SusChEM: Carbonylative Polymerization of Heterocycles and Heteroalkenes

化学催化项目支持阿克伦大学李佳教授对过渡金属催化羰基聚合杂环（如叠氮嘧啶和环氧化物）和杂烯烃（含碳氧和碳氮双键）的研究。该研究包括两个主要目标：1)全面了解钴催化氮化吡啶羰基聚合的机理；2)开发一类用于环氧化物和醛类羰基聚合的新型两性离子镍（Ni）和钯（Pd）催化剂。机理研究利用了互补实验方法的组合，包括原位红外光谱，催化剂静息状态模型化合物的合成，以及催化过程的动力学研究。在已有的钴催化剂机理知识的基础上，合理设计了新型两性离子Ni和Pd催化剂。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，应用于防污涂料和高性能热塑性弹性体的物理交联剂。聚酯是用于商品应用的环境可降解塑料。该项目属于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（例如镍）来生产潜在的商品规模产品。化学催化项目支持阿克伦大学李佳教授对催化聚合反应的研究。一氧化碳作为催化聚合所产生的聚合物（塑料）的原料；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更具环境可持续性。聚合的产物也旨在有利于环境。其中一种聚合物可以用作防污涂层，并有可能取代目前应用于船舶上的锡和铜杀菌剂，以防止海洋污染。另一种聚合物产品可用作可回收热塑性橡胶的成分，以取代不可回收热固性橡胶。目前催化聚合生产的聚酯是“绿色”塑料，在环境中可降解为无害物质。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。

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.