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Lewis酸碱对催化的可再生环状缩醛酯单体的开环聚合研究
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作者 汤家栋 李茂盛 陶友华 《高分子学报》 SCIE CAS CSCD 北大核心 2023年第3期356-364,共9页
从生物质原料3,4-二氢吡喃出发,合成了可再生环状缩醛酯单体(H-AE),从结构上看,该单体在γ-丁内酯中引入了缩醛单元,在开环聚合过程中,通过释放甲醛分子有希望在温和条件下得到聚(γ-丁内酯).选用合适的Lewis酸碱对催化剂,基本抑制了聚... 从生物质原料3,4-二氢吡喃出发,合成了可再生环状缩醛酯单体(H-AE),从结构上看,该单体在γ-丁内酯中引入了缩醛单元,在开环聚合过程中,通过释放甲醛分子有希望在温和条件下得到聚(γ-丁内酯).选用合适的Lewis酸碱对催化剂,基本抑制了聚合过程中的链回咬副反应,实现了单体的可控聚合.详细研究了催化剂的酸/碱性强度及其位阻大小对于合成的聚合物的组成和比例的影响,通过设计和优化催化剂的结构,实现了聚合物中聚丁内酯单元和聚缩醛酯单元比例的调控.对所得聚合物进行了1H-NMR、13C-NMR及扩散排序核磁共振(DOSY)表征,结合聚合过程的核磁与SEC监测,证实所得聚合物为丁内酯与缩醛酯的无规共聚物.根据实验数据和表征结果,推测聚合遵循Lewis酸碱对调控的阴离子开环聚合机理,酸碱催化剂共同稳定活性链末端,实现了亲核进攻和甲醛的脱除. 展开更多
关键词 开环聚合 Lewis酸碱对 环状缩醛酯 聚(γ-丁内酯)
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Fully Chemical Recyclable Poly(γ-butyrolactone)-based Copolymers with Tunable Structures and Properties
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作者 Yi-Huan Liu Xin Yuan +4 位作者 Jia-Qi Wu Ming-Xuan Luo Xin Hu Ning Zhu Kai Guo 《Chinese Journal of Polymer Science》 SCIE EI CAS CSCD 2022年第5期456-461,共6页
The emerging chemical recyclable polymers,such as poly(γ-butyrolactone)(PGBL)and poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),provide a good solution to the plastic pollution.However,these homopolymers s... The emerging chemical recyclable polymers,such as poly(γ-butyrolactone)(PGBL)and poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),provide a good solution to the plastic pollution.However,these homopolymers suffer from limited structures and properties.Herein,we reported a fully chemical recyclable copolymer P(GBL-co-((R)-M))through ring-opening copolymerization(ROCOP)of GBL and(R)-M.By employing organomagnesium as the catalyst and regulating the reaction conditions,the chemical structures of copolymers were wellcontrolled(GBL content=13%-78%,Mn=6560-15600 g/mol,DM=1.08-1.59).The resultant P(GBL-co-((R)-M))exhibited fully chemical recyclability,which rapidly and quantitatively depolymerized into initial GBL and(R)-M monomer through chemolysis.By varying GBL content,tunable thermal properties were achieved for P(GBL-co-((R)-M)).The onset decomposition temperatures of copolymers varied from 193°C to 234°C.A linear evolution of glass transition temperature(T_(g))of P(GBL-co-((R)-M))versus GBL content was obtained as following equation of Tg=-1.06×GBL mol%×100+39.6.We hope that the reported fully chemical recyclable copolymers with tunable structures and properties would serve as the candidate material for sustainable applications. 展开更多
关键词 poly(γ-butyrolactone)-based copolymers Ring-opening copolymerization Chemical recyclability Organomagnesium
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