RUI: Thiol-ene/yne Poly(ionic liquid) Networks for Separation and Electroactive Technologies

RUI：用于分离和电活性技术的硫醇-烯/炔聚（离子液体）网络

• 批准号: 1708632
• 负责人: Kevin Miller
• 金额: $ 23.39万
• 依托单位: Murray State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-07-01 至 2021-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1708632&HistoricalAwards=false
• 关键词: RUI; Thiol; ene; yne; Poly

NON-TECHNICAL SUMMARY:This RUI award supports fundamental research at Murray State University (MSU) in the area of electroactive materials while enhancing the education and training of undergraduate and high school students. The PIs will utilize a relatively novel, cost-effective, rapid-processing approach to prepare a library of polymers containing electrical charges with tunable thermal, mechanical, and conductive properties. Such charge-containing polymers have been implemented in a number of societally important applications, including batteries, fuel cells, power plant flue-gas separations, and pharmaceutical materials. From the polymer-property relationships established as a result of this work, the principal investigators (PIs) will explore the applicability of these new materials in carbon dioxide separation/capture, ion-sensing devices, and in the formation of electroactive fibers. The challenging work proposed here will be performed primarily by a team of undergraduate students from the rural counties of far-western Kentucky and surrounding communities with participation also of local high school students. Student participants will receive a rewarding, cutting-edge research experience that will deepen their understanding of and appreciation for scientific research, thus better preparing them for STEM-related majors, careers and/or pre-professional school. In addition to the hands-on laboratory training and education that these students will receive, the PIs will explore how the techniques/data acquired from this proposal will be used to develop new laboratory experiments to supplement current course offerings in organic, analytical, and polymer chemistry,and will further enhance the new Polymer and Materials Science degree track offered by the Department of Chemistry at MSU. TECHNICAL SUMMARY: This RUI award focuses on the development of a new class of poly(ionic liquid) (PIL) materials utilizing thiol-ene/yne click-photopolymerization with a strong focus on how changes in monomer structure and stoichiometry affect the thermal, mechanical, and conductive properties of the resulting PIL networks. The underlying hypothesis of this project is that thiol-ene/yne photopolymerization represents a significant advancement in the formation of solventless, one-part, homogeneous PIL networks due to the rapid and robust nature of the chemistry and the variability that exists with careful modification and selection of monomers. Specifically, fundamental structure-activity relationships will be established by varying the cation, anion, and thiol structures of the starting ionic liquid monomers and analyzing material properties such as glass transition temperature, thermal stability, crosslink density and ionic conductivity. Additionally, FTIR experiments will be conducted in order to explore how structural changes affect polymerization kinetics, as well as dielectric relaxation spectroscopy to elucidate the roles that chain dynamics and ion mobility play on the conductivities of the networks. Once fundamental relationships and kinetics are established, the PIs will explore the potential impact of these thiol-ene/yne PIL materials on a variety of important applications, including carbon dioxide separation/capture, as microchip electrophoresis devices for support of electro-osmotic flow, as membranes in ion-selective electrodes,and as electroactive fibers from electrospinning. The award will support a large number of undergraduate STEM students from the far-western Kentucky region and several local high school students, thereby expanding the educational impact and outreach of the university and department while enhancing the ability of the participating students to pursue a STEM-related career. Synthetic approaches, materials analyses and applications will provide student participants with rewarding research experiences, all while generating results that will be disseminated in internationally recognized, peer-reviewed journals and presented at professional meetings.

非技术概述：该奖项支持默里州立大学(MSU)在电活性材料领域的基础研究，同时加强对本科生和高中生的教育和培训。PI将利用一种相对新颖、经济高效、快速处理的方法来制备包含具有可调热、机械和导电特性的电荷的聚合物库。这种含电荷聚合物已在许多具有重要社会意义的应用中得到应用，包括电池、燃料电池、发电厂烟气分离和制药材料。根据这项工作建立的聚合物-性质关系，主要研究人员(PI)将探索这些新材料在二氧化碳分离/捕获、离子传感设备和电活性纤维形成中的适用性。这里提出的具有挑战性的工作将主要由来自肯塔基州偏远西部农村县和周边社区的本科生团队完成，当地高中生也将参与其中。学生参与者将获得有益的尖端研究体验，加深他们对科学研究的理解和欣赏，从而为他们进入STEM相关专业、职业和/或预科学校做好更好的准备。除了这些学生将接受的动手实验室培训和教育外，PIS还将探索如何利用从这项建议中获得的技术/数据来开发新的实验室实验，以补充现有的有机、分析和聚合物化学课程，并将进一步加强密歇根大学化学系提供的新的聚合物和材料科学学位课程。技术摘要：RUI奖的重点是开发一种新型的利用硫醇-烯/炔点击-光聚合的聚离子液体(PIL)材料，重点关注单体结构和化学计量比的变化如何影响所产生的PIL网络的热、机械和导电性能。该项目的基本假设是，硫醇-烯/炔的光聚合代表了形成无溶剂、一组分的均相PIL网络的重大进展，这是由于化学的快速和稳健的性质以及通过仔细修改和选择单体而存在的可变性。具体地说，通过改变起始离子液体单体的阳离子、阴离子和硫醇结构并分析材料性质，如玻璃化转变温度、热稳定性、交联度和离子导电性，将建立基本的结构-活性关系。此外，还将进行FTIR实验，以探索结构变化如何影响聚合动力学，以及介电弛豫光谱，以阐明链动力学和离子迁移率对网络电导率的影响。一旦建立了基本的关系和动力学，PI将探索这些硫醇/炔PIL材料在各种重要应用中的潜在影响，包括二氧化碳分离/捕获、作为支持电渗透流动的微芯片电泳设备、作为离子选择电极的膜以及作为电纺丝的电活性纤维。该奖项将支持来自遥远西部肯塔基州的大量STEM本科生和几名当地高中生，从而扩大大学和系的教育影响和外联，同时增强参与学生从事与STEM相关的职业的能力。综合方法、材料分析和应用将为学生参与者提供有益的研究经验，同时产生的结果将在国际公认的同行评议的期刊上传播，并在专业会议上公布。

项目成果

Designing Ionic Liquid-Derived Polymer Composites from Poly(Ionic Liquid)–Ionene Semi-interpenetrating Networks

• DOI: 10.1021/acsapm.1c00080
• 发表时间: 2021-03
• 期刊: ACS Applied Polymer Materials
• 影响因子: 5
• 作者: Kathryn E. O'Harra;George M. Timmermann;J. Bara;K. Miller

Influence of counteranion and humidity on the thermal, mechanical and conductive properties of covalently crosslinked ionenes

• DOI: 10.1016/j.polymer.2021.123641
• 发表时间: 2021-04
• 期刊: Polymer
• 影响因子: 4.6
• 作者: Nicholas C Bontrager;S. Radomski;Samantha P. Daymon;R. Johnson;K. Miller