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Data from Bus eld [1989] unless otherwise noted. Dreyfuss and Dreyfuss [1989]. c Okada et al. [1976]. d Okada et al. [1978]. e Xu et al. [1987]. f Rentsch and Schulz [1978].



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The H values for the various cyclic ethers and acetals follow closely the order expected based on considerations of relative stability as a function of ring size (Secs. 7-1a, 2-5). The 3and 4-membered cyclic monomers undergo the most exothermic polymerizations. There is a fast decrease in the exothermicity of polymerization for the larger-sized rings. Trioxane, the only 6-membered ring monomer to undergo polymerization, has a H very close to zero. Substituents on a ring structure decrease the tendency to polymerize, as noted by the less exothermic polymerizations for the substituted 1,3-dioxolane, 1,3-dioxepane, and 1,3,6trioxocane monomers relative to the corresponding unsubstituted monomers. Substituted oxetanes are an exception to this generalization. 7-2b-7 Commercial Applications

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There are a number of commercial applications of ring-opening polymerization of cyclic ethers. Polymerizations and copolymerizations of ethylene and propylene oxides as well as polymerization of tetrahydrofuran are used to produce polyether macrodiols, speci cally, telechelic polyethers having hydroxyl end groups [Clinton and Matlock, 1986; Dreyfuss et al., 1989; Gagnon, 1986]. The commercial materials are typically in the molecular weight range 500 6000 and are used to produce polyurethane and polyester block copolymers, including the thermoplastic polyurethane and polyester elastomers (Secs. 2-12e, 2-13b-3, 2-13c-2). The polyether macrodiols are also referred to as polyether glycols or polyols (trade names: Carbowax, Jeffox, Polyglycol, Polymeg, Terathane). Ethylene oxide and propylene oxide polymers and copolymers are also available in molecular weights of up to $20,000 and are used as hydraulic uids and lubricants, additives in cosmetics, and binders in ceramic and powder metallurgy. Ethylene oxide polymers with molecular weights of 105 106 ,

,~e ( -a W)

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referred to as poly(ethylene oxide), nd applications that take advantage of the high viscosity of their aqueous solutions. This includes occulation, denture adhesives, packaging lms (pesticides, herbicides, seed tapes), thickening of acid cleaners and water-based paints, and friction reduction. There is considerable effort aimed at using ethylene oxide polymers and copolymers complexed with ionic salts as the electrolyte in all-solid rechargeable batteries. Polyepichlorohydrin and copolymers and terpolymers of epichlorohydrin with ethylene oxide and allyl glycidyl ether are useful elastomers [Body and Kyllinstad, 1986].

e*(W)

These materials (trade names: Epichlomer, Herclor, Hydrin) have good resistance to fuel, oil, ozone, and heat combined with low-temperature exibility and resistance to vapor permeation by air, hydrocarbons, and uorocarbons. Polyoxymethylene, also referred to as acetal resin or POM, is obtained either by anionic polymerization of formaldehyde or cationic ring-opening copolymerization of trioxane with a small amount of a cyclic ether or acetal (e.g., ethylene oxide or 1,3-dioxolane) [Cherdron et al., 1988; Dolce and Grates, 1985; Yamasaki et al., 2001]. The properties and uses of POM have been discussed in Sec. 5-6d. Both anionic and cationic initiation are used to cure (polymerize and crosslink) epoxy resins (Sec. 2-12d) by ROP of the oxirane end groups. Photochemical cationic initiation (Sec. 5-2a-4) is important in various coating applications (3-4c) [Decker et al., 2001]. 7-3 LACTAMS The polymerization of lactams (cyclic amides) can be initiated by bases, acids, and water [Reimschuessel, 1977; Sebenda, 1976, 1978; Sekiguchi, 1984]. Initiation by water, referred to as hydrolytic polymerization, is the most often used method for industrial polymerization of lactams. Anionic initiation is also practiced, especially polymerization in molds to directly produce objects from monomer. Cationic initiation is not useful because the conversions and polymer molecular weights are considerably lower.

(7.160)

7-50

where e* (w) is the complex conjugate of the classical dielectric permittivity (7.122) derived in Section 7.7. As in Problem 7.4, we can use (7.145) to write a in terms of C(w) and ct(w), (7.161) Using this equation in (7.59), with al(w) given by (7.160) and a2(w) given by (7.153), we see that in terms of the operators C(w) and Ct (w), for which the total Hamiltonian is a continuous sum (integral) of uncoupled harmonic oscillators, the electric displacement is given by

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