硼烷/膦刘易斯对快速活性聚合可再生亚甲基丁内酯

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry Pub Date : 2025-10-09 DOI:10.1039/d5py00789e

Yun Bai, Lieqiang Liao, Shuang Liu, Yibao Li, Jianghua He, Yuetao Zhang

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引用次数: 0

摘要

活性聚合技术是聚合物合成和应用的关键技术。然而，开发可再生单体的活性/可控聚合体系仍然具有挑战性。本研究提出了一种高效的有机Lewis对体系，将三（五氟苯基）硼烷（B(C6F5)3）与强有机磷超碱P(NIiPr)Ph2结合，在室温下在二氯甲烷中快速活性聚合可再生亚甲基丁内酯（α-亚甲基-γ-亚甲基-γ-丁内酯（MMBL））。活的路易斯对聚合（LPP）体系证明了聚合物分子量与单体转化率之间的线性关系，持续的窄分布（Đ），成功的链延伸，以及合成具有低Đ值的定义良好的随机和双嵌段共聚物。DOSY、DSC和GPC分析证实形成了结构明确的PMMBL-b-PMBL双嵌段共聚物。在48000 h-1的周转频率（TOF）下，该体系表现出了MMBL活性聚合的最高聚合活性。

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Rapid and Living Polymerization of Renewable Methylene Butyrolactones via Borane/Phosphine Lewis Pairs

Living polymerization techniques are crucial for polymer synthesis and applications. However, developing living/controlled polymerization systems for renewable monomers remains challenging. This study presents a highly effective organic Lewis pair system, combining tris(pentafluorophenyl)borane (B(C6F5)3) with the strong organophosphorus superbase P(NIiPr)Ph2, enabling rapid and living polymerization of renewable methylene butyrolactones (α-methylene-γ-butyrolactone (MBL) and γ-methyl-α-methylene-γ-butyrolactone (MMBL)) in dichloromethane at room temperature. The living Lewis pair polymerization (LPP) system was evidenced by a linear correlation between polymer molecular weight and monomer conversion, consistently narrow distribution (Đ), successful chain extension, and the synthesis of well-defined random and diblock copolymers with low Đ values. DOSY, DSC, and GPC analyses confirmed the formation of a structurally defined PMMBL-b-PMBL diblock copolymer. With 48,000 h-1 turnover frequency (TOF), this system demonstrated the highest polymerization activity yet recorded for the MMBL living polymerization.

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来源期刊

Polymer Chemistry POLYMER SCIENCE-

CiteScore

8.60

自引率

8.70%

发文量

535

审稿时长

1.7 months

期刊介绍： Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.