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

该奖项将支持一项基于可聚合液晶(LCS)开发功能性纳米结构聚合物系统的研究计划。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，这可能在性能和控制方面提供两全其美的结果。一个具体的新研究方向是设计形成含有强Bronsted酸基的HII相的溶致液晶单体。据我们所知，具有这种组合特征的可聚合两亲分子是史无前例的。这方面的工作将包括研究液晶单体设计中官能团相容性的基本问题，以及研究纳米级结构和限制对所得聚合物中Bronsted酸碱平衡的影响。还将进行更多的应用研究，以确定这些建议的纳米结构聚合物树脂相对于更传统的无机和有机酸材料在酸催化中的有效性。第二个新的研究方向是设计含有强Lewis酸性Sc(III)头基的新型溶致单体。尽管已经实现了无定形、聚合物负载的Sc(III)催化剂，但纳米结构的含Sc的聚合物催化剂是前所未有的。LC网络负载的Sc(III)材料可以制备独特的多相Lewis酸催化剂，不仅可以在水中操作，而且与传统的各向同性Sc(III)体系相比，具有不同的反应动力学和选择性。%从更广泛的影响来看，拟议的研究将为学生提供重要的纳米科学领域的培训。纳米科学最近已成为国家科技重点。这项拟议的研究为聚合物化学专业的学生提供了一个新的培训基础，以检验纳米结构对重要材料性能的影响，如催化和反应活性。这项研究本身可能会为设计具有新功能的聚合物材料带来新的基本见解，这是纳米级有序控制的结果。

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.