聚合诱导自组装制备嵌段聚合物/多酸杂化纳米材料及其催化性能研究

This project will focus on the development of novel preparation methods of hybrid materials of Block copolymers (BCPs) and Polyoxometalates (POMs). POMs will be modified by covalent and non-covalent means to be the polymerizable crosslinkers with multiple vinyl groups. RAFT polymerization will be employed to obtain BCP/POM hybrid nanoparticles in solution in the presence of POM crosslinkers, macromolecular chain transfter agents and monomers through Polymerization-induced Self-Assembly (PISA). This simple one-pot synthesis can used to prepare the concentrated stable BCP/POM hybrid nanoparticles with diverse chemical structures in the mass production. The polymerizaiton condition will be optimized, and sevel key parameteres,i.e. the topological structure and charge density of POMs, the number of vinyl moieties of POM crosslinkers, feed ratio, will be investigated for their effects on the polymerization process and self-assembly morphologies. The mechanism on the polymerization controlled and by thermodynamical and kinetical factors will be discovered. Senstive blocks to light and heat stimuli will be incorporated into BCP/POM hybrid nanoparticles, and their stimuli responsive properties of the polymerization and assembly behavior wil be investigated. The BCP/POM hybrid nanoparticles will be used as catalytic microreactors and the relationship of catalytic performance on the chemical structure of organic block, morphologies of hybrid nanoparticles will be discovered. In combination of excellent stimuli-responsive and catalytic properties, the smart catalytic microreactor will be constructed for controlled catatlysis and recyclability.

本项目拟发展构筑嵌段共聚物/多酸杂化纳米粒子的聚合诱导自组装新方法，在嵌段共聚物的RAFT聚合诱导自组装合成中引入表面含有可聚合基团的多酸交联剂，“一锅法”简单高效的获得稳定性好、高浓度的嵌段共聚物/多酸杂化纳米粒子溶液，适合大规模工业应用。优化聚合条件，探索多酸交联剂的拓扑结构、官能度、投料比等对聚合及自组装的影响，探索聚合过程中自组装动力学和热力学规律和组装体形貌的关键影响因素。引入具有光、热等敏感性链段，研究外界刺激对聚合诱导自组装过程以及自组装形貌的影响。考察嵌段共聚物/多酸杂化纳米粒子作为微反应器的催化性能，探索自组装结构与催化性能的构效关系。结合嵌段聚合物刺激响应性能与多酸催化性能，实现催化反应和回收利用的智能控制。

本项目发展了构筑嵌段共聚物/多酸杂化纳米粒子的聚合诱导自组装新方法，在嵌段共聚物的RAFT聚合诱导自组装合成中引入表面含有可聚合基团的多酸交联剂，“一锅法”简单高效的获得稳定性好、高浓度的嵌段共聚物/多酸杂化纳米粒子溶液，适合大规模工业应用。优化了聚合条件，探索多酸交联剂的拓扑结构、官能度、投料比等对聚合及自组装的影响，探索聚合过程中自组装动力学和热力学规律和组装体形貌的关键影响因素。引入具有光、热等敏感性链段，研究外界刺激对聚合诱导自组装过程以及自组装形貌的影响。完成了五个方面的工作:(1) 聚合诱导自组装方法合成核交联杂化纳米微球；(2)核交联杂化纳米微球催化合成金属纳米颗粒；(3) 光响应性的圆偏振荧光杂化纳米粒子; (4)核交联杂化纳米微球制备光子晶体；(5)聚合诱导自组装法合成螺旋嵌段聚合物及其杂化微球。