CAS: Terpene-Derived Polymers as Platforms for Structure-Property Studies of Sustainable Materials

非技术总结：迫切需要了解生物基聚合物的化学结构和整体物理性质之间的内在关系。这一点尤其正确，因此生物衍生材料可以被设计成反映石油基塑料的特性。萜烯显示出丰富多样的结构，是制备聚合物的宝贵基石，使其能够进行这种系统的结构-性质研究。这一建议需要合成从萜烯原料衍生的新型聚合物，以及表征它们的基本性质，以便将分子和中尺度结构与性能联系起来。重点将致力于理解骨干连通性和取向如何调节萜烯基（co）聚合物的热性能和机械性能。在这项工作中获得的见解将加速具有精确定制特性和功能的生物衍生塑料的开发。此外，这项工作可以为如何利用独特的结构元素来设计具有目标性能的广泛聚合物提供新的思路。这项研究将与一项更广泛的努力相结合，以促进科学素养，并让州和国家层面的学术和公共社区参与进来。一项多方面的计划将通过将研究成果与现实世界的应用和挑战联系起来，制定新的课程倡议，促进协作学习，并通过基于网络的平台（即YouTube）提高科学素养。技术概述：迫切需要了解生物基聚合物丰富的结构复杂性与其物理性质之间的内在关系。在设计能够反映石油基塑料特性的生物衍生材料的背景下尤其如此。萜类化合物具有广泛的碳环结构，是制备聚合物的有价值的平台，可用于系统的结构性质研究。事实上，由刚性碳环基序组成的聚合物（例如，环烯烃共聚物）是具有独特（并且在某些情况下是可预测的）物理性质的诱人材料。不幸的是，可以纳入大分子结构的碳环范围有限，这极大地阻碍了系统地探索更微妙的结构-性质关系的努力。本研究旨在阐明环烯烃（co）聚合物萜类类似物的结构异构、骨架立体化学和体热力学性质之间的相互作用。这项工作有望极大地扩展聚合物科学的化学空间，并揭示对尚未开发的生物衍生聚合物家族的基本见解。从这项研究中获得的见解将加速具有精确定制性能和功能的生物衍生塑料（包括热塑性弹性体）的发展。这项研究将与一项更广泛的努力相结合，以促进科学素养，并让州和国家层面的学术和公共社区参与进来。一项多方面的计划将通过将研究成果与现实世界的应用和挑战联系起来，开发新的课程倡议，促进协作学习，并通过基于网络的平台（即YouTube）提高科学素养。该奖项反映了美国国家科学基金会的法定使命，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。

NON-TECHNICAL SUMMARY:There is a critical need to understand the intrinsic relationships between chemical structure and the bulk physical properties of bio-based polymers. This is especially true so that biologically-derived materials can be designed to mirror the properties of petroleum-based plastics. Terpenes, which display a rich variety of structures, are valuable building blocks for preparing polymers that lend themselves to such systematic structure-property studies. This proposal entails the synthesis of novel polymers that are derived from terpene feedstocks, as well as the characterization of their fundamental properties in order to connect molecular and mesoscale structure to performance. Emphasis will be devoted to understanding how backbone connectivity and orientation modulate the thermal and mechanical properties of terpene-based (co)polymers. The insights achieved during this work will accelerate the development of biologically-derived plastics with precisely tailored properties and functions. Moreover, this work could shed new light on how unique structural elements can be leveraged to design a wide range of polymers with targeted properties. This research will be integrated with a broader effort to promote science literacy and engage academic and public communities at the state and national levels. A multifaceted plan will develop new curriculum initiatives, promote collaborative learning, and promote science literacy through web-based platforms (i.e., YouTube) by connecting research outcomes to real-world applications and challenges.TECHNICAL SUMMARY:There is a critical need to understand the intrinsic relationships between the rich structural complexity of bio-based polymers and their physical properties. This is especially true in the context of designing biologically-derived materials that can mirror the properties of petroleum-based plastics. Terpenoids, which display a wide range of carbocyclic structures, are valuable platforms for preparing polymers that lend themselves to systematic structure-property studies. Indeed, polymers comprised of rigid carbocyclic motifs (e.g., cyclic-olefin copolymers) are enticing materials that exhibit unique (and, in certain cases, predictable) physical properties. Unfortunately, the limited scope of carbocycles that can be incorporated within macromolecular architectures has significantly hindered efforts to systematically probe more subtle structure-property relationships. This research seeks to elucidate the interplay between constitutional isomerism, backbone stereochemistry, and bulk thermomechanical properties in terpenoid analogues of cyclic olefin (co)polymers. The work is expected to dramatically expand the chemical space available to polymer science and reveal fundamental insights into an unexplored family of biologically-derived polymers. The insights gained from this research will accelerate the development of biologically-derived plastics (including thermoplastic elastomers) with precisely tailored properties and functions. This research will be integrated with a broader effort to promote science literacy and engage academic and public communities at the state and national levels. A multifaceted plan will develop new curriculum initiatives, promote collaborative learning, and promote science literacy through web-based platforms (i.e., YouTube) by connecting research outcomes to real-world applications and challenges..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.