Synthesis and Properties of Polyol Copolymer with Alternating Methacrylate–Vinyl Ether Backbone,Macromolecular Rapid Communications

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Synthesis and Properties of Polyol Copolymer with Alternating Methacrylate–Vinyl Ether Backbone
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2022-11-15 , DOI: 10.1002/marc.202200796
Min Cao ₁ , Hai Deng ₁

Affiliation

Radical polymerization of a tailored diphenylsilane-bridged bi-functional monomer consisting of methacrylate and vinyl ether moieties is conducted in diluted monomer concentration, in which both two moieties are consumed at almost the same rate despite their huge difference in monomer reactivity ratio. The vinyl ether content in the backbone is quantified as 45% by ¹H NMR after removal of the silane bridge. Since vinyl ether alone cannot be polymerized in such radical polymerization, it should be incorporated in an alternating fashion with methacrylate into the copolymer main chain. The cleavage of silane bridge also yields a series of polyol materials composed of ethylene glycol monovinyl ether (EGVE) and hydroxyethyl methacrylate (HEMA), and the EGVE content in the backbone can be regulated from 45% to 18% by increasing the bi-functional monomer concentration. Interestingly, although containing more than 50% HEMA units, the alternating copolymer exhibits new properties totally different from poly(HEMA), but more similar to poly(EGVE), e.g., good water solubility and a markedly low glass transition temperature (T_g) of –31 °C, which is attributed to the major HEMA-EGVE repeating unit that replaced HEMA-HEMA consecutive segments so that the properties of poly(HEMA) such as 95 °C T_g are completely altered.

中文翻译：

交替甲基丙烯酸酯-乙烯基醚骨架多元醇共聚物的合成与性能

由甲基丙烯酸酯和乙烯基醚部分组成的特制二苯基硅烷桥联双功能单体的自由基聚合反应是在稀释的单体浓度下进行的，尽管这两个部分在单体反应率上存在巨大差异，但它们的消耗速度几乎相同。主链中的乙烯基醚含量通过^{1量化为 45%}去除硅烷桥后的 H NMR。由于在这种自由基聚合中不能单独聚合乙烯基醚，因此它应该以与甲基丙烯酸酯交替的方式结合到共聚物主链中。硅烷桥的裂解还生成了一系列由乙二醇单乙烯基醚（EGVE）和甲基丙烯酸羟乙酯（HEMA）组成的多元醇材料，主链中的EGVE含量可以通过增加双官能团来调节，从45%到18%不等。单体浓度。有趣的是，虽然含有超过 50% 的 HEMA 单元，交替共聚物表现出与聚（HEMA）完全不同但更类似于聚（EGVE）的新特性，例如良好的水溶性和显着低的玻璃化转变温度（T _g) –31 °C，这归因于主要的 HEMA-EGVE 重复单元取代了 HEMA-HEMA 连续片段，因此聚 (HEMA) 的特性（例如 95 °C T g）被完全_改变。

更新日期：2022-11-15

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