Nanoporous polymer particles and gels containing functionalized semi-rigid copolymer structures

该项目的基础和探索性研究旨在发现新的专门设计的聚合物材料，这些材料可以作为特定气体和金属离子吸附剂技术创新的赋能材料。 这种材料可以用作涉及气体排放和水污染的应用的工具。该项目将专注于高表面积聚合物颗粒的创造和研究。 这些将含有高负载量的由特别设计的聚合物单元递送的特别选择的化学基团，并且可以通过工业实践的聚合方法容易地制备。 这些聚合物材料可以提供用于酸性气体和重金属离子捕获的实际候选物（例如，二氧化碳、硫化氢、重金属离子）。 这些聚合物中的一些还可以导致用于增强氢的可逆存储的实用的高表面积聚合物颗粒。 该项目的成果将在主要的科学会议上报告，并在高影响力的期刊上发表。经过跨学科激烈互动训练的学生是这项研究的重要成果。 在新的功能高分子材料的科学发展的学科和跨学科的培训的紧密耦合将准备学生进入科学劳动力做好充分准备，为推进国家的技术增长作出重要贡献。技术总结在这个项目中描述的研究重点是制备和研究新型半刚性，空间拥挤和精确官能化的纳米多孔超交联聚合物材料。 将交替共聚物的半刚性链段精确插入到超交联聚合物颗粒中，提供新的化学主链单元以改变网络系统的性质。 精确控制来自严格交替序列的官能团的放置将使得能够实现独特的固态构建体，所述固态构建体预期提供对所得网络的物理性质的优异控制。对于超交联体系，这些半刚性单元在超交联步骤期间减缓孔塌陷。 计算协作将有助于指导设计更高表面积功能粒子的基础的发展。这些新的超交联聚合物材料将具有高表面积，具有高浓度的官能团，这些官能团被设计用于与气体山梨酸酯、金属离子或其他反应性分子的特定相互作用。 半刚性链硬化序列的空间拥挤的功能共聚物序列的比较将有助于阐明基本结构性能关系的链刚度的作用。最近发现的含有羧酸官能团的半刚性结构将扩展到具有伯胺和仲胺基团以及精确地连接在聚合物主链中的酚基的超交联聚合物材料。 预计这些新的功能性纳米多孔颗粒将是二氧化碳和其他酸性气体的有效固体吸附剂。 含有芳香胺的超交联纳米多孔聚合物颗粒也将成为目标，并研究其储氢潜力。

NON-TECHNICAL SUMMARYThe fundamental and exploratory research of this project is directed toward the discovery of new specifically designed polymeric materials that can serve as enabling materials for innovations in specific gas and metal ion sorbent technologies. Such materials could be employed as tools for applications involving gas emissions and water pollution. This project will focus on creation and study of high-surface-area polymer particles. These would contain high loadings of specifically chosen chemical groups delivered by specially designed polymer units and could be readily prepared by industrially practiced polymerization processes. These polymeric materials could provide practical candidates for acid gas and heavy metal ion capture (e.g., carbon dioxide, hydrogen sulfide, heavy-metal ions). Some of these polymers could also lead to practical high-surface-area polymer particles for enhancing reversible storage of hydrogen. Results from this project will be reported at major scientific conferences and published in high-impact journals. Students trained with intense interactions across discipline boundaries are an important output of this research. The tight coupling of disciplinary and interdisciplinary training in the scientific development of new functional polymeric materials will prepare students to enter the scientific workforce well-prepared to make important contributions for advancing the technological growth of the nation.TECHNICAL SUMMARYThe research described in this project focuses on preparing and studying novel semi-rigid, sterically crowded and precisely functionalized nanoporous hypercrosslinked polymeric materials. Precise insertion of semi-rigid segments from alternating copolymers into hypercrosslinked polymer particles delivers new chemical backbone units to modify properties of network systems. Precise control of placement of functional groups from strictly alternating sequences will enable unique solid state constructs that are expected to provide excellent control over physical properties of the resulting networks. For hypercrosslinked systems, these semi-rigid units slow pore collapse during the hypercrosslinking step. Computational collaboration will help guide the development of the fundamentals for designing higher surface area functional particles. These new hypercrosslinked polymeric materials will possess high surface areas with high concentrations of functional groups designed for specific interactions with gas sorbates, metal ions, or other reactive molecules. Comparison of semi-rigid chain stiffening sequences to less sterically crowded functional copolymer sequences will assist in elucidating the role of chain stiffness on fundamental structure property relationships. Recent discoveries with semi-rigid structures containing carboxylic acid functional group will be expanded to hypercrosslinked polymeric materials with primary and secondary amine groups and phenolic groups precisely enchained in the polymer backbone. It is anticipated that these new functional nanoporous particles will be effective solid sorbents for carbon dioxide and other acidic gases. Hypercrosslinked nanoporous polymer particles containing aromatic amines will be targeted also and their potential for hydrogen storage studied.