含二苯酮基光敏性冠醚的研究

STUDY OF PHOTOSENSITIVE CROWN ETHERS CONTAINING BENZOPHENONE MOIETY

光敏冠醚、苯甲酰苯井-15-冠-5(BPC)和双(4-苯并-15-冠-5)甲酮(CBPC),用光谱方法和动力学方法进行了研究,吸收光谱和发射光谱数据表明,BPC和CBPC的最低激发态具有ππ~*特性,它们的光化学性质和烷氧基取代的二苯酮相似,在紫外光照射下,BPC和CBPC很容易和叔胺进行光反应生成自由基碎片,光还原过程用吸收光谱测定进行了跟踪,这些光敏冠醚BPC和CBPC,配合叔胺可用作烯类光聚合的引发剂,测得的聚合速度(R_p)和[BPC]^(0.17)[TEA]^(0.29)及[MMA]^(0.81)成正比。

The photochemical behavior of photosensitive crown ethers, benzoylbenzo-15-crown-5(BPC) and bis(4-benzo-15-crown-5) ketone(CBPC), were studied spectrophotometrically and kinetical-ly. The absorption and emission spectral data showed that BPC and CBPC are characteristic of ππ* at lowest excited state. Their photochemical properties are similar to that of r.lkoxyl substituted benzophenone. Under UV irradiation compounds of BPC and CBPC readily undergo photoreaction with tertiary amine to produce radical species. This photoreduction process was monitored by absorption spectroscopy. These photosensitive crown ethers, BPC and CBPC, have been used as the initiators in combination with tertiary amine for vinyl photopo-lymerization. The polymerization rate (Rp) is directly proportional to (BPC)0.17 (TEA)0.29 and (MMA)0.81.