SusChEM: Carbonylative Polymerization of Heterocycles and Heteroalkenes

化学催化计划支持阿克伦大学李佳教授研究过渡金属催化的杂环(如氮杂环和环氧化物)和杂烯(含碳-氧和碳-氮双键)的羰基化聚合。这项研究包括两个主要目标：1)全面了解钴催化氮杂环丙烷的羰基化聚合反应机理；2)开发一类新型的两性离子镍(Ni)和钯(Pd)催化剂，用于环氧化物和醛的羰基化聚合。该机理研究采用了多种互补的实验方法，包括原位红外光谱、催化剂休眠状态模型化合物的合成以及催化过程的动力学研究。在已有钴催化剂机理知识的基础上，对新型两性离子镍、钯催化剂进行了合理的设计。该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，在防污涂料和高性能热塑性弹性体中用作物理交联剂。聚酯是用于商品应用的环境可降解塑料。该项目属于SusChEM计划，因为它利用非石油为基础的原料(如CO)以及一些非贵金属催化剂(如镍)来生产潜在的商品化产品。化学催化计划支持阿克伦大学李佳教授对催化聚合反应的研究。一氧化碳是催化聚合产生的聚合物(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。与依赖化石原料的化学过程相比，这些化学过程在环境上更可持续。聚合产物的目的也是为了保护环境。一种聚合物可用作防污涂层，并有可能取代目前应用于海洋船舶的锡和铜杀菌剂，以防止海洋污染。另一种聚合物产品可以用作可回收热塑性橡胶的原料，以取代不可回收的热固性橡胶。目前催化聚合产生的聚酯是在环境中降解成无害物质的“绿色”塑料。研究生、本科生和高中生将获得重要的环境观点以及与工业相关的研究领域的经验。

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.