Efficient Polymerization and Selective Depolymerization of Poly(cyclopentene carbonate) Mediated Solely by Heterometallic Rare-Earth(III)/Zinc(II) Complexes

IF 5.1 1区化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2024-10-30 DOI:10.1021/acs.macromol.4c02086

Ziyue Deng, Dan Yuan, Yingming Yao

引用次数: 0

Abstract

Poly(cyclopentenyl carbonate) (PCPC) is a recyclable polymer with great potential applications. However, the selective preparation of PCPC from cyclopentene oxide (CPO) and CO₂ copolymerization and the chemical recycling of PCPC back to the original monomer CPO are of great challenge. In this work, it was found that the heterometallic rare-earth metal(III)/Zn(II) complexes (RE(III)-Zn(II) complexes) supported by phenylenediamine-bridged triphenols could serve as highly active catalysts for the copolymerization of CPO and CO₂ to give pure PCPC. Remarkably, the same complexes alone could also promote the selective depolymerization of PCPC to CPO only by simply raising the reaction temperature up to ca. 160 °C. The copolymerization and depolymerization mechanisms were also proposed.

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仅由稀土(III)/锌(II)异金属配合物介导的聚环戊烯碳酸酯的高效聚合和选择性解聚过程

聚（环戊烯碳酸酯）（PCPC）是一种可回收聚合物，具有巨大的应用潜力。然而，如何从环戊烯氧化物（CPO）和二氧化碳共聚中选择性地制备 PCPC，并将 PCPC 化学回收到原始单体 CPO 中，是一个巨大的挑战。在这项工作中，研究人员发现以苯二胺桥接三苯酚为支撑的异金属稀土金属（III）/锌（II）配合物（RE（III）-锌（II）配合物）可作为高活性催化剂，用于 CPO 和 CO2 的共聚，生成纯 PCPC。值得注意的是，只需将反应温度升高至约 160 ℃，同样的络合物也能促进 PCPC 选择性解聚为 CPO。此外，还提出了共聚和解聚机理。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.