Method for determining the kinetic parameters in diffusion-controlled free-radical homopolymerizations

被引:110
作者
Goodner, MD [1 ]
Lee, HR [1 ]
Bowman, CN [1 ]
机构
[1] UNIV COLORADO,DEPT CHEM ENGN,BOULDER,CO 80309
关键词
VOLUME RELAXATION; MULTI(METH)ACRYLATE MONOMERS; HIGH-CONVERSION; POLYMERIZATION; PHOTOPOLYMERIZATION; BEHAVIOR;
D O I
10.1021/ie9605387
中图分类号
TQ [化学工业];
学科分类号
0817 ;
摘要
Free-radical homopolymerizations of 2-hydroxyethyl methacrylate (HEMA) and diethylene glycol dimethacrylate (DEGDMA) photoinitiated by 2,2-dimethoxy-2-phenylacetophenone (DMPA) were studied. A novel analytical method for elucidating the free-volume dependencies of the propagation and termination kinetic constants from a single set of kinetic data is developed. The polymerization is divided into four regimes, nondiffusion Limited, autoacceleration, reaction-diffusion without propagation limitations, and autodeceleration, in order to glean the parameters that describe the free-volume dependency. The parameters found via this method are used in a concurrently developed model to predict the polymerization rates and kinetic constant evolution throughout the polymerization. The rates and kinetic constants predicted by the model agree well with the experimentally determined rates and kinetic constants.
引用
收藏
页码:1247 / 1252
页数:6
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