Pseudo first-order rate constants of the reaction of diethyl(ethyl cyanoacetato)aluminum [(C2H5)(2)Al(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(CCF3) COOCH(CH3)(2) > CH2=CHCOOCH2C6F5 > CH2=C(CF3)COOC(CH3)(3) > CH2= C(CF3)COOCH2C6F5 > CH2=C(CF3)COOCH(CF3)(2) CH2=CHCOOCH3 > CH2=CH COOCH2C6H5 > CH2=C(CF3)COOCH2CF3 > CH2=C(CH3)COOCH2C6F5 > CH2= CHCOOCH2CF3 > CH2=CHCOOCH2C2F5 > CH2=CHCOOCH(CF3)(2) > CH2= C(CH3)COOCH3 > CH2=C(CH3)COOCH2C6H5 >= CH2C=C(CH3)COOCH2CH2 C8F17 > CH2=C(CH3)COOCH(CH3)(2) > CH2=C(CH3)COOCH2C2F5 >= CH2=C(CH3)COO CH2CF3. 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. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7011-7021, 2008