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本文研究了在365nm光照下二苯酮-苯胺体系引发丙烯腈光聚合,在DMF中溶液聚合的动力学方程式为R_p∝[二苯酮]~(0.32)[苯胺]~(0.27[丙烯腈]~(1.1)。不同芳胺引发聚合的速度顺序为:N,N-二甲基苯胺>N-甲基苯胺>苯胺。考察了溶剂极性对聚合的影响,提出质子转移发生在二苯酮和苯胺的激基复合物的紧密离子对状态。聚合物端基分析表明质子转移后产生的两个自由基中主要是苯胺自由基引发聚合。
In this paper, we studied the photopolymerization of acrylonitrile initiated by the benzophenone-aniline system under 365 nm light irradiation. The kinetic equations of solution polymerization in DMF were R_pα [benzophenone] ~ (0.32) [aniline] ~ (0.27 [acrylonitrile] ~ (1.1). The order of polymerization of different aromatic amines is N, N-dimethylaniline> N-methylaniline> aniline.The influence of solvent polarity on the polymerization was investigated, and the proton transfer was proposed to occur in the presence of benzophenone And aniline. The analysis of the polymer end groups showed that the two free radicals generated after the proton transfer mainly were aniline radical initiating polymerization.