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3When dealing with dimensions higher than two, this is interpreted a path parallel to some line contained in the decision hyperplane, which itself is a translate of a maximal (dimension - 1) subspace of the feature space.

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7-107

7-108

involve a nucleophilic attack on monomer analogous to the anionic polymerization of epoxides [Mazurek and Chojnowski, 1977; Mazurek et al., 1980]. An interesting aspect of this polymerization is that H is nearly zero and, amazingly, S is positive by 6.7 J mol 1 K 1 [Lee and Johannson, 1966, 1976]. The driving force in this polymerization is the increase in entropy (disorder) on polymerization. A positive value of

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However, when -+ f w along a path parallel to the decision boundary, w7x will take a constant value and the will also be constant. However, the (8.4), will have a magnitude depending solely on the term. This leads to the following observations:

S is very rare for a polymerization process. The only other reported instances of positive S values are those for the polymerizations of the cyclic octamers of sulfur and selenium and cyclic carbonate oligomers (Sec. 7-5c) [Brunelle et al., 1989]. All other polymerizations involve a decrease in entropy because of the decreased disorder for a polymer relative to its monomer. The positive S values for the cyclic siloxane, S, and Se probably result from the high degree of exibility of the linear polymer chains due to the large-sized atoms that they contain. This exibility leads to greater degrees of freedom in the linear polymer compared to the cyclic monomer. Cationic polymerization has been initiated by a variety of protonic and Lewis acids [Kubisa, 1996; Toskas et al., 2001]. The cationic process is more complicated and less understood than the anionic process. Polymerization under most reaction conditions involves the presence of a step polymerization simultaneously with ROP. This appears to be the only way to reconcile the observed (complicated) kinetics for the overall process [Chojnowski and Wilczek, 1979; Chojnowski et al., 2002; Cypryk et al., 1993; Rubinsztain et al., 1993; Sigwalt, 1987; Wilczek et al., 1986]. Initiation consists of protonation of monomer followed by subsequent reaction with monomer to form the tertiary oxonium ion LXXXI (Eq. 7-109). Propagation for the ring-opening

7-109

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chain polymerization follows in the same manner with nucleophilic attack of monomer on the tertiary oxonium ion (Eq. 7-110). (This is analogous to the cationic polymerization of cyclic ethers; see Eq. 7-20.)

the paths;

7-110

The silicenium ion (LXXXII) has been proposed as an alternative to the oxonium ion as the propagating center [Sigwalt and Stannett, 1990].

(4n+2)

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