CAREER: SusChEM: Polymers Derived from Vegetable Oils: Synthesis, Structure-Property Relationships and Sustainability

技术概述：该项目的目标是解决关键的科学挑战，使甘油三酯植物油能够广泛应用，作为具有可调物理性能的聚合物的环境友好来源。植物油资源丰富、价格低廉、易于功能化，是一种很有吸引力的原料。这项研究计划围绕四个具体目标展开：植物油衍生聚合物合成技术的设计、植物油衍生聚合物结构-性质关系的研究、针对目标应用的生物质衍生纳米结构聚合物的开发以及生物质衍生聚合物的环境影响评估。这种方法将从合成策略开始，利用复分解化学和超分子相互作用来改变聚合物的化学结构。详细了解这些聚合物的结构-性能-功能关系将强调它们的热、机械和流变性能，目标是热塑性弹性体、刺激响应性和形状记忆材料。通过光谱和散射实验表征生物可再生聚合物中的热力学相互作用将允许对纳米级结构的先验预测。量化植物油衍生聚合物对环境的影响将指导未来的材料设计方面，纳入绿色工程原则。拟议工作的结果将为从植物油中设计功能聚合物提供路线图。这个项目将解决一些重大挑战。与石油衍生的单体相比，单体的笨重性质可能会导致合成方面的挑战，并对聚合物的物理性质产生关键影响。生物质衍生材料可能表现出生物降解性和氧化降解性。特定相互作用的存在可能需要超越平均场理论来对这些聚合物及其混合物进行建模。重要的是，这些新材料的结构-性质-功能关系预计将与石油衍生聚合物的大量文献中描述的显著不同。非技术综述：世界石油供应有限，未来有必要利用可持续资源生产聚合物。来自农业来源的聚合物为社会提供了提高生物降解性、减少环境影响和利用每年可再生资源的好处。在许多情况下，已经成功地开发了商品塑料的替代品；然而，将生物质作为纳米结构材料的来源的研究相对较少。具有纳米结构的聚合物具有可调的物理性能，这最终导致材料功能的重要进展。拟议的研究将使人们能够从一种广泛可用的农业来源：植物油中实施聚合物。此外，该项目将培养学生、教育工作者和普通公众关于能源、可持续性和材料对环境影响之间的关系的知识，方法是让代表不足的群体广泛参与外联计划，包括妇女、西班牙裔学生和其他少数群体的学生。将开展以下活动：将为当地社区大学生制定以研究为重点的外联计划；将扩大针对目标当地高中学生和教师的实践教育计划；将在研究项目中指导高中生、本科生和研究生；将为休斯顿自然科学博物馆设计关于可持续聚合物的展览。

TECHNICAL SUMMARY:The objective of this project is to address key scientific challenges enabling the broad implementation of triglyceride vegetable oils as an environmentally beneficial source for polymers with tunable physical properties. Vegetable oils are an attractive feedstock, based on their abundance, low cost, and ease of functionalization. This research plan is structured around four specific aims: design of synthetic techniques for vegetable oil-derived polymers, investigation of structure-property relationships in vegetable oil-derived polymers, development of biomass-derived nanostructured polymers for targeted applications, and assessment of the environmental impact of biomass-derived polymers. This approach will begin with synthetic strategies to modify the chemical structure of the polymers, employing metathesis chemistry and supramolecular interactions. A detailed understanding of structure-property-function relationships for these polymers will emphasize their thermal, mechanical, and rheological properties, targeting thermoplastic elastomers, stimuli-responsive and shape memory materials. Characterization of the thermodynamic interactions through spectroscopy and scattering experiments in the biorenewable polymers will allow for the a priori prediction of the nanoscale structure. Quantification of the environmental impacts of vegetable oil-derived polymers will guide future material design aspects, incorporating green engineering principles. The outcomes of the proposed work will provide a roadmap for the design of functional polymers from vegetable oils. A number of major challenges will be addressed in this project. The bulky nature of the monomers may lead to synthetic challenges relative to their petroleum-derived counterparts and have key implications for the physical properties of the polymers. Biomass-derived materials may exhibit biodegradability and oxidative degradation. The presence of specific interactions may require looking beyond mean-field theories for modeling these polymers and their mixtures. Importantly, the structure-property-function relationships for these new materials are expected to be significantly different from those described in the vast body of literature for petroleum-derived polymers. NON-TECHNICAL SUMMARY:The world supply of petroleum is finite and in the future it will be necessary to utilize sustainable resources for the production of polymers. Polymers derived from agricultural sources offer benefits to society of enhanced biodegradability, reduced environmental impact, and utilization of an annually renewable resource. Replacements for commodity plastics have in many cases been successfully developed; however, relatively few studies have focused on biomass as a source for nanostructured materials. Polymers which exhibit nanoscale structure have tunable physical properties, which ultimately lead to important advances in material function. The proposed research will enable the implementation of polymers from a widely available agricultural source: vegetable oils. Additionally, this project will cultivate knowledge in students, educators and the general public on the relationships between energy, sustainability and the environmental impact of materials, through the broad participation of underrepresented groups in outreach programs, including women, Hispanic students and students from other minority groups. The following activities will be undertaken: a research-focused outreach program will be developed for local community college students; hands-on educational programs for students and teachers at targeted local high schools will be expanded; high school, undergraduate and graduate students will be mentored in the research project; and an exhibit will be designed for the Houston Museum of Natural Science on sustainable polymers.