热响应性可降解共聚物的设计与合成:羟基功能化乙烯基醚与环烯酮缩醛的整合

IF 3.9 2区 化学 Q2 POLYMER SCIENCE
Shinji Sugihara, Atsushi Endo, Komal Raje, Atsushi Matsumoto, Satoshi Fujita and Yasushi Maeda
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引用次数: 0

摘要

通过羟基官能团乙烯醚(OH-VEs),如2-羟乙基乙烯醚(HEVE)或二(乙二醇)乙烯醚(DEGV)与2-亚甲基-1,3-二氧基乙烷(MDO)自由基共聚,合成了具有可调热响应特性的可降解共聚物。机理研究,包括反应性比测定和1H NMR谱分析,表明乙烯基醚中羟基的氢键同时影响OH-VEs的自由基乙烯基聚合和MDO的自由基开环聚合。所得聚(HEVE-co-MDO)和聚(DEGV-co-MDO)共聚物在特定MDO组成范围(分别为23-28 mol%和35-37 mol%)的水溶液中表现出lcst型热响应行为,而不含氧乙烯基的聚(乙烯醇-co-MDO)在任何温度下都保持完全可溶或不溶。聚(DEGV-co-MDO)由于其增强的亲水性而独特地在混浊溶液中形成凝聚,聚(HEVE-co-MDO)没有观察到这种现象。RAFT聚合有利于分子量控制,表明分子量与云点温度成反比关系。共聚物在碱性条件下表现出选择性降解MDO单元的能力,并有望表现出良好的生物相容性,正如细胞毒性试验所表明的那样。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Design and synthesis of thermoresponsive degradable copolymers: integrating hydroxy-functional vinyl ethers with cyclic ketene acetals†

Design and synthesis of thermoresponsive degradable copolymers: integrating hydroxy-functional vinyl ethers with cyclic ketene acetals†

Degradable copolymers with adjustable thermoresponsive characteristics are synthesized through radical copolymerization of hydroxy-functional vinyl ethers (OH-VEs), such as 2-hydroxyethyl vinyl ether (HEVE) or di(ethylene glycol) vinyl ether (DEGV), with 2-methylene-1,3-dioxepane (MDO). Mechanistic investigations, including reactivity ratio determination and 1H NMR spectroscopy, reveal that hydrogen bonding from the hydroxy groups in vinyl ethers affects both radical vinyl polymerization of OH-VEs and radical ring-opening polymerization of MDO. The resulting poly(HEVE-co-MDO) and poly(DEGV-co-MDO) copolymers exhibit LCST-type thermoresponsive behavior in aqueous solutions within specific MDO composition ranges (23–28 mol% and 35–37 mol%, respectively), whereas poly(vinyl alcohol-co-MDO) without oxyethylene moieties remains either fully soluble or insoluble, irrespective of temperature. Poly(DEGV-co-MDO) uniquely forms coacervates in turbid solutions due to its enhanced hydrophilicity, a phenomenon not observed with poly(HEVE-co-MDO). RAFT polymerization facilitates molar mass control, demonstrating an inverse relationship between molar mass and cloud point temperature. The copolymers exhibit selective degradability of MDO units under alkaline conditions and are expected to demonstrate good biocompatibility, as suggested by cytotoxicity assays.

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来源期刊
Polymer Chemistry
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.
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