School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 62 Nanyang Drive, Singapore, 637459.
Hiroshima R&D Center, Mitsubishi Chemical Corporation, 20-1 Miyuki-cho, Otake, Hiroshima, 739-0693, Japan.
Macromol Rapid Commun. 2024 Mar;45(6):e2300635. doi: 10.1002/marc.202300635. Epub 2024 Feb 6.
Polymerization-induced self-assembly (PISA) is conducted in a non-polar medium (n-dodecane) via reversible complexation-mediated polymerization (RCMP). Stearyl methacrylate (SMA) is used to synthesize a macroinitiator, and subsequent block polymerization of benzyl methacrylate (BzMA) from the macroinitiator in n-dodecane afforded a PSMA-PBzMA block copolymer, where PSMA is poly(stearyl methacrylate) and PBzMA is poly(benzyl methacrylate). Because PSMA is soluble but PBzMA is insoluble in n-dodecane, the block copolymer formed a self-assembly during the block polymerization (PISA). Spherical micelles, worms, and vesicles are obtained, depending on the degrees of polymerization of PSMA and PBzMA. "One-pot" PISA is also attained; namely, BzMA is directly added to the reaction mixture of the macroinitiator synthesis, and PISA is conducted in the same pot without purification of the macroinitiator. The spherical micelle and vesicle structures are also fixed using a crosslinkable monomer during PISA. RCMP-PISA is highly attractive as it is odorless and metal-free. The "one-pot" synthesis does not require the purification of the macroinitiator. RCMP-PISA can provide a practical approach to synthesize self-assemblies in non-polar media.
聚合诱导自组装（PISA）是在非极性介质（正十二烷）中通过可逆配位聚合（RCMP）进行的。使用甲基丙烯酸硬脂酯（SMA）合成大分子引发剂，然后从大分子引发剂在正十二烷中聚合苯甲基甲基丙烯酸酯（BzMA），得到 PSMA-PBzMA 嵌段共聚物，其中 PSMA 是聚（硬脂基甲基丙烯酸酯），PBzMA 是聚（苯甲基甲基丙烯酸酯）。由于 PSMA 可溶但 PBzMA 不溶于正十二烷，因此嵌段共聚物在嵌段聚合过程中形成自组装（PISA）。根据 PSMA 和 PBzMA 的聚合度，可以得到球形胶束、蠕虫和囊泡。还实现了“一锅法”的 PISA；即 BzMA 直接添加到大分子引发剂合成的反应混合物中，在同一锅中进行 PISA，无需对大分子引发剂进行纯化。在 PISA 过程中，还使用可交联单体固定球形胶束和囊泡结构。RCMP-PISA 具有无臭和无金属的特点，非常有吸引力。“一锅法”合成不需要对大分子引发剂进行纯化。RCMP-PISA 为在非极性介质中合成自组装体提供了一种实用的方法。
