Polystyrene with acrylonitrile

Another polyolefin of interest is polystyrene, a clear, brittle plastic that, by itself, is rarely used in composites. However, several copolymers and alloys of polystyrene with acrylonitrile or butadiene have been used with fiber glass or glass spheres to form composites (7). 

Copolymers of polystyrene with acrylonitrile (SAN), a-methylstyrene (SMS), acryl-styrene-acrylester (ASA), or acrylonitrile-ethylene-propylene styrene (AES) exhibit better weathering stability than homo-polystyrenes, Table 5.3. All polymerized styrenes will yellow under long-term weathering conditions, however, and their... 

Styrene is a commercially important monomer that is used extensively in the manufacture of polystyrene resins and in co-polymers with acrylonitrile and 1,3-butadiene (reinforced plastics). Exposure to styrene occurs due to intake of food that has been in contact with styrene-containing polymers. lARC has determined that styrene is possibly carcinogenic to humans. There is no restriction on using styrene within the European Union (i.e., there is no SML). 

Copolymerization allows the synthesis of an almost unlimited number of different products by variations in the nature and relative amounts of the two monomer units in the copolymer product. A prime example of the versatility of the copolymerization process is the case of polystyrene. More than 11 billion pounds per year of polystyrene products are produced annually in the United States. Only about one-third of the total is styrene homopolymer. Polystyrene is a brittle plastic with low impact strength and low solvent resistance (Sec. 3-14b). Copolymerization as well as blending greatly increase the usefulness of polystyrene. Styrene copolymers and blends of copolymers are useful not only as plastics but also as elastomers. Thus copolymerization of styrene with acrylonitrile leads to increased impact and solvent resistance, while copolymerization with 1,3-butadiene leads to elastomeric properties. Combinations of styrene, acrylonitrile, and 1,3-butadiene improve all three properties simultaneously. This and other technological applications of copolymerization are discussed further in Sec. 6-8. 

A wide variety of polymers have been analyzed by gel-permeation, or size-exclusion, chromatography (sec) to determine molecular weight distribution of the polymer and additives (86—92). Some work has been completed on expanding this technique to determine branching in certain polymers (93). Combinations of sec with pyrolysis—gc systems have been used to show that the relative composition of polystyrene or acrylonitrile—polystyrene copolymer is independent of molecule size (94). Improvements in gpc include smaller cross-linked polystyrene beads having narrow particle size distributions, which allow higher column efficiency and new families of porous hydrophilic gels to be used for aqueous gpc (95). 

Prolongation of polystyrene dicarbanion with acrylonitrile was recently demonstrated by extracting unreacted polystyrene with chloroform, block copolymers were obtained their molar acrylonitrile content ranged from 35 up to 77% depending on the reaction conditions (65). 

PVC can be blended with numerous other polymers to give it better processability and impact resistance. For the manufacture of food contact materials the following polymerizates and/or polymer mixtures from polymers manufactured from the above mentioned starting materials can be used Chlorinated polyolefins blends of styrene and graft copolymers and mixtures of polystyrene with polymerisate blends butadiene-acrylonitrile-copolymer blends (hard rubber) blends of ethylene and propylene, butylene, vinyl ester, and unsaturated aliphatic acids as well as salts and esters plasticizerfrec blends of methacrylic acid esters and acrylic acid esters with monofunctional saturated alcohols (Ci-C18) as well as blends of the esters of methacrylic acid butadiene and styrene as well as polymer blends of acrylic acid butyl ester and vinylpyrrolidone polyurethane manufactured from 1,6-hexamethylene diisocyanate, 1.4-butandiol and aliphatic polyesters from adipic acid and glycols. 

The potential problem of styrene taint in foods is well known and documented in the literature (Saxby 1996). Styrene (see Chapter 2) is the monomer that is polymerized to make polystyrene (PS) (also known as general purpose or GPPS grade). It is also commonly used with butadiene rubber (5-20 % w/w) as a block copolymer to form high impact polystyrene (HIPS). In addition there are less common copolymer grades such as acrylonitrile-butadiene-styrene (ABS) having a mixture of 25 %, 15-25 % and 50-65 % of each monomer respectively or a copolymer with acrylonitrile (styrene-acrylonitrile, SAN). 

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. 

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 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. 

The heat resistance of polyvinyl chloride was also improved by post chlorination, the ductility of polyethylene was Improved by increasing the molecular weight and the usefulness of polystyrene was Increased by copolymerization with acrylonitrile. Nevertheless, in spite of improvement in performance, resulting from these modifications, most general purpose plastics were under engineered for many applications. 

U.S. Pat. No. 3,878,143 (April 15,1975). H. Baumann, A. Kriisa, andH.E. Grahn. Method of preventing corrosion in connection with extrusion of mixtures containing polyvinyl chloride and wood flour or similar cellulosic material, and analogous mixtures containing polystyrene or acrylonitrile-butadiene-styrene resin, respectively. 

Many of the practical examples of miscible blends involve poly(vinylchloride) including those with butadiene-acrylonitrile copolymers2), possibly the first put into use, and various poly acrylates and vinyl acetate copolymers3,4) which are extensively used in PVC formulations at present. Others involve high performance engineering plastics such as blends of polystyrene with poly(2,6-dimethyl-1,4-phenylene oxide) (Noryl )5). In some cases a useful compromise or averaging of properties can be obtained whereas in others a useful combination of different desirable properties can be achieved. 

Studies on the morphology and on the melt rheological, tensile, and impact properties were carried out on ternary blend of iPP with two of the following polymers low and high density polyethylene, styrene-b-ethylene butylene-b-styrene triblock copolymer, polystyrene, and acrylonitrile-butadiene-styrene terpolymer (30-33). The results are interpreted for the effect of each individual component by comparing the ternary blends with the respective iPP-based binary blends as the reference systems. 

HIPS) is produced commercially by the emulsion polymerization of styrene monomer containing dispersed particles of polybutadiene or styrene-butadiene (SBR) latex. The resulting product consists of a glassy polystyrene matrix in which small domains of polybutadiene are dispersed. The impact strength of HIPS depends on the size, concentration, and distribution of the polybutadiene particles. It is influenced by the stereochemistry of polybutadiene, with low vinyl contents and 36% d5-l,4-polybutadiene providing optimal properties. Copolymers of styrene and maleic anhydride exhibit improved heat distortion temperature, while its copolymer with acrylonitrile, SAN — typically 76% styrene, 24% acrylonitrile — shows enhanced strength and chemical resistance. The improvement in the properties of polystyrene in the form of acrylonitrile-butadiene-styrene terpolymer (ABS) is discussed in Section VILA. 

Polystyrene with a mixture of butadiene and acrylonitrile monomers. 

In spite of some imeertainties in the individual steps of the HAS meehanism in polymer stabilization due to the speerfie effeets of the polymer matrix and the environmental stress, the HAS-based nitroxides are eonsidered the key intermediate in the HAS reaetivity meehanism. Detection and quantification of the formed nitroxides using ESRI spectroscopic technique has been exploited for confirmation of the primary transformation step in HAS mechanism [15, 16, 20], as a consequence of interactions of HAS with oxygenated radical and molecular products of polyolefins (5). Monitoring of the nitroxide development enables tracing of the oxidation process within the polymer matrix. Consequently it is also a tool for marking the heterogeneity of the oxidative transformation of semicrystalline carbon chain polymers [polypropylene (PP), polyethylenes (PE)] or amorphous polymers [copolymers of ethylene with norbomene, polystyrene (PS), high impart polystyrene (HIPS), acrylonitrile-butadiene-styrene polymer (ABS)]. 

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