Synthetic Phosphorus Chemistry: The Systematic Development of Phosphorus-Containing Molecules and Polymers

合成磷化学：含磷分子和聚合物的系统发展

• 批准号: RGPIN-2020-06506
• 负责人: Gates, Derek
• 金额: $ 5.76万
• 依托单位: University of British Columbia
• 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=747871
• 关键词: Synthetic; Phosphorus; Chemistry; Systematic; Development

This goal of this research proposal is to systematically develop the chemistry of phosphorus and its compounds. Phosphorus is an important element, not only being essential for life but being used in a wealth of commercial products. The primary objective of our work is to develop polymers that contain phosphorus as a key component of the main chain. Most polymers in use today are comprised of chains containing carbon, oxygen, and/or nitrogen atoms in well-defined sequences. The incorporation of phosphorus into a polymer provides a additional chemical functionality due to its wide range of oxidation states, coordination numbers and bonding environments. Thus, phosphorus-containing macromolecules possess unique physical properties and chemical functionality that are not possible with solely organic polymers. For instance, phosphorus can reversibly bind to metals, thereby potentially providing access to a polymeric on-off switch. Despite the exciting prospects for phosphorus-containing polymers, they are still extremely rare. The key challenge to the widespread usage of P-containing polymers is the lack of general synthetic routes to incorporate inorganic elements into long chains. The addition polymerization of the C=C bond of olefins is perhaps the most important method of industrial polymer production being used to make polyethylene, polypropylene polystyrene, acrylics, and Teflon, to name a few. It was long believed that heteroatom-containing multiple bonds were not suited for addition polymerization methods. We were the first to extend addition polymerization to P=C bonds. In doing so, we discovered that P=C bonds are fascinating building blocks for a variety of new molecules and materials. The development of P=C molecules and polymers comprises a key topic of this proposal, including in new areas such as self-healing materials. We will also develop an entirely new area of heteroatom analogues of poly(isoprene) and related dienes. Polyisoprene is natural rubber, a hugely important commercial going back to the discovery of Goodyear. By polymerizing phosphorus-versions of natural rubber, we are opening up huge possibilities of functional versions of natural rubber (including flame retardancy). In a final area of pursuit, we are developing p-conjugated polymers with unique photophysical properties. The presence of phosphorus in these materials can function as a chemical switch whereby the luminescence of the polymer may be turned on and off through the binding to certain metal analytes. Thus, these materials are attractive as sensors. In closing, the work proposed herein further expands the fascinating chemistry of phosphorus. This work will lead to gains in fundamental knowledge of inorganic chemistry and polymer science, and will provide a foundation for future technological applications.

该研究建议的目标是系统地发展磷及其化合物的化学。磷是重要的因素，不仅对生活至关重要，而且在大量商业产品中使用。我们工作的主要目的是开发包含磷作为主链的关键组成部分的聚合物。当今使用的大多数聚合物包括含有明确定义的序列中的碳，氧和/或氮原子的链。将磷掺入聚合物中，由于其广泛的氧化态，配位数和粘结环境，提供了额外的化学功能。因此，含有磷的大分子具有独特的物理特性和化学功能，而仅具有有机聚合物。例如，磷可以可逆地与金属结合，从而有可能提供对聚合物开关开关的访问。尽管含磷的聚合物的前景令人兴奋，但它们仍然极为罕见。对含P的聚合物广泛使用的主要挑战是缺乏将无机元素纳入长链中的一般合成途径。烯烃的C = C键的添加聚合可能是最重要的工业聚合物产生方法，用于制造聚乙烯，聚丙烯聚苯乙烯，丙烯酸和特氟龙，仅举几例。长期以来，人们一直认为，含有杂种的多个键不适合添加聚合方法。我们是第一个将添加聚合扩展到P = C键的人。在此过程中，我们发现P = C键是各种新分子和材料的引人入胜的构建块。 P = C分子和聚合物的发展是该提案的关键主题，包括在新领域，例如自我修复材料。我们还将开发一个全新的聚（异戊二烯）和相关二烯类似物的全新领域。聚异丙烯是天然橡胶，这是一个非常重要的广告，可以追溯到固特异的发现。通过将天然橡胶的磷酸化合物聚合，我们正在为天然橡胶的功能性版本（包括阻燃性）开放。在追求的最后一个区域中，我们正在开发具有独特的光物理特性的P偶联聚合物。 The presence of phosphorus in these materials can function as a chemical switch whereby the luminescence of the polymer may be turned on and off through the binding to certain metal analytes.因此，这些材料作为传感器很有吸引力。结束时，本文提出的工作进一步扩大了磷的迷人化学。这项工作将带来无机化学和聚合物科学的基本知识的收益，并将为未来的技术应用奠定基础。