CAS: Polymers from biomass using monomers derived from lignin

CAS：使用木质素单体制成的生物质聚合物

• 批准号: 2003863
• 负责人: Andrea Kasko
• 金额: $ 35.07万
• 依托单位: University of California-Los Angeles
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-06-01 至 2024-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2003863&HistoricalAwards=false
• 关键词: CAS; Polymers; biomass; using; monomers

In this project funded by the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Professor Andrea M. Kasko of the Department of Bioengineering at University of California-Los Angeles is preparing polymers from biomass using starting materials (monomers) derived from lignin. Lignin is one of the most important structural polymers in nature. As the second most abundant natural polymer after cellulose, lignin is an inexpensive and widely available source of carbon. In this research, monomers or polymer building blocks based on lignin are first chemically functionalized to enhance their solubility in common organic solvents. These monomers are then polymerized by themselves or in the presence of other synthetic monomers to yield high molecular weight polymers and copolymers. The physical properties of the generated polymers are then systematically evaluated and compared to other high performance, commodity plastics. The properties that are being investigated include mechanical properties, thermal stability, solvent resistance and degradability or recyclability. The broader impacts of this work involve potentially substantial societal benefits by transforming natural resources into polymers, thereby decreasing society's dependence on petroleum resources for raw materials. This project also broadens participation in a number of ways. The multi-disciplinary nature of the research provides training to graduate and undergraduate students in organic, polymer and physical chemistry. Undergraduate students are involved in the project throughout the school year and during the summer through undergraduate research programs at University of California-Los Angeles. A strong emphasis is placed on recruiting and retaining under-represented populations in research, and promoting research to non-STEM undergraduates. A summer internship module on biopolymers is developed for veterans who have re-entered civilian life and are pursuing STEM degrees at local community colleges through the Project SERVES program.The overall objective of this research is to synthesize polymers and copolymers incorporating hydroxycinnamate monomers derived from lignin. The team evaluates the properties of the generated polymers and copolymers as plant-derived alternatives to commodity and high performance polymeric materials. A series of substituted monomers and dimers based on hydroxycinnamic acids (monolignol biosynthetic precursors) and monolignols are first prepared, and then copolymerized via condensation polymerizations to produce poly(ester amide)s, poly(ester)s, poly(ether amide)s and poly(amide)s. Small molecules and polymers are also grafted to/from the double bond in the backbone of these poly(ester amide)s, poly(ester)s, poly(ether amide)s, and poly(amide)s. Flexible blocks (siloxane and poly(ethylene oxide)) are additionally incorporated into the polymers to broaden the range of achievable properties. The research team is also synthesizing benzoxazine-based polymers. Lastly, the material properties of the polymers, copolymers, and their blends and composites (mechanical properties, thermal stability, solvent resistance, and degradability/recyclability) are characterized. This research could have a positive impact on the environmental and economic sustainability because it focuses on the synthesis of polymers from abundant renewable feed stock.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.

在这个由化学系大分子、超分子和纳米化学项目资助的项目中，Andrea M。加州大学洛杉矶分校生物工程系的Kasko正在使用来自木质素的起始材料（单体）从生物质中制备聚合物。 木质素是自然界中最重要的结构聚合物之一。 作为仅次于纤维素的第二大天然聚合物，木质素是一种廉价且广泛可用的碳源。 在这项研究中，基于木质素的单体或聚合物结构单元首先被化学官能化，以提高它们在常见有机溶剂中的溶解度。 然后这些单体本身或在其它合成单体存在下聚合，得到高分子量聚合物和共聚物。 然后对生成的聚合物的物理性能进行系统评估，并与其他高性能商品塑料进行比较。 正在研究的性能包括机械性能、热稳定性、耐溶剂性和降解性或可回收性。 这项工作的更广泛影响涉及潜在的重大社会效益，将自然资源转化为聚合物，从而减少社会对石油资源的依赖。 该项目还以多种方式扩大了参与。 该研究的多学科性质为有机、聚合物和物理化学领域的研究生和本科生提供了培训。 本科生在整个学年和夏季通过加州大学洛杉矶分校的本科研究项目参与该项目。 一个非常强调的是在研究中招募和保留代表性不足的人群，并促进研究非STEM本科生。 生物聚合物的暑期实习模块是为退伍军人开发的，他们已经重新进入平民生活，并通过项目SERVES计划在当地社区学院攻读STEM学位。这项研究的总体目标是合成聚合物和共聚物，其中包含来自木质素的羟基肉桂酸酯单体。 该团队评估了所产生的聚合物和共聚物作为商品和高性能聚合物材料的植物来源替代品的性能。 以羟基肉桂酸（单体生物合成前体）和木质素单体为原料，合成了一系列取代的单体和二聚体，然后通过缩聚反应合成了聚酯酰胺、聚酯、聚醚酰胺和聚酰胺。 小分子和聚合物也接枝到这些聚（酯酰胺）、聚（酯）、聚（醚酰胺）和聚（酰胺）的主链中的双键上/从其上接枝。 柔性嵌段（硅氧烷和聚（环氧乙烷））被额外纳入到聚合物中，以扩大可实现的性能范围。 该研究小组还在合成苯并恶嗪基聚合物。 最后，聚合物，共聚物，及其共混物和复合材料的材料性能（机械性能，热稳定性，耐溶剂性和降解性/可回收性）的特点。 这项研究可能对环境和经济的可持续性产生积极影响，因为它专注于从丰富的可再生原料中合成聚合物。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。