Telomerisation of trifluoroethylene with dimethyl phosphite. Part 1. Preparation of the monoadduct

Sandy Gosset , Alaaeddine Elhalil , Olinda Carreon Gimello (1) , Vincent Ladmiral (1) , Bruno Ameduri (1)

1 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

The radical telomerisation of trifluoroethylene (TrFE) with dimethyl phosphite (DMP) was investigated to synthesize fluorinated monoadducts bearing a phosphonate end-group such as HTrFEP(O)(OCH3)2. Among various radical initiators, di-tert-butyl peroxide (DTBP) was the most efficient one at 80–140 C. This telomerisation protocol successfully yielded mainly the monoadduct of TrFE and DMP. A structural study of the TrFE-DMP monoadduct was carried out using 1H, 13C, 19F and 31P NMR spectroscopies and showed that a mixture of dimethyl-1,2,2-trifluoroethylphosphonate and dimethyl-1,1,2-trifluoroethyl- phosphonate was obtained. The best experimental conditions to reach high yields of monoadduct were achieved at T = 140 C, using initial molar ratios R0 = [DMP]0/[TrFE]0 and C0 = [DTBP]0/[TrFE]0 of 3 and 0.05, respectively, and a reaction time of 15 h. Higher telomeric adducts were also detected by MALDI-TOF mass spectrometry.

Mots clés: Dimethyl phosphite; MALDI-TOF spectrometry; Nuclear magnetic resonance; Radical telomerisation; Trifluoroethylene

Domaines: Polymères

Sandy Gosset, Alaaeddine Elhalil, Olinda Carreon Gimello, Vincent Ladmiral, Bruno Ameduri. Telomerisation of trifluoroethylene with dimethyl phosphite. Part 1. Preparation of the monoadduct. Journal of Fluorine Chemistry, 2016, 183, pp.74-81. ⟨10.1016/j.jfluchem.2016.01.016⟩. ⟨hal-01272786⟩