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Anionic Ring-opening Polymerization: Epoxides and Episulfides-32

Elsevier Ltd
DOI: 10.1016/b978-0-08-096701-1.00094-x


Extensive studies of the mechanism and kinetics of the anionic polymerization of epoxides and episulfides have been reported during the last few decades, and they were reviewed quite recently by several authors.1–5 Most of the experiments were carried out with ethylene oxide (oxirane) and propylene sulfide (2-methylthiirane) because the living character of the polymerization of these two monomers, under specific conditions, has been well established;6, 7 propylene oxide (2-methyloxirane) polymerizes anionically with transfer to monomer, and poly(ethylene sulfide) is insoluble. In this chapter, the kinetics and mechanisms of the ring-opening reactions of epoxides and episulfides with nucleophilic initiators, as well as with the living ends during propagation, will be presented.

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