Design of Nanoporous Polymers with New Functional Capabilities via Monomer Self-Assembly

技术总结本项目的重点是扩展基于可聚合溶致(即两亲性)液晶(LLC)的有序纳米孔聚合物的功能能力。我们小组以前的工作表明，含有有序的圆柱形纳米通道(HII相)的LLC网络可以用作分子筛的催化有机类似物，以及作为分子尺寸选择的过滤介质。将探索两个新的研究方向，以扩展这些有限责任公司网络的功能能力，并增加我们对如何设计这种材料的理解。第一个新的方向是探索是否可以将结构上更多样化、具有催化活性以外的能力的头基加入到这些聚合物材料中。具体地说，将探索在纳米孔中含有能够响应于特定刺激而可逆地改变其孔尺寸、结构或化学性质的部分的LLC网络的设计(即响应门控传输)。主动和选择性地控制LLC树脂的传输性能的能力将极大地增加这些纳米孔聚合物已经展示的分子尺寸排除和催化能力。第二个新的方向是设计具有更复杂的孔道结构的新的功能有限责任公司网络，这将允许在与运输和接入相关的领域获得更好的性能。具体地说，将研究包含三维互连纳米孔的交联型双连续立方体(Q)LLC组件的设计。这项工作的目标是设计更容易获得的纳米多孔聚合物材料，它可以包含与我们最初的HII系统相同水平的功能功能。总而言之，该项目将为如何将新的官能团/功能设计成交联型LLC组件提供新的见解，并产生具有前所未有的功能特性组合的新的纳米孔聚合物。这项研究还将作为培训学生在聚合物化学和应用纳米科学方面的平台。将探索将新的功能功能加入到具有1至2纳米范围内统一孔的表面活性剂液晶(LC)聚合物中的非技术性总结方法。这种材料此前已被证明是有用的增强型固态催化剂，以及可以根据分子大小分离分子的新过滤材料。在这个项目中，将探索纳米多孔聚合物的设计，这种聚合物可以根据特定的刺激可逆地改变其孔大小、结构或化学性质。主动控制这些材料的分子传输特性的能力将极大地提高它们的实用性。此外，还将探索设计具有更复杂纳米孔结构的新型液晶聚合物，作为改善传输和内部访问性能的一种手段。总而言之，这项研究可能导致新的功能性多孔聚合物，可应用于许多有益的应用，如用于环境和个人化学保护的高选择性、适应性膜；用于过程化学的优质高通量聚合物载体催化剂等。该研究项目还将成为聚合物化学和新兴应用纳米科学领域的交叉培训学生的平台。

TECHNICAL SUMMARYThe focus of this project is to expand the functional capabilities of ordered, nanoporous polymers based on polymerizable lyotropic (i.e., amphiphilic) liquid crystals (LLCs). Prior work in our group has shown that LLC networks containing ordered, cylindrical nanochannels (the HII phase) can be used as catalytic organic analogs to molecular sieves, and as molecular size-selective filtration media. Two new research directions will be explored for extending the functional capabilities of these LLC networks, and for increasing our understanding of how to design such materials. The first new direction is focused on exploring whether structurally more diverse headgroups with capabilities other than catalytic activity can be incorporated into these polymeric materials. Specifically, the design of LLC networks containing moieties in the nanopores that can reversibly change their pore dimensions, structure, or chemical character in response to specific stimuli, will be explored (i.e., responsive gated transport). The ability to actively and selectively control the transport properties of LLC resins would greatly add to the molecular size-exclusion and catalytic capabilities already demonstrated in these nanoporous polymers. The second new direction is focused on the design of new functional LLC networks with more sophisticated pore architectures, which will allow better performance in areas related to transport and access. Specifically, the design of cross-linked bicontinuous cubic (Q) LLC assemblies containing three-dimensional interconnected nanopores, will be investigated. The goal of this work is the design of more accessible nanoporous polymer materials that can incorporate the same level of functional capabilities as our initial HII systems. Collectively, this project will provide new insights into how to design new functional groups/capabilities into cross-linked LLC assemblies, and generate new nanoporous polymers with unprecedented combinations of functional properties. This research will also serve as a platform for training students in polymer chemistry and applied nanoscience.NON-TECHNICAL SUMMARYMethods for incorporating new functional capabilities into surfactant liquid crystal (LC) polymers that have uniform pores in the 1 to 2 nanometer range, will be explored. Such materials have previously been shown to be useful as enhanced solid-state catalysts, and as new filtration materials that can separate molecules based on their size. In this project, the design of nanoporous polymers that can reversibly change their pore size, structure, or chemical character in response to specific stimuli will be explored. The ability to actively gate the molecular transport properties of these materials would greatly increase their utility. In addition, the design of new LC polymers with more sophisticated nanopore structures will be explored, as a means of improving transport and internal access properties. Collectively, this research may lead to new functional porous polymers that can be applied to a number of beneficial applications, such as highly selective, adaptive membranes for environmental and personal chemical protection applications; superior high-throughput polymer-supported catalysts for process chemistry; etc. This research project will also serve as a platform for cross-training students in polymer chemistry and the emerging area of applied nanoscience.