(7-N,N-二甲氨基)香豆素基-3-甲酸乙酯/二芳基碘鎓盐光敏引发聚合反应体系

PHOTOSENSITIZATION INITIATION SYSTEM OF ETHYL 7 N,N DIMETHYLAMINO COUMARINYL 3 FORMATE/DIARYLIODONIUM SALT

本工作合成了（７－Ｎ，Ｎ－二甲氨基）香豆素基－３－甲酸乙酯（ＥＤＡＣＦ）光敏剂．在光作用下，激发态的ＥＤＡＣＦ分子与二芳基碘盐ＯＰＰＩＰ分子之间发生电子转移反应，伴随发生ＥＤＡＣＦ的褪色反应和ＯＰＰＩＰ的光解反应，后者生成具有引发活性的芳基自由基．由于ＥＤＡＣＦ具有ＣＴ态特性，使得它与ＯＰＰＩＰ之间的光电子转移反应速度随着溶剂极性增加明显减慢．ＥＤＡＣＦ／ＯＰＰＩＰ体系可有效地引发ＭＭＡ聚合反应，聚合反应动力学方程为Ｒｐ＝Ｋ［ＯＰＰＩＰ］０．４７［ＥＤＡＣＦ］０．４２［ＭＭＡ］０．９８．

Photosensitizer ethyl 7 N,N dimethylamino coumarinyl 3 formate (EDACF) was synthesized in this work. Upon irradiation, an electron transfer reaction occurred between excited EDACF and diaryliodonium salt (OPPIP) following with the photobleaching of EDACF and the photolysis of OPPIP, and the latter could yield the active aryl radical. CT characteristics of EDACF might cause the distinct decrease in rate of electron transfer reaction with the increase of solvent polarity. EDACF/OPPIP system can effectively initiate polymerization of MMA, and the kinetic equation of polymerization is R p = K 0.47 0.42 0.98 .