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首页> 外文期刊>Polymers >Selective Controlled/Living Photoradical Polymerization of Glycidyl Methacrylate, Using a Nitroxide Mediator in the Presence of a Photosensitive Triarylsulfonium Salt
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Selective Controlled/Living Photoradical Polymerization of Glycidyl Methacrylate, Using a Nitroxide Mediator in the Presence of a Photosensitive Triarylsulfonium Salt

机译：甲基丙烯酸缩水甘油酯的选择性控制/活性光自由基聚合，在光敏三芳基ulf盐存在下使用一氧化氮介体

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摘要

The controlled/living photoradical polymerization of glycidyl methacrylate (GMA) was attained using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS,2'RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate (tBuS). Whereas the polymerization in the absence of MTEMPO yielded a gel-containing polymer, the MTEMPO-mediated polymerization produced poly(GMA) bonded at the vinyl site, and retained the oxirane ring structure. No occurrence of the cationic ring-opening photopolymerization of the oxirane ring even in the presence of the photosensitive onium salt indicated that tBuS served as the photoelectron transfer agent between MTEMPO in their excited states at the propagating chain end. The resulting polymers had comparatively narrow molecular weight distributions of Mw/Mn = 1.46–1.48. The living nature of the MTEMPO-mediated polymerization was confirmed on the basis of a linear increase in the conversion-molecular weight plots and gel permeation chromatography (GPC) analysis.
机译：使用4-甲氧基-2,2,6,6-四甲基哌啶-1-氧基（MTEMPO）作为介体和（2RS，2'RS）-azobis（4）实现甲基丙烯酸缩水甘油酯（GMA）的受控/活性光自由基聚合（4-叔丁基苯基）二苯基s三氟甲磺酸盐（ t BuS）存在下，以-甲氧基-2,4-二甲基戊腈为引发剂。尽管在没有MTEMPO的情况下的聚合反应产生了含凝胶的聚合物，但是由MTEMPO介导的聚合反应产生了在乙烯基位置键合的聚（GMA），并保留了环氧乙烷环结构。即使在存在光敏鎓盐的情况下，也没有发生环氧乙烷环的阳离子开环光聚合反应，这表明 t BuS充当了MTEMPO之间在传播链末端处于激发态的光电子转移剂。 。所得聚合物的分子量分布M w / M n 相对较窄，为1.46–1.48。基于转化分子量图和凝胶渗透色谱法（GPC）分析的线性增加，证实了MTEMPO介导的聚合反应的活性。

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