SusChEM: Carbonylative Polymerization of Heterocycles and Heteroalkenes

SusChEM：杂环和杂烯烃的羰基化聚合

• 批准号: 1266442
• 负责人: Li Jia
• 金额: $ 42万
• 依托单位: University of Akron
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-08-01 至 2017-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1266442&HistoricalAwards=false
• 关键词: SusChEM; Carbonylative; Polymerization; Heterocycles; Heteroalkenes

The Chemical Catalysis Program supports the efforts of Professor Li Jia of the University of Akron for the investigation of the transition metal-catalyzed carbonylative polymerization of heterocycles (e.g., aziridines and epoxides) and heteroalkenes (containing carbon-oxygen and carbon-nitrogen double bonds). The research encompasses two major objectives: 1) a comprehensive understanding of the mechanism of the cobalt-catalyzed carbonylative polymerization of aziridines and 2) the development of a novel class of zwitterionic nickel (Ni) and palladium (Pd) catalysts for the carbonylative polymerization of epoxides and aldehydes. The mechanistic study utilizes a combination of complementary experimental approaches, including in situ infrared spectroscopy, synthesis of model compounds for catalyst resting states, and a kinetic study of the catalytic process. The novel zwitterionic Ni and Pd catalysts are rationally designed on the basis of the existing mechanistic knowledge obtained from known cobalt catalysts. The polymerization reactions developed in this project are powerful tools for the synthesis of polyamides and polyesters. Polyamides are specialty polymers with applications in antifouling coatings and as physical crosslinkers in high-performance thermoplastic elastomers. The polyesters are environmentally-degradable plastics for commodity applications. This project falls under the SusChEM initiative as it utilizes non-petroleum based starting materials (e.g., CO) as well as some non-precious metal catalysts (e.g., nickel) for the production of potential commodity-scale products.The Chemical Catalysis Program supports the efforts of Professor Li Jia of the University of Akron for the investigation of a catalytic polymerization reactions. Carbon monoxide serves as the raw material for the polymers (plastics) produced by the catalytic polymerizations; carbon monoxide can be obtained from biomass and from the conversion of carbon dioxide (a greenhouse gas). These chemical processes are more environmentally sustainable than those that rely on fossil feedstock. The products of the polymerization are also aimed to benefit the environment. One type of the polymers can be used as an antifouling coating and can potentially replace the tin and copper biocides currently applied to marine vessels to prevent marine fouling. Another polymer product can be used as an ingredient for recyclable thermoplastic rubbers that replace the non-recyclable thermoset rubbers. The polyesters produced by the present catalytic polymerization are "green" plastics that degrade into harmless substances in the environment. The graduate, undergraduate, and high school students will gain important environmental perspectives as well as experience in industrially-relevant areas of research.

化学催化计划支持阿克伦大学的李佳教授对杂环（例如，氮丙啶和环氧化物）和杂烯烃（含有碳-氧和碳-氮双键）。 本论文的主要研究内容包括两个方面：1）对钴催化的氮丙啶羰基化聚合反应机理的全面认识; 2）开发新型的两性离子镍（Ni）和钯（Pd）催化剂，用于环氧化物和醛的羰基化聚合反应。机理研究利用互补的实验方法，包括原位红外光谱，催化剂静止状态的模型化合物的合成，和催化过程的动力学研究的组合。 新型两性离子Ni和Pd催化剂是基于从已知钴催化剂获得的现有机理知识而合理设计的。 本项目开发的聚合反应是合成聚酰胺和聚酯的有力工具。 聚酰胺是一种特种聚合物，可用于防水涂料和高性能热塑性弹性体中的物理交联剂。聚酯是用于商品应用的环境可降解塑料。 该项目福尔斯SusChEM倡议，因为它使用非石油基起始材料（例如，CO）以及一些非贵金属催化剂（例如，化学催化项目支持阿克伦大学的李佳教授对催化聚合反应的研究。 一氧化碳作为催化聚合生产的聚合物（塑料）的原材料;一氧化碳可以从生物质和二氧化碳（一种温室气体）的转化中获得。 这些化学过程比那些依赖化石原料的过程在环境上更可持续。 聚合产物也旨在有益于环境。 一种类型的聚合物可用作防污涂料，并可潜在地取代目前应用于海洋船舶以防止海洋污染的锡和铜杀生物剂。 另一种聚合物产品可用作可回收热塑性橡胶的成分，以取代不可回收的热固性橡胶。 通过本发明的催化聚合生产的聚酯是“绿色”塑料，其在环境中降解成无害物质。 研究生，本科生和高中生将获得重要的环境观点以及工业相关研究领域的经验。