Dimethyl Dihydroacridines as Photocatalysts in Organocatalyzed Atom Transfer Radical Polymerization of Acrylate Monomers
Dimethyl Dihydroacridines as Photocatalysts in Organocatalyzed Atom Transfer Radical Polymerization of Acrylate Monomers
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DOI：
10.1002/anie.201910828
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发表时间：
2020-01-21
影响因子：
16.6
通讯作者：
Miyake, Garret M.
中科院分区：
文献类型：
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作者：
Buss, Bonnie L.;Lim, Chern-Hooi;Miyake, Garret M.
开发具有不同性质的光催化剂是有机催化原子转移自由基聚合（O-ATRP）的关键。二甲基二氢吖啶在这里提出作为一个新的家庭的有机PC，第一次使具有挑战性的丙烯酸酯单体的O-ATRP控制聚合。建立了七种PC的结构-性质关系，证明了可调的光化学和电化学性质，并获得了强氧化性（PC.+）- P-2中间体，用于有效灭活。在O-ATRP中，PC的组合、连续流反应器的实施以及通过添加LiBr促进失活对于生产分散度低至1.12的定义明确的丙烯酸酯聚合物是至关重要的。这种方法的效用是建立通过演示的耐氧性的系统和应用程序，以不同的丙烯酸酯单体，包括定义明确的二嵌段和三嵌段共聚物的合成。
Development of photocatalysts (PCs) with diverse properties has been essential in the advancement of organocatalyzed atom transfer radical polymerization (O-ATRP). Dimethyl dihydroacridines are presented here as a new family of organic PCs, for the first time enabling controlled polymerization of challenging acrylate monomers by O-ATRP. Structure-property relationships for seven PCs are established, demonstrating tunable photochemical and electrochemical properties, and accessing a strongly oxidizing (PC.+)-P-2 intermediate for efficient deactivation. In O-ATRP, the combination of PC, implementation of continuous-flow reactors, and promotion of deactivation through addition of LiBr are critical to producing well-defined acrylate polymers with dispersities as low as 1.12. The utility of this approach is established through demonstration of the oxygen-tolerance of the system and application to diverse acrylate monomers, including the synthesis of well-defined di- and triblock copolymers.