Redox‐initiated reversible addition‐fragmentation chain transfer (RAFT) miniemulsion polymerizations are successfully conducted with an employment of trithiocarbonate‐based macro‐RAFT agents and surfactant. Two macro‐RAFT agents—hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA₂₇) and amphiphilic poly(poly(ethylene glycol) methyl ether methacrylate)‐b‐polystyrene (PPEGMA₂₇‐b‐PS₃₃)— are examined for the miniemulsion polymerization of styrene. The use of PPEGMA₂₇ (in the presence of sodium dodecyl sulfate (SDS)) results in a slow polymerization rate with a broad particle size. In the absence of SDS, the use of PPEGMA₂₇‐b‐PS₃₃ results in a broad particle size distribution due to its inability to form uniform initial droplets whereas the same amphiphilic block copolymer in the presence of SDS yields resulting products with a uniform particle size distribution. The latter exhibits a fashion of controlled polymerization with a high consumption of monomer (98% in 100 min) and a narrow molecular weight distribution throughout the polymerization. This is attributed to the formation of uniform droplets facilitated by SDS in a miniemulsion. The amphiphilic macro‐RAFT agent is able to anchor efficiently on the monomer droplet or particle/water interface and form stabilized particles of well‐defined PPEGMA₂₇‐b‐PS block copolymer, confirmed using dynamic light scattering and transmission electron micrographs.

中文翻译：

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使用基于PPEGMA的Macro-RAFT试剂，苯乙烯的氧化还原引发的可逆加成-断裂链转移（RAFT）细乳液聚合。

氧化还原引发的可逆加成-断裂链转移（RAFT）微乳液聚合成功地通过使用基于三硫代碳酸酯的大分子RAFT剂和表面活性剂进行。两种大分子RAFT试剂-亲水性聚（聚乙二醇甲基丙烯酸甲酯）（PPEGMA ₂₇）和两亲性聚（聚甲基丙烯酸乙二醇酯甲基丙烯酸酯）-b-聚苯乙烯（PPEGMA ₂₇ - b -PS ₃₃）-检查了苯乙烯的细乳液聚合。使用PPEGMA ₂₇（在十二烷基硫酸钠（SDS）存在下）会导致较慢的聚合速度和较宽的粒径。在没有SDS的情况下，使用PPEGMA ₂₇ - b‐PS ₃₃由于无法形成均匀的初始液滴而导致较宽的粒径分布，而在SDS存在下相同的两亲嵌段共聚物可产生具有均匀粒径分布的产物。后者表现出受控聚合的方式，具有高单体消耗（100分钟内98％）和整个聚合过程中窄的分子量分布。这归因于细乳液中SDS促进了均匀液滴的形成。两亲的macro-RAFT剂能够有效地锚定在单体液滴或颗粒/水界面上，并形成稳定的PPEGMA ₂₇ - b稳定颗粒‐PS嵌段共聚物，通过动态光散射和透射电子显微照片得到证实。