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O‐to‐S Substitution Enables Dovetailing Conflicting Cyclizability, Polymerizability, and Recyclability: Dithiolactone vs. Dilactone
Author(s) -
Wang Yanchao,
Li Maosheng,
Chen Jinlong,
Tao Youhua,
Wang Xianhong
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202109767
Subject(s) - monomer , polymer , crystallinity , selectivity , raw material , substitution (logic) , organic chemistry , chemistry , materials science , polymer science , copolymer , combinatorial chemistry , polymer chemistry , computer science , catalysis , composite material , programming language
Developing chemically recyclable polymers represents a greener alternative to landfill and incineration and offers a closed‐loop strategy toward a circular materials economy. However, 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. Here we describe the subtle O‐to‐S substitution, dithiolactone monomers derived from abundant feedstock α‐amino acids can 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 kDa), atactic yet high crystallinity, structurally diversity, and chemical recyclability. These polythioesters well addresses the formidable challenges of developing chemically recyclable polymers by having an unusual set of desired properties, including easy‐to‐make monomer from ubiquitous feedstock, and high polymerizability, crystallinity and precise tunability of physicochemical performance, as well as high depolymerizability and selectivity. Computational studies explain why O‐to‐S modification of polymer backbone enables dovetailing desirable, but conflicting, performance into one polymer structure.