EAGER: Poly(Ionic Liquids)

技术概述：室温离子液体（RTILs）是具有低熔点（通常低于室温）的盐，通常由季磺酸、磷或铵（咪唑、吡啶、吡啶）阳离子与低路易斯碱度阴离子（BF4-、PF6-、CF3SO3- (CF3SO2)2N-等）配对组成。目前，人们正在探索RTILs在锂离子电池、燃料电池、电容器、太阳能电池和致动器等先进电化学设备中的应用。由于离子液体的阴离子和阳离子组分都具有迁移性，因此有人提出，如果将溶剂化膜或传统的离子液体替换为成膜的离子液体聚合物，其中离子的迁移性受到限制，则这些装置的功能可能会得到改善。然而，当离子液体中阴离子和阳离子组分的迁移率因掺入聚合物体系而降低时，离子电导率也会受到很大影响。这种限制可以通过降低纳米结构、精密嵌段共聚物和聚合物共混物中离子扩散的维度来调解。本提案概述了离子液体1,3-二烷基-4-和5-乙烯基咪唑盐的合成和表征的选择，这些离子液体易于均聚或在各种乙烯基和丙烯酸共聚物体系中作为嵌段序列并入。此外，还强调了含有这些咪唑类聚合物的聚合物共混物和嵌段共聚物体系的潜在装置效用。该研究的具体目标是合成和表征由1-甲基-4-和5-乙烯基咪唑、2-烷基-1-甲基-4-和5-乙烯基咪唑和1-甲基-4-和5-乙烯基咪唑-2-丙烷磺酸盐衍生的非对称非质子离子液体单体家族；阐明这些单体的均聚、无规共聚和嵌段共聚的选择；表征这些单体和聚合物的热学和电化学性能；研究了1,3-二烷基-4-乙烯基咪唑盐聚合物与PVF2共混物的热学、电学性能和形貌。非技术概述：室温离子液体（RTILs）是具有低熔点的盐，通常低于室温。如今，人们正在探索RTILs在锂离子电池、燃料电池、电容器、太阳能电池和致动器等先进电化学设备中的应用。然而，在实际应用中只取得了有限的成功。由于RTILs的液态特性，如果用成膜离子液体聚合物代替RTILs，其在商用器件中的功能可能会得到改善。然而，在聚合物体系中掺入通常会导致离子电导率的大幅下降。这一限制可能在精确的二维或一维纳米材料中被克服。本提案概述了从离子液体聚合物衍生的纳米材料的合成和表征的选择。具体的研究目标是合成和表征新的离子液体单体；阐明纳米复合材料制备的选择；并对这些材料的形貌、热性能和电化学特性进行了评价。在本提案中描述的新型材料，可以用聚（离子液体）的代理制造，可能是离子液体系统在从锂离子电池到光伏和燃料电池等坚固的轻型电子设备中的商业应用的关键。最近有报道称，咪唑基RTILs是碳纳米管分散的优良溶剂，并且在分散后碳纳米管的固有结构和性能可以通过利用这些新的聚离子液体转化为实用的器件选择。这项研究将在罗彻斯特理工学院（RIT）进行，这是一所综合性大学，提供化学和理学硕士学位，并为研究生和本科生提供有意义的研究经验。3名研究生和2名本科生将直接接受培训和指导。此外，PI将指导锡拉丘兹/RIT的一名暑期学生，NSF路易斯斯托克斯少数民族参与联盟-北部联盟，以及一名ACS项目SEED学生。与Peggy Cebe（塔夫茨大学）的独特合作，表征聚合物复合材料的晶体习惯，并为耳聋和听力障碍学生提供研究经验，也将得到支持。

TECHNICAL SUMMARY:Room temperature ionic liquids (RTILs) are salts with low melting points (often below room temperature), and are typically comprised of quaternary sulfonium, phosphonium, or ammonium (imidazolium, pyridinium, pyrrolidinium) cations paired with anions of low Lewis basicity (BF4-, PF6-, CF3SO3- (CF3SO2)2N-, etc.). Today the utility of RTILs in advanced electrochemical devices ranging from lithium ion batteries, to fuel cells, capacitors, solar cells and actuators is being explored. Because of the mobility of both the anionic and cationic components of ionic liquids, it is proposed that the function of such devices might be improved if solvated membranes or conventional ionic liquids were replaced by film-forming ionic liquid polymers in which the mobility of the ions is constrained. However, when the mobility of the anionic and cationic components in ionic liquids is reduced by incorporation in a polymer system, ionic conductivity is also substantially impacted. This limitation can possibly be mediated by reduction of the dimensionality of ion diffusion in nanostructured, precision block copolymers and polymer blends. The present proposal outlines options for the synthesis and characterization of ionic liquid 1,3-dialkyl-4- and 5-vinylimidazolium salts that are amenable to facile homopolymerization or incorporation as block sequences in a wide variety of vinyl- and acrylic copolymer systems. In addition, the potential device utility of polymer blends and block copolymer systems containing these imidazolium polymers is highlighted. Specific goals of the research are to synthesize and characterize families of dissymmetric, aprotic ionic liquid monomers formally derived from 1-methy-4- and 5-vinylimidazoles, 2-alkyl-1-methyl-4- and 5-vinylimidazoles and 1-methyl-4-and 5-vinylimidazole-2-propane sulfonate; elucidate options for the homopolymerization, random copolymerization and block copolymerization of these monomers; characterize the thermal and electrochemical properties of these monomers and polymers; and, study the thermal and electrical properties, and morphology of blends of polymers of 1,3-dialkyl-4-vinylimidazolium salts with PVF2.NON-TECHNICAL SUMMARY:Room temperature ionic liquids (RTILs) are salts with low melting points, often below room temperature. Today, the utility of RTILs in advanced electrochemical devices ranging from lithium ion batteries, to fuel cells, capacitors, solar cells and actuators is being explored. Nevertheless, only limited success has been achieved in practical applications. Because of their liquid state, the function RTILs in commercial devices might be improved if they were replaced by film-forming ionic liquid polymers. However, incorporation in a polymer system typically results in a substantial drop in ionic conductivity. This limitation can possibly be overcome in precision 2-D or 1-D nanomaterials. The present proposal outlines options for the synthesis and characterization of nanomaterials derived from ionic liquid polymers. Specific goals of the research are to synthesize and characterize new ionic liquid monomers; elucidate options for the preparation of nanocomposites; and, evaluate the morphology, thermal properties and electrochemical characteristics of these materials.Novel materials, that can be fabricated with the agency of the poly(ionic liquids), described in the present proposal, might be the key to commercial utility of an ionic liquid system in robust light-weight electronic devices ranging from Li ion batteries to photovotaics and fuel cells. Recent reports that imidazolium-based RTILs are excellent solvents for the dispersion of carbon nanotubes, and that the intrinsic structure and properties of the carbon nanotubes are retained after dispersion might be translated into practical device options by utilizing these new poly(ionic liquids). The research will be carried out at the Rochester Institute of Technology (RIT), a comprehensive university, offering terminal M.S. degrees in Chemistry and MS&E, and providing meaningful research experiences to graduate and undergraduate students alike. Three graduate students and two undergraduate students will be directly trained and mentored. In addition, the PI will mentor a summer student in the Syracuse/RIT, NSF Louis Stokes Alliance for Minority Participation - Upstate Alliance, and an ACS Project SEED student. A unique collaboration with Peggy Cebe (Tufts University), characterizing the crystal habit of polymer composites and providing research experiences to deaf and hard-of-hearing students will also be supported.