State Key Laboratory of Molecular Engineering of Polymers, Collaborative Innovation Center of Polymers and Polymer Composite Materials, Department of Macromolecular Science, Fudan University, Shanghai, 200433, China.
School of Science, North University of China, Taiyuan, Shanxi, 030006, China.
Macromol Rapid Commun. 2019 Jan;40(2):e1800332. doi: 10.1002/marc.201800332. Epub 2018 Jun 26.
Polymerization-induced self-assembly (PISA) and in situ crosslinking of the formed nanoparticles are successfully realized by activators regenerated by electron-transfer atom transfer radical polymerization (ARGET ATRP) of glycidyl methacrylate (GMA) or a mixture of GMA/benzyl methacrylate (BnMA) monomers in ethanol. Poly(oligo(ethylene oxide) methyl ether methacrylate) was employed as macroinitiator/stabilizer, and a cupric bromide/tris(pyridin-2-ylmethyl)amine complex as catalyst. Tin (2-ethylhexanoate) was used as reducing agent for ARGET ATRP, and simultaneously acted as a catalyst for ring-opening polymerization of oxirane ring in GMA. The kinetics shows that the double bond in GMA was completely polymerized in 4.0 h, while only a 33% conversion of oxirane ring in GMA was reached at 117.0 h. Such a large difference would guarantee a smooth PISA and a subsequent in situ crosslinking of formed nanoparticles. The transmission electron microscopy and dynamic light scattering show spherical nanoparticles formed. With a feed molar ratio [BnMA] /[GMA] = 150/50, 100/100, and 50/150, the nanoparticles formed in ethanol can dissociate or swell in toluene. When pure GMA was used, the solid nanoparticles were observed in toluene or ethanol. The ARGET ATRP provides an efficient strategy to stabilize the nanoparticles formed in the PISA of GMA-containing system.
通过引发剂再生电子转移原子转移自由基聚合（ARGET ATRP）的甲基丙烯酸缩水甘油酯（GMA）或 GMA/苯甲基甲基丙烯酸酯（BnMA）单体在乙醇中成功实现了聚合诱导自组装（PISA）和形成的纳米颗粒的原位交联。聚（聚（氧化烯）甲基醚甲基丙烯酸酯）被用作大分子引发剂/稳定剂，而溴化亚铜/三（吡啶-2-基甲基）胺配合物用作催化剂。二月桂酸丁锡用作ARGET ATRP 的还原剂，同时作为 GMA 中环氧化合物开环聚合的催化剂。动力学表明，GMA 中的双键在 4.0 h 内完全聚合，而 GMA 中环氧化合物的转化率仅在 117.0 h 时达到 33%。如此大的差异将保证 PISA 的顺利进行和随后形成的纳米颗粒的原位交联。透射电子显微镜和动态光散射显示形成了球形纳米颗粒。当 BnMA/GMA 的进料摩尔比为 150/50、100/100 和 50/150 时，在乙醇中形成的纳米颗粒可以在甲苯中解离或溶胀。当使用纯 GMA 时，在甲苯或乙醇中观察到固体纳米颗粒。ARGET ATRP 为稳定含 GMA 的体系的 PISA 中形成的纳米颗粒提供了一种有效的策略。
