Anionic ring-opening polymerization epoxide

Boileau, S., Anionic Ring-Opening Polymerizations Epoxides and Episulfides, pp. 467 487 in Comprehensive Polymer Science, Vol. 3, G. C. Eastmond, A. Ledwith, S. Russo, and P. Sigwalt, eds., Pergamon Press, London, 1989. 

BoUeau S. Anionic ring-opening polymerizations epoxides and episulfldes. In Eastmond GC, Ledwith A, Russo S, Sigwalt P, editors. Comprehensive Polymer Science. Chain polymerization. Volume 3. Oxford Pergamon 1989, Part I. p 467. 

Tsuruta, T. and Kawakami, Y., Anionic Ring-opening Polymerization Stereospecificity for Epoxides, Episulfides and Lactones , in Comprehensive Polymer Science, Pergamon Press, Oxford, 1989, Vol. 3, pp. 489-500. 

Tsuruta T, Kawakami Y (1989) Anionic ring-opening polymerization stereospecificity for epoxides, episulfides and lactones. In AUen G, Bevington J (ed) Comprehensive polymer science. Pergamon Press, Oxford, p 489... 

J.4.2.3 Heterocyclic Monomers A variety of heterocyclic monomers can be polymerized by anionic ring-opening polymerizations. The types of anionically polymerizable heterocyclic monomers include oxiranes (epoxides), thiacyclopropanes, thiacyclobutanes, lactones, lactides, lactams, anhydrides, carbonates, and silicones... 

T. Tsuruta, J. Polymer Sci., Polymer Symp., 67,73 (1980) T. Tsuruta and Y. Kawakami, Anionic Ring- Opening Polymerization Stereospecificity for Epoxides, Episulfides, and Lactones, Chapt 33, Comprehensive Polymer Science, Vol. 3, (G.C. Eastmond, A. Ledwith, S. Russo, andP. Sigwalt, eds.), Pergamon Press, London, 1989 T. Saegusa, H. Fujii, S. Kabayashi, H. Ando, and R. Kawase, Macromolecules, 9Ti, 6, 26 P.E. Black and D.J. Worsford, Can. J. Chem., 1976,54, 3326... 

Polyether synthesis From activated or metal-free anionic ring-opening polymerization of epoxides to functionahzation 13PPS845. 

Anionic Ring-Opening Polymerization of Epoxides and Related Nucleophilic Polymerization Processes... 

Imidazole is a well-known initiator for the anionic ring-opening polymerization of epoxides. The photogeneration of imidazole and its subsequent use as an initiator for the polymerization of multifunctional epoxy-novolak resins have been reported by Nishikubo et Photolysis of the nitro-benzyl derivative 119 as shown in Scheme 36 generates imidazole, 120, which forms zwitterionic intermediate, 121, by reaction with the epoxide. The latter species is a rather weak nucleophile and the application of heat (120 °C) was required to drive the polymerization to completion. 

An alternate way to make block copolymers involving PDMS blocks 124,125) is to have these chains fitted with epoxide functions at chain end, and to react them with a vinylic or dienic polymer carrying terminal COOH functions. Sequential addition of monomers has also been used, the ring opening polymerization of the cyclic trimer (D3) being initiated by the anionic site of a living polymer126). 

For the (coordination) anionic polymerization, metal alkoxides are often employed as initiators. In this system, the ring opening of epoxide takes place by a nucleophilic attack of an alkoxide on the (activated) epoxide carbon to generate another metal alkoxide which behaves as the propagating species (Scheme 3), The nature of metal-alkoxide... 

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