Pseudo first-order rate constants of the reaction of diethyl(ethyl cyanoacetato)aluminum [(C 2 H 5) 2 Al(NCCHCOOC 2 H 5)] 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: CH 2 ¼ ¼C(CF 3)COOC 2 H 5 [ CH 2 ¼ ¼C(CF 3) COOCH(CH 3) 2 [ CH 2 ¼ ¼CHCOOCH 2 C 6 F 5 [ CH 2 ¼ ¼C(CF 3)COOC(CH 3) 3 [ CH 2 ¼ ¼ C(CF 3)COOCH 2 C 6 F 5 [ CH 2 ¼ ¼C(CF 3)COOCH(CF 3) 2 ! CH 2 ¼ ¼CHCOOCH 3 [ CH 2 ¼ ¼CH COOCH 2 C 6 H 5 ! CH 2 ¼ ¼C(CF 3)COOCH 2 CF 3 [ CH 2 ¼ ¼C(CH 3)COOCH 2 C 6 F 5 [ CH 2 ¼ ¼ CHCOOCH 2 CF 3 [ CH 2 ¼ ¼CHCOOCH 2 C 2 F 5 [ CH 2 ¼ ¼CHCOOCH(CF 3) 2 [ CH 2 ¼ ¼ C(CH 3)COOCH 3 [ CH 2 ¼ ¼C(CH 3)COOCH 2 C 6 H 5 ! CH 2 ¼ ¼C(CH 3)COOCH 2 CH 2 C 8 F 17 [ CH 2 ¼ ¼C(CH 3)COOCH(CH 3) 2 [ CH 2 ¼ ¼C(CH 3)COOCH 2 C 2 F 5 ! CH 2 ¼ ¼C(CH 3)COO CH 2 CF 3. No rate constants for CH 2 ¼ ¼C(CH 3)COOCH(CF 3) 2 , CH 2 ¼ ¼CFCOOC(CH 3) 3 , and CH 2 ¼ ¼CFCOOCH 2 C 2 F 5 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.

Novel fluorinated polymer synthesis with anionic polyaddition by double Michael addition reaction of 2‐trifluoromethylacrylate derivatives with ethyl cyanoacetate (ECA) was proposed. Diaddition product of ECA with phenyl 2‐trifluoromethylacrylate was yielded in high yield by the catalysis of sodium ethoxide in tetrahydrofuran at 60 °C. Sodium hydroxide catalyzed double Michael addition reaction also produced diaddition product in high yield. Novel anionic polyaddition of 1,4‐phenylene bis(2‐trifluoromethylacrylate) [CH2C(CF3)COOC6H4OCOC(CF3)CH2] (PBFA) with ECA afforded the polymer of 1.2 × 104 as the highest molecular weight. The isolated polymer gave the polymer of 2.8 × 104 as a molecular weight by the reaction of the isolated polymer with PBFA in the presence of sodium ethoxide; which proved that the polymer end groups were mainly ECA moieties. The reaction mechanism that the proton abstraction from ECA followed by the addition of 2trifluoromethylacrylate was proposed. The reaction of acetylacetone with PBFA was also examined to give the polymer of 7.6 × 103 as the highest molecular weight catalyzed by sodium hydroxide at room temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5698–5708, 2009

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