EAGER: CAS: Metal Mediated Perfluoroalkyl Halide Activation towards Functional Group Interconversion and Coordination Polymerization of Fluoroalkenes

在化学系大分子，超分子和纳米化学项目的支持下，Alexandru D。康涅狄格大学的Asandei正在开发合成氟化聚合物的新方法。 与传统塑料不同，通常不易燃的氟化聚合物不仅具有高的耐化学性和耐热性，而且还具有非常重要的电子性能，使其在建筑和建筑、汽车、航空和航天工业应用中不可或缺。 本研究将致力于开发高效的合成方法来制备具有不同结构和功能的含氟聚合物。 该项目将为合成聚合物化学的本科生和研究生提供培训和教育，并为康涅狄格大学向行业专业人士提供的远程学习课程开发教育材料。 外联活动将侧重于让少数民族和女高中生参与研究，并将通过与高中教师合作来完成。 氟化烯烃是可控自由基聚合或配位聚合中最具挑战性的单体之一。这是由于它们的低固有反应性、它们的聚合物链端的低活性以及特别是由于缺乏用于这种反应的适当化学，包括引发剂和催化剂。因此，复杂的氟化结构的合成、表征和应用远远落后于那些由非氟化单体衍生的。这项研究将集中在新的氟化学的发展，以克服这些不足之处。过渡金属催化剂将被开发并用于将惰性全氟化烷基卤化物相互转化为在含氟单体的自由基或离子聚合的引发和控制中更容易均裂或异裂的那些。这些研究将包括催化循环的详细机理研究，旨在将反应参数（氟化烷基-拟卤素键的强度、单体、金属、配体、溶剂和温度）与聚合动力学相关联。该研究旨在提供具有独特性能的新型聚合物，以及在污染性全氟烷基物质的再循环/升级中的潜在应用。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry, Alexandru D. Asandei of the University of Connecticut is developing new approaches to the synthesis of fluorinated polymers. Unlike conventional plastics, the typically nonflammable fluorinated polymers display not only high chemical and thermal resistance, but also very important electronic properties which render them indispensable in building and construction, automotive, aeronautics and aerospace industrial applications. This research will focus on developing efficient synthetic methodology to prepare fluorinated polymers with different architectures and functionalities. This project will provide training and education to undergraduate and graduate students in synthetic polymer chemistry, and development of educational material for distance-learning programs offered by the University of Connecticut to industry professionals. Outreach activities will focus on involvement of minority and female high school students in research and will be accomplished via collaborations with high school teachers. Fluorinated alkenes are among the most challenging monomers for controlled radical or coordination polymerizations. This is due to their low inherent reactivity, the low activity of their polymeric chain ends and especially to the lack of appropriate chemistry for such reactions, including initiators and catalysts. Thus, the synthesis, characterization and applications of complex fluorinated architectures lag far behind those derived from nonfluorinated monomers. This research will focus on the development of novel fluorine chemistry to overcome these deficiencies. Transition metal catalysts will be developed and utilized to interconvert inert perfluorinated alkyl halides to ones more susceptible to homolytic or heterolytic cleavage in the initiation as well as in the control of radical or ionic polymerizations of fluoromonomers. The studies will include detailed mechanistic investigations of the catalytic cycle aiming at correlating reaction parameters (strength of fluorinated alkyl-pseudohalogen bond, monomer, metal, ligand, solvent and temperature) with polymerization kinetics. This research aims to provide novel polymers with unique properties as well as potential applications in the re/upcycling of polluting perfluoroalkyl substances.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.