KINETICS AND MECHANISM OF URETHANE REACTIONS - PHENYL ISOCYANATE ALCOHOL SYSTEMS

被引:68
作者
CHANG, MC [1 ]
CHEN, SA [1 ]
机构
[1] NATL TSING HUA UNIV,DEPT CHEM ENGN,HSINCHU 300,TAIWAN
关键词
CATALYSIS - Reaction Kinetics;
D O I
10.1002/pola.1987.080250919
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Urethane reactions of phenyl isocyanate/alcohol systems with toluene as solvent and various aprotic polar solvents (including tertiary amines) as additives were carried out at constant temperature of 10-40 degree C. Analysis of the variation of the second order rate constants of these systems and those available in the literature indicates that formation of the hydrogen bonding complexes (alcohol with phenyl isocyanate and with aprotic solvent) and electron donor number (DN) of the aprotic solvent are the two factors allowing satisfactory explanation of the catalysis and inhibition effects of the wide range of aprotic solvents (including amines, amides, etc. ). Based on these considerations, an ion-pair mechanism and the resulting kinetic equation for the urethane reaction are proposed.
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页码:2543 / 2559
页数:17
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