ACRYLONITRILE POLYMER

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 

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Poly (acrylonitrile). Poly(acrylonitrile) polymers have the following formula ... 

SAN modifier [ACRYLONITRILE POLYMERS - SURVEY AND SAN (STYRENE-ACRYLONITRILECO-POLYMERS)] (Vol 1) Poly( a-methylstyrene) [25014-31-7]... 

C. H. Bamford and G. E. Eastmond, "Acrylonitrile Polymers" iu N. M. Bikales, ed., Engclopedia of Polymer Science andTechnology, Vol. 1, Interscience Publishers, a Division of John Wiley Sons, Inc., New York, 1964, pp. 374—425. 

The first reported synthesis of acrylonitrile [107-13-1] (qv) and polyacrylonitrile [25014-41-9] (PAN) was in 1894. The polymer received Htde attention for a number of years, until shortly before World War II, because there were no known solvents and the polymer decomposes before reaching its melting point. The first breakthrough in developing solvents for PAN occurred at I. G. Farbenindustrie where fibers made from the polymer were dissolved in aqueous solutions of quaternary ammonium compounds, such as ben2ylpyridinium chloride, or of metal salts, such as lithium bromide, sodium thiocyanate, and aluminum perchlorate. Early interest in acrylonitrile polymers (qv), however, was based primarily on its use in synthetic mbber (see Elastomers, synthetic). 

Acrylonitrile—Butadiene—Styrene. Available only as sheet, ABS has good toughness and high impact resistance. It is readily therm oform able over a wide range of temperatures and can be deeply drawn. ABS has poor solvent resistance and low continuous-use temperature. It is often used in housings for office equipment (see Acrylonitrile polymers). 

Itaconic acid is a specialty monomer that affords performance advantages to certain polymeric coatings (qv) (see Polyesters, unsaturated). Emulsion stabihty, flow properties of the formulated coating, and adhesion to substrates are improved by the acid. Acrylonitrile fibers with low levels of the acid comonomer exhibit improved dye receptivity which allows mote efficient dyeing to deeper shades (see Acrylonitrile polymers Fibers, acrylic) (10,11). Itaconic acid has also been incorporated in PAN precursors of carbon and graphite fibers (qv) and into ethylene ionomers (qv) (12). 

The principal use of the peroxodisulfate salts is as initiators (qv) for olefin polymerisation in aqueous systems, particularly for the manufacture of polyacrylonitrile and its copolymers (see Acrylonitrile polymers). These salts are used in the emulsion polymerisation of vinyl chloride, styrene—butadiene, vinyl acetate, neoprene, and acryhc esters (see Acrylic ester polymers Styrene Vinyl polymers). 

Acrylic ESTER POLYMERS Acrylonitrile POLYMERS Cellulose esters). Engineering plastics (qv) such as acetal resins (qv), polyamides (qv), polycarbonate (qv), polyesters (qv), and poly(phenylene sulfide), and advanced materials such as Hquid crystal polymers, polysulfone, and polyetheretherketone are used in high performance appHcations they are processed at higher temperatures than their commodity counterparts (see Polymers containing sulfur). 

Automotive appHcations account for about 116,000 t of woddwide consumption aimuaHy, with appHcations for various components including headlamp assembHes, interior instmment panels, bumpers, etc. Many automotive appHcations use blends of polycarbonate with acrylonitrile—butadiene—styrene (ABS) or with poly(butylene terephthalate) (PBT) (see Acrylonitrile polymers). Both large and smaH appHances also account for large markets for polycarbonate. Consumption is about 54,000 t aimuaHy. Polycarbonate is attractive to use in light appHances, including houseware items and power tools, because of its heat resistance and good electrical properties, combined with superior impact resistance. 

Rubber-Modified Copolymers. Acrylonitrile—butadiene—styrene polymers have become important commercial products since the mid-1950s. The development and properties of ABS polymers have been discussed in detail (76) (see Acrylonitrile polymers). ABS polymers, like HIPS, are two-phase systems in which the elastomer component is dispersed in the rigid SAN copolymer matrix. The electron photomicrographs in Figure 6 show the difference in morphology of mass vs emulsion ABS polymers. The differences in stmcture of the dispersed phases are primarily a result of differences in production processes, types of mbber used, and variation in mbber concentrations. 

Uses. The largest use for sodium thiocyanate is as the 50—60 wt % aqueous solution, as a component of the spinning solvent for acryUc fibers (see Fibers, acrylic Acrylonitrile polymers). Other textile appHcations are as a fiber swelling agent and as a dyeing and printing assist. A newer commercial use for sodium thiocyanate is as an additive to cement in order to impart early strength to concrete (376). 

ABS is the sixth largest volume thermoplastic resin and the principal engineering (stmctural or load bearing) plastic (89). ABS is a terpolymer manufactured by copolymerizing acrylonitrile and styrene in the presence of polybutadiene mbber. Important producers of ABS plastics include General Electric, Monsanto (Lustran), and Dow (Abtec) (see Acrylonitrile polymers). 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

As of 1992, the first specialty platable plastic, acrylonitrile—butadiene—styrene (ABS) terpolymer (see Acrylonitrile polymers, ABS resins), is used ia over 90% of POP appHcatioas. Other platable plastics iaclude poly(pheayleae ether) (see PoLYETPiERs), ayloa (see Polyamides), polysulfoae (see Polymers CONTAINING sulfur), polypropyleae, polycarboaate, pheaoHcs (see Pphenolic resins), polycarboaate—ABS alloys, polyesters (qv), foamed polystyreae (see Styrene plastics), and other foamed plastics (qv). 

Polypropylene block and graft copolymers are efficient blend compatibilizers. These materials allow the formation of alloys, for example, isotactic polypropylene with styrene-acrylonitrile polymer or polyamides, by enhancing the dispersion of incompatible polymers and improving their interfacial adhesion. Polyolefinic materials of such types afford property synergisms such as improved stiffness combined with greater toughness. 

Durihg recent years a considerable amount of re-.search has been undertaken to understand what in the makeup of a polymer affects the processability. In the late 1980s, the Rubber Manufacturers Association in the United States undertook a research project with the Department of Polymer Engineering at the University of Akron to evaluate the laboratory equipment available using specially made butadiene-acrylonitrile polymers with different acrylonitrile levels, molecular weights, and molecular weight distributions. The results from the study confirmed that, from the processing variables viewpoint, the major factors are frequency (shear rate), temperature (temperature), and deformation (strain). 

An alternate approach was taken by a shaft seal manufacturer and a polymer producer working together [2]. The project involved making a series of butadiene-acrylonitrile polymers of known acrylonitrile contents with various molecular weights and molecular weight distributions then making seals under normal manufacturing conditions. There were four polymers evaluated ... 

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