Styrene-butadiene rubber emulsion-polymerized

Other polymers used in the PSA industry include synthetic polyisoprenes and polybutadienes, styrene-butadiene rubbers, butadiene-acrylonitrile rubbers, polychloroprenes, and some polyisobutylenes. With the exception of pure polyisobutylenes, these polymer backbones retain some unsaturation, which makes them susceptible to oxidation and UV degradation. The rubbers require compounding with tackifiers and, if desired, plasticizers or oils to make them tacky. To improve performance and to make them more processible, diene-based polymers are typically compounded with additional stabilizers, chemical crosslinkers, and solvents for coating. Emulsion polymerized styrene butadiene rubbers (SBRs) are a common basis for PSA formulation [121]. The tackified SBR PSAs show improved cohesive strength as the Mooney viscosity and percent bound styrene in the rubber increases. The peel performance typically is best with 24—40% bound styrene in the rubber. To increase adhesion to polar surfaces, carboxylated SBRs have been used for PSA formulation. Blends of SBR and natural rubber are commonly used to improve long-term stability of the adhesives. 

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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. 

Production of emulsion-polymerized styrene-butadiene rubber... 

Most, if not all, of the large-toimage grades of emulsion-polymerized styrene-butadiene rubbers are produced by continuous emulsion polymerization. The advantages over batch and setni[Pg.684]

TYPICAL POLYMERIZATION RECIPES FOR HOT AND COLD EMULSION POLYMERIZED STYRENE-BUTADIENE RUBBERS... 

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). 

Over 5.5 billion pounds of synthetic rubber is produced annually in the United States. The principle elastomer is the copolymer of butadiene (75%) and styrene (25) (SBR) produced at an annual rate of over 1 million tons by the emulsion polymerization of butadiene and styrene. The copolymer of butadiene and acrylonitrile (Buna-H, NBR) is also produced by the emulsion process at an annual rate of about 200 million pounds. Likewise, neoprene is produced by the emulsion polymerization of chloroprene at an annual rate of over 125,000 t. Butyl rubber is produced by the low-temperature cationic copolymerization of isobutylene (90%) and isoprene (10%) at an annual rate of about 150,000 t. Polybutadiene, polyisoprene, and EPDM are produced by the anionic polymerization of about 600,000, 100,000, and 350,000 t, respectively. Many other elastomers are also produced. 

The most important hydrocarbon copolymers are styrene-butadiene rubbers (SBR) produced by free-radical emulsion or anionic polymerization. Anionic polymerization allows the manufacture of styrene-butadiene and styrene-isoprene three-block copolymers. 

Styrene-butadiene rubber, or E-SBR as it is known in manufacturing circles, was first developed in the 1930s. Known as Buna S, the compound was prepared by I.G. Farbenindustrie in Germany. Manufacturing styrene-butadiene rubber was through an emulsion polymerization process which produced a material that had a low reaction viscosity, yet had all the attributes of natural rubber. 

As discussed in Chapter 4, emulsion polymerization received a significant boost in the United States during the Second World War. When Japan overran countries that supplied natural rubber to the West, a crash program to manufacture synthetic rubber was initiated in the United States and Canada. The product was called Government Rubber-Styrene (GR-S), and was produced by the emulsion polymerization of butadiene and styrene. The fundamental recipe for GR-S is still used as a teaching tool for those learning the art and science of emulsion polymerization. 

The polymerization process parallels the emulsion process used for styrene-butadiene rubber. Either a hot or a cold process can be used, with the cold polymerization providing the same improved processing and vulcanizate properties as seen in SBR. Polymerizations are carried to 70-80 percent conversion and terminated to avoid gel formation. The latex must be stripped to remove unreacted butadiene and acrylonitrile. 

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. 

Emulsions Emulsions have particles of 0.05 to 5.0 pm diameter. The product is a stable latex, rather than a filterable suspension. Some latexes are usable directly, as in paints, or they may be coagulated by various means to produce massive polymers. Figures 2Z-2Zd and 2Z-2Ze show bead and emulsion processes for rinyl chloride. Continuous emulsion polymerization of butadiene-styrene rubber is done in a CSTR battery with a residence time of 8 to 12 h. Batch treating of emulsions also is widely used. 

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. 

Emulsion polymerization is the basis of many industrial processes, and the production volume of latex technologies is continually expanding—a consequence of the many environmental, economic, health, and safety benefits the process has over solvent-based processes. A wide range of products are synthesized by emulsion polymerization, including commodity polymers, such as polystyrene, poly(acrylates), poly (methyl methacrylate), neoprene or poly(chloroprene), poly(tetrafluoroethylene), and styrene-butadiene rubber (SBR). The applications include manufacture of coatings, paints, adhesives, synthetic leather, paper coatings, wet suits, natural rubber substitutes, supports for latex-based antibody diagnostic kits, etc. ... 

Free-radicals generated in many oxidation-reduction (or redox) reactions can be used to initiate chain poymerization. An advantage of this type of initiation is that, depending on the redox system used, radical production can occur at high rates at moderate (0-50°C) and even lower temperatures. Redox systems are generally used in polymerizations only at relatively low temperatures, a significant commercial example being the production of styrene-butadiene rubber by emulsion copolymerization of butadiene and styrene at 5-10°C ( cold recipe ). 

Materials. Styrene-Butadiene Rubber (SBR) Latex. SBR latex was prepared by redox emulsion polymerization using (in parts) butadiene (69) and styrene (31) at 6°-40°C (pinane hydroperoxide/sodium formaldehyde sulfoxylate/Fe++ as initiator) in the presence of potassium oleate (2.7) inorganic electrolytes (0.45) as polymerization aids, and demineralized water (135) until a conversion of 70% was achieved. Residual monomers were then removed. 

Styrene-butadiene rubber is the largest volume synthetic elastomer commercially available. It ean be produced by free-radical emulsion polymerization of styrene and butadiene either at 50 to 60°C (hot emulsion SBR) or at about 5°C (cold emulsion SBR). The two kinds of SBR have sigmfieantly different properties. The hot emulsion SBR process, which was developed st, leads to a more branehed polymer than the cold emulsion process. Cold SBR has a better abrasion resistance and, eonsequently, provides better tread wear and dynamic properties. 

High-volume products such as styrene-butadiene rubber (SBR) often are produced by continuous emulsion polymerization. This is most often done in a train of 5-15 CSTRs in series. CSTR polymerization will result in a broader PSD than batch polymerization due to the wide residence time distribution in a CSTR, though the use of a CSTR train will tend to mitigate this effect. 

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