Polymerization of tetrafluoroethylene in acetic acid photoinitiated by metal carbonyls

Photochemically Enabled Iodine Degenerative Transfer Controlled Radical Homo- and Block Copolymerization of Vinylidene Fluoride at Ambient Temperatures with Mn2(CO)10and Visible Light

“…While this does represent the first example of metal mediated VDF-CRP and the first example of visible light mediated VDF-CRP, mechanistically, with the exception of iodide chain end reactivation by Mn(CO) 5 • to compensate for termination, it remains a conventional IDT. Indeed, while IDT catalysis by Mn complexes would decrease PDI (3,10), control experiments (51) show that, similar to the IDT of VAc (102,103), Mn(CO) 5 -I is photochemically inactive (142,143) and unable to donate iodine.…”

“…Thus, CRPs based on reversible termination with Mn(CO) 5 • are not likely to be effective. Nonetheless, very early reports did propose photo or thermal Mn 2 (CO) 10 or Re 2 (CO) 10 mediated FRPs initiated via either H abstraction from the monomer (101), addition of the metalloradical to tetrafluoroethylene to initiate its homopolymerization (102,103) or the MMA (88, 104, 105) block copolymerization (106), as well as the addition to 1,2-disubstituted acetyls and alkenes (107). However, while polymerizations initiated by Mn 2 (CO) 10 or Re 2 (CO) 10 and CCl 4 (108) or grafting from N-halogenated polyamides (109) were carried out in the 60s, Mn 2 (CO) 10 was only recently utilized in the thermal (60-90 °C) (110) FRP of MMA, or in PMMA initiation from -CCl 3 groups on SiO 2 (111), chitosan (112) or from PSt-Br (113)(114)(115).…”

Photomediated Controlled Radical Polymerization and Block Copolymerization of Vinylidene Fluoride

“…Indeed, no initiation of VDF by Mn 2 (CO) 10 alone and no control in VDF/alkyl halide/excess Mn 2 CO 10 polymerizations were observed under irradiation . Nevertheless, very early research did suggest that photo or thermal Mn 2 (CO) 10 - and Re 2 (CO) 10 -mediated FRPs might be initiated by H abstraction from the monomer, the addition of the metalloradical to tetrafluoroethylene to initiate its homopolymerization, , the methyl methacrylate (MMA) ,, block copolymerization, or the addition to alkenes and 1,2-disubstituted acetyls …”

Mn2(CO)10‐Visible Light Photomediated, Controlled Radical Polymerization of Main Chain Fluorinated Monomers and Synthesis of Block Copolymers Thereof

“…Interestingly, early reports proposed photo or thermal Mn 2 (CO) 10 or Re 2 (CO) 10mediated polymerizations initiated via either H abstraction from the monomer [86], addition of the metaloradical to tetrafluoroethylene to initiate its polymerization [87,88], MMA [87,89,90] block copolymerization [91], or addition to 1,2-disubstituted acetyls and alkenes [92]. However, while preliminary polymerizations with Mn 2 (CO) 10 or Re 2 (CO) 10 and CCl 4 [93] or grafting from N-halogenated polyamides [94] were carried out in the 1960s, Mn 2 (CO) 10 was only recently employed in the thermal (60-90 • C) [95] FRP of MMA or in the PMMA chain extensions from -CCl 3 groups on SiO 2 [96], chitosan [97], or from polystyrene-Br [98][99][100].…”