基于氨基酸基交硫酯单体的闭环回收高分子  

Amino Acid-based Dithiolactone Monomers towards Chemically Recyclable Polymers

作　　者：朱忆诺 陶友华[1] Yi-nuo Zhu;You-hua Tao(Key Laboratory of Polymer Ecomaterials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022)

机构地区：[1]中国科学院长春应用化学研究所,中国科学院生态环境高分子材料重点实验室,长春130022

出　　处：《高分子学报》2022年第9期1023-1031,共9页Acta Polymerica Sinica

摘　　要：发展闭环回收高分子被认为是解决塑料污染问题和发展循环经济的最佳选择,该方法通过设计特定的单体合成高分子材料,再将其直接转化为原单体,从而实现资源循环和同级使用.近年来,中国学者在可闭环回收的聚酯及聚硫酯的合成方面取得了一系列重要进展.尽管如此,“理想单体”的设计以及聚合物的使用性能始终是制约闭环回收高分子进一步发展的主要因素.我们课题组提出氨基酸来源的交硫酯单体可以作为一类“理想单体”用于闭环回收高分子.交硫酯单体在热力学上更有利于成环,在动力学上更有利于开环聚合,从而成功地将2种看似矛盾的性质结合到一种单体上,使交硫酯单体更容易合成、更容易聚合、其聚合物也更容易实现闭环回收.特别是来源于缬氨酸的异丙基交硫酯的开环聚合,所得聚合产物具有无规但是结晶的不同寻常的特性.相信进一步发展氨基酸基交硫酯单体的高效成环和可控聚合,将为闭环回收高分子的大规模制备和应用奠定基础.Developing chemically recyclable polymers represents a greener alternative to landfill and incineration and offers a closed-loop strategy toward a circular materials economy.Although some progress has been achieved in the synthesis of closed-loop recycled polymers,the synthesis of chemically recyclable polymers is still plagued with certain fundamental limitations,including trade-offs between the monomer’s cyclizability and polymerizability,as well as between polymer’s depolymerizability and properties.Very recently,our research group has proposed that amino acid-based dithiolactone monomers is a kind of“ideal monomer”for chemically recyclable polymers.These dithiolactone monomers demonstrate appealing chemical properties different from those of dilactone,including accelerated ring closure,augmented kinetics polymerizability,high depolymerizability and selectivity,and thus constitute a unique class of polythioester materials exhibiting controlled molecular weight(up to 100.5 k Da),atactic yet high crystallinity,structurally diversity,and chemical recyclability.In particular,the ring-opening polymerization of isopropyl dithiolactone derived from valine,delivered atactic yet crystalline polythioester.These amino acid-based chemically recyclable plastics show promise as next-generation sustainable materials.

关 键 词：闭环回收高分子 氨基酸 交硫酯 聚硫酯 开环聚合 

分 类 号：TQ317[化学工程—高聚物工业]