电子给体结构对丙烯腈光聚合的影响

The Structral Effect of Electron Donors on the Photo-Polymerization of Acrylonitrile

电子受体与烯类单体间通过电荷转移机理的引发聚合已有很多研究^([1,2]),而电子给体如芳香叔胺、二苯硫醚等引发丙烯腈(AN)光聚合^([3,4])亦已证明都是通过电荷转移机理进行的。本文简要报导周期表第五族氮、磷、砷、锑、铋以及第六族氧和硫诸元素的苯基化合物作为电子给体对丙烯腈的光引发聚合,以研究电荷转移引发与电子给体结构的关系.

The photopolymerization of acrylonitrile (AN) using the triphenyl compounds of N, P, As, Sb, Bi elements (represented as (C_(6)H_(5))_(3)D) and the diphenyl compounds of O, S elements (represented as (C_(6)H_(5))_(2)D) as initiators and some relationship between the centre atom D of the donor compounds and their situations in the periodic table were suggested. The order of Rp initiated with different (C_(6)H_(5))_(x)D as follows.(C_(6)H_(5))_(3)P>(C_(6)H_(5))_(2)S>(C_(6)H_(5))_(3)N>(C_(6)H_(5))_(2)O and (C_(6)H_(5))_(3)As>(C_(6)H_(5))_(3)Sb>(C_(6)H_(5))_(3)BiFor O, N, S, P elements this order is in agreement with increasing of the atom radius as well as the decreasing of the electron-negativities.The tentative mechanism of photopolymerization of AN using (C_(6)H_(5))_(x)D as initiator has been proposed and discussed.