TIME-RESOLVED ELECTRON-SPIN-RESONANCE STUDY ON RADICAL POLYMERIZATION WITH (2,4,6-TRIMETHYLBENZOYL)DIPHENYLPHOSPHINE OXIDE - DIRECT ESTIMATION OF RATE CONSTANTS FOR ADDITION-REACTIONS OF DIPHENYLPHOSPHONYL RADICALS TO VINYL MONOMERS

被引:66
作者
KAJIWARA, A
KONISHI, Y
MORISHIMA, Y
SCHNABEL, W
KUWATA, K
KAMACHI, M
机构
[1] OSAKA UNIV,FAC SCI,DEPT MACROMOLEC SCI,TOYONAKA,OSAKA 560,JAPAN
[2] HAHN MEITNER INST KERNFORSCH BERLIN GMBH,BEREICH S,W-1000 BERLIN 39,GERMANY
关键词
D O I
10.1021/ma00059a025
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Rate constants for addition reactions of diphenylphosphonyl radicals (Ph2P=O) to vinyl monomers were directly estimated by time-resolved electron spin resonance (ESR) spectroscopy. The rate constants were on the order of 10(6)-10(7) s-1 M-1, being 1 or 2 orders of magnitude larger than those of carbon-centered radicals, which were obtained by photolysis of benzoin, benzoin methyl ether, or 1-phenyl-2-hydroxy-2-methylpropanone-1. The fact that (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TMDPO) is a more effective initiator than alpha,alpha'-azobis(isobutyronitrile( (AIBN) was made clear in the radical polymerizations of vinyl pivalate at -30 and 70-degrees-C.
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页码:1656 / 1658
页数:3
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