高分子体系中降冰片二烯的光异构化反应

doi:10.7517/j.issn.1674-0475.1995.02.129

影像科学与光化学 ›› 1995, Vol. 13 ›› Issue (2): 129-135.DOI: 10.7517/j.issn.1674-0475.1995.02.129

高分子体系中降冰片二烯的光异构化反应

王雪松, 张宝文, 曹怡

中国科学院感光化学研究所, 北京100101

收稿日期:1994-07-16 修回日期:1994-09-22 出版日期:1995-05-20 发布日期:1995-05-20
通讯作者: 曹怡
基金资助:
国家自然科学基金

PHOTO INDUCED VALENCE ISOMERIZATION OFNORBORNADIENE IN POLYMER SYSTEMS

WANG XUE-SONG, ZHANG BAO-WEN, CAO YI

Institute of Photographic Chemistry, The Chinese Academy of Sciences, Beijing 100101, P. R. China

Received:1994-07-16 Revised:1994-09-22 Online:1995-05-20 Published:1995-05-20

摘要/Abstract

摘要： 本文合成了降冰片二烯和咔唑为侧基的甲基丙烯酸酯共聚物,并与仅带有降冰片二烯侧基的聚甲基丙烯酸酯进行了光异构化反应的对比研究。实验结果表明,当入射光波长小于350nm时,两种降冰片二烯聚合物均发生了光异构化反应;当入射光波长大于350nm时,只有共聚物的降冰片二烯侧基能够异构化为相应的四环烷。利用荧光猝灭实验及化学诱导动态核极化(CIDNP)等研究了咔唑的敏化机理,利用三氟乙酸作催化剂实现了四环烷的反向异构化。

关键词: 降冰片二烯, 四环烷, 光诱导价键异构化反应

Abstract: A copolymer bearing norbornadiene and carbazole as pendants was synthesized and apolymer only having norbornadiene pendants was also prepared for comparision. The valenceisomerization of the norbornadiene molety to quadricy clane moiety proceeded smoothly when the two kinds of polymers were irradiated with the light below 350nm. If the wavelength ofthe incident light was above 350nm, the isomerization reaction was only found in copolymersystem. Utilizing fluorescence quenching experiment and CIDNP technique, the mechanismof sensitized valence isomerization was studied. The isomerization of quadricyclane moiety tonorbornadiene moiety was also achieved by using trifluoroacetic acid as catalyst.

Key words: norbornadiene, quadricyclane, photoinduced valence isomerization

王雪松, 张宝文, 曹怡. 高分子体系中降冰片二烯的光异构化反应[J]. 影像科学与光化学, 1995, 13(2): 129-135.

WANG XUE-SONG, ZHANG BAO-WEN, CAO YI. PHOTO INDUCED VALENCE ISOMERIZATION OFNORBORNADIENE IN POLYMER SYSTEMS[J]. Imaging Science and Photochemistry, 1995, 13(2): 129-135.

高分子体系中降冰片二烯的光异构化反应

PHOTO INDUCED VALENCE ISOMERIZATION OFNORBORNADIENE IN POLYMER SYSTEMS

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