CAS: Synthetic Methodologies to Harness the Chemical Diversity of Natural Products for the Sustainable Production of High Value Macromolecular Materials

在这个由化学学部大分子、超分子和纳米化学项目资助的项目中，德克萨斯农机大学化学系的Karen L. Wooley教授和Donald J. Darensbourg教授正在开发新的合成路线，利用天然产物和消耗二氧化碳来可持续地生产高价值聚合物。这些聚合物一旦完成其使用寿命，就能够进行降解以再生相同的天然构建块。该团队量化了聚合物降解产物，并定义了聚合物的潜在用途。这项研究的更广泛的影响包括将自然资源转化为有用的聚合物材料，这些材料可以随时和可持续地降解，从而减少石化原料的使用，减少塑料在垃圾填埋场和水系统中的环境持久性。该项目还有助于在高度跨学科的研究环境中培训多样化的学生群体，并通过外展活动和招聘下一代STEM劳动力的努力加以补充。这项研究的重点是开发合成化学方法来生产一系列源于可再生资源的聚碳酸酯、聚磷酸酯、聚酰胺和聚氨酯。这些材料表现出新的化学、物理和机械性能，并经过水解分解产生对生物有益或良性的副产物。碳水化合物重复单元之间的连接被设计成包括碳酸盐，以便在水解时分解成碳水化合物、二氧化碳和其他副产物。为了达到二氧化碳中性，二氧化碳被用作进入聚碳酸酯的原料。碳水化合物也通过磷酸酯连接，类似于DNA中的多磷酸酯骨架。多酚类化合物作为双酚A在工程塑料或聚氨酯结构中的替代品进行了研究。此外，对聚氨酯工业很重要的是，研究了几种天然二胺和二醇通过避免光气和处理异氰酸酯的工艺转化为聚氨酯。与这项工作相关的聚合包括阶梯生长缩聚或链生长开环聚合。这项工作包括研究和教育部分，对先进制造业有很大的影响。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。

In this project funded by the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Professors Karen L. Wooley and Donald J. Darensbourg of the Department of Chemistry at Texas A&M University are developing new synthetic routes that harness natural products and consume carbon dioxide for the sustainable production of high value polymers. These polymers are capable of undergoing degradation to regenerate the same natural building blocks once they have completed their useful lifetime. The team quantifies the polymer degradation products and defines the potential uses of the polymers. The broader impacts of this research include the transformation of natural resources into useful polymer materials that can be readily and sustainably degraded, thereby reducing the use of petrochemical feedstocks and reducing the environmental persistence of plastics in landfills and water systems. The project also contributes to the training of a diverse group of students in a highly interdisciplinary research environment and is complemented by outreach activities and efforts at recruiting the next generation STEM workforce. This research is focused on developing synthetic chemistry approaches to the production of a series of polycarbonates, polyphosphoesters, polyamides and polyurethanes that originate from renewable resources. These materials exhibit novel chemical, physical and mechanical properties, and undergo hydrolytic breakdown to biologically-beneficial or benign by-products. Linkages between carbohydrate repeat units are designed to include carbonates to allow for breakdown to carbohydrates, carbon dioxide and other byproducts upon hydrolysis. To be carbon dioxide neutral, carbon dioxide is used as a feedstock to access the polycarbonates. Carbohydrates are also connected via phosphoesters, analogous to polyphosphoesters backbones in DNA. Polyphenolic compounds are investigated as alternatives to bisphenol A in the construction of engineering plastics or polyurethanes. Additionally, and of importance for polyurethane industry, several natural diamines and diols are studied for conversion into polyurethanes via processes that avoid phosgene and handing of isocyanates. Polymerizations associated with this work involve step-growth condensation or chain-growth ring opening polymerization. This work includes research and educational components that have a high potential to impact advanced manufacturing.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.