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Figure 9.2 The cavity is formed by the perfect mirror at x = - L and the semitransparent mirror at x = O. The perfect mirror has an amplitude reflectivity coefficient of -1 and vanishing transmissivity, of course. The semitransparent mirror has an amplitude reflectivity r and transmissivity t, which can be complex in general. We assume that there is no absorption, so Irl2 + Itl 2 = 1 and r*t+t*r = 0 (see [317]). The modes ofthe universe can be determined using a scattering approach, as in Section 2.5.2. In this schematic drawing, we depict the incident plane wave e- ikx coming from infinity, its first reflection on the semitransparent mirror re ikx and some of its mUltiple reflections inside the cavity as well as some of its partial transmissions to the outside.



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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

Ein(X) Bin (x)





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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).

-i21 O = -21

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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,

to exible PVC. Plasticization involves blending PVC with plasticizers (e.g., diisooctyl phthalate, tritolyl phosphate, epoxidized oils). The plasticizer imparts exibility by acting effectively as an internal lubricant between PVC chains. (Plasticization accomplishes for PVC what copolymerization and polymer blending accomplishes for polystyrene changing a rigid material into a exible one. The plasticization route is not useful for polystyrene as PS is not so compatible with plasticizers.) Blending of PVC with rubbery polymers to improve impact strength is also practiced. More than 14 billion pounds of PVC products, about evenly divided between rigid and exible grades, were produced in 2001 in the United States. Rigid pipe for home and other construction accounts for more than 40% of the total PVC market. Vinyl siding, window frames, rain gutters, and downspouts account for another 10 15%. Packaging applications (bottles, box lids, blister packaging) account for about 8%. More than 10% of PVC is used for ooring (large sheet and tile). Other applications include wire and cable insulation for buildings, telecommunications and appliance wiring, garden hose, surgical and other protective gloves, and coated products. Trade names for PVC include Carina, Corvic, Darvic, Geon, Koroseal, Marvinol, Nipeon, Opalon, and Vygen. The generic term vinyl is often used for PVC products. 3-14c-2 Other Members of Vinyl Family

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More than 500 million pounds of poly(vinyl acetate) (PVAc), poly(vinylidene chloride), and their copolymers and polymers derived from them are produced annually in the United States. PVAc does not have suf cient strength for producing the types of products obtained from polyethylene, polystyrene, and poly(vinyl chloride) since it is noncrystalline and has a Tg of only 28 C. However, poly(vinyl acetate) (XLI) and its copolymers nd uses as

dk vac(k)e ikL .c(k) sin ([x + L]k) a(k)

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