| Abstract: | A living polymerization of ethylphenylketene (EPK) was accomplished. When polymerization of EPK was carried out with butyllithium as an initiator in tetrahydrofuran (THF) at ?20 °C, EPK was completely consumed within 5 min, and the corresponding polyester with narrow molecular weight distribution (Mw /Mn ～ 1.1) was obtained almost quantitatively. Kinetic study of the polymerization at ?78 °C revealed that conversion of EPK agreed with the first‐order kinetic equation, and that Mn of the polymer increased in virtually direct proportion to the conversion. Along with these results, successful results in postpolymerization at ?20 °C strongly supported living mechanism of the present polymerization. Further, lithium alkoxides having a methoxy group, styryl moiety, and nitroxyl radical, also successfully initiated polymerization of EPK to afford the corresponding polymers having functional initiating ends. In the polymerization with varying feed ratio EPK]0/initiator]0, the linear relationship between the feed ratio and Mn of the obtained polymer was observed, while maintaining narrow Mw /Mn. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1073–1082, 2000 |
