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5TH/ CH51FA1



NOVEMBER 22, 2016

What is styrene-butadiene?
Styrene-butadiene or styrene-butadiene rubber pertains to the families of synthetic rubbers derived
from styrene and butadiene. These materials have good abrasion resistance and good aging stability when
protected by additives. In 2012, more than 5.4 million tons of SBR were processed worldwide. About 50%
of car tires are made from various types of SBR. The styrene/butadiene ratio influences the properties of the
polymer: with high styrene content, the rubbers are harder and less rubbery. SBR is not to be confused with
a thermoplastic elastomer made from the same monomers, styrene-butadiene block copolymer.

Styrene-butadiene is a mixture of approximately 75 percent butadiene (CH2=CH-CH=CH2) and 25 percent

styrene (CH2=CHC6H5). In most cases these two compounds are copolymerized (their single-unit molecules
linked to form long, multiple-unit molecules) in an emulsion process, in which a soap-like surface-acting agent
disperses, or emulsifies, the materials in a water solution. Other materials in the solution include free-radical
initiators, which begin the polymerization process, and stabilizers, which prevent deterioration of the final
product. Upon polymerization, the styrene and butadiene repeating units are arranged in a random manner
along the polymer chain. The polymer chains are cross-linked in the vulcanization process.

For many purposes SBR directly replaces natural rubber, the choice depending simply on economics. Its
particular advantages include excellent abrasion resistance, crack resistance, and generally better aging
characteristics. Like natural rubber, SBR is swollen and weakened by hydrocarbon oils and is degraded over
time by atmospheric oxygen and ozone. In SBR, however, the main effect of oxidation is increased
interlinking of the polymer chains, so, unlike natural rubber, it tends to harden with age instead of softening.
The most important limitations of SBR are poor strength without reinforcement by fillers such as carbon
black (although with carbon black it is quite strong and abrasion-resistant), low resilience, low tear strength
(particularly at high temperatures), and poor tack (i.e., it is not tacky or sticky to the touch). These
characteristics determine the use of the rubber in tire treads; essentially, its proportions decrease as the need
for heat resistance increases until 100 percent natural rubber is reached in the heaviest and most severe
uses, such as tires for buses and aircraft.

A large amount of SBR is produced in latex form as a rubbery adhesive for use in applications such as carpet
backing. Other applications are in belting, flooring, wire and cable insulation, and footwear.

SBR is a product of synthetic rubber research that took place in Europe and the United States under
the impetus of natural rubber shortages during World Wars I and II. By 1929 German chemists at IG
Farben had developed a series of synthetic elastomers by copolymerizing two compounds in the presence
of a catalyst. This series was called Buna, after butadiene, one of the copolymers, and sodium (natrium), the
polymerization catalyst. During World War II the United States, cut off from its East Asian supplies of natural
rubber, developed a number of synthetics, including a copolymer of butadiene and styrene. This general-
purpose rubber, which had been called Buna S by German chemists Eduard Tschunkur and Walter Bock,
who had patented it in 1933, was given the wartime designation GR-S (Government Rubber-Styrene) by the
Americans, who improved upon its production. Subsequently known as SBR, this copolymer soon became
the most important synthetic rubber, representing about one-half of the total world production.
Types of SBR
SBR is derived from two monomers, styrene and butadiene. The mixture of these two monomers is
polymerized by two processes: from solution (S-SBR) or as an emulsion (E-SBR). E-SBR is more widely
Emulsion polymerization
E-SBR produced by emulsion polymerization is initiated by free radicals. Reaction vessels are typically
charged with the two monomers, a free radical generator, and a chain transfer agent such as an
alkyl mercaptan. Radical initiators include potassium persulfate and hydroperoxides in combination with
ferrous salts. Emulsifying agents include various soaps. By "capping" the growing organic radicals,
mercaptans (e.g. dodecylthiol), control the molecular weight, and hence the viscosity, of the product.
Typically, polymerizations are allowed to proceed only to ca. 70%, a method called "short stopping". In this
way, various additives can be removed from the polymer.
Solution polymerization
Solution-SBR is produced by an anionic polymerization process. Polymerization is initiated by alkyl lithium
compounds. Water is strictly excluded. The process is homogeneous (all components are dissolved), which
provides greater control over the process, allowing tailoring of the polymer. The organolithium compound
adds to one of the monomers , generating a carbanion that then adds to another monomer, and so on.
Relative to E-SBR, S-SBR is increasingly favored because it offers improved wet grip and rolling
resistance, which translate to greater safety and better fuel economy, respectively.

Buna S
The material was initially marketed with the brand name Buna S. Its name derives Bu for butadiene and Na
for sodium (natrium in several languages including Latin, German, and Dutch), and S for styrene.

Property S-SBR E-SBR

Tensile strength (MPa) 18 19
Elongation at tear (%) 565 635
Mooney viscosity (100 C) 48.0 51.6
Glass transition temperature (C) -65 -50
Polydispersity 2.1 4.5
Styrene Butadiene Rubber (SBR) Production and
Manufacturing Process
SBR is produced by the copolymerisation of butadiene with styrene in the approximate proportion of 3:1 by

In the emulsion process, producing general purpose grades, the feedstocks are suspended in a large
proportion of water in the presence of an initiator or a catalyst and a stabiliser. A continuous process is

In the solution process, the copolymerisation proceeds in a hydrocarbon solution in the presence of an
organometallic complex. This can be either a continuous or batch process. Some manufacturing facilities
have swing capacity with PBR.

Process modifications can produce higher performance polymers. Companies, such as Asahi Chemical, are
pursuing the development of premium products by such means