CAREER: Precise Synthesis of Polymers with Tunable Properties Through Stereocontrolled Olefin Metathesis

职业：通过立体控制烯烃复分解精确合成具有可调性能的聚合物

• 批准号: 2238888
• 负责人: Quentin Michaudel
• 金额: $ 71.39万
• 依托单位: Texas A&M University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-06-01 至 2028-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2238888&HistoricalAwards=false
• 关键词: CAREER; Precise; Synthesis; Polymers; Tunable

With the support of the Macromolecular, Supramolecular and Nanochemistry program in the Division of Chemistry, Quentin Michaudel of Texas A&M University is developing catalytic methods that will provide access to polymers with specific main-chain stereochemistry across several families of macromolecules. Stereochemistry is a branch of chemistry that is concerned with the study of 3D spatial arrangements of atoms in a molecule and the manipulation thereof. In this research, systematic studies will first be conducted to design efficient metal catalysts based on ruthenium and optimize reaction conditions. The developed synthetic routes will then be utilized to prepare a variety of stereoregular polymers, including industrially relevant polyesters and polycarbonates. Finally, the stereoregularity of polymers is to be correlated with their thermal and mechanical properties, as well as their degradability. The education plan will complement and amplify research efforts by broadening access to chemical education. Laboratory opportunities will be built for students with autism spectrum disorder. The research team will also foster awareness and inclusiveness through outreach with local support groups supporting autistic children and their families. The activities will include visits to the chemistry department at Texas A&M University and demonstrations focused on polymer science. Additional outreach will expose students with disabilities to science through collaboration with the Aggie ACHIEVE (academic courses in higher inclusive education and vocational experiences) program developed at the university. This project will focus on the development of stereocontrolled polymerizations utilizing ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET). A variety of monomers will be investigated in processes relying on a combination of stereoselective ruthenium catalysts and external stimuli (light, temperature, and exogenous reagents) to yield macromolecules with variable, yet predictable, cis:trans ratios of olefins in the main chain. The stimuli will provide an external lever with which to modulate the overall stereochemistry of the olefinic backbone through activation of either the repeating units, the catalyst, or the chain end. The outlined processes have the potential to provide a high level of control over the 3D architecture of many families of polymers and should permit systematic studies of the influence of alkene stereochemistry upon the thermal, mechanical, and optical/electronic properties of the synthesized soft materials.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系高分子、超分子和纳米化学项目的支持下，德克萨斯农工大学的 Quentin Michaudel 正在开发催化方法，该方法将提供跨多个大分子家族的具有特定主链立体化学的聚合物。立体化学是化学的一个分支，涉及分子中原子的 3D 空间排列及其操纵的研究。在这项研究中，首先将进行系统研究，设计基于钌的高效金属催化剂并优化反应条件。开发的合成路线将用于制备各种有规立构聚合物，包括工业相关的聚酯和聚碳酸酯。最后，聚合物的立构规整性与其热性能、机械性能以及可降解性相关。该教育计划将通过扩大化学教育的机会来补充和扩大研究工作。将为患有自闭症谱系障碍的学生建立实验室机会。研究团队还将通过与支持自闭症儿童及其家庭的当地支持团体进行外展活动，提高认识和包容性。这些活动将包括参观德克萨斯农工大学化学系以及以聚合物科学为重点的演示。通过与大学开发的 Aggie ACHIEVE（高等包容性教育和职业体验学术课程）项目合作，额外的外展活动将让残疾学生接触科学。该项目将重点开发利用开环复分解聚合（ROMP）和无环二烯复分解（ADMET）的立体控制聚合。将在依靠立体选择性钌催化剂和外部刺激（光、温度和外源试剂）组合的过程中研究各种单体，以产生主链中烯烃顺式：反式比例可变但可预测的大分子。刺激将提供一个外部杠杆，通过激活重复单元、催化剂或链端来调节烯属主链的整体立体化学。概述的过程有可能对许多聚合物家族的 3D 结构提供高水平的控制，并且应该允许系统研究烯烃立体化学对合成软材料的热、机械和光学/电子性能的影响。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。