Initiation reactivity of anionic polymerization of fluorinated acrylates and methacrylates with diethyl(ethyl cyanoacetato)aluminum |
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| Authors: | Youhei Umino Tadashi Narita Hiroshi Hamana |
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| Institution: | 1. Department of Applied Chemistry, Graduate School of Engineering, Saitama Institute of Technology, 1690 Fusaiji, Fukaya 369‐0293, Japan;2. Department of Life Science and Green Chemistry, Saitama Institute of Technology, 1690 Fusaiji, Fukaya 369‐0293, Japan |
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| Abstract: | Pseudo first‐order rate constants of the reaction of diethyl(ethyl cyanoacetato)aluminum (C2H5)2Al(NCCHCOOC2H5)] with 17 fluorinated acrylates and methacrylates and five hydrocarbon analogs for references were investigated to examine the initiation reactivities of the anionic polymerization of fluorinated vinyl monomers to afford the reactivity order: CH2?C(CF3)COOC2H5 > CH2?C(CF3)COOCH(CH3)2 > CH2?CHCOOCH2C6F5 > CH2?C(CF3)COOC(CH3)3 > CH2?C(CF3)COOCH2C6F5 > CH2?C(CF3)COOCH(CF3)2 ≥ CH2?CHCOOCH3 > CH2?CHCOOCH2C6H5 ≥ CH2?C(CF3)COOCH2CF3 > CH2?C(CH3)COOCH2C6F5 > CH2?CHCOOCH2CF3 > CH2?CHCOOCH2C2F5 > CH2?CHCOOCH(CF3)2 > CH2?C(CH3)COOCH3 > CH2?C(CH3)COOCH2C6H5 ≥ CH2?C(CH3)COOCH2CH2C8F17 > CH2?C(CH3)COOCH(CH3)2 > CH2?C(CH3)COOCH2C2F5 ≥ CH2?C(CH3)COOCH2CF3. No rate constants for CH2?C(CH3)COOCH(CF3)2, CH2?CFCOOC(CH3)3, and CH2?CFCOOCH2C2F5 were obtained because of too fast polymerization. The incorporation of a trifluoromethyl group into the vinyl group enhanced the reactivity toward the delocalized carbanion. The reactivity of other fluorinated acrylates and methacrylates was concluded to approximately be controlled by the fluorine contents and the bulkiness of substituents of monomers. The reactivity was generally decreased by increasing fluorine contents of fluoroalkyl substituents in ester groups. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7011–7021, 2008 |
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| Keywords: | anionic polymerization diethyl(ethyl cyanoacetato)aluminum fluoropolymers initiators kinetics (polym ) |
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