Poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) Modification via Organocatalyzed Atom Transfer Radical Polymerization

Abstract

To address the challenge of metal contamination, a "graft from" approach via organocatalyzed atom transfer radical polymerization (O-ATRP) is developed to synthesize poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE)) graft copolymers. N-phenylphenothiazine is utilized as a model organic photoredox catalyst for catalyzing the (co)polymerization of methyl methacrylate (MMA), methacrylate (MA), and n-butyl acrylate (BA). By employing this technique, high temporal control of polymerization and graft content are achieved. A series of P(VDF-co-CTFE)-g-PMMA, P(VDF-co-CTFE)-g-PMA, and P(VDF-co-CTFE)-g-PBA is prepared under mild conditions. The resultant graft copolymer can be used as macroinitiator to re-initiate O-ATRP to synthesize P(VDF-co-CTFE)-g-(PMMA-b-PMA), which might exhibit the potential application as novel dielectric material.

Advances in Organocatalyzed Atom Transfer Radical Polymerization

“…Our group developed a P(VDF-co-CTFE) gra modi cation strategy via O-ATRP by using N-phenylphenothiazine as the catalyst (Figure 3) [41]. A series of P(VDF-co-CTFE)-g-PMMA, P(VDF-co-CTFE)-g-PMA, and P(VDF-co-CTFE)-g-PBA were prepared under mild conditions with high temporal control.…”

“…Poly(vinylidene uoride-co-chlorotri uoroethylene) modi cation via organocatalyzed atom transfer radical polymerization. (Adapted with permission from Ref [41]…”

Continuous Flow Photoinduced Reversible Deactivation Radical Polymerization

“…Since the initial discovery in 2014, [71][72] series of organic photoredox catalysts (PCs) have been developed to mediate socalled organocatalyzed atom transfer radical polymerization (O-ATRP) or metal-free ATRP. [83][84][85][86][87][88][89][90][91] It offers a fascinating avenue to fabricate tailor-made polymers without metal residue. [92] Miyake and co-workers [93] firstly transferred O-ATRP from the batch reactor to the flow mode.…”

Metal-Free ATRP Catalyzed by Visible Light in Continuous Flow

“…Despite their effectiveness, metal contamination limits their interest for biomedical and electronic applications. Significant effort has therefore been dedicated to develop photoredox metal-free ATRP (Chen et al, 2016 ; Pan et al, 2016b ; Hu et al, 2017 ; Ryan et al, 2017 ; Discekici et al, 2018 ). Pioneering work by Hawker's group demonstrated that 10-phenylphenothiazine (PTH) can be an effective organic photoredox catalyst for the polymerization of methacrylates under ultraviolet irradiation (Treat et al, 2014b ).…”