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

非技术总结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。这种材料可以用作涉及气体排放和水污染的应用工具。该项目将专注于高比表面积聚合物颗粒的创造和研究。它们将包含由特殊设计的聚合物单元提供的特定选择的化学基团的高负载量，并且可以通过工业实践的聚合过程容易地制备。这些聚合物材料可以为酸性气体和重金属离子(例如二氧化碳、硫化氢、重金属离子)的捕获提供实用的候选材料。其中一些聚合物还可能产生实用的高比表面积聚合物颗粒，以增强氢气的可逆存储。该项目的成果将在重要的科学会议上报告，并在影响较大的期刊上发表。这项研究的一个重要成果是，接受过跨学科激烈互动培训的学生。在新型功能聚合物材料的科学开发中，学科和跨学科培训的紧密结合将使学生为进入科学大军做好充分准备，为促进国家的技术发展做出重要贡献。技术总结本项目中描述的研究重点是制备和研究新型的半刚性、空间密集和精确功能化的纳米多孔超交联聚合物材料。将交替共聚物中的半刚性链段精确地插入到超交联聚合物颗粒中，可提供新的化学主链单元来改变网络系统的性能。从严格交替的序列精确控制官能团的放置将实现独特的固态结构，这些结构有望提供对所得到的网络的物理性质的良好控制。对于超交联体系，这些半刚性单元在超交联化步骤中减缓了孔洞的坍塌。计算协作将有助于指导设计更高表面积功能粒子的基本原理的发展。这些新型的超高交联聚合物材料将具有高比表面积和高密度的官能团，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。比较半刚性链硬化序列和空间拥挤程度较低的功能共聚物序列将有助于阐明链刚性对基本结构性质关系的作用。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酚基精确包裹在聚合物主链上的超交联聚合物材料。预计这些新的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。含有芳香胺的超交联纳米多孔聚合物颗粒也将成为目标，并研究它们的储氢潜力。

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.