Synthetic Phosphorus Chemistry: The Systematic Development of Organophosphorus Molecules and Polymers

合成磷化学：有机磷分子和聚合物的系统发展

• 批准号: RGPIN-2015-04908
• 负责人: Gates, Derek
• 金额: $ 6.48万
• 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: 2016
• 资助国家: 加拿大
• 起止时间: 2016-01-01 至 2017-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=613247
• 关键词: Synthetic; Phosphorus; Chemistry; Systematic; Development

The research proposed herein aims 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. The properties and potential applications of a particular polymer are a direct consequence of the arrangement and type of atoms that make up the chain structure. Most polymers in use today are comprised of chains containing carbon, oxygen, and/or nitrogen atoms in well-defined sequences. The development of polymers composed of other elements is at its infancy, however, there is considerable promise for these so-called inorganic polymers due to their unique physical properties and chemical functionality. For example, the commercial polymer silicone, consisting of alternating silicon and oxygen atoms, has extreme flexibility and temperature stability that is unattainable with organic polymers. The key challenge to inorganic polymer development 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 have shown that the addition polymerization of the P=C bond in a phosphaalkene is a route to phosphorus-containing polymers. This is a subject that will be rigorously pursued during the next five years. The mechanism of this new polymerization reaction is still in question and our proposed investigations are outlined herein. We will also explore the synthesis of chiral phosphaalkenes that may be employed directly as ligands for transition metal-catalysis and small-molecule activation or as monomers to afford polymeric ligands for use in polymer-supported catalysis. In a final area of pursuit, we propose to develop new types of p-conjugated phosphorus-containing polymers that exploit the chemical functionality of phosphorus as a means to tailor the electronic properties for application in areas such as small molecule sensor materials. 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.

本文提出的研究旨在系统地发展磷及其化合物的化学。磷是一种重要的元素，不仅是生命所必需的，而且被用于大量的商业产品。我们工作的主要目标是开发含有磷作为主链关键组分的聚合物。特定聚合物的性质和潜在应用是构成链结构的原子的排列和类型的直接结果。目前使用的大多数聚合物由含有碳、氧和/或氮原子的链以明确的顺序组成。由其他元素组成的聚合物的发展仍处于起步阶段，然而，由于其独特的物理性质和化学功能，这些所谓的无机聚合物具有相当大的前景。例如，由交替的硅原子和氧原子组成的商业聚合物硅酮具有有机聚合物无法达到的极端柔性和温度稳定性。无机聚合物开发的关键挑战是缺乏将无机元素引入长链的通用合成路线。 烯烃的C=C键的加成聚合可能是用于制造聚乙烯、聚丙烯聚苯乙烯、丙烯酸树脂和特氟隆等的工业聚合物生产的最重要方法。长期以来，人们认为含杂原子的多重键不适合于加成聚合方法。我们已经表明，磷烯中P=C键的加成聚合是含磷聚合物的一条途径。这是一个将在今后五年中积极探讨的问题。这种新的聚合反应的机制仍然是一个问题，我们提出的调查概述在这里。我们还将探索手性磷杂烯烃的合成，其可直接用作过渡金属催化和小分子活化的配体或作为单体以提供用于聚合物支撑催化的聚合物配体。在追求的最后一个领域中，我们建议开发新型的p-共轭含磷聚合物，其利用磷的化学官能度作为一种手段来定制电子性质，以应用于诸如小分子传感器材料等领域。 最后，本文提出的工作进一步扩展了磷的迷人化学。这项工作将导致无机化学和聚合物科学的基础知识的收益，并将为未来的技术应用提供基础。