Telomerisation Reactions of fluorinated alkenes

Radical telomerization of 1,3-butadiene with perfluoroalkyl iodides

“…-m oinitiatior -(m 0R F I -m iod. ))/m obutadiene (1) where m oinitiator , m 0R F I , m iod. , and m obutadiene , represent the initial amounts of initiator, telogen, iodine content and monomer, respectively.…”

“…5. Telomerization reaction of 1,3-butadiene with perfluoroalkyl iodides in a 1 liter Hastelloy autoclave; T = 145 8C; monomer: 300 g; acetonitrile: 200 g; 1% of di-tert-butyl peroxide with respect to monomer; functionality: number of R F per polymer chain (deduced from the microstructure characterized by 1 Kinetics of telomerization was followed by gas chromatography (GC) using a Delsi apparatus (model 330) equipped with an OV17 column, 2 m61/8 inch. The nitrogen pressure at the entry of the column was maintained at 0.5 bar, detector and injector temperature was 250 8C (T i = 50 8C; T f = 70 8C; 1 8C N min -1 ).…”

“…The solvent was removed under heating and reduced pressure (20 mmHg) to give 76 g of a slightly viscous brown oil. 1 H NMR (CDCl 3 ) d = 1.6 (m, 1CH 2 1CH(CHCH 2 )1); 2.0 (m, 1CH2CH1CH 2 1, 1CH 2 1CH(CHCH 2 )1); 2.7 (td, 1CF 2 CH 2 , J HF = 17.6 Hz, J HH = 6.4 Hz); 5.0 (m, CH 2 2CH1); 5.5 (m, CH 2 2CH1, 1CH2CH1). 19 F NMR (CDCl 3 ) d = -81.1 (t, CF 3 ); -113.7 (AB system, CF 2 CH 2 ); -122.3 (m, C 3 F 7 CF 2 ); -123.4 (m, C 2 F 5 CF 2 ); -123.9 (m, CF 2 CF 2 CH 2 ); -126.5 (m; CF 3 CF 2 ); intensity ratio: 3 : 2 : 2 : 2 : 2 : 2. tert-butyl peroxide and 70 g of acetonitrile were introduced into a 500 ml Hastelloy reactor.…”

“…(4.10 -2 mbar): 116 8C) and isolated as a light brown solid (R = 70% after distillation based on R F I). 1 H NMR (CDCl 3 ) d = 1.0 -2.5 (m, CH 2 , CH); 2.8 (m, C 8 F 17 CH 2 CHI1); 4.4 (m, C 8 F 17 CH 2 CHI1); 5.7 (s, 1CH2CH1); intensity ratio 7 : 2 : 1 : 2.…”

Use of Originalω-Perfluorinated Dithioesters for the Synthesis of Well-Controlled Polymers by Reversible Addition-Fragmentation Chain Transfer (RAFT)

“…In that field of research, telomerization of fluorinated monomers [17] or hydrosoluble monomers [32,33] (e. g., acrylamide, acrylic acid, N-vinylpyrrolidone) in the presence of an appropriate perfluorinated transfer agent (e. g. C n F 2n+1 C 2 H 4 SH, C n F 2n+1 I with n = 6, 8, 10) allowed us to synthesize diblock oligomers, containing a perfluorinated group at one end of the polymeric chain (e. g., C 6 F 13 C 2 H 4 S-[CH 2 CH(CONH 2 )] n H with n ranging between 8 and 80). These oligomers appeared to have surfactant properties and were used, for example, in fire-fighting aqueous foams.…”