Sustainable Triblock Copolymers with Supramolecular Interactions for Improved Performance

第一部分： 非技术总结我们的社会对聚合物的石油原料的依赖具有以下缺点：有限的原材料供应、有害环境排放物和塑料废物的产生以及原料价格和可用性的不可预测性。尽管许多先前的研究已经开发了从各种资源（例如植物糖、植物油、植物萜烯、二氧化碳、多糖、松香和微生物聚酯）获得可持续材料的途径，但在其在社会中的广泛实施中仍然存在挑战。一个重要的挑战是，新聚合物必须满足现有材料的性能和性能预期，才能被采用。然而，从可持续来源开发的新聚合物很少是传统聚合物的简单替代品。该项目解决的持续挑战是，许多可持续聚合物具有对其性能产生重大不利影响并限制其使用的特征。在这个项目中开发的知识将提供一个克服这些限制的途径，使应用程序中广泛采用的潜力。 该项目还将利用推广计划，培养学生和公众对聚合物在社会中的重要作用及其对环境的影响的认识。材料日在UH计划，提供动手实验室经验的机会，将扩大与可持续聚合物的新模块。本科生和研究生将通过参与研究项目获得宝贵的经验。最后，可持续聚合物的示范将为休斯顿能源日节开发。第二部分： 从可持续来源开发具有上级物理性能和更大功能的先进聚合物材料是减少聚合物对环境影响的根本性重要挑战。植物油及其脂肪酸是聚合物的方便来源，因为它们广泛可用，易于官能化，并且没有毒性。包含植物油的脂肪酸的长烷基链对所得聚合物性质具有很大影响，其可通过选择植物油原料来调节。不幸的是，具有大体积组分的聚合物，例如脂肪酸衍生的聚合物的长烷基侧链，由于缺乏缠结而通常表现出差的机械性能。在这个项目中，超分子相互作用将被纳入植物油衍生的聚合物作为一种途径，以改善其机械行为。这项工作的中心假设是，在可持续的三嵌段共聚物中掺入超分子相互作用将导致一类新的可持续材料具有增强的物理性能。长链聚（甲基）丙烯酸酯将用官能团改性以促进氢键和离子相互作用。这些材料将作为阿坝三嵌段共聚物的中间嵌段引入。将量化材料的有效交联密度和粘弹性能。最后，将建立超分子相互作用的强度、动力学和类型与聚合物物理性质之间的关系。 这些材料将被探索为热塑性弹性体，形状记忆材料和自修复材料。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

PART 1: NON-TECHNICAL SUMMARYOur society's dependence on petroleum feedstocks for polymers has drawbacks of a limited raw material supply, generation of harmful environmental emissions and plastic waste, and unpredictability in feedstock prices and availability. Though many prior studies have developed routes to sustainable materials from a variety of resources such as plant sugars, plant oils, plant terpenes, carbon dioxide, polysaccharides, rosins, and microbial polyesters, challenges still persist in their broad implementation in society. One significant challenge is that new polymers must meet the performance and property expectations of existing materials in order to be adopted. However, new polymers developed from sustainable sources are rarely simple drop-in replacements for conventional polymers. The persistent challenge that this project addresses is that many sustainable polymers have features which significantly and adversely impact their properties and limit their use. The knowledge developed in this project will provide a route to overcoming these limitations, enabling the potential of widespread adoption in applications. This project will also use outreach programs to cultivate knowledge among students and the general public on the important role of polymers in society and their environmental impacts. The Materials Day at UH program, providing opportunities for hands-on laboratory experiences, will be expanded with new modules in sustainable polymers. Undergraduate and graduate students will gain valuable experiences through involvement in the research projects. Finally, demonstrations on sustainable polymers will be developed for the Houston Energy Day festival. PART 2: TECHNICAL SUMMARYDeveloping advanced polymeric materials from sustainable sources with superior physical properties and greater function is a fundamentally important challenge in reducing the environmental impact of polymers. Vegetable oils and their fatty acids are convenient sources for polymers due to their wide availability, ease of functionalization, and lack of toxicity. The long alkyl chains of the fatty acids comprising vegetable oils have a large impact on the resulting polymer properties, which are tunable through choice of vegetable oil feedstock. Unfortunately, polymers with bulky constituents, such as the long alkyl side-chains of fatty acid-derived polymers, typically exhibit poor mechanical performance due to lack of entanglements. In this project, supramolecular interactions will be incorporated into the vegetable oil-derived polymers as a route to improve their mechanical behavior. The central hypothesis of this work is that the incorporation of supramolecular interactions in sustainable triblock copolymers will lead to a new class of sustainable materials with enhanced physical properties. Long-chain poly(meth)acrylates will be modified with functional groups to promote hydrogen bonding and ionic interactions. These materials will be incorporated as the midblock of ABA triblock copolymers. The effective crosslink density and viscoelastic properties of the materials will be quantified. Finally, relationships between the strength, dynamics, and type of supramolecular interactions and the polymer physical properties will be established. These materials will be explored as thermoplastic elastomers, shape memory materials, and self-healing 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.