Styrene-butadiene rubber solution-polymerized

Styrene-butadiene rubber could be produced by using emulsion and solution process, thus it can be divided into emulsion-polymerized styrene-butadiene rubber (E-SBR) and solution-polymerized styrene-butadiene rubber (S-SBR). In this entry, we will describe their development and introduce their synthesis process, relationship between structure and property, processing property, blends, and applications. 

Noguchi, K., Yoshioka, A., Komuro, K. and Ueda, A., Structure and properties of newly developed chemically modified high vinyl polybutadiene and solution polymerized styrene-butadiene rubbers , ACS Rubber Division 129th Meeting May, 1986, Paper No. 36. 

Sun J, Song Y, Zheng Q, Tan H, Yu J, Li H (2007) Nonlinear rheological behavior of silica filled solution-polymerized styrene butadiene rubber. J Polym Sci B Polym Phys 45 2594-2602... 

After the war when natural rubber became available again the consumption of styrene-butadiene rubber began to fall however, the trend was reversed in 1949 with the advent of a copolymer made at low temperature. This product gives a passenger-tyre rubber superior to natural rubber and styrene-butadiene rubbers have remained the most important of the large-tonnage rubbers (Table 20.2). In the early 1960s, solution polymerized styrene-butadiene rubbers became available. These rubbers show further improvements in tyre performance. In 1965, styrene-butadiene thermoplastic elastomers were introduced. 

Butadiene copolymers are mainly prepared to yield mbbers (see Styrene-butadiene rubber). Many commercially significant latex paints are based on styrene—butadiene copolymers (see Coatings Paint). In latex paint the weight ratio S B is usually 60 40 with high conversion. Most of the block copolymers prepared by anionic catalysts, eg, butyUithium, are also elastomers. However, some of these block copolymers are thermoplastic mbbers, which behave like cross-linked mbbers at room temperature but show regular thermoplastic flow at elevated temperatures (45,46). Diblock (styrene—butadiene (SB)) and triblock (styrene—butadiene—styrene (SBS)) copolymers are commercially available. Typically, they are blended with PS to achieve a desirable property, eg, improved clarity/flexibiHty (see Polymerblends) (46). These block copolymers represent a class of new and interesting polymeric materials (47,48). Of particular interest are their morphologies (49—52), solution properties (53,54), and mechanical behavior (55,56). 

Styrene—Butadiene Rubber (SBR). This is the most important synthetic mbber and represents more than half of all synthetic mbber production (Table 3) (see Styrene-butadiene rubber). It is a copolymer of 1,3-butadiene, CH2=CH—CH=CH2, and styrene, CgH5CH=CH2, and is a descendant of the original Buna S first produced in Germany during the 1930s. The polymerization is carried out in an emulsion system where a mixture of the two monomers is mixed with a soap solution containing the necessary catalysts (initiators). The final product is an emulsion of the copolymer, ie, a fluid latex (see Latex technology). 

The free-radical kinetics described in Chapter 6 hold for homogeneous systems. They will prevail in well-stirred bulk or solution polymerizations or in suspension polymerizations if the polymer is soluble in its monomer. Polystyrene suspension polymerization is an important commercial example of this reaction type. Suspension polymerizations of vinyl ehloride and of acrylonitrile are described by somewhat different kinetic schemes because the polymers precipitate in these cases. Emulsion polymerizations aie controlled by still different reaetion parameters because the growing macroradicals are isolated in small volume elements and because the free radieals which initiate the polymerization process are generated in the aqueous phase. The emulsion process is now used to make large tonnages of styrene-butadiene rubber (SBR), latex paints and adhesives, PVC paste polymers, and other produets. 

S.3.4 Styrene-Butadiene Rubber (SBR). SBR is produced by both emulsion and solution polymerization of mixtures of 1,3-butadiene and st5Tene. The general chemical structure of SBR polymers is as follows ... 

Some styrene-butadiene rubber is manufactured by solution processes using alkyllithium catalysts. Production techniques resemble those used for the polymerization of isoprene (Section 18.3.3) and butadiene (Section 18.4.3). Solution styrene-butadiene rubbers have microstructures similar to those of the emulsion copolymers but show narrower molecular weight distribution, less long chain branching and lower non-rubber content. The two types of materials have very similar bulk properties. 

The solution polymerization system with anionic catalysts is best suited for the preparation of rubbers of controlled structure. The well-known structural control that is attainable in styrene/butadiene rubbers in such systems is given in Table 2. Of particular interest is... 

Characterization of Styrene Sequence Distribution in Solution Styrene-Butadiene Rubbers by Anionic Polymerization... 

The broad range of control of solution polymer structure and macrostructure of styrene-butadiene rubbers that is only possible using lithium catalysts was discussed in Section 2. We have seen how the microstructure of the butadiene units in the chain and comonomer sequence distribution can be controlled with the addition of polar modifiers and/or variations in pol5onerization process variables. Additionally, the unique control of macrostructure features and the new possibilities offered by reactive functional groups were discussed as part of the molecular engineering capabilities of solution anionic polymerizations. 

Continuous stirred tank reactor polymerization reactors can also be subject to oscillatory behavior. A nonisothermal CSTR free radical solution polymerization can exhibit damped oscillatory approach to a steady state, unstable (growing) oscillations upon disturbance, and stable (limit cycle) oscillations in which the system never reaches steady state and never goes unstable, but continues to oscillate with a fixed period and amplitude. However, these phenomena are more commonly observed in emulsion polymerization. High-volume products such as styrene-butadiene rubber (SBR) often are produced by continuous emulsion polymerization. As noted earlier, this is... 

RESINS (Acrylonitrile-Butadiene-Styrene). Commonly referred to as ABS resins, these materials are thermoplastic resins which are produced by grafting styrene and acrylonitrile onto a diene-rubber backbone. The usually preferred substrate is polybutadiene because of its low glass-transition temperature (approximately —80°C). Where ABS resin is prepared by suspension or mass polymerization methods, stereospedfic diene rubber made by solution polymerization is the preferred diene. Otherwise, the diene used is a high-gel or cross-linked latex made by a hot emulsion process. 

Through polymerization of a styrene rubber solution, one obtains SB mass (styrene-butadiene). SB forms a twophase system in which the styrene is the continuous phase and the rubber, usually a butadiene base, is the discontinuous phase. The rubber phase also contains pockets of styrene. The SB polymer, because of its properties, is also known as impact resistant or high impact PS (HIPS). 

Butadiene-Styrene Rubber occurs as a synthetic liquid latex or solid rubber produced by the emulsion polymerization of butadiene and styrene, using fatty acid soaps as emulsifiers, and a suitable catalyst, molecular weight regulator (if required), and shortstop. It also occurs as a solid rubber produced by the solution copolymerization of butadiene and styrene in a hexane solution, using butyl lithium as a catalyst. Solvents and volatiles are removed by processing with hot water or by drum drying. 

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