Novel anionic polyaddition of 2‐trifluoromethylacrylate by double Michael reaction with ethyl cyanoacetate

Abstract

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

Stimulation on the addition reactivity of fluorinated vinyl monomers—Facile carbon–carbon bond formation by the aid of fluorine substituents

“…Acrylonitrile and methyl vinyl ketone show the high reactivity to the carbanion to yield double Michael addition products with active methylene compounds such as diethyl malonate and ethyl cyanoacetate [NCCH 2 COOC 2 H 5 ] (ECA) which work as difunctional compounds under specific reaction conditions. The high reactivity of 2-trifluoromethylacrylates as an anion acceptor might be developed to the preparation of polymers by the double Michael reaction [20].…”

Synthesis of novel fluorinated polymers: facile carbon–carbon bond formation aided by fluorine substituents

“…The high reactivity of 2-trifluoromethylacrylate as an anion acceptor might make this reaction an appropriate candidate for the preparation of polymers by the double Michael addition. 5,9 The reaction of phenyl 2-trifluoromethylacrylate (CH 2 ¼C(CF 3 ) COOC 6 H 5 ) with ECA was investigated as a model reaction catalyzed by sodium ethoxide or sodium hydroxide in the presence of excess ECA at 60 1C for 24 h. The results showed that the di-addition compound of ECA was produced in high yields. Table 5 shows the results of the novel anionic polyaddition of 1,4-phenylene bis(2-trifluoromethylacrylate) (CH 2 ¼C(CF 3 )COO-C 6 H 4 -OCOC(CF 3 )¼CH 2 ) with ECA.…”

“…Table 5 shows the results of the novel anionic polyaddition of 1,4-phenylene bis(2-trifluoromethylacrylate) (CH 2 ¼C(CF 3 )COO-C 6 H 4 -OCOC(CF 3 )¼CH 2 ) with ECA. 5,9 Increasing the amount of ECA in the feed increases the yields and molecular weights of the polymers obtained (runs 1, 4, 6 and 10) catalyzed by sodium ethoxide in ethanol. The yield and the molecular weight of the resulting polymer are satisfactorily high when ECA is present in significant excess in the feed (run 9).…”

“…The addition of BPFP with triethylamine afforded ordinary yields as compared with many reports on the radical addition of trifluorovinyl compounds with amine derivatives. 4 The radical polyaddition of BFP with triethylamine was then examined to yield a polymer of 6.3Â10 3 as the highest molecular weight following initiation with benzoyl peroxide and reaction at 60 1C for 72 h, as shown in Equation (9), although the yield of polymer was very low. To increase the fluorine content of polymers obtained from BFP with 1,4-dioxane, the copolymerization of BFP and bis(1-trifluoromethyl-2,2-difluorovinyl) 2,3,5,6-tetrafluoroterephthalate (CF 2 ¼C(CF 3 )OCO-C 6 F 4 -COOC(CF 3 )¼CF 2 ) with 1,4-dioxane was investigated and shown to afford polymers of molecular weight 1.1Â10 4 following initiation with di-tert-butyl peroxide and reaction at 80 1C for 72 h, as shown in Equation (10).…”

“…Scheme 2 presents the reaction mechanism. 5,9 The addition reaction of the ECA anion to the a-trifluoromethylvinyl moiety takes place at the polymer chain end, followed by sodium ion transfer to ECA to yield sodium salt again. This cycle may yield the polymer.…”