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，康涅狄格大学的Alexandru D.Asandei正在开发合成含氟聚合物的新方法。与传统塑料不同，典型的不可燃含氟聚合物不仅表现出高的化学和耐热性，而且还具有非常重要的电子性能，使其在建筑、汽车、航空和航空航天工业应用中不可或缺。这项研究将致力于开发高效的合成方法来制备不同结构和功能的含氟聚合物。该项目将为本科生和研究生提供合成聚合物化学方面的培训和教育，并为康涅狄格大学为行业专业人员提供的远程学习项目开发教材。外联活动将侧重于少数民族和女高中生参与研究，并将通过与高中教师的合作来完成。含氟烯烃是最具挑战性的自由基聚合或配位聚合单体之一。这是由于其固有的低反应性，其聚合链端的低活性，特别是由于缺乏适当的化学反应，包括引发剂和催化剂。因此，含氟化合物的合成、表征和应用远远落后于非含氟单体。本研究将致力于开发新型的氟化学来克服这些不足。过渡金属催化剂将被开发和利用来将惰性全氟烷卤化物在引发过程中转化为更容易发生均解或异解裂解的化合物，并用于控制氟单体的自由基聚合或离子聚合。这些研究将包括详细的催化循环机理研究，旨在将反应参数(氟化烷基仿卤键强度、单体、金属、配体、溶剂和温度)与聚合动力学相关联。这项研究旨在提供具有独特性能的新型聚合物以及在污染全氟烷基物质再循环/升级方面的潜在应用。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势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.