Development of ICAR ATRP–Based Polymerization‐Induced Self‐Assembly and Its Application in the Preparation of Organic–Inorganic Nanoparticles
Development of ICAR ATRP–Based Polymerization‐Induced Self‐Assembly and Its Application in the Preparation of Organic–Inorganic Nanoparticles
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基于ICAR ATRP的聚合诱导自组装技术的发展及其在有机无机纳米颗粒制备中的应用
DOI：
10.1002/marc.201900547
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发表时间：
2019
影响因子：
4.6
通讯作者：
Guowei Wang
中科院分区：
文献类型：
--
作者：
Boyang Shi;Hao Zhang;Yi Liu;Jian Wang;Peng Zhou;Mengya Cao;Guowei Wang
近年来，聚合诱导自组装（比萨）方法制备的纳米物体的功能化和应用正成为一个焦点。以乙醇为溶剂，聚（低聚（环氧乙烷）甲基醚甲基丙烯酸酯）（POEOMA）为大分子引发剂/稳定剂，甲基丙烯酸2-（全氟己基）乙酯（PFHEMA）和甲基丙烯酸缩水甘油酯（GMA）为共聚单体，实现了基于连续活化剂再生原子转移自由基聚合（ICAR ATRP）的比萨引发剂。较低GMA含量的体系倾向于形成具有大直径和高对比度的球体，而较低PFHEMA含量的体系倾向于形成具有小直径的球体或短蠕虫。然而，具有进一步增加的GMA含量的系统导致ICAR ATRP比萨程序失败，并通过侧环氧基团之间的交联反应形成沉淀物。此外，利用GMA上的环氧基与巯基丁二酸试剂上的巯基之间的高效反应，将羧基引入纳米物体的内腔，并用于与Fe 2+和Fe 3+离子的结合，最终在还原剂的存在下制备了有机-无机纳米粒子Fe3O4@POEOMA。
The functionalization and application of nano‐objects generated using a polymerization induced self‐assembly (PISA) procedure is becoming a focus in recent years. In this contribution, using ethanol as solvent, poly(oligo(ethylene oxide) methyl ether methacrylate) (POEOMA) as macro‐initiator/stabilizer, and 2‐(perfluorohexyl)ethyl methacrylate (PFHEMA) and glycidyl methacrylate (GMA) as comonomers, the initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP)‐based PISA is realized. The lower GMA content system tends to form spheres with large diameters and heavy contrast, while the lower PFHEMA content system tends to form the spheres or short worms with small diameters. However, the system with further increased GMA content results in the failed ICAR ATRP PISA procedure with the formation of precipitates by the cross‐linking reaction between pendant epoxy groups. Furthermore, using the efficient reaction between the epoxy group on GMA and thiol group on mercapto‐succinic acid agent, the carboxyl groups can be introduced into the inner cavity of the nano‐objects and used for incorporation with the Fe2+and Fe3+ions, and the organic–inorganic nanoparticles Fe3O4@POEOMA are finally prepared in the presence of a reductant.