Tuning the Degradability Profiles of Polyesters with Indium-Catalyzed Incorporation of Poly(ε-thiocaprolactone) Blocks.

IF 15.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-10-06 DOI:10.1021/jacs.5c12988

Joseph Chang,Chatura Goonesinghe,Hootan Roshandel,Takeo Iwase,Ana Luisa Granja,Sophia Zhang,Kimia Hosseini,Kritika Sharma,Padmapriya Srinivasan,Jason Wai-Lok Poon,Maria Ezhova,Hyuk-Joon Jung,Paula L Diaconescu,Parisa Mehrkhodavandi

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引用次数: 0

Abstract

There are no examples of high molecular weight (>100 000 g/mol) poly(ε-thiocaprolactone) (PtCL), and the mechanism of ε-thiocaprolactone (tCL) polymerization with organometallic complexes has not been investigated. In this work, we demonstrate the synthesis of the highest reported molecular weight PtCL (Mn = 109 000 g/mol) by using a cationic indium thiolate catalyst formed in situ via the addition of benzyl mercaptan. The mechanism of the polymerization is thoroughly investigated and the reaction coordinate is elucidated via computational calculations; the polymerization propagates through a coordination-insertion mechanism. If the PtCL is not isolated during the polymerization, the resulting indium-PtCL macromolecule can be used as an initiator to form copolymers with poly(lactide) (PLA) and poly(ε-caprolactone) (PCL). Incorporating 10% PtCL in these polymers alters their degradation behavior: the hydrolytic degradation period of PLA is reduced by nearly half, while PCL becomes more resistant to hydrolysis.

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铟催化掺入聚（ε-硫代己内酯）嵌段调控聚酯的可降解性。

目前还没有高分子量（100 000 g/mol）聚ε-硫代内酯（PtCL）的例子，也没有研究过ε-硫代内酯（tCL）与金属有机配合物聚合的机理。在这项工作中，我们证明了利用添加苄基硫醇在原位形成的阳离子硫酸铟催化剂合成了最高分子量的PtCL （Mn = 109 000 g/mol）。对聚合机理进行了深入的研究，并通过计算确定了反应坐标；聚合反应通过配位插入机制进行。如果聚合过程中未分离出PtCL，则得到的铟-PtCL大分子可作为引发剂与聚乳酸（PLA）和聚ε-己内酯（PCL）形成共聚物。在这些聚合物中加入10%的PtCL改变了它们的降解行为：PLA的水解降解周期缩短了近一半，而PCL则变得更耐水解。

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

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.