Molecularly Porous Non-network Polymer Membranes with Superior Resistance to Physical Aging for Gas Separations

提案编号：1603414，PI：Guo，Ruilan标题：用于气体分离的具有上级物理老化抗性的分子多孔非网络聚合物膜气体分离是清洁能源工业中许多技术创新的核心（例如，H2纯化）和环境修复（例如，碳捕获）。膜技术利用了材料的选择性，由于其低能耗、模块化和可靠性，为复杂流中的分离提供了强有力的手段。快速和选择性的传输与可扩展性和长期耐用性相结合是理想分离膜材料的关键属性。然而，目前使用的聚合物膜经常受到气体渗透性和选择性之间的折衷的挑战，这主要是由于微孔性不足和/或微孔的宽尺寸分布随时间塌陷（称为物理老化）。该项目将专注于开发一种基于超刚性梯形聚合物家族的创新膜平台，该聚合物家族利用形状持久结构单元赋予的新特性来构建基于构型的不可塌陷分子多孔结构。新的膜将满足广泛的关键气体分离的需求。要解决的分离问题对于更有效地利用化石燃料和应对碳捕获方面的挑战具有重大意义。同样重要的是，该项目还将制作示范材料和流程，作为生动的教育和培训工具，供各级学生使用，包括研究生和本科生以及高中教师。通过教师研究经验（RET）的努力该计划及其推广活动将激发公众对材料研究的兴趣，通过其清洁燃料生产和碳捕获的目标，通过节能膜技术进行环境修复，从而实现社会重要性。该项目的总体目标是识别和阐明控制分子的关键材料的结构和功能特征。微孔聚合物的运输和物理老化性能。本项目的主要任务是通过将具有大体积桥头取代基的形状稳定的戊蝶烯单元共价键合到各种主链轮廓的聚合物中来合成超刚性梯形聚合物。然后，新材料将用于制造具有系统控制的加工条件的膜。表征工作将包括物理老化和自由体积结构的原子级检测，以与结构和工艺参数相关联，从而评估膜的气体传输性能和物理老化性能。通过膜的传输和老化行为来确定结构参数对分离性能的定量影响，从而建立基本的结构-性能关系来指导新膜的设计。该项目的成功实施将提供适用于各种关键气体分离的变革性膜材料。该项目将提供聚合物的局部构型和构象变化如何通过链内和链间以及超分子相互作用传播的基本理解，以构建具有最大分离生产率和效率以及长期耐用性的分子多孔膜。

Proposal Number: 1603414, PI: Guo, RuilanTitle: Molecularly Porous Non-network Polymer Membranes with Superior Resistance to Physical Aging for Gas SeparationsGas separations are central to many of the technological innovations in clean energy industries (e.g., H2 purification) and environmental remediation (e.g., carbon capture). Membrane technology, which takes advantage of materials selectivity, provides a powerful means to effect separations in complex streams because of its low energy consumption, modularity and reliability. Fast and selective transport combined with scalability and long term durability are key attributes of an ideal separation membrane material. However, currently used polymer membranes are frequently challenged by a tradeoff between gas permeability and selectivity largely due to insufficient microporosity and/or a broad size distribution of micropores that collapse over time (known as physical aging). This project will focus on developing an innovative membrane platform based on a family of super rigid, ladder-like polymers that exploit the novel properties imparted by shape-persistent structural unit to construct configuration-based non-collapsible molecularly porous structure. The new membranes will meet the needs for a broad range of critical gas separations. The separations to be addressed are of enormous significance to more efficiently exploit fossil fuels and to address the challenges in carbon capture. Equally important, the project will also produce exemplary materials and processes that will serve as vivid educational and training tools for students at all levels including graduate and undergraduate students and high school teachers. The efforts via the Research Experiences for Teachers (RET) program and its outreach activities will excite the general public about materials research that carries societal importance through its objectives of clean fuel production and carbon capture for environment remediation via energy efficient membrane technologies.The overarching goal of this project is to identify and to elucidate the key material's structural and functional features that control the molecular transport and physical aging properties of microporous polymers. The major task of this project is to synthesize super rigid ladder polymers via covalently bonding shape-persistent pentiptycene units with bulky bridgehead substitutions into various main polymer chain contour profiles. The novel materials will then be used to fabricate membranes with systematically controlled processing conditions. Characterization work will include physical aging and atomic-level detection of free volume architecture to correlate with structural and processing parameters to evaluate membrane gas transport properties and physical aging properties. The transport and aging behavior will be used to determine the quantitative effect of structural parameters on the separation performance to establish fundamental structure-property relationships to guide new membrane design. Successful execution of this project will deliver transformative membrane materials applicable for a broad range of critical gas separations. The project will provide fundamental understanding of how the polymer's local configurational and conformational variations propagate through intra- and inter-chain and supramolecular interactions to construct molecularly porous membranes with maximized separation productivity and efficiency as well as long term durability.