原位聚电解质复合驱动离子单体可见光活化室温RAFT水溶液分散聚合

By the combination of controlled/living radical polymerization and block copolymer self-assembly, polymerization-induced self-assembly (PISA) is emerging as a robust and versatile platform for scale-up synthesis of advanced functional nanomaterials in concentrated reaction solutions. One important extension of state-of-the-art is to explore monomers suitable for RAFT aqueous dispersion polymerization and search potentials for facile synthesis of advanced functional nanomaterials. To this end, this project will explore a PISA for precise synthesis of advanced polyelectrolyte nanomaterials in concentrated aqueous reaction solutions, in which a wide range of hydrophilic ionic monomers will be used for RAFT aqueous dispersion polymerization through in situ polyion complexation (PIC) of the hydrophilic ionic chain-growing blocks and hence a new PISA termed as PIC-PISA will be established by the use of visible light mediated room temperature aqueous RAFT polymerization technique that was developed by our group. Effects of ionic monomers, polymeric chain structures, counterion types, solutes, and solids contents on this PIC-PISA will be studied, and the correlations between polymerizing kinetics and the intermediate processes, which involve in situ PIC chain-length recognition, dehydration, phase transition, assembly, disassembly and multicompartmentalization, will be explored, such that reaction characters will be unveiled. Furthermore, a precise kinetic control over self-assembly and a tailor-made nanoscale confinement of assembled core-forming blocks in the concentrated aqueous reaction solutions will be validated. In short, the implementation of this project will lead to the significant breakthroughs in extension of the monomers available for RAFT aqueous dispersion polymerization, in development of a novel platform for eco-friendly efficient synthesis of advanced polyelectrolyte functional nanomaterials, and in consolidation of robustness and versatility of our photo-mediated polymerization.

聚合诱导自组装(PISA)集可控活性自由基聚合反应和嵌段共聚物溶液自组装于一体，是浓溶液中批量制备纳米材料的新方法，拓展RAFT水溶液分散聚合的适用单体并挖掘其功能纳米材料的合成潜力是该领域未来发展方向。本项目拟探索原位聚离子复合(PIC)驱动亲水性离子单体可见光活化室温RAFT水溶液分散聚合，构建高浓度精准合成聚电解质纳米材料的PIC-PISA新方法。探讨其单体和链结构因素，反离子、溶液介质和浓度效应，及其与成核嵌段的原位PIC链长识别、去水合化、相转变、自组装、解组装和多腔室化等过程的关联，以此揭示其聚合反应特征。在此基础上，探索高浓度水溶液中成核嵌段原位自组装的聚合反应动力学控制和精准纳米限域。本项目的实施，必将突破传统RAFT水溶液分散聚合的单体局限性，为生物纳米科技领域提供复杂形貌聚电解质纳米材料的绿色高效合成新方法，充实并拓展我们前期创建的可见光活化室温水溶液RAFT聚合。

聚电解质复合凝聚纳米材料在生命科学、绿色化学、信息科技、材料科学发挥举足轻重的作用。探索复杂有序结构和开发高级功能是化学和材料科学的前沿研究方向。本项目采用原位聚电解质复合驱动离子单体可见光活化室温RAFT水溶液分散聚合，率先提出了聚合诱导静电自组装新概念，系统阐述了聚合诱导静电自组装形貌演变机制和复合凝聚母体程序化摄入凝聚生长机制，成功构建了热响应型聚合诱导自组装、静电调控聚合诱导自组装、共聚序列调控聚合诱导自组装、聚合诱导跨尺度静电自组装、液-液相分离驱动聚合诱导静电自组装、界面液-液相分离驱动聚合诱导跨尺度静电自组装、大分子拥挤作用驱动液-液相分离聚合诱导静电自组装等一系列新策略，首次实现了聚电解质复合凝聚纳米结构的动态共价交联、氢键盐桥锁定新技术。本项目充实并拓展我们前期创建的可见光活化室温水溶液RAFT聚合，为药物/蛋白质/核酸递送、纳米反应器、生物传感、人工细胞等新兴领域亟需的聚电解质复合凝聚纳米材料提供了坚实的合成方法学基础。项目资助发表Angew. Chem. Int. Ed.论文1篇，Chem. Commun.论文1篇，ACS Macro Lett.论文7篇，Macromolecules论文4篇。1篇论文入选高被引论文。应邀在澳大利亚凯恩斯IUPAC世界高分子大会、土耳其埃斯克谢希尔市第七届高分子科技大会、2021年全国高分子学术论文报告会报告3次。培养毕业博士2名，硕士11名，指导完成本科毕业论文16名。综上所述，我们圆满完成了本项目的科学研究任务，达到并超过了既定的科学研究和人才培养目标，取得了科学研究和人才培养双丰收。