Synthesis and Characterization of Nickel(II) Complexes for Catalyzing the Ring-Opening Polymerization of l-Lactide

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-11-14 DOI:10.1021/acs.organomet.4c0029510.1021/acs.organomet.4c00295

Xuhao Li, Manqi Zang, Lipeng Zhang, Wei Jiang, Xiuxian Zhao*, Xuchuan Jiang* and Wei Yao*,

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Abstract

Industrial polylactide (PLA) production typically uses stannous octoate as a catalyst for lactide (LA) polymerization, which has drawback that PLA degradation caused by tin residual. This study explores the synthesis and application of tetradentate nitrogen-coordinated Ni(II) complexes (L¹Ni–L⁴Ni) as alternative catalysts for the ring-opening polymerization of unpurified l-LA. The robust Ni(II) complexes were synthesized and characterized, and their catalytic performance was evaluated. Results indicated that in the presence of benzyl alcohol, the Ni(II) complexes demonstrated relatively good catalytic activity, achieving over 90% conversion of l-LA within 4 h. The polymerization reaction even can be operated in air without affecting the catalytic effect. The molecular weight of the resulting PLA showed a linear relationship with the [LA]/[Ni] ratio, indicating characteristics of living polymerization. The polymerization mechanism was proposed based on MALDI–TOF, NMR, FT-IR and DFT calculation.

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催化 l-乳内酯开环聚合的镍(II)配合物的合成与表征

工业聚乳酸（PLA）生产通常使用辛酸亚锡作为聚乳酸（LA）聚合的催化剂，其缺点是锡残留会导致聚乳酸降解。本研究探索了四价氮配位镍（II）配合物（L1Ni-L4Ni）的合成和应用，将其作为未净化 l-LA 开环聚合的替代催化剂。我们合成并表征了坚固的 Ni(II) 复合物，并评估了它们的催化性能。结果表明，在苄醇存在下，Ni(II) 复合物表现出较好的催化活性，在 4 小时内实现了 90% 以上的 l-LA 转化率。聚乳酸的分子量与[LA]/[Ni]比值呈线性关系，表明了活聚合的特点。根据 MALDI-TOF、NMR、FT-IR 和 DFT 计算，提出了聚合机理。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.