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技术创新的使能材料。这类材料可作为工具用于涉及气体排放和水污染的应用。该项目将专注于高表面积聚合物颗粒的创造和研究。这些将包含高负荷的特定选择的化学基团，由专门设计的聚合物单元提供，并且可以很容易地通过工业上实践的聚合过程制备。这些聚合材料可以为酸性气体和重金属离子捕获（如二氧化碳、硫化氢、重金属离子）提供实用的候选材料。这些聚合物中的一些也可能导致实用的高表面积聚合物颗粒，以增强氢的可逆储存。该项目的结果将在主要科学会议上报告，并在高影响力期刊上发表。通过跨学科的密切互动培养学生是本研究的重要成果。在新型功能高分子材料的科学开发中，学科和跨学科训练的紧密耦合将使学生准备好进入科学劳动力队伍，为推动国家的技术发展做出重要贡献。本项目主要研究制备和研究新型半刚性、立体拥挤和精确功能化的纳米多孔超交联聚合物材料。从交替共聚物的半刚性段精确插入到超交联聚合物颗粒提供新的化学骨干单位，以改变网络系统的性质。从严格交替序列中精确控制官能团的位置将实现独特的固态结构，从而有望对所得到的网络的物理性质提供出色的控制。对于超交联体系，这些半刚性单元减缓了超交联过程中孔隙的坍塌。计算协作将有助于指导设计高表面积功能粒子的基本原理的发展。这些新的超交联聚合物材料将具有高表面积和高浓度的官能团，专为与气体吸附物、金属离子或其他活性分子的特定相互作用而设计。比较半刚性链强化序列和较少空间拥挤的功能共聚物序列将有助于阐明链刚度在基本结构性能关系中的作用。最近发现的含有羧酸官能团的半刚性结构将扩展到在聚合物主链上精确连接伯胺、仲胺和酚基的超交联聚合物材料。预计这些新型功能纳米多孔颗粒将成为二氧化碳和其他酸性气体的有效固体吸附剂。此外，还将研究含芳胺的超交联纳米多孔聚合物颗粒及其储氢潜力。

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.