超分子微凝胶的多层次自组装和智能材料构筑

As a micro-sized hydrogel colloid, microgel exhibits faster responsiveness to external stimuli than macro-hydrogel. As a dispersion system, microgel suspension can form varieties of self-assembly structures. Therefore, microgel has become an important building block of intelligent materials. Due to its dynamic and reversible characters, supramolecular interactions provide new routes to design microgel-based materials. Current studies about supramolecular microgel are focused on the size change of a single particle or the realizing of certain functions. However, studies of hierarchical self-assembly of supramolecular microgels and their functions are still lagging. In this project, microgels with guest molecules as side groups or host-guest complexes as cross-linkers will be prepared. The supramolecular interactions inside microgel particle, between microgel and small molecules, between microgel and macromolecules, and among microgel particles will be studied. The stimuli-responsiveness of the assembled microgels will be investigated, and several kinds of intelligent materials on the basis of supramolecular microgel with tunable optical, mechanical or rheological properties will be further constructed. This project explores the chemistry of introducing supramolecular functional groups into microgel, and unravels the physics of hierarchical self-assembly of supramolecular microgel. This research will provide new strategies for fabricating microgel-based intelligent materials.

凭借小尺寸带来的响应灵敏性和自组装结构的多样性,微凝胶成为智能高分子材料的重要构筑基元。超分子作用的引入为智能微凝胶的设计开辟了新方向，然而目前此类研究多集中于单个粒子的尺寸变化和某特定功能的实现，缺乏对超分子微凝胶的多层次自组装过程和组装体功能的系统认识。本项目拟制备一系列以客体分子为侧基或以主客体络合物为交联剂的微凝胶；考察微凝胶内部、微凝胶与小分子、微凝胶与大分子和微凝胶之间等不同层次上的自组装过程；发掘通过超分子作用调控自组装结构和组装体功能的规律；构筑一系列光学、力学和流变等宏观性质可调的智能材料。本项目将探索把超分子作用引入微凝胶体系的化学方法，阐明超分子微凝胶分子自组装和胶体自组装的物理规律，为基于微凝胶的智能材料设计提供新思路。

本项目拟制备一系列以客体分子为侧基或以主客体络合物为交联剂的微凝胶；考察微凝胶内部、微凝胶与小分子、微凝胶与大分子以及微凝胶之间等不同层次上的自组装过程；发掘通过超分子作用调控其自组装结构和组装体功能的规律；构筑一系列的智能材料。研究过程中，我们利用微凝胶与水凝胶网络之间的主客体作用，制备了自修复性能可光调控的智能水凝胶；利用微凝胶胶体间的主客体作用，构筑了可光调控的胶体自组装构有序结；利用超分子交联来调控聚合物网络的应力松弛行为，制备了永久形状可编辑的形状记忆水凝胶；利用外界刺激调控超分子交联聚合物网络的应力松弛，制备了永久形状可编辑的形状记忆水凝胶；利用聚合物间氢键作用在宏观尺度上的不对称分布，制备了多重响应性的自驱动水凝胶。此外，我们开展了关于聚合物间的氢键作用与聚合物的温度响应性的研究，为水相温敏性聚合物的分子设计上建立了一个理论框架，并成功的指导了一系列在水中具有上临界溶解温度（UCST）的温度响应性聚合物的分子设计。上述工作为基于超分子作用的智能聚合物的多层次组装和材料设计提供了新的思路。