Organometallic‐Mediated Radical Polymerization of Vinylidene Fluoride

Banerjee, Sanjib; Ladmiral, Vincent; Debuigne, Antoine; Detrembleur, Christophe; Poli, Rinaldo; Améduri, Bruno

doi:10.1002/ange.201712347

Cited by 26 publications

(24 citation statements)

References 40 publications

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“…Another puzzling result is that, although the occurrence of RRT (stoichiometrically oxidizing the ATRP activator complex L/Cu I to an inactive L/Cu II X complex) is promoted by water and other proton donors, the complexes investigated in the present study are quite robust ATRP catalysts even in water, to give well-controlled halogen-capped macromolecules with high chain-end fidelity. A full understanding of how radicals interact with L/Cu I complexes under polymerization conditions is paramount not only to rationalize the good performance of ATRP catalysts and possibly further improve them, but also for implementing polymerizations successfully controlled by only OMRP, which presents certain advantages in particular for less activated monomers, [69][70][71] without interference of metal-catalyzed or mediated terminations (CRT or RRT).…”

Section: Resultsmentioning

confidence: 99%

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

et al. 2019

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Cyanoisopropyl radicals, generated thermally by the decomposition of azobis(isobutyronitrile) (AIBN), participate in reductive radical termination (RRT) under the combined effect of copper(I) complexes and proton donors (water, methanol, triethylammonium salts) in acetonitrile or benzene. The investigated copper complexes were formed in situ from [Cu I (MeCN)4] + BF4in CD3CN or Cu I Br in C6D6 using tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA) and 2,2'-bipyridine (BIPY) ligands. Upon keeping all other conditions constants, the impact of RRT is much greater for the Me6TREN and TPMA systems than for the BIPY system. RRT scales with the proton donor acidity (Et3NH + >> H2O > CH3OH), it is reduced by deuteration (H2O > D2O and CH3OH > CD3OD) and it is more efficient in C6D6 than in CD3CN. The collective evidence gathered in this study excludes the intervention of an outer-sphere proton-coupled electron transfer (OS-PCET), while an innersphere PCET (IS-PCET) cannot be excluded for coordinating proton donors (water and methanol). On the other hand, the strong impact of RRT for the non-coordinating Et3NH + in CD3CN results from the formation of an intermediate Cu I-radical adduct, suggested by DFT calculations to involve binding via the N atom to yield keteniminato [L/Cu-N=C=CMe2] + derivatives with only partial spin delocalization onto the Cu atom.

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Section: Resultsmentioning

confidence: 99%

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

et al. 2019

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“…Successful controlled radical polymerizations (CRP) of VDF have also been reported including iodine transfer polymerization (ITP), reversible addition-fragmentation transfer (RAFT) polymerization and borane-mediated polymerization [19,27,28].…”

Section: Pvdf Homopolymersmentioning

confidence: 99%

Poly(vinylidene fluoride)-based complex macromolecular architectures: From synthesis to properties and applications

Ζάψας

Patil

Gnanou

et al. 2020

Progress in Polymer Science

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This review highlights the synthesis, properties and applications, as well as the potential, of poly(vinylidene fluoride) (PVDF)-based complex macromolecular architectures (CMAs), a class of materials that has not received much attention in the literature. PVDF, the second in production fluoropolymer, is an attractive material due to its outstanding properties (high thermal stability and chemical inertness) along with its piezo-, pyro-and ferro-electrical performance. Even though only a small number of reports on PVDF-based CMAs have been published, growing interest in the synthesis/properties of non-linear structures (graft, miktoarm star, star and dendrimers) has emerged due to their potential for application in areas such as drug/gene delivery, electronics and energy harvesting devices. The aim of this review is to present primary strategies for the synthesis of PVDF-based polymer materials with CMAs and critically discuss strategies and opportunities that may facilitate their commercialization. It can be anticipated that PVDF-based CMA polymers will play a progressively important role in materials science and nanotechnology, both in academia and industry. Abbreviations AAc Acrylic acid APCN Amphiphilic polymer conetworks ATRC Atom transfer radical coupling ATRP Atom transfer radical polymerization BDFO 8-bromo-1H,1H,2H-perfluorooct-1-ene BCP Block copolymer BVPE Bis(vinyl phenyl) ethane BSA Bovine serum albumen CMA Complex macromolecular architectures CuAAC Copper(I)-catalyzed azide-alkyne cycloaddition CRP Controlled radical polymerization CTFE Chlorotrifluoroethylene DMA Dimethyl acetamide DMAEMA 2-(dimethylamino)ethyl methacrylate DMAPS N, N'-dimethyl-(methylmethacryloyl ethyl) ammonium propanesulfonate DMF Dimethylformamide DMSO Dimethyl sulfoxide DVB Divinylbenzene EB Electron beam EGMA Ethylene glycol methacrylate GMA Glycidyl methacrylate GPE Gel polymer electrolyte HFP Hexafluoropropylene ITP Iodine transfer polymerization MF Micro-filtration

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“…Interestingly, the device can regulate VDF polymerization that acts as a counter-radical [23,25]. For the controlled synthesis of PVDF, the organometallic-mediated radical polymerization (OMRP) of vinylidene fluoride (VDF) using an alkyl cobalt(III) compound as the initiator has recently proven successful [26]. The straightforward synthesis of well-defined poly(VDF) and its block copolymers through OMRP was performed from readily available compounds using a two-component initiating method.…”

Section: Fig 1α β and γ Crystalline Phases Chain Conformation Diagmentioning

confidence: 99%

A Brief Review on Prospective of Polyvinylidene Fluoride as a Tissue Engineered Scaffold Material

Hamzah¹,

Razak²,

Ramli³

et al. 2020

JAITA

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This review focuses on the potential of polyvinylidene fluoride (PVDF) as tissue scaffolding materials. PVDF is defined in terms of the synthesis mechanisms and the method of the β phase formation process. General properties are fundamentally discussed in terms of their wettability and electroactive characteristics, which play an essential role in modifying other potential materials for tissue-based applications. The latest technologies for the replacement of artificial tissue scaffolds are evaluated, and the applications of PVDF-based scaffolds are discussed.

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Organometallic‐Mediated Radical Polymerization of Vinylidene Fluoride

Cited by 26 publications

References 40 publications

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton–Electron Transfer?

Poly(vinylidene fluoride)-based complex macromolecular architectures: From synthesis to properties and applications

A Brief Review on Prospective of Polyvinylidene Fluoride as a Tissue Engineered Scaffold Material

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