乙烯基醚与七元环硫羰内酯阳离子杂化共聚研究  

Cationic Hybrid Copolymerization of Vinyl Ether and Seven-membered Thionolactone

作　　者：杨鹏 熊雨 卢宗斌 洪春雁 张泽 尤业字 Peng Yang;Yu Xiong;Zong-bin Lu;Chun-yan Hong;Ze Zhang;Ye-zi You(School of Chemistry and Materials Science,University of Science and Technology of China,Hefei 230026)

机构地区：[1]中国科学技术大学化学与材料科学学院,合肥230026

出　　处：《高分子学报》2024年第5期594-603,共10页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52322301,22131010,22071232);安徽省高校协同创新项目(项目号GXXT-2023-035)资助项目。

摘　　要：报道了七元环联苯连接的硫羰内酯(DOT)的阳离子开环聚合,得到了一种T_(g)达到98℃的新型聚硫酯高分子.随后对DOT与乙烯基醚的阳离子共聚进行探索,系统研究了催化剂等对DOT与异丁基乙烯基醚共聚的影响.并基于阳离子聚合型链转移试剂的调控,成功构建了DOT和异丁基乙烯基醚的可控阳离子杂化共聚,制备了一种新型聚乙烯基醚-聚硫酯嵌段共聚物(数均分子量7.6~8.0 kg/mol,PDI<1.40).研究结果为发展杂化共聚新方法和制备新型共聚物材料提供了设计思路.Designing novel copolymerization methods for preparing new copolymers is of significance to synthesize high-value polymer materials.Vinyl and heterocyclic compounds are the most important types of monomers in polymer chemistry,but the controlled copolymerization of the two is a great challenge due to the distinct polymerization mechanisms and reactive centers,which limits the development and application of new copolymer materials.Based on the thionolactone monomers which are studied widely,the cationic ring-opening polymerization of a seven-membered biphenyl-fused thionolactone(DOT)via using common cationic catalyst BF_(3)·Et_(2)O was studied.The structure of this newly synthesized polythioester was confirmed using~1H nuclear magnetic resonance(^(1)H-NMR)and ^(13)C-NMR.Differential scanning calorimeter method(DSC)and thermogravimetric analysis(TGA)indicated that the polythioester exhibits good thermal stability and a high T_(g)(98℃).Subsequently,cationic hybrid copolymerization of DOT and vinyl ether was explored.According to the effects of three types of cationic catalysts on the copolymerization of DOT and isobutyl vinyl ether(IBVE)without a chain transfer reagent(CTA),trifluoromethanesulfonic acid(CF_(3)SO_(3)H)was selected for further investigation.Subsequently,with the use of a scalable and green cationic CTA and the catalyst CF_3SO_3H,the controlled cationic hybrid copolymerization of DOT and IBVE was developed,producing a new poly(vinyl ether)-block-poly(thioester)copolymer(M_(n)=7.6-8.0 kg/mol,PDI<1.40).The block structure of the polymer was further confirmed by diffusion ordered spectroscopy(DOSY)NMR.This study provides design ideas for the development of new methods of hybrid copolymerization and the preparation of new copolymer materials.

关 键 词：阳离子 杂化聚合 硫羰内酯 乙烯基醚 

分 类 号：TQ316[化学工程—高聚物工业]