Solvent effects on TEMPO-mediated radical polymerizations: behaviour of 3-vinylpyridine in a protic solvent

被引：10
作者：
Ding, XZ
Fischer, A
Yang, SW
Wu, P
Brembilla, A
Lochon, P
机构：
[1] Grp ENSIC, UMR CNRS INPL 7568, Lab Chim Phys Macromol, F-54001 Nancy, France
[2] Inst High Performance Comp, Singapore 118262, Singapore
[3] UHP Nancy 1, UMR CNRS 7565, Lab Etud Syst Organ & Colloidaux, F-54506 Vandoeuvre Nancy, France
来源：
EUROPEAN POLYMER JOURNAL | 2001年 / 37卷 / 08期
关键词：
3-vinylpyridine; TEMPO; controlled free radical polymerization; solvents;
D O I：
10.1016/S0014-3057(01)00022-2
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ; 080501 ; 081704 ;
摘要：
Solvents can strongly influence the equilibrium between dormant and active species which is involved in 2,2,6,6-tetramethyl-1 -piperidinyloxy (TEMPO)-mediated radical polymerizations. At 110 degreesC, the overall polymerization rate of 3-vinylpyridine in pyridine was logically found lower than that in bulk, due to dilution. However, in ethylene-glycol, the opposite behaviour was observed. According to infrared spectroscopy, this unexpected increase in the overall polymerization rate was attributed to hydrogen bonding between ethylene-glycol and the pyridine rings, which weakens the C-O-N bond of the TEMPO-terminated polymers. Semi-empirical molecular orbital calculations were used to support the FTIR results and to calculate the decrease in the dissociation enthalpy of the polymer-nitroxide bond. (C) 2001 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码：1561 / 1569
页数：9
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