Course: Chemical Technology (Organic)

Module VIII

Lecture 2

Polymers: Polyolefins:
Polyethylene, Poly Propylene
And Polystyrene

LECTURE 2
POLYMERS: POLYOLEFINS: POLYETHYLENE,
POLY PROPYLENE AND POLYSTYRENE,
STYRENE COPOLYMERS
Polyolefinsis family of polymers derived from a particular group of base materials known as
olefins, are the worlds fastest growing polymer family. Polyolefins such as polyethylene (PE)
and polypropylene (PP) are commodity plastics found in applications varying from house hold
items such as grocery bags, containers, carpets, toys and appliances, to high tech products such
as engineering plastics, industrial pipes, automotive parts, medial appliances and even prosthetic
implants [Kapur et al., 2008]. Ethylene and propylene are monomers for polyethylene and
polypropylene respectively. Global polyolefin market is likely to be 150 million tones by 2015
and 200 million tones by the year 2020. In India, the domestic polymer industry (like global
industry) is dominated by polyolefins (polyethylene, polypropylene) [Shashi Kant & Kapur,
2011]. Market coverage of polyethylene, polypropylene is given in Table M-VIII 2.1.
Polystyrene is another important polyolefin and find wide application in manufacture of all sorts
of packaging material. Styrene co-polymerised with acryloonitrile resulting in SAN polymer is
characterized with high tensile strength than polystyrene. Another important styrene copolymer
is Acrylonitrile Butadiene styrene (ABS) plastic find use in engineering plastic and is
characterized with special mechanical properties.

Table M-VIII 2.1: Polyethylene/Polypropylene Market Coverage

Polymer
Types

Grade
Film grade
Pipe grade
Large BM grade

Small BM grade
HDPE
Raffia grade

Market Coverage
Blown film with paper like quality, suitable for
counter bags, carrier bags & wrapping films
Pipes PE-80/100 class, drinking water & gas
pipes, waste pipes & sewer pipes their fitting etc.
Universal container grade, vol. approx.
1,500lit;heating oil storage tanks, transport
containers
Disinfectant bottles, up to 2 lit, tubes for the
cosmetics, containers from few ml up to 10 lit.
Stretched films and tapes for production of high
strength knitted & woven sacks/bags/nets etc.
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Injection Molding
Films
Roto Molding
LLDPE
Injection Molding
Homo polymer

PP

Random Copolymer

Impact Copolymer

For transport and stacking crates, particularly

bottle crates
Garment bags, grocery sacks, liner, blends, trash
bags, cast like film diapers etc.
Large industrial parts used indoors, large
industrial /agricultural tanks, shipping drums, toys
etc.
House wares, crates, master batches, pails, food
container etc.
Injection molding (Battery cases, crates, furniture,
house ware, luggage, sports/toys), Blow molding,
Sheets, Tape/Raffia, FIBC,TQPP/BOPP
films(food packaging, bottle labels etc. )
Extrusion coatings etc.
Thin walled injection moulding, low heat seal &
high transparency films, Blow moulding,
packaging parts, automotive parts etc.
Automotive parts (bumper, exterior trims,
instrument panels, interior trims), Appliances,
House wares, rigid packaging, thermoforming etc.

Source: Kapur et. al., 2008, courtesy: Journal of the petrotech society

CATALYST FOR POLYOLEFIN

There are four major families of catalyst used for olefin polymerization. Characteristics of
catalyst is given in Table M-VIII 2.2.

Ziegler Natta
Phillips(chrome)
Metallocene
Late transition metal catalyst

Table M-VIII 2.2: Characteristics of Polyolefin Catalyst

Type
Ziegler/
Ziegler-Natta

State
Heterogeneous
Heterogeneous

Typical examples
TiCl3 , TiCl 4 / MgCl 2

Phillips(chrome)

Heterogeneous

CrO3 / SiO2

Metallocene

Homogeneous
Heterogeneous
Homogeneous

Cp2ZrCl2
Cp2ZrCl2/MgCl2
Ni, Pd, Co, Fe, with diimine, and other ligands

Late transition metalabsed

VCl4 , VOCl3

Source: Kapur et al. 2008

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POLYETHYLENE
Polyethylene is one of the most widely used thermoplastic and its ever increasing demand is due
to availability of monomer ethylene from naphtha and Gas cracker plant. First polyethylene plant
in India was based on ethylene from molasses. Some of the other deriving force for fast growth
and use of polyethylene are ease of processing the polymer, its relative cost, resistance to
chemicals and its flexibility [Hatch & Matar, 1979]. A wide variety of polyethylene varying
intensity and characteristics for wide range of application is available.

Low density polyethylene (Branched) produced by high pressure

LDPE 0.910 925
M.P. 105-110oCCrystallinity 60-70%

Medium density MDPE

0.920 940
High density HDPE
0.941 0.959 M.P. 125-130oC
Crystallinity 75-90%
Very few side chains. Produced by low pressure

Linear High density to Ultra high density homopolymers

Linear low density polyethylene (LLDPE)0.916-0.940a-olefin as comonomer density
70.941
High molecular weight High density P.E. (HMW-HDPE)

H H

H H H H

H H

C C

CH2

CH2

CH2

CH2

H
H
H H H C
C
H
H

H H H H H
C

C C

H H H H H

Branched

Linear

Molecular mass 200,000 500,000

Advantage: Low cost, excellent dielectric properties, moisture resistance, very good chemical
resistance, available in food grade, processed by all thermoplastic methods.

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Process Technology for Polyethylene: Several processes has been commercialised for
the manufacture of polyethylene with varying densities. Various processes for manufacture
of polyethylene are given in Table M-VIII 2.3.

Table M-VIII 2.3: Various Polyethylene Processes

Process

Licensor

Process

Poduct

Innovene

B.P.Chemicals

Polymerisation in Fluidised bed

reactor using Ziegler Natta catalyst
or Chromium catalyst
Temperature 75oC -110oC
Uses gas phase low pressure reactor.
Ziegler Natta catalyst
Comonomer hydrogen.
Prepolymerisation in slurry loop
reactor and fluidised bed reactor.
Temperature 75oC -100oC

LDPE,HDPE

Process
Broster Process

BorealisA/S

High

pressure Exxon

free

radicals Chemicals Co

Bimodal

and

unimodel
LLDPE,
MDPE

Polymerisation occurs in autoclave LLDPE,

reactors or Tubular reactor

process
Speriline

gas Montell

phase Process

Technology Co

Polymeristion in Gas phase reactor LLDPE, HDPE

using Zigler natta catalyst

Phillips Co, LPE Phillip

Lineal

process

polyethylene

UNIPOL
process
Sclairtech
Process

Polymerisation takes place in an

isobutene slurry using very high
Petroleum Co.
activity properietry catalyst in loop
reactor.
PE Union carbide Low pressure polymerization in
fluidised bed reactor at 25kg/cm2
Corp
and 100oC
Dupont
Polyethylene is produced by solution
polymerization using ethylene gas
and
cyclohexane
as
solvent.
Comonomer butane or Octane or
both) Catalyst: Ziegle Natta catalyst

Source: Hydrocarbon processing petrochemical process 2003

400

LLDPE

to

HDPE
HDPE, MDPE,
LLDPE

UNIPOL Process
The process produces low density polyethylene and high density polyethylene using low pressure
in gas phase. Wide range of polyethylene is produced using proprietary solid and slurry catalyst.
The process produces wide range of polyethylene in a gas phase, fluidised bed reactor using
proprietary solid and slurry catalyst. Gaseous ethylene, comonomer and catalyst are fed to
fluidised bed reactor containing a fluidized bed of growing polymer particles operating at
25kg/cm2 and 100oC. Polymer density is easily controlled from 0.915 to 0.97 g/cm. Process flow
diagram for polyethylene manufacture is given in Figure M-VIII 2.1.

Figure M-VIII 2.1: Fluidized-bed Gas Phase PE Process.

DUPONT SCLAIRTECH Process
A broad range of poluethylene with density varying from 0.919 to 0.9605 g/cm2with varying
melt index can be made by this process. The process can be divided into three major areas

Reaction area
Recycle/recovery Area,
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Extrusion and Finishing

Dowtherm Vaporiser

The process involves solution polymerization of gaseous ethylene using cycolhexane solvent and
comonomer butene or octane comonomer (incase of low density polymers). Zigler catalyst is
used to polymerise ethylene using cycloheaxane as solvent. A chain terminator is used to control
the molecular weight at the reactor outlet a catalyst deactivator is added to terminate the reaction.
The polymer is depressurized to flash off solvent, unreacted ethylene and comonomer from the
molten polyethyelene which are separated and recovered using distillation. The polymer after
stripping the residual solvents fed to main extruder and resulting polymer pellets are dried and
send to blender for homogenizing and finally conveyed to storage silo. In the process Dowtherm
is added as heating media. Process flow diagram for the manufacture of polyethylene by
sclairtech Process is given in Figure M-VIII 2.2.

Figure M-VIII 2.2: LLDPE Process by SCLAIRTECH Process

402

POLYPROPYLENE
Polypropylene is a low density semi-crystalline stereo-regular polymer which exists in three
forms- isotactic, syndiotactic and atactic. Polypropylene was discovered in March 1954 by
Professor Giulio Natta demand of polypropylene is growing at a much faster rate due to its
strong demand per capita consumption of polypropylene is given in Figure M-VIII 2.3.
PP Per Capita Consumption (Kg)
India, 1.7
Global, 7
Middle East,
9.5

China, 8.6

N E Asia, 10.3
S E Asia, 5.5

Source:CMAI

Figure M-VIII 2.3: Per capita Consumption of Polypropylene

Source: Shah,A., Indian propylene markets (India Petrochem 09)

Process Technology for Polypropylene

Polypropylene polymerisation process have undergone a number of revolutionary changes since
the production of crystalline polypropylene were commercialised in 1957 by Motecatini in Italy
and Hercules in U.S. Commercial polypropylene processes are based on low pressure processes
using Ziegler-Natta catalyst that produces a product with an isotactic content of 90percent or
more. Various processes for polypropylene manufacturing are given in Table M-VIII 2.4. A
typical polypropylene process is given in Figure M-VIII 2.4.
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Table M-VIII 2.4: Polypropylene Manufacturing Process

Process and licensor

Summary of process

Product

Borstar Polypropyene Produced

by
bulk
process
Polymerisationin loop reactor
Licensor Borealis A/S followed by final gas phase a
fluidised bed reactor( temp. 8090oC and 25-35 bar.
Spheripol Process
Montell technology

A versatile process and through the

choice of reactor combinations,
homopolymer,random copolymers,
heterophasic copolymers and a very
high rubber content heterophasic
copolymers can be produced
Process produces propylene based
polymers including homopolymer
PP, random and heterophasic
impact and specialty impact
copolymers

Homopolymer and Random

copolymer polymeristion takes
place in liquid propylene in a
loop reactor. Heterophasic impact
compolymerisation is done by
adding a gas phase reactor.
Novolen Process
Polymerization is conducted in Polypropylene
homopolymer,
Krupp Uhde GmbH
one or two gas phase reactors random copolymer and impact
connected in series.
copolymer including Metallocene
PP
Union carbide gas A wide range of polypropylene is Homopolymer, random polymer
phase UNIPOL PP made in a gas phase, fluidised and
impact
copolymer
process
bed reactor using proprietary polypropylene
catalyst
Sperizone Process
Sperizone Process is new A broad range of propylene based
Technology
owner: proprietary gaseous technology polymer can be produced including
Basell polyolefins
based on a multi-zone circulating mono and biomedal (medium/wide,
concept reactor
very wide MWD0
Source: Petrochemical Processes 2003, Hydrocarbon Processing March 2003

Figure M-VIII 2.4: Polypropylene Process

404

UNIPOL Process: The process produces homopolymer, random copolymer and impact
copolymer polypropylene. Polymerisation takes place in a fluidized bed reactor using slurry
reactor (TiCl4 supported on MgCl2 in slurry form in mineral oil. Co-catalyst TEAL, purified
propylene and ethylene incase of random PP), purified H2 and selectivity control agent is
continuously fed to the reactor. Temperature 35oC and pressure 33 kg /cm2 is maintained in the
reactor. Figure M-VIII 2.5 illustrate the Unipol process for manufacturing of polypropylene.

Figure M-VIII 2.5: Polypropylene by Unipol process

Sources: Petrochemical Processes Hydrocarbon Processing, March 2003, Page 124

POLYSTYRENE
Polystyrene is an important thermoplastic. Polystyrene because of itsease of fabrication, low
specific gravity, thermal stability and low cost, find wide applications in consumer durable
goods, electronics, packaging toys, structural foams, wall tiles, shoe soles, blister packages,
lenses, bottle caps, wire and cable sheathing, small jars, vacuum formed refrigerator liners,

405

containers of all kinds, transparent display boxes and automobile interior parts. When styrene is
copolymerized with acrylonitrile, the polymer Styrene Acrylonitrile (SAN) resin has a higher
tensile strength than polystyrene. Acrylonitrile butadiene styrene (ABS) polymer has special
mechanical properties and find application as engineering plastics.
Styrene is produced by dehydrogenation of ethyl benzene which is made by alkylation of
benzene. Ethylbenzene by UOP EB One process is produced by liquid phase alkylation of
benzene using proprietary zeolite catalyst which can be regenerated repeatedly thereby avoiding
significant catalyst disposal problems associated with other aluminium chloride catalyst. The
process offers better product quality, better heat integration, low investment and a more rugged
and reliable catalyst system.[http://www.uop.com/aromatics/3020.html]
Lumus/UOP Classic SM process: in this process styrene is made by catalytically
dehydrogenating ethylbenzene in presence of steam in multistage reactor system. The reaction is
carried out at high temperature under vacuum. The process uses a oxidative rehet technology.
Polystyrene is clear transparent resin with a wide range of melting points and good flow
properties which make it suitable for injection moulding [Hatch & Matar,1979]

Process Technology
There are two major processes for the production of polystyrene are NOVAs Polystyrene
Technology and UOP Polystyrene Technology

NOVAs Polystyrene Technology: The process produces a complete range of general

purpose (crystal) and impact resistant polystyrene. This is based on bulk continuous
polymerization technology.

UOP Polystyrene Technology: this process is based on continuous bulk polymerization to

produce a wide range of general purpose polystyrene, high impact polystyrene and SAN resin. A
typical plant includes feed preparation, reactor section, devolatilisation section, monomer
recovery section, water removal, product pelletizing and bulk resin handling.

406

RREFERENCE
1. Hatch, L.F., Matar, S., From hydrocarbon to petrochemicals Part 16-thermoplastics,
Hydrocarbon, Processing, Vol.58, Sep 1979, p.175 & 141.
2. http://www.uop.com/aromatics/3020.html
3. Hydrocarbon processing, Petrochemical process, 2003
4. Kapur, G.S., Tuli, D.K., Malhotra, R.K. , Kumar, A Polyolefin materials and catalysts: An
Introduction J of The petrotech society, June, 2008, p 10
5. Shah, A, Indian polypropylene markets, Indian Petrochem 2009
6. Shashi Kant, Kapur, G.S. Polypropylene J. of petrotech, March 2011, 27

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