Modulating Polymerization Behaviors of Ether–Ester Monomers and Physicochemical Properties of Poly(ether-alt-ester)s by Heteroatom Substitutions

• DOI: 10.1021/acs.macromol.3c02140
• Publication Date: 2024-01-24T07:19:46Z
• Authors: Mingqian Wang; Zhiqiang Ding; Xincui Shi; Zhe Ma; Bin Wang; Yuesheng Li
• Keywords: Heteroatom

The design of cyclic monomers is crucial for the development polymers with ideal thermal and mechanical properties by ring-opening polymerization. Herein, we provide a systematic investigation into thio-modification effects on polymerization behavior ether–ester final corresponding poly(ether-alt-ester)s. position significantly affected thermodynamics thus could regulate ceiling temperature (Tc). O-to-S substitutions in monomer′s ether/ester sites would increase α-H acidity, catalytic system strictly determined chain initiation process as well chain-end groups. Density functional theory calculations experimental studies revealed that at ester site accelerate under same conditions, thanks to high reactivity thioester group strong nucleophilicity end. resulting poly(ether-alt-ester)s exhibited crystallinity, precisely tunable physicochemical properties, recyclability, high-density polyethylene-like which exemplifies potential heteroatom modification modulating poly(ether-alt-ester)′s properties. This detailed structure–(de)polymerizability structure–property relationships will inspire future monomer toward performance.