off. The polypropylene is corrosion resistant and
colored all the way through.
In addition to the housings which are practical with many
plastics, it is possible to make many of the working parts
themselves out of polypropylene, because of its superior
physical properties.
The vacuum-cleaner polisher and buffer shown in Fig-
ure 7.8 has polypropylene-backed brushes as well as housing.
The great strength of polypropylene makes it possible to use
it for housings that have heretofore been made of metal,
because the weight of the contents was considered too great
for plastics. The air-conditioner housing shown in Figure 7.9
is a case in point. It can be seen that this is no mere cover,
but the main load-bearing frame of the appliance. Polypropy-

lene should permit increased use of plastic housings that are
also load-bearing members. This not only will reduce costs
by decreasing assembly operations, but the reduction in metal
parts will reduce weight and decrease noise.
Other extremely heavy-duty housings being made out of
polypropylene are the hoods for a rotary lawn mower. This
enhances the appearance of the mower, muffles engine noise,
and is extremely resistant to the abrasion, vibration, and
impact experienced in this service. A combination power
mower and outboard motor recently introduced has a poly-
propylene engine shroud. The choice of a thermoplastic for
an application where there are potentially such high tempera-
turesshows clearly how far superior polypropylene is to other
212 Polypropylene
^.__.
'
m^^M
Figure 7.8. Vacuum cleaner-polisher-buffer showing polypropylene

parts. (Courtesy Montecatini)
thermoplastics. Polypropylene, in this instance, was chosen

for its heat resistance, appearance, rigidity, and ease of mold-
ing, after careful consideration of cast aluminum, high-impact
styrene, and hnear polyethylene.
Figure 7.9. Air-conditioner housing of polypropylene. {Courtesy

Montecatini)
Polypropylene has proved to be an excellent material for

fans, both of the propeller type and the squirrel-cage blower.
The entire blade assembly can be made in one piece and at
one time. Its light weight reduces the inertia of the fan; thus
it can reach full speed more rapidly, has less bearing load.
214 Polypropylene
and is much less dangerous if fingers accidentally get into

the blades. Housing and grill, as well as the blades, can be
made of polypropylene. These fans are quieter than metal
fans, because the polypropylene parts have less tendency to
vibrate in audible frequencies, and the light weight of the
rotating parts makes imbalance less of a problem. The injec-
tion-molding method makes it economical to produce blades
of complex shapes conforming to the best aerodynamic prin-
ciples, thus increasing efiiciency.
Humidifiers and medicinal vaporizers are another type of

appliance for which polypropylene is being used. Rust and
corrosion make metal very poor for this service, and other
plastics are, at best, marginal where vaporization is accom-
plished by boiling water. Water can be boiled in a polypro-

pylene container without any danger of distortion, discolora-
tion, or embrittlement with age.
Polypropylene has shown itself to be particularly well
adapted to use in automatic dishwashers; almost every major
dishwasher brand has at least one polypropylene part, and
some have many. The reasons for this are the resistance of
polypropylene to chemical attack, especially by the strong
detergents used in dishwashing; the good finish obtainable;
high resistance to abrasion; and good impact strength.
Typical polypropylene parts include a molded distributor
arm in the water-distribution system, the impeller in the main
water pump, trim rings and grommets, detergent cups, and
rails.
A dispensing unit for a floor waxer has also been made

out of polypropylene. It was chosen for its ease of fabrica-
tion and for its resistance to the solvents used in the wax. It
should be noted that polypropylene is quite permeable to
turpentine, one of the solvents involved, but this is no

obstacle to this application. Many of the weaknesses of poly-
propylene turn out not to cause practical problems.

Polypropylene Film for Magnetic Tape
The increasing use of magnetic tape for sound recording

and its potential for television-signal recording will undoubt-
edly create a great market for superior tape material.
Oriented polyester film is probably the best material for
this purpose now available, but its high price creates a de-
mand for a less expensive substitute.
Ordinary unoriented polypropylene film is much too exten-
sible for this purpose, permitting signal distortion at slight
differences in tension. By orienting polypropylene film suffi-
ciently its extensibility can be greatly decreased. Probably the
ideal tape material would be oriented lengthwise to obtain
the highest possible strength in this direction. Although such
material is not yet in commercial production it appears to
be technically feasible and should compete very favorably
in this market.
Polypropylene as Photographic-Film Support
Polypropylene film has a great potential as a photographic-

film support. Its stiffness and strength characteristics are
considerably better than those of the cellulose acetate base
now commonly used, and it has the advantage of being much
more resistant to moisture and processing chemicals. Poly-
propylene movie film should resist the drying and embrittle-
ment that now limits the life of such film. In addition, it
should be appreciably cheaper.

As with so many appUcations, good physical properties
and low cost are not going to convert the long-established
photographic film industry overnight.
Polypropylene has several drawbacks as a film base, the
most serious of which is that photographic emulsion will not
adhere to it. This is not likely to prove an obstacle for very
long, because many techniques for improving adhesion are
216 Polypropylene
known. Work is in progress on this problem, and Montecatini

has obtained a patent on an adhesive layer composed of
amorphous polypropylene which is partially sulfonated or
chlorosulfonated.They claim that this material gives excel-
lent adhesion between gelatin emulsions and isotactic poly-
propylene film. Abrasion tests are cited to show that the
gelatin is well bonded. The existence of a patent does not
necessarily prove that the process will be competitive with
presently available methods, but it does mean that promising
work has been done. It seems quite probable that polypro-

pylene will be a major factor in photographic film in the
future.
Automotive Uses for Polypropylene

In spite of the gradual increase in the use of plastics in
automobiles, this industry has been slow to adopt plastics
on any large scale. There are many reasons for this. One of
the greatest is and reliability
that the standards of durability
in the automotive field are extremely high. Until recently,
only steel parts could meet these standards. Very few plastics
are able to withstand the severe service requirements.
The automotive industry in America has, for years, been
extremely conservative. For all its emphasis on modernity,
this has generally been only in matters of style. The main
working parts of an automobile have changed very little in
20 years or more, and the materials of construction are like-
wise unchanged.
To a great extent the American automobile industry
considers itself not as a purveyor of transportation, but rather
as a seller of elegance and prestige. These are, by their
nature, traditional and opposed to changes made in the inter-
ests of economy and efiiciency. The success of the small
European car in recent years has shown that the American
people are tired of spending a large part of their income
merely on a symbol of conspicuous consumption. A lot of

them want economical transportation. Although the "compact
car" is a start in this direction, Detroit is poorly equipped
to compete with low European wages in producing them.

To make a real transportation bargain under American con-
ditions, radical changes are needed. Costs must be cut, espe-
cially labor costs, and the clearest road open to the kinds of
Figure 7.10. Motorcycle shock absorber with polypropylene parts.

cuts required is to make many of the assemblies —

now made
out of numerous metal parts, by means of several operations
on one part —from one plastic part molded in a single
operation.
European motorcar makers have been quicker to adopt
plastics for functional parts than have our own manufac-
turers. The shock absorbers shown in Figure 7.10 are a case
in point. They are made almost entirely of polypropylene,
except for the internal steel rod and spring. Many other func-
undoubtedly be made of polypropylene before
tional parts will
long. Fiat has a polypropylene fan under development.
218 Polypropylene
The actual motor parts are probably out of reach of poly-

propylene for reasons of high temperature; and parts in direct
contact with gasoHne, such as fuel lines, pumps, carburetors,
etc., are better made out of nylon because polypropylene is
too readily permeated and softened by gasoline. This is,
however, not as serious a limitation as might be thought.

Body and running gear are the largest part of a car. Direct
load-bearing members will be steel for a long time yet, but
that is about the only limitation. Various plastics, especially
cellulose acetate butyrate, have been used for items in the
car interior, such as steering wheels, arm rests, etc. The
between polypropylene and
similarity in physical properties
butyrate has been pointed out before. Lighter weight and
lower cost should put polypropylene into these applications.
Polypropylene dashboards have already appeared in Eu-
rope and are much better than metal ones, safer for the
passengers in case of accidents, and not prone to rattles and
vibrations. The real economy will come when the entire dash
is molded in one piece, including all instrument dials and
the necessary fasteners so that instruments and controls can
be assembled very rapidly and economically. Quite possibly,
electrical wiringcan be molded in, thus eliminating the pres-
ent tangle underneath the dashboard. This archaic and waste-
ful construction is long overdue for a sweeping redesign,
and the availabiHty of polypropylene may stimulate the
change.
Automobile air-conditioner ducts, and other parts of the
air-conditioning equipment, have already been made of plas-
tics and are also suitable polypropylene applications. Knobs,
handles, push buttons, switches, window moldings, parts of
seat frames, door liners, and many such items are within the
range of present technology and should improve durability as
well as economy. The strength-weight ratio of polypropylene
is favorable enough to make it possible, when suitable fabri-
cation techniques are developed, to consider its use even on

major parts such as body panels.
Other applications now under active development include
electrical connectors, terminal blocks, fuse blocks, horns,
lamp sockets, reflectors, dome-light lenses, etc.
It is conservatively estimated that 1962 will see 2 to 3 lb
of polypropylene in a new car, which would put 15 to 20
million pounds into automotive uses.
Polypropylene Furniture
Many people see a great future in polypropylene in the
furniture field, and this viewpoint is being strengthened by
the appearance of several highly successful items. One of the
first furniture-like was in self-stacking utility
applications
shelves. More recently, a bookcase has been introduced. The
combination of good appearance, durability, and low cost
will inevitably bring about an increase in such items. Most
furniture is rather large for injection molding, and this will
keep initial introduction to relatively small pieces, or to ones
that can be built up in sections. It cannot, however, be ex-
pected that this will always be a handicap, because technology
is constantly improving, so that a piece that is large for in-
jection molding today may be very commonly handled in
this manner few years.
in a
In addition to the molded pieces mentioned above, poly-
propylene is appearing as webbing, woven from monofila-
ment. This webbing forms the back and seating of metal
outdoor furniture. Polypropylene monofilaments have weather
resistance superior to competitive filaments. They also show
very low residual shrinkage on exposure to hot summer sun,
thus preventing tightening and warpage of frames. The excel-
lent resilience of polypropylene monofilament and its resist-
ance to cold flow keeps polypropylene webbing from deteri-

orating with time.
220 Polypropylene
A very ingenious polypropylene assembly clip for holding

the webbing to the frame has been devised. This clip is
molded directly to the end of the piece of webbing, giving
uniform load over the entire width, and eliminating the stress
concentration which causes premature failure when other
methods of fastening are used.
8. APPLICATIONS OF POLYPROPYLENE
IN THE SOFT-GOODS INDUSTRIES
Soft goods include all the many things we use every day
that are not expected to last long —
we use up
the things
and wear Although the requirements for many of these
out.
applications are quite severe and entail very special prop-
erties, they are rarely as extreme as in the hard-goods field.
It is for this reason that polypropylene has not yet penetrated

this field as far as it has the hard-goods area. There are many
other materials that serve reasonably well and, at present, are
cheaper. It also takes more salesmanship to sell 200 miUion
consumers on the idea of using a new material than it does
to sell the relatively few engineers and executives who can
put the material into a hard-goods item.
This chapter starts with a discussion of fibers. Many people
expect this to be the largest single application for polypropy-
lene, yet, except for a rather small amount of coarse fiber,
the material is practically unknown on the American market.
POLYPROPYLENE FIBERS
In marked contrast to the rapid growth of the plastics

industry, the textile-industry growth has not even kept up with
the population increase. consumption in the
Textile-fiber
United States has averaged 6 billion pounds a year since
World War II, with rather wide fluctuations but no net
growth.
221
222 Polypropylene
The composition of this total has seen a gradual change,

however, with various synthetic fibers taking an increasing
share of the market, and the natural fibers declining. Despite
the trend toward synthetics, their performance has not been
spectacular. Nylon was the first true synthetic, and its per-
formance has been the best by far. Nylon consumption for
1960 will probably approach 400 million pounds, as com-
pared with about 30 million in 1945. The acrylics may hit
180 million in 1960 after 10 years of intensive effort, and the
polyesters will have achieved markets of only 80 million in
about the same length of time. This is in marked contrast to
the billion-pound total polyethylene achieved in a similar
time. Obviously, markets are not lying around waiting for a
product in this industry.
It is estimated that the development of a new synthetic
textile fiber costs over 10 million dollars, and the promotion
budget needed to make a market for it is greater than that.
In spite of this, an American Viscose stated that
official of
"in five years we will all be making polypropylene fiber."

While firms other than Montecatini and the Industrial
Rayon Corp. have been very quiet about their plans, there is
littledoubt that practically every firm involved in the syn-
thetic-fiber business is taking a very close look at polypro-
pylene With the synthetic-fiber industry operating well
fiber.
below capacity, none of the producers are eager to launch

a new product and add more capacity unless it is absolutely
essential.
A very brief glance at the polypropylene-fiber picture
shows that it is going to be essential for synthetic-fiber pro-
ducers to be in the polypropylene field also. Polypropylene
fiber is any synthetic in the market and it has
as strong as
good abrasion low specific gravity,
resistance. It has a very
so that the area of goods of any given thickness produced by
Applications in the Soft-Goods Industries 223
a pound of polypropylene is greater than that from any other

synthetic or natural fiber. A domestic price for polypropylene
fiber is yet to be established, but, considering probable manu-
facturing costs, it will eventually be in the general range of
rayon — well below the cost of the other true synthetics.
Polypropylene fibers demonstrated by Montecatini show
which makes them very easy to spin
negligible static effects,
and weave. This is in marked contrast to other synthetics,
which were very troublesome in this respect until special
means of destaticizing them were found. Polypropylene
fabrics are also quite free from the "pilling" that has been
a serious drawback of most synthetics.
The low moisture absorption of the fabric makes it drip
dry readily, and properly designed fabrics will satisfactorily
"wash and wear" without ironing. Like all thermoplastic
fibers, care must be taken not to apply too much heat in
ironing or the fiber will melt; however, Americans are con-

ditioned to this idea by now, and it should cause no trouble.
Polypropylene-fiber cloth can be machine-washed without
damage. Perhaps the most remarkable fact about polypro-
pylene fiber is its versatility.
Coarse Polypropylene Fiber for Heavy-Duty Use

Polypropylene monofilament has already achieved a sub-
stantial production in this country. It is the second largest
market after the injection-molding industry. Figure 8.1 shows
some typical polypropylene monofilament. It is taking over
the markets pioneered by polyethylene monofilament, which
are mainly in the cordage field. It is the best available cordage
for marine mooring lines. Being completely immune to rot
and weakening by salt water, a polypropylene rope wîll out-
last a manila fine by a wide margin. Its light weight not only
facilitates handling but enables it to float if accidentally lost

224 Polypropylene
Figure 8.1. FolypTopylene monofilament (Courtesy Spencer

Chemical Co.)
overboard. It also dries out rapidly, since it does not absorb

water, and retains its excellent handling properties even when
wet. These advantages are, of course, shared by polyethylene,
but the superior strength and abrasion resistance make poly-
propylene the fiber of choice in heavy-duty applications. In
tanker service it has the additional advantage of superior
resistance to oil and grease.
In towline applications compete favorably with nylon

it will
I line. The which makes it

great extensibility of nylon line,
unsuitable for mooring service, has not been such a serious
obstacle in towing work; however, the less extensible poly-
propylene line has stretch enough to cushion sudden
stresses, but still gives better control of the tow. Polypropy-
lene line is as strong as nylon, considerably lighter, and
appreciably cheaper.
Table 8.1 compares polypropylene rope with manila and
polyester types. Ropes were chosen that have about the same
Table 8.1. Comparison of Ropes

Inches Breaking Weight per Cost per
Fiber type around strength (lb) ft (lb) ft (dollars)
Manila 12 105,000 4.36 2.57

Polyester 8 103,000 2.07 7.90
Polypropylene 81/2 106,000 1.70 3.91
breaking strength. Although the polyester rope has a slightly

smaller diameter, it is much heavier than the polypropylene
rope and a great deal more expensive. The manila rope is
much and heavier, which, for many applications, will

larger
outweigh its relatively small cost advantage. This shows
clearly why polypropylene is penetrating this field so rapidly.
A recent development is the introduction of multifilament
polypropylene cordage. This is rope made up of fibers as fine
as silk. Somewhat higher can be obtained in these
tenacities
very fine fibers, but the main advantage is that the cordage
is much more flexible and easily handled. Polypropylene has
revolutionized the material base for heavy cordage, and it
may revolutionize the entire technique of manufacturing it as

well.
Polypropylene monofilament also has applications in chem-
icallyresistant filter cloths and other heavy-duty fabric
which needs strength and chemical resistance.
226 Polypropylene
It is highly probable that polypropylene monofilament will

be a strong competitor for many of the uses now served by
saran and vinyl monofilament, such as automobile seat covers,
insect screens, lawn-furniture covers, furniture upholstery,
webbing, etc. Its much fighter weight should make it possible
to compete with these cheaper resins on a price basis, and
its physical properties are far superior.
Wool-like Polypropylene Fabrics
In April, 1957, Montecatini exhibited polypropylene

fabrics at the Milan
These consisted of pure polypro-
Fair.
pylene, and polypropylene-wool blends; they were indistin-
guishable in texture, hand, and appearance from pure natural
woolens. Figure 8.2 shows wool-like polypropylene fabrics.
The blanket in the upper left is pure polypropylene, and so
are the hound's-tooth check below it and the modified plaid
at the upper right. The glen plaid in the center is a poly-
propylene-wool blend.
Everyone who has had an opportunity to handle these
fabrics is impressed by their very "natural" feel and texture.
There appears to be no reason to expect any consumer
resistance to these materials. Even at current prices for poly-
propylene fibers (and they can be expected to decrease as
competition develops), wool-like polypropylene fabrics can be
made less expensively than an equivalent quality of woolens.
The care of these fabrics should be a good deal simpler
than the care of woolens, since they are essentially shrink-
proof and unaffected by water, completely inedible to moths,
and immune to mold. They should be extremely durable
because of the high tenacity and abrasion resistance of the
fiber, and their heat-insulating value is excellent.
As technology and public acceptance develop, polypropy-
lene should make serious inroads into the traditional wool
appHcations.
Figure 8.2. Polypropylene fiber fabrics. (Courtesy Montecatini)
Montecatini has since extended its line of textile materials

to a wide variety of fibers, and in the form of staple, multi-
filament, and monofilament yarns suitable for every textile-
manufacturing operation.
228 Polypropylene
Silk-like Polypropylene Fibers

The multifilament yarns are very similar to silk and
produce fabrics v/ith the traditional finishes typical of fine
silk. Although this market is rather limited and has been the
traditional target of synthetics, it still should be taken into
account. Since polypropylene can be expected, before long,
to compete in the price range of viscose rayon, it should
readily take over a considerable amount of this market.
Rayon, of course, has serious weaknesses, such as its poor
wet strength and general moisture susceptibility. The other
man-made fibers that compete in this field are more expensive
and have properties that do not appear to be superior to those
of polypropylene fiber and this also would seem to be a
fertile field for polypropylene fiber.
Polypropylene Fibers Resembling Cotton and Linen

The latest development in polypropylene fibers was intro-
duced by Montecatini in 1959. This consists of polypropy-
lene fabrics, and blends of polypropylene and viscose, that
closely resemble cotton and linen. The synthetics have here-
tofore kept away from this market, in spite of the fact that
cotton is still the most widely used fiber. This is because price
competition from cotton has made it unattractive. The
ultimate cost of polypropylene fiber should be low enough to
make it possible to compete in this field, and considerable
penetration of the market should be possible even at a con-
siderably higher price. The polypropylene fiber has greater
strength and better abrasion resistance, and it should be
much more durable than cotton. Unlike other synthetics, the
polypropylene fibers have no tendency to develop static
charges.
Montecatini has exhibited all of these fabrics in bright, gay
colors. Figure 8.3 shows some examples. The floral print in
Figure 8.3. Polypropylene fiber fabrics. (Courtesy Montecatini)
the upper left corner and the period print at the lower right
are made of 65 per cent polypropylene and 35 per cent
viscose. The floral design at the lower left is 100 per cent
polypropylene.
These fabrics have the cool, crisp, hand characteristics of
230 Polypropylene
cotton and linen and should be well adapted to a wide variety

of characteristic cotton and linen uses. From the samples
shown, they should make excellent summer clothing for
women and shirts for men, as well as curtains, draperies, and
other uses in the home.
By use of the proper manufacturing techniques it appears
that polypropylene will be able to compete in any textile
market.
As with other synthetic fibers, there are problems con-
nected with the dyeing of polypropylene fiber, and Monte-
catini has been quite successful in solving them. They are
essentially no different from the problems successfully solved
with other synthetics. Polypropylene, being a pure hydro-
carbon resin, does not offer dyes the active sites necessary
for dyeing. One of the methods for solving this is to copoly-
merize a small percentage of monomer containing an active
grouping with the base monomer. Montecatini has patent
coverage on a number of such combinations. This produces a
polymer that offers the necessary reactive sites for satisfac-
tory dyeing. It is probable that this is the way polypropylene
fiber is rendered dyeable, although other techniques are also
available.
Some organizations with experience in the dyeing field are
actively investigating, and soon many others will follow and
be offering dyed polypropylene fibers.
At this time the Industrial Rayon Corp. is the only Amer-

ican firm that has definitely announced plans to produce
polypropylene fiber. Since this company specializes in indus-
trial applications, they may feel that they have sufficient
markets available without a complete answer to the dyeing

problem.
The technological problems involved and the traditionally
conservative nature of the textile market will prevent very
rapid growth of this market. Fifteen million pounds in 1963
appears to be a reasonable estimate, and it should ultimately

grow to be the largest-volume synthetic fiber, with 500 million
pounds a year or more before the end of the 60's, and the
bilhon-pound goal not impossible.
NONWOVEN NETTING
Polypropylene has recently been made available in the

form of netting which is made from sheeting in the same way
that expanded metal grids are made. Staggered rows of slits
are made in the sheeting, and then, under carefully regulated
conditions of temperature and tension, the sheet is stretched
sideways to expand the slits into diamond-shaped holes.
This material has a wide variety of uses. The fact that it
cannot rust or corrode makes it valuable for flooring chicken
or turkey coops, and for decorative fencing around shrubbery
or flower beds. It is also useful for many applications for
which the metal is used — decorative grids and grids to support
filters, for instance.
Attractive all-through color should be an advantage in the
decorative applications, and as a filter support its corrosion
resistance should be of importance. It should be a useful
material for the fabrication of wastebaskets, fruit or vegetable
bins,and containers of all sorts. When made from thin sheet-
ing, thiswebbing is quite flexible and has possibilities for
conveyor belts, hammocks, and outdoor furniture.
POLYPROPYLENE SHOE PARTS
Plastics have been associated with the heels of women's

shoes since the start of the industry. The thin black nitrate
cover on the wooden heels of women's shoes dates back to
the days of the celluloid collar, and survived that piece of
232 Polypropylene
flammable finery by many years. Up to the time of World

War II, there were many shoe heels covered this way.
The tide had, however, begun to change before that, and
as long as 25 years ago the first injection-molded cellulose
acetate women's shoe heels had their first vogue. Almost
every other plastic —
has had its turn butyrate, acrylic,
and impact styrene. Even nylon had a short-lived promotion.
In recent years shoe designers constantly have gone to
thinner and higher heels on women's shoes. In part, this has
been a response to the design freedom given them by the
availability of molded heels. It would have been ridiculous
to make such heels of wood.
The extremes of style, however, have gone beyond what
even the strongest plastic can stand, so that the modern
women's shoe heel is a steel spike, gracefully contoured, and
fastened to the shoe by means of a plastic.
In the last few years, polypropylene has had good accept-
ance in women's shoe heels in Europe, and it appears very
likely that the market will go in the same direction in this
country.
Although it seems very simple, the shoe heel really presents
many remarkably complex problems, not the least of which
is that the shoe manufacturers insiston treating it as if it
were still made
wood. They nail it to the shoe and also nail
of
a lift to the bottom of it. They even insist on using a
curious blunt-pointed nail that was very reliable on wooden
heels.
It should not be a great surprise, therefore, that plastics
give them some trouble; the nails are hard to drive in, the
plastic distorts near the nail, and the heels loosen with time.
Polypropylene shows very good properties in all these re-
spects. Its resilience makes for easy nailing, and its resistance
to creep helps it grip the nail for a long time.
In spite of the availability of all-through color in plastics.
—
the shoe manufacturers Uke to paint the heels. This is a

tradition even older than the wooden heel, and is so firmly
entrenched that it is unlikely to be changed soon. The solvents
used in the stains and lacquers tend to attack, craze, and
weaken most plastics quite seriously. Polypropylene is ex-
tremely resistant to such attack.
A shoe heel also is by no means an easy object to mold.
A very thin covering over the spike at the bottom spreads out
quickly to a thick mass at the top, which tapers off to a very
thin edge around the top. These rapid changes in cross sec-
tion, and the presence of the steel insert, create problems
with flow marks, sink marks, splitting around the insert, and
others. The combination of free flow and good physical
properties makes polypropylene one of the easiest plastics
to mold in this application. Since the steel insert in modern
heels makes the strength of the plastic secondary to other
properties, polypropylene makes extremely strong heels.
It now appears very likely that polypropylene will even-
tually take a good proportion of the women's shoe-heel
business. Although the shoe industry is still dominated to a
surprising extent by the handcraft technology it has inherited
from the use of natural materials, it has been quick to adopt
the new synthetics. There is no shoe part that has not, at
some time or under some circumstances, been made out of
plastic. The plastic parts generally are better looking and
more durable than leather.
Some shoe parts are conventionally made of polyethylene
counters, insoles, dutchmen, and toe boxes, for instance.
In almost every instance a somewhat thinner polypropylene
piece would be better and cheaper.
Styrene copolymers are not likely to be displaced by poly-
propylene as soles, and styrene copolymer and vinyl "uppers"
also give such good service that they are probably not very
vulnerable.
234 Polypropylene
What is vulnerable, however, is this entire musty and

antiquated industry. It is inconceivable that people will long
continue to nail and glue shoes together out of dozens of bits
and pieces as they now do.
A few crude attempts at making a shoe by more modern
methods have been made, and the products have found a
limited market. A real program for producing footgear from
a plastic material, however, starting with fundamentals and
not just adapting current practice, is still in the future. When
this happens, and it be long delayed, the combination
will not
of flexibility in thin sections and stiffness in heavy ones,
resilience, resistance to long-time creep, abrasion resistance,
and easy fabrication should make polypropylene a strong
contender as the material for the job.
k
<;
HOUSEWARES APPLICATIONS OF POLYPROPYLENE
(I)
"I
? Housewares are one of the largest traditional applications

makes it possible to predict with confidence
for plastics. This
not only what will be done with polypropylene in this area,
but also how much of it is likely to be consumed for this
purpose.
Polypropylene has already established a certain position in
this field. It is difficult to estimate just how the injection-
molding poundage reported is split into the various uses, but
it is probable, judging from advertising and items exhibited
at various shows, that the largest single item is for house-

wares.
In 1959, 170,000,000 lbs of polyethylene and about three
times that much polystyrene was injection molded. The largest
polyethylene item in this total was housewares. Polystyrene
housewares totaled about 50,000,000 pounds.
In the past few years plastics, especially polyethylene and
polystyrene, have taken a very large percentage of the house-
wares business away from the traditional metals, glass, and

ceramics. Polypropylene has already shown that it will con-
I
tinue the trend. A few items already in production give a good
indication of what is to come.
Drinking Glasses
Plastic drinking "glasses" are already quite familiar. Many
have been made of polystyrene, and more recently more of
polyethylene. The former were too brittle and cracked
quickly in service, in addition to distorting when used for hot
liquids or washed in hot water. The polyethylene types were
too soft, squeezing out of shape in the hand, readily bitten
by children, and so low in abrasion resistance as to present
a poor appearance quite quickly. Polypropylene has taken
over several drinking-glass applications because it is almost
as hard and stiff and nearly as tough as poly-
as polystyrene,
ethylene. In addition, it has ample heat resistance for any
temperature likely to be used, and is very abrasion-resistant.
In addition to glasses of normal design, polypropylene is
being used in some ingenious double-walled glasses designed
to keep hot drinks hot and cold drinks cold. Since this glass
is made of two molded pieces that must fit into each other
accurately, the ability of polypropylene to make reproducible

parts is valuable.
Dinnerware
One field that has seen little penetration by plastics, and
practicallynone by thermoplastics is that of dinnerware.
It is amounts of "picnic" plates and cups
true that limited
have been made of polystyrene, but this was insignifi-
cant. The only real penetration of plastics in this field was
with melamine, a thermosetting resin that must be compres-
sion-molded. Both the melamine resin and the method of
molding are comparatively expensive. The great durability
236 Polypropylene
of this dinnerware has brought it many markets, especially

by institutional users where breakage is an important cost
item. It has also achieved some success as a second or "every-
day" table setting in the home. Good "china" has such a
strong place in the tradition of the American people that it
Figure 8.4. Polypropylene picnic setting. (Courtesy Spencer

Chemical Co.)
seems unlikely that any substitute, no matter how great its
practical superiority, will soon replace it entirely.

Polypropylene dinnerware, however, has already been
quite well received. The relatively inexpensive resin, made
by economical injection molding, makes it possible
fast-cycle,
to produce inexpensive items. The strength and abrasion
resistance of polypropylene should make it as durable as
melamine. In addition, polypropylene is enough stronger
and tougher than melamine to permit production of thinner-
walled and more graceful pieces. Melamine, because of its
strength limitation and the difficulty of making complex
shapes by compression molding, was limited to rather thick

and stolid designs, reminiscent of cheap stoneware rather
than elegant china. Polypropylene is free from such limita-
tions. It cannot be made quite as thin as the most delicate
porcelain teacup because it is a little too flexible, but
it is adequately stiffmoderate thicknesses. The free-
at very
flowing properties of polypropylene make the molding of the
most complex shapes quite easy. Polypropylene should con-
tinue its growth in this field. Figure 8.4 shows a complete
picnic setting of polypropylene.
Kitchenware
Polypropylene is falling heir to the upgrading trend that
carried polyethylene into so many kitchenware items. At pres-
ent, only a few are produced in polypropylene, but these are
generally by firms emphasizing quality. Almost any kitchen-
ware item is better, if perhaps at present prices a little more
expensive, in polypropylene. Mixing bowls, pitchers, dish-

pans, measuring spoons, funnels, pails, water bottles, colan-
ders, and many other such items are natural applications for
polypropylene, some having been marketed and many more
being in the process of development.
Polypropylene also makes excellent handles of all sorts
knife, fork,and spoon handles, and handles for strainers,

ladles, and can openers, for instance. The kitchenware
handles can be washed in an automatic dishwasher without
fear of softening or distorting them.
A line of polypropylene-handled paintbrushes has also
been introduced. These handles are attractive and will retain
their original appearance indefinitely, because the color is all
the way through —
not a coating. They will not scratch or mar
easily, and they are not attacked by any materials with which
they will come in contact.
Their thermoplastic nature makes it possible to fasten
238 Polypropylene
handles very solidly to the article, either by molding them in

place or by softening them for insertion in the piece. This
makes for economical mounting without need of extra parts,
and in a single quick operation. Although the polypropylene
handle will cost more than a painted wooden one, the rapid
assembly may save a good part of the extra cost.
Figure 8.5. A polypropylene basin, which can be sterilized.

{Courtesy Nalge Co.)
At present, it appears that some of the very largest mold-

ings, such as garbage cans, laundry baskets, etc., are difficult
to make in presently available polypropylene, although items
as large as baby's bathtubs have been made of polypropylene
in Europe. As molding and resin technology advance, these
also should be likely polypropylene applications.
Figure 8.5 shows a polypropylene basin suitable for steri-
hzation.
SANITARY PRODUCTS
Hospital and sickroom equipment that must be steriHzable

has, until recently, been beyond the capabilities of thermo-
plastic materials. Recently, nylon has made a little headway
in this field, but polypropylene should be much more success-
ful. In spite of the excellent qualities of nylon sanitary ware,
Figure 8.6. Polypropylene sanitary ware. (Courtesy Montecatini)
it is just too expensive. Polypropylene articles can be pro-

duced much more economically.
For most purposes the polypropylene article will be just
as good as the nylon. For some purposes the superior mois-
240 Polypropylene
ture resistance of the polypropylene makes it even better.

It will withstand sterilization at any ordinarily used steam
pressure, being entirely free of the hydrolysis that deteriorates
nylon on repeated steam sterilization. It will not chip like
enamel, or dent like aluminum. It is lightweight and easy
to clean, and can be made in attractive colors.
One of the oldest plastic applications, the toothbrush
handle, has been made out of a wide variety of plastics during
the development of the industry. It seems quite likely that
polypropylene will be able to take a large share of this
business. Figure 8.6 shows some sanitary items and some
toothbrushes made of polypropylene.
A related item made in this country is a carafe and tumbler
set for hospital use. The carafe has a disposable plastic-film
liner which assures clean water at all times without daily
sterilization. When the patient leaves the hospital, carafe and
tumbler must, of course, be sterilized by autoclaving.
POLYPROPYLENE LABORATORY WARE
One of the first American applications of polypropylene

was in laboratory ware. Previous experience with polyethylene
laboratory ware had shown that there were many applica-
tions where the plastic is better than glass. The superior heat
resistance and strength of polypropylene obviously extend
this range of usefulness considerably.
The first uses were those where glass is unsuitable, such
as procedures using hydrofluoric acid or other fluorides that
attack glassware. Many procedures that can be carried out
perfectly wefl in glass, however, are preferably done in poly-
propylene, simply because it is less fragile. Polypropylene
beakers are not recommended for heating over direct flame
or even a hot plate, because their thermal conductivity is so
low that the outside will overheat; however, hot water can
be poured into polypropylene beakers, and exothermic reac-

tions resulting in boiling-water temperatures can be safely
carried out in them.
Most pieces of laboratory apparatus never are subjected to
flame temperatures, but often experience rough handling.
Funnels are a typical example. Polypropylene funnels are
made in a large variety of sizes and shapes, including analyt-
WW ^ ^
i
Figure 8.7. Polypropylene laboratory funnels in several sizes.
(Courtesy Nalge Co.)
ical funnels designed specifically for use with the most pop-
ular standard sizes of filter paper. These funnels are less
expensive than glass ones and will not break if accidentally
dropped. Their heat resistance is quite adequate for the
filtration of boiling solutions.
Graduated cylinders are also available with dimensions in

accordance with federal specifications. In addition to un-
breakabihty, these cyUnders have the advantage that the
liquid level can be read more easily than in glass, because
water solutions in polypropylene have practically no menis-
cus; the water level is perfectly flat. Typical examples of
laboratory ware are shown in Figures 8.7 and 8.8.
In addition to beakers in the familiar glassware shapes.
242 Polypropylene
heavy-handled beakers are available in polypropylene which

are graduated both in EngUsh and metric units for approx-
imate measurement of liquid volume. These are especially
recommended for handling acids, alkalies, and photographic
chemicals.
Figure 8.8. A polypropylene graduate with graduations molded in.

(Courtesy Nalge Co.)
POLYPROPYLENE TOYS
The toy industry was one of the first to use plastics in

volume. The celluloid doll was a standard article for many
years,and polystyrene is used in large volumes for toys.
Recent years have seen a steady upgrading in toys, using
more durable and more expensive resins to replace polysty-
rene. Polyethylene, vinyls, styrene copolymers, and even

cellulosics have benefited from this trend. The low cost and
excellent physical properties of polypropylene make for a
natural continuation of the trend.
The current explosive growth of blow molding is opening
up tremendous toy markets for polypropylene. The strength
and resihence of polypropylene make it possible to blow
lightweight thin-walled toys of low cost and excellent dura-
bility. Dolls, animals, rocket models, and many other com-
plex hollow toys will be made in this way. For the present,
polypropylene is limited mostly to the high-quality segment
of the market, but once its good performance is recognized it
should penetrate widely.
Formed polypropylene sheet is excellent for the bodies of
toy wagons, automobiles, etc., and for parts of tricycles,
bicycles, etc.
The great volume in plastic toys is in injection-molded
articles. The high cost of molds tends
to retard changes
Using polystyrene or polyethylene molds with
in this field.
polypropylene increases the cost of the article, because no
advantage can be gained from the superior strength of the
polypropylene. To achieve the full advantages, molds will
have to be designed especially for polypropylene. This is
being done, and a gradual increase in injection-molded poly-
propylene toys can be expected. This will, however, probably
not be any great volume when compared with many of the
other applications mentioned. Some of the largest polystyrene-
toy volume, the model kits, is almost completely closed to
polypropylene because the basic appeal of these kits is home
assembly. This can be done very easily with polystyrene, but
a convenient and effective cement for polypropylene is not
available at present. Similarly, some of the largest vinyl-toy
volume is in the inflatables, which are not susceptible to poly-
propylene competition.
244 Polypropylene
The immediate volume for polypropylene in the

largest
toy field appears to be for dolls and doll parts. Blow-molded
polypropylene doll parts have had good success recently, and
it appears that the combination of low cost and excellent
serviceability will enable polypropylene to replace much of
the slush-molded vinyl plastisol now going into this business.
Polypropylene is also going into some applications where
its high strength and resilience make it superior to other
materials. A typical molded yoke for a pull toy
example is a
which is press-fitted to a wooden handle. With other plastics,
there were problems with breakage, and the handle loosened
because of cold flow. Polypropylene obviated this trouble.
This easy adaptability to snap-and-press fits is one great

advantage in this field.
INTEGRAL-HINGE APPLICATIONS
may be used for a variety of appli-

Since hinged articles
cations,from luggage to notebooks, it seems worth while to
make special mention of the one-piece molding with a narrow
thin section that acts as a hinge.
These designs were originally developed for polyethylene
and enjoyed a fair degree of popularity. The flex resistance
of polyethylene is, however, quite variable, and many such
hinged parts did not stand up too well, although some were
very good. Polypropylene seems much better adapted to this
application; the flex life of the hinge is very good, and,
because of the greater strength of the material, it has more
tear resistance as well.
The greater stiffness of the polypropylene molding makes
it possible to produce a precision-fitted piece of excellent
appearance, which will retain that appearance owing to its
good abrasion resistance. Thus hinged polypropylene cases

for high-value appUcations, where a long life with good

appearance retention is essential, should be in demand.
Several firms are working on luggage of this design. It
could greatly simplify luggage manufacture and produce a

superior piece at low cost.
Up to this time, relatively small cases, such as spectacle
cases and fishing-tackle boxes have been made in this way.
A luggage-type record-carrying case with an integral hinge
has also appeared.
9. FUTURE DEVELOPMENTS
There are many kinds of future developments coming in

polypropylene.The commercial development, as more and
more producers put in plants, and various phases of the
market are tested, is one kind. The technical developments,
as the tremendous versatility of the material is exploited to
make a wider range of products, vîll be equally important.
New ideas in processing technology, as applications of poly-
propylene multiply, constitute a third class and applications a
fourth. We will start with the commercial phase.
COMMERCIAL DEVELOPMENT
Development of the Industry
It seems very likely that the development of the poly-

propylene industry will see a marked departure from the
pattern that has been characteristic of the plastics industry
during the past three decades. The traditional pattern of a
large chemical company making resin by mass-production
methods and selling this raw material to a host of small
molders, extruders, and fabricators who make finished or
semifinished products from which they market in a Umited
it,
geographical area, has already shown its inadequacy in the

case of polyethylene.
The polyethylene-film markethad grown in size and com-
plexity to the point where the limited financial and technical
resources of the film-extrusion industry could no longer keep
246
Future Developments 247
up with it. The material manufacturers found themselves sup-

porting large technical staffs and great development labora-
tories which had no other purpose than furnishing tech-

nical support for their customers. The processor was no longer
able to afford the technical staff essential for him to remain
in business.
In addition, resin suppliers, by credit arrangements and
otherwise, found themselves supplying a large part of the
financing of the industry as well. This meant that they were
bearing most of the expenses of the film industry without
having any control over it, or making any profit from it,
except in their sales.

This resulted in a sweeping wave of integrations in which
the resin producers, for all practical purposes, took over the
film industry. Most of the few surviving film extruders were
absorbed by other large corporations who will, in all prob-
ability, integrate backward and start making resin, as has
happened with other plastics. At least one large molder has
already done this with polystyrene, and the vinyl industry has
seen similar developments.
Except for the injection-molding phase, the polypropylene
industry will be integrated from the start. Montecatini is
setting the pattern, and AviSun is following it. The fiber and
film will be made by the same firm that makes the resin.
Blow molding may develop along similar lines. At least

temporarily, the injection-molding portion of the business
has been able to resist this tendency to some extent. The
tremendous variety of the molders products makes a national

market of the kind needed by the large corporation very
difficult to achieve. The molding industry has also shown a
greater ability to solve its own technical problems than have
the other parts of the plastics industry.
Integration in this industry has been in the other direction.
Large consumers of molded parts have set up their own mold-
248 Polypropylene
ing shops. The vacuum-forming industry is similarly charac-

terized by captive shops operated by the consuming in-
dustries.
Increasingly, the traditional custom molder and extruder
is being confined to small markets for specialty products, and
the large volume is all taken by integrated organizations.
Probably very few independent film producers will be
willing to undertake the cost of developing polypropylene-
film technology or markets, in the face of the large integrated
production now in near prospect. It is doubtful that the few
who try will benefit from it, unless they have great financial
resources.
The fiber industry will be completely integrated, except
perhaps for a little monofilament production which is affili-
ated with the consuming industries.
Any estimate of the polypropylene market that fails to
take into account this basic change in the character of the
plastics industry will be in serious error. This was, perhaps,
the basic error in linear-polyethylene market estimates. It was
not so much that the markets did not exist, but that the
consuming industries lacked the technical and financial re-
sources to develop them at anything like the speed necessary
to use the resin production capacity.
There is little sign that the polypropylene industry will
make a similar mistake. Facilities for processing the resin
will be built at the same time as the production facilities
and the resin will be sold as fiber, film, or other finished
or semifinished goods. The customers for these products will
be other large corporations who will use them in large volume
in their own manufacturing operations. This new industry
pattern will enable polypropylene to achieve the fantastic
growth predicted for it.
The small plastic processor who has filled thousands of

garages, lofts, and defunct textile plants in the past decades
has served his purpose in lifting plastics from a tiny special

business to a great mass-production industry. He must now
go the way of the family farm or the village gristmill.
Companies Entering Polypropylene Field

The list of companies entering the polypropylene picture
is impressive. In addition to those listed in the historical
section as having announced plans to construct plants, the
following have indicated in one way or another that they are
going to manufacture polypropylene:
E.I. duPont de Nemours & Co.
Union Carbide Plastics Co.

U.S. Industrial Chemicals Div. of National Distillers
Phillips Petroleum Corp.
Monsanto Chemical Co.
Grace Chemical Co.
Many others are known to be active, but their intentions are

not yet clear.
The Rexall Company has recently announced that it will
produce polypropylene. This company has for several years
been acquiring plastics-consuming companies, and now owns
important film and bottle-blowing operations. This is an
example of the integrating trend where a large consumer
starts to make resin. RexaU has not made any specific state-
ment regarding the timing or the size of its projected produc-

tion operations except that they will be substantial.
Fibers. The polypropylene fiber field is beginning to show
signs of developing as more companies announce their plans.
Reeves Brothers, long active in the monofilament field,
started production in August, 1959, of low-denier polypro-

pylene fiber. This material is trade marked "Reevon" and has
had some success in rugs, upholstery fabric and padding, and
250 Polypropylene
batting for pillows, comforters, and cushions. It is available

from 3 denier up as staple and multifilament yarn.
AviSun Corporation has announced the name "Olane" for
its new polypropylene fiber. Production from a pilot plant
at New Castle, Delaware, is expected "early in 1960."

Beaunit Mills will start making polypropylene fiber in
February, 1961. They have bought machinery expected to
give an annual capacity of 12 million pounds of staple fiber
a year.
Beaunit will buy polymer to make the fiber from anyone
who can supply it, thus breaking the pattern of close tie-ins
between polymer producer and fiber producer that has been
characteristic of developments so far.
The United States Rubber Company has started to market
polypropylene fiber. Although no announcement of produc-
tion facilities has been made, it seems evident that, if the
marketing program is successful, they will manufacture both
fiber and resin.
Capacity Prospects
The development of polypropylene will not be held back

by lack of work or money. Capacities, even of those already
announced, are not always known, and the timing of new
capacity can only be estimated. There could, however, easily
be over 500 million pounds of polypropylene a year available
by the end of 1963.
Such a capacity expansion would dwarf that of linear poly-
ethylene, which shot up to about 300 million pounds in the
first two years but has grown little since.
It is almost inconceivable that a market of this magnitude
could be developed in the next four years. Linear polyethylene

had the fastest initial growth of any plastic in history and
took four or five years to reach the 1959 sales of 83 million
pounds. Despite optimistic predictions of accelerated growth,
it seems unlikely that markets for the 300-milHon-pound

capacity will be reached in less than four or five years more.
It is only the change in the industry pattern and the
difference in the approach to the marketing problem indicated
by the polypropylene producers that give any hope that poly-
propylene will be able to achieve the goals set for it.
Market Prospects
It is customary to estimate markets by estimating the rate
of growth of the economy, and of the particular industry,
and then applying suitable factors to present production. This
is evidently useless at this stage, since no reasonable base
has been established, and, in order to come anywhere near

the expectations held for it, polypropylene must grow as no
plastic has ever before grown in history. Hercules Powder
reported capacity operation for the last quarter of 1959. This
plant had been described as a 20-million-pound plant when
itwas constructed, but it is beUeved to be considerably larger.
Montecatini has also been selling a small amount of material
in this country, and AviSun went into production in August,
1959. It is doubtful, however, that a total of 10 million
pounds of polypropylene was sold in 1959.
The annual rate at the end of that year may have been up
to 30 million pounds a year. If this is true, it represents a
phenomenal growth and acceptance of a new material, partic-
ularly as this includes only monofilament and molding
material. Film and true fiber markets have not yet been
touched.
Some people in the industry are confidently predicting
billion-pound sales sometime in the mid 60's. It seems quite
likely that the production capacity will be available. Whether
the sales will or not is another matter. It is true that polyethy-
lene sales have grown at an annual rate of about 200 million
pounds a year since 1955, and at such a rate for polypropy-
:
252 Polypropylene
lene would reach 1 billion in 1965, but this was only done
it
after polyethylenehad established a solid technological base

through years of experience, and the production capacity of
the consuming industries has been under constant strain to
achieve these totals.
The big difference is that the polypropylene industry shows
no intention of waiting for the consuming industry to build
up the capacity to consume the resin. The resin producers
themselves are building the consuming plants. The only prob-
lem will be marketing the goods.
All things considered, the billion-pound goal is very con-
servative, and polypropylene will probably exceed this goal
eventually; however, it appears more likely that the time for

its achievement will be late 60's rather than middle.
A possible market timetable might as follows
1960 30,000,000 lb
1961 100,000,000 lb
1963 250,000,000 lb
1968 1,000,000,000 lb
This would be an unprecedented rate of growth, but the

power of the organizations behind the development of poly-
propylene is such that it may be possible.
Price Prospects
The intention of polypropylene producers to go after mass

markets is shown by their willingness to reduce prices even
in the initial stages of market development. At present, poly-
propylene has a premium of 7 cents over linear polyethylene,
but this cannot be expected to last when competition becomes
acute. A reasonable estimate of price for the near future
is that producers will try to maintain the present IVz-CQni
between high-pressure and linear polyethylene,
differential
and perhaps about the same premium for polypropylene over
the linear polyethylene.
As noted before, this resin price is really of little impor-

tance as such, as the greatest part of the polypropylene resin
produced will probably never change hands as resin.
The important facts are that polypropylene film will be
cheaper than cellophane and that polypropylene fiber will be
cheaper than any other synthetic. Montecatini has already put
a 60-cent lb price on its fiber which, considering the weight
advantage, puts it in a class with viscose rayon. The ultimate
price may be much lower.
TECHNICAL DEVELOPMENTS
The prospects for technical developments in polypropylene

are perhaps the most interesting of all. Actually, a good deal
of the material in this book has described future possibilities
rather than present actualities.
There are two broad classes of technical developments to
be considered —
developments in the resin, or resin tech-
nology, and developments in processing or application tech-
nology.
Developments in Resin Technology

Present polypropylene applications are all concerned with
the largely isotactic, hard, stiff resin that was the first one on
the market. Polypropylene is capable of tremendous variation
simply in degree of tacticity. It seems certain that products
of lower tacticity will be developed and tried in certain
markets. For instance, a flexible polypropylene might be de-
veloped to compete for many markets held by vinyls and
rubbers.
Polypropylenes of practically 100 per cent isotactic
polymer have also been produced. When these are made in
high molecular weights, they produce materials much stiff er
and stronger than any that have been described here. Process-
254 Polypropylene
ing problems will prevent their wide acceptance, but for

high-value applications the processing, difficulties can be
overcome.
This is particularly true because the typical polypropylene
processor will not be the small firm limited both in finances
and technical resources that has processed other plastic
material, but will generally be one quite adequately financed
and having the support of large corporation laboratory and
engineering staffs. A processing problem that would be dif-
ficult or even impossible with conventional equipment used
in the traditional manner may be easily solved by firms of

this caliber.
Stereoblock Polymers. The stereoblock polymers men-
tioned in the section on polypropylene chemistry will cer-
tainly be produced commercially, and if they live up to their
promise of giving resins that behave lik6 a vulcanized elas-
tomer, without the need for the time-consuming vulcanizing
step, this could easily lead to a revolution in this field.
Copolymers. In addition to these variations which relate to

polypropylene as such, there will be great strides made in co-
polymerization. The stereospecific catalysts are well suited to
forming a variety of copolymers. A great number of these
have been made experimentally, and it is highly probable that
many technically valuable ones will be found. Readily dye-
able polypropylene may be produced by the inclusion of a
comonomer that has a strong affinity for dyestuffs in the poly-
merization. Polypropylene film that is printable and glueable
may be made of a copolymer. Some other physical-
also
property variation may be more readily made by copoly-
merization; permeability is an example. Specific resistance to
specific permeants may be made possible by certain copoly-
merizations.
Increased heat resistance, improved thermal and light
stability, improved low-temperature performance, and a host
of other developments can also be expected from copolymers.

Montecatini is already producing copolymers of ethylene
and propylene which can be vulcanized to give an excellent
elastomer. This is competitive with natural and synthetic
rubber in many fields. The precise direction of the rubber
industry as regards basic monomers cannot be clearly defined
at this time. It is, however, very clear that, whatever the
monomer base may be, stereospecific catalysts will be used,
and the materials will have their valuable properties by virtue
of the control of molecular configuration first demonstrated
with polypropylene.
High-pressure Polypropylene. There have been recent ru-
mors that a high-pressure process, similar to that used to
make polyethylene, is being developed for polypropylene.
There are serious theoretical problems in such a process.
Almost certainly a simple free-radical catalyst, such as is
used for polyethylene, would produce an atactic polypro-
pylene with few useful properties. Metallic catalysts, however,
such as are used in the solvent polymerization of polypropy-
lene, have been used in high-pressure reactors with some
success, and these might produce polypropylene with useful
properties. This would retain the high-capacity advantage of
the high-pressure reactor, but would still require the removal
of catalyst residues. This might be considerably more difiicult
in the bulk resin produced by the high-pressure reactor than

it is in the finely divided resin produced by present processes.
This is only one of many possible technological changes
"^--that could change the entire polypropylene picture in the
next few years.
Other Ordered Polymers. Since we are studying the first
great sterically ordered plastic, we are perhaps justified in in-

cluding in our considerations other plastics of this type
that may be expected. The rubbers produced from sterically
ordered diene polymers have already been mentioned. Mono-
256 Polypropylene
olefins higher than propylene can be polymerized into steri-

cally ordered polymers of valuable properties. Somewhat
surprisingly, polymers of higher melting point and greater
tenacity can be produced from some of the higher mono-
olefins.The monomers involved are not present in refinery
gases to quite the same extent as propylene, and pyrolytic
reactions producing them from saturated hydrocarbons are
rather more difficult; however, their production should not be
costly compared to the cost of many commonly used plastic
monomers.
Polybutene-1 is already being produced in pilot-plant quan-
titiesby Montecatini in Ferrara, Italy. Its usefulness for many

of the applications mentioned in this book for polypropylene
has been demonstrated. Petro-Tex Chemical is building a
pilot plant in Houston, Texas, to produce this polymer, and
many others are also interested. PetroTTex has been study-
ing this polymer since 1955, and they feel that it has great
possibilities in pipe and film. Especially for the latter use,
superior tear strength recommends it over polypropylene.
Many of the traditional monomers such as styrene and the
acrylates also give sterically ordered polymers of vastly dif-
ferent properties from those of their ordinary random poly-
mers. Certainly many valuable products will be developed
from this tremendous range of possibilities.
Polymer Blends. There has also been an increasing interest
in simple blends of polymers. The success of blends of linear
and high-pressure polyethylene has aroused great interest in
this very simple way of obtaining variations in polymer prop-
erties. Polypropylene is closely enough related to polyethylene
so that blends of the two can easily be made. Although many

of these blends exhibit properties that are only an average of
the two materials, or worse, there are some blends that appear
to have valuable special properties.
Blends of polypropylene with elastomers such as butyl
rubber give considerable promise as a means of improving

the low-temperature brittleness of polypropylene. As was the
case with polyethylene and polystyrene, this sort of blend
will probably be only a temporary measure until the time
when a more sophisticated answer can be found in copolymer-
ization or in other means of controlling the structure of the
molecule.
The use of reinforcing fillers to enhance the strength and
dimensional stability of polypropylene is a highly probable
development; also, polypropylene foams are very promising
and, as yet, completely unexploited. It is possible to foam
polypropylene by any of the techniques used for other thermo-
plastics, and its strength, light weight, and abrasion resistance
should give these foams wide utility.
It is probable that all these avenues toward fitting poly-

propylene more exactly to specific applications will be ex-
plored in the near future, as well as many more, some
perhaps now unknown.
DEVELOPMENTS IN PROCESSING TECHNOLOGY
Two developments in processing technology which high-

lighted 1959 have great implications for polypropylene. The
first is the growth surge in blow molding. This process, which
for years took some three per cent of the nation's poly-
ethylene, matching the growth rate of this skyrocketing ma-
terial was no mean feat, has suddenly taken off on an acceler-
ated expansion that may make it a real rival of injection
molding. Polypropylene an excellent blow-molding material
is
and should profit from this development.

The other feature of 1959 was the replacement of metal
detergent cans by containers of linear polyethylene. Poly-
propylene apppears to have superior properties for this appli-
cation, and will certainly offer stiff competition. Many other

258 Polypropylene
applications now being served by metal cans will be vulner-

able to competition from polypropylene containers as this
technology develops. The all-plastic aerosol containers which
have been much discussed as a possible nylon application
may be more nearly economically feasible using polypro-
pylene.
Biaxially Oriented Pipe
A very interesting technical development being exploited

inGermany is a process for making biaxially oriented pipe.
The great gain in strength that polypropylene gets from
biaxial orientation means that this process should broaden
polypropylene applications, not only in strong lightweight
pipe but also as a source of strong cylinders for a variety of
purposes, such as can bodies.
A recent announcement of the Kordite Company may well
be the beginning of an entirely new development in poly-
propylene film. They are offering 0.5-mil biaxially oriented
polypropylene film that is coated on both sides with a thermo-
plastic resin which heat-seals at well below the melting point
of the polypropylene. This makes it possible to heat-seal at
temperatures of 250° to 350°F, and, even more important,
the seal can be made without melting the body of the resin.
This makes it possible to use this resin on machinery which
has sliding-type sealer bars without the film sticking to the
bar and tearing. Many overwrap machines designed for use
on cellophane and coated papers use such heater bars, and
their use on ordinary polypropylene film requires expensive
conversion of the equipment. The coated polypropylene film
should be usable without any such conversion.
The film is, at present, being offered at prices slightly
below those of the premium grades of cellophane with which
it competes, and officials of the Kordite Company have pre-
dicted that it will eventually be the cheapest available film.

It is quite possible that this and similar developments will

greatly facilitate the conversion of the packaging industry to
polypropylene.
Cold Stamping
Another processing development that has seen only small
may well assume major dimen-
use with previous plastics but
sions with polypropylene is cold stamping. Polypropylene, at
temperatures well below its softening point, can be formed and
stamped in ways entirely analagous to sheet-metal forming
and stamping. This process has the advantage that, when
properly performed, it orients the polypropylene and increases
its strength. Since the part is entirely rigid as soon as it is
formed, no cooling is required, and cycles can be much

shorter than with traditional hot-forming methods. This
makes the process very inexpensive and especially suitable
to large-scale mass production.
Polypropylene Paper
There are also some entirely new fields that may be
important in polypropylene. For instance, Montecatini has
a patent on a process for making paperlike polypropylene
film,which can be written and printed on just like paper.
Paper made from synthetic fibers has been known for years,
and polypropylene fibers, being highly oriented, will fibrillate
under beating as well as any other synthetic. Such paper may
well have considerable specialty uses.
The material made by the Montecatini process mentioned,
however, is not a true paper in this sense, but a film made
with the use of solvents, which is very different from film
drawn from hot melt. Such film will, of course, be more ex-
pensive than paper, but there are many applications for
paper where price is unimportant. For instance, present evi-
dence leads us to believe that, in the absence of direct sun-
260 Polypropylene
light, polypropylene is much more durable than paper, neither

drying out and becoming brittle nor being attacked by damp-
ness and microorganisms. It could well become the writing
base for valuable documents whose long preservation is nec-
essary. It is also possible that its wear resistance would be
enough better to justify its use on library or schoolbooks that
have a very heavy use.
Polypropylene is also entering into technology in forms
that are far from those mentioned here.
Polypropylene Waxes
Low-molecular-weight isotactic polypropylene waxes have
a great deal of promise. They have high melting points, great
surface hardness, and a low melt viscosity. Possible applica-
tions are polishing waxes and modifiers for other plastics,
coatings, etc. These waxes may be polymerized directly under
some conditions but are more conveniently made by thermal
cracking of high polymers.
Atactic polypropylene also has possibilities, one patented
use being as a thickener for oils and greases. It may also
enter the adhesives field, especially for adhesives suitable for
bonding polypropylene.
PROGRESS IN APPLICATION
The tendency toward integrated operations which will con-

centrate polypropylene processing into large organizations
will affect the pattern of growth in applications. Whereas the
logical customer for a small independent plastics processor
was a retail or wholesale marketing group dealing with an
end user, the large integrated processor will naturally look for
other equally large corporations as customers.
In addition to the packaging previously mentioned, these
customers will have need for component parts for their prod-
ucts. Examples of industries are machinery, appliance, auto-

motive, etc. These fields have already begun to use some
plastic parts but are still largely oriented toward the metal
trades from which they originated. To a great extent they
have been discouraged from considering plastic parts because
the independent plastic processor did not have the financial
resources to furnish the volume of parts required, or the tech-
nical resources to make them with the necessary control and
precision. This situation is rapidly changing, and these in-
dustries will soon either have suitably financed and techni-
cally competent suppliers, or they themselves will build
processing facilities.
The economic lever that will accomplish these changes is
that business will become increasingly competitive through

the 60's. The consumer will increasingly expect, and get, a
better bargain. With metals and traditional metals trades
facing mounting costs, the only recourse will be an increas-
ing use of plastics.
The building industry faces a similar challenge and will go
in the same direction. Up to the present time, the progress of
plastics in the building industry has been hampered by the
relatively high cost of plastic materials and the marginal
properties of most of them. Polypropylene has the combina-
tion of excellent physical properties with low cost that is
needed in this industry.
Plastics have also been hampered by the opposition of
the craftsman in the building trades to new materials whose
primary advantage is to reduce labor costs. As long as con-
struction performed mainly by small contractors operating

is
in local areas and using on-the-job production methods, poly-

propylene can be used in building merely in the small special
items such as are now being served by other plastics.
The building industry is not going to remain at this stage
of development very long. The prefabricated house, which
262 Polypropylene
was an interesting curiosity only a few years ago, now rep-

resents a substantial industry, and a constantly growing pro-
portion of the new houses being built are more or less
prefabricated.With the increase of mass production and fac-
tory methods, the path is open for greatly increased use of
plastics.
The great traditional obstacle to the use of plastics in
building, and for that matter to any change or advance in
building practices, is the presence of building codes in many
communities that require the use of certain specific tradi-
tional materials.Although it would be foolish to expect this
obstacle to evaporate quickly, more and more communities
are showing a willingness to consider updating of building
codes to permit the use of modern materials.
There has also been an increasing trend toward the con-
solidationand unification of building codes which decreases
the number of authorities that have to be convinced of the
value of a change. In addition, the authorities in charge of
the consolidated codes aremore likely to be trained engineers
who will look proposed changes objectively, rather than
at
the local craftsmen or small contractors who dominate code
authorities at the local level and consider building codes
mainly as a means for protecting their traditional ways of
making a living. This will make it increasingly easier to in-
troduce new materials into the building trades.
A few specific applications that have been mentioned so
recently that their significance is difficult to assess, but which
appear to be potentially important, are discussed in the fol-
lowing pages.
Thermoplastic Recording Tape
The use of polypropylene film as a base for magnetic-

recording tape has already been mentioned. A newly de-
veloped tape-recording process has recently been announced
that may broaden this market considerably. This is called

thermoplastic tape recording. In this process an electrical
signal is used to modulate the discharge from an electron gun
which is directed at a thermoplastic tape. The discharge of
the electron gun is captured by the plastic, setting up electro-
static stresses in the material. The plastic is then softened
enough to permit these electrostatic stresses to deform the
surface into a series of fine ripples. These ripples can be
reconverted into electrical impulses by an optical system which
uses the ripples as a diffraction grating to modify a light
beam sent through the tape. In its present form the heating
is by radio-frequency heaters, so the low dielectric loss factor
of polypropylene makes it unsuitable for recording. The great
potential market here, however, is not in the recording tape
but in the fact that a metaUic master can be made from these
tapes, and used to produce a large number of reproductions
in a manner analogous to the production of phonograph rec-
ords. For this purpose polypropylene tape would be entirely
satisfactory. The thermoplastic tape can store a good deal
more information on a given area than can magnetic tape,
and should be cheaper. Both audio and video signals can be
stored. This system brings the home video player much nearer.
Polypropylene Fiber as Tire-Cord Material
Preliminary testing is in progress to determine if poly-

propylene will join in the fierce fight now going on between
rayon and nylon for the automobile-tire business.
The high strength and resilience of polypropylene fiber
make it very attractive for this application, and its poten-
tially low cost makes it able to enter this strongly cost-com-
petitive situation with reasonable profit expectations.
The main drawback of polypropylene fiber in this applica-
tion is its comparatively low softening point. Heat build-up
is quite severe in automobile tires, and there is some question
264 Polypropylene
about the ability of the polypropylene fiber to stand up. It is,

however, quite probable th^t the heat resistance of polypro-
pylene fiber can be improved beyond its present temperature
range, and make it satisfactory for this appHcation. If this is
not possible it is quite likely that other isotactic polymers,

known to have superior heat resistance, will be developed
for this purpose.
No mention whatsoever has been made of the many "blue
sky" possibilities open to polypropylene. This is because they
would take a book in themselves. We are entering a synthetic-
remake the whole structure and
materials revolution that will
operation of our society. The
industrial and mechanical revo-
lutions were only new ways of handling and using materials
that have been known for centuries.
The primitiveness of our culture, from a raw-materials
point of view, is quite amazing if one stops to analyze it.
The primary metals — iron, copper, lead, zinc, etc. —long pre-
ceded industrialization. Of the mass-produced metals, only
aluminum is modern. Our home-building materials, wood and
brick, are the most primitive possible, going back to the
beginning of civilization, and the Romans could make con-
crete. Fabrics are still largely plant and animal hairs twisted
together, the way they were at the dawn of civilization.
We are currently seeing the end of this dependence on
primitive materials. In the next few decades the synthetics
will take over and transform life and technology more than
it has been transformed in all history before. Polypropylene
is one of the first of the great new materials that will make
this transformation.
1
INDEX
Abrasion resistance, 10, 14, 16 Containers, molded, 189

Aerosol containers, 187 Cooling towers, 210
Air knife. 111, 116 Copolymers, 254
Apparent density, 12 Corrosive chemical uses, 192
Appliance parts, 210 Creep, 26
Atactic polymer, 66 Crystallinity, 75
Automotive parts, 216 Crystallite size, 91
AviSun Corp., 7 Crystal structure, 71
Biaxial orientation, 53, 58, 122, Deflection temperature, 14, 16

258 Deformation under load, 10
Blow molding, 155 Density, 13, 16
Bottles, 184 Dielectric constant, 11, 15, 17, 60
Boxes, 190 Dielectric strength, 10, 15, 60
Brittle point, 53 Dinnerware, 235
Building industry, 261 Diolefin polymers, 84
Bulk resistivity, 12 Dissipation factor, 11, 15
Burning rate, 13 Dow Chemical Co., 7
Burst strength, 62 Drinking glasses, 235
Capacity prospects, 250 Eastman Chemical Products Co.,

Carbon dioxide permeability, 58 7
Catalysts, 81,97 Elasticmodulus, 13, 16
Chill roll casting, 110 204
Electrical uses,
Closures, 188 Electronic components, 208
Coating, 128 Elongation, 10, 13, 16, 19
Cold stamping, 259 "Engel" process, 161
Coloring, 104 Environment, effect of, 3
Communications wire, 206 "Escon" resin, 13
Companies entering field, 249 Expansion coefficient, 10, 12, 14,
Compressive strength, 12, 14, 16 16
265
266 Index
Extractables, 80 Isotactic index, 46, 76

Extraction, 100 Izod impact, 10, 12, 16, 25, 51
Extrusion, 107, 120, 124
Extrusion coating, 128 Kitchenware, 237
Extrusion die design, 108, 114
Laboratory ware, 240
Light stabilizers, 41
Ferro Corporation, 105
Linear polyethylene, 1, 5, 22
Fibers, 4, 221, 226
Liners for tanks, 195
Film, 6, 54, 163
Loss factor, 27
Film extrusion, 109
Film insulation, 209 Machining, 160
Firestone Chemicals Co., 8
Magnetic tape, 215
Flame spraying, 161
Market prospects, 251
Flexural modulus, 11, 13, 49
Melt index, 13, 16
Flexural strength, 20
Melting point, 10, 14
Flow vs. temperature, 138
Modulus of elasticity, 13, 16
Fluidization on heating, 147
Moldability area, 144
Fluidized powder, 161
Mold design, 145
Furniture, 219
Mold shrinkage, 10, 13, 17, 143
Molding variables, 149
Gas permeability, 58 Molecular weight, 87
Gels in film, 118 Monofilament extrusion, 129
Monofilament uses, 223
Hardness, 10, 12, 13, 16, 20, 48 Montecatini, 4, 6, 12
Heat distortion temperature, 10, "Moplen," 12

16, 21 Multifilament yarn, 132
Heat resistance, 44
Natta, Professor, 2, 3, 83
Heat scalability, 57, 59
Nonwoven netting, 231
Hercules Powder Co., 10
High pressure process, 255 Optical activity, 74
Hot gas welding, 159 Ordered dienes, 3
Housewares, 234
Oriented 58
film,
Overwrap packages, 167
Immersion, effect of, 32 Oxidation, 42, 86
Industrial Rayon Corp., 8 Oxidation stabilizers, 43
Industry development, 246 Oxygen transmission, 58
In phase modulus, 29
Injection molding, 134 Packaging, 163
Integral hinges, 244 baked goods, 168
Intrinsic viscosity, 88 confectionery, 178
Index 267
dairy products, 179 Resin developments, 253
dried products, 166 Resistivity, 11, 17
fresh produce, 172 Rockwell hardness, 12, 20, 48
frozen foods, 174 Rope, 225
meat and poultry, 177
paper, 183
Sanitary products, 238
textile products, 180
Shear rate, shear stress, 140
tobacco, 182
Shear strength, 50
Paper, 259
Sheet extrusion, 124
Permeability. 77
Shoe parts, 231
resistance to
Silk like fibers, 228
chloroform. 37
Skin packaging, 154, 190
"Clorox," 40
Specific gravity, 10, 12
hexane. 38 '"^
Specific heat, 12, 16
hydrogen peroxide, 39
Specific heat vs. temperature, 127
isopropyl alcohol, 37
Specific volume, 12, 18
methyl alcohol, 36
Spencer Chemical Co., 7, 16
methyl-ethyl ketone, 35
Spherical venturi, 105
silicone oil, 36
Spherulites, 92
water, 34
Stabilizers, light, 41
Photographic film, 215
Standard Oil of New Jersey, 7, 13
Pipe, 6, 197, 258
Stereoblock polymers, 72, 254
Pipe extrusion, 125
Stereo-chemical fundamentals, 66
Polybutadiene. 85
Stiffness, 10. 12, 14, 16, 19
Polymer blends, 256
Stress cracking, 10. 13, 17
Polymerization, 96
Sulfochlorination, 87
"Poly-Pro," 16
Surface resistivity, 60
Powder, 161
Syndiotactic polymer, 70
Power factor, 12, 17
Synthetic rubber, 3, 84
Power wire; 204
Pressure forming, 153
Price prospects, 252 Tacticity, 65
Processing conditions, film, 122 Tanks, 194
Production, 94 Tensile modulus, 10, 16
"Pro-Fax," 10 Tensile strength, 10, 13, 16, 18
Propane propylene separation, 94 Textile machinery, 203
Puckering of film. 117 Thermal conductivity, 12, 14
Thermal expansion, 10, 16
Recording tape, 262 Thermoforming, 151
Relative volatility, propane-pro- Tire cord, 263
pylene, 95 Torsion modulus, 23
268 Index
Toys, 243 Water absorption, 10, 13

Trays, 190 Water bath extrusion, 1 19
Waxes, 260
Vacuum forming, 151 Weld values, 160
Valve gating, 141 Wool-like fabrics, 226
Valves, 196
Vicat softening point, 12, 14, 52
Viscosity, intrinsic, 88 Yarn, 132
Volume resistivity, 11, 14, 17, 60 Yield stress, 10, 13, 16, 47
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Connecticut
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-

REINHOLD PUBLISHING CORPORATION

REINHOLD PUBLISHING CORPORATION

All rights reserved

Library of Congress Catalog Card Number 60-53435

Printed in the United States of America

This series, which started in 1957, has now grown to greater

Acrylic Resins, Milton B. Horn

Cellulosics, Walter Paist

Epoxy Resins, Irving Skeist

Fluorocarbons, Merritt A. Rudner

Gum Plastics, M. Stafford Thompson

Metallizing of Plastics, Harold Narcus

Phenolic Resins, David F. Gould

Plastic Sheet Forming, Robert L. Butzko

Poly amide Resins, Don E. Floyd

Polyethylene, Theodore O. J. Kresser

Polystyrene, William C. Teach and George C. Kiessling

Polyurethanes, Bernard A Dombrow

Runnerless Molding, Ernest P. Moslo

SiUcones, Robert N. Meals and Frederick M. Lewis

In this day when scientific advances are looked upon with

taken almost entirely from Professor Natta's pubhcations,

The Hercules Powder Company was very kind in making

The only real possibility that polypropylene may fail to

fulfill present expectations is that closely related polyolefin

in the text; however, in many cases the information has been

tory at Orange, Texas, and Dr. G. Ham, Technical Director

5. Processing of Polypropylene 107

6. Packaging Applications 163

7. Applications of Polypropylene in the

8. Applications in Soft-Goods Industries 221

9. Future Developments 246

Polypropylene is a thermoplastic resin, and in this sense its

history starts with the first thermoplastics discussed in the

Some understanding of the major developments that oc-

necessary to appreciate the position of polypropylene.

long held by traditional materials such as paper, metals, etc.,

has caused people to be much more open minded regarding

faction with polyethylene articles has done much to erase the

group of sterically regulated polymers.

and duplicating processes heretofore impossible except within

Subsequent events, however, have shown that the most

of endless examples of stereospecific polymerization. The

Curiously enough, some of the most startling and perhaps,

expectations, and large-scale capacity has begun to come on

that was known to produce a useful addition polymer by any

strongly affect another great use of synthetic polymers in

it is quite impossible for problems of technology or custom

long to delay widespread use.

tional ways, but Montecatini has shown polypropylene fibers

In this country there has been a great deal of interest in

commercial product was polypropylene film for packaging

purposes, but it can hardly be doubted that it will also go

undoubtedly due to the overcapacity in the synthetic-fiber

a new material. In 1958 the synthetic-fiber industry operated

also closely linked with that of low-pressure polyethylene.

matter of fact it now appears that the major use of low-pres-

quite brief. Montecatini was the first commercial producer;