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diols. Since the two routes differ considerably in their reaction characteristics, one can visualize situations where ROP is the preferred route, such as when it is desirable to take advantage of the different dependence of polymer molecular weight (MW) on reaction parameters. MW is dependent on stoichiometric balance and conversion in step polymerization. In ROP, MW generally depends on conversion and the monomer : initiator ratio. However, the cyclic monomers required for ROP are not nearly as available as the bifunctional reactants for step polymerization.

dry !V(ry) ,2



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7-2 CYCLIC ETHERS Cyclic ethers can be named simply as oxacycloalkanes, such as oxacyclopropane, oxacyclobutane, oxacyclopentane, and oxacyclohexane, where the pre x oxa indicates the replacement of CH2 by O in corresponding cycloalkanes. Most cyclic ethers, however, are known by other names. The 3-, 4-, 5-, and 6-membered rings are oxirane, oxetane, oxolane, and oxane, respectively, or ethylene oxide (or epoxide), trimethylene oxide, tetrahydrofuran, and tetrahydropyran. The carbon oxygen bond in ethers is a strong bond, and the ether oxygen is basic in the Lewis sense. The result is that ring-opening polymerization of cyclic ethers is generally initiated only by cationic species except for epoxides. Epoxides are polymerized by both anionic and cationic initiators because of the high degree of strain in the 3-membered ring. The polymerization of simple cyclic ethers (i.e., those with a single ether linkage) has been generally limited to those of 3, 4 and 5 members, although some work has been done with the 7-membered (oxepane) ring. The study of larger-sized rings has been carried out mostly with cyclic acetals (Sec. 7-2b-4). The reactivity of different-sized cyclic ethers follows the generally expected order. Cyclic ethers of less than 5 members or more than 6 members are relatively easily polymerized. The 5-memebered cyclic ethers polymerize with more dif culty. Substituted 5-membered cyclic ethers are usually unreactive, although some cyclic acetals undergo polymerization. The 6-membered cyclic ethers such as tetrahydropyran (III) and 1,4-dioxane (IV) are unreactive under a wide range of reaction conditions, but the 6-membered cyclic acetal, trioxane (V), undergoes polymerization.





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dt' e i (t'-t)71(3(t').

7-2a-1 Reaction Characteristics The anionic polymerization of epoxides such as ethylene and propylene oxides can be initiated by metal hydroxides, alkoxides, oxides, and amides as well as metal alkyls and aryls, including radical anion species such as sodium naphthalene [Boileau, 1989; Dreyfuss and Drefyfuss, 1976; Inoue and Aida, 1984; Ishii and Sakai, 1969]. Thus the polymerization of ethylene oxide by M A involves initiation

(7.104)

7-7

In the golden rule regime (wo ~ .Do ~ J<i.) considered here, the integrals on last term on the right-hand side of (7.104) can be done (Problem 7.1) and we find 9 that

(n + 1)

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:t(3

Some initiators polymerize epoxides through an anioninc coordination mechanism. These initiators include a ferric chloride propylene oxide adduct ClFe[OCH(CH3)CH2Cl]2 (referred to as the Pruitt-Baggett initiator), adducts such as Zn(OCH3)2 and ([Zn(OCH3)2]2 [C2H5ZnOCH3]6) derived by reaction of dialkylzinc with alcohol, bimetallic m-oxoalkoxides such as [(RO)2AlO]2Zn, and metalloporphyrin derivatives of aluminum and zinc (e.g., VI with Z Cl, OR, R, OOCR, SR) [Aida and Inoue, 1996; Hagiwara et al., 1981; Hasebe and Tsurata, 1988; Inoue, 1988, 2000; Kasperczyk and Jedlinski, 1986; Kuroki et al., 1988a, b; Nuytens et al., 2000; Slomkowski and Duda, 1993; Sugimoto and Inoue, 1999].

+ iwo) (3 -

Propagation with the anionic coordination initiators, especially the aluminum and zinc initiators such as aluminum isopropoxide or the metalloprophyrins such as VI, involves covalent propagation in which the epoxide monomer is inserted into a metal oxygen bond [Penczek and Duda, 1993; Penczek et al., 1995; Szwarc and Van Beylen, 1993] (Eq. 7-9). The propagation is categorized as an anionic coordination process since one can visualize

7-9

iG (a + a*).

the formation of an incipient alkoxide anion on cleavage of the metal oxygen bond at the propagating center. (Polymerization with some initiators such as AlR3/H2O and AlR3/ROH probably proceed as cationic, not anionic, processes [Antelmann et al., 2001; Bansleban et al., 1984].) Although generally presented as a covalent propagation, it is dif cult to preclude the possibility that propagation occurs mostly or even exclusively through a small concentration of

(7.105)

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