伯胺单体离子缔合调控的可见光活化室温水溶液RAFT聚合

Thanks to the particularly fascinating properties, primary-amine-based water soluble polymers have been evidenced to have wide potential applications for fabricating nanomaterials and biomedical related functional materials. Exploring facile technique for the rapid and well-controlled synthesis of these water soluble polymers under mild conditions is essential to push forward such applications. To this end, the effect of monomer ion asociation on the visible light activated ambient aqueous RAFT polymerization of primary-amine-based monomers will be intensively studied, accordingly a new approach to the facile and rapid synthesis of well-defined primary-amine-based water soluble polymers under ambient aqueous conditions will be explored. To this end, the primary-amine-based water soluble methacrylamides with the targeted molecular structures will be synthesized. The monomer ion association will be modulated either by changing their molecular structures or counter-ions, or adjusting monomer concentration or solution temperature. The ion clusters of these monomers will be induced by complexing with alkyl sulfonic acid or alkylbenzene sulfonic acid etc. Moreover, this polymerization will be started up or ceased off periodically by turning on or off the visible light periodically in the duration of RAFT polymerization.By means of such processes, the influence of monomer ion association on the visible light activated ambient aqueous RAFT polymerization and copolymerization of these particular monomers will be disclosed, and the polymerizing processes will be finely controlled, thus well-defined primary-amine-based water soluble copolymers with the targeted compositions and comonomer distributions will be rapidly synthesized under such mild ambient aqueous conditions. In short, this project will not only get an in-depth understanding of aqueous polymerization of ionized monomers, but also open a new avenue toward the facile and rapid synthesis of well-defined primary-amine-based water soluble functional polymers, thus significantly enrich the concept and extend the application fields of the visible light activated ambient- temperature RAFT polymerization that was developed previously by our group.

水溶性伯胺聚合物在纳米材料和生物医药等新兴领域已显现巨大的应用潜力。探索温和条件下伯胺聚合物的快捷可控合成新方法，必将促进相关领域的发展。本项目拟探讨伯胺单体离子缔合调控的可见光活化室温水溶液RAFT聚合特征，进而探索在室温水溶液中伯胺聚合物的快捷可控合成新方法。为达此目标，我们拟合成不同结构特征的甲基丙烯酰胺类伯胺单体；改变单体结构或反离子种类，调节单体浓度或水溶液温度，从而调控单体离子缔合状态；采用烷基磺酸或烷基苯磺酸等，诱导单体离子团簇化；通过间歇性光开关，实时启动或终止聚合；进而探讨伯胺单体离子缔合调控的可见光活化室温水溶液RAFT聚合和共聚合特征，实现聚合过程的间歇性光开关控制，快捷可控合成设定组成和共聚分布的水溶性伯胺聚合物。本项目的实施将加深对离子化单体水溶液聚合特性的理解，为快捷可控合成伯胺衍生功能聚合物提供新方法，充实并拓展我们前期创建的可见光活化室温RAFT聚合。

水溶性伯胺聚合物在纳米技术和生物医药等新兴领域显现巨大应用潜力，探索温和条件下伯胺聚合物快捷可控合成新方法势在必行。本项目针对离子缔合调控伯胺单体聚合、生长链静电效应和高分子反应性等基本属性，展开了卓有成效的探索。我们发现离子缔合主导伯胺单体链引发和链增长，凸显低温加速、反离子和介质效应。发现了与阴离子单体共聚合的反常机制(等当量交替共聚，较少单体快速共聚)，受控离子对效应。结合这些特性和光激活-避光休眠，发展了室温水溶液迭代聚合制备序列可控伯胺高分子新方法；伯胺生长链与聚阴离子复合，发展伯胺单体聚合诱导自组装(PISA)新机制，发现了独特丰富相行为；非离子单体溶液中少量伯胺单体离子团簇化，发展了伯胺微区纳米限域的纳米球、囊泡、空心管批量制备新技术，发现了空心管敏感的介质响应开闭孔行为。探索了伯胺反应纳米功能化。发现了高分子亚组分自组装的高分子配位选择性，揭示了金属中心和配体空间选择主导亚组分自组装，实现了亚胺化配体配位的超胶体自组装行为以及柱状胶束横向排列、自纠错、自分类、间断融合的多腔室薄片织构机制，构建了高分子金属杂化单链纳米材料。发现了光控氢键调控热响应机制，少量客体序列调控高分子氢键温敏协同，光控长程有序表面纳米图案化。胱胺丙烯酰胺盐酸盐单体具有上述聚合所有特征，其动态反应驱动一系列的胶束－纳米线－溶胀纳米线－支化纳米线－三维网络相态转变，金属配位催化驱动其类似蛋白质自催化多层次自分类。发表论文18篇，包括2篇ACS Macro Letters、1篇Macromolecules、6篇Macromolecular Rapid Communications、6篇Polymer Chemistry、3篇Soft Matter论文，泛太平洋高分子国际会议、中国化学会学术年会、全国高分子学术论文报告会报告8次。获资助培养出站博士后1名，毕业博士1名、硕士12名。综上所述，我们圆满完成了本项目研究任务，超过了既定科学研究和人才培养目标，为模仿生物蛋白构效关系的后续探索奠定了坚实的合成方法学基础。

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