Library of Stereoregular Polythioesters for Stereocomplex Formation Enabled by Isomerization‐Driven Cationic Ring‐Opening Polymerization
Abstract
Abstract Supramolecular stereocomplexation is an important tool to advance sustainable polymers, and oxygen‐containing polymers represent the most widely studied materials for stereocomplexation. However, the sulfur‐containing analogues, a newly emerged class of sustainable polymers, remain essentially unexplored because of a significant challenge encountered in the synthesis of stereoregular polymers and relatively low supramolecular interaction. In this contribution, by the utilization of [Et 3 O] + [B(C 6 F 5 ) 4 ] − as a metal‐free cationic initiator, controlled isomerization‐driven ring‐opening polymerizations (IROPs) of nine examples of chiral five‐membered thionolactones have been achieved with free or suppressed racemization via unique monomer‐stabilized S N 2 propagation mechanism, which allows an unprecedented access to a library of new stereoregular polythioesters with high isotacticities (80.0%–99.5%). The investigations into structure–stereocomplexation relationship led to the disclosure of two new polythioester stereocomplexes with high melting temperatures (117.0–161.0 °C). The fundamental aspects of stereocomplex formation mechanism and critical factors that affect stereocomplexed ability have also been revealed.
Article Details
Authors (6)
Pengjun Yuan
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering College of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai 200237 China
Yongliang Xia
State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai 200032 China
Xi Zhang
Yangyang Sun
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry
Yifeng Chen
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China
Miao Hong
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry