机械氧化还原催化高分子量聚合物的全氟阴离子催化RAFT阳离子聚合

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry Pub Date : 2025-10-02 DOI:10.1039/d5py00638d

Longfei Zhang, Ziye Ren, Kai Chen, Huanyu Lei, Zhao Wang

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引用次数: 0

摘要

外场调节阳离子可逆加成-破碎链转移聚合（RAFT）为大分子的精确合成提供了一种很有前途的策略。然而，由于链过早终止，在温和条件下获得高分子量聚乙烯醚（pve）仍然具有挑战性。在这项工作中，我们报告了一种全氟阴离子辅助策略，该策略促进了乙烯基醚在溶剂最小化条件下的机械化学阳离子RAFT（机械工艺）聚合。所得pve的数平均分子量超过170 kDa，具有较高的链端保真度，可实现高效的链延伸。密度泛函理论（DFT）计算表明，阳离子链末端与全氟反离子之间的相互作用增强，从而稳定了传播物种并抑制了链终止。该方法为在温和条件下合成具有良好定义的高分子量pve提供了一个强大的平台。

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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Mechanoredox Catalyzed Cationic RAFT Polymerization via Perfluorinated Anion Assistance for High-Molecular-Weight Polymers

External-field-regulated cationic reversible addition-fragmentation chain transfer (RAFT) polymerization provides a promising strategy for the precise synthesis of macromolecules. However, achieving high-molecular-weight poly(vinyl ether)s (PVEs) under mild conditions remains challenging due to premature chain termination. In this work, we report a perfluorinated anion-assisted strategy that facilitates mechanochemical cationic RAFT (mechano-cRAFT) polymerization of vinyl ethers under solvent-minimized conditions. The resulting PVEs achieve number average molecular weights exceeding 170 kDa, with high chain-end fidelity for efficient chain-extension. Density functional theory (DFT) calculations revealed enhanced interactions between cationic chain terminals and perfluorinated counterions, which stabilizes propagating species and suppresses chain termination. This methodology offers a robust platform for the synthesis of well-defined PVEs with high-molecular-weight under mild conditions.

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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.