新型光引发剂的理论研究

用含时密度泛函方法对新型光引发剂BDPB紫外吸收进行了计算，从前线分子轨道，共轭效应和电子效应角度考察了BDPB相对于BDMB产生红移的原因，并分析了不同溶剂对BDMB和BDPB紫外吸收光谱的影响. 结果表明BDPB具有比BDMB更高的引发效率，是一种潜在的光引发剂. 虽然BDMB具有更好的共轭效应，但是BDPB中的哌啶基团比BDMB中的吗啉基团具有更强的供电子效应，这是产生红移根本原因，在羰基附近的苯环对位上引入强供电子基团有利于提高光引发剂的引发效率. 极性溶剂和非极性溶剂相比，极性溶剂使得光引发剂的最大吸收波长红移.

THEORETICAL STUDY ON NOVEL PHOTOINITIATORS

UV absorption of novel photoinitiators has been investigated by time-dependent density function theory. The reason for red shift of BDPB compared to BDMB is analyzed by frontier molecular orbitals,conjugated effect and electronic effect. Solvent effect is also studied for BDMB and BDPB. It is found that BDPB has a better photoinitiation activity than BDMB,which is a more prospective photoinitiator. Although the conjugated effect of BDMB is better than BDPB,the electronic effect is stronger on BDPB. That is a fundamental reason for red shift. It is benefit to synthesize more efficient photoinitiator that para-position of benzene near carbonyl is substituted by electron donor groups. The maximum absorption becomes red shift on polar solvent compared to nonpolar solvent.