Citation: Hui-jing Han, Sha Zhang, Ru-yi Sun, Jian-hua Wu, Mei-ran Xie, Xiao-juan Liao. Photocrosslinkable Polynorbornene-based Block Copolymers with Enhanced Dielectric and Thermal Properties[J]. Chinese Journal of Polymer Science, ;2016, 34(3): 378-389. doi: 10.1007/s10118-016-1753-0 shu

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

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School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, China

Received Date: 27 September 2015
Revised Date: 8 November 2015

Fund Project: This work was financially supported by the National Natural Science Foundation of China (Nos. 21574041 and 21374030), and Large Instruments Open Foundation of East China Normal University (No. 20151006).

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 exo-PTNP served as the high dielectric functional chain, and exo-PCONBI acted as the crosslinking segment. The endo-PTNP-b-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 photo-crosslinking, the polymer film has an increased of 16.6, a dielectric loss of 0.03, an elevated glass-transition temperature of 137 ℃, and an enhanced decomposition temperature of 405 ℃, compared to those of polymer films without irradiation.
- ROMP,
- Block copolymer,
- Photocrosslinking,
- Thermal stability,
- Dielectric performance
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沈阳化工大学材料科学与工程学院沈阳 110142