Photoinitiated polymerization-induced self-assembly (photo-PISA) is an emerging method for scalable preparation of block copolymer nanoparticles at room temperature. However, the use of small molecular photoinitiators in photo-PISA is detrimental to further applications of block copolymer nanoparticles. Herein, α,ω-functionalized polymers with a photoinitiator end group and a RAFT end group were synthesized and employed as macromolecular photoinitiators/chain transfer agents in aqueous photo-PISA at room temperature. A kinetic study suggested that photo-PISA exhibited a high rate of polymerization with near quantitative monomer conversion being achieved within 30 min. Gel permeation chromatography (GPC) analysis indicated that moderate RAFT controllability was achieved during photo-PISA. The effects of the degree of polymerization (DP) of the core-forming block, the monomer concentration, and the DP of the α,ω-macromolecular photoinitiator/chain transfer agent on the morphologies of block copolymer nanoparticles were investigated. Finally, a direct comparison between thermally initiated PISA and photo-PISA using the α,ω-macromolecular photoinitiator/chain transfer agent was performed. This study not only expands the scope of photo-PISA, but also provides mechanistic insights into the process of polymerization-induced self-assembly.

中文翻译：

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多功能聚合物：用于水性光引发聚合诱导自组装的α,ω-大分子光引发剂/链转移剂

光引发聚合诱导自组装 (photo-PISA) 是一种在室温下可扩展制备嵌段共聚物纳米粒子的新兴方法。然而，在光 PISA 中使用小分子光引发剂不利于嵌段共聚物纳米粒子的进一步应用。在此，合成了具有光引发剂端基和 RAFT 端基的 α,ω-官能化聚合物，并在室温下在水性 photo-PISA 中用作大分子光引发剂/链转移剂。动力学研究表明，光 PISA 表现出高聚合速率，在 30 分钟内实现了接近定量的单体转化。凝胶渗透色谱 (GPC) 分析表明，在 photo-PISA 期间实现了适度的 RAFT 可控性。研究了成核嵌段的聚合度(DP)、单体浓度和α,ω-大分子光引发剂/链转移剂的DP对嵌段共聚物纳米粒子形貌的影响。最后，对使用 α,ω-大分子光引发剂/链转移剂的热引发 PISA 和光 PISA 进行了直接比较。该研究不仅扩大了光 PISA 的范围，而且为聚合诱导的自组装过程提供了机理见解。进行了ω-大分子光引发剂/链转移剂。该研究不仅扩大了光 PISA 的范围，而且为聚合诱导的自组装过程提供了机理见解。进行了ω-大分子光引发剂/链转移剂。该研究不仅扩大了光 PISA 的范围，而且为聚合诱导的自组装过程提供了机理见解。