Fundamentals of Polymer Chemistry

1
Fundamentals of Polymer Chemistry

H. Warson
1 THE CONCEPT OF A POLYMER

1.1 Historical introduction
The differences between the properties of crystalline organic materials of low
molecular weight and the more indefinable class of materials referred to by
Graham in 1861 as ‘colloids’ has long engaged the attention of chemists. This
class includes natural substances such as gum acacia, which in solution are
unable to pass through a semi-permeable membrane. Rubber is also included
among this class of material.
The idea that the distinguishing feature of colloids was that they had a
much higher molecular weight than crystalline substances came fairly slowly.
Until the work of Raoult, who developed the cryoscopic method of estimating
molecular weight, and Van’t Hoff, who enunciated the solution laws, it was
difficult to estimate even approximately the polymeric state of materials. It also
seems that in the nineteenth century there was little idea that a colloid could
consist, not of a product of fixed molecular weight, but of molecules of a broad
band of molecular weights with essentially the same repeat units in each.
Vague ideas of partial valence unfortunately derived from inorganic chem-
istry and a preoccupation with the idea of ring formation persisted until after
1920. In addition chemists did not realise that a process such as ozonisation
virtually destroyed a polymer as such, and the molecular weight of the ozonide,
for example of rubber, had no bearing on the original molecular weight.
The theory that polymers are built up of chain formulae was vigorously
advocated by Staudinger from 1920 onwards [1]. He extended this in 1929 to
the idea of a three-dimensional network copolymer to account for the insolu-
bility and infusibility of many synthetic polymers, for by that time technology
had by far outstripped theory. Continuing the historical outline, mention must
be made of Carothers, who from 1929 began a classical series of experiments
which indicated that polymers of definite structure could be obtained by the
use of classical organic chemical reactions, the properties of the polymer being
controlled by the starting compounds [2]. Whilst this was based on research
in condensation compounds (see Section 1.2) the principles hold good for
addition polymers.
2 Fundamentals of polymer chemistry
The last four decades have seen major advances in the characterisation of
polymers. Apart from increased sophistication in methods of measuring molec-
ular weight, such as the cryoscopic and vapour pressure methods, almost the
whole range of the spectrum has been called into service to elucidate polymer
structure. Ultraviolet and visible spectroscopy, infrared spectroscopy, Raman
and emission spectroscopy, photon correlation spectroscopy, nuclear magnetic
resonance and electron spin resonance all play a part in our understanding of
the structure of polymers; X-ray diffraction and small-angle X-ray scattering
have been used with solid polymers. Thermal behaviour in its various aspects,
including differential thermal analysis and high-temperature pyrolysis followed
by gas–liquid chromatography, has also been of considerable value. Other
separation methods include size exclusion and hydrodynamic chromatography.
Electron microscopy is of special interest with particles formed in emulsion
polymerisation. Thermal and gravimetric analysis give useful information in
many cases. There are a number of standard works that can be consulted [3–6].
1.2 Definitions
A polymer in its simplest form can be regarded as comprising molecules of
closely related composition of molecular weight at least 2000, although in
many cases typical properties do not become obvious until the mean molec-
ular weight is about 5000. There is virtually no upper end to the molecular
weight range of polymers since giant three-dimensional networks may produce
crosslinked polymers of a molecular weight of many millions.
Polymers (macromolecules) are built up from basic units, sometimes
referred to as ‘mers’. These units can be extremely simple, as in addition
polymerisation, where a simple molecule adds on to itself or other simple
molecules, by methods that will be indicated subsequently. Thus ethylene
CH2 :CH2 can be converted into polyethylene, of which the repeating unit
is —CH2 CH2 —, often written as —CH2 CH2 n , where n is the number of
repeating units, the nature of the end groups being discussed later.
The major alternative type of polymer is formed by condensation polymeri-
sation in which a simple molecule is eliminated when two other molecules
condense. In most cases the simple molecule is water, but alternatives include
ammonia, an alcohol and a variety of simple substances. The formation of a
condensation polymer can best be illustrated by the condensation of hexam-
ethylenediamine with adipic acid to form the polyamide best known as nylon :
H H
H2N(CH2)6NH + HOOC(CH2)4CO.OH + HN(CH2)6NH2
1
= H2N(CH2)6NH.OC(CH2)4CONH(CH2)6NH2
+ H2O + H2O
The concept of a polymer 3
This formula has been written in order to show the elimination of water.
The product of condensation can continue to react through its end groups
of hexamethylenediamine and adipic acid and thus a high molecular weight
polymer is prepared.
Monomers such as adipic acid and hexamethylenediamine are described
as bifunctional because they have two reactive groups. As such they can
only form linear polymers. Similarly, the simple vinyl monomers such as
ethylene CH2 :CH2 and vinyl acetate CH2 :CHOOCCH3 are considered to
be bifunctional. If the functionality of a monomer is greater than two,
a branched structure may be formed. Thus the condensation of glycerol
HOCH2 CH(OH)CH2 OH with adipic acid HOOCCH2 4 COOH will give a
branched structure. It is represented diagrammatically below:
HOOC(CH2)4COOCH2CHCH2OOC(CH2)4COOCHCH2O
CH2O
O
CO
(CH2)4
CO
O
CH2 O
H COOC(CH2)4COOCH2CHCH2O
CH2
O
CO(CH2)4COO
The condensation is actually three dimensional, and ultimately a three-

dimensional structure is formed as the various branches link up.
Although this formula has been idealised, there is a statistical probability of
the various hydroxyl and carboxyl groups combining. This results in a network
being built up, and whilst it has to be illustrated on the plane of the paper,
it will not necessarily be planar. As functionality increases, the probability of
such networks becoming interlinked increases, as does the probability with
increase in molecular weight. Thus a gigantic macromolecule will be formed
which is insoluble and infusible before decomposition. It is only comparatively
recently that structural details of these crosslinked or ‘reticulated’ polymers
have been elucidated with some certainty. Further details of crosslinking are
given in Chapter 5.
Addition polymers are normally formed from unsaturated carbon-to-carbon
linkages. This is not necessarily the case since other unsaturated linkages
including only one carbon bond may be polymerised.
Addition polymerisation of a different type takes place through the opening
of a ring, especially the epoxide ring in ethylene oxide CH2.CH2. This opens as
O
—CH2 CH2 O—; ethylene oxide thus acts as a bifunctional monomer forming a
polymer as HCH2 CH2 On CH2 CH2 OH, in this case a terminal water molecule
being added. A feature of this type of addition is that it is much easier to
control the degree of addition, especially at relatively low levels, than in the
vinyl polymerisation described above.
Addition polymerisations from which polymer emulsions may be available
occur with the silicones and diisocyanates. These controlled addition poly-
merisations are sometimes referred to as giving ‘stepwise’ addition polymers.
This term may also refer to condensation resins. Further details are given in
Chapter 7.
2 ADDITION POLYMERISATION
Addition polymerisation, the main type with which this volume is concerned,
is essentially a chain reaction, and may be defined as one in which only a small
initial amount of initial energy is required to start an extensive chain reaction
converting monomers, which may be of different formulae, into polymers.
A well-known example of a chain reaction is the initiation of the reaction
between hydrogen and chlorine molecules. A chain reaction consists of three
stages, initiation, propagation and termination, and may be represented simply
by the progression:
Activation +M +M +nM
M M* M2* M3* Mn+3 etc.
The termination reaction depends on several factors, which will be discussed

later.
The mechanism of polymerisation can be divided broadly into two main
classes, free radical polymerisation and ionic polymerisation, although there
are some others.† Ionic polymerisation was probably the earliest type to be
noted, and is divided into cationic and anionic polymerisations. Cationic poly-
merisation depends on the use of catalysts which are good electron acceptors.
Typical examples are the Friedel–Crafts catalysts such as aluminium chloride
AlCl3 and boron trifluoride BF3 .
Monomers that polymerise in the presence of these catalysts have
substituents of the electron releasing type. They include styrene C6 H5 CH:CH2
and the vinyl ethers CH2 :CHOCn H2nC1 [7].
Anionic initiators include reagents capable of providing negative ions,
and are effective with monomers containing electronegative substituents such
† Some modern sources prefer to refer to addition polymerisation and stepwise polymerisation.
Addition polymerisation 5
as acrylonitrile CH2 :CHCN and methyl methacrylate CH2 :CCH3 COOCH3 .
Styrene may also be polymerised by an anionic method. Typical catalysts
include sodium in liquid ammonia, alkali metal alkyls, Grignard reagents and
triphenylmethyl sodium C6 H5 3 C-Na.
Amongst other modern methods of polymerisation are the Ziegler–Natta
catalysts [8] and group transfer polymerisation catalysts [9]. Ionic polymeri-
sation is not of interest in normal aqueous polymerisation since in general
the carbonium ions by which cationic species are propagated and the corre-
sponding carbanions in anionic polymerisations are only stable in media of
low dielectric constant, and are immediately hydrolysed by water.
2.1 Free radical polymerisation

A free radical may be defined as an intermediate compound containing an odd
number of electrons, but which do not carry an electric charge and are not free
ions. The first stable free radical, triphenylmethyl C6 H4 3 CÐ, was isolated by
Gomberg in 1900, and in gaseous reactions the existence of radicals such as
methyl CH3 Ð was postulated at an early date.
The decomposition of oxidizing agents of the peroxide type, as well as
compounds such as azodiisobutyronitrile
(CH3)2C.N:NC(CH3)2
NC CN
CN
which decomposes into two radicals, (CH3)2 C. and nitrogen N2 , is well-
known. Thus a free radical mechanism is the basis of addition polymerisation
where these types of initiator are employed. For a transient free radical the
convention will be used of including a single dot after or over the active
element with the odd electron.
A polymerisation reaction may be simply expressed as follows. Let R be a
radical from any source. CH2 :CHX represents a simple vinyl monomer where
X is a substituent, which may be H as in ethylene CH2 :CH2 , Cl as in vinyl
chloride CH2 :CHCl, OOC.CH3 as in vinyl acetate CH2 :CHOOCCH3 or many
other groups, which will be indicated in lists of monomers.
The first stage of the chain reaction, the initiation process, consists of the
attack of the free radical on one of the doubly bonded carbon atoms of the
monomer. One electron of the double bond pairs with the odd electron of
the free radical to form a bond between the latter and one carbon atom. The
remaining electron of the double bond shifts to the other carbon atom which
now becomes a free radical. This can be expressed simply in equation form:
H
R + CH2:CHX R.CH2C. 2
X
The new free radical can, however, in its turn add on extra monomer units,
and a chain reaction occurs, representing the propagation stage:
H H
R.CH2C. + n (CH2CHX R:(CH2CHX)n CH2C . 3
X X
The final stage is termination, which may take place by one of several
processes. One of these is combination of two growing chains reacting
together:
P
RCH2 CHXn CH2 CHX P
C RCH2 CHXm CH2 CHX
D RCH2 CHn CH2 CHXCH2 CHXCH2 CHXm R 4a
An alternative is disproportionation through transfer of a hydrogen atom:

P
RCH2 CHXn CH2 CHX C RCH2 CHXm
D RCH2 CHXn CH2 CH2 X C RCH2 CHXm CH:CHX 4b
A further possibility is chain transfer. This is not a complete termination

reaction, but it ends the propagation of a growing chain and enables a new
one to commence. Chain transfer may take place via a monomer, and may be
regarded as a transfer of a proton or of a hydrogen atom:
X X
Z-CH2C. + CH2CHX = Z-CH:CHX + CH3C. 5
H H
where Z is a polymeric chain.

Chain transfer takes place very often via a fortuitous impurity or via a
chain transfer agent which is deliberately added. Alkyl mercaptans with alkyl
chains C8 or above are frequently added for this purpose in polymerisation
formulations. A typical reagent is t-dodecyl mercaptan, which reacts as in the
following equation:
H
R(CH2CHX)nCH2C . + t-C12H25SH
6a
X
= R(CH2CHX)nCH2CH2X + C12H25S.
Chlorinated hydrocarbons are also commonly used as chain transfer agents,

and with carbon tetrachloride it is a chlorine atom rather than a hydrogen atom
that takes part in the transfer:
H
R(CH2CHX)n CH2C · + CCl4 = R(CH2CHX)n CHXCl + Cl3C· 6b
X
Most common solvents are sufficiently active to take part in chain transfer
termination, the aliphatic straight-chain hydrocarbons and benzene being
amongst the least active. The effect of solvents is apparent in the following
equation, where SolH denotes a solvent:
H
R(CH2CHX)n CH2C· + SolH = RCH2CHX)n CH2X + Sol· 6c
X
In all the cases mentioned, the radicals on the right-hand side of the equations
must be sufficiently active to start a new chain; otherwise they act as a retarder
or inhibitor (see the next section)
Derivatives of allyl alcohol CH2 :CHCH2 OH, although polymerisable by
virtue of the ethylenic bond, have marked chain transfer properties and produce
polymers of low molecular weight relatively slowly (see also Section 2.1.2).
Stable intermediate products do not form during a polymerisation by a free
radical chain reaction, and the time of formation of each polymer molecule is
of the order of 103 s.
Kinetic equations have been deduced for the various processes of polymeri-
sation. These have been explained simply in a number of treatises [10–13].
The classic book by Flory [10] derives these equations in greater detail.
A useful idea which may be introduced at this stage is that of the order of
addition of monomers to a growing chain during a polymerisation. It has been
assumed in the elementary discussion that if a growing radical M-CH2 CÐ is
considered, the next unit of monomer will add on to produce
H H H
M CH2 C C C ·
X H X
It is theoretically possible, however, for the next unit of monomer to add on,
producing
H H H
M CH2 C C C ·
X X H
The latter type of addition in which similar groups add in adjacent fashion is
known as ‘head-to-head’ addition in contrast to the first type above, known
as ‘head-to-tail’ addition. The head-to-tail addition is much more usual in
polymerisations, although in all cases head-to-head polymerisation occurs at
least to some extent.
There are various ways of estimating head-to-head polymerisation, both
physical and chemical. Nuclear magnetic resonance data should be mentioned
amongst the former. The elucidation of polyvinyl acetate CH2 CHOOCCH3 n
may be taken as representative of a chemical investigation. A head-to-tail
polymer when hydrolysed to polyvinyl alcohol would typically produce units
of CH2 CHOHCH2 CHOH. A head-to-head unit is CH2 CHOHCHOHCH2 .
In the latter case there are two hydroxyl groups on adjacent carbon atoms, and
the polymer is therefore broken down by periodic acid HIO4 , which attacks
this type of unit. It is possible to estimate the amount of head-to-head addition
from molecular weight reduction or by estimation of the products of oxidation.
2.1.1 Retardation and inhibition

If the addition of a chain transfer agent to a polymerising system works
efficiently, it will both slow the polymerisation rate and reduce the molec-
ular weight. This is because the free radical formed in the equivalent of
equation (6a) may be much less active than the original radical in starting
new chains, and when these are formed, they are terminated after a relatively
short growth.
In some cases, however, polymerisation is completely inhibited since the
inhibitor reacts with radicals as soon as they are formed. The most well known
is p-benzoquinone.
C C
O C C O
C C
This produces radicals that are resonance stabilised and are removed from a
system by mutual combination or disproportionation. Only a small amount
of inhibitor is required to stop polymerisation of a system. A calculation
shows that for a concentration of azodiisobutyronitrile of 1 ð 103 mole1 in
benzene at 60 ° C, a concentration of 8.6 ð 105 mole L1 h1 of inhibitor is
required [10]. p-Hydroquinone C6 H4 OH2 , probably the most widely used
inhibitor, only functions effectively in the presence of oxygen which converts
it to a quinone–hydroquinone complex giving stable radicals. One of the most
effective inhibitors is the stable free radical 2 : 2-diphenyl-1-picryl hydrazyl:
NO2
C6H5
N N NO2
C6H5
NO2
This compound reacts with free radicals in an almost quantitative manner to
give inactive products, and is used occasionally to estimate the formation of
free radicals.
Aromatic compounds such as nitrobenzene C6 H5 NO2 and the dinitroben-
zenes (o-, m-, p-)C6 H4 NO2 2 are retarders for most monomers, e.g. styrene,
but tend to inhibit vinyl acetate polymerisation, since the monomer produces
very active radicals which are not resonance stabilised. Derivatives of allyl
alcohol such as allyl acetate are a special case. Whilst radicals are formed
from this monomer, the propagation reaction (equation 3) competes with that
shown in the following equation:
Mx C CH2 :CHCH2 OOCCH3 D Mx H C H2 C.CH:CHOOCCH3 7
In this case the allylic radical is formed by removal of an alpha hydrogen

from the monomer, producing an extremely stable radical which disappears
through bimolecular combination. Reaction (7) is referred to as a degradative
chain transfer [11–14].
2.1.2 Free radical initiation

Initiators of the type required for vinyl polymerisations are formed from
compounds with relatively weak valency links which are relatively easily
broken thermally. Irradiation of various wavelengths is sometimes employed
to generate the radicals from an initiator, although more usually irradiation
will generate radicals from a monomer as in the following equation:

CH2 CHX!CH2 CHXŁ 8
The activated molecule then functions as a starting radical. Since, however,

irradiation is not normally a method of initiation in emulsion polymerisation, it
will only be given a brief mention. The decomposition of azodiisobutyronitrile
has already been mentioned (see Section 2.1), and it may be noted that the
formation of radicals from this initiator is accelerated by irradiation.
Another well-known initiator is dibenzoyl peroxide, which decomposes in
two stages:
C6 H5 CO.OO.OCC6 H5 ! 2 C6 H5 COOÐ 9a
C6 H5 COO. ! C6 H5 Ð CCO2 9b
Studies have shown that under normal conditions the decomposition proceeds
through to the second stage, and it is the phenyl radical C6 H5 . that adds
on to the monomer. Dibenzoyl peroxide decomposes at a rate suitable for
most direct polymerisations in bulk, solution and aqueous media, whether
in emulsion or bead form, since most of these reactions are performed at
60–100 ° C. Dibenzoyl peroxide has a half-life of 5 h at 77 ° C.
A number of other diacyl peroxides have been examined. These include
o-, m- and p-bromobenzoyl peroxides, in which the bromine atoms are
useful as markers to show the fate of the radicals. Dilauroyl hydroperoxide
C11 H23 CO.OO.OCC11 H23 has been used technically.
Hydroperoxides as represented by t-butyl hydroperoxide CH3 3 C.O.O.H
and cumene hydroperoxide C6 H5 C(CH3 .O.O.H represent an allied class with
technical interest. The primary dissociation
R.CX.O.O.H. ! R.CXO Ð C OHÐ
is by secondary decompositions, which may include various secondary reac-

tions of the peroxide induced by the radical in a second-order reaction and
by considerable chain transfer. These hydroperoxides are of interest in redox
initiators (see Section 2.1.3).
Dialkyl peroxides of the type di-t-butyl peroxide CH3 3 C.O.O.CCH3 3
are also of considerable interest, and tend to be subject to less side reactions
except for their own further decomposition, as shown in the second equation
below:
CH3 3 COOCCH3 3 ! 2CH3 3 COÐ 10a

CH3 3 CO. ! CH3 2 CO C CH3 Ð 10b
These peroxides are useful for polymerisations that take place at 100–120 ° C,
whilst di-t-butyl peroxide, which is volatile, has been used to produce radicals
for gas phase polymerisations.
A number of peresters are in commercial production, e.g. t-butyl perben-
zoate CH3 3 C.O.O.OC.C6 H5 , which acts as a source of t-butoxy radicals at
a lower temperature than di-t -butyl hydroperoxide, and also as a source of
benzoyloxy radicals at high temperatures. The final decomposition, apart from
some secondary reactions, is probably mainly
CH3 3 C.O.O.OCC6 H5 ! CH3 3 CO C CO2 C C6 H5 Ð 11
For a more detailed description of the decomposition of peroxides a mono-

graph by one of the current authors should be consulted [15]. Whilst some
hydroperoxides have limited aqueous solubility, the water-soluble initiators
are a major type utilised for polymerisations in aqueous media. In addition,
some peroxides of relatively high boiling point such as tert-butyl hydroper-
oxide are sometimes added towards the end of emulsion polymerisations (see
Chapter 2) to ensure a more complete polymerisation. These peroxides are also
sometimes included in redox polymerisation (see Section 2.1.3), especially to
ensure rapid polymerisation of the remaining unpolymerised monomers.
Hydrogen peroxide H2 O2 is the simplest compound in this class and is
available technically as a 30–40 % solution. (This should not be confused
with the 20–30 volume solution available in pharmacies.) Initiation is not
caused by the simple decomposition H2 O2 D 2 OHÐ, but the presence of a
trace of ferrous ion, of the order of a few parts per million of water present,
seems to be essential, and radicals are generated according to the Haber–Weiss
mechanism:
H2 O2 C Fe2C ! HO Ð CFe3C C HOÐ
The hydroxyl radical formed commences a polymerisation chain in the usual

manner and is in competition with a second reaction that consumes the radical:
Fe2C C HOÐ D Fe3C C OH Ð
When polymerisations are performed it seems of no consequence whether the

soluble iron compound is in the ferrous or ferric form. There is little doubt
that an equilibrium exists between the two states of oxidation, probably due
to a complex being formed with the monomer present.
The other major class of water-soluble initiators consists of the persulfate
salts, which for simplicity may be regarded as salts of persulfuric acid H2 S2 O8 .
Potassium persulfate K2 S2 O8 is the least soluble salt of the series, between 2
and 4 % according to temperature, but the restricted solubility facilitates its
manufacture at a lower cost than sodium persulfate Na2 S2 O8 or ammonium
persulfate NH4 2 S2 O8 . The decomposition of persulfate may be regarded as
thermal dissociation of sulfate ion radicals:
S2 O8 2 ! 2 SO4 .
A secondary reaction may, however, produce hydroxyl radicals by reaction

with water, and these hydroxyls may be the true initiators:
SO4 Ð C H2 O ! HSO4 C HOÐ
Research using 35 S-modified persulfate has shown that the use of a persulfate
initiator may give additional or even sole stabilization to a polymer prepared
in emulsion. This may be explained by the polymer having ionised end groups
from a persulfate initiator, e.g. ZOSO3 Na, where Z indicates a polymer residue.
A general account of initiation methods for vinyl acetate is applicable to
most monomers [16].
2.1.3 Redox polymerisation

The formation of free radicals, which has already been described, proceeds
essentially by a unimolecular reaction, except in the case where ferrous ions are
included. However, radicals can be formed readily by a bimolecular reaction,
with the added advantage that they can be formed in situ at ambient or even
subambient temperatures. These systems normally depend on the simultaneous
reaction of an oxidizing and a reducing agent, and often require in addition a
transition element that can exist in several valency states. The Haber–Weiss
mechanism for initiation is the simplest case of a redox system.
Redox systems have assumed considerable importance in water-based
systems, since most components in systems normally employed are water
soluble. This type of polymerisation was developed simultaneously during
the Second World War in Great Britain, the United States and Germany,
with special reference to the manufacture of synthetic rubbers. For vinyl
polymerisations, as distinct from those where dienes are the sole or a
major component, hydrogen peroxide or a persulfate is the oxidizing moiety,
with a sulfur salt as the reductant. These include sodium metabisulfite
Na2 S2 O5 , sodium hydrosulfate (also known as hyposulfite or dithionite)
Na2 S2 O4 , sodium thiosulfate Na2 S2 O3 and sodium formaldehyde sulfoxylate
Na(HSO3 .CH2 O. The last named is one of the most effective and has
been reported to initiate polymerisations, in conjunction with a persulfate, at
temperatures as low as 0 ° C. In almost all of these redox polymerisations,
a complete absence of oxygen seems essential, possibly because of the
destruction by oxygen of the intermediate radicals that form.
However, in redox polymerisations operated under reflux conditions, or in
otherwise unsealed reactors, it is often unnecessary in large-scale operations to
continue the nitrogen blanket after polymerisation has begun, probably because
monomer vapour acts as a sealant against further oxygen inhibition.
There have been relatively few detailed studies of the mechanisms of redox
initiation of polymerisation. A recent survey of redox systems is available [17].
The review already quoted [15] gives a number of redox initiators, especially
suitable for vinyl acetate, most of which are also suitable for other monomers.
Since almost all such reactions take place in water, a reaction involving ions
may be used as an illustration. Hydrogen peroxide is used as the oxidizing
moiety, together with a bisulfite ion:
H2 O2 C S2 O5 2 D HO Ð C HS2 O6 Ð
The HS2 O6 represented here is not the dithionate ion, but an ion radical whose
formula might be
O− O−
S O S.OH
O O
Alternatively, a hydroxyl radical may be formed together with an acid dithionate

ion. Some evidence exists for a fragment of the reducing agent rather than the
oxidizing agent acting as the starting radical for the polymerisation chain. This
seems to be true of many phosphorus-containing reducing agents; e.g. hypophos-
phorous acid with a diazonium salt activated by a copper salt when used as an
initiating system for acrylonitrile shows evidence of a direct phosphorus bond
with the polymer chain and also shows that the phosphorus is present as one
atom per chain of polymer [18]. Many of the formulations for polymerisation
quoted in the various application chapters are based on redox initiation.
2.2 Copolymerisation
There is no reason why the process should be confined to one species of
monomer. In general, a growing polymer chain may add on most other
monomers according to a general set of rules which, with some exceptions,
will be enunciated later.
If we have two monomers denoted by Mi and Mn and Mi Ð and Mn Ð denote
chain radicals having Mi and Mii as terminal groups, irrespective of chain
length four reactions are required to describe the growth of polymer:
Mi . C Mi ! K11 Mi Ð
Mi . C Mn ! K12 Mii Ð
Mii Ð CMii ! K22 Mii Ð
Mii Ð CMi ! K21 Mi Ð
where K has the usual meaning of a reaction rate constant. These reactions
reach a ‘steady state’ of copolymerisation in which the concentration of radi-
cals is constant; i.e. the copolymerisation is constant and the rates of formation
of radicals and destruction of radicals by chain termination are constant. Under
these conditions the rates of formation of each of the two radicals remain
constant and without considering any elaborate mathematical derivations we
may define the monomer reactivity rations r1 and r2 by the expressions
K11 K22
r1 D and r2 D
K12 K21
These ratios represent the tendency of a radical formed from one monomer
to combine with itself rather than with another monomer. It can be made
intelligible by a practical example. Thus, for styrene C6 H5 CH:CH2 (r1 ) and
butadiene CH2 :CHCH:CH2 (r2 ), r1 D 0.78 and r2 D 1.39. These figures tend
to indicate that if we start with an equimolar mixture, styrene radicals tend to
copolymerise with butadiene rather than themselves, but butadiene has a slight
preference for its radicals to polymerise with each other. This shows that if we
copolymerise an equimolar mixture of styrene and butadiene, a point occurs
at which only styrene would remain in the unpolymerised state. However,
for styrene and methyl methacrylate, r1 D 0.52 and r2 D 0.46 respectively.
These two monomers therefore copolymerise together in almost any ratio.
As the properties imparted to a copolymer by equal weight ratios of these
two monomers are broadly similar, it is often possible to replace one by the
other on cost alone, although the inclusion of styrene may cause yellowing of
copolymer films exposed to sunlight.
Nevertheless, if an attempt is made to copolymerise vinyl acetate with
styrene, only the latter will polymerise, and in practice styrene is an
inhibitor for vinyl acetate. The reactivity ratios, r1 and r2 for styrene
and vinyl acetate respectively have been given as 55 and 0.01. However,
vinyl benzoate CH2 :CHOOCC6 H5 has a slight tendency to copolymerise
with styrene, probably because of a resonance effect. If we consider the
case of vinyl acetate and trans-dichlorethylene (TDE) trans-CH2 Cl:CH2 Cl,
r1 vinyl acetate D 0.85 and r2 D 0. The latter implies that TDE does not
polymerise by itself, but only in the presence of vinyl acetate. Vinyl acetate,
on the other hand, has a greater tendency to copolymerise with TDE than with
itself, and therefore if the ratios are adjusted correctly all of the TDE can be
copolymerised.
Let us consider the copolymerisation of vinyl acetate and maleic anhydride:
O
r1 = 0.055, r2 = 0
CH C
O
CH C
O
Sometimes a very low r2 is quoted for maleic anhydride, e.g. 0.003. Vinyl
acetate thus has a strong preference to add on to maleic anhydride in a growing
radical rather than on to another vinyl acetate molecule, whilst maleic anhy-
dride, which has practically no tendency to add on to itself, readily adds
to a vinyl acetate unit of a growing chain. (Note that homopolymers of
maleic anhydride have been made by drastic methods.) This is a mathemat-
ical explanation of the fact that vinyl acetate and maleic anhydride tend to
alternate in a copolymer whatever the starting ratios. Excess maleic anhy-
dride, if present, does not homopolymerise. Surplus vinyl acetate, if present,
forms homopolymer, a term used to distinguish the polymer formed from a
single monomer in contradistinction to a copolymer. Styrene also forms an
alternating copolymer with maleic anhydride.
Only in one or two exceptional cases has both r1 and r2 been reported to
be above 1. Otherwise it is a general principle that at least one of the two
ratios is less than 1. It will be readily seen that in a mixture of two monomers
the composition of the copolymer gradually changes unless an ‘azeotropic’
mixture is used, i.e. one balanced in accord with r1 and r2 , provided that r1
and r2 are each <1.
Polymers of fixed composition are sometimes made by starting with a small
quantity of monomers, e.g. 2–5 % in the desired ratios, and adding a feedstock
which will maintain the original ratio of reactants. This is especially noted, as
will be shown later, in emulsion polymerisation. If it is desired to include the
more sluggishly polymerising monomer, and an excess is used, this must be
removed at the end, by distillation or extraction.
However, as a general principle it should not be assumed that, because
two or more monomers copolymerise completely, the resultant copolymer is
reasonably homogeneous. Often, because of compatibility variations amongst
the constantly varying species of polymers formed, the properties of the final
copolymer are liable to vary very markedly from those of a truly homogeneous
copolymer.
The term ‘copolymer’ is sometimes confined to a polymer formed from two
monomers only. In a more general sense, it can be used to cover polymers
formed from a larger number of monomers, for which the principles enunciated
in this section apply. The term ‘terpolymer’ is sometimes used when three
monomers have been copolymerised.
When copolymerisation takes place in a heterogeneous medium, as in emul-
sion polymerisation (see Chapter 2), whilst the conditions for copolymerisation
still hold, the reaction is complicated by the environment of each species
present. Taking into account factors such as whether the initiator is water or
monomer soluble (most peroxidic organic initiators are soluble in both), the
high aqueous solubility of monomers such as acrylic acid CH2 :CHCOOH and,
if partition between water-soluble and water-insoluble monomers is significant,
the apparent reactivities may differ markedly from those in a homogeneous
medium. Thus, in an attempted emulsion polymerisation, butyl methacrylate
CH2 :CCH3 COOC4 H9 and sodium methacrylate NaOOCCCH3 :CH2 poly-
merise substantially independently. On the other hand, methyl methacrylate
and sodium methacrylate will copolymerise together since methyl methacry-
late has appreciable water solubility [19, 20].
More unusually vinyl acetate and vinyl stearate CH2 :CHOOCC17 H35 will
only copolymerise in emulsion if a very large surface is present due to very
small emulsion particles (of order <0.1 m) or a class of emulsifier known as a
‘solubiliser’ is present, which has the effect of solubilising vinyl stearate to a
limited extent in water, increasing the compatibility with vinyl acetate which
is about 2.3 % water soluble.
Problems relating to copolymerisation in emulsion will be found in
Chapter 3 and Sections 2.2.1 and 8.5. For more advanced texts, see the
Appendix, Section 8.
2.2.1 The Q, e scheme

Several efforts have been made to place the relative reactivities of monomers on
a chemical–mathematical basis. The chief of these has been due to Alfrey and
Price [21]. Comparison of a series of monomers with a standard monomer is
most readily made by using the reciprocal of r with respect to that monomer; i.e.
the higher the value of 1/r the poorer the copolymerisation characteristics. Thus,
taking styrene as an arbitrary 1.0, methyl methacrylate 2.2 and acrylonitrile 20,
vinyl acetate is very high on this scale. However, the relative scale of reactivities
is not interchangeable using different radicals as references [22].
It has been observed that the product r1 r2 tends to be smallest when one of
the two monomers concerned has strongly electropositive (electron-releasing)
substituents and there are electronegative (electron-attracting) substituents on
the other. Thus alternation tends to occur when the polarities of the monomers
are opposite.
Alfrey and Price therefore proposed the following equation:
K12 D P1 Q2 expe1 e2
where P1 and Q2 are constants relating to the general activity of the monomers
M1 and M2 respectively and e1 and e2 are proportional to the residual elec-
trostatic charges in the respective reaction groups. It is assumed that each
monomer and its corresponding radical has the same reactivity. Hence, from
the reactions in Section 2.2,
r1 r2 D exp[e1 e2 2 ]
The product of the reactivity ratios is thus independent of Q. The following

equation is also useful:
Q1
Q2 D exp[e, e1 e2 ]
r1
A series of Q and e values has been assigned to a series of monomers by
Price [23]. Typical e values are 0.8 for butadiene, 0.8 for styrene, 0.3
for vinyl acetate, C0.2 for vinyl chloride, C0.4 for methyl methacrylate and
C1.1 for acrylonitrile.
Whilst the Q, e scheme is semi-empirical, it has proved highly useful in
coordinating otherwise disjointed data.
3 CHAIN BRANCHING; BLOCK AND GRAFT COPOLYMERS

3.1 Chain branching
Occasionally chain transfer (Section 2.1) results in a hydrogen atom being
removed from a growing polymer chain. Thus in a chain that might be
represented as CH2 CHXn , the addition of further units of CH2 :CHX might
P
produce an intermediate as CH2 CHXn .CH2 C.X.C.CH 2 CHX. A short side
chain is thus formed by hydrogen transfer. For simplicity, this has been shown
on the penultimate unit, but this need not be so; nor is there any reason why
there should only be one hydrogen abstraction per growing chain. From the
radicals formed branched chains may grow.
Chain branching occurs most readily from a tertiary carbon atom, i.e. a
carbon atom to which only one hydrogen atom is attached, the other group-
ings depending on a carbon to carbon attachment, e.g. an alkyl or an aryl
group. The mechanism is based on abstraction of a hydrogen atom, although of
Chain branching; block and graft copolymers 17
course abstraction can also occur with a halogen. atom. With polyvinyl acetate,
investigations have shown that limited chain transfer can occur through the
methyl grouping of the acetoxy group ÐOOCCH3 . The result of this type of
branching is a drastic reduction of molecular weight of the polymer during
hydrolysis, since the entire branch is hydrolysed at the acetoxy group at which
branching has occurred, producing an extra fragment for each branch of the
original molecule. It has also been shown that in a unit of a polyvinyl acetate
polymer the ratio of the positions marked (1), (2) and (3) is 1 : 3 : 1.
CH2 CH.OOCCH3
(1) (2) (3)
It is now known that there is significant chain transfer on the vinyl H atoms
of vinyl acetate [24].
Another method of forming branched chains involves the retention of a
vinyl group on the terminal unit of a polymer molecule, either by dispro-
portionation or by chain transfer to monomer. The polymer molecule with
residual unsaturation could then become the unit of a further growing chain.
Thus a polymer molecule of formula CH2 CHX—(Mp), where Mp represents
a polymer chain, may become incorporated into another chain to give a struc-
ture (Mq).CH2 .CX—(Mp)(Mr), where Mq and Mr represent polymer chains
of various lengths, that may be of the same configuration or based on different
monomers, depending on conditions.
Ethylene, CH2 :CH2 , which is normally a gas (b.p. 760 mm Hg: 104 ° C,
critical temperature 9.5 ° C) is prone to chain branching when polymerised by
the free radical polymerisation process at high temperatures and pressures,
most branches having short chains. In this case intramolecular formation of
short chains occurs by chain transfer, and is usually known as ‘back biting’.
CH2 CH3
CH2 CH2 (CH2)3
*CH CH *CH
2 2
CH3 CH3
(CH2)3 + n C2H4 (CH2)3
*CH *CH (CH CH ) E
2 2n
where E represents an end group. The carbon with the asterisk is the same
throughout to illustrate the reaction.
Excessive chain branching can lead to crosslinking and insolubility (Chapter
5). It is possible for chain branching to occur from completed or ‘dead’ molecules
by hydrogen abstraction, and although this impinges on grafting, it is treated as
a chain branching phenomenon if it occurs during a polymerisation.
3.2 Graft copolymers
The idea of a graft copolymer is a natural extension of the concept of chain
branching and involves the introduction of active centres in a previously
prepared chain from which a new chain can grow. In most cases this is an
added monomer, although two-polymer molecules can combine directly to
form a graft. The graft base need not be an ethylene addition polymer. Various
natural products, including proteins and water-soluble gums, have been used
as a basis for graft copolymers by formation of active centres.
A block copolymer differs from a graft in only that the active centre is
always at the end of the molecule. In the simplest case, an unsaturated chain
end arising from a chain transfer can act as the basis for the addition of
a block of units of a second monomer, whilst successive monomers or the
original may make an additional block. Another possibility is the simultaneous
polymerisation of a monomer which is soluble only in water with one which
is water insoluble, provided that the latter is in the form of a fine particle
size emulsion. Whether the initiator is water soluble or monomer soluble, an
extensive transfer through the surface is likely, with the continuation of the
chain in the alternate medium.
There are a number of ways of achieving active centres, many of which
depend on an anionic or cationic mechanism, especially the former. However,
since in water-based graft polymerisation only free radical polymerisations
and possibly a few direct chemical reactions involving an elimination are of
interest, the discussion here will be confined to these topics.
Graft centres are formed in much the same manner as points of branching,
with the difference that the graft base is preformed. It may be possible to perox-
idise a polymer directly with oxygen, to provide hydroperoxide O.OH groups
directly attached to carbon. This is facilitated, particularly, where numerous
tertiary carbon occur as, for example, in polypropylene CH2.CH . In
CH3
other cases the direct use of a peroxide type of initiator encourages the forma-
tion of free radicals on existing polymer chains. Particularly useful in this
respect is tert-butyl hydroperoxide, tert-C4 H9 .O.OH, because of the strong
tendency of the radical formed from it to abstract hydrogen atoms. Dibenzoyl
peroxide C6 H5 CO.O2 is also frequently used as a graft initiator. In aqueous
systems initiators such as tert-butyl hydroperoxide may be used in conjunction
with a salt of a sulfur-reducing acid to lower the temperature at which radicals
are generated.
Graft methods make it possible to add to polymers such as
butadiene–styrene chains of a monomer that is not normally polymerisable,
such as vinyl acetate. The polymerisation medium in which a graft can take
place is in general not restricted; the process may take place fairly readily in
emulsion. There is a vast amount of literature available on the formation and
properties of graft copolymers [25].
Polymer structure and properties 19
There are very often special considerations in respect of graft copoly-
merisations that take place in emulsion form, with particular reference to
water-soluble stabilisers of the polyvinyl alcohol type [26]. In some cases
halogen atoms may be removed by a radical. This occurs particularly with
polymers and copolymers based on vinyl chloride CH2 :CHCl, vinylidene chlo-
ride CH2 .CCl2 and chloroprene CH2 .CClCH:CH2 . Ultraviolet light and other
forms of irradiation are particularly useful in this respect.
Properties of graft copolymers are sometimes unique, and not necessarily an
intermediate or balance between those of polymers derived from the respec-
tive monomers. This is particularly noticeable with solubility properties and
transition points. A brief reference may be made here to the more direct chem-
ical types of graft formation that do not involve free radicals. These depend
on the direct reaction of an active group on the polymer. The simplest group
is hydroxyl ÐOH, which under suitable conditions may react with carboxyl
ÐCOOH, carboxyanhydride . C:OOO:C. or carbochloride ÐCOCl to form esters
or polyesters depending on the nature of the side chain. Equally, hydroxyl
groups may react with oxirane CH3.CHX groups. This applies especially
O
with ethylene oxide CH2 CH2 to form oxyethylene side chains, giving graft
O
copolymers of the type
CHOH CH2 CH CH2

OC2H4(OC2H4)n OH
This will be of special interest in dealing with emulsions.
4 POLYMER STRUCTURE AND PROPERTIES

4.1 Polymer structure
The physical properties of a polymer are determined by the configuration
of the constituent atoms, and to some extent by the molecular weight. The
configuration is partly dependent on the main chain, and partly on the various
side groups. Most of the polymers which we are considering are based on long
chains of carbon atoms. In representing formulae we are limited by the plane
of the paper, but a three-dimensional structure must be considered. The C—C
internuclear distance is 1.54 Å, and where free rotation occurs the C—C—C
bond is fixed at 109° (the tetrahedral angle).
By tradition, we represent the polyethylene chain in the full extended
fashion:
CH2 CH2 CH2
CH2 CH2
Figure 1.1 Diagrammatic molecular coil. (Reproduced from Moore [27].)
In practice the polymer is an irregular coil, as shown in Figure 1.1. The dimen-
sion most frequently used to describe an ‘average’ configuration is the ‘root
mean square’, symbolised as r, which can be symbolised mathematically as
0.5
n1 r1 2

n1
where there are n individual polymer molecules, and the distance apart of
the chain ends is r1 , r2 , etc. This concept of root mean square is necessary in
dealing with certain solution properties, and also certain properties of elasticity.
No real polymer molecule can have completely free and unrestricted rota-
tion, although an unbranched polythene C2 H4 n approaches closest to this
ideal. (The theoretical polymethylene CH2 m has been prepared by the poly-
merisation of diazomethane CH2 N2 , with elimination of nitrogen.) The prop-
erties of polyethylene over a wide range of molecular weights are, at ambient
temperatures, those of a flexible, relatively inelastic molecule, which softens
fairly readily. Chain branching hinders free rotation and raises the softening
point of the polymer. Even a small number of crosslinks may, however, cause
a major hindrance to the free rotation of the internal carbon bonds of the chain,
resulting in a sharp increase in stiffness of the resulting product.
Many side chain groups cause steric hindrance and restrictions in the free
rotation about the double bonds. A typical example is polystyrene, where the
planar zigzag formulation is probably modified by rotations of 180° a round
alternate double bonds to produce a structure of minimum energy, such as
C6H5
C6H5
CH CH2 CH CH2
CH2 CH CH2 CH CH2
C6H5 C6H5
Because of the steric hindrance, polystyrene is a much harder polymer than
polyethylene.
Other molecular forces that effect the physical state of the polymers are
the various dipole forces and the London or dispersion forces. If different
parts of a group carry opposite charges, e.g. the carbonyl :CDO and hydroxyl
—O—HC , strong interchain attraction occurs between groups on different
chains by attraction of opposite charges. This attraction is strongly tempera-
ture dependent. A special, case of dipole forces is that of hydrogen bonding,
by which hydrogen atoms attached to electronegative atoms such as oxygen
or nitrogen exert a strong attraction towards electronegative atoms on other
chains. The principal groups of polymers in which hydrogen bonding occurs
are the hydroxyl and the amino .NHX or amide .CONH2 groups and are
illustrated by the following:
H
O O O H O CH N H O C
H H O
The net effect of dipole forces, especially hydrogen bonding, is to
stiffen and strengthen the polymer molecules, and in extreme cases to
cause crystalline polymers to be formed (see below). Examples of polymers
with strong hydrogen bonding are polyvinyl alcohol —CH2 CHOH—n ,
polyacrylamide (CH2CH−)n and all polymers including carboxylic acid
CONH2
groups, e.g. copolymers including units of acrylic acid CH2 :CHCOOH and
crotonic acid CH2 :CH.CH2 COOH.
The London forces between molecules come from time-varying dipole
moments arising out of the continuously varying configurations of nuclei and
electrons which must, of course, average out to zero. These forces, which
are independent of temperature, vary inversely as the seventh power of the
distance between the chains, as do dipole forces, and only operate at distances
below 5 Å.
Forces between chains lead to a cohesive energy, approximately equal to the
energies of vaporisation or sublimation. A high cohesive energy is associated
with a high melting point and may be associated with crystallinity. A low
cohesive energy results in a polymer having a low softening point and easy
deformation by stresses applied externally.
Whilst inorganic materials often crystallise and solid organic polymers
generally possess crystallinity, X-ray diffraction patterns have shown that in
some polymers there are non-amorphous and crystalline regions, or crystal-
lites. Whilst crystallinity is a characteristic of natural products such as proteins
and synthetic condensation products such as the polyamide fibres, crystallinity
sometimes occurs in addition polymers. Even if we discount types prepared by
special methods, such as use of the Ziegler–Natta catalysts [8], which will not
be discussed further here since they are not formed by classical free radical
reactions, a number of polymers prepared directly or indirectly by free radical
methods give rise to crystallinity.
One of these already mentioned is polyvinyl alcohol, formed by hydrolysis
of polyvinyl acetate. It must, however, be almost completely hydrolysed, of
the order of 99.5 %, to be effectively crystalline, under which conditions it can
be oriented and drawn into fibres. If hydrolysis is partial, the resulting disorder
prevents crystallinity. This is the case with the so-called ‘polyvinyl alcohol’
of saponification value about 120, which is used for emulsion polymerisation.
This polymer consists, by molar proportions, of about 88 % of vinyl alcohol
and 12 % of vinyl acetate units.
Polymers of vinylidene chloride CH2 CCl2 are strongly crystalline. Poly-
mers of vinyl chloride CH2 CHCl and acrylonitrile CH2 CHCN are partially
crystalline, but crystallinity can be induced by stretching the polymer to a
fibre structure to induce orientation. Polyethylene, when substantially free
from branching, is crystalline and wax-like because of the simple molec-
ular structure. It does not, of course, have the other properties associated with
crystallinity caused by hydrogen bonding, such as high cohesive strength.
Another type of crystallinity found in polymers is side chain crystallinity,
e.g. in polyvinyl stearate (−CH2CH−)n or polyoctadecyl acrylate
OOC.C17H35
(−CH2CH−)n This type of crystallinity has relatively little application,
COOC16H37
since the products tend to simulate the crystalline properties of a wax.
However, this property may be useful in connection with synthetic resin-based
polishes, the subject of a later chapter.
In considering the effect of side chains on polymer properties, it is conve-
nient to take a series of esters based on acrylic acid and compare the derived
polymers. These are most readily compared by the second-order transition
points (Tg ). Technical publications show some variation in these figures, prob-
ably because of variations in molecular weight. However, polymers prepared
under approximately the same conditions have much the same degree of
polymerisation (DP), and emulsion polymers are preferred as standards in
this connection.
Figure 1.2 shows the variations in Tg of a series of homologous
polymers based on acrylic acid CH2 :CHCOOH and methacrylic acid
CH2 :CCH3 COOH. The striking difference in Tg of the polymers based on
the methyl esters should be noted, being almost 100 ° C. This is due to the
steric effect of the angular methyl .CH3 group on the carbon atom to which
the carboxyl group is attached. Polymethyl methacrylate is an extremely hard
solid, used inter alia for ‘unbreakable’ glass.
The effect of the angular methyl group slowly diminishes as the alcohol side
chains become longer; these latter keep the chains apart and reduce the polar
100
80
60
Brittle point (°C)
40
n-Alkyl
methacrylates
20
−20
n-Alkyl
acrylates
−40
−60
2 4 6 8 10 12 14 16
Carbon atoms in the alkyl group
Figure 1.2 Brittle points of polymeric n-alkyl acrylates and methacrylates. (Repro-
duced with permission from Riddle [28].)
forces. In consequence the Tg diminishes in the case of alkyl ester polymers

of acrylic acid until the alkyl chain reaches about 10 carbon atoms. It then
increases again with side chain crystallinity. The methacrylate ester polymers,
however, continue to drop in Tg , usually until a C13 alkyl group is reached,
since the steric effect of the angular methyl group on the main chain also
prevents side chain crystallinity at first.
Similar conditions prevail in the homologous series of vinyl esters of straight
chain fatty acids based on the hypothetical vinyl alcohol CH2 .CHOH. From
polyvinyl formate (−CH2CH−)n through polyvinyl acetate (−CH2CH−)n to
OOCH OOCCH3
vinyl laurate (−CHCH−)n there is a steady fall in Tg , the polymers varying
OOC11H23
from fairly brittle films derived from a latex at ambient temperature to viscous
sticky oils as the length of the alcohol chain increases. Note, however, that
the polymerisation and even copolymerisation of monomers with long side
chains, above about C12 , becomes increasingly sluggish.
The above examples, in both the acrylic and the vinyl ester series, have
considered the effect of straight chains inserted as side chains in polymer
molecules. The effect of branched chains, however, is different. As chain
branching increases, the effect of the overall size of the side chain diminishes.
An example of this will be illustrated in Chapter 9 when considering specific
examples of monomers that might be the basis of emulsions for paints. Thus
polyisobutyl methacrylate has a higher Tg than polybutyl methacrylate. Poly-
mers based on tert-butyl acrylate or tert-butyl methacrylate have a higher
softening point than the corresponding n-butyl esters.
Another interesting example of the effect of branched chains is that of
the various synthetic branched chain acids in which the carbon atom in the ˛
position to the carbon of the carboxyl is quaternary, corresponding to a general
formula HOOC.CR1 R2 R3 ., where R1 is CH3 , R2 is CH3 or C2 H5 and R3
is a longer chain alkyl group, which may be represented as C4 – 6 H9 – 13 . These
form vinyl esters which correspond in total side chain length to vinyl caprate
CH2 :CHOOCC9 H19 but do not impart the same flexibility in copolymers [29].
It is often more practical to measure the effect of monomers of this type
by copolymerising them with a harder monomer such as vinyl acetate and
measuring the relative effects. Thus the vinyl esters of these branches chain
acids, although they are based on C10 acids on average, are similar to a C4
straight chain fatty acid as far as lowering of the Tg is concerned. It is also
interesting to note that polymers and copolymers of these acids afford much
greater resistance to hydrolysis than polymers of vinyl esters of n-alkyl acids.
In copolymers these highly branched groups have a shielding effect on neigh-
bouring ester groups, reducing their ease of hydrolysis by alkali [30, 31]. In
this connection the angular methyl group in methacrylate ester polymers has
the effect of making hydrolysis of these products extremely difficult.
4.2 Molecular weight effects

The molecular weight scatter formed as a result of any polymerisation is
typical of a Gaussian type. Thus a fractionation of polystyrene is shown in
Figure 1.3, in which the distribution and cumulative weight totals are shown
as a percentage.
Before discussing the general effect of molecular weight on polymer charac-
teristics, some further definitions are desirable. The number average molecular
weight Mn is the simple arithmetical average of each molecule as a summation,
divided by the number of molecules, the ‘popular’ idea of an average. Another
measurement of average is the ‘weight’ average, and is an expression of the
fact that the higher molecular weight fractions of a polymer play a greater role
in determining the properties than do the fractions of lower molecular weight.
Its definition is based on multiplying the number of identical molecules of
molecular weight Mn by the overall weight of molecules of that weight and
100 Integral and differential

distribution curves
80
60
Wx and wx
40
20
0 2 4 6 8 10 12 14 16 18
M × 10−5
Figure 1.3 Molecular weight distribution for thermally polymerised polystyrene as

established by fractionation. (From the results of Merz and Raetz [32].)
dividing by the sum total of the weights. Mathematically, this is given by

w1 M1
Mw D
w1
where w1 represents the overall weight of molecules of molecular weight
M1 . The weight average molecular weight Mw is invariably greater than the
number average as its real effect is to square the weight figure. For certain
purposes, the z average is used in which M1 in the equation above is squared,
giving even higher prominence to the higher molecular weight fractions.
In practice all the viscosity characteristics of a polymer solution depend
on Mw rather than Mn . Thus nine unit fragments of a monomer of molecular
weight 100 individually pulled off a polymer of molecular weight 1 000 000
reduces its Mn to 100 000. The Mw is just over 999 000. This corresponds to
a negligible viscosity change.
A number of methods of measuring molecular weight are used and are
summarised here:
(a) Osmometry. This is a vapour pressure method, useful for polymers of

molecular weight up to about 25 000; membrane osmometry is used for
molecular weights from 20 000 to 1 000 000. These are number average
methods.
(b) Viscometry. This is a relative method, but the simplest, and its application
is widespread in industry. Viscometry is approximately a weight average
method.
(c) Light scattering. This is a weight average method.
(d) Gel permeation chromatography. This is a direct fractionation method
using molecular weight. It is relatively rapid and has proved to be one of
the most valuable modern methods.
(e) Chemical methods. These usually depend on measuring distinctive end
groups. They are number average methods.
In some cases selective precipitation can be used to fractionate a polymer

according to molecular weight. This is essentially a relative method based on
known standards. This method also differentiates between varying species in
a copolymer.
The properties of polymers are governed to some extent by molecular weight
as well as molecular structure. Properties also depend partly on the distribu-
tion of molecular weights, and in copolymers on the distribution of molecular
species. The differences in solubility in solvents in exploited in fractiona-
tion where blended solvents are used, only one being a good solvent for the
polymer. The added poor solvent will tend to precipitate the higher molec-
ular weight fractions first. Thus polyvinyl acetate may be fractionated by
the gradual addition of hexane C6 H14 to dilute solutions of the polymer in
benzene.
In some cases molecular weight variations have an extreme effect on
polymer properties. This is particularly significant in the polyvinyl ethers
( CH2CH) in which a polymer can vary from an oil at a molecular
OCnH2n+1
weight of about 5000 to a rubbery material if the molecular weight is above
100 000. The polyvinyl ethers, however, are not prepared as homopolymers by
a free radical mechanism. The differences are usually illustrated by the change
in the second-order transition point (see the next section). The softening points,
which correspond approximately to melting ranges, and which are estimated
by standard methods [33], are also affected by molecular weight.
The overall effect of solvents on polymers is too complex to be considered
here. However, the reader is referred to the treatise by Flory [10] or the simpler
treatment as shown in references [3] to [6], [11] and [12].
4.3 Transition points

Although when dealing with a crystalline substance there is a sharp melting
point, sometimes denoted Tm , when dealing with a polymer containing
molecules with a range of molecular weights it is not possible to describe
the changes in state on heating in a similar manner. Amorphous materials,
unless crosslinked or decomposing at a relatively low temperature, will soften
gradually, and although a softening point or range may be quoted, this depends
on an arbitrarily chosen test, usually on the time taken for a steel ball to
penetrate a known thickness of the polymer.
Technology of polymerisation 27
However, an amorphous polymer has a number of physical changes of
condition, the most important being the second-order transition point, usually
referred to as Tg , already mentioned previously. Physically this transition point
is connected with the mobility of the polymer chains. Below Tg , the chains
may be regarded as substantially immobile, except for movements around
an equilibrium position. Above this temperature appreciable movement of
segments occurs in the polymer chains. Below the Tg , the polymer is a hard,
brittle solid; above this temperature increased flexibility and possibly rubber-
like characteristics are observed.
The second-order transition point may be measured in various ways; e.g.
the rate of change of polymer density varies with temperature, as does the rate
of change of other properties such as specific heat. Most useful is differential
thermal analysis (DTA), which indicates the differential in the heating capacity
of a substance. Modern DTA instruments are extremely sensitive.
The significance of Tg in emulsion polymers is indicated in Chapter 4
(Section 4.4). It may be noted that an alternative temperature, known as the
minimum film formation temperature (MFT) is frequently a substitute for Tg
This is the lowest temperature at which a drying emulsion containing polymer
particles will form a continuous film. Because of the conditions of film forma-
tion, this temperature is usually 3–5 ° C higher than the Tg . DTA results have
shown that many polymers have transition points other than Tg . These are
associated with the thermal motion of the molecules.
In many cases where a polymer has practical utility, it may be desirable that
Tg should be reduced to achieve reasonable flexibility for the polymer. This
is accomplished by plasticisation which reduces Tg to a level below ambient,
or below the MFT in the case of a latex. As an example of plasticisation,
about 40 parts of di-2-ethylhexyl phthalate are required to transform 60 parts
of polyvinyl chloride from a hard, horny material to a flexible sheet. ‘Internal
plasticisation’ is a term used for the formation of a copolymer, the auxiliary
monomer of which gives increased flexibility to the polymer formed from the
principal monomer.
5 TECHNOLOGY OF POLYMERISATION
Monomers may be polymerised by free radical initiation by one of five
methods: polymerisation in bulk, in solution, dispersed as large particles in
water or occasionally in another non-solvent (suspension polymerisation), or
dispersed as fine particles, less than 1.5 µm, usually less than 1 µm in diameter.
The last-named process is usually known as emulsion polymerisation. As the
applications of polymers in emulsion is the basis of this series of volumes,
emulsion polymerisation is the subject of Chapter 3. A variant of suspension
polymerisation may be described as solution precipitation. It is often applied
to copolymers, e.g. a copolymer of methyl methacrylate and methacrylic acid.
In concentrated solution, the acid solubilises the methyl methacrylate. On
polymerisation a fine water-insoluble powder is produced, which, depending
on the monomer ratios, is usually alkali soluble.
In the past two decades a variation of emulsion polymerisation has been
introduced, the polymers being known as ‘dispersymers’. To form dysper-
symers, a liquid monomer forms an emulsion-like product in an organic
liquid, usually a liquid hydrocarbon, in which the polymer is insoluble. The
final emulsion closely resembles an aqueous polymer emulsion in physical
appearance [34].
5.1 Bulk polymerisation

Whilst in most cases laboratory experiments may be performed on undiluted
monomers, or on controlled dilutions with solvents do not affect the polymeri-
sation seriously, this process produces difficulties in large-scale production,
which may be of the order of 5 tonnes in a single batch. Problems are caused by
an increase in viscosity of the mass during polymerisation, and in particular the
removal of the heat of polymerisation, which for most monomers is of the order
of 20 kg cal gm1 mole1 . Special equipment with a high surface–volume
ratio is desirable, as with the polymerisation of methyl methacrylate which is
polymerised in thin sheets with a very low initiator ratio. Bulk polymerisation
of vinyl acetate was described in reports of German factory production after
the Second World War [35]. In this case the hot polymer is sufficiently fluid to
be discharged directly from a cylindrical reactor. In an alternative continuous
process the monomer is passed down a polymerisation tower [36]. Processes
have been developed for the bulk polymerisation of vinyl chloride which is
insoluble in its own monomer [37].
5.2 Solution polymerisation

Polymerisation with a solvent diluent can be readily accomplished as the major
problems of bulk polymerisation are overcome with increasing dilution. Some
practical problems persist, however. Commercial solvents are seldom pure and
the impurities may have an inhibiting or retarding effect on polymerisation; this
is especially so with monomers such as vinyl acetate which are not resonance
stabilised. In addition, many solvents have a chain transfer effect (Section 2.1).
Towards the end of a polymerisation the degree of dilution of the monomer is
extremely high; the efficiency of initiator therefore falls, and it is lost by chain
transfer with the solvent or by mutual destruction of the radicals. Thus several
repeat initiations are necessary towards the end of a practical polymerisation
in solvent to achieve the 99C % polymerisation generally desired.
Practical experience has shown that molecular weights in solution polymeri-
sation are also susceptible to a number of other factors, such as the type and
nature of stirring, and the type and nature of the reactor, including its shape
and the surface–volume ratio. There is likely to be a ‘wall effect’, which
may terminate growing radicals. In addition, stirring conditions affect the rate
Technology of polymerisation 29
of attainment of equilibrium, whilst the amount of reflux, where present, also
affects the nature of the final polymer. Since it is not usually desirable and may
be difficult to distill unpolymerised monomer, even if a satisfactory azeotrope
with the solvent exists, direct solvent polymerisation has limited practical
application and is of principal interest where the solutions are used directly,
either as solvent-based coatings or as adhesives [37]. Solvent polymerisation
can normally be used only to prepare polymers of relatively low molecular
weight.
5.3 Suspension polymerisation

Suspension polymerisation may be described as a water-cooled bulk polymeri-
sation, although initiators that are water soluble may create some variations.
The fundamental theory is simple and depends on the addition to the water of
a dispersing agent. This may be a natural water-soluble colloid such as gum
acacia, gum tragacanth, a semi-synthetic such as many cellulose derivatives
(see Chapter 2) or a fully synthetic polymer. These include polyvinyl alcohol,
or alternatively a water-soluble salt derived from a styrene/maleic anhydride
1 : 1 copolymer
CH CH2 CH CH
C6H5 OC CO
O
These dispersing agents may be mixed; occasionally a small quantity of surfac-

tant of the order of 0.01 % is added. The normal concentration of dispersing
agents is about 0.1 %, based on the water present. Monomer or monomers are
added so that overall concentration is 25–40 %, although occasionally specific
formulations claim 50 %.
The function of the dispersing agent is that of forming an ‘envelope’ around
the beads as formed by stirring and preventing their coagulation and fusion
during polymerisation. An intermediate or ‘sticky’ state occurs in almost all
polymerisations in which a solution of polymer in monomer of high viscosity is
formed, and the beads would fuse together very readily, except for the energy
supplied by the stirring in keeping them apart and the stabilising action of
the dispersing agent. Certain monomers, e.g. vinyl chloride, which are not
solvents for their own monomers are an exception to this rule, but the same
principle applies to the dispersant acting as a particle stabiliser. This type of
polymerisation is sometimes referred to as ‘bead’ polymerisation.
There is a very clear distinction between suspension polymerisation and
emulsion polymerisation. Whilst emulsion polymerisation produces particles
usually 1 µm in diameter, occasionally up to 2.5 µm, suspension particles
are at least ten times larger in diameter, often of the order of 1 mm, although
they are not necessarily spherical in shape. The kinetics of polymerisation of
the two types are often quite different. To ensure that beads or ‘pearls’ (another
term used) are formed, the second-order transition point Tg (see Chapter 4,
Section 4.4.2) must be below the ambient temperature; otherwise the beads
will flow together as soon as stirring is stopped. This tendency can be reduced
somewhat, e.g. by coating a bead dispersion of low molecular weight polyvinyl
acetate with cetyl alcohol, which is present during the polymerisation. Bead
polymerisation is only practicable as a general rule, where the Tg is above
about 25 ° C and preferably above 35 ° C. A summary of some suspension
polymerisation processes for vinyl chloride is available [38].
It is possible to perform suspension polymerisation using solid dispersants.
Thus styrene may be polymerised in suspension with organic peroxidic initia-
tors with a tricalcium ortho-phosphate dispersant and sodium dodecylbenzene
sulfonate [39].
6 THE PRINCIPAL MONOMERS AND THEIR POLYMER

6.1 Hydrocarbons
The simplest hydrocarbon capable of free radical addition polymerisation is
ethylene C2 H4 , which as a gas is treated under pressure. Higher aliphatic
hydrocarbons such as propylene CH3 CH:CH2 , 1-butene CH3 CH2 CH:CH2 and
a number of longer chain aliphatic ethenes cannot in general be polymerised
by themselves by free radical, as distinct from ionic methods, because of
their allylic character. However, they are capable of copolymerisation, and
some specifications have claimed their copolymerisation with vinyl acetate in
emulsion. Only hydrocarbons with their unsaturation in the 1-position can be
copolymerised satisfactorily in this manner.
Styrene C6 H5 CH:CH2 is the simplest aromatic hydrocarbon monomer.
Others are vinyl-toluene and o-, m- and p -methylstyrene CH3 C6 H4 CH:CH2 .
˛-Methylstyrene C6 H4 C(CH3 :CH2 is also a technical product, but its
polymerisation has problems because it has a low ceiling temperature; i.e. the
propagation and depropagation rates during formation tend to become equal
and hence no polymer is formed unless a low-temperature initiator system
is used.
The divinyl-benzenes, written
CH2:CH CH:CH2
a notation used when it is desired to leave the positions of the substituents

undecided, are a by-product of styrene manufacture and are used for
crosslinking.
The dienes are described in Section 6.8. There have been a few other
specialised monomers based on condensed rings, but as they are generally
solids their use in emulsion systems in very limited, if at all.
The principal monomers and their polymer 31
6.2 Vinyl esters
Vinyl esters are derived from the hypothetical vinyl alcohol, CH2 :CHOH, an
isomer of acetaldehyde CH3 CHO, which is normally formed when an attempt
is made to prepare the monomer. The esters, however, whether derived from
acetylene or ethylene (see later), are of major importance in many latex appli-
cations. The principal ester of commerce is vinyl acetate CH2 :CHOOCCH3 , a
liquid which is fairly readily hydrolysed, of b.p. 73 ° C. Vinyl acetate has the
advantage of being one of the cheapest monomers to manufacture.
Vinyl propionate CH3 CH2 COOCH:CH2 is fairly well established as
a monomer, probably by direct acetylene preparation. Other esters are
encountered less frequently, and in most cases are probably prepared by
vinylolysis rather than directly, using vinyl acetate as an intermediate [40–42].
Vinylolysis is not the same as trans-esterification and involves a mercury salt
such as p-toluene sulfonate as an intermediate. Thus vinyl caprate is prepared
by reacting vinyl acetate with capric acid in the presence of a mercuric salt,
using an excess of vinyl acetate; the reaction is reversible:
CH3 .CO.O.CH:CH2 C C9 H19 COOH
C9 H19 CO.O.CH:CH2 C CH3 COOH
The capric acid can be conveniently removed with sodium carbonate after
removal of excess acetic acid with sodium bicarbonate, which does not react
with the higher fatty acids. The vinyl esters of mixed C8 , C10 and C12
fatty acids have been used technically in forming copolymers with vinyl
acetate [43].
Vinyl butyrate CH3 CH2 CH2 OOCCH:CH2 is referred to in the liter-
ature, but is probably not in commercial production. Vinyl laurate
CH3 CH2 8 COOCH:CH2 has been in technical production in Germany. Of
other esters of fatty acids, only vinyl stearate C17 H35 COOCH:CH2 , a solid,
has been manufactured on a technical scale. The most interesting vinyl esters
have been derivatives of pivalic acid CH3 3 C.COOH, the simplest branched
chain fatty acid in which the carbon atom adjacent to the carboxyl group is
quaternary. In these vinyl esters, one methyl group may be replaced by ethyl,
and a second by a longer alkyl chain, and thus the general formula for the
esters is CH3 C7 – 8 H14 – 16 CCH3 C1 – 2 H2 – 4 OOCCH:CH2 [44].
Vinyl chloroacetate CH3 CICOOCH:CH2 is occasionally quoted. Because of
the relatively labile atom, copolymers including this monomer take part in a
number of crosslinking reactions.
Vinyl benzoate C6 H5 COOCH:CH2 is the only aromatic vinyl ester that finds
some application if relatively hard polymers with some alkali resistance are
required [43].
6.3 Chlorinated monomers

Vinyl chloride CH2 :CHCI, a gas, is the cheapest monomer of the series, and
has widespread commercial use. It may be polymerised in bulk with specialised
apparatus, but it is also polymerised both in suspension and in emulsion. It is
frequently copolymerised, especially with vinyl acetate.
Vinylidene chloride CH2 :CCl2 , a low boiling liquid, is also a relatively
low cost monomer. It forms a polymer with a marked tendency to crystallise
because of its relatively symmetrical structure. In most cases it is copoly-
merised, especially with vinyl chloride or methyl acrylate.
The corresponding symmetrical compound in the trans form, trans-
dichloroethylene CHCI:CHCI, has been used in limited quantities as a
comonomer with vinyl acetate [45]. Trichlorethylene CHCI:CCI2 , although not
normally considered as a monomer, may take part in some copolymerisations,
especially with vinyl acetate.
Chloroprene CH2 :CCI.CH:CH2 a diene (see Section 5.8), is mainly used in
the formulation of elastomers, but occasionally a polymer containing chloro-
prene is used as an alternative to a hydrocarbon diene.
Vinyl bromide CH2 :CHBr is technically available, and finds some appli-
cation in specialist polymers with fire-resistant properties. The boiling point
is 15.8 ° C. A number of highly chlorinated or brominated alcohol esters of
acrylic and methacrylic acids have been described, and are probably in limited
production, often for captive use for the production of fire-resistant polymers.
Vinyl fluoride CH2 CHF, vinylidene fluoride CH2 :CF2 , tetrafluoroethylene
F2 C:CF2 and hexafluoropropylene CF3 CF:CF2 have found industrial applica-
tions in recent years. The monomers are gaseous. For perfluoroalkyl acrylates
see the next section.
6.4 Acrylics
6.4.1 Acrylic and methacrylic acids
The most numerous class of monomers are the acrylics, viz. esters of acrylic
acid CH2 :CHCOOH and methacrylic acid CH2 :CCH3 COOH. Both are
crystalline solids at low ambient temperatures, becoming liquid at slightly
higher temperatures (see Figure 1.2). These acids polymerise and copolymerise
extremely readily, being frequently employed in copolymers to obtain alkali-
soluble polymers. Whilst both acids are water soluble, methacrylic acid, as
might be expected because of its angular methyl group, is more soluble in
ester monomers, and to some extent in styrene, and as such is more useful in
copolymerisation, especially if water based.
Whilst esters of acrylic acid give soft and flexible polymers, except for those
with long alkyl chains, methyl methacrylate polymerises to an extremely hard
polymers. The polymers in this series become softer with increasing alkyl
chain lengths up to C12 . The highest alkyl chain acrylics in both series tend
to give side chain crystallisation.
6.4.2 Individual acrylic and methacrylic esters
A range of esters of acrylic acid are available commercially from methyl
acrylate through ethyl acrylate to n-heptyl acrylate and 2-ethylhexyl acrylate
CH2 :COOCH2 CHC2 H5 C4 H9 . They vary from the fairly volatile, pungent
liquids of the lowest member of the series to characteristic, but not neces-
sarily unpleasant, odour of the higher members of the series. The highest
members require distillation under reduced pressure to avoid simultaneous
decomposition and polymerisation.
The methacrylic ester series closely parallels the acrylics, but boiling points
tend to be somewhat higher, especially with the short chain esters (Table 1.1).
Methyl methacrylate CH2 :CCH3 COOCH3 is by far the most freely available
and least costly of the monomers of the series.
As an alternative to the simple alkyl esters, several alkoxyethyl
acrylates are available commercially, e.g. ethoxyethyl methacrylate
CH3 :CCH3 COOC2 H4 OC2 H5 and the corresponding acrylate. The ether
oxygen which interrupts the chain tends to promote rather more flexibility
than a simple carbon atom.
Some technical perfluorinated alkyl acrylates have been described.
They include N-ethylperfluorooctanesulfonamido)ethyl acrylate Cn F2nC1 SO2 N
C2 H5 –CH2 O–C(O)–CHDCH2 (n approximately 7.5, fluorine content
51.7 %), the corresponding methacrylate and the corresponding butyl
derivatives. The ethyl derivatives are waxy solids, the ethyl acrylate and the
corresponding methacrylate derivative having a melting range of 27–42 ° C.
The butyl acrylic derivative is a liquid, freezing at 10 ° C.
Various glycol diacrylates and dimethacrylates are available. Ethylene glycol
dimethacrylate CH2 :CCH3 COOC2 H4 OOCCH3 :CH2 is extremely reactive,
and is sometimes marketed as a solution in methyl methacrylate. It polymerises
extremely readily and acts as a powerful crosslinking agent. The dimethacry-
lates of triethylene glycol and higher glycols, some of which are also readily
available, are less reactive, retain better flexibility and are more controllable
in their polymerisation characteristics.
Glycidyl methacrylate CH2CHCH2OOCC(CH3):CH2 has two reactive
O
groups, the epoxide group being distinct in nature from the vinyl double bond
(see also Chapters 5 and 7). The epoxide group is only slowly reactive in
water, and even in emulsion polymerisation does not hydrolyse excessively.
However, the presence of the group makes the methacrylate moiety much
more prone to ready polymerisation.
The half esters of both ethylene glycol and propylene glycol
are now monomers of commerce, propylene glycol monoacrylate
CH3 CHOHCH2 OOCCH:CH3 being typical (the primary alcohol unit is the
active one in the formula). These monomers provide a source of the mildly
reactive and hydrophilic groups on polymer chains. A problem with these
monomers is that traces of a glycol dimethacrylate may be present as impurities
at a low level.
6.4.3 Acrylics based on the amide group

Acrylamide CH2 :CHCONH2 and methacrylamide CH2 .CCH3 CONH2 are
articles of commerce, especially the former. Polymers of the former are
water soluble, but the solubility of the latter depends on conditions of prepa-
ration, e.g. molecular weight of the polymers. Both are very frequently
used in copolymerisation. Polyacrylamide is often used as a flocculating
agent. Certain derivatives, viz. methylolacrylamide CH2 :CHCONHCH2 OH,
methoxymethylacrylamide CH2 :CHCONHCH2 OCH3 and isobutoxyacry-
lamide CH2 :CHCONHCH2 OC4 H9 -iso, are of interest in crosslinking. The
last named has the advantage of being monomer soluble but water insol-
uble, making it more amenable to handling in emulsion polymerisation.
Diacetoneacrylamide N-(1,1,-dimethyl-3-oxobutyl) acrylamide [also known as
1-dimethyl-3-oxobutyl)acrylamide] (CH2 :CHNHC(O)CH3 2 CH2 COCH3 has
the advantage of both water and monomer solubility [46].
6.4.4 Cationic acrylic monomers

If a compound such as dimethylaminoethyl alcohol (CH3 2 .NC2 H4 OH
is esterified via the hydroxyl groups with acrylic or methacrylic acids
instead of neutralising the amino group, a cationic monomer, e.g.
(CH3 2 NC2 H4 OOCCH:CH2 ., is formed. At acid pH levels this monomer is
cationic, with the amino group forming salts that polymerise and copolymerise
in the normal way via the acrylic double bond. Another typical monomer is
t-butylaminoethyl methacrylate t-C4 H9 NHC2 H4 OOCC(CH3 :CH2 . At neutral
or higher pH levels, ionisation of this weak base is suppressed, and it acts as
a nonionic monomer. However, hydrolysis tends to be rapid in aqueous media
at high pH, forming the alkanolamine salts of the acids. Cationic monomers
from the corresponding aminopropyl compound are also known.
6.4.5 Acrylonitrile
Acrylonitrile CH2 :CHCN, and the less frequently used methacrylonitrile
CH2 :C(CH3 CN, give extremely hard polymers and are employed as
comonomers to give solvent resistance. Acrylonitrile monomer, like vinyl
chloride, is not a solvent for its own polymer and is about 7 % soluble in
water, although its polymer is insoluble, making it of interest in theoretical
studies. These monomers are unusually toxic because of the nitrile group.
6.5 Polymerisable acids and anhydrides
Besides acrylic and methacrylic acid, crotonic acid (strictly the cis acid)
CH3 CH:CHCOOH, a white powder, often takes part in copolymerisations,
especially with vinyl acetate, but it only self-polymerises at low
pH and with great difficulty. Itaconic acid (methylenesuccinic acid)
CH2 :CCH3 COOHCOOH, a water-soluble solid, also readily takes part in
copolymerisation, although it will only homopolymerise at about pH2.
Maleic acid cis-HOOCCH:CHCOOH, the simplest dibasic acid, is rarely
copolymerised on its own, but frequently as the anhydride, maleic anhydride:
CHCO
O
CHCO
which is much more reactive. However, it cannot be directly polymerised

in water, although its rate of hydrolysis is slow. It readily forms copoly-
mers, e.g. with styrene, ethylene or vinyl acetate, most readily as alternating
(equimolar) copolymers, irrespective of the initial molar ratios. These copoly-
mers are water soluble in their alkaline form after hydrolysis and frequently
occur as stabilisers in emulsion polymerisation.
Fumaric acid trans-HOOCCH:CHCOOH, the isomer of maleic acid and
thermodynamically the most stable form, is occasionally used as a comonomer,
although there is some doubt as to its reactivity, and it may do little more than
provide end groups, thus acting as a chain transfer agent.
Aconitic acid, an unsaturated carboxylic acid of formula HOOCCH3 C
(COOH):CHCOOH, obtained by removing the elements of water from
citric acid, is occasionally quoted as a monomer in patents and theoretical
studies. Citraconic acid (methylmaleic acid) CH3 C(COOH):CHCOOH, its
isomer mesaconic acid(methylfumaric acid) and citraconic anhydride are also
occasionally used for copolymerisation. The acids in this paragraph are not
articles of commerce as far as has been ascertained.
Various alkyl and alkoxy diesters of itaconic acid have been introduced,
but as far as is known, production has not been sustained, although they are
extremely good internal plasticisers for polyvinyl acetate. Their relatively high
cost migitated against their use.
6.6 Self-emulsifying monomers

A number of monomers have the property of stabilising emulsions without
the assistance of emulsifiers (see Chapter 2) or with a minimal quantity.
Their polymers are generally water soluble and often so are their copolymers,
depending on monomer ratios. These monomers contain strongly hydrophilic
groups, the sulfonate .SO3 Na being the most usual. They usually copolymerise
readily with most of the standard monomers used in emulsion polymerisation.
Amongst the earliest was sodium vinyl sulfonate CH2 :CHSO3 Na, which was
in use in Germany in the 1940s. Other monomers of this class include sodium
sulfoethyl methacrylate CH2 :CHC(:O)NHCH3 2 CH2 SO3 Na.
Of unusual interest is 2-acrylamido-2-methylpropanesulfonic acid (AMPS
monomer ) CH2 :CHC(:O)NHCCH3 2 CH2 SO3 H, normally used as the
sodium salt. This monomer also copolymerises readily. A monograph describes
these compounds in greater detail [47].
The salts of the polymerisable acids have appreciable self-emulsifying
powers when used as comonomers, especially when they are about 10 %
or more by weight. The alkylolamine unsaturated esters (Section 6.4.3), when
used in the form of their alkali or amine salts, come into this category [48].
6.7 Esters for copolymerisation

Esters of maleic and fumaric acids are often used in copolymerisation, both
the diesters and more unusually the monoesters being reacted. The fumarate
diesters, which are rather non-volatile liquids, have a feeble tendency to form
homopolymers on prolonged heating with initiators, but little, if any, evidence
exists to suggest that maleic esters can homopolymerise. Copolymerisation
characteristics of fumarate esters are more favourable than those of maleate
esters, and they are mainly copolymerised with vinyl acetate to impart internal
plasticisation. It has been suggested that maleate and fumarate esters isomerise
to identical products during a polymerisation reaction, but this has not been
proved. Although in theory the units entering a polymer should become iden-
tical with the disappearance of the double bond, there are many steric factors
associated with the polymer molecules as a whole.
The principal esters are those of n-butyl alcohol, 2-ethylhexyl alcohol, a
technical mixture of C9–11 alcohols and ‘nonyl alcohol’, which is 1,3,3-
trimethylhexanol.
The half esters of maleic acid and their salts are occasionally quoted in
patents and other technical literature, and seem, probably because of their
polar–non-polar balance to polymerise fairly readily. The methyl half ester
cis-CH3OOCCH:CHCOOH is a solid; some of the higher alkali half esters are
liquids. Half esters of other polymerisable acids such as fumaric and itaconic
acids have been reported, but are more difficult to prepare. The half esters
tend to disproportionate fairly readily, especially in the presence of water, to
the free acid and the diester:
2CH3 OOCCH:CHCOOH D HOOCCH:COOH C CH3 OOCCH:CHCOOCH3
A number of successful copolymerisations in emulsion of half esters of long-

chain alcohol and sterically hindered alcohols have been disclosed [49].
6.8 Monomers with several double bonds
Unsaturated hydrocarbons containing two double bonds constitute a

special class of monomer. The principal representatives of this class are
butadiene CH2 :CH.CH:CH2 , isoprene CH2 :CCH3 .CH:CH2 and chloroprene
CH2 CCl.CH:CH2 .
When a monomer contains more than one double bond which can
polymerise approximately equally freely, crosslinking can occur readily,
and small quantities of this type of monomer are added to other
polymerising systems to obtain controlled crosslinking. Examples are p-
divinyl benzene (see Section 6.1), and ethylene glycol dimethacrylate
CH2 :CCH3 COOCH2 CH2 OOCCCH3 :CH2 .
In these cases the radicals formed are resonance stabilised, so that two
chains can form simultaneously, and when a biradical is added to a growing
chain, two points occur from which the chain can continue, resulting in rapid
branching and crosslinking.
The dienes are a special class in distinction to monomers such as the divinyl
benzenes and the diesters such as a glycol acrylate. If a monomer such as buta-
diene is polymerised, the monoradical formed is highly stabilised by resonance.
The two resonance forms can be represented as
RH—CH2 DCH—CH2 and R—CH2 —CH—CHDCH2
where R represents a residual monovalent group.

As a result, two methods of addition are possible, one being known as 1 : 2
addition, the other as 1 : 4 addition, and may be represented by the following:
CH2 CH CH2 CH
CH CH
CH2 CH2
Bi-unit of a 1 : 2 addition
CH2 CH CH CH2 CH2 CH CH CH2

Bi-unit of 1 : 4 addition
During a free radical polymerisation in emulsion, about 20 % of a 1 : 2

polymer addition and 80 % of 1.4 addition takes place. Copolymerisation with
other monomers such as styrene tends to increase 1 : 2 units at the expense of
1 : 4 units.
A further possibility of variation occurs because the 1 : 2 unit possesses an
asymmetric carbon atom, while due to the double bond, 1 : 4 addition may
occur in the cis or trans positions, giving the following isomers:
H2C CH2 H2C H

C C C C
H H H CH2
cis trans
It has been found possible to deduce various structures by infrared absorp-

tion bonds, trans formation having been shown to decrease with temperature.
During a polymerisation including butadiene, there is a greater than usual
tendency for side reactions to occur. These involve the residual double bonds
in completed molecules or growing chains. This often causes gel formation, as
measured by the insoluble fractions in acetone, or another standard solvent. Gel
formation and other crosslinking reactions occur with increasing frequency as
the degree of polymerisation increases. In consequence, when solid products
of controlled properties are required, polymerisations and copolymerisations
involving butadiene are not taken to completion. The reaction is inhibited
before polymerisation is complete and surplus monomer is removed by distil-
lation. Possibilities for isomerism in the polymerisation of chloroprene and
isoprene are even more complex than with butadiene.
The application of diene polymers and copolymers is largely associated with
synthetic rubber, but these copolymers have other applications; e.g. copoly-
mers with a styrene content of 40 % and above have been used for coatings
and for carpet backing. In these copolymers the residual double bonds render
them prone to degradative oxidation.
The structure of butadiene copolymers is interesting and accounts for their
physical properties. A polymer molecule may be considered to be a randomly
coiled chain—an irregular spiral—in the unstretched state. Elastomers in the
fully stretched state, particularly natural rubber, i.e. polyisoprene C5 H8 n ,
tend to crystallise, this crystallisation being lost when the stress causing the
extension is removed. Ideally a limited number of crosslinks is desirable for
elastic recovery to occur. Because of their less regular structure, copolymers
of butadiene do not tend to crystallise.
Modern work has shown that where polymerisation takes place by methods
that produce a highly stereoregular or stereospecific products, the tendency
is for crystallisation to occur on stretching. In most copolymers that we
will consider in these volumes, the high quantity of comonomer causes the
normal plastic type of property to predominate, rather than the rubber-like
extensibility. Thus the bulky phenyl C6 H5 groups in the styrene copolymers
effectively prevent crystallisation, and the copolymers in film form tend to
approximate more closely in properties to other vinyl-type polymers.
The double bonds in polymers involving dienes facilitate crosslinking,
which in rubber technology is known as vulcanisation. The utilization of the
double bonds for crosslinking has increased in recent years.
6.9 Allyl derivatives
Allyl alcohol CH3 :CHCH2 OH and its simple derivatives, such as allyl acetate
CH2 :CH2 OOCCCCH3 , have little practical application in vinyl polymerisa-
tion, because of their powerful tendency to degradation chain transfer (p. xx).
Similar considerations apply to methallyl alcohol CH2 :CCH3 CH2 OH and its
derivatives. A practical difficulty also arises with allyl alcohol and its more
volatile derivatives because of their extreme lachrimatory character.
Certain other allyl derivatives, however, are of greater utility. Diallyl
o-phthalate o-CH2 :CHCH3 OOCC6 H4 OOCCH2 CH:CH2 contains two vinyl
groups, and as such the tendency to crosslink is in competition with that
of chain transfer. Whilst this diester is not normally used in emulsion
polymerisation, it is frequently included in the thermosetting polyesters,
especially in conjunction with a monomer such as styrene, which will reduce
the tendency to premature crosslinking. These derivatives find particular
application in reinforced polyesters, viz. those reinforced with glass fibres.
Allyl derivatives containing epoxide groups seem to copolymerise somewhat
more readily, probably because the nucleophilic epoxide group reduces the
tendency to resonance. These derivatives are of interest as they are potentially
crosslinking monomers. They include allyl glycidyl ether
CH2:CHCH2OCH2CH CH2
O
and allyl dimethyl glycidate
CH3
C CHCOOCH2CH:CH2
CH3 O
which is formed by Darzen’s reaction.

This little-known reaction would repay further study, at any rate as far
as polymer production is concerned. It is fundamentally the reaction of a
chlorinated ester, such as allyl chloroacetate with acetone in the presence of a
stoichiometric quantity of alkali near 0 ° C, sodium hydride being particularly
effective [49].
Monomers such as allyl methacrylate CH2 :CHCH2 OOCCCH3 :CH2 are
occasionally quoted, having mild crosslinking properties. A useful volume
describing allyl compounds is available [14].
6.10 Vinyl ethers

Whilst the vinyl ethers have long been known as monomers, they have been
unimportant in aqueous polymerisation. By themselves they only form copoly-
mers, not homopolymers under free radical conditions, and ionic catalysts are
used when a homopolymer is required. Although the vinyl ethers copolymerise
readily with many vinyl monomers under free radical conditions, difficulty
arises during polymerisation in the presence of water since they hydrolyse
readily to acetaldehyde and alcohols below a pH of about 5.5. This makes
emulsion polymerisation with a monomer such as vinyl acetate difficult, except
under careful control of pH.
Except for the tendency to hydrolysis, the physical properties of
the vinyl ether monomers closely resemble that of the corresponding
saturated compounds. Available monomers, including vinyl methyl ether
CH2 CHOCH3 , vinyl ethyl ether CH2 :CHOC2 H5 , both n- and isobutyl
vinyl ethers CH2 :CHOC4 H9 and a long-chain alkyl ether, vinyl cetyl ether
CH3 :CHOC16 H33 , have been available.
6.11 Miscellaneous monomers containing nitrogen

N-Vinylpyrrolidone is a completely water-miscible cyclic monomer which can
be regarded as a cyclic imide. It readily forms polymers and copolymers, the
water soluble types being used as protective colloids. The monomer is
H2C C:O
N CH:CH2
H2C CH2
2-Vinylpyridine, 4-vinylpyridine and to a lesser extent 2-methyl-5-

vinylpyridine have been prepared commercially, and polymerise to give
products that are the basis of polymeric cationic electrolytes. They are most
frequently in copolymers with butadiene and styrene in tyre cord adhesives
(see Chapter 8). The physical properties of the polymers tend to resemble
those of styrene. The formulae of the monomers are shown below:
CH CCH:CH2 CH
HC CH HC CH HC CH
HC CCH:CH2 HC CH H2C:CHC CCH3
N N N
2-Vinylpyridine 4-Vinylpyridine 2-Methyl-5-vinylpyridine
1-Vinyl imidazole and the allied 1-vinyl 2-methylimidazole are basic

monomers produced on a small scale, and their major function is improvement
of adhesion:
CH N CH N
CH CH CH C CH3
N CH:CH2 N CH:CH2
1-Vinylimidazole 1-Vinyl-2-methylimidazole
Vinyl caprolactam is occasionally used as a reactive thinner:
H2C CH2
H2C CH2
H2C C O
N CH CH2
It has a melting point of 34 ° C, and may be distilled under reduced pressure.

It also has the property of improving adhesion.
Divinylethylene urea and divinylpropylene urea, with melting points of 66
and 65 ° C respectively, find utilization as reactive thinners:
CH2
CH2 CH2 CH2 CH2
CH2 CH N N CH CH2 CH2 CH N N CH CH2
C:O C:O
Divinylethylene urea Divinylpropylene urea
6.12 Toxicity and handling

As a general rule, all the quoted monomers should be handled with at least the
precautions associated with the corresponding saturated compounds. In some
cases, e.g. the acrylic esters, the toxicity, in particular the vapour, is more
toxic than the corresponding saturated esters. The lower acrylic esters, but
not the methacrylic esters, have an extremely unpleasant odour, but the level
of intolerance is well below the maximum safety level recommended. Some
precautions are advised in handling acrylamide.
Acrylonitrile and methacrylonitrile have the characteristic toxicity of
cyanides. On the laboratory scale they should be handled in well-ventilated
fume cupboards and prevented from coming into direct contact with the skin.
Special precautions, including the wearing of oilskins and fresh air breathing
apparatus, are required for large-scale manufacturing processes.
Allyl alcohol and some of its derivatives are lachrimatory.
The above comments are of a general character only. In all cases manufac-
turers’ literature and official literature should be consulted, safety information
being obligatory in many countries.
The following are synthetic monomers based on the vinyl esters of mixed
branched chain acids, known as Versatic acids, the feature being that the
carbon atom is in the alpha position of quaternary:
Veova 9 is the vinyl ester of acids averaging 9 carbon atoms; b.p.

185–200 ° C, s.g. 0.89. The Tg of the homopolymer is 60 ° C. Veova 10 is
the vinyl ester of acids averaging 10 carbon atoms and is less branched than
Veova 9; b.p. 133–136 ° C, s.g. 0.875–0.885. Some perfluorinated acrylic
derivatives are described in Section 6.4.
Table 1.1 Physical properties of the principal monomers
Monomer Formula b.p. (° C) m.p. (° C) s.g. Pressure
(mm) (d20/20 )
Ethylene CH2 :CH2 104
Propylene CH2 :CHCH3 31 0.5139 d20/4
I-Butene CH2 :CHCH2 CH3 6.3 0.5951 d204
I-Hexene CH2 :CHC3 H6 CH3 C63.5 0.6734 d20/4
I-Octene CH2 :CHC5 H10 CH3 121.3 0.7194d15.5/15.5
Styrene C6 H5 CH:CH2 145.2 0.905 d25/25
Vinyl toluene CH3 C6 H4 CH:CH2 167.7 0.8930
o-Methyl styrene C6 H4 CCH3 :CH2 163.4 0.9062 d25/25
Divinyl benzene C6 H4 CH:CH2 2 195
(55 % technical product)
m-Diisopropenylbenzene m-C6 H4 [CCH3 :CH2 ]2 231 0.925
p-diisopropenylbenzene p-C6 H4 [CCH3 :CH2 ]2 0.965
(sublimes at 64.5 ° C)
Butadiene 1:3 CH2 :CHCH:CH2 4.7 0.6205a
Isoprene CH2 :CCH3 CH:CH2 34.07 0.686d15.6/15.6
Vinyl chloride CH2 :CHCl 14 0.912
Vinylidene chloride CH2 :CCl2 31.7 1.1219d20/4
trans-Dichloroethylene CHCl:CHCl 49 1.265d15/4
Chloroprene CH2 :CClCH:CH2 59.4 0.9583
Vinyl fluoride CH2 :CHF 57
Vinylidene fluoride CH2 :CF2 84
Tetrafluoroethylene CF2 :CF2 76
Vinyl formate CH2 :CHOOCH3 46.6 0.9651
Vinyl acetate CH2 :CHOOCCH3 72.7 0.9338
a under own vapour at 21° C
Vinyl propionate CH2 :CHOOCC2 H5 94.9 0.9173
Vinyl butyrate CH2 :CHOOCC3 H7 116.7 0.9022
Vinyl caprate CH2 :CHOOCC9 H19 148/50
Vinyl laurate CH2 :CHOOCC11 H23 142/10
Vinyl stearate CH2 :CHOOCC17 H35 187–188/4.3 35-36
Vinyl chloroacetate CH2 :CHOOCCH2 Cl 44-46/20 1.1888
Vinyl benzoate CH2 :CHOOCC6 H5 203 1.0703
Acrylic acid CH2 :CHCOOH 141.3 12.3 1.0472
Methacrylic acid CH2 :CCH3 COOH 161 15 1.015
Methyl acrylate CH2 :CHCOOCH3 80 0.950
Ethyl acrylate CH2 :CHCOOC2 H5 99.6 0.9230
n-Butyl acrylate CH2 :CHCOOC4 H9 148.8 0.9015
n-Heptyl acrylate CH2 CHCOOC7 H15 106/25 0.8794d25/4
2-Ethylhexyl acrylate CH2 :CHCOOC8 H17 128/50 0.8869
Lauryl acrylate CH2 :CHCOOC11 H23
Methyl methacrylate CH2 :CCH3 COOCH3 100.5 0.939
Ethyl methacrylate CH2 :CCH3 COOC2 H5 118.4 0.909
n-Butyl methacrylate CH2 :CCH3 COOC4 H9 166 0.893
Lauryl methacrylate CH2 :CCH3 COOC12 H23 8 0.868d25/15.6
Ethoxyethyl acrylate CH2 :CHCOOC2 H4 OC2 H5 174.1 0.9834
Ethoxyethyl methacrylate CH2 :CCH3 COOC2 H4 OC2 H5 91–93/35 0.971d15.5/15.5
Ethylene glycol dimethacrylate
(96 % technical) CH2 :CCH3 COOC2 H4 OOCC CH3 :CH2 96–98/4 1.06d15.5/15.5
Glycidyl acrylate CH2:CHCOOCH2CHCH2 57/2 1.1074
O
(continued overleaf )
Table 1.1 (continued )
Monomer Formula b.p. (° C) m.p. (° C) s.g. Pressure
(mm) (d20/20 )
Glycidyl methacrylate CH2:C(CH3)COOCH2CHCH2 75/10 1.073(25)
O
Ethylene glycol monoacrylate CH2 :CHCOOC2 H4 OH 76/8 1.11
Ethylene glycol monomethacrylate CH2 :CCH3 COOC2 H4 OH 84/5 1.07
Propylene glycol monoacrylate CH2 :CHCOOC3 H6 OH 85/9 1.05
Propylene glycol monomethacrylate CH2 :CCH3 COOC3 H6 OH 92/8 1.03
Acrylamide CH2 :CHCONH2 125/25 85 1.22230°
Methacrylamide CH2 :CCH3 CONH2 110
Acrylonitrile CH2 :CHCN 77.3 0.8060
Methacrylonitrile CH2 CCH3 CN 90.3 0.8001d20/4
Methylolacrylamide CH2 CHCONHCH2 OH
(available as 60 % solution)
Methylenediacrylamide CH2 CHCONH2 CH2 97.5/40 0.933d25/4
Diethylaminoethyl methacrylate C2 H5 2 NC2 H4 OOCCCH3 :CH2 103/12 0.914d20/4
t-Butyl aminoethyl methacrylate t-C4 H9 NHC2 H4 OOCCHCH3 :CH2 97.5/40 0.933
trans-Crotonic acid CH2 CH:CHCOOH 72 0.963d80/4
Itaconic acid CH2 :CCH2 COOHCOOH 167 1.6
Maleic acid cis-:CHCOOH2 200 130 1.609d20/4
Fumaric acid trans-:CHCOOH2 290 286 1.635d20/4
Aconitic acid HOOCCH2 C(COOH):CHCOOH 191
Maleic anhydride :CHCO2 0 202 52.5 1.48
Di-n-butyl maleate :CHCOOC4 H9 2 280.6 0.9964
Di-2-ethylhexyl maleate :CHCOOC8 H17 2 209/10 0.9436d15.5/15.5
Dinonyl maleate :CHCOOC9 H19 2 0.9030d15.5/15.5
Di-n-butyl fumarate :CHCOOC4 H9 2 138/8 0.9869(d20/4 )
Di-2-ethylhexyl fumarate :CHCOOC8 H17 2
Methyl acid maleate HOOCCH:CHCOOCH3
Butyl acid maleate HOOCCH:CHCOOC4 H9
Dimethyl itaconate CH3 OOCCH2 C:CH2 COOCH3 91.5/10 1.27d2/4
Dibutyl itaconate C4 H9 OOCCH2 C:CH2 COOC4 H9 140/10 0.9833d2/2
Allyl alcohol CH2 :CHCH2 OH 96 0.8540d20/4
Allyl chloride CH2 :CHCH2 C1 45 0.9397(d20/4 )
Allyl acetate CH2 :CHCH2 OOCCH3 103.5 0.928
Diallyl phthalate CH2 :CHCH2 OOC2 C6 H4 290(150/1)
Allyl glycidyl ether CH2 :CHCH2 OCH2 CHCH2 O 50–52/15 0.967d20/4
Allyl dimethyl glycidate CH2:CHCH2OCCHC(CH3)2 89/8
O
Vinyl methyl ether CH2 :CHOCH3 6 0.7500
Vinyl ethyl ether CH2 :CHOC2 H5 35.5 0.7541
Vinyl n-butyl ether CH2 :CHOC4 H9 94 0.7803
Vinyl isobutyl ether CH2 :CHOC4 H9 83 0.7706
Vinyl cetyl ether CH2 :CHOC16 H33
N-Vinyl pyrrolidone CH2 C(O)NCH:CH2 CH2 CH2 148/100 13.5 1.04
2-Vinyl pyridine CHCHCHCHCCH:CH2 N 110/150 0.9746
4-Vinyl pyridine CHCHCCH:CH2 CHCHN 121/150 0.988
2-Methyl 5-vinylpyridine CHCCH:CH2 CHCHCCH3 N 75/15
7 PHYSICAL PROPERTIES OF MONOMERS
Table 1.1 is not intended to be exhaustive, but gives the b.p and m.p.
values where they are above about 5 ° C and density (s.g.) of the principal
monomers. The order in which they are given is that of previous sections.
8 APPENDIX
This section is devoted to a list of references to which the reader may refer if
more information is required on the subjects listed in this chapter, with special,
but not exclusive, reference to monomers and their general and polymerisation
properties. It is not intended to be exhaustive, and as far as possible is based
on monographs and surveys, to avoid the necessity of obtaining copies of
numerous original works.
There have been few, if any, publications in English or other Western
languages in the quarter century specifically devoted to monomers. A few
earlier works, still useful, are quoted here. For a general account of monomers,
the following is suggested:
C.E. Schildknecht, Vinyl and Related Monomers, Wiley, New York, 1952
Although more than 40 years old, this volume is still very valuable.
R.H. Boundy and R.F. Boyer (eds.), Styrene, Its Polymers, Copolymers and
Derivatives, Reinhold, New York, 1952
E.H. Riddle, Monomeric Acrylic Esters, Reinhold, New York, 1954
S.A. Miller (ed.), Acetylene, Its Properties, Manufacture and Uses, Vol. 1,
Ernest Benn, London, 1965
S.A. Miller (ed.), Ethylene and Its Industrial Derivatives, Chapters 6 and 11,
Ernest Benn, London, 1969
J.V. Koleske and L.H. Wartman (eds.), Polyvinyl Chloride, Its Preparation
and Properties, Gordon and Breach, New York, and Macdonald Technical
and Scientific, London, 1969
Many of the major producers issue bulletins on properties and polymerisation
of the various monomers. The following multivolume Encyclopaedias have
many articles of interest:
Encyclopedia of Polymer Science, 2nd edn, eds. H.F. Mark, G. Gaylord and
N.M. Bikales, Wiley, New York
Comprehensive Polymer Science, eds. C. Booth and C. Price, Pergamon Press,
Oxford, 1989
Handbook of Polymer Science and Technology, eds. G. Allen and
J.C. Bevington, Marcel Dekker, New York
P.A. Lovell, M.S. El-Aasser, eds, Emulsion Polymerisation, and Emulsion
Polymers, John Wiley, 1997.
References 47
REFERENCES
1. H. Staudinger et al., Ber., 53 1073 (1929); Angew. Chem., 42, 37–40 (1929)
2. W.H. Carrothers, in Collected Papers on High Polymeric Substances, H. Mark and
G. Stafford Whitby (eds.), Interscience Publishers, 1940
3. C. Booth and C. Price (eds.), Comprehensive Polymer Science, Vol. 1, Pergamon Press, 1989
4. H.R. Allcock and F.W. Lampe, Contemporary Polymer Chemistry, Vol. 1, 2nd edn, Prentice-
Hall, 1990
5. M.P. Stevens, Polymer Chemistry, 2nd edn., Oxford University Press, 1990
6. G. Odian, Principles of Polymer Chemistry, 3rd edn., Wiley, 1991
7. P.E.M. Allen, in, The Chemistry of Cationic Polymerisation, Plesch (ed.), Pergamon Press,
1963, Ch. 3; As ref 3; Vol. 3, Part 1, G. Sauvet and P. Sigwalt, pp. 579–637; H.st.D. Nuyken,
Pask, pp. 639–710
8. G. Natta and F. Danusso, Stereoregular Polymers and Stereospecific Polymerisation, Perg-
amon Press, Oxford, 1967; Y.V. Kissin in Handbook of Polymer Science and Technology,
Chereminosoff (ed.), Vol. 8, Marcel Dekker, 1989, pp. 9–14
9. M.A. Doherty, P. Gores and A.H.E. Mueller, Polym. Prepr. (Am. Chem. Soc.), 29(2), 72–3
(1988)
10. P.J. Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, Ch. 4, p. 106
et seq.
11. G.C. Eastmond, A. Ledwith, S. Russo and P. Sigwalt, Comprehensive Polymer Science,
Sec. 1, Pergamon Press, 1989
12. F.W. Billmeyer, Textbook of Polymer Science, 3rd edn, Wiley, 1985
13. C.H. Bamford, Encyclopedia of Polymer Science and Engineering, 2nd edn, Vol. 13, pp.
729–35 1988 (refers specifically to retardation and inhibition)
14. C.E. Schildknecht, Allyl Compounds and Their Polymers, Ch. 1, pp. 195 et seq.
15. H. Warson, Per-Compounds and Per-Salts in Polymer Processes, Solihull Chemical Services,
1980
16. M. El-Aaser and J.W. Vanderhoff (eds.), Emulsion Polymerisation of Vinyl Acetate, Applied
Science Publishers, 1981
17. G.S. Misra, and U.D.-N. Bajai, Progress in Polymer Science, Vol. 8, Pergamon Press, 1982–3
18. H. Warson, Makromol. Chemie, 105, 228–45 (1967)
19. H. Warson and R.J. Parsons, J. Polym. Sci., 34(127), 251–269 (1959)
20. H. Warson, Peintures, Pigments, Vernis, 43(7), 438 –446 (1967)
21. T. Alfrey and D. Price, J. Polym. Sci., 2, 101–106 (1947)
22. P.J. Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, Table 20, p. 188
23. D. Price, J. Polym. Sci., 3, 772, (1949)
24. H.N. Friedlander, H.E. Harris and H.E. Pritchard, J. Polym. Sci., 4A(1) 649–64 (1966)
25. J.M.G. Cowie, Comprehensive Polymer Science, Vol. 3, Pergamon Press, 1989, pp. 33–42
26. H. Warson, Chem. Ind., 983, 220–2 (21 March 1983)
27. W.R. Moore, An Introduction to Polymer Chemistry, University of London Press, 1967,
p. 278
28. E.H. Riddle, Monomeric Acrylic Esters, Reinhold, 1964
29. H. Warson, in Properties and Applications of Polyvinyl Alcohol, Society of Chemical
Industry, 1968, pp. 46–76
30. R.K. Tubbs, H.K. Inskip and P.M. Subramanian, in Properties and Applications of Polyvinyl
Alcohol, Society of Chemical Industry, 1968, pp. 88–103
31. K. Noro, in Polyvinyl Alcohol, Properties and Applications, C.A. Finch (ed.), Wiley, 1973,
Ch. 7, pp. 147–166
32. E.H. Merz and R.W. Raetz, J. Polym. Sci., 5, 587 (1950)
33. American Society for Testing Materials (ASTM), Vicat Softening Point D-1525-65T; Ring
and Ball Apparatus E28-67
34. K.E.J. Barrett (ed.), Dispersion Polymerisation in Organic Media, Wiley, 1975
35. S.J. Baum and R.D. Dunlop, FIAT No. 1102, US Department of Commerce, 1947, pp. 13–17
and 42–3
36. S.J. Baum and R.D. Dunlop, FIAT No. 1102, US Department of Commerce, 1947, p. 49
37. L.I. Nass, C.A. Heiberger and M. Langsam (eds.), Encyclopedia of Polymer Science, 2nd
edn, Vol. 1, Wiley, 1985, pp. 127–38
38. H. Warson, Polym., Paint, Col. J., 178, 625–7 and 865–7 (1988)
39. Y. Kobayashi and T. Yoshikawa (Hitachi Chemical), JP 92 339,805–6, 1993; Chem. Abstr.,
119, 118076, 140017 (1993)
40. W.J. Toussaint, and L.G. McDowell (Carbide and Carbon), USP 2,299,862, 1942
41. R.L. Adelman, J. Org. Chem., 14, 1057 (1949)
42. J.E.O. Mayne, H. Warson, and R.J. Parsons (Vinyl Products), BP 827,718, 1960; equivalent
to USP 2,989,544, 1961
43. J.E.O. Mayne and H. Warson (Vinyl Products), BP 877,103, 1961
44. Shell Chemicals, Technical Manuals, VM 1.1, VM1.2, 1991
45. F. Brown and C.D. Mitchell (Dunlop), BP 701,258, 1951
46. H. Warson, Derivatives of Acrylamide, 1990, pp. 46–51
47. H. Warson, Polymerisable Surfactants and Their Applications (Self-Emulsification), Solihull
Chemical Sevices, 1989
48. H. Warson, The Polymerisable Half Esters; Their Polymers and Applications, Solihull Chem-
ical Services, 1978
49. H. Warson et al. (Vinyl Products), BP 995,726, 1965

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1

Fundamentals of Polymer Chemistry

1 THE CONCEPT OF A POLYMER

The condensation is actually three dimensional, and ultimately a three-

The termination reaction depends on several factors, which will be discussed

2.1 Free radical polymerisation

An alternative is disproportionation through transfer of a hydrogen atom:

A further possibility is chain transfer. This is not a complete termination

where Z is a polymeric chain.

Chlorinated hydrocarbons are also commonly used as chain transfer agents,

2.1.1 Retardation and inhibition

Mx C CH2 :CHCH2 OOCCH3 D Mx H C H2 C.CH:CHOOCCH3 7

In this case the allylic radical is formed by removal of an alpha hydrogen

2.1.2 Free radical initiation

The activated molecule then functions as a starting radical. Since, however,

R.CX.O.O.H. ! R.CXO Ð C OHÐ

is by secondary decompositions, which may include various secondary reac-

CH3 3 COOCCH3 3 ! 2CH3 3 COÐ 10a

CH3 3 C.O.O.OCC6 H5 ! CH3 3 CO C CO2 C C6 H5 Ð 11

For a more detailed description of the decomposition of peroxides a mono-

The hydroxyl radical formed commences a polymerisation chain in the usual

Fe2C C HOÐ D Fe3C C OH Ð

When polymerisations are performed it seems of no consequence whether the

A secondary reaction may, however, produce hydroxyl radicals by reaction

SO4  Ð C H2 O ! HSO4  C HOÐ

2.1.3 Redox polymerisation

Alternatively, a hydroxyl radical may be formed together with an acid dithionate

2.2.1 The Q, e scheme

The product of the reactivity ratios is thus independent of Q. The following

3 CHAIN BRANCHING; BLOCK AND GRAFT COPOLYMERS

CHOH CH2 CH CH2

This will be of special interest in dealing with emulsions.

4 POLYMER STRUCTURE AND PROPERTIES

Figure 1.1 Diagrammatic molecular coil. (Reproduced from Moore [27].)

forces. In consequence the Tg diminishes in the case of alkyl ester polymers

4.2 Molecular weight effects

100 Integral and differential

Figure 1.3 Molecular weight distribution for thermally polymerised polystyrene as

dividing by the sum total of the weights. Mathematically, this is given by

(a) Osmometry. This is a vapour pressure method, useful for polymers of

In some cases selective precipitation can be used to fractionate a polymer

4.3 Transition points

5.1 Bulk polymerisation

5.2 Solution polymerisation

5.3 Suspension polymerisation

These dispersing agents may be mixed; occasionally a small quantity of surfac-

6 THE PRINCIPAL MONOMERS AND THEIR POLYMER

a notation used when it is desired to leave the positions of the substituents

6.3 Chlorinated monomers

6.4.3 Acrylics based on the amide group

6.4.4 Cationic acrylic monomers

which is much more reactive. However, it cannot be directly polymerised

6.6 Self-emulsifying monomers

6.7 Esters for copolymerisation

2CH3 OOCCH:CHCOOH D HOOCCH:COOH C CH3 OOCCH:CHCOOCH3

A number of successful copolymerisations in emulsion of half esters of long-

Unsaturated hydrocarbons containing two double bonds constitute a

RH—CH2 DCH—CH2 and R—CH2 —CH—CHDCH2

where R represents a residual monovalent group.

R.CX.O.O.H. ! R.CXO Ð C OHÐ

CH3 3 COOCCH3 3 ! 2CH3 3 COÐ 10a

CH3 3 C.O.O.OCC6 H5 ! CH3 3 CO C CO2 C C6 H5 Ð 11

Fe2C C HOÐ D Fe3C C OH Ð

SO4 Ð C H2 O ! HSO4 C HOÐ