Exploring room temperature dynamic covalent bonds in adaptive materials

探索适应性材料中的室温动态共价键

• 批准号: 2104694
• 负责人: Stuart Rowan
• 金额: $ 62.23万
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-05-01 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2104694&HistoricalAwards=false
• 关键词: Exploring; room; temperature; dynamic; covalent

PART 1: NON-TECHNICAL SUMMARY Polymers/plastics play a critical role in almost every aspect of our daily life. Generally, most plastics in everyday use are passive, that is, designed for a single purpose (e.g., food containers, plastic bags, or adhesives) and once used these plastics are thrown away and impact the environment. This project is focused on developing a class of adaptive polymers that have the ability to heal or change shape on demand. In addition, these materials have the ability to be reprocessed after use, and by controlling the temperature and time employed during reprocessing it is possible to tailor their physical properties (e.g., stiffness, elasticity, temperature response). The ability to precisely retool the material properties opens the door to targeting materials that can be easily and systematically changed by processing, which in turn expands the potential applications areas that they can be used for. The research is a mix of different disciplines within the polymer area, from chemistry to polymer processing and mechanical characterization. Importantly, this broad research approach provides students (at all levels) with wide-ranging educational experiences covering this swath of topics. Graduate students will participate in a two-year outreach training program to develop and refine their abilities to engage and effectively communicate with the general public. Using this training they will participate in a series of outreach events, including Junior Science Cafés, the No Small Matter Molecular Engineering Fair, as well as a number of programs aimed at outreach to students from local Chicago public schools. These outreach activities, in conjunction with additional integrated high-school and undergraduate research opportunities, are designed to increase the fraction of underrepresented minorities in science and engineering. PART 2: TECHNICAL SUMMARY Recent work by the Rowan group has shown that room temperature dynamic thia-Michael (tM) chemistry (based on benzalcyanoacetate/amide Michael acceptors) can be used to access mechanically robust polymer networks through a process coined dynamic reaction-induced phase separation (DRIPS). These phase separated dynamic materials exhibit properties such as healing, shape memory, and reversible adhesion. Furthermore, the exchange kinetics and thermodynamics of tM reactions can be systematically altered by the electronic nature of the tM acceptor, allowing an investigation of how the dynamic exchange properties impact both the phase-separated morphology and the overall materials properties of the network. The planned research investigates the manipulation of dynamic tM materials through annealing conditions, light exposure, and cross-reactivity with additional dynamic bonding systems. In addition, the phase separated morphology (and therefore mechanical properties) of these materials can be directly manipulated through thermal processing conditions (cooling rates, annealing steps, etc.). As such, the first goal of this work is aimed at developing fundamental structure / processing / morphology / property relationships in this class of adaptive materials. The second goal of this work is to develop photo-responsive dynamic tM bonds by taking advantage of the inherent E/Z isomerism of the benzalcyanoacetate/amide Michael acceptor structure, to give access to a new class of photo-activated dynamic materials. Finally, a new program will be initiated aimed at using a Systems Polymer Science approach (inspired by systems chemistry) to functional polymer design with the goal of accessing pluripotent polymers, namely polymer systems whose properties can be significantly altered upon exposure to chemical or environmental cues allowing them to be used in a wide variety of applications. To do this, the PI will investigate the potential of incorporating multiple communicating dynamic reaction cycles into polymer networks..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.

第1部分：非技术摘要聚合物/塑料在我们日常生活的几乎每个方面都起着至关重要的作用。通常，每天使用中的大多数塑料都是被动的，也就是说是为了一个目的而设计的（例如，食品容器，塑料袋或粘合剂），一旦使用这些塑料就会扔掉并影响环境。该项目的重点是开发一类自适应聚合物，这些聚合物能够按需治愈或改变形状。另外，这些材料在使用后具有重新处理，并且通过控制使用的温度和时间，可以调整其物理特性（例如刚度，弹性，温度响应）。精确修复材料属性的能力为靶向材料打开了大门，可以通过处理可以轻松而系统地改变，从而扩大了可以使用的潜在应用领域。研究是聚合物区域内不同学科的混合，从化学到聚合物加工和机械表征。重要的是，这种广泛的研究方法为学生（各个层面）提供了涵盖这一主题的广泛教育经验。研究生将参加为期两年的推广培训计划，以发展和完善其与公众互动并有效沟通的能力。他们将使用此培训参加一系列的外展活动，包括初级科学咖啡馆，不小的分子工程博览会，以及旨在向当地芝加哥公立学校的学生推广的许多计划。这些外展活动与其他综合的高中和本科研究机会结合使用，旨在增加科学和工程中代表性不足的少数群体的比例。第2部分：Rowan组的技术总结表明，室温动态thia-Michael（TM）化学（基于苯甲酰氧乙酸/酰胺乙酸/酰胺迈克尔受体）可用于通过工艺固定的动态反应诱导的相位分离（DRIPS）来机械访问机械稳健的聚合物网络。这些相分离的动态材料具有愈合，形状记忆和可逆粘合剂等特性。此外，TM反应的交换动力学和热力学可以通过TM受体的电子性质系统改变，从而可以投资动态交换性能如何影响相分化的形态和网络的整体材料。该计划的研究通过退火条件，轻曝光以及与其他动态键合系统的交叉反应来调查动态TM材料的操纵。此外，可以通过热处理条件（冷却速率，退火步骤等）直接操纵这些材料的相分离形态（因此以及机械性能）。因此，这项工作的第一个目标旨在在此类的自适应材料中开发基本的结构 /加工 /形态 /财产关系。这项工作的第二个目标是通过利用苯甲酰乙酸苯甲酸苯甲酸苯甲酸苯甲酸酯/酰胺迈克尔受体结构的继承E/Z同构的利用来开发照片响应动态TM键，以访问一类新的光激活动态材料。最后，将开始使用系统聚合物科学方法（受系统化学的启发）进行功能性聚合物设计，以访问多能聚合物的目的，即聚合物系统，即在暴露于化学或环境提示的情况下，可以在各种应用中使用它们的属性。为此，PI将调查将多个通信动态反应周期纳入聚合物网络的潜力。该奖项反映了NSF的法定任务，并使用基金会的知识分子优点和更广泛的影响审查标准，被认为是通过评估而被视为珍贵的支持。

项目成果

Vinylogous Urea—Urethane Vitrimers: Accelerating and Inhibiting Network Dynamics through Hydrogen Bonding

乙烯基尿素 – 聚氨酯 Vitrimers：通过氢键加速和抑制网络动力学

• DOI: 10.1002/anie.202318412
• 发表时间: 2024
• 期刊: Angewandte Chemie International Edition
• 作者: Engelen, Stéphanie;Dolinski, Neil D.;Chen, Chuqiao;Ghimire, Elina;Lindberg, Charlie A.;Crolais, Alex E.;Nitta, Natsumi;Winne, Johan M.;Rowan, Stuart J.;Du Prez, Filip E.
• 通讯作者: Du Prez, Filip E.

Connecting Molecular Exchange Dynamics to Stress Relaxation in Phase-Separated Dynamic Covalent Networks

将分子交换动力学与相分离动态共价网络中的应力松弛联系起来

• DOI: 10.1021/acsmacrolett.3c00717
• 发表时间: 2024
• 期刊: ACS Macro Letters
• 影响因子: 7.015
• 作者: Dolinski, Neil D.;Tao, Ran;Boynton, Nicholas R.;Kotula, Anthony P.;Lindberg, Charlie A.;Petersen, Kyle J.;Forster, Aaron M.;Rowan, Stuart J.
• 通讯作者: Rowan, Stuart J.

Accessing pluripotent materials through tempering of dynamic covalent polymer networks

通过动态共价聚合物网络的回火获得多能材料

• DOI: 10.1126/science.adi5009
• 发表时间: 2024
• 期刊: Science
• 影响因子: 56.9
• 作者: Boynton, Nicholas R.;Dennis, Joseph M.;Dolinski, Neil D.;Lindberg, Charlie A.;Kotula, Anthony P.;Grocke, Garrett L.;Vivod, Stephanie L.;Lenhart, Joseph L.;Patel, Shrayesh N.;Rowan, Stuart J.
• 通讯作者: Rowan, Stuart J.