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 used.
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-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.
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