Nanostructured Polymers for Bronsted and Lewis Acid Catalysis via Monomer Self-Assembly

该奖项将支持基于可聚合液晶（LC）的功能性纳米结构聚合物系统开发的研究计划。 拟议项目的目标是设计和研究基于溶致液晶组装的纳米结构聚合酸催化剂，这些催化剂可能在性能和控制方面提供两全其美的效果。 一个具体的新的研究方向是设计形成Hii相的溶致液晶单体，其含有强布朗斯台德酸基团。 据我们所知，具有这种组合特征的可聚合两亲物是前所未有的。 这方面的拟议工作将涉及调查的基本问题，在LC单体设计中的官能团相容性，以及调查的影响的纳米结构和限制布朗斯台德酸碱平衡在所得的聚合物。 更多的应用研究也将进行，以确定这些拟议的纳米结构的聚合物树脂在酸催化相对于更传统的无机和有机酸材料的有效性。 第二个新的研究方向是设计新的含强刘易斯酸性Sc（III）头基的溶致单体。 虽然已经实现了无定形的聚合物负载的Sc（III）催化剂，但纳米结构的含Sc聚合物催化剂是前所未有的。 LC网络负载的Sc（III）材料可以产生独特的非均相刘易斯酸催化剂，其不仅在水中操作，而且与传统的各向同性Sc（III）体系相比还提供不同的反应动力学和选择性。就更广泛的影响而言，拟议的研究将为纳米科学这一重要领域的学生提供培训。 纳米科学最近已成为国家科学和技术的重点。 这项研究为高分子化学专业的学生提供了一个新的训练基地，以研究纳米结构对重要材料性能的影响，如催化和反应性。 这项研究本身可能会导致新的基本见解，设计具有新的能力的聚合物材料作为控制的结果，在纳米尺度上。

This award will support a research program in the development of functional, nanostructured polymeric systems based on polymerizable liquid crystals (LCs). The goal of the proposed project is to design and examine nanostructured, polymeric acid catalysts based on lyotropic LC assemblies that would potentially offer the best of both worlds in terms of properties and control. One specific new research direction is the design of lyotropic LC monomers that form the Hii phase which contain strong Bronsted acid groups. To out knowledge, polymerizable amphiphiles with this combination of features are unprecedented. This aspect of the proposed work will involve investigating fundamental issues of functional group compatibility in LC monomer design, as well as investigating the effect of the nanoscale architecture and confinement on Bronsted acid-base equilibria in the resulting polymer. More applied studies will also be undertaken to determine the effectiveness of these proposed nanostructured polymer resins in acid catalysis relative to the more conventional inorganic and organic acid materials. The second new research direction is the design of new lyotropic monomers which contain strongly Lewis acidic Sc(III) headgroups. Although amorphous, polymer-supported Sc(III) catalysts have been realized, nanostructured Sc-containing polymeric catalysts are unprecedented. LC network-supported Sc(III) materials may yield unique heterogeneous Lewis acid catalysts that not only operate in water but also afford different reaction kinetics and selectivities compared to traditional isotropic Sc(III) systems.%%%In terms of broader impact, the proposed research will provide training for students in the important area of nanoscience. Nanoscale science has recently become a national science and technology priority. The proposed research provides a novel training ground for students in polymer chemistry to examine the effect of nanostructure on important materials properties, such as catalysis and reactivity. The research itself may lead to new fundamental insights for designing polymeric materials with novel capabilities as a result of control of order on the nanometer scale.