Photocrosslinkable Polynorbornene-based Block Copolymers with Enhanced Dielectric and Thermal Properties  

作　　者：hui-jing han sha zhang ru-yi sun jian-hua wu 谢美然 廖小娟 

机构地区：[1]School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, China

出　　处：《Chinese Journal of Polymer Science》2016年第3期378-389,共12页高分子科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(Nos.21574041 and 21374030);Large Instruments Open Foundation of East China Normal University(No.20151006)

摘　　要：Block copolymers poly（endo-N-3,5-bis（trifluoromethyl）biphenyl-norbornene-pyrrolidine）-block-poly（exo-N-（cinnamoyloxyethyl）-7-oxanorborn-5-ene-2,3-dicarboximide）（endo-PTNP-b-exo-PCONBI） and poly（exo-N-3,5-bis（trifluoromethyl）biphenyl-norbornene-pyrrolidine）-block-poly（exo-N-（cinnamoyloxyethyl）-7-oxanorborn-5-ene-2,3-dicarboximide）（exo-PTNP-b-exo-PCONBI） were synthesized by ring-opening metathesis polymerization. The endo- or exoPTNP served as the high dielectric functional chain, and exo-PCONBI acted as the crosslinking segment. The endo-PTNPb-exo-PCONBI, in which endo-PTNP has a high content of trans double bond and adopts isotactic configuration, shows a dielectric constant（？） of 15.5, whereas exo-PTNP-b-exo-PCONBI, in which exo-PTNP has 67% trans double bonds and atactic microstructure, displays relatively low ？ of 7.1. The cinnamate groups in exo-PCONBI were crosslinked to form three-dimensional network by cycloaddition reaction under UV irradiation. Exposed to UV-light for 10 min, the cinnamate group in polymer films has a crosslinking conversion of 36%, as determined by UV-Vis absorption measurements. By photocrosslinking, the polymer film has an increased ？ of 16.6, a dielectric loss of 0.03, an elevated glass-transition temperature of 137 ？C, and an enhanced decomposition temperature of 405 ？C, compared to those of polymer films without irradiation.Block copolymers poly（endo-N-3,5-bis（trifluoromethyl）biphenyl-norbornene-pyrrolidine）-block-poly（exo-N-（cinnamoyloxyethyl）-7-oxanorborn-5-ene-2,3-dicarboximide）（endo-PTNP-b-exo-PCONBI） and poly（exo-N-3,5-bis（trifluoromethyl）biphenyl-norbornene-pyrrolidine）-block-poly（exo-N-（cinnamoyloxyethyl）-7-oxanorborn-5-ene-2,3-dicarboximide）（exo-PTNP-b-exo-PCONBI） were synthesized by ring-opening metathesis polymerization. The endo- or exoPTNP served as the high dielectric functional chain, and exo-PCONBI acted as the crosslinking segment. The endo-PTNPb-exo-PCONBI, in which endo-PTNP has a high content of trans double bond and adopts isotactic configuration, shows a dielectric constant（？） of 15.5, whereas exo-PTNP-b-exo-PCONBI, in which exo-PTNP has 67% trans double bonds and atactic microstructure, displays relatively low ？ of 7.1. The cinnamate groups in exo-PCONBI were crosslinked to form three-dimensional network by cycloaddition reaction under UV irradiation. Exposed to UV-light for 10 min, the cinnamate group in polymer films has a crosslinking conversion of 36%, as determined by UV-Vis absorption measurements. By photocrosslinking, the polymer film has an increased ？ of 16.6, a dielectric loss of 0.03, an elevated glass-transition temperature of 137 ？C, and an enhanced decomposition temperature of 405 ？C, compared to those of polymer films without irradiation.

关 键 词：ROMP Block copolymer Photocrosslinking Thermal stability Dielectric performance 

分 类 号：O631[理学—高分子化学]