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tetra uoroethylene with ethylene, per uoropropyl vinyl ether, and per uoropropene; and the copolymer of ethylene and chlorotri uoroethylene. The uoropolymers are obtained mainly by suspension polymerization; emulsion polymerization is also practiced. Commercial polymerization in supercritical carbon dioxide (scCo2 ) (Sec. 2-17b) was achieved by DuPont in 2002 for the copolymerization of tetra uoroethylene with hexa uoropropene and a per uoroalkyl vinyl ether. The molecular weights of the polymers are high, ranging up to 105 106 for PTFE, apparently due to the lack of appreciable chaintransfer reactions and the precipitation of growing radicals (leading to greatly decreased termination). The commercial production of uoropolymers is very small compared to commodity polymers such as polyethylene or PVC. But the production is still signi cant on an absolute basis, about 20 million pounds annually in the United States, and it nds a wide range of important specialized applications [Gangal, 1989]. PTFE is the largest-volume uoropolymer. This family of polymers offer unique performance. Within the uoropolymers are polymers that withstand a wide variety of chemical environments and are useful at temperatures as low as 200 C and as high as 260 C. Most uoropolymers are totally insoluble in common organic solvents and unaffected by hot concentrated acids and bases. They have outstanding electrical resistance and low coef cient of friction (self-lubricating and nonstick parts), and will not support combustion. The properties of polytetra uoroethylene, high crystallinity, Tm of 327 C, and very high melt viscosity, preclude its processing by the usual techniques for plastics. Fabrication requires the powder and cold extrusion techniques of metal forming. The various copolymers of tetra uoroethylene and the other uoropolymers, possessing lower Tm and crystallinity, were developed to overcome the lack of melt processability of PTFE.



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Fluoropolymer applications include electrical (coaxial cable, tape, spaghetti tubing), mechanical (seals, piston rings, bearings, antistick coatings for cookware, self-lubricating parts), chemical (pipe liners, overbraided hose liners, gaskets, thread sealant tapes), and micropowders used in plastics, inks, lubricants, and lacquer nishes. A unique application of uoropolymers is protection of the Statue of Liberty against corrosion. Trade names for uoropolymers include A on, Fluon, Halar, Hosta on, Kel-F, Kynar, Poly on, Tedlar, Te on, and Tefzel. 3-14f Polymerization of Dienes The polymerization of dienes (i.e., monomers with two double bonds per molecule) can proceed in a variety of ways depending on the chemical structure of the diene. Dienes are classi ed as conjugated or nonconjugated dienes depending on whether the two double bonds are conjugated with each other. Conjugated dienes are also referred to as 1,3-dienes. The polymerization of nonconjugated dienes often yields branched and crosslinked products. Nonconjugated dienes are often used to bring about crosslinking in other alkene monomers by the technique of copolymerization (Sec. 6-6a). Certain nonconjugated dienes undergo a special type of cyclization polymerization (cyclopolymerization) by an alternating intramolecular reaction mechanism (Sec. 6-6b). The polymerization of conjugated dienes is of special interest. Two different types of polymerization reactions occur with 1,3-dienes such as 1,3-butadiene, isoprene(2-methyl1,3-butadiene), and chloroprene (2-chloro-1,3-butadiene)

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Fig. 1-9 Determination of glass transition and crystalline melting temperatures by changes in speci c volume.

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maintain a zero temperature differential between an inert reference material and the polymer sample The melting of a polymer takes place over a wider temperature range than that observed for small organic molecules such as benzoic acid, due to the presence of different-sized crystalline regions and the more complicated process for melting of large molecules Tm , generally reported as the temperature for the onset of melting, is determined as the intersection from extrapolation of the two linear regions of Fig 1-9 (before and after the onset) Tg also occurs over a wide temperature range and is determined by extrapolation of the two linear regions, before and after Tg The glass transition is a less well understood process than melting There are indications that it is at least partially a kinetic phenomenon The experimentally determined value of Tg varies signi cantly with the timescale of the measurement.

(9.6)

Faster cooling rates result in higher Tg values Further, signi cant densi cation still takes place below Tg with the amount dependent on the cooling rate Perhaps the best visualization of Tg involves the existence of a modest range of temperatures at which there is cessation of segmental motion for polymer chain segments of different lengths ($5 20 chain atoms) Some polymers undego other thermal transitions in addition to Tg and Tm These include crystal crystal transitions (ie, transition from one crystalline form to another and crystalline-liquid crystal transitions The values of Tg and Tm for a polymer affect its mechanical properties at any particular temperature and determine the temperature range in which that polymer can be employed The Tg and Tm values for some of the common polymers are shown in Table 1 3 [Brandrup et al, 1999; Mark, 1999].

(9.7)

(These are the values at 1 atm pressure) Consider the manner in.

is the modulation factor introduced by the multiple reflections on the cavity mirrors. The annihilation and creation operators obey the continuum commutation relations

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