Grant: Discovery Grants Program - Individual

NATURE OF THE WORK: Forming and stabilizing perfluoroalkoxides (PFAs) has been historically challenging for synthesis. However in 2015, we paved the way with groundbreaking work in non-metal PFAs (CnF2nO-NR4+) derived from hydrofluoroethers (HFEs). In 2019, we reported the first use of silver(I) fluoride as a mild fluorination method to generate HFEs. Non-metal PFAs are thermally stabile and can be affixed to medicinal and agrochemical analogues reported by us in 2020. We also demonstrated an innovative use of PFAs for manufacturing high performance lubricating polymers known as perfluoropolyalkylethers (PFPAEs). Building upon our original works, we propose research objectives which are two-fold but yet interconnected: in the short-term 1) Construct formally unobtainable building blocks (monomers) and in the long-term 2) Develop new fluorination protocols incrementally derived from the naturally occurring ore, fluorospar (CaF2) to simultaneous improve aerospace and medical materials. WHY AND TO WHOM THE RESEARCH IS IMPORTANT: developing aromatic terminated PFPAE monomers from aryl-HFE PFAs is an effective training ground for the next generation of industry chemists and yet greatly expands material pathways in three important industries: A) The fluoropolymer industry is looking towards monomers which can be readily incorporated into biodegradable polymers to enhance their temperature performance but yet maintain environmental degradation. With our techniques we can synthesize aryl-HFE PFAs to form unique aromatic terminated polymers suitable as protective coatings, surfactants, and in the reuse of discarded plastics. B) The medical industry needs better diagnostic and therapeutic drug delivery devices (i.e. theranostics) for personalized patient care and lipophilic drugs. With aryl-HFE PFAs, we can create polymeric tools for patient care applications. New methods in specified, rapid late-stage fluorination in lipophilic drug manufacturing are desirable for yield improvements and lowering cost (40% of current drugs contain fluorine). C) Aerospace Industry is pushing the boundaries of space exploration and the reusability of rocket transport. New materials are required to handle these newer demands. Some of the space application need chemistries to perform without solvent, heat, and gravity. By introducing aromatic terminated PFPFAEs within biopolymeric blends using mechanochemical processes can improve extreme temperature performance. ANTICIPATED OUTCOMES: In the next 5 years, we will 1) Develop new aromatic terminated PFPAE monomers using aryl-HFE PFAs for polymer applications in aerospace materials and chronic pain theranostics; 2) Improve methodologies in late-stage fluorination of polymers and/or pharmaceuticals for improved thermal performance or lipophilicity, respectfully. In summary, we will develop innovative fluorine chemistries to impact bio-based aerospace materials and medical monitoring systems.