The organocatalyzed photo‐atom transfer radical polymerization (photoATRP) using 10‐phenylphenothiazine as catalyst is studied toward its use in methacrylic acid (MAA) polymerization and surface grafting. The organocatalyzed photoATRP of methyl methacrylate (MMA) is first optimized for continuous flow synthesis in order to assess the livingness of the polymerization. MMA can be polymerized in batch and in flow; however, conversions are limited by the loss of bromine functionality and hence high conversions have to be traded in with increasing dispersities. Also, MAA is polymerized successfully in continuous flow with similar limitations. Flow conditions are transferred to surface grafting from silanized silicon wafers. The presence of ATRP initiators after silanization is confirmed by secondary ion mass spectrometry and X‐ray photoelectron spectroscopy. Dense polymethacrylic acid brush films are successfully produced, which is not directly accessible via classical copper‐mediated ATRP techniques.

中文翻译：

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连续流动和表面接枝中甲基丙烯酸的有机催化光原子转移自由基聚合

研究了以10-苯基吩噻嗪为催化剂的有机催化的光原子转移自由基聚合（photoATRP），以用于其在甲基丙烯酸（MAA）聚合和表面接枝中的应用。甲基丙烯酸甲酯（MMA）的有机催化光ATRP首先针对连续流合成进行了优化，以评估聚合的活性。MMA可以分批聚合和流动聚合。然而，转化率受到溴官能度损失的限制，因此必须以增加的分散度来换取高转化率。同样，MAA在连续流中成功聚合，但存在类似的局限性。流动条件从硅烷化的硅片转移到表面接枝。二次离子质谱和X射线光电子能谱证实了硅烷化后ATRP引发剂的存在。成功生产了致密的聚甲基丙烯酸刷膜，这是经典的铜介导的ATRP技术无法直接获得的。