Module TCN1422: Materials for Chemical Engineers

Fundamentals Structures and Properties of Styrene Butadiene Rubber

and Its Applications in Industry

Name : Erick Hadinata

Lecturer in Charge : Prof. Hong Liang

Date : 12 March 2018

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1. Introduction

1.1 Reason for Material Selection

SBR rubber is selected for this report is because the importance of this polymer in
industries such as automobiles and footwear. SBR was made initially to replace natural
rubber as low-cost alternative with better physical properties and also it is easier to
produce in large quantity as compared to natural rubber. Other advantages of SBR
rubber over natural rubber such as:

 More superior low temperature flexibility

 Higher heat resistance and heat aging properties
 More widely used in modern industries
 Higher abrasion and wear resistance as natural rubber

However, SBR like other rubbers have properties weaknesses as well such as:

 Low steam and oil resistance so if used for a long period of time, the rubber will
swell and degrade
 Low tolerance against sunlight, ozone and high temperature

The importance of SBR is very high because most of the automobile industries depend
on this rubber and without this SBR rubber maybe the car tires that we used now will
not sustain for long period of usage, so it is important that we have more understanding
about this polymer.

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1.2 History of Material and Technological Development of Material

1.2.1 History of Material

In the 1930s, a German chemist named Walter bock researched about the new
rubber material which could replace the expensive natural rubber and this rubber
was a new synthetic rubber which had much better properties as compared to
that of natural rubber. He initially tried to copolymerise dimethyl butadiene with
isoprene and butadiene, the experiment underwent smoothly and the results was
outstanding as the new polymer had similar properties to the natural rubber,
cheaper to produce and with higher properties compared to natural rubber. He
was then thinking of using other type of monomers hoping to invent other
similar type of synthetic rubber and he proceeded to replace the monomer
dimethyl butadiene with styrene and copolymerised with butadiene, which
resulting in another type of polymer with also gives higher properties compared
to natural rubber and thus, the polymer was named as SBR (styrene-butadiene
rubber).

1.2.2 Development of Material

Styrene butadiene rubber (SBR) was the first synthetic rubber to be produced in
large amounts commercially. The very first SBR grade was produced in
Germany by Buna S and in the United States by Standard Oil Company/The
Rubber Reserve Company during the Second World War. The technology back
then was based on the emulsion polymerization technology which was
developed by I.G. Farbenindustrie AG of Germany.

SBR technology is still developing even though the rubber business is seen to
be proceeding to profitable and can be considered to have matured. But further
development of technology of SBR is needed because of the higher demands
from the tyre producers to have rubber with even more superior properties as
more high tech cars are being produced by car manufacturers. The
enhancements and customizations of solution processes has enabled the rubber

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 producers to develop various "tailored and custom" SBR grades, which improve
the overall mechanical properties (e.g. traction, handling, cornering
performance, high speed performance, rolling resistance and wet traction and
grip performance) and processing characteristics.

Recently, rubber manufacturers tend to put their effort on the effect of adding
additives into the mixture of the SBR solutions to control and alter the structure
and properties of the diene polymerization process and to optimize the form of
the polymer structure from micro to macrostructure in order to produce many
type of the SBR solution grades each with their properties and to find optimum
properties among these SBR grades.

Conventional process of making SBR rubber has optimized the fundamental

properties of the polymer itself but, by further modifying the addition amounts
of the monomers, the polymerization conditions (at specific temperature and
pressure, the use of catalysts, randomizing agents, modifying agents, the
proportion of cis and vinyl isomers, resulting in different of SBR properties can
be produced. Nevertheless, the properties of "tailored" solution SBR are still
unable to meet the expectations of most tyre industry requirements (e.g. better
rolling performance , better wear and tear, better abrasion resistance, better grip
under wet weather).

Required tyre properties have been partly achieved through the production
technology but more modifications are still needed such as reactors type and
conditions.

SBR is created and processed inside the vulcanization system, reinforcing filler
(usually carbon black), extending oil, and an antioxidant/stabilizer components
prior to feeding into the reactors. Tire compounds usually uses various kind of
combination of elastomers in order to achieve desirable properties at the end
product. There are developments still undergoing some research even until now.

The SBR worldwide market is currently controlled by car tyre manufacturers,

which accounts for 75 percent of total demand in major economies.

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 Six percent of demand is accounted for by other automotive applications.
Consequently, tyre manufacturers factor most of the business of SBR rubber
market.

There was a growing competition between emulsion SBR and solution SBR
grades before solution SBR dominates over emulsion SBR in the rubber market.
Solution SBR has superior physical properties (wear and tear resistance) and
high compatibility and blend ability with other rubbers. However, they have
been failing to compete within the market because of the complexibility of the
manufacturing process. The SBR industry is undergoing rationalization due to
low profitability and continued growing capacity. There has been no
technological advancement in emulsion SBR because of lack of investments in
recent years and thus, no new plants are planned to be built, reflecting the
negligible growth prospects for emulsion SBR. New investments currently has
undergone to the flexible plants that produces BR type polymer. And this kind
of polymer might have to replace SBR type rubber if the technology of
producing SBR rubber has reached to the stagnation point, but up till now SBR
rubber is still developing as tyre manufactures still need to use SBR as main
rubber for the car tyres.

2.Material Structure and Properties

SBR is polymer which made up of butadiene and 10 to 25 percent of styrene.

Main Properties
Temp. Range, °C -25 / 100
Compression Set Good
Strength Properties Good
Low Temp. Prop. Fair
Abrasion Resist. Excellent
Gas Permeability Good
Weather Resist. Poor
Water Resistance Good
Ozone Resistance Poor
Mineral Oil Resist. Poor
Chemical Resist. Poor/Fair
Flame Resistance Poor
Heat Resistance Fair

The addition of styrene decreases the overall polymer cost and contributes to the good wear
and tear properties and bonding properties. The addition of styrene also improves the polymer
strength, grip and rolling performance of the rubber.

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In most cases these two monomers are usually polymerized together (their single-unit
molecules will linkup together to form long, multiple and repeating-unit molecules) in an
emulsionization process, in which addition of emulsifiers or surface acting agent will produce
soaplike solution. Other materials in the solution include catalysts and initiators, which begin
the polymerization process followed by increasing the rate of polymerization, and antioxidants,
which prevent degradation of the final product. Upon polymerization, the styrene and butadiene
repeating units are dispersed and they will arrange themselves in a random manner along the
polymer chain. The polymer chains are cross-linked in the vulcanization process.

Polystyrene and polybutadiene are insoluble and incompatible with each other, so that the
polystyrene end-chain associate together to form domains of glassy polystyrene in a sea of
elastic polybutadiene. The polybutadiene centre will form elastomeric network formation
which is held together by rigid domains of polystyrene end-blocks, which are relatively stable
up to the glass transition temperature of polystyrene (about 100 °C, or 212 °F). Thus, the
material is a rubbery solid at room temperatures.

The emulsifiers for the dispersion of the monomers during polymerization are usually anionic
in nature. Carbon black or extender oil is usually added at the end of polymerization process
in order to increase molecular weight of polymer. With the increase in molecular weights
usually will results in higher tensile strength and higher wet grip which are desirable physical
properties of the SBR itself. SBR however, lacks the self-reinforcing properties compared to
natural rubber because of self-induced crystallizations. (Mechanical Properties)

As SBR is a non-polar polymer, it is poor conductor of electricity and its electrical properties
depend on amount and type of the emulsifiers and coagulating agents used in the
polymerization process. (Electrical Properties)

SBR is resistant to most polar solvents such as dilute acids and bases but they will tend to swell
when in contact with fats, oils and gasoline. That is why SBR cannot be used in applications
that require direct contact with hydrocarbon solvents. (Chemical Properties)

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3.Material Application and Its Impact on Sustainability

About 60 % of synthetic rubber produced worldwide is used to manufacture car tyres. Synthetic
rubber is kind of product which derives from hydrocarbon (Petrochemicals). The
environmental problems come from the production of synthetic rubber derives primarily from
energy consumption, chemical emission discharged to air and water, and waste products.

3.1 Energy Consumption

Consumption of fossil fuels for polymerization processes and heating process (steam
usage) in the rubber industry is very high in usage. Emissions generated from the
transportation of raw materials and final products also contribute to carbon dioxide
build-up in environment. The use of car tires will contribute to the consumption of fuel
and the tires properties also affect the fuel consumption such as rolling resistance. With
higher resistance means more energy is needed to rotate the tires and thus, higher fuel
is used, and higher carbon dioxide is emitted.

3.2 The Uses of Chemicals

The production of SBR rubber requires large number of raw materials and chemical
products to achieve the worldwide demands. Many of the chemicals used are harmless
to environment or health perspective. However, there are certain number of chemicals
that can damage the environment and cause injury to humans. Some of these substances
are classified as environmental toxins.

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3.3 Waste

Annual consumption of rubber worldwide is in the range of 15 million tonnes, of which

natural rubber accounts for around 38 % and synthetic rubber for around 62 %. Most
of the rubber listed is used for the manufacture of car tyres, while the remainder is used
for other range of applications such as footwear. About 2 million tonnes of tyres are
scrapped annually in Europe and 2,8 million tonnes in the US. Other rubber products
will end up as waste once they reach the end of product life, and the quantity of waste
rubber worldwide is substantial. As waste rubber is very difficult to be recycled, most
of the countries resort to using incineration for the disposal of the waste rubber.

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3.4 Emissions to Air

The rubber industry waste can cause harm to the surrounding atmosphere through
various types of industrial emission, starting from energy consumption from the heating
and cooling process, polymerization process and the transportation of raw materials and
finished products. Many of the environmental pollutant is similar to that caused by other
conventional industrial processes. However, emissions from the vulcanization process
are unique to the rubber industry.

3.5 Acidifying Substances

Since the end of the 19th century there have been growing frequency in acid rain. One
of the reasons is the sulphur dioxide emission which is generated from the burning of
fossil fuels (oil, coal) as the result of energy production, industrial processes and
transportation of the raw materials and finished products. In addition to sulphur dioxide,
nitrogen oxides are also produced during combustion processes. Majority of these
emissions are produced by automobiles and they are a major cause of the acidification
of soil and water.

The rubber industry also takes a part in the acidification of the soil and also water by
producing sulphur dioxide and nitrogen oxides, mostly from the combustion of fossil
fuels and combustion from the vehicles during transportation.

3.6 Localization

Many industries, factories and chemical plants cause noise pollution and chemical
waste pollution. These pollutions are magnified when they are located near schools and
housing areas. This problem does not apply only to the rubber industry, but localization
issues are not easy to solve due to land scarcity in some countries. A lot of rubber
factories have been built and lasted for 50 to 100 years old. As time goes by, more
urban development started around the industries.

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4.Prospective Improvements of Material for Industrial Application

4.3 XSBR Grade Rubber (Carboxyl-based SBR rubber)

As demands for the SBR rubber grows, rubber industries have developed some of the
various grades of SBR to accommodate various properties required by automobile
companies. One of the promising grade of SBR is XSBR (Carboxylate SBR).
Carboxylate rubber, is a new class of rubber grade with superior physical and
mechanical properties compared to their non-carboxylate grade. By introducing
carboxyl group inside the polymer chain, range of elasticity, tensile strength,
compatibility with various fillers, enhancement of resistance to chemical solvents,
hydrocarbons and possibility of cross-linking with non-sulphur based reagents. All the
improvements are because of the stable interface that created between carboxyl group
and polymer phase creating enhancements on the host polymer. As for now this rubber
grade is still undergoing testing phase and when it is successful, it will be very useful
for the rubber manufacturers to produce even better

4.2 Enhancement of SBR Properties by Introducing Silica Nanofiller to

SBR Compound

Research have been conducted on the reinforcing effect of large number of synthetic
precipitated amorphous white silica nanofiller on polymers such as SBR in this case.
The surface of the silica filler was pretreated with bis(3-triethoxysilylpropyl)
tetrasulfane (TESPT). TESPT is a bifunctional organosilane that will help silica to
chemically link together with the rubber and also to prevent silica from interfering with
the reaction mechanism of sulfur cure in the rubber. The silica will be fully dispersed
inside the rubber compound and with the addition of accelerator catalyst and initiator
inside the compound, the mechanical properties of the rubber was shown to improve
significantly. This test was only conducted in the pilot plant at the current stage, but the
test results shows promising results which next stage of the testing can be further
upscaled and hopefully, this can be used in actual production in the near future.

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4.3 Modification of SBR Compound by Imidazole Derivatives Additives

The imidazole derivatives such as 2-undecylimidazole (UI) and 2-mercapto-1-

methylimidazole (MMI) are being tested as additional additives for modifying styrene
butadiene rubber (SBR)/carbon black (CB) composites. The imidazole groups on UI
and MMI can be hydrogen-bonded with oxygen-containing groups on the surface of
CB, and the undecyl or thiol groups can be reacted with the SBR chains via physical
entanglement or thiol-ene chemistry. The results showed that the overall mechanical
static and dynamic properties of the SBR rubber with addition of MMI and UI have
improved significantly as compared to the blank SBR/Carbon Black composite.

4.4 Properties Enhancement of SBR by using Graphene

Nanofiller is very promising to enhance SBR rubber properties but the current challenge
is the process to make stable and homogeneous dispersion of the nanofiller inside the
rubber matrix very difficult to achieve. So in order to solve this problem, alternative
way has been proposed by scientists which is by synthesizing nanocomposites of rubber
with homogenous and stable dispersed low defect graphene flakes (l-GFs), which are
prepared using l-GFs/SBR composites via aqueous-phase mixing of exfoliated l-GFs
with SBR latex. The 1-GFs embedded SBR composite have shown great improvements
in tensile strength and modulus strength at low loading rate. This proves that the 1-GFs
help to improve the dispersion rate of the filler to the rubber matrix.

The 1-GFs also helps to increase the thermal and electrical conductivities of the rubber
and also increases the gas barrier properties of the SBR composites. This method is
water-mediated, not harmful to the environment and it is an upscalable process,
showing great potential for the production of various l-GFs-based rubber composites at
an industrial level.

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5.References

 AZoM, W. by. Emulsion Styrene Butadiene Rubber (E-SBR) – History, Development

and Applications of Emulsion Styrene Butadiene Rubber
https://www.azom.com/article.aspx?ArticleID=1848 (accessed Mar 8, 2018).
 Britannica, T. E. E. Styrene-butadiene rubber
https://www.britannica.com/science/styrene-butadiene-rubber (accessed Mar 8, 2018).
 SBR Rubber Polymer: Properties, Characteristics and Resistances
http://www.warco.com/polymer/sbr/ (accessed Mar 8 2018).
 https://www.tut.fi/ms/muo/vert/6_elastomeric_materials/sbr.htm (accessed Mar 9,
2018).
 ENVIRONMENTAL ISSUES CAUSED BY RUBBER INDUSTRY
https://businessimpactenvironment.wordpress.com/2011/10/03/environmental-issues-
caused-by-rubber-industry/ (accessed Mar 9, 2018).
 Environmental Impact of Scrap Tires http://www.rerubber.com/environmental-
impact/ (accessed Mar 9, 2018).
 Hardcastle, J. L. Rubber Industry to Create Sustainability Standards
https://www.environmentalleader.com/2013/09/rubber-industry-to-create-
sustainability-standards/ (accessed Mar 9, 2018).
 Styrene Butadiene Rubber (SBR) Global Market to 2020 - Demand for Solution-
Styrene Butadiene Rubber (S-SBR) Increasing In-line with Uptake of High-
Performance Tires http://www.chemie.de/marktstudien/8668/styrene-butadiene-
rubber-sbr-global-market-to-2020-demand-for-solution-styrene-butadiene-rubber-s-
sbr-increasing-in-line-with-uptake-of-high-performance-tires.html (accessed Mar 10,
2018).
 Choi, S. E. S. Improvement of properties of silica‐filled styrene–butadiene rubber
compounds using acrylonitrile–butadiene rubber
http://onlinelibrary.wiley.com/doi/10.1002/1097-
4628(20010207)79:6%3C1127::AID-APP170%3E3.0.CO;2-8/abstract (accessed Mar
10, 2018).

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