双亲性连续调变的聚离子液体Janus粒子的制备与性能研究

In this project, the following related systematic research, where snowman-like poly(ionic liquid)s Janus particles with regular morphology, various structures and properties are selected as a representative object of study and their emulsifying property and the interfacial behavior in Pickering emulsions are used as functional parameters, is carried out for some key problems needed to solve for the extensive applications of Janus particles, e.g. precise control of their morphology and microstructures, diversification of chemical components and effective loading of functional groups or species on their surfaces, and mass production: A novel general method for preparing snowman-like poly(ionic liquid)s Janus particles will be developed, and a series of snowman-like poly(ionic liquid)s Janus particles with continuously modulated amphipathy will be prepared. The influence of the continuously modulated amphipathy of the snowman-like poly(ionic liquid)s Janus particles as particle emusifier on their emulsifying property and interfacial behavior in various double-solvent Pickering emulsion systems will be investigated. Based on the integration of the interface stabilization effect, supporters function and the Pickering emulsions feature of the Janus particles, the Pickering emulsions are expected to have a stable bicontinuous phase which can be used for developing new materials, and the Janus particles are expected to stabilize the emulsions containing ionic liquids with small emulsion droplets and large interface for developing green catalytic systems. This project will provide theoretical and technical basis for the research and application of Janus particles.

本项目针对Janus粒子广泛应用中急需解决的形貌和微结构的精确调控、表面化学分区组分的多样化、功能基团或物种的有效分区导入和量产性制备等重要问题，选取结构和性能内容丰富、形貌规整且具有代表性的雪人状离子液体基Janus粒子为研究对象，以乳化性能和界面行为为功能指标，开展相关系统研究。发展制备雪人状聚离子液体Janus粒子的普适性方法，获得双亲性连续调变的雪人状聚离子液体Janus纳米和微米粒子，考察双亲性连续调变下其作为颗粒乳化剂在各种双溶剂体系中的乳化性能，探讨界面行为的影响因素及规律；将离子液体Janus粒子的界面稳定功能、载体作用和乳液体系特性有机结合，探索获得稳定的Pickering双连续乳液体系，构筑具有小尺寸乳滴、大界面的稳定离子液体乳液，分别应用于新材料的创制和特色催化体系的开发，为Janus粒子的研究与应用提供理论和技术基础。

本项目发挥离子液体和Janus结构的特性，通过离子液体的引入赋予Janus微纳材料良好的界面分散性、催化和分离等独特性能，为离子液体基微纳材料的研发提供理论和技术基础。本项目首先探索了利用各种微球的种子聚合直接获得离子液体基雪人状Janus微纳粒子的可行性，成功地开发了离子液体基Janus粒子的直接合成法。例如，以疏水性离子液体和聚甲基丙烯酸甲酯（PMMA）的微凝胶球为种子，硅烷经种子聚合相分离后能够形成离子液体基雪人状Janus粒子；以PMMA微球为种子、以疏水的甲基丙烯酰氧乙基三甲基铵类离子液体为聚合单体，利用种子乳液聚合法制备了多种形貌可调的补丁型各向异性粒子PMMA-PIL。进而，本项目采用后修饰法，通过亲疏水基团的区域选择性修饰，获得了多种双亲性连续调变的系列离子液体基雪人状Janus微纳粒子，考察了包括其在内的多种微纳颗粒在各种乳液界面上的排布、乳液类型、稳定性和液滴形貌等的影响因素及规律，构筑了各种乳滴大小可调的稳定Pickering乳液。研究结果表明，离子液体基雪人状Janus粒子两端的亲疏水性调变对其乳化性能影响很大，通过对其精确调节能够调控乳液的类型、液滴形貌、响应性和稳定性等。目前获得的雪人状Janus粒子一般粒径较大，难以稳定双连续相乳液，与之相比，纳米片状Janus颗粒在这方面具有相对优势，但雪人状Janus粒子在催化剂分区负载方面优势明显。最后，本项目将各种催化剂分区负载于包括离子液体雪人状Janus粒子在内的多种微纳颗粒上，发展了几种新的乳液催化体系和基于稳定乳滴的流动催化体系。此外，本项目还制备了若干新型离子液体基及其相关微纳材料，探讨了其在催化、电化学、光电转化和锂电池等领域的应用性能。.本项目研究结果表明，微纳材料中离子液体的引入，可以简便地实现对其结构的精确调控和功能化，是微纳材料达到高性能和多功能的有效途径之一。