Poly(methyl methacrylate/n-butyl acrylate) [P(MMA/BA)] copolymer with an alternating structure was synthesized via an activator regenerated by electron transfer (ARGET) atom transfer radical (co)polymerization (ATRP) of 2-ethylfenchyl methacrylate (EFMA) and n-butyl acrylate (BA) with subsequent postpolymerization modifications (PPM). Due to the steric hindrance of the bulky pendant group of EFMA, as well as the low reactivity ratio of BA in copolymerization with methacrylates, copolymerization of EFMA and BA generated a copolymer with a high content of alternating dyads. A subsequent PPM procedure of the alternating EFMA/BA copolymer was comprised of the hydrolysis of a tertiary ester by trifluoroacetic acid and methylation by (trimethylsilyl)diazomethane. After the modifications, the architecture of the obtained alternating MMA/BA copolymers was compared with gradient and statistical copolymers with overall similar compositions, molecular weights, and dispersities. ¹³C NMR indicated the absence of either MMA/MMA/MMA or BA/BA/BA sequences, in contrast to an abundance of homotriads in either the statistical or especially in the gradient copolymer. All three copolymers had similar glass transition temperatures, as measured by differential scanning calorimetry (DSC), but the alternating copolymer had the narrowest range of glass transition.

中文翻译：

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原子转移自由基聚合制备甲基丙烯酸甲酯/丙烯酸正丁酯交替共聚物

通过甲基丙烯酸 2-乙基苯苄酯的电子转移 (ARGET) 原子转移自由基 (共) 聚合 (ATRP) 再生活化剂, 合成了具有交替结构的聚 (甲基丙烯酸甲酯/丙烯酸正丁酯) [P(MMA/BA)] 共聚物(EFMA) 和n-丙烯酸丁酯 (BA)，随后进行后聚合改性 (PPM)。由于 EFMA 庞大的侧基的空间位阻，以及 BA 在与甲基丙烯酸酯的共聚反应中的低反应率，EFMA 和 BA 的共聚产生了具有高含量交替二元组的共聚物。交替 EFMA/BA 共聚物的后续 PPM 程序包括通过三氟乙酸水解叔酯和通过（三甲基甲硅烷基）重氮甲烷进行甲基化。改性后，将获得的交替 MMA/BA 共聚物的结构与具有总体相似组成、分子量和分散性的梯度和统计共聚物进行比较。¹³C NMR 表明不存在 MMA/MMA/MMA 或 BA/BA/BA 序列，这与统计或特别是梯度共聚物中的大量同源三联体形成对比。通过差示扫描量热法 (DSC) 测量，所有三种共聚物都具有相似的玻璃化转变温度，但交替共聚物的玻璃化转变温度范围最窄。