The Copolymerization of CO_(2) and Cyclic Ethers and Their Degradation Pathways
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Polycarbonates are found in a variety of common products in daily life due to their favorable mechanical and electrical properties. In addition, they are widely used in biomedical areas due to their stability and biological inertness. Therefore, the production of polycarbonates became an important industrial process in the past decades. However, the current industrial process usually requires toxic phosgene gas as a starting material. Thus, the environmentally benign route by using metal catalyzed couplings of epoxides and CO_(2) to produce polycarbonates has received attention from researchers. In this dissertation, metal catalyzed CO_(2)/cyclic ether copolymerization, depolymerization of polycarbonates, and the equilibria between polycarbonate and corresponding six-membered cyclic carbonate will be investigated. First, the Co(III) catalyzed copolymerizations of CO_(2) and various epoxides with electron-withdrawing substituents to afford polycarbonates are examined. Comparative kinetic studies were performed via in situ infrared measurements as a function of temperature to assess the activation barriers for the production of cyclic carbonate versus copolymer involving electronically different epoxides: styrene oxide, epichlorohydrin, and propylene oxide. Thermodynamically stable cyclic carbonate byproducts are produced during the course of the reaction from the degradations of propagating polymer chains. The depolymerization reactions of several polycarbonates produced from the completely alternating copolymerization of styrene oxide, epichlorohydrin, propylene oxide, cyclohexene oxide, indene oxide, and cyclopentene oxide with carbon dioxide have been investigated. Various reaction pathways can be found under different reaction conditions, including process involving chain-end backbiting and radical intermediates. Temperature-dependent kinetic studies have provided energy of activation barriers for cyclic carbonate formation. In addition, the generated monomeric materials from the degradation of select polycarbonates show the possibility of chemical recycling of plastic waste. For the copolymers made from CO_(2) and oxetane derivatives, this study focuses on the influence of steric hindrance in the 3-position of the monomer oxetane. The (salen)CrCl/onium salt catalyzed coupling reactions of these oxetane derivatives and carbon dioxide are reported. Depolymerizations of copolymers to their corresponding cyclic carbonates were also studied. In addition, several six-membered cyclic carbonates were synthesized to examine their equilibria between monomeric cyclic carbonates and their corresponding polycarbonates.
Wei, Sheng-Hsuan (2013). The Copolymerization of CO_(2) and Cyclic Ethers and Their Degradation Pathways. Doctoral dissertation, Texas A & M University. Available electronically from