In Situ Crosslinking of Nanoparticles in Polymerization-Induced Self-Assembly via ARGET ATRP of Glycidyl Methacrylate
In Situ Crosslinking of Nanoparticles in Polymerization-Induced Self-Assembly via ARGET ATRP of Glycidyl Methacrylate
复制标题
通过甲基丙烯酸缩水甘油酯的 ARGET ATRP 聚合诱导自组装纳米颗粒的原位交联
DOI：
10.1002/marc.201800332
复制
发表时间：
2019
影响因子：
4.6
通讯作者：
Krzysztof Matyjaszewski
中科院分区：
文献类型：
--
作者：
Jian Wang;Zhigang Wu;Guowei Wang;Krzysztof Matyjaszewski
通过甲基丙烯酸缩水甘油酯（GMA）或GMA/甲基丙烯酸苄酯（BnMA）单体的混合物在乙醇中的电子转移原子转移自由基聚合（ARGET ATRP）再生活化剂，成功实现了聚合诱导自组装（比萨）和形成的纳米颗粒的原位交联。采用聚（低聚（环氧乙烷）甲基醚甲基丙烯酸酯）作为大分子引发剂/稳定剂，溴化铜/三（吡啶-2-基甲基）胺络合物作为催化剂。采用2-乙基己酸锡作为ARGET ATRP的还原剂，同时作为环氧乙烷环在GMA中开环聚合的催化剂。动力学结果表明，GMA中双键在4.0h内聚合完全，而环氧乙烷环在117.0h时转化率仅为33%。这样大的差异将保证平滑的比萨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表明形成了球形纳米颗粒。在进料摩尔比[BnMA]0/[GMA]0= 150/50、100/100和50/150的情况下，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提供了一种有效的策略来稳定含GMA系统的比萨中形成的纳米颗粒。
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]0/[GMA]0= 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.