规模制备Janus聚合物单链@纳米颗粒杂化体  

Scalable Synthesis of Janus Single-chain/Nanoparticle Hybrids

作　　者：李枫霖 杨雅静 孙大吟 叶一兰 杨振忠 Feng-lin Li;Ya-jing Yang;Da-yin Sun;Yi-lan Ye;Zhen-zhong Yang(Institute of Polymer Science and Engineering,Department of Chemical Engineering,Tsinghua University,Beijing 100084)

机构地区：[1]清华大学化学工程系高分子研究所,北京100084

出　　处：《高分子学报》2025年第1期114-123,共10页Acta Polymerica Sinica

基　　金：鄂尔多斯实验室企事业委托项目(项目号20242000416)资助。

摘　　要：非对称Janus聚合物单链与纳米颗粒杂化体系具有精细结构及功能耦合特性,其规模制备具有重要意义.以三嵌段瓶刷聚合物为基础,基于静电介导单链分子内交联方法同时实现Fe_(3)O_(4)原位负载,规模合成了Janus纳米复合颗粒,最高合成浓度达150 mg/mL.该复合颗粒两侧的聚合物链可分别改性获得官能团,为组装和荧光染色观察提供了条件.在纳米复合颗粒表面通过溶胶-凝胶反应包覆SiO2并引入溴丙基,为终止活性阴离子聚合物提供位点.基于空间位阻效应,可在纳米复合颗粒表面顺次键接两根活性阴离子聚合物链,其结构与组成可控,获得了表面具有4根不同聚合物单链的多价态Janus聚合物单链@纳米颗粒功能杂化体,为组装构筑超结构提供重要材料.Asymmetric polymer single-chain@nanoparticle hybrids demonstrate fine microstructures and synergetic performances,which serve as important building blocks toward functional materials.It is crucial to develop methodologies for the large-scale preparation of hierarchically structured functional hybrids.Starting from the triblock bottlebrush polymers,Janus nanoparticles composed of Fe_(3)O_(4)are synthesized on a large scale through electrostatic-mediated intramolecular crosslinking,involving coordination with metallic ions at the central region,which is rich in PVP side chains at a high concentration of 150 mg/mL.Shape of the nanoparticles is controllable from spherical to ellipsoidal by alteration of the length ratio of the backbone and the grafting side chain.PVSt and PBBzSt blocks at the opposite ends of the nanoparticle could be modified orthogonally to derive amino-or(and)carboxylic acid groups.AB type Janus nanoparticles are thus derived,which are able to self-assembly into diverge superstructures upon alteration of pH values.The self-assembly and the superstructures could be easily visualized under stimulated emission depletion microscope(STED)upon fluorescent dyeing the functional groups.A layer of SiO2 is formed at the Fe3O4 NP by the sol-gel process,and bromopropyl-groups are further introduced by using the silane.At the Janus composite nanoparticle,single-chains could be sequentially grafted by steric hindrance assisted termination of living anionic polymer single-chains with tunable composition and microstructure.The Janus composite nanoparticles bearing four different polymer chains display multivalent directional interactions,which are promising to self-assembly functional superstructures.

关 键 词：瓶刷聚合物 静电介导 分子内交联 JANUS 纳米复合颗粒 

分 类 号：TB383.1[一般工业技术—材料科学与工程] O631.12[理学—高分子化学]