Living Free Radical Ring-opening Polymerization of 5,6-Benzo-2-methylene-1,3-dioxepane

Abstract

Abstract: In order to clarify whether Atom Transfer Radical Polymerization(ATRP) method could be extended to free radical ring-opening polymerization, the polymerization of a kind of unsaturated cyclic acetal: 5,6-benzo-2-methylene-1,3-dioxepane(BMDO) in the presence of α,α'-dibromoxylene as the initiator and CuBr/2,2'-bipyridine as the catalyst and ligand at 120 ℃ was investigated. IR, ¹H NMRand ¹³C NMRspectra of the polymer obtained showed that BMDOunderwent quantitatively ring-opening polymerization and linear polyesters were prepared. GPCcurves indicated that the polyesters had a narrower molecular weight distribution. Molecular weight of the polyesters could be controlled by polymerization time and adjusting the molar ratio of monomer/intiator consumed. The polymers with narrower polydispersities were obtained, and first-order kinetics of polymerization was observed. These facts proved that BMDOunderwent “living” free radical ring-opening polymerization. And this is the firsr report on the “living” free radical ring-opening polymerization of unsarurated cyclic acetal using atom transfer radical polymerization method. The results of ln([M]₀)/[M]) against polymerization time, M_n vs. conversion, and molecular weight distribution of the polymers are indicative of the “living” polymerization process.

Key words: Living free radical polymerization, Atom transfer radical polymerization, Ring-opening polymerization

CLC Number:

O631

TrendMD:

YUAN Jin-Ying, ZOU Ying-Fang, PAN Cai-Yuan  . Living Free Radical Ring-opening Polymerization of 5,6-Benzo-2-methylene-1,3-dioxepane[J]. Chem. J. Chinese Universities, 2000, 21(9): 1494.

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Living Free Radical Ring-opening Polymerization of 5,6-Benzo-2-methylene-1,3-dioxepane

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