单核和双核四价锆化合物催化合成脂肪族聚酯和脂肪族聚碳酸酯

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Pub Date : 2025-05-05 DOI:10.1016/j.polymer.2025.128496

Sriparna Sarkar , Sourav Singha Roy , P.K. Sudhadevi Antharjanam , Debashis Chakraborty

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引用次数: 0

摘要

采用希夫碱前配体（L1H−L5H）和合适的Zr（IV）醇氧试剂合成了两类四价Zr（IV）化合物。异丙醇Zr（IV）化合物（1-5）为二聚体，两个Zr（IV）中心通过异丙醇基团连接，Zr（IV）中心周围的几何形状为扭曲的八面体。叔丁醇类Zr（IV）化合物（6 ~ 8）为单体，Zr（IV）中心配位数为5。二聚体配合物对rac-LA的开环聚合（ROP）具有催化活性，对环氧环己烯与CO2的开环共聚（ROCOP）具有可忽略的催化活性。单体配合物通过ROP和ROCOP反应生成聚酯和通过ROCOP反应生成脂肪族聚碳酸酯。单核化合物导致聚碳酸酯链中99%的碳酸盐键。

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Mononuclear and dinuclear tetravalent zirconium compounds as catalysts for the synthesis of aliphatic polyesters and aliphatic polycarbonates

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Mononuclear and dinuclear tetravalent zirconium compounds as catalysts for the synthesis of aliphatic polyesters and aliphatic polycarbonates

Two categories of tetravalent Zr(IV) compounds were synthesized using Schiff base proligands (L1H−L5H) and appropriate Zr(IV) alkoxide reagents. The isopropoxide Zr(IV) compounds (1–5) were dimeric, where the two Zr(IV) centers were connected through the isopropoxide group, and the geometry around the Zr(IV) center was distorted octahedral. The tert-butoxide Zr(IV) compounds (6–8) were monomeric, with the Zr(IV) center having a coordination number of five. The dimeric complexes showed catalytic activity towards the ring-opening polymerization (ROP) of rac-LA and negligible activity for ring-opening copolymerization (ROCOP) of cyclohexene oxide with CO₂. The monomeric complexes produced polyesters (through ROP and ROCOP) and aliphatic polycarbonates through ROCOP reactions. The mononuclear compounds resulted in >99 % carbonate linkage in the polycarbonate chain.

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来源期刊

Polymer 化学-高分子科学

CiteScore

7.90

自引率

8.70%

发文量

959

审稿时长

32 days

期刊介绍： Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics. The main scope is covered but not limited to the following core areas: Polymer Materials Nanocomposites and hybrid nanomaterials Polymer blends, films, fibres, networks and porous materials Physical Characterization Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films Polymer Engineering Advanced multiscale processing methods Polymer Synthesis, Modification and Self-assembly Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization Technological Applications Polymers for energy generation and storage Polymer membranes for separation technology Polymers for opto- and microelectronics.