Plastics acrylonitrile/butadiene/styrene

Styrene is at the centre of an important industry, with a value of some 66 billion euros. The styrene production capacity is ca. 20 Mt/a worldwide. Most is obtained by ethylbenzene dehydrogenation and all the production is used for the synthesis of polymers (polystyrene, styrene-acrylonitrile, styrene-butadiene) used as plastics and rubbers in the manufacture of household products packaging, tubes, tires, and endless other applications (see also Chapter 7). 

Styrene [100-42-5] (phenylethene, viaylben2ene, phenylethylene, styrol, cinnamene), CgH5CH=CH2, is the simplest and by far the most important member of a series of aromatic monomers. Also known commercially as styrene monomer (SM), styrene is produced in large quantities for polymerization. It is a versatile monomer extensively used for the manufacture of plastics, including crystalline polystyrene, mbber-modifted impact polystyrene, expandable polystyrene, acrylonitrile—butadiene—styrene copolymer (ABS), styrene—acrylonitrile resins (SAN), styrene—butadiene latex, styrene—butadiene mbber (qv) (SBR), and unsaturated polyester resins (see Acrylonithile polya rs Styrene plastics). 

Not only ate ABS polymers useful engineering plastics, but some of the high mbber compositions are excellent impact modifiers for poly(vinyl chloride) (PVC). Styrene—acrylonitrile-grafted butadiene mbbers have been used as modifiers for PVC since 1957 (87). 

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. 

Acrylonitrile is mainly used to produce acrylic fibers, resins, and elastomers. Copolymers of acrylonitrile with butadiene and styrene are the ABS resins and those with styrene are the styrene-acrylonitrile resins SAN that are important plastics. The 1998 U.S. production of acrylonitrile was approximately 3.1 billion pounds. Most of the production was used for ABS resins and acrylic and modacrylic fibers. Acrylonitrile is also a precursor for acrylic acid (by hydrolysis) and for adiponitrile (by an electrodimerization). 

ISO 11468 1997 Plastics - Preparation of PVC pastes for test purposes - Dissolver method ISO 12092 2000 Fittings, valves and other piping system components made of unplasticized poly(vinyl chloride) (PVC-U), chlorinated poly(vinyl chloride) (PVC-C), acrylonitrile-butadiene-styrene (ABS) and acrylonitrile-styrene-acrylester (ASA) for pipes underpressure - Resistance to internal pressure - Test method... 

Some of the nonrubber applications are as a chemical intermediate to make adiponitrile and hexamethylenediamine, precursors to making Nylon 66 whose primary application is carpeting. Other nonrubber applications are styrene-butadiene latexes for paper coatings and carpet backing, and acrylonitrile-butadiene-styrene (ABS) resins for plastic pipe and automotive/appliance parts. 

Uses. Plastics and synthetic rubber are the major uses for styrene. They account for the exponential growth from a few million pounds per year in 1938 to more than 8 billion pounds today. The numerous plastics include polystyrene, styrenated polyesters, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), and styrene-butadiene (SB). Styrene-butadiene rubber (SBR) was a landmark chemical achievement when it was comrner-cialized during World War II. The styrene derivatives are found everywhere—in food-grade film, coys, construction pipe, foam, boats, latex paints, tires, luggage, and furniture. 

Copolymers. Mixtures of two or more different bifunctional monomers can undergo additional polymerization to form copolymers. Why copolymerize Well, polymers have different properties that depend on their composition, molecular weight, branching, crystallinity, etc. Many copolymers have been developed to combine the best features of each monomer. For example, polystyrene is low cost and clear, but it is also brittle with no toughness. It needs internal plasticization. By copolymerizing styrene with a small amount of acrylonitrile or butadiene, the impact and toughness properties are dramatically improved. 

ABS (30% acrylonitrile, 20% butadiene, and 50% styrene) is a tough plastic with outstanding mechanical properties ABS is one of the few plastics that combines both toughness and hardness. So the applications include ballpoint pen shells, fishing boxes, extruded pipes, and space vehicle mechanical parts. There s more than 20 pounds of ABS molded parts in an automobile. 

When polymerization proceeds in the presence of modifiers, the mechanochemical process enhances cross-linking and, correspondingly, improves the physicochemical properties of final plastics. For example, mechanochemical treatment of acrylonitrile butadiene styrene (ABS) plastic in the presence of tolnene diisocyanate improves thermal oxidative stability of the plastic (Chetverikov et al. 2002). 

In Table 8.4 we see that most butadiene is polymerized either by itself or with styrene or acrylonitrile. The most important synthetic elastomer is styrene-butadiene rubber (SBR). SBR, along with polybutadiene, has its biggest market in automobile tires. Specialty elastomers are polychloroprene and nitrile rubber, and an important plastic is acrylonitrile/butadiene/styrene (ABS) terpolymer. Butadiene is made into adiponitrile, which is converted into hexamethylenediamine (HMDA), on of the monomers for nylon. 

Butadiene is used primarily in the production of synthetic rubbers, including styrene-butadiene rubber (SBR), polybutadiene nibber (BR), styrene-butadiene latex (SBL), chloroprene rubber (CR) and nitrile rubber (NR). Important plastics containing butadiene as a monomeric component are shock-resistant polystyrene, a two-phase system consisting of polystyrene and polybutadiene ABS polymers consisting of acrylonitrile, butadiene and styrene and a copolymer of methyl methacrylate, butadiene and styrene (MBS), which is used as a modifier for poly(vinyl chloride). It is also used as an intermediate in the production of chloroprene, adiponitrile and other basic petrochemicals. The worldwide use pattern for butadiene in 1981 was as follows (%) SBR + SBL, 56 BR, 22 CR, 6 NR, 4 ABS, 4 hexamethylenediamine, 4 other, 4. The use pattern for butadiene in the United States in 1995 was (%) SBR, 31 BR, 24 SBL, 13 CR, 4 ABS, 5 NR, 2 adiponitrile, 12 and other, 9 (Anon., 1996b). 

B.J. Jody, B. Arman, D.E. Karvelas, J.A. Pomykala, Jr., and E.J. Daniels, Method for the separation of high impact polystyrene (HIPS) and acrylonitrile butadiene styrene (ABS) plastics, US Patent 5 653867, assigned to The University of Chicago (Chicago, IL), August 5,1997. 

Internal plasticizing demands a chemical relationship between the components which constitute the product. Therefore, good effects can be expected from copolymers of styrene and isobutylene, ethylene, or diolefins like butadiene or isoprene. Internal plasticizing of PVC can be effected by copolymerizing vinyl chloride with acrylates of higher alcohols or maleates and fumarates. The important ABS products are internal copolymers of butadiene, styrene, and acrylonitrile. The hardness of the unipolymers of styrene and acrylonitrile can be modified by butadiene which, as a unipolymer, gives soft, rubberlike products. As the copolymerization parameters of most monomers are known, it is relatively easy to choose the most suitable partner for the copolymerization. When the product of the r—values is l, there is an ideal copolymerization, because the relative reactivity of both monomers toward the radicals is the same. Styrene/butadiene, styrene/vinyl thiophene, and... 

Fig. 1. US total sales and captive use of selected thermoplastic resins by major market for 2001. Major market volumes are derived from plastic resins sales and captive use data as compiled by VERIS Consulting, LLC and reported by the American Plastics Council s Plastic Industry Producers Statistics Group. Selected thermoplastics are low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, nylon, polyvinyl chloride, thermoplastic polyester, engineering resins, acrylonitrile-butadiene-styrene, styrene-acrylonitrile, other styrenics, polystyrene, and styrene butadiene latexes. (Data from ref. 25.)...

The thermoplastic polymers we studied included the polyolefins as polyethylene and polypropylene the polyacrylates and methacrylates as poly (methyl methacrylate) styrene polymers including both clear and impact types and acrylonitrile-butadiene-styrene (ABS) plastics. Fire retardance was evaluated by the D-635 procedure as described previously (19). 

The benzene-derived petrochemicals in Figure 4.15 are intermediate feedstocks for styrenic and phenolic plastics. In the styrenics chain, ethylbenzene is dehydrogenated to styrene, to be used as polystyrene monomer or as a copolymer with acrylonitrile and butadiene. In the phenolics chain, cumene is an intermediate for making phenol. Bisphenol A is the condensation product of two moles of phenol and acetone. Phenol and Bisphenol A are used to manufacture resins and polycarbonates. Phenol and cyclohexane are the starting materials for the manufacture of nylon 6. 

ABS and Related Materials. The so-called ABS (acrylonitrile-buta-diene-styrene—monomers 1, 2, and 3) materials comprise a class of compounds that consists of either blends or grafts (41). All have three monomers divided between two different polymers in a 1,2 and 1,3 combination mode. Blends of styrene-butadiene (1,2) random copolymers with styrene-acrylonitrile (1,3) random copolymers result in toughened plastics the common-mer, styrene, improves compatibility. The material may be described ... 

Acrylonitrile-butadiene-styrene (ABS) and acrylonitrile-styrene-acry- late (ASA) are rubber-toughened plastics based upon the styrene-acrylonitrile (SAN) copolymer matrix. The combination of the stiffness and toughness exhibited by these materials has made them increasingly attractive in engineering applications, and the activity of the patent literature testifies to a continuing interest in improving properties through modifications of structure. The aim of this paper is to discuss a quantitative approach to structure-property relationships in ABS and ASA polymers. 

ABS plastic is a tough, hard plastic used in applications requiring shock resistance. (See Chapter 22.) The polymer consists of three monomer units acrylonitrile (C3H3N), butadiene (C4H6), and styrene (QHs). 

Plastics copolymerized from styrene, butadiene and acrylonitrile offer a wide application scope, thus high-impact polystyrene (HIPS, styrene-butadiene copolymer), styrene-... 

Butadiene is used as a chemical intermediate and as a polymer component in the synthetic rubber industry, the latter accounting for 75% of the butadiene produced. Styrene-butadiene rubber, polybutadiene rubber, adiponitrile, styrene-butadiene latex, acrylonitrile-butadiene-styrene resins, and nitrile rubber are used in the manufacture of tires, nylon products, plastic bottles and food wraps, molded rubber goods, latex adhesives, carpet backing and pads, shoe soles, and medical devices. 

Styrene is produced by the alkylation of benzene with ethylene followed by catalytic dehydrogenation. It is used in the manufacture of general-purpose and high-impact polystyrene plastics ( 50%), expanded polystyrene ( 7%), copolymer resins with acrylonitrile and butadiene ( 7%) or acrylonitrile only ( 1%), styrene-butadiene latex ( 6%) and synthetic rubber ( 5%), unsaturated polyester resins ( 6%), and as a chemical intermediate. 

Ethylbenzene is a colorless aromatic liquid. It is only slightly soluble in water, but infinitely soluble in alcohol and ether. Additional properties are listed in Table 1. Ethylbenzene is chemically reactive with the most important reaction being its dehydrogenation to form styrene. Styrene is used to produce polystyrene, which is used in the manufacture of many commonly used products such as toys, household and kitchen appliances, plastic drinking cups, housings for computers and electronics, foam packaging, and insulation. In addition to polystyrene, styrene is used to produce acrylonitrile-butadiene-styrene polymer (ABS), styrene-acrylonitrile polymer (SAN), and styrene-butadiene synthetic rubber (SBR). 

---