Kirk-Othmer Encyclopedia of Chemical Technology.

Copyright

c John Wiley & Sons, Inc. All rights reserved.

STYRENE-BUTADIENE RUBBER
Attempts to produce synthetic rubber have been carried out since the 1800s. The introduction of automobiles
in the early 1900s gave added impetus to find a substitute for natural rubber, the price of which tripled from
$2.16/kg in 1900 to $6.73/kg in 1910 (1). The advent of World War I gave Germany incentive to start a crash
program on an alternative to natural rubber. From this work, products based on dimethylbutadiene were used,
but these were not found to be good substitutes.
In the late 1920s Bayer & Company began reevaluating the emulsion polymerization process of polybuta-
diene as an improvement over their Buna technology, which was based on sodium as a catalyst. Incorporation
of styrene (qv) as a comonomer produced a superior polymer compared to polybutadiene. The product Buna
S was the precursor of the single largest-volume polymer produced in the 1990s, emulsion styrene–butadiene
rubber (ESBR).
When the United States entered World War II, access to the source of natural rubber was eliminated and
the federal government set up a consortium of American rubber manufacturers under the auspices of the Office
of Rubber Reserve. A total of 15 styrene–butadiene rubber (SBR) plants were constructed between 1941 and
1942. These plants, devoted to the production of a natural rubber substitute, were run by the four principal
rubber companies in the United States: Goodyear, U.S. Rubber, B.F. Goodrich, and Firestone. To increase the
number of rubber companies participating in the program, two additional companies were formed from smaller
rubber producers: Copolymer Corporation and National Synthetic Rubber Corporation (2). The product agreed
upon was called GR-S, an abbreviation for Government Rubber–Styrene, and was based on Buna S. It was
the standard general-purpose SBR manufactured until right after World War II, when Germany’s work on a
low temperature system to generate free radicals for cold emulsion polymerization of SBR became known. The
properties of this product were so much better than the hot GR-S that the Office of Rubber Reserve ordered all
of the consortium’s plants to install refrigeration equipment and begin phasing in the cold-polymerized GR-S.
This product has been the basis of the emulsion polymer industry in the United States ever since.
In the mid-1950s, the Nobel Prize-winning work of K. Ziegler and G. Natta introduced anionic initiators
which allowed the stereospecific polymerization of isoprene to yield high cis-1,4 structure (3, 4). At almost the
same time, another route to stereospecific polymer architecture by organometallic compounds was announced
(5).
In the 1960s, anionic polymerized solution SBR (SSBR) began to challenge emulsion SBR in the automotive
tire market. Organolithium compounds allow control of the butadiene microstructure, not possible with ESBR.
Because this type of chain polymerization takes place without a termination step, an easy synthesis of block
polymers is available, whereby glassy (polystyrene) and rubbery (polybutadiene) segments can be combined
in the same molecule. These thermoplastic elastomers (TPE) have found use in nontire applications. Styrene–
butadiene–styrene blocks are formed by the anionic solution polymerization technique. The long styrene block
portion of the polymer chain imparts a rigidity similar to that of vulcanized rubber. Being thermoplastic, the
polymers are easily worked on conventional equipment. Also, because the styrene segments soften on heating,
the polymer scrap can be reworked, unlike vulcanized rubber.

1
2 STYRENE-BUTADIENE RUBBER

1. Physical Properties

Desirable properties of elastomers include elasticity, abrasion resistance, tensile strength, elongation, modu-
lus, and processibility. These properties are related to and dependent on the average molecular weight and
mol wt distribution, polymer macro- and microstructure, branching, gel (cross-linking), and glass-transition
temperature (Tg ) (see Elastomers, synthetic).
Emulsion polymerization gives SBR polymer of high molecular weight. Because it is a free-radical-initiated
process, the composition of the resultant chains is heterogeneous, with units of styrene and butadiene randomly
spaced throughout. Unlike natural rubber, which is polyisoprene of essentially all cis-1,4 configuration, giving
an ordered structure and hence crystallinity, ESBR is amorphous. For cold ESBR polymerized at 4–10◦ C, the
typical microstructure of the butadiene portion is 72% trans-1,4, 12% cis-1,4, and 16% 1,2. In hot polymerized
ESBR (51.5◦ C), the typical ratio is changed somewhat to 65% trans-1,4, 18.5% cis-1,4, and 16.5% 1,2 (6).
Unlike SSBR, the microstructure of which can be modified to change the polymer’s Tg , the Tg of ESBR
can only be changed by a change in ratio of the monomers. Glass-transition temperature is that temperature
where a polymer experiences the onset of segmental motion (7).
For ESBR polymerized at 50◦ C, knowing the percentage of bound styrene in the copolymer allows esti-
mation of the Tg by the following, where S is the weight fraction of the styrene (% bound styrene) (8).

Tg (◦ C) = (−85 + 135 S) / (1 − 0.5 S) (1)

Similarly, for ESBR made at 5◦ C, the Tg is given by equation 2:

Tg (◦ C) = (−78 + 128 S) / (1 − 0.5 S) (2)

The glass-transition temperaturesfor solution-polymerized SBR as well as ESBR are routinely determined
by nuclear magnetic resonance (nmr), differential thermal analysis (dta), or differential scanning calorimetry
(dsc).
Among the techniques employed to estimate the average molecular weight distribution of polymers
are end-group analysis, dilute solution viscosity, reduction in vapor pressure, ebulliometry, cryoscopy, va-
por pressure osmometry, fractionation, hplc, phase distribution chromatography, field flow fractionation, and
gel-permeation chromatography (gpc). For routine analysis of SBR polymers, gpc is widely accepted. Table 1
lists a number of physical properties of SBR (random) compared to natural rubber, solution polybutadiene, and
SB block copolymer.
Advantages of NR/IR are high resilience and strength, and abrasion-resistance. BR shows low heat buildup
in flexing, good resilience, and abrasion-resistance. Random SBR is low in price, wears well, and bonds easily.
Block SBR is easily injection-molded, and is not cross-linked. Applications of NR/IR include tires, tubes, belts,
bumpers, tubing, gaskets, seals, foamed mattresses, and padding. BR is used in tire treads and mechanical
goods, as is random SBR. Block SBR is used in toys, rubber bands, and mechanical goods.

2. Raw Materials

The monomers, butadiene (qv) and styrene (qv), are the most important ingredients in the manufacture of SBR
polymers. For ESBR, the largest single material is water; for solution SBR, the solvent.
The quality of the water used in emulsion polymerization has long been known to affect the manufacture
of ESBR. Water hardness and other ionic content can directly affect the chemical and mechanical stability of
the polymer emulsion (latex). Poor latex stability results in the formation of coagulum in the polymerization
stage as well as other parts of the latex handling system.
 STYRENE-BUTADIENE RUBBER 3

Table 1. Properties and Applications of Cross-Linked Rubber Compoundsa

Property NR/IRb BRc SBR randomd SBR blocke
Gum stock f
density, g/cm3 0.93 0.93 0.94 0.94–1.03
tensile strength, MPag 17–21 1.4–7 1.4–2.8 11.7–25.5
resistivity,
·cm , log 15–17 15 13
dielectric con-stant at 1 2.3–3.0 2.3–3.0 3.0 3.4
kHz
dissipation factor at 1 kHz 0.0002–0.0003 0.0002–0.0003
dielectric strength, 18.9
MV/mh
Reinforced stock
tensile strength, MPag 21–28 14–24 14–24 7–21
elongation at break, % 300–700 300–700 300–700 500–1000
hardness, Shore A 20–100 30–100 40–100 40–85
resilience excellent excellent good excellent
stiffening tem-perature, −30 to −45 −35 to −50 −20 to −45 −50 to −60
◦C

brittle tem-perature, ◦ C −60 −70 −60 −70

continuous high 100 100 110 65
temperature limit, ◦ C
Resistance to solvents and conditions
acid good good good good
alkali good good good good
gasoline and oil poor poor poor poor
aromatic hydrocarbons poor poor poor poor
ketones good good good poor
chlorinated solvents poor poor poor poor
oxidation good good good good
ozone poor poor poor poor
γ -radiation good good good good
a Ref. 9.
b cis-1,4-Polyisoprene, natural rubber (NR), also made synthetically (IR).
c cis-1,4-Polybutadiene.
d Styrene–butadiene random copolymer, 25 wt % styrene.
e Styrene–butadiene block copolymer, ∼25% SBR styrene (YSBR).
f Cross-linked and unfilled.
g To convert MPa to psi, multiply by 145.
hTo convert MV/m to kV/in., multiply by 25.65.

In converting ESBR latex to the dry rubber form, coagulating chemicals, such as sodium chloride and
sulfuric acid, are used to break the latex emulsion. This solution eventually ends up as plant effluent. The
polymer crumb must also be washed with water to remove excess acid and salts, which can affect the cure
properties and ash content of the polymer. The requirements for large amounts of good-quality fresh water
and the handling of the resultant effluent are of utmost importance in the manufacture of ESBR and directly
impact on the plant operating costs.
Solution polymerization can use various solvents, primarily aliphatic and aromatic hydrocarbons. The
choice of solvent is usually dictated by cost, availability, solvency, toxicity, flammability, and polymer structure.
SSBR polymerization depends on recovery and reuse of the solvent for economical operation as well as operation
under the air-quality permitting of the local, state, and federal mandates involved.
4 STYRENE-BUTADIENE RUBBER

2.1. Styrene

Commercial manufacture of this commodity monomer depends on ethylbenzene, which is converted by several
means to a low purity styrene, subsequently distilled to the pure form. A small percentage of styrene is
made from the oxidative process, whereby ethylbenzene is oxidized to a hydroperoxide or alcohol and then
dehydrated to styrene. A popular commercial route has been the alkylation of benzene to ethylbenzene, with
ethylene, after which the crude ethylbenzene is distilled to give high purity ethylbenzene. The ethylbenzene is
directly dehydrogenated to styrene monomer in the vapor phase with steam and appropriate catalysts. Most
styrene is manufactured by variations of this process. A variety of catalyst systems are used, based on ferric
oxide with other components, including potassium salts, which improve the catalytic activity (10).
In 1990, the annual U.S. capacity to manufacture styrene monomer was 4,273,000 t/yr, and production
was 3,636,000 t/yr (11). Polystyrene resin is the dominant user of styrene monomer. SBR use is about 7% of
U.S. domestic styrene monomer production. Worldwide production in 1995 was projected to be 77% of capacity
as demand increased just under 5% per year, from 1990 consumption of 13,771,000 to 17,000,000 metric tons
in 1995.

2.2. Butadiene

Although butadiene was produced in the United States in the early 1920s, it was not until the start of World War
II that significant quantities were produced to meet the war effort. A number of processes were investigated
as part of the American Synthetic Rubber Program. Catalytic dehydrogenation of n-butenes and n-butanes
(Houdry process) and thermal cracking of petroleum hydrocarbons were chosen (12).
Economic considerations in the 1990s favor recovering butadiene from by-products in the manufacture of
ethylene. Butadiene is a by-product in the C4 streams from the cracking process. Depending on the feedstocks
used in the production of ethylene, the yield of butadiene varies. For use in polymerization, the butadiene must
be purified to 99+% . Crude butadiene is separated from C3 and C5 components by distillation. Separation of
butadiene from other C4 constituents is accomplished by salt complexing/solvent extraction. Among the solvents
used commercially are acetonitrile, dimethylacetamide, dimethylformamide, and N-methylpyrrolidinone (13).
Based on the available crude C4 streams, the worldwide forecasted production is as follows: 1995, 6,712,000;
1996, 6,939,000; 1997, 7,166,000; and 1998, 7,483,000 metric tons (14). As of January 1996, the 1995 actual
total was 6,637,000 t.

2.3. Soap

A critical ingredient for emulsion polymerization is the soap (qv), which performs a number of key roles,
including production of oil (monomer) in water emulsion, provision of the loci for polymerization (micelle),
stabilization of the latex particle, and impartation of characteristics to the finished polymer.
Fatty acid soap was first used for ESBR. Its scarcity prompted the investigation of rosin acids from
gum and wood as substitutes (1). The discovery of the disproportionation of rosin allowed rosin acid soaps to
overcome the polymerization inhibition of untreated rosin acids. Rosin acid soaps gave the added benefit of
tack to the finished polymer. In the 1990s, both fatty acid and rosin acid soaps, mainly derived from tall oil, are
used in ESBR.
 STYRENE-BUTADIENE RUBBER 5

3. Polymerization

ESBR and SSBR are made from two different addition polymerization techniques: one radical and one ionic.
ESBR polymerization is based on free radicals that attack the unsaturation of the monomers, causing addition
of monomer units to the end of the polymer chain, whereas the basis for SSBR is by use of ionic initiators.
Free-radical initiation of emulsion copolymers produces a random polymerization in which the trans/cis
ratio cannot be controlled. The nature of ESBR free-radical polymerization results in the polymer being hetero-
geneous, with a broad molecular weight distribution and random copolymer composition. The microstructure
is not amenable to manipulation, although the temperature of the polymerization affects the ratio of trans to
cis somewhat.
In solution-based polymerization, use of the initiating anionic species allows control over the trans/cis
microstructure of the diene portion of the copolymer. In solution SBR, the alkyllithium catalyst allows the 1,2
content to be changed with certain modifying agents such as ethers or amines. The use of anionic initiators to
control the molecular weight, molecular weight distribution, and the microstructure of the copolymer has been
reviewed (15).

3.1. Emulsion Polymerization

Emulsion SBR was commercialized and produced in quantity while the theory of the mechanism was being
debated. Harkins was among the earliest researchers to describe the mechanism (16); others were Mark (17)
and Flory (18). The theory of emulsion polymerization kinetics by Smith and Ewart is still valid, for the most
part, within the framework of monomers of limited solubility (19). There is general agreement in the modern
theory of emulsion polymerization that the process proceeds in three distinct phases, as elucidated by Harkins
(20): nucleation (initiation), growth (propagation), and completion (termination).
The nucleation stage for sparingly water-soluble monomers, such as styrene and butadiene, lasts up to 15
to 20% conversion of monomer to polymer. Free radicals from some source initiate polymerization in one of four
loci: (1) in the water phase where a free radical attacks a soluble monomer molecule (homolytic nucleation);
(2) at some part of the monomer-swollen micelle (micellar nucleation); (3) at the combined surfactant molecule
and solvated monomer oligomer in the dispersed phase (nucleation by hydrophobic association); and (4) at
the surface of the stabilized monomer droplet. In the first case, the growing oligomer reaches a finite chain
length and collapses to form a polymer particle. Available soap then stabilizes this particle. For SBR, the
most important source of polymer generation is the micelle. Nucleation by hydrophobic association, similar
to homogenous nucleation, forms particles as the oligomer chain reaches a finite length and precipitates out
of solution as a particle stabilized with a layer of soap. In the fourth case, because the number of monomer
droplets is small in relation to the number of available monomer-swollen micelles, polymer formation in the
droplet is not statistically significant on account of the great difference in surface area of micelles compared to
the monomer droplets and is therefore generally ignored.
The onset of the growth stage is characterized by the disappearance of the micelles. At this point, the
growing micelle undergoes a metamorphosis, becoming a polymer particle, now surrounded by a charged layer
of surfactant. During this phase, monomer from the shrinking droplets continues to diffuse through the water
phase. Polymerization proceeds at a constant rate under steady-state conditions. It is during this stage that
free surfactant is made available. The surfactant arises from the following sources: the shrinking monomer
droplets, released surfactant from agglomeration of latex particles, and released surfactant from the growing
polymer particles which need less surfactant coverage at a larger size because of the surface-to-volume ratio.
If enough soap becomes available then more micelles can form. This results in another particle population that
gives a bimodal particle distribution. This stage for SBR ends at 55–65% conversion.
The completion stage is identified by the fact that all the monomer has diffused into the growing poly-
mer particles (disappearance of the monomer droplet) and reaction rate drops off precipitously. Because the
6 STYRENE-BUTADIENE RUBBER

free radicals that now initiate polymerization in the monomer-swollen latex particle can more readily attack
unsaturation of polymer chains, the onset of gel is also characteristic of this third stage. To maintain desirable
physical properties of the polymer formed, emulsion SBR is usually terminated just before or at the onset of
this stage.
Advantages of emulsion polymerization of SBR include the following: (1) high molecular weight polymer
at high rates; (2) relatively low viscosity of the latex formed to give good heat transfer of the generated
exotherm; (3) good control of the polymerization temperature; (4) ease of removing unreacted monomers and
their recovery; and (5) ease of processing the finished latex into dry polymer product.
The original emulsion SBR was run at high temperature (50◦ C) using a fatty acid soap system (Table 2).
This was because the available free-radical source was potassium peroxydisulfate, K2 S2 O4 , which depends on
elevated temperature for the production of free radicals (thermal decomposition). It was found early on that
dodecyl mercaptan played a key role in the polymerization initiation, as well as in the regulation of the polymer
molecular weight. It was proposed that the mercaptan radical formed from the action of the persulfate radical
as the initiating species for polymerization (22). More recently it has been shown that the enhancement of
the mercaptan promoting effect is specific to fatty acid soap containing persulfate-initiated diene systems (23).

Originally, the production of emulsion SBR was conducted by the batch method, which involves the
charging of the entire recipe ingredients at the same time. As the polymerization advances, the amount of
solids (polymer) increases. The percentage of solids is related to the percentage of conversion of monomer to
polymer. At the proper conversion rate, in this case 75%, a dilute solution of a chemical called a shortstopping
agent is added to the reactor. Hydroquinone, at low levels, is effective. The termination of polymerization
is accomplished in two ways. First, shortstopping agents, ie, reducing agents, combine with the initiating
species, ie, an oxidizing agent, and effectively destroy the source of free radicals. The second step is to trap
and neutralize the free radicals already generated. In the case of hydroquinone, it reduces the persulfate and
effectively destroys the generation of any free radicals (24). As it is oxidized to the quinone structure, it becomes
an effective free-radical acceptor, scavenging any remaining free radicals.
The shortstopped latex is transferred to one of a series of large vessels, referred to as blowdown tanks,
which hold two batches in addition to adequate vapor space. The hot latex is then transferred to large horizontal
tanks by pressure differential. These tanks are referred to as flash tanks, for as the latex enters the tank it
degasses, that is, releases the residual butadiene, gaseous monomer. The degassed latex is then pumped to
the top of a plate column where it is contacted by steam entering the bottom, with the column operating
under vacuum. This countercurrent steam distillation of the hot latex efficiently removes the residual styrene
monomer. Because SBR contains a high percentage of unsaturation (double bonds) from the butadiene, it is
susceptible to degradation by heat, light (uv energy), and O2 (oxidation). Certain chemicals called antioxidants
effectively protect polymers from this degradation. The finished latex containing antioxidant is then subjected
to a two-stage coagulation that breaks the emulsion, resulting in a slurry of rubber crumb. The crumb is then
passed through a series of washes and dewatering, finally reground and then dried to a low moisture content
in large, continuous-belt dryers heated by direct gas-fired burners or steam pipes. The crumb exiting the dryer
is then baled in a hydraulic baler in standard 80-lb bales (∼36 kg ), bagged or film-wrapped, and boxed for
shipment in standardized containers.
Through the years, improvements in the finishing process eliminated the need of two-stage coagulation, ie,
creaming the latex with sodium chloride and coagulating this agglomerated latex with sulfuric acid. The same
results are achieved by mixing the salt and acid and coagulating in one step. To aid the complete coagulation
of the SBR latex, small amounts of coagulant aids are added. These coagulant aids are usually based on
polyamines. In the mid-1970s, many commercial ESBR manufacturers replaced the brine (NaCl) by increasing
the level of polyamine coagulants. A significant benefit from the change was in the reduction of ash residue
in the polymer. Single-screw dewatering presses replaced vacuum filters for effective dewatering of the crumb.
The screw dewaterers express large amounts of water at its boiling point as a result of the work put into the
 STYRENE-BUTADIENE RUBBER 7

Table 2. Typical SBR Recipesa

Cold SBR
Elastomer Hot SBR 1000 1500 1502
Composition, phm
butadiene 71 71 71
styrene 29 29 29
potassium peroxydisulfate 0.3
p-menthane hydroperoxide (PMHP) 0.12 0.12
n-dodecyl mercaptan (DDM) 0.5
t-dodecyl mercaptan (TDM) 0.2 0.18
Emulsifier makeup, phm
waterb monomer/water 200 200 200
disproportionated tall oil rosin acid 4.5–5 4.5 1.35
soap
hydrogenated tallow fatty acid soap 4.5 3.15
potassium chloride 0.3 0.3 0.3
DARVAN WAQ (secondary 0.1 0.1
emulsifier)
Versene Fe-3 (iron complexing agent) 0.01 0.01
sodium dithionate (oxygen 0.025 0.025
scavenger)c
Sulfoxylate activator makeup, phm
ferrous sulfate heptahydrate 0.04 0.04
Versene Fe-3 0.06 0.06
sodium formaldehyde
sulfoxylate (SFS) 0.06 0.06
Shortstop makeup, phm
methyl namate 0.05 0.05 0.05
diethylhydroxylamine 0.015 0.015 0.015
Polymerization conditions
temperature, ◦ C 50 5 5
final conversion, % 72 60–65 60–65
coagulation acid/amine acid/amine acid/amine
antioxidant, ∼0.5 − 0.75 on rubber stainer stainer nonstainer
organic acid content, by weight 5–7 5–7 5–7
styrene content, by weight 24 24 24
mooney viscosity ML-4, min at 100◦ C 48 46–58 46–58
a Ref. 21.
b Monomer/water ratio adjusted to 1:2.
c pH of solution to 10–10.5.

polymer as it passes through the machine. Soluble salts are released with the water, resulting in lower ash
content of the polymer. Figures 1 and 2 illustrate a modern production flow sheet for manufacturing solid
ESBR.
Initially, all of the SBR polymer known as GR-S produced during World War II was by the batch process.
Later, it was thought that a higher volume of polymer would be needed for the war effort. The answer was found
in switching from batchwise to continuous production. This was demonstrated in 1944 at the Houston, Texas,
synthetic rubber plant operated by The Goodyear Tire & Rubber Company. One line, consisting of 12 reactors,
was lined up in a continuous mode, producing GR-S that was more consistent than the batch-produced polymer
(25). In addition to increased productivity, improved operation of the recovery of monomers resulted because
of increased (20%) reactor capacity as well as consistent operation instead of up and down, as by batchwise
polymerization.
8 STYRENE-BUTADIENE RUBBER

Fig. 1. Typical continuous emulsion SBR polymerization.

Continuous polymerization is accomplished by making up all recipe ingredients in solutions, which are
mixed with the monomer streams, brought to desired temperature, and initiated by addition of the free-radical
source. Of critical importance is the accurate makeup of the solutions and precise metering of all the streams.
Modern ESBR plants depend on computer control (distributive control systems). The reactors are connected
in series so that the liquid flow is into the bottom and out the top of each agitated vessel. The residence time
in the reactor train is controlled by either a variable volume last reactor or a series of large-diameter pipes
(displacement columns), whereby at the correct solids percentage (conversion), the shortstop is added to the
exiting latex (see Fig. 1).
After World War II, it was reported that the Germans had been working on a cold emulsion polymerization
based on a redox initiation system that gave far superior SBR to the conventional hot polymerization (see Table
2). The principal differences were a polymerization temperature of 5◦ C instead of 50◦ C, monomer-to-polymer
conversion of 60–65% instead of 75%, and the use of a reduction/oxidation system (redox) to supply free radicals
by chemical rather than thermal means. The superiority of cold over hot SBR was attributed, in part, to the
greater linearity and less gel of the cold polymer. It was shown that in the cross-linking reaction of butadiene,
the ratio of the rate of cross-linking to the rate of propagation is constant up to the point where the monomer
phase disappears (26). This ratio decreases as the polymerization temperature is lowered. Thus, there are
fewer cross-linking sites at lower temperatures. At the point of monomer depletion (Smith-Ewart third stage),
cross-linking increases rapidly. By lowering the conversion rate at which the polymerization is terminated,
that point is not reached.
 STYRENE-BUTADIENE RUBBER 9

Fig. 2. Typical emulsion SBR finishing.

The impact of cold GR-S was quite pronounced. The U.S. government edicted that all of the emulsion
SBR plants switch to the cold process. This required addition of refrigeration capacity in these plants as well
as other significant changes, such as insulation of reactors, improved vacuum to reduce oxygen that retards
polymerization, and the heating of latex in blowdown tanks to aid in the disengagement of butadiene when
transferred to the flash tanks.
It was found that cold emulsion SBR could be made at very high molecular weight, combined with
petroleum-based oils at a very high level. Although the polymer could take up oil to the extent of 60 parts
of oil per 100 parts of polymer, a standard level of 37.5 parts of oil per 100 parts of polymer was established
because the plasticizing power of the oil would require extremely high polymer molecular weight at the 60 part
level. The oil was added to the latex as an emulsion and cocoagulated in the standard system. The resultant
oil-extended polymer had the benefits of very high molecular weight (improved stress–strain properties) with
the processibility of medium Mooney viscosity SBR. Extending pure polymer with oil increased the amount of
product over 25%. In addition, the economics of oil-extended SBR was quite attractive considering that a 36-kg
bale contained about 10 kg of a low cost process oil.
Several different petroleum process oils are used as extenders for SBR. These are classified as highly
aromatic, aromatic, naphthenic, and paraffinic. The highly aromatic oils give the most desirable physical
properties to the polymer and are widely used in tire treadstock. However, these oils impart a black color to
10 STYRENE-BUTADIENE RUBBER

the polymer and produce staining, ie, discoloration of light-colored articles that come in contact with products
containing the oil. For light-colored articles and products in contact with light-colored materials, naphthenic
or paraffinic oils are preferred.
The properties of emulsion SBR are comparable to those of natural rubber only when SBR is reinforced
with carbon black. Carbon black can be slurried in water and then combined with the SBR latex and coco-
agulated to give a product called black masterbatch. The black masterbatch would require considerably less
time and energy to get the carbon black dispersed in the nonproductive compound than if it were dry-mixed
with the polymer. Other advantages of handling black masterbatch are the elimination of inventorying and
handling carbon black, less energy demand in mixing stocks, and better dispersability of the carbon black in
the compound.
Black masterbatch can be made with or without oil-extended SBR. Commercially there are available,
worldwide, 11 numbered ESBR cold black masterbatches and 15 ESBR cold oil-black masterbatches (27).
These types range in black type and content as well as oil type and amount. Of course, not every listed product
is available from every supplier.

3.2. Solution SBR

Addition polymerization is accomplished in three steps: initiation, propagation, and termination. The
alkyllithium-initiated polymerization in hydrocarbon solvent has no termination step, resulting in living poly-
mer. The mechanism for initiation is thought to be dependant on the addition of the lithium alkyl across
the vinyl double bond giving an organolithium compound. Propagation is effected by the further addition of
monomer as a stepwise reaction, reforming the same type of carbon–lithium bond (28).
Without the termination step in the alkyllithium polymerization, the batch polymerization results in a
copolymer composition of styrene and butadiene that markedly changes with polymer conversion. This produces
blockiness, ie, long segments of one constituent in the copolymer chains. An explanation for this behavior is
that the butadiene reactivity is considerably greater than that of styrene in the copolymerization and has been
shown to be caused by the high cross-propagation rate of the styryllithium anion (29). This mechanism actually
allows great flexibility in producing very different types of polymers. The so-called tapered block polymer is
made by polymerizing styrene and butadiene monomers with butyllithium as the initiator. By addition of
certain chemicals such as ethers, tertiary amines, and phosphites, random distribution of the comonomers is
achieved. Certain of these additives also affect the microstructure of the butadiene portion. It is thus possible to
control polymer composition, monomer distribution sequence, microstructure (trans-1,4/cis-1,4 ratio constant
at variable vinyl level), molecular weight, molecular weight distribution, and polymer chain structure. Figure
3 shows a flow diagram for the continuous production of solution SBR. The kinetics of alkyllithium solution
copolymerization of styrene and butadiene in hydrocarbon solvent, along with techniques to randomize the
resultant polymer, have been reviewed (30).
Once the ability to control the randomization of solution SBR was understood and established, the com-
mercialized SSBR began to displace some of the ESBR in tire applications. It was found that the SSBR alone
could achieve the same desired properties that blends of ESBR and polybutadiene gave, thus simplifying the
compound recipes. The combination of low rolling resistance and high wet traction without sacrificing abra-
sion resistance (tread wear) is attainable with SSBR but not with ESBR alone. Also, by controlling the vinyl
microstructure to a low level, a lower Tg is achieved than for ESBR at the same styrene content. This allows
for a higher level of oil and carbon black to be added (31).
Because the styrene segments of block copolymers soften on heating, properties that depend on stiffness,
hardness, abrasion, etc, may suffer. Conversely, the polymers flow much more readily on molding, extruding,
etc. This property allows them to be used in shoe soling and wire insulation applications. Until more recently,
the use of block SSBR in tire tread applications was not considered because of the significantly higher running
temperature associated with compounds containing them. A Japanese patent claims that the use of a low
 STYRENE-BUTADIENE RUBBER 11

Fig. 3. Solution SBR manufacture by continuous process where Bd=butadiene, HC=hydrocarbon, AO=antioxidant , and SS=shortstop .

molecular weight random block copolymer of styrene and butadiene (A–B–A block SSBR) as part of a tire tread
composition imparts improved grip (adhesion) and abrasion resistance to the tire (32).

4. SBR Compounding and Processing

The initial production of GR-S rubber required a learning period in processing before rubber workers were
comfortable with the new synthetic rubber. Although softer and more plastic initially, the GR-S did not break
down as much as natural rubber. Once familiar with the differences, processing GR-S was handled quite
comfortably. The same was true when the cold GR-S was introduced, followed by the oil-extended version, and
SSBR.
Development of the Mooney viscometer gave compounders an indication of the processibility of different
lots of the uncompounded polymer. This machine measures the torque resistance encountered by a rotor
12 STYRENE-BUTADIENE RUBBER

revolving in a chamber surrounded by polymer at a constant temperature. The resulting Mooney number
describes the toughness of the polymer and is an indirect measure of molecular weight.
Gel, the insoluble fraction of polymer formed by high conversion of monomer to polymer, excessive mixing,
poor antioxidant protection, etc, increases the difficulty of mixing, reduces tensile strength, increases modulus,
and decreases the resistance to cut growth. Polymers with significant gel content have reduced elastic memory
(but lower shrinkage and lower surface roughness) and improved dimensional stability, two important qualities
in extrusion and calendering operation.
Vulcanization was discovered by Goodyear in 1839 (33). By incorporating elemental sulfur with natural
rubber and heating the mass, he found that the resultant compound yielded a tough, elastic material, markedly
different from the unvulcanized state. Modern rubber compounding (qv) has come a long way since the discovery
of vulcanization, but its explanation still remains quite theoretical (34). As a class, SBR is slower curing than
natural rubber. This is thought to be caused by the lower unsaturation in SBR.
The art of compounding requires extensive experience and knowledge of the many compound ingredients.
A typical rubber compound in addition to polymer contains one or more ingredients from the following general
classes: vulcanizing agents, accelerators, accelerator activators, antioxidants, pigments, and softeners (see
Rubber chemicals) (35).
The vulcanizing agent, which supplies the bridge between the polymer chains, is still furnished predomi-
nantly by the sulfur molecule in commercial formulations. Peroxide vulcanizers that produce carbon-to-carbon
cross-links are also important. Thiuram disulfides are used in special applications, such as improved heat
resistance. Other agents are of more academic interest.
Accelerators are chemical compounds that increase the rate of cure and improve the physical properties of
the compound. As a class, they are as important as the vulcanizing agent itself. Without the accelerator, curing
requires hours or even days to achieve acceptable levels. Aldehyde amines, thiocarbamates, thiuram sulfides,
guanidines, and thiazoles are all classified as accelerators. By far, the most widely used are the thiazoles,
represented by mercaptobenzothiazole (MBT) and benzothiazyl disulfide (MBTS).
Accelerator activators are chemicals required to initiate the acceleration of the curing process. They also
improve the polymer compound quality. This class includes zinc oxide (pure) and stearic acid. Other compounds
that have been in use are litharge, magnesium oxide, amines, and amine soaps.
Antioxidants (qv) are routinely added to the compounds over and above those contained in the polymer
at manufacture. Finished products are subjected to a wide variety of activities causing degradation. Molecules
with the propensity to neutralize free radicals by destruction, absorption, or disproportionation can accomplish
this phenomenon in different ways. Incorporation of two or more different chemical categories often enhances
protection much better (synergism) than the use of higher levels of individual additives. The most popular
chemical classes shown to have good antioxidant properties are phenols, phosphites, thioesters, and amines.
Because many antioxidant compounds are highly colored, they may tint the finished article. Amines and
quinolines have the propensity to stain, that is, to transfer some of the color they impart from the compound
in which they are used to a surface in contact with that compound, and are classified as stainers. These
characteristics must be kept in mind when choosing the antioxidant system.
Antiozonants (qv) prevent or reduce polymer degradation by the active ozone molecule. Some antioxidant
compounds, such as the para-phenylenediamines, are excellent as antiozonants (36). The protection by these
compounds is thought to be either a reaction with the ozone before it can react with the surface of the rubber
or an aid in reuniting chains severed by ozone (37).
Pigments (qv) improve or change polymer properties as well as lower product costs. Reinforcement of SBR
by carbon blacks allows this family of polymers to compete with natural rubber (see Carbon, carbon black). It
is the most important attribute of the pigment in SBR processing. Two other important groups of pigments
are the silicates and silicas. Other materials such as zinc oxide, clays, and calcium carbonate act more as
inert fillers to lower the overall compound cost rather than to impart reinforcement. Softeners, ie, plasticizers,
 STYRENE-BUTADIENE RUBBER 13

Table 3. Synthetic Rubber Productiona, b, 103 t

% Change,
Typec 1985 1990 1992 1994 1993/1994
SBR
solid 2284 2398 2358 2433 5.0
latexd 289 264 300 299 −2.3
polybutadiene elastomer (BR) 978 1164 1264 1452 5.9
polyisoprene rubber (IR) 110 142 115 111 16.8
chloroprene rubber (CR) 321 306 260 276 15.0
ethylene propylene diene 453 622 617 672 11.3
monomer (EPDM)
nitrile rubber (NBR) 213 246 255 277 9.1
others 563 574 606 543e −11.3
Total 5211 5716 5775 6063e 4.5
a Ref. 40.
b Excludes Central Europe, Socialist Countries of Asia, CIS.
c Forall polymers latices are included, except for SBR where they are shown separately.
d Excludes carboxylated latices.
e The change reflects a change in the International Institute of Synthetic Rubber Producers (IISRP) reporting base; growth rates

not available in 1994.

reinforcing agents, extenders, lubricants, tackifiers, and dispersing aids, are used as processing aids to enhance
mixing of uncured stocks and soften cured compounds.
SBR rubber compounds are prepared in two stages: the nonproductive and the productive phases. In the
nonproductive phase the compound ingredients are mixed, usually in internal mixers (Banbury). The mixing
time is usually short and the compound temperature is in the 160–195◦ C range. This stock is discharged from
the mixer to equipment that allows cooling and a convenient storage form, such as a mill or an extruder/die plate
that yields a sheet or pelletized form. Usually the material is coated with a slurry of clay, calcium carbonate,
or zinc stearate to prevent self-adhesion.
The productive stock, ie, the curable compound, is made up by mixing the nonproductive stock in the
Banbury once more with the curative package (sulfur, accelerators, etc). This time the drop temperature is
lower, in the range of 95–112◦ C. The productive stock is then sheeted or pelletized and coated with the dip coat,
cooled, and finally stored, ready for further processing for final fabrication.

5. Economic Aspects and Uses

Styrene–butadiene elastomers, emulsion and solution types combined, are reported to be the largest-volume
synthetic rubber, with 28.7% of the world consumption of all synthetic rubber in 1994 (38). This percentage
has decreased steadily since 1973 when SBR’s market share was 57% (39). The decline has been attributed
to the switch to radial tires (longer milage) and the growth of other synthetic polymers, such as polyethylene,
polypropylene, polyester, and polystyrene. Since 1985, production of SBR has been flat (Table 3).
Worldwide long-term consumption of SBR is projected to increase 2.5% per year through 1999 (Table 4).
SBR is forecast to remain the dominant elastomer of all synthetic polymers in the same time frame. In 1993,
use of SBR encompassed the following: tires and tire-related products, including tread rubber, 80%; mechanical
goods, 11%; other automotive uses, 6%; and adhesives, chewing gum base, shoe products, flooring, etc, for the
remaining 3% (41).
North America has led the world in consumption of SBR and will continue for the rest of the twentieth
century. As shown in Table 5, total demand for SBR, including emulsion (solid) and solution (solid), was 852,000
14 STYRENE-BUTADIENE RUBBER

Table 4. Worldwide Long-Term New Rubber Consumption by Elastomer Typea, 103 t

Elastomer 1994 1995b 1999b
SBR
solid 2,589 2,774 3,085
latex 400 413 467
carboxylated SBR latex 1,473 1,509 1,670
polybutadiene 1,427 1,541 1,726
ethylene propylene diene monomer 653 679 750
(EPDM)
chloroprene rubber (CR) 252 258 293
nitrile rubber (NBR) 319 337 391
other syntheticsc 1,176 1,369 1,549
Total Central Europe SR 250 268 351
Total Asia CPEC SR 485 519 680
Total synthetics 9,022 9,666 10,962
natural rubber 5,425 5,595 6,264
Total new rubber 14,447 15,289 17,226
synthetic, % 62.4 63.2 63.6
a Ref. 40.
b 1995 and 1999 values are forecast.
c Includes isoprene–isobutyl rubber (IIR), polyisoprene rubber (IR), and other synthetic rubbers (SR).

metric tons in 1994, up from 811,000 metric tons in 1993. Since the early 1990s growth has averaged about
3.2% per year. Projected growth in the near future, based on the tight supply of natural rubber, is 4–5%, through
1999.

6. Health and Safety Factors

Air quality and plant effluent have been monitored and more or less regulated from the inception of SBR
manufacture. Between the 1970s and 1990s, regulatory restrictions on plant operations have increased signifi-
cantly. The ever-decreasing limits on exposure levels include styrene and butadiene monomers as well as their
dimers and by-products. Most local and state governments have strict discharge permits that limit what kind
of chemicals and how much of it can be emitted into the environment.
The American Conference of Governmental Industrial Hygienists (ACGIH) has set a time-weighted aver-
age (TWA) of 50 ppm for styrene monomer (42). For butadiene monomer, ACGIH has set the exposure limit of
TWA at 10 ppm (43). As of this writing (1996), the Occupational Safety and Health Administration (OSHA) is
reviewing their TWA, which is set at 1000 ppm for butadiene. It is likely that the new TWA will be set at 1 or
2 ppm. Both styrene and butadiene are considered suspect carcinogens.
Title V of the Clean Air Act Amendments of 1990 covers federally approved state operating permits for
manufacturing facilities. One requirement of this regulation is that manufacturers must report emissions
information of identified hazardous air pollutants specific to their operation from a list of 189 named in the
Clean Air Act Amendments. Rubber and tire manufacturers had to meet this requirement by the end of 1995.
The Rubber Manufacturers Association has begun an industrywide project to develop accurate and reliable
emissions data to aid manufacturers to comply with these requirements (44).
In 1988, the German government issued technical regulation for hazardous materials, TRGS 552. Among
other things, 12 volatile nitrosamines were specified and an orientation value of 2.5 µg/m3 was set for the rubber
industry. In 1992 the regulation was redefined. The following levels/action are being enforced in Germany: (1)
up to 0.1 µg/m3 constitutes no exposure; (2) if levels exceed 0.25 µg/m3 , action needs to be taken; (3) if level
 STYRENE-BUTADIENE RUBBER 15

Table 5. Worldwide Long-Term New Rubber Consumption by Area and Typea, 103 t
Western Europe North America
Elastomer 1994b 1995c 1999c 1994b 1995c 1999c
SBR
solid 568 586 620 852 860 883
latexd 125 125 125 79 80 83
carboxylated SBR 570 584 645 634 646 699
polybutadiene elastomer (BR) 280 288 312 500 507 510
ethylene propylene diene monomer 225 236 266 264 270 274
(EPDM)
chloroprene rubber (CR) 66 66 67 76 77 79
nitrile rubber (NBR) (solid and 89 92 100 122 124 125
latex)
other syntheticse 241 251 278 408 420 426
Total synthetic rubber 2164 2228 2413 2935 2984 3080
natural rubber 900 930 1010 1106 1111 1103
Total new rubber 3064 3159 3423 4041 4094 4183
synthetic, % 70.6 70.5 70.5 72.6 72.9 73.6
thermoplastic elastomer (TPE) 299 314 371 358 387 496
a Ref. 40.
b Estimated December 1994.
c Forecast prepared during first quarter of 1995.
d Noncarboxylated.
e Includes isoprene–isobutyl rubber (IIR), polyisoprene rubber (IR), and others.

Table 6. (Continued)
Asia and Oceania Africa and Middle East
1994b 1995c 1999c 1994b 1995c 1999c

684 714 832 60.7 63.2 71.5

141 146 164 4.0 4.1 6.0
231 241 280
445 464 540 28.0 28.7 31.5
141 146 165 5.0 5.3 7.0
84 87 101 6.0 6.1 6.5
77 80 94 3.2 3.2 3.7
217 227 267 21.0 21.8 25.0
2020 2105 2443 127.9 132.5 151.3
2070 2120 2340 188.0 194.9 215.2
4090 4224 4783 315.8 327.4 366.5
49.4 49.8 51.0 40.5 40.5 41.3
148 154 179 5.5 5.9 7.7

exceeds 0.65 µg/m3 , respirators and medical monitoring must be offered; and (4) if levels exceed 1.00 µg/m3 ,
respirators are mandatory.
This regulation is only concerned with volatile nitrosamines in the workplace air. A principal problem in
enforcement is in the detection method. Only certain analytical laboratories are certified and reproducibility
is difficult to achieve. Epidemiological studies have shown volatile nitrosamines to be carcinogenic in animals
(45). Volatile nitrosamines are formed when secondary amine compounds break down and are nitrosated.
In rubber this occurs primarily during the vulcanization stage, where accelerators, which are predominantly
16 STYRENE-BUTADIENE RUBBER

secondary amine compounds, decompose, forming lower molecular weight compounds, and are nitrosated either
from oxides of nitrogen in the air or from nitrate–nitrite salts in the vulcanization process. Other sources of
these secondary amines are as contaminants in compounding ingredients and as trace amounts in emulsion
SBR, from the residue of certain shortstopping chemicals used in its manufacture.
There is an industry trend to supply SBR certifiably free of volatile nitrosamines or nitrosatable com-
pounds. This has generally been accomplished by replacing shortstop systems based on carbamates and hy-
droxyl amines with products that are not based on secondary amines or are secondary amines of high molecular
weight, such as dibenzyldithiocarbamate. A more recently issued patent for ESBR shortstop is based on iso-
propylhydroxylamine, a primary amine that does not form nitrosamine (46).
Of primary concern to local, state, and federal governments is the growing stockpile of scrap tires. It
was estimated by the Rubber Manufacturer’s Association that for the year 1994, 242 million tires were added
to the staggering number stockpiled haphazardly throughout the United States. The threat of huge piles of
scrap tires catching fire is cited as a principal concern. Past experience has shown how such fires pollute
the air and threaten groundwater as the large quantities of oil released in the incomplete burning become
a serious runoff problem. In 1991 the federal government instituted the Intermodal Surface Transportation
Act, which, among other things, mandates the use of ground rubber from scrap tires in asphalt paving. Being
an unfunded mandate, it was ignored by most states and the Federal Highway Administration has not been
authorized money to enforce this provision (47). There is heated debate on whether or not this technology is in
fact worthwhile (48). Although use of scrap tires is projected to increase rapidly in the next three to five years,
the only economically feasible use has been as a fuel or fuel supplement in utility and industrial applications
(see Recycling, rubber) (49).

BIBLIOGRAPHY

“Styrene Resins and Plastics” in ECT 1st ed., Vol. 13, pp. 146–179, by J. A. Struthers, R. F. Boyer, and W. C. Goggin, The
Dow Chemical Co.; “Styrene Plastics” in ECT 2nd ed., Vol. 19, pp. 85–134, by H. Keskkula, A. E. Platt, and R. F. Boyer, The
Dow Chemical Co.; in ECT 3rd ed., Vol. 21, pp. 801–847, by A. E. Platt and T. C. Wallace, The Dow Chemical Co.

Cited Publications

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2. J. W. Livingston and J. T. Cox, Jr., in Ref. 1, p. 180.
3. K. Ziegler and co-workers, Angew. Chem. 67, 541 (1955).
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8. L. A. Wood, J. Polym. Sci. 28, 319 (1958).
9. Ref. 7, 540–545.
10. D. H. James, J. B. Gardner, and E. C. Mueller, in J. I. Kroschwitz, ed., Encyclopedia of Polymer Science and Engineering,
2nd ed., Vol. 16, John Wiley & Sons, Inc., New York, 1989, 6–10.
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12. C. E. Morrell, in Ref. 1, 59–61.
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14. Chemical Market Associates, Inc., CMAI Monomers Market Report 1994, Houston, Tex.
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16. W. D. Harkins, J. Am. Chem. Soc. 69, 1428–1444 (1947).
 STYRENE-BUTADIENE RUBBER 17

17. H. Mark and R. Raff, High Polymeric Reactions, Interscience, New York, 1941.
18. P. J. Flory, J. Am. Chem. Soc. 59, 241–253 (1937).
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20. D. C. Blackley, Emulsion Polymerization Theory and Practice, Applied Science Publishers Ltd., London, 1975, 58–72.
21. The Vanderbilt Rubber Handbook, 13th ed., R. T. Vanderbilt Co., Inc., Norwalk, Conn., 1990, 58–59.
22. I. M. Kolthoff and A. I. Medalic, J. Polymer Sci. 6, 189–207 (1951).
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24. S. A. Sundet, Government Synthetic Rubber Report, Vol. 28, CR-650, May 10, 1945.
25. J. W. Livingston and J. T. Cox, Jr, in Ref. 1, p. 209.
26. M. Morton and P. P. Salatiello, J. Polym. Sci. 8, 111–121, 215–224 (1951).
27. The Synthetic Rubber Manual, 12th ed., International Institute of Synthetic Rubber Producers, Inc., Houston, Tex.,
1992, 19–20, 26–28.
28. S. Bywater and D. J. Worsfold, ACS Advances in Chemistry, No. 52, ACS, Washington, D.C., 1966, p. 37.
29. M. Morton and F. Ellis, J. Polym. Sci. 61, 25 (1962).
30. T. C. Bouton and S. Futamura, Rubber Age, 106(3), 33–35 (Mar. 1974).
31. Cariflex Technical Manual, GPR 1.2, Shell Chemicals, Houston, Tex., 1983.
32. U.S. Pat. 4,396,743 (July 2, 1983), Fujimaki and co-workers (to Bridgestone Tire Co, Ltd.).
33. L. E. Oneacre, in M. Morton, ed., Introduction to Rubber Technology, Reinhold Publishing Corp., New York, 1956, p. 93.
34. W. A. Wilson and D. C. Grimm, Molecular Structures from Polymerization and Vulcanization, Southern Rubber Group,
Knoxville, Tenn., 1994.
35. B. S. Garvey, Jr., in Ref. 33, 34–40.
36. Antioxidants and Antiozonants for Rubber and Rubber-like Products, The Goodyear Tire & Rubber Co., Akron, Ohio,
1988.
37. F. W. Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley & Sons, Inc., New York, 1984, p. 517.
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39. Chem. Ind. Newsletter, 11 (Nov./Dec. 1993).
40. Technical data, International Institute of Synthetic Rubber Producers, Inc., Houston, Tex., Feb. 24, 1995.
41. Chemical Marketing Reporter, 22, 45 (May 30, 1994).
42. Suspect Chemicals Sourcebook, Master Index 3, Roytech Publications, Bethesda, Md., 1993, p. 144.
43. Ref. 42, p. 159.
44. Rubber World, 210(6), 11 (Sept. 1994).
45. P. N. Magee and J. M. Barnes, Brit. J. Cancer, 10, 114–122 (1956).
46. U.S. Pat. 5,384,372 (Jan. 24, 1995), R R. Lattime (to The Goodyear Tire & Rubber Co.).
47. Akron Beacon J. (224-94) B-15 (Nov. 24, 1994).
48. M. Moore, Tire Bus. 11(24), 3/20 (Mar. 21, 1994).
49. J. Paul, in Ref. 10, Vol. 14, p. 788.

RICHARD R. LATTIME
The Goodyear Tire & Rubber Company

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