RADICAL CHAIN POLYMERIZATION in .NET

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RADICAL CHAIN POLYMERIZATION
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contains both monomers in the polymer chain in the alternating, statistical, block, or graft arrangement depending on the detailed chemistry of the speci c monomers and reactions conditions (Chap. 6). Polymer blends are physical mixtures of two different materials (either homopolymers or copolymers). All the elastomeric styrene products are copolymers or blends; none are homopolystyrene. No more than about one-third of the styrene plastic products are homopolystyrene. The structural details of the copolymers and blends will be considered in Sec. 6-8a. About 2 billion pounds of styrene homopolymer are produced annually in the United States in the form of a product referred to as crystal polystryene. Although the term crystal is used to describe the great optical clarity of the product, crystal polystyrene is not crystalline; it is completely amorphous. A variety of products are formed by injection molding, including tumblers, dining utensils, hairbrush handles, housewares, toys, cosmetic containers, camera parts, audiotape cassettes, computer disk reels, stereo dust covers, and of ce xtures. Medical applications include various items sterilized by ionizing radiation (pipettes, Petri dishes, medicine containers). Extruded sheet is used for lighting and decoration applications. Biaxially oriented sheet is thermoformed into various shapes, such as blister packaging and food-packaging trays. Expandable polystyrene, either crystal polystyrene or styrene copolymers impregnated with a blowing agent (usually pentane), is used to produce various foamed product. Among the products are disposable drinking cups (especially coffee cups), cushioned packaging, and thermal insulation used in the construction industry. Extruded foam sheets are converted by thermoforming into egg cartons, meat and poultry trays, and packaging for fast-food takeouts. The production of expandable polystyrene and styrene copolymers probably exceeds one billion pounds annually in the United States. Trade names for PS include Carinex, Cellofoam, Dylene, Fostarene, Hostyren, Lustrex, Styron, and Styrofoam. 3-14c Vinyl Family
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The vinyl family of polymers consists of poly(vinyl chloride), poly(vinylidene chloride), poly(vinyl acetate), and their copolymers and derived polymers. 3-14c-1 Poly(vinyl chloride)
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Most poly(vinyl chloride) (PVC) is commercially produced by suspension polymerization [Brydson, 1999; Endo, 2002; Saeki and Emura, 2002; Tornell, 1988]. Bulk and emulsion
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CH2 CH Cl CH2CH Cl
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polymerizations are used to a much lesser extent, and solution polymerization is seldom used. Suspension polymerization of vinyl chloride is generally carried out in a batch reactor such as that shown in Fig. 3-20. A typical recipe includes 180 parts water and 100 parts vinyl chloride plus small amounts of dispersants (<1 part), monomer-soluble initiator, and chaintransfer agent (trichloroethylene). All components except monomer are charged into the reactor, which is then partially evacuated. Vinyl chloride is drawn in, sometimes by using pressurized oxygen-free nitrogen to force monomer into the reactor. The reactants are then heated in the closed system to about 50 C and the pressure rises to about 0.5 MPa. The temperature is maintained at about 50 C as polymerization proceeds. When the pressure is about
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SPECIFIC COMMERCIAL POLYMERS
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Fig. 3-20 Typical polymerization vessel for suspension polymerization of vinyl chloride. After Brydson [1999] (by permission of Butterworth-Heinemann and Elsevier, Oxford).
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0.05 MPa, corresponding to about 90% conversion, excess monomer is vented off to be recycled. Removal of residual monomer typically involves passing the reaction mixture through a countercurrent of steam. The reaction mixture is then cooled, and the polymer separated, dried in hot air at about 100 C, sieved to remove any oversized particles, and stored. Typical number-average molecular weights for commercial PVC are in the range 30,000 80,000. Poly(vinyl chloride) has very low crystallinity but achieves strength because of the bulky polymer chains (a consequence of the large Cl groups on every other carbon). This is apparent in the high Tg of 81 C, although Tg is not so high that processing by a variety of techniques (injection molding, extrusion, blow molding, calendering) is impaired. Poly(vinyl chloride) is relatively unstable to light and heat with the evolution of hydrogen chloride, which can have deleterious effects on the properties of nearby objects (e.g., electrical components) as well as physiological effects on humans. The commercial importance of PVC would be greatly reduced were it not for the fact that this instability can be controlled by blending with appropriate additives such as metal oxides and carbonates as well as fatty acid salts. These additives stabilize PVC by slowing down the dehydrochlorination reaction and absorption of the evolved hydrogen chloride. Poly(vinyl chloride) is a very tough and rigid material with extensive applications. Its range of utilization is signi cantly expanded by plasticization, which converts rigid PVC,
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