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

技术摘要：该项目的目标是解决关键的科学挑战，使甘油三酯植物油作为具有可调物理特性的聚合物的环境有益来源得到广泛应用。 植物油是一种有吸引力的原料，基于它们的丰富性、低成本和易于官能化。 该研究计划围绕四个具体目标进行结构化：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-性能关系的研究，生物质衍生纳米结构聚合物针对性应用的开发，以及生物质衍生聚合物对环境影响的评估。 这种方法将开始与合成策略，以修改聚合物的化学结构，采用复分解化学和超分子相互作用。 对这些聚合物的结构-性能-功能关系的详细理解将强调它们的热、机械和流变性能，目标是热塑性弹性体、刺激响应和形状记忆材料。 通过光谱学和散射实验在生物可再生聚合物的热力学相互作用的表征将允许的纳米级结构的先验预测。 植物油衍生聚合物的环境影响的量化将指导未来的材料设计方面，纳入绿色工程原则。 所提出的工作的结果将提供一个路线图的功能性聚合物的设计从植物油。 该项目将处理若干重大挑战。 单体的庞大性质可能导致相对于其石油衍生的对应物的合成挑战，并对聚合物的物理性质具有关键影响。 生物质衍生材料可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模拟这些聚合物及其混合物。 重要的是，预计这些新材料的结构-性能-功能关系与大量文献中描述的石油衍生聚合物的结构-性能-功能关系显著不同。非技术性总结：世界石油供应是有限的，未来有必要利用可持续资源生产聚合物。 来源于农业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益处。 商品塑料的替代品在许多情况下已经成功开发;然而，相对较少的研究集中在生物质作为纳米结构材料的来源。 呈现纳米级结构的聚合物具有可调的物理性能，最终导致材料功能的重要进步。 拟议的研究将使聚合物的实施从一个广泛可用的农业来源：植物油。 此外，该项目将通过代表性不足的群体广泛参与外联方案，包括妇女、西班牙裔学生和其他少数群体的学生，培养学生、教育工作者和公众对能源、可持续性和材料对环境影响之间关系的认识。 将开展以下活动：将为当地社区大学学生制定一个以研究为重点的外联方案;将扩大针对当地高中学生和教师的实践教育方案;将指导高中生、本科生和研究生参与研究项目;将为休斯顿自然科学博物馆设计一个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.