Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

Abstract

The radical co-and terpolymerization of 4-[(␣,␤,␤-trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1-difluoroethylene (or vinylidene fluoride, VDF, or VF 2 ), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side-groups. The conditions of co-and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the coand terpolymers were assessed by 19 F and 1 H-NMR spectroscopy. The thermal and physico chemical properties were also studied.

Proton‐Conducting Polymer Electrolyte Membranes Based on Fluoropolymers Incorporating Perfluorovinyl Ether Sulfonic Acids and Fluoroalkenes: Synthesis and Characterization

“…Experiment 9 exhibited the lowest T g , and is due to the fact that the fluorinated macromolecules prepared incorporated a high level of VDF (T gPVDF = ±40 C). Furthermore, the T g s values increase with the molar percentage of TFVOBSC in the terpolymer, which confirmed a previous study [55]. The T g s values for the VDF/PMVE/TFVOBSC system are very low and are characteristics of a (co)polymer incorporating perfluoromethyl vinyl ether [58].…”

“…The 19 F NMR spectrum (Figure 3) [55]. Finally, the peaks centred at ±113.4 (I ±113.4 ) and ±136.3 (I ±136.3 ) ppm are attributed to the difluoromethylene group and tertiary fluorine atom of the TFVOBSC unit in the terpolymer, respectively (Table 7).…”

“…[(a,b,b-Trifluorovinyl)oxy]bromobenzene (TFVOBB) was used as the model monomer. First, it was shown that aryl a,b,b-trifluorovinyl ether does not homopolymerise under radical initiation but undergoes thermo-cyclodimerisation [2p+2p] [26,28,45,49,50,51,55]. Furthermore, this study showed that copolymerisation with commercially available fluoroalkenes, initiated by 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, led to better massic yields.…”

“…The peaks located in the ±134.8 to ±137.2 ppm region (denoted I ±136.3 ) are assigned to the tertiary fluorine atom in the CF group of TFVOBSC, as observed for the copolymers containing TFVOBB [55].…”

“…Previously, a model of radical (co)polymerisation of aryl a,b,b-trifluorovinyl ether was achieved [55]. [(a,b,b-Trifluorovinyl)oxy]bromobenzene (TFVOBB) was used as the model monomer.…”