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有机化学
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有机化学 ›› 1988, Vol. 8 ›› Issue (5): 423-435. 上一篇    下一篇

研究论文

油溶和水溶性羰基引发剂的光化学

N.S.Allen;F.Catalina;P.N.Green;陈文祥   

  1. 中国科学院感光化学研究所
  • 发布日期:1988-10-25

Photochemistry of oil and water soluble carbonyl

N.S.Allen;F.Catalina;P.N.Green;CHEN WENXIANG   

  • Published:1988-10-25

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677

被引次数

1

本文回顾了在羰基引发剂的作用下烯烃单体光引发聚合的最新机理. 报道了有关多种当前通用的新型羰基引发剂的光物理和光化学的近期工作. 其中包括UV吸收, 发光光谱和闪光光解的研究. 还报道了油溶性引发剂对丙烯酸丁酯的光聚合效应. 证明油溶性引发剂实质上是经过三重态来起作用, 其中包含一个从溶剂中攫取氢的引发步骤. 对于硫杂蒽酮衍生物来说, 它们从叔胺接受电子的能力及其光聚合效应之间有一定的关系.从闪光光解获得的证据说明在这种情况下存在着自由基阴离子, 但是基于二苯酮和苯基酮的引发剂则没有. 预料后者直接从胺攫氢是通过三重态羰基或是引发剂的自由基. 有证据表明联苯甲酰主要是通过光裂解来起作用. 水溶性硫杂蒽酮引发剂的作用主要是经过单重态, 其中包含引发时攫氢一步. 在这种情况下, 自由基的形成不受氧的影响.

关键词: 丙烯酸酯 P, 光聚合, 引发剂, 光化学, 裂解, 光谱分析, 羰基化合物, 丁醇 P, 激光, 闪光光解, 噻吨 P

The efficiency of aryl ketone and thioxanthone derivative catalysts for photopolymn. of n-Bu methacrylate was studied. For thioxanthone derivatives a correlation existed between their electron-accepting ability with a tertiary amine and their photopolymn. efficiency. Evidence from flash photolysis indicated the presence of the radical anion in this case but not with benzophenone or Ph ketone catalysts. In the latter cases, direct H atom abstraction from the amine was predicted to occur by either the triplet carbonyl or catalyst free radicals. Benzil was activated primarily by photochem. fragmentation. Water-sol. thioxanthone catalysts operated primarily via the singlet state involving an initial step of H atom abstraction and the free radical formation was unaffected by the presence of O.

Key words: PROPENOIC ACID ESTER P, PHOTO POLYMERIZATION, INITIATOR, PHOTOCHEMISTRY, PYROLYSIS, SPECTROGRAPHIC ANALYSIS, CARBONYL COMPOUNDS, BUTANOL P, LASER, FLASH PHOTOLYSIS, THIOXANTHENE P

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