Circularizing Squarate-Based Materials: Novel Dynamic Networks

非技术总结该项目寻求开发下一波可持续聚合物，将可持续性与材料耐用性和实用性相结合。一个中心目标是克服目前聚合物科学中的二分法，在这种二分法中，可回收和可再加工的材料往往缺乏稳定性，而更坚固的材料由于其长期的环境持久性而导致负面后果。通过创新的设计和精确的分子操纵，该项目旨在开发既可长期使用又可天生可修复的聚合物，同时保持其坚固的性质以及对溶剂和高温的耐受性。这项研究将探索未得到充分利用的化学部分的关键分子参数，该部分将支配聚合物的生命周期-从合成到降解-平衡可加工性和性能。该项目的成功将导致需要较少频繁更换的材料，从而减少浪费并促进可持续性。该项目的关键组成部分包括针对当地各级学生的教育和外展活动，以及在新兴的化学和聚合物科学领域对研究生和本科生的培训和专业发展。技术总结本研究集中在四个具体目标上，共同寻求扩大共价适应材料(CAN)的能力。目的1研究使用侧链方酸酯作为一种新型的罐头动态交换机制，以提高玻璃体材料无催化剂交换化学的多样性。目的2探讨侧基方酰胺对超分子聚合物网络的影响，旨在了解方酰胺对网络性质和响应行为的影响。目标3中的工作将结合方酰胺和乙烯基氨基甲酸酯交换来生成动态共价和超分子的材料，旨在说明通过直接方法可以获得的增强性能。目标4旨在通过逐步增长缩聚开发一种新的动态交换方法，旨在为罐头引入独特的交换化学。这项研究采用了一套全面的分子操作，旨在阐明基本的结构-性质关系。该方法的模块化为理解链结构、拓扑结构和官能度在缔合交联聚合物的动态行为中的作用提供了一个可行的平台。这项研究的科学影响范围更广，通过设计具有更长寿命和可回收利用的聚合物来促进可持续性。这项工作将动态网络的好处扩展到新的交换机制，提供了一条通往可持续材料的替代途径。教育目标包括将该项目作为下一代科学家的培训基地。学生将获得各种合成和材料表征方法的专业知识，对聚合物科学的当代和基础方面有一个平衡的理解。一项多管齐下的外展计划旨在培养人们对科学的兴趣，并扩大对科学的参与。该计划包括研究经验，重点是代表性不足的少数族裔。通过将科学研究与教育和推广活动相结合，该项目旨在为聚合物科学领域做出重大贡献，同时也满足更广泛的社会需求。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

NON-TECHNICAL SUMMARYThis project seeks to develop the next wave of sustainable polymers, merging sustainability with material durability and practicality. A central objective is to overcome the current dichotomy within polymer science wherein recyclable and reprocessable materials often lack stability, while more robust ones lead to negative consequences because of their long-term environmental persistence. Through innovative design and precise molecular manipulation, this project aims to develop polymers that offer both long-term usability and innate reparability while maintaining their robust nature and resistance to solvents and high temperatures. The research will explore the critical molecular parameters of an underutilized chemical moiety that will govern polymer lifecycle—from synthesis to degradation—balancing processability with performance. The success of this project will lead to materials that require less frequent replacement, thereby reducing waste and promoting sustainability. Critical components of this project involve educational and outreach activities directed toward local students of all levels, as well as training and professional development of graduate and undergraduate students in emerging areas of chemistry and polymer science.TECHNICAL SUMMARYThe research focuses on four specific aims that collectively seek to expand the capabilities of covalent adaptable materials (CANs). Aim 1 investigates using pendent squarate esters as a novel dynamic exchange mechanism for CANs to improve the diversity of catalyst-free exchange chemistries for vitrimer materials. Aim 2 will explore the influence of pendent group squaramides on supramolecular polymer networks, aiming to understand how squaramides contribute to network properties and responsive behavior. The work in Aim 3 will combine squaramide and vinylogous urethane exchange to generate materials that are both dynamic-covalent and supramolecular, aiming to illustrate the enhanced properties that can be attained through straightforward methods. Aim 4 seeks to develop a new dynamic exchange approach through step-growth polycondensation, aiming to introduce unique exchange chemistry for CANs. The research employs a comprehensive set of molecular manipulations designed to elucidate fundamental structure-property relationships. The modularity of the approach provides a viable platform for understanding the roles of chain structure, topology, and functionality in the dynamic behavior of associatively crosslinked polymers. The scientific broader impacts of this research contribute to sustainability by designing polymers with longer life spans and recyclability. The work extends the benefits of dynamic networks to new exchange mechanisms, offering an alternative route to sustainable materials. The educational goals include this project serving as a training ground for the next generation of scientists. Students will acquire expertise in various synthetic and materials characterization methods, gaining a balanced understanding of both contemporary and foundational aspects of polymer science. A multi-pronged outreach program aims to foster excitement and broaden participation in science. The program includes research experiences with a focus on underrepresented minorities. By integrating scientific research with educational and outreach activities, the project aims to make a significant contribution to the field of polymer science while also addressing broader societal needs..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.