Synthesis of unsaturation containing P(VDF‐co‐TrFE‐co‐CTFE) from P(VDF‐co‐CTFE) in one‐pot catalyzed with Cu(0)‐based single electron transfer living radical polymerization system

Abstract

Poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene) (P(VDF-co-TrFE-co-CTFE)) with internal double bond has been reported with high dielectric constant and energy density at room temperature, which is expected to serve as a promising dielectric film in high pulse discharge capacitors. An environmentally friendly one-pot route, including the controllable hydrogenation via Cu(0) mediated single electron transfer radical chain transfer reaction (SET-CTR) and dehydrochlorination catalyzed with N-containing reagent, is successfully developed to synthesize P(VDF-co-TrFE-co-CTFE) containing unsaturation. The resultant polymer was carefully characterized with 1 H NMR, 19 F NMR, and FTIR. The composition of the resultant copolymer is strongly influenced by reaction conditions, including the reaction temperature, catalyst concentration, the types of ligands and solvents. The kinetics data of the chain transfer and elimination reaction demonstrate their wellcontrolled feature of the strategy. By shifting the equilibrium between the CTR and elimination reactions dominated by Ncompounds serving as ligands in SET-CTR and catalyst in the dehydrochlorination of P(VDF-co-CTFE), P(VDF-co-TrFE-co-CTFE) with tunable TrFE and double-bond content could be synthesized in this one-pot route.

Fluorinated Methacrylate-Grafted P(VDF-CTFE) and Albumin Layers for Reducing Fibrinogen Adsorption

“…Under the ATRP reaction conditions, internal unsaturation can occur by the β-hydrogen elimination mechanism, as previously reported. 44,45 By comparing the peak integrals in the 1 H NMR spectra, the chemical compositions of P(VDF-CTFE)-g-PFMMAs were obtained, and they are listed in Table 1; these were further confirmed from the 19 F NMR spectra (Figure 1c). The mole fraction of reacted CTFE and the average numbers of attached monomers in a side chain ranged from 9.3 to 11.1 mol % and 10.6 to 13.8 mol %, respectively, although the mole fraction of the generated double bond was in the range of 4.0−7.0 mol %.…”

Photoinduced Cu(II)-Mediated RDRP to P(VDF-co-CTFE)-g-PAN

“…This Cu(I)-mediated process required relative high catalyst loading and elevated reaction temperature to initiate the less active C–Cl bond in P(VDF- co -CTFE) backbone, which resulted in unexpected chain transfer reactions and dehydrochlorination reactions [ 56 ]. Cu(0)-mediated RDRP of acrylonitrile (AN) and methyl methacrylate (MMA) in the presence of P(VDF- co -CTFE) allowed colorless and purer P(VDF- co -CTFE)- g -PAN and P(VDF- co -CTFE)- g -PMMA copolymers for its mild reaction conditions and lower catalyst concentration [ 57 , 58 , 59 ]. Improvements were achieved by transferring the polymerization from a batch reactor to a copper tubular reactor, such as diminished inconsistent induction time, suppressed “hot spot” effect, and decreased copper and ligand concentration [ 60 ].…”

Synthesis and characterization of multifunctional polyamide 1 using CO2 and urea via environment‐friendly method

“…For example, Newman reported that the ferroelectric nature and piezoelectric properties increased with the increasing of hydrogen bond and dipole density for polyamides . For odd polyamides, the NH and CO groups can fully form hydrogen bonds between molecular chains . Figure shows the structure of hydrogen bond between molecular chains for polyamide 11 (PA11), polyamide 9 (PA9), polyamide 7 (PA7), and polyamide 3 (PA3), in which the hydrogen bond density increases with the decreasing of methylene in molecular chains.…”