Styrene-butadiene production

Integrated monomer extraction and styrene-butadiene production on same site... 

The pH of polymer dispersions varies greatly, being acidic in the case of some Ethylene Vinyl Acetate (EVA) and Poly Vinyl Acetate (PVA) types whilst some acrylic, styrene acrylic and styrene butadiene products can be relatively alkaline. 

Styrene is manufactured by alkylating benzene with ethene followed by dehydrogenation, or from petroleum reformate coproduction with propylene oxide. Styrene is used almost exclusively for the manufacture of polymers, of which the most important are polystyrene, ABS plastics and styrene-butadiene rubber. U.S. production 1980 3 megatonnes. 

Styrene-butadiene rubber is prepared from the free-radical copolymerization of one part by weight of styrene and three parts by weight of 1,3-butadiene. The butadiene is incorporated by both 1,4-addition (80%) and 1,2-addition (20%). The configuration around the double bond of the 1,4-adduct is about 80% trans. The product is a random copolymer with these general features ... 

Acrylics. Acetone is converted via the intermediate acetone cyanohydrin to the monomer methyl methacrylate (MMA) [80-62-6]. The MMA is polymerized to poly(methyl methacrylate) (PMMA) to make the familiar clear acryUc sheet. PMMA is also used in mol ding and extmsion powders. Hydrolysis of acetone cyanohydrin gives methacrylic acid (MAA), a monomer which goes direcdy into acryUc latexes, carboxylated styrene—butadiene polymers, or ethylene—MAA ionomers. As part of the methacrylic stmcture, acetone is found in the following major end use products acryUc sheet mol ding resins, impact modifiers and processing aids, acryUc film, ABS and polyester resin modifiers, surface coatings, acryUc lacquers, emulsion polymers, petroleum chemicals, and various copolymers (see METHACRYLIC ACID AND DERIVATIVES METHACRYLIC POLYMERS). 

The most common VI improvers are methacrylate polymers and copolymers, acrylate polymers (see Acrylic ester polymers), olefin polymers and copolymers, and styrene—butadiene copolymers. The degree of VI improvement from these materials is a function of the molecular weight distribution of the polymer. VI improvers are used in engine oils, automatic transmission fluids, multipurpose tractor fluids, hydrautic fluids, and gear lubricants. Their use permits the formulation of products that provide satisfactory lubrication over a much wider temperature range than is possible using mineral oils alone. 

Elastomers. Elastomers are polymers or copolymers of hydrocarbons (see Elastomers, synthetic Rubber, natural). Natural mbber is essentially polyisoprene, whereas the most common synthetic mbber is a styrene—butadiene copolymer. Moreover, nearly all synthetic mbber is reinforced with carbon black, itself produced by partial oxidation of heavy hydrocarbons. Table 10 gives U.S. elastomer production for 1991. The two most important elastomers, styrene—butadiene mbber (qv) and polybutadiene mbber, are used primarily in automobile tires. 

MBS polymers are prepared by grafting methyl methacrylate and styrene onto a styrene—butadiene mbber in an emulsion process. The product is a two-phase polymer useful as an impact modifier for rigid poly(vinyl chloride). 

Synthetic. The main types of elastomeric polymers commercially available in latex form from emulsion polymerization are butadiene—styrene, butadiene—acrylonitrile, and chloroprene (neoprene). There are also a number of specialty latices that contain polymers that are basically variations of the above polymers, eg, those to which a third monomer has been added to provide a polymer that performs a specific function. The most important of these are products that contain either a basic, eg, vinylpyridine, or an acidic monomer, eg, methacrylic acid. These latices are specifically designed for tire cord solutioning, papercoating, and carpet back-sizing. 

Styrene—butadiene, acrylonitrile—butadiene, and butyl latices have also been prevulcanised, but this usually results in a lower wet gel strength. Where the mbber is to be deposited onto a fabric substrate, as in manufacture of fabric-lined gloves, the lower gel strength is not a problem. For unsupported dipped synthetic mbber products, however, the use of post-vulcanised compounds is more common. 

In the late 1920s Bayer Company began reevaluating the emulsion polymerisation process of polybutadiene as an improvement over their Buna technology, which was based on sodium as a catalyst. Incorporation of styrene (qv) as a comonomer produced a superior polymer compared to polybutadiene. The product Buna S was the precursor of the single largest-volume polymer produced in the 1990s, emulsion styrene—butadiene mbber... 

Styrene—butadiene elastomers, emulsion and solution types combined, are reported to be the largest-volume synthetic mbber, with 28.7% of the world consumption of all synthetic mbber in 1994 (38). This percentage has decreased steadily since 1973 when SBR s market share was 57% (39). The decline has been attributed to the switch to radial tires (longer milage) and the growth of other synthetic polymers, such as polyethylene, polypropylene, polyester, and polystyrene. Since 1985, production of SBR has been flat (Table 3). 

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). 

Commercially, anionic polymerization is limited to three monomers styrene, butadiene, and isoprene [78-79-5], therefore only two useful A—B—A block copolymers, S—B—S and S—I—S, can be produced direcdy. In both cases, the elastomer segments contain double bonds which are reactive and limit the stabhity of the product. To improve stabhity, the polybutadiene mid-segment can be polymerized as a random mixture of two stmctural forms, the 1,4 and 1,2 isomers, by addition of an inert polar material to the polymerization solvent ethers and amines have been suggested for this purpose (46). Upon hydrogenation, these isomers give a copolymer of ethylene and butylene. 

The common feature of these materials was that all contained a high proportion of acrylonitrile or methacrylonitrile. The Vistron product, Barex 210, for example was said to be produced by radical graft copolymerisation of 73-77 parts acrylonitrile and 23-27 parts by weight of methyl acrylate in the presence of a 8-10 parts of a butadiene-acrylonitrile rubber (Nitrile rubber). The Du Pont product NR-16 was prepared by graft polymerisation of styrene and acrylonitrile in the presence of styrene-butadiene copolymer. The Monsanto polymer Lopac was a copolymer of 28-34 parts styrene and 66-72 parts of a second monomer variously reported as acrylonitrile and methacrylonitrile. This polymer contained no rubbery component. 

In 1942 the Japanese overran Malaya and the then Dutch East Indies to cut off the main sources of natural rubber for the United States and the British Commonwealth. Because of this the US Government initiated a crash programme for the installation of plants for the manufacture of a rubber from butadiene and styrene. This product, then known as GR-S (Government Rubber-Styrene), provided at that time an inferior substitute for natural rubber but, with a renewed availability of natural rubber at the end of the war, the demand for GR-S slumped considerably. (Today the demand for SBR (as GR-S is now known) has increased with the great improvements in quality that have been made and SBR is today the principal synthetic rubber). 

Ozone cracking is a physicochemical phenomenon. Ozone attack on olefinic double bonds causes chain scission and the formation of decomposition products. The first step in the reaction is the formation of a relatively unstable primary ozonide, which cleaves to an aldehyde or ketone and a carbonyl. Subsequent recombination of the aldehyde and the carbonyl groups produces a second ozonide [58]. Cross-linking products may also be formed, especially with rubbers containing disubstituted carbon-carbon double bonds (e.g. butyl rubber, styrene-butadiene rubber), due to the attack of the carbonyl groups (produced by cleavage of primary ozonides) on the rubber carbon-carbon double bonds. 

Methods have been developed for improving batch process productivity in the manufacture of styrene-butadiene latex by the continuous addition of reactants so the reaction occurs as the reactor is being filled. These are not continuous processes even though the reactants are added continuously during most of a batch cycle. The net result is that reactants can be added almost as fast as heat can be removed. There is relatively little hazardous material in the reactor at any time because the reactants, which are flammable or combustible, are converted to non-hazardous and non-volatile polymer very quickly. 

Butadiene is by far the most important monomer for synthetic rubber production. It can be polymerized to polybutadiene or copolymerized with styrene to styrene-butadiene rubber (SBR). Butadiene is an important intermediate for the synthesis of many chemicals such as hexa-methylenediamine and adipic acid. Both are monomers for producing nylon. Chloroprene is another butadiene derivative for the synthesis of neoprene rubber. 

Polystyrene (PS) The volume of expanded polystyrene produced probably exceeds the volume production of all other plastics (excluding the polyurethanes) put together. At least half the weight of polystyrene produced is in the form of high impact polystyrene (HIPS)—a complex blend containing styrene-butadiene rubber or polybutadiene. 

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

A proposed expansion of the company s styrene-butadiene rubber production will require an additional 10,000 tons/year of butadiene as a raw material. 

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