Hydrofluoroethers (HFEs), Aryl-Based Fluorinated Alkoxides, Diaryl-perfluoropolyalkylethers (PFPAEs) for Theranostics and Extreme Temperature Aerospace Materials

用于治疗诊断和极端温度航空航天材料的氢氟醚 (HFE)、芳基氟化醇盐、二芳基全氟聚烷基醚 (PFP​​AE)

• 批准号: RGPIN-2022-05143
• 负责人: Friesen, Chadron
• 金额: $ 2.11万
• 依托单位: Trinity Western University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=747864
• 关键词: Hydrofluoroethers; HFEs; Aryl; Based; Fluorinated

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.

工作性质：形成和稳定全氟醇盐（PFA）历来是合成的挑战。然而，在2015年，我们在氢氟醚（HFE）衍生的非金属PFA（CnF 2nO-NR 4+）方面的开创性工作铺平了道路。于二零一九年，我们报告首次使用氟化银（I）作为温和的氢化方法来产生HFE。非金属PFAs具有热稳定性，可附着于我们在2020年报告的医药和农用化学品类似物上。我们还展示了PFAs用于制造高性能润滑聚合物（称为全氟聚烷基醚（PFPAE））的创新用途。在我们最初的工作基础上，我们提出了双重但相互关联的研究目标：在短期内1）构建正式无法获得的构建块（单体），并在长期内2）开发新的可再生协议，逐步从天然矿石氟石（CaF 2）中获得，以同时改善航空航天和医疗材料。研究的重要性：从芳基-HFE PFAs开发芳族封端的PFPAE单体是下一代工业化学家的有效培训基地，同时也极大地扩展了三个重要行业的材料途径：A）氟聚合物行业正在寻找可以容易地掺入可生物降解聚合物中的单体，以提高其温度性能，但仍保持环境降解。利用我们的技术，我们可以合成芳基-HFE PFA，形成独特的芳香族封端聚合物，适用于保护涂层、表面活性剂和废弃塑料的再利用。B）医疗行业需要更好的诊断和治疗药物输送装置（即治疗诊断学），用于个性化患者护理和亲脂性药物。使用芳基-HFE PFAs，我们可以为患者护理应用创建聚合物工具。亲脂性药物生产中特定的、快速的后期纯化的新方法对于提高产量和降低成本是理想的（目前40%的药物含有氟）。航空航天工业正在推动太空探索和火箭运输的可重复使用性的界限。需要新的材料来满足这些新的需求。一些太空应用需要化学物质在没有溶剂、热量和重力的情况下进行。通过使用机械化学方法在生物聚合物共混物中引入芳族封端的PFPFAE可以改善极端温度性能。预期结果：在接下来的5年里，我们将1）使用芳基-HFE PFAs开发新的芳族封端的PFPAE单体，用于航空航天材料和慢性疼痛治疗诊断学中的聚合物应用; 2）改进聚合物和/或药物的后期聚合方法，分别改善热性能或亲脂性。总之，我们将开发创新的氟化学品，以影响生物基航空航天材料和医疗监测系统。