Radical telomerization of 3,3,3-trifluoropropene with diethyl hydrogen phosphonate: Characterization of the first telomeric adducts and assessment of the transfer constants

Random and sequential radical cotelomerizations of 3,3,3‐trifluoropropene (H2CCHCF3) with vinylidene fluoride (F2CCH2)

“…10,16,17 Other transfer agents have been used such as silanes, phosphonates, disulfides or hydrogen bromide yielding the monoadduct. 3 Recently, the Great Lakes/Chemtura Company has patented the telomerization of TFP with either perfluoroalkyl iodides 20 or other non-fluorinated chain-transfer agents 21 and their further chemical modifications to get useful surfactants, coating materials, or block copolymers. [22][23][24] On the other hand, vinylidene fluoride (VDF) is a non-toxic, non-explosive, and environmentally friendly gas (it does not contain any Cl or Br atoms).…”

“…These cotelomers and their derivatives are interesting precursors of various fluoropolymers, such as telechelics 44 or block copolymers 45 , and have found potential applications such as fluorinated surfactants. [46][47][48] The durability and the common use of perfluorinated surfactants such as perfluorooctanoic acid (PFOA) 49 or perfluorooctane sulfonic acid (PFOS) 50 is a major environmental and health issue 51,52 (besides their toxicity and persistency, both these surfactants are bioaccumulable in the human and animal species) and major companies such as Arkema, Asahi Glass, Chemtura, Daikin, DuPont, 3M/Dyneon, Merck, Solvay…”

Original fluorinated surfactants potentially non-bioaccumulable

“…These latters can be produced by the radical telomerization of various fluoroalkenes (tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, dichlorodifluoroethylene), [55][56][57][58][59][60][61][62][63] with dialkyl hydrogenophosphate as listed in Table 2 and Scheme 5:…”

Telomerization of 3,3,3-Trifluoroprop-1-ene and Functionalization of Its Telomers

“…175 °C. In addition for other transfer agents, diiodoperfluoroalkanes, silanes, phosphonates, disulfides react with TFP, yielding the monoadduct predominantely (Table 1) [5][6][7][8][9][10][11][12] .…”

“…Vassileva et al [14][15][16][17][18][19] used different telogens such as C 6 H 5 CH 2 Cl, CBr 4 , CHBr 3 , CH 2 Br 2 (but not CHCl 3 and CBrCl 3 ) with the initiating system Fe(CO) 5 -DMF or hexamethylphosphoramide (HMPA) ( Table 1). In the presence of Fe(CO) 5 -DMF, a radical mechanism was proved to take place and chain transfer constants of the telogens involved in telomerizations were determined. Keim et al.…”