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用二苯碳酸酯和二醇在乙酰丙酮锌(II)上合成脂肪族聚碳酸酯。

Synthesis of Aliphatic Polycarbonates from Diphenyl Carbonate and Diols over Zinc (II) Acetylacetonate.

机构信息

Key Laboratory for Green Process of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China.

Xinjiang Tianye (Group) Coporation Limited, Shihezi 832000, China.

出版信息

Molecules. 2022 Dec 16;27(24):8958. doi: 10.3390/molecules27248958.

Abstract

APCs (aliphatic polycarbonates) are one of the most important types of biodegradable polymers and widely used in the fields of solid electrolyte, biological medicine and biodegradable plastics. Zinc-based catalysts have the advantages of being low cost, being non-toxic, having high activity, and having excellent environmental and biological compatibility. Zinc (II) acetylacetonate (Zn(Acac)) was first reported as a highly effective catalyst for the melt transesterification of biphenyl carbonate with 1,4-butanediol to synthesize poly(1,4-butylene carbonate)(PBC). It was found that the weight-average molecular weight of PBC derived from Zn(Acac) could achieve 143,500 g/mol with a yield of 85.6% under suitable reaction conditions. The Lewis acidity and steric hindrance of Zn could obviously affect the catalytic performance of Zn-based catalysts for this reaction. The main reasons for the Zn(Acac) catalyst displaying a higher yield and M than other zinc-based catalysts should be ascribed to the presence of the interaction between acetylacetone ligand and Zn, which can provide this melt transesterification reaction with the appropriate Lewis acidity as well as the steric hindrance.

摘要

APCs(脂肪族聚碳酸酯)是最重要的可生物降解聚合物类型之一,广泛应用于固体电解质、生物医学和可生物降解塑料等领域。

锌基催化剂具有成本低、无毒、活性高、环境和生物相容性好等优点。锌(II)乙酰丙酮(Zn(Acac))首次被报道为双酚碳酸酯与 1,4-丁二醇熔融酯交换合成聚(1,4-丁二醇碳酸酯)(PBC)的高效催化剂。研究发现,在合适的反应条件下,Zn(Acac)合成的 PBC 的重均分子量可达 143500g/mol,产率为 85.6%。锌的路易斯酸度和空间位阻明显影响了锌基催化剂对该反应的催化性能。Zn(Acac)催化剂表现出更高的产率和 M 的主要原因归因于乙酰丙酮配体与 Zn 之间的相互作用,这为熔融酯交换反应提供了适当的路易斯酸度和空间位阻。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/934a/9788399/c936cde5d320/molecules-27-08958-g001.jpg

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