Chemoselective Polymerizations from Mixtures of Epoxide, Lactone, Anhydride, and Carbon Dioxide

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• 作者：Charles Romain ; Yunqing Zhu ; Paul Dingwall ; Shyeni Paul ; Henry S. Rzepa ; Antoine Buchard ; Charlotte K. Williams
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：March 30, 2016
• 年：2016
• 卷：138
• 期：12
• 页码：4120-4131
• 全文大小：832K
• ISSN：1520-5126

文摘

Controlling polymer composition starting from mixtures of monomers is an important, but rarely achieved, target. Here a single switchable catalyst for both ring-opening polymerization (ROP) of lactones and ring-opening copolymerization (ROCOP) of epoxides, anhydrides, and CO<sub>2sub> is investigated, using both experimental and theoretical methods. Different combinations of four model monomers—ε-caprolactone, cyclohexene oxide, phthalic anhydride, and carbon dioxide—are investigated using a single dizinc catalyst. The catalyst switches between the distinct polymerization cycles and shows high monomer selectivity, resulting in block sequence control and predictable compositions (esters and carbonates) in the polymer chain. The understanding gained of the orthogonal reactivity of monomers, specifically controlled by the nature of the metal-chain end group, opens the way to engineer polymer block sequences.