Amine-Borane Dehydropolymerisation for the Synthesis and Exploitation of Polyaminoboranes as Routes to New BN-Containing Materials

胺-硼烷脱氢聚合合成和开发聚氨基硼烷作为新型含氮化硼材料的途径

• 批准号: 2742579
• 金额: --
• 依托单位: University of York
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2022
• 资助国家: 英国
• 起止时间: 2022 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2742579
• 关键词: Amine; Borane; Dehydropolymerisation; Synthesis; Exploitation

Polyaminoboranes, -(H2BNHR)n-, are polymers with main-chain B-N backbones that are closely related to polyolefins, -(H2CCHR)n-. However, their fundamental materials and chemical properties are essentially unexplored, despite potential applications as processable precursors to high-performance boron-based ceramics and hex-boron nitride. This is because the challenging combination of efficient and robust organometallic catalyst systems that give polymer of controllable molecular weight and dispersity is missing. However, recent results from the Weller lab have demonstrated a significant advance in understanding and harnessing both organometallic catalyst design and mechanism, and the controlled amine-borane dehydropolymerisation "to order" is now a possibility. The ambitious objectives of this PhD are to develop robust, scalable, routes to bespoke polyaminoboranes, that allows for their wider materials exploitation. New group 9 (Co, Rh, Ir) transition metal catalyst systems will be synthesised and explored for polymer synthesis of exciting new "BN" polymeric materials, through a mechanism-led design strategy. By targeting the desirable metrics of control of polymer chain length and dispersity and cost and practicality of use, catalyst systems that operate on larger scale will be developed. Taking these forward into materials discovery, user friendly methods that allow for the use of these polymers as molecular precursors to new materials will be explored. Low temperature processing will lead to a variety of exciting new "BN" materials where the polymer characteristics (using the catalysts developed) will help define the materials properties of the resulting technologically important materials, especially 3D BN materials: hexagonal boron nitride and boron carbon nitride have very interesting optical, electronic, thermal and chemical properties. There will be a cycle of innovation, with promising leads in materials chemistry leading to the refinement of new and known catalyst systems. The project is collaborative between the groups of Andrew Weller (York, catalysis) and Dr Richard Douthwaite (York, inorganic materials synthesis and characterisation). The PhD student will become expert in a wide range of techniques, that will allow them to develop new organometallic catalyst systems (synthesis), detailed kinetics and mechanism studies, and then take these through to materials synthesis and characterisation. In particular skills will be developed in: organometallic synthesis, elucidation of mechanism in catalysis, NMR spectroscopy, x-ray crystallography and materials synthesis and characterisation techniques. At the end of the PhD the candidate will have broad and deep expertise in a wide range of fundamental, and more applied, organometallic/inorganic materials chemistry techniques.

聚氨基硼烷，-(H2BNHR)n-，是具有主链B-N主链的聚合物，与聚烯烃-(H2CCHR)n-密切相关。然而，尽管它们有可能作为高性能硼基陶瓷和六氮化硼的可加工前体，但它们的基本材料和化学性质基本上尚未被探索。这是因为缺乏有效且强大的有机金属催化剂系统的挑战性组合，这些催化剂系统可以提供可控分子量和分散性的聚合物。然而，韦勒实验室的最新结果表明，在理解和利用有机金属催化剂设计和机理方面取得了重大进展，“按订单”控制胺-硼烷脱氢聚合现在成为可能。该博士的雄心勃勃的目标是开发强大的、可扩展的定制聚氨基硼烷路线，从而实现更广泛的材料开发。通过机制主导的设计策略，将合成和探索新的第 9 族（Co、Rh、Ir）过渡金属催化剂体系，用于令人兴奋的新型“BN”聚合物材料的聚合物合成。通过以控制聚合物链长度和分散性以及成本和使用实用性的理想指标为目标，将开发更大规模运行的催化剂系统。将这些推进到材料发现中，将探索用户友好的方法，允许使用这些聚合物作为新材料的分子前体。低温加工将产生各种令人兴奋的新型“BN”材料，其中聚合物特性（使用开发的催化剂）将有助于定义所得技术重要材料的材料特性，特别是 3D BN 材料：六方氮化硼和碳氮化硼具有非常有趣的光学、电子、热学和化学性质。将会出现一个创新周期，材料化学领域有希望的领先优势将导致新的和已知的催化剂系统的完善。该项目是 Andrew Weller（约克，催化）和 Richard Douthwaite 博士（约克，无机材料合成和表征）小组之间的合作。博士生将成为多种技术的专家，这将使他们能够开发新的有机金属催化剂系统（合成）、详细的动力学和机理研究，然后将其用于材料的合成和表征。具体技能将在以下领域得到发展：有机金属合成、催化机制阐明、核磁共振波谱、X 射线晶体学以及材料合成和表征技术。在博士学位结束时，候选人将在广泛的基础和更多应用的有机金属/无机材料化学技术方面拥有广泛而深入的专业知识。