Abstract The ability to (co)polymerize acrylates, methacrylates and styrene with one alkoxyamine/nitroxide has been regarded as challenging in nitroxide mediated polymerization (NMP). The alkoxyamine 3-(((2-cyanopropan-2-yl)oxy)(cyclohexyl)amino)-2,2-dimethyl-3-phenylpropanenitrile (Dispolreg 007) has recently emerged as a robust regulator to mediate the (co)polymerization of methacrylates and styrene. Herein, the versatility of the alkoxyamine is tested to produce random and block copolymers based on n-butyl acrylate (BA). The formation and influence of dead polymer (mostly macromonomers) was studied for the homopolymerziation of n-butyl acrylate. At temperatures above 100 °C, control over the polymerization could be retained up to about 50% conversion, with relatively narrow molar mass distributions (Mn = 34000 g·mol−1, Ð ∼ 1.7). Above this conversion side reactions, namely β-scission of mid-chain radicals generated by chain transfer to polymer and monomer self-initiation led to loss of control. This effect could be mitigated by lowering to 50 wt% the concentration of BA and/or by lowering the temperature, or by copolymerizing BA with MMA or styrene. The chain extension of acrylate based macro-alkoxyamines led to non linear structures, due to the presence of macromonomers and residual dead chains during the production of PBA macro-alkoxyamines.

中文翻译：

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丙烯酸酯、甲基丙烯酸酯和苯乙烯的氮氧化合物介导的共聚：副反应在丙烯酸酯聚合中的重要性

摘要 用一种烷氧基胺/氮氧化物（共）聚合丙烯酸酯、甲基丙烯酸酯和苯乙烯的能力一直被认为是氮氧介导聚合 (NMP) 中的一项挑战。烷氧基胺 3-(((2-cyanopropan-2-yl)oxy)(cyclohexyl)amino)-2,2-dimethyl-3-phenylpropanenitrile (Dispolreg 007) 最近已成为一种强有力的调节剂来介导（共）聚合甲基丙烯酸酯和苯乙烯。在此，测试烷氧基胺的多功能性以生产基于丙烯酸正丁酯 (BA) 的无规和嵌段共聚物。研究了死聚合物（主要是大分子单体）的形成和对丙烯酸正丁酯均聚的影响。在高于 100 °C 的温度下，对聚合的控制可以保持高达约 50% 的转化率，摩尔质量分布相对较窄（Mn = 34000 g·mol−1，Ð ∼ 1.7）。在这种转化副反应之上，即由链转移到聚合物和单体自引发产生的中链自由基的 β 断裂导致失控。这种影响可以通过将 BA 的浓度降低到 50%（重量）和/或通过降低温度，或通过将 BA 与 MMA 或苯乙烯共聚来减轻。由于在 PBA 大烷氧基胺的生产过程中存在大分子单体和残留的死链，丙烯酸酯类大烷氧基胺的扩链导致非线性结构。