Special Report

SERIES ON RUBBER

Polybutadiene Rubber: A Techno-commercial

Profile

olybutadiene rubber (PBR) is a

homopolymer of 1,3-butadiene
(CH2=CH-CH=CH2 ). It is the
double bonds in the butadiene molecule that are the key to polymer formation. They are attacked by catalysts
to maintain a repetitive chain growth
process, which continues until something is added to terminate the reaction at the desired molecular weight.
For a typical PBR, the number
average molecular weight is usually
>100,000 grams per mole. This represents a chain that contains over 2,000
butadiene units.
Chemistry and manufacturing
process
Most PBRs are made by a solution
process, using either a transition metal
(Nd, Ni, or Co) complex or an alkyl
metal, like n-butyllithium, as catalyst.
Since the reaction is very exothermic, and can be explosive, particularly
with alkyllithium catalysts, the reaction is normally carried out in solvents
like hexane, cyclohexane, benzene or
toluene. The solvents are used to reduce the rate of reaction, control the
heat generated by the polymerization
and to lower the viscosity of the polymer solution in the reactor. A typical
PBR polymerization would be run at
about 20% monomer and 80% solvent.
Batch vs continuous process
The polymerization can either be a
batch process or a continuous process.
In batch mode, monomer, solvent
and catalyst are charged to the reactor, heated to initiate the proChemical Weekly October 13, 2009

cess, and then allowed to continue

to completion. The polymer solution is then transferred to another
vessel or process unit to remove
the solvent.
In continuous mode, monomer, solvent and catalyst are continuously
fed into the bottom of the first of a
series of reactors at a temperature
suitable for polymerization. The
polymerization progresses as the
solution flows through the reactors
and polymer solution is taken off
at the top of the last reactor without stopping the process.
The continuous process is the
most economical. In both processes,
the finished product is usually in the
form of bales, which weigh from 20-35
kg each.

was introduced using the emulsion

polymerisation system. Although this
is not considered to be satisfactory
today, it is used in some plants mainly
due to historical reasons.
The solution polymerisation process, developed in the 1950s, is the
most popular today.
Two types of solution PBR have
emerged as important commercial rubbers the high cis and the medium
cis PBRs. The production of the former
involves co-ordination catalyst systems based on Ti, Co, Ni and Nd, while
that of the latter involves alkyl-lithium
catalyst systems.

Process research underway includes:

High conversion of monomer and
low gel formation in the polymerisation;
Production of high cis PBR;
Improved mechanical properties;
Better catalyst systems; and
Use of safer solvents.

Types of PBR
The polymerisation of butadiene
results in the formation of a number of
stereo isomers. Depending on the disposition of the double bonds present
in the polymer chain, PBR can be classified into five configurations:
Cis-1,4;
Trans-1,4;
Vinyl-1,2 isotactic;
Vinyl-1,2 syndiotactic; and
Vinyl-1,2 atactic.

Emulsion vs solution process

During the 1930s and 1940s, PBR

Depending on the choice of catalyst system, PBR can be prepared rang-

Table 1
Typical composition of PBR with different catalyst systems [%]
Catalyst type
Neodymium
Cobalt
Nickel
Titanium
Lithium

Cis-1,4

Trans-1,4

Vinyl

99
96
96
93
36

1
2
3
3
52

1
2
1
4
12

Source: Chemsystems

213

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ing from almost 100% cis to 100% trans
or 100% vinyl. Out of these configurations, medium and high cis varieties
are of commercial importance and the
most important commercial is the
cis-1,4 whose configuration is similar
to that of natural rubber (NR). NR has
properties of high tack and high
green (unvulcanised) strength, which
are hard to replicate in synthetic rubbers.
Catalyst systems used
Five main catalyst types are used
to produce PBR and the catalyst type
affects the proportion of cis-1,4.
Commercially, the Ziegler-Natta
catalyst system, based on transition
metal compositions and on the rare
earth neodymium (Nd), is used to
manufacture high cis types due to their
selectivity in promoting polymerisation of this type of stereo-regularity.
The properties of high cis PBR vary
between the catalyst systems and
even for one catalyst system. Products
with unbranched chains and narrow
molar mass distributions tend to provide high strength, but are difficult to
process. Long linear chains tend also
to be subjected to greater cold flow,
which is when the green rubber flows
and distorts in storage.
Polymers made with neodymium catalyst are highly linear with broad molar mass distribution, giving good
properties, except for extrudability
and cold flow. This catalyst system
produces the highest cis content of
about 99%, and produces a polymer
with the best tensile and hysteresis
(low heat build-up) properties of all
the high cis types.
Nickel systems tend to produce
rather more highly branched products, with better processability,
but lower tensile strength and fatigue resistance.
214

Titanium and cobalt based products are between these two extremes and the degree of branching can in any case be varied in the
cobalt catalysed system. The cobalt system produces a highly
branched PBR with a low solution
viscosity that makes a good polystyrene and ABS modifier.
Branching can be intentionally introduced into high cis PBR by postpolymerisation reactions, such as with
sulphur dichloride.
High molar mass PBR has improved
tensile strength, abrasion resistance
and fatigue resistance. However, mixing and processing is more difficult
with high molar mass product. Oil extension with naphthenic or aromatic
oil is used to make this material more
easily processed.
High cis-PBR
High cis-1,4 polymer has a very low
glass transition temperature (Tg), compared to alkyllithium-based PBR because it has almost no vinyl structure,
leading to high resilience, good lowtemperature properties and low heat
build-up on repeated deformation.
This makes high cis PBR ideal for
golf ball cores. These cores are cured
with peroxides, which tend to over
cure the vinyl units, making a very
hard and slow golf ball.
High cis-rubber (i.e. 4% or less of
1,2 vinyl) does not crosslink readily
and withstands high temperature without increase in melt viscosity, making
it preferred for tyres where significant
heat build-up can take place.
High cis PBR is used widely in
tyres, where its properties are of benefit in sidewalls, carcass stocks and
tyre treads. However, the high cis PBR
has poor wet grip performance to
counter the advantages of the low roll-

ing resistance and high abrasion resistance. Blending with other polymers, such as SBR, is typically used
to achieve the desired properties of the
tyre tread.
High cis PBR will usually have cis
content >95%, which gives rise to better green strength and increased cut
growth resistance in the cured product. Green strength, which is the
strength of the uncured rubber compound, is important for the tyre building process and cut growth resistance
is necessary for tyre performance. Cut
growth resistance is the resistance to
the propagation of a tear or crack during a dynamic operation like the flexing of a tyre in use.
Lithium-based PBR
The alkyllithium or anionic catalyst
system produces a polymer with about
40% cis, 50% trans and 10% vinyl
when no special polar modifiers are
used in the process. The alkyllithium
process is probably the most versatile, because the growing chain end
contains a living anion, which can be
further reacted with coupling agents
or functional groups to make a variety
of modified PBRs. It also produces gelfree PBR making it ideal for plastics
modification.
Vinyl increases the Tg of the PBR
by creating a stiffer chain structure.
Vinyl also tends to crosslink or cure
under high heat conditions so the high
vinyl polymers are less thermally
stable than low vinyl.
High trans PBR
In the trans configuration, the main
polymer chain is on opposite sides of
the internal carbon-carbon double
bond. High trans PBR is a crystalline
plastic material similar to high trans
polyisoprene, which was used in golf
ball covers. Trans PBR has a melting
point of about 80C. It is made with
transition metal catalysts similar to the
Chemical Weekly October 13, 2009

Special Report
high cis process (La, Nd, and Ni).
These catalysts can make polymers
with >90% trans, again using the solution process.
Low cis PBR is primarily used as a
modifier for polystyrene.
Application for styrenics modification
High impact polystyrene (HIPS)
resins
High impact polystyrene (HIPS)
resins are conventionally prepared by
heat-polymerizing a styrene-PBR solution at a temperature of about 100150C or graft-polymerizing using an
initiator. Such rubber modified HIPS is
a phase in which rubber particles are
dispersed in the matrix of PS, the rubber particles having the sizes of 1.56.0m. When an external impact is applied to the HIPS resin, the rubber particles function to absorb the impact.
Accordingly, the dispersion, sizes and
size distribution of the rubber particles
affect the mechanical properties of the
resin such as impact strength, toughness, surface gloss and heat resistance.
Although conventional rubber
modified HIPS resins are widely used
in electrical household goods and office equipments housing, they are inferior to ABS resin in appearance of
the molded articles such as gloss and
colour. As molded articles with high
gloss are needed in various products,
including sheets for packing containers, the weakness of the appearance
character of HIPS has been an obstacle
for expanding the use of the resin.
In general, the smaller the sizes of
the rubber particles dispersed in PS, the
better the toughness and surface gloss
are, but the worse the impact strength.
However, the larger the sizes of the rubber particles dispersed in PS, the better
the impact strength, but the worse the
toughness and surface gloss.
Chemical Weekly October 13, 2009

ABS resin
ABS resin is a two-phase polymer
system in which a finely dispersed PBR
phase is embedded in a continuous
matrix of SAN copolymer. The rubber
phase is chemically grafted to SAN
during the polymerization of ABS.
The chemical connection between
elastomer molecules and the SAN copolymer is created by polymerizing
styrene and acrylonitrile in the presence of polymerized elastomer. The
resulting grafts serve to compatibilize
the rubber and SAN copolymer
phases.
As to manufacturing, two important changes have occurred. One is the
development and commercial success
achieved by the hybrid emulsion/mass
process. The second is the refinement
of the mass ABS process and the further penetration of grades made by this
process into selected market segments.
Emulsion process
In the emulsion process, ABS resins are prepared by emulsifying a mixture of a latex of PBR (or SBR) together
with styrene and acrylonitrile in water, in the presence of an initiator, an
emulsifier, and a chain length regulator/modifier. This emulsion is then
heated to effect the graft copolymerization of styrene-acrylonitrile containing branches onto the elastomer. The
copolymerization of styrene with acrylonitrile can be conducted simultaneously with the grafting, but recently
it has become more prevalent for this
copolymerization to be conducted
separately at optimal conditions.
Mass or bulk process
The mass or bulk process for ABS
production is based on the polymerization of styrene-acrylonitrile mixtures
in the presence of a rubber substrate
dissolved in this monomer phase. This
is in contrast to the emulsion process,

which takes place in an aqueous phase

that affords lower viscosity of the reaction medium and better heat transfer.
Rubber is usually introduced to the
process in large bales or slabs, which
are ground into small particles and dissolved in a mixture of styrene and acrylonitrile monomers. Since no preformed rubber particles are present at
the beginning of the grafting reaction
as in the emulsion process, a different
distribution of elastomer phase in the
SAN matrix results from the mass process. To maintain manageable processing viscosities, rubber content of
mass polymerized ABS is usually limited to 15%, at most 20%.
Hybrid process
As the name implies, the hybrid
emulsion/mass process combines features of the emulsion process, which
forms the PBR latex and grafts styrene
and acrylonitrile, and the mass process, which makes the SAN component.
The recovered graft rubber and
SAN are compounded together to give
the final ABS product. This approach
permits producing a wide range of ABS
products using two or three basic SAN
polymers and a similar number of high
rubber ABS graft resins and compounding them together in various
combinations and proportions.
In the hybrid emulsion/mass process, the SAN component is prepared
by mass polymerization of styrene and
acrylonitrile. The monomers are mixed
together with additives and up to
about 5% ethylbenzene diluent to
lower viscosity, preheated, and fed to
a series of three vertical tower reactors. Reaction heat is rejected to cooling water. The main difference from a
pure mass process for ABS is the absence of PBR dissolved in the monomers. Thus, phase inversion is not in215

Special Report
volved and intense agitation is not
needed to tailor the rubber particle
size and distribution.

Toyo and Mitsui Chemicals, Inc.,

to provide an example, have been
jointly promoted the R&D and the licensing of the Toyo-Mitsui PS Process
based on the continuous bulk polymerization technology. The process
covers all of styrenics resins (GPPS,
HIPS, SAN and ABS resin).
Properties of PBR
All forms of PBR share certain important characteristics. They have
very high resilience in fact they are
the only type of synthetic rubber with

HIPS

Impact Strength

Transparency

Commercial process
The first commercial grades of ABS
polymer, originally introduced in 1948,
were simply mechanical blends of rubber with SAN copolymer. These
blends reportedly used nitrile rubber
since it was found to be more compatible with the SAN resin than was PBR.
Although these early ABS polymers
were superior to HIPS then on the market, it was recognized that the properties were inferior to graft copolymers
where there is an actual chemical link-

age between the continuous and elastomeric phases.

+ Rubber

SAN

Figure 1: Modification of properties of styrenics

Prepolymerisation

Rubber
Disolver

Devolatiliser(s)

Vacuum
System

Reactor(s)
Devolatiliser
Condenser

Styrene
Tank

PBR can also take heavier loadings

of carbon black. This enables manufacturers to obtain increased abrasion
resistance in tyre-tread compounds
without reducing flexibility or adding
to the heat build-up.

The use of PBR made it possible

to increase the proportion of synthetic rubber used for bus and truck
tyres. Its greatest usage is for small
truck and passenger vehicle tyres
in this application it has improved the wearing properties of
these tyres and has eliminated
groove cracking.

+ Acrylonitrile
Chemical Resistance

Rubber(s)

PBR can tolerate a large proportion

of oil extension without a serious loss
in properties. Adding oil to the rubber
makes it easier to process into downstream products.

The disadvantage of PBR is that it

tends to have low tear strength and
has relatively poor resistance to cut
growth. Therefore it is rarely used
alone, but blended with various proportions of SBR, NR and synthetic
polyisoprene.

ABS

GPPS

a higher resilience than NR. The rubber also has outstanding resistance to
abrasion and good flexibility at low
temperatures.

Pellet
Slip

Table 2
Properties of PBR
Favourable
Low heat build-up

(Acrylonitrile)
Tank

Solvent
Tank

Monomer
Feed Tank

Pelletizing
Unit
Product
HIPS
*(ABS)

Recycle Monomer
Tank
Figure 2: Rubber based styrenics process scheme (HIPS or ABS)

216

Unfavourable

Very high air

permeability
High resilience
Poor tack
Better flex resistance Poor road grip
Good heat stability Poor tear
and tensile
strength
International market scenario
PBR is the second-largest end-use
for butadiene worldwide, accounting
for about 26-28% of total butadiene
Chemical Weekly October 13, 2009

Special Report
consumption, second only to SBR,
which accounts for about 36-44% of
butadiene consumption.
PBR is also the second largest volume synthetic rubber produced, again
next to only to SBR. The major use of
PBR is in tyres with over 70% of the
polymer produced going into treads
and sidewalls. The dominance of tyres
in PBR demand has slightly declined
since 1980, when it accounted for 78%.
Cured PBR imparts excellent abrasion resistance (good tread wear), and
low rolling resistance (good fuel
economy) due to its low glass transition temperature. However, this also
leads to poor wet traction properties,
so PBR is usually blended with other
elastomers like NR or SBR for tread
compounds.
PBR also has a major application
as an impact modifier for polystyrene
and acrylonitrile-butadiene-styrene
(ABS) resin, with about 17-21% of the
total volume going into these applications. Typically about 7% PBR is

added to the polymerization process

to make rubber-toughened resins.
Polystyrene modification accounts
for the majority of use. In this application, PBR provides toughness and impact resistance for high-impact polystyrene (HIPS). In fact, HIPS is the largest non-tyre end-use for PBR. The
next-largest market is ABS, where PBR
again adds impact resistance to the
copolymer.
Other non-tyre uses in footwear,
other rubber products and golf balls
are a relatively small part of the market, contributing 7-12% of PBR demand.
High cis PBR is generally used
worldwide for manufacturing of golf
balls. This application is growing
since the golf ball industry seems to
have moved away from the traditional
wound ball technology to the twopiece, solid core construction.
Specialty applications such as carboxyl- and hydroxyl-terminated PBR

ABS 4%

Tyres 68%

Figure 3: Global PBR application

Chemical Weekly October 13, 2009

Global production and consumption of PBR in 2008 were both approximately 2.9-mt. Global capacity utilization was 86% in 2008; up from 85% in
2007. PBR consumption is estimated
to have increased by less than 1% in
2008, and is forecast to average
moderate growth of around 2.1% per
year from 2008 to 2013, dropping under 2% per year from 2013 to 2018.
Average global utilization rates are
expected to increase to the mid to
high-80s range throughout the forecast period.
Tyre and tyre products represent
the major use of global PBR, accounting for around 68% of consumption in
2008. Polystyrene (GPPS and HIPS)
resins and ABS resins modification
consume approximately 13% and 4%, respectively, of the total. Specialty applications for PBR include carboxyl- and hydroxyl-terminated PBR grades, golf ball
centres, non-tyre rubber pro-ducts, and
other specialty adhesives and binders.
Certain trends in different regions
have influenced PBR consumption.

Others 15%

PS 13%

grades are used in binders for rocket

propellants and in sealants and waterproof membranes.

Russia and other Eastern European

countries had a catastrophic dropoff in use during the 1990s because
of the weakness of their economies
and other problems associated
with shifting from centrally planned
governments. From 1990 to 1999,
consumption of PBR declined by
about 10% per year. However,
since 1999, PBR consumption has
experienced growth because of
more stability in their economies
and governments. Annual growth
of about 4-5% is expected during
2007 to 2012, especially with increased economic cooperation
among European nations.
In Asia, China is currently under217

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Table 3
Production, imports, consumption of PBR in India
[Kilotons]
Year
2000-01
2001-02
2002-03
2003-04
2004-05
2005-06
2006-07
2007-08
2008-09

Capacity

Production

Import

Consumption

Capacity
Utilisation [%]

Import:
Consumption [%]

50.00
50.00
50.00
50.00
50.00
50.00
73.92
73.92
73.92

41.00
43.00
56.00
63.00
65.00
71.00
74.00
72.00
74.00

26.00
24.00
8.00
7.00
11.00
9.10
10.00
10.98
14.16

67.00
67.00
64.00
70.00
76.00
80.10
84.00
82.98
88.16

82.00
86.00
112.00
126.00
130.00
142.00
100.11
97.40
100.11

38.81
35.82
12.50
10.00
14.47
11.00
12.00
13.00
16.00

Source: Petrochemical Statistics; Dept. of Chemicals & Petrochemicals

Table 4
Consumption pattern of PBR in India
2003-04
Sector

Consumption [tons]

Automotive Tyres
Tyre retreading
Plastic modification (HIPS/ABS)
Other uses
Total

Share [%]

Consumption [tons]

Share [%]

45,000
15,000
7,000
3,000

64.3
21.4
10.0
4.3

57,300
17,630
9,730
3,500

65.0
20.0
11.0
4.0

70,000

100.0

88,160

100.0

going rapid economic development

and technological improvements,
causing PBR production and consumption to increase. PBR capacity operating rates in Asia are expected to be high in the next few
years, as demand continues to
grow. Chinas output of cis-1,4PBR
was 460,000-tons in 2007, up 2.9%
year on year.
Indian scenario
In the early 1970s, Indian Petrochemicals Ltd. (IPCL), now a Reliance Group
company, set up manufacturing facilities
for PBR with technology from Polymer
Corporation of Canada. The commercial
production in this plant with an installed
capacity of 20,000-tpa started in 1978. The
plant produces mainly high cis-PBR, us218

2008-09

ing a Ziegler Natta type catalyst system

based on cobalt. The project cost at the
time of project implementation was Rs. 30crore.
To meet increased demand, IPCL
set up a second plant at Baroda based
on technology provided by Japan Synthetic Rubber (JSR). This 30,000-tpa
plant, based on a nickel catalyst system, cost Rs. 150-crore at the tine of
installation. Commercial production at
this plant began in 1995-96.
Currently, IPCL, has an installed
capacity of 73,920-tpa of PBR. The
company makes two grades 1220
and 01 both for the tyre sector.
Production of PBR has increased

from 40-kt in 2000-01 to 74-kt in 200809, thereby registering compounded

annual growth rate of 7.6%, while consumption has registered a CAGR of
3.5% during the same period. The share
of imports to total consumption has
come down from around 39% in 200001 to 16% in 2008-09.
Consumption pattern
The automotive tyre sector consumes 85% of the total PBR consumption in the country. Of this 85%, 75%
is used by the virgin tyre sector, while
25% is used by the retreading sector.
Plastic modification for HIPS/ABS
accounts for around 10-11% of total
consumption of PBR and the balance
4% is for other applications.
Chemical Weekly October 13, 2009