An Experimental Study of Structure-Property Relationships Governing Sorption, Transport, and Permeation of Small Molecules in Rodlike and Semi-Rodlike Aromatic Polyamides

该实验研究计划旨在探索一类新型高可溶性全芳香族聚酰胺的合成和气体吸附、传输和渗透特性，这些聚酰胺具有无杆（可能是介源的）骨架或半棒状骨架和结构元素，这些结构元素可能是进一步反应的前体，如交联或悬垂刚性或柔性基团的附着。这些基础研究的目标是发展一种更广泛和更微妙的结构修饰，有助于合理地剪裁超级膜和超级屏障。本论文的核心观点是，所提出的主要化学结构变化可能显著影响聚合物的上层结构（即聚合物链填充）、聚合物与渗透物的相互作用，进而强烈影响气体的吸附、传输和渗透特性。提出了一种具有取代基的高可溶性全芳聚酰胺的可控合成实验方案，取代基可用于交联聚合物或连接刚性或柔性侧链。这些聚合物的化学结构、物理性质和气体传输性质将被表征，以明确确定侧链和主链分子结构、侧链刚度以及交联对整体吸附、传输和渗透行为的影响。该研究项目将受益于与赫斯特塞拉尼斯公司（Hoechst Celanese Corporation）研究人员的合作，该公司是生产高性能、高势垒液晶聚合物的全球领导者。这项合作将包括每年由主要研究人员和与拟议项目有关的学生访问赫斯特，埃拉尼斯的设施。此外，赫斯特塞拉尼斯的员工每年都会访问北卡罗来纳州立大学几次，以协调我们的研究项目与他们的目标。此外，计算机建模和合成将由西班牙马德里高等科学研究委员会（CSIC）的科学与技术研究所的西班牙研究人员提供。这个小组在哈维尔·德·阿巴霍博士的指导下，在过去几年中与pi密切合作。这一合作研究项目已经产生了大约10篇与本提案中描述的聚合物类似的聚合物的合成和气体传输特性相关的研究论文。这次交流刺激了双方pi和学生的多次访问。合作将在拟议的研究计划中扩大，以利用我们西班牙合作伙伴广泛的计算机建模能力和专业知识，以及他们在新型聚合物合成领域的丰富经验。＊＊＊

9402055 Freeman This experimental research program is designed to explore the synthesis and gas sorption, transport, and permeation properties of a new class of highly soluble wholly aromatic polyamides, having either ridded rod, possibly mesogenic, backbones or semi-rodlike backbones and structural elements which could be precursors for further reactions such as crosslinking or the attachment of pendent rigid or flexible groups. These fundamental studies are directed toward developing an expanded and more subtle repertoire of structural modifications useful for the rational tailoring of super-membranes and super-barriers. Central to the thesis under consideration is the notion that the proposed primary chemical structure variations could markedly influence polymer suprastructure (i.e. polymer chain packing), polymer-penetrant interactions, and, in turn, strongly affect gas sorption, transport, and permeation properties. An experimental program is proposed involving controlled synthesis of highly soluble wholly aromatic polyamides having substituents which could be used to crosslink the polymers or attach rigid or flexible side chains. The chemical structure, physicals properties, and gas transport properties of these polymers would be characterized to determine explicitly the influence of side and main chain molecular architecture and side chain stiffness, plus the potential for crosslinking, on the overall sorption, transport, and permeation behavior. This research program would benefit from collaborative interactions with researchers at the Hoechst Celanese Corporation, a world leader in the production of high performance, high barrier liquid crystalline polymers. This collaboration would involve several visits per year by principal investigators and students associated with the proposed program to Hoechst ,elanese facilities. Moreover, Hoechst Celanese personnel would visit NC State several times per year to coordinate the objectives of our research program with theirs. In addition, computer modeling and synthesis will be provided by Spanish researchers at the Instituto de Ciencia Y Tecnologia de Polimeros of the Consejo Superior de Investigaciones Cientificas (CSIC) in Madrid, Spain. This group, under the direction of Dr. Javier de Abajo, has worked very closely with the PIs during the past several year. This collaborative research program has already resulted in approximately 10 research publications related to the synthesis and gas transport characterization of polymers similar to the polymers described in this proposal. The exchange has stimulated several visits by PIs from both sides and students. The collaboration would be expanded in the proposed research program to take advantage of the extensive computer modeling capabilities and expertise of our Spanish partners as well as their extensive experience in the area of novel polymer synthesis. ***