Synthesis and polymerization of novel bis(2‐trifluoromethylacrylate)

Abstract

Syntheses and radical polymerizations of novel ethylene 2‐trifluoromethylacrylate [(CH2C(CF3)COOCH2CH2OCOC(CF3)CH2] was examined in the presence of 1,4‐dioxane to afford a polymer possessing the molecular weight of as high as 5.6 × 104 possessing 1,4‐dioxane moieties in side chains although radical addition polymerization of 2‐trifluoromethylacrylate hardly takes place. The 5 wt % loss temperature of the polymer was 309 °C determined by thermogravimetric analysis.

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

“…1(A) although the poor dependency is indicated in the case of 2-trifluoromethylacrylates and methacrylates. The linear relationship is shown in the case of 2,2,2-trifluoroethyl esters such as CH 2 5 5C(CH 3 )COOCH 2 CF 3 (4), CH 2 5 5CHCOOCH 2 CF 3 (21), and CH 2 5 5C(CF 3 )COOCH 2 CF 3 (13). Pseudo first-order rate constants of CH 2 5 5CFCOOC(CH 3 ) 3 and CH 2 5 5CFCOOCH 2 C 2 F 5 might be drastically different from those of other fluoroalkyl acrylates since chemical shifts of b-carbons are 101.4 and 104.8 ppm, respectively, which are considerably smaller than those of other fluoroalkyl acrylates.…”

“…BFP shows the high radical polyaddition reactivity to form polymers with DOX, as has been demonstrated in previous section. Then radical polyaddition of a novel bis(2-trifluoromethylacrylate), ethylene bis(2-trifluoromethylacrylate) [CH 2 5 5C(CF 3 )COOCH 2 CH 2 OCOC(CF 3 )5 5CH 2 ] (EBFA), was of interest [13].…”

“…Log k 0 at 40 8C (A) and at 0 8C (B) vs 13. C NMR chemical shifts of carbonyl carbons of fluorinated acrylates and methacrylates (refer toTable 5) (È) 2-trifluoromethylacrylate; (*) methacrylate; (*) acrylate[21].…”

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

“…The reactivity of BPFP with diethyl carbonate was found to be lower than that of tetrahydrofuran and 1,4-dioxane, as the yield was 53% when the reaction was initiated with benzoyl peroxide. The reaction was found to take place as shown in Equation (19) by NMR and gas chromatography-mass spectrometry measurements of the product. The reaction takes place predominantly at the methylene group.…”

“…The results show that the anionic polymerization has not yet worked well for a-trifluoromethylstyrene, a-difluoromethylstyrene or trifluorovinylbenzene. The tacticity of poly(ethyl 2-trifluoromethylacrylate) has not yet been studied by 19 F NMR measurement, which might afford more information than 1 H and 13 C NMR because of the ability to detect long-range interactions of fluorine atoms. The investigation on the reactivity of fluorinated vinyl monomers should be a high priority for the field of anionic polymerization methodology from the academic point of view.…”