Straightforward Synthesis of Well-Defined Poly(vinylidene fluoride) and Its Block Copolymers by Cobalt-Mediated Radical Polymerization

Falireas, Panagiotis G.; Ladmiral, Vincent; Debuigne, Antoine; Detrembleur, Christophe; Poli, Rinaldo; Améduri, Bruno

doi:10.1021/acs.macromol.8b02252

Cited by 36 publications

(34 citation statements)

References 57 publications

(187 reference statements)

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“…In addition to catalytic CCTP, cobalt complexes have also shown a remarkable capability to achieve the controlled/living radical polymerization (C/LRP) of both conjugated vinyl monomers and unconjugated vinyl monomers . Cobalt(II) porphyrin complex, Co II (TMP) [Scheme (c)], was first reported to mediate the controlled/living radical polymerization (C/LRP) of methyl acrylate (MA) by Wayland et al Another milestone was attributed to Jérôme et al who used cobalt(II) acetylacetonate [Co II (acac) 2 , Scheme (d)] to control the VAc polymerization .…”

Section: Introductionmentioning

confidence: 99%

“…11,12 Recently, Engelis et al used the cobaloxime to unconjugated vinyl monomers. [16][17][18][19][20][21][22][23] Cobalt(II) porphyrin complex, Co II (TMP) [Scheme 1(c)], was first reported to mediate the controlled/living radical polymerization (C/LRP) of methyl acrylate (MA) by Wayland et al 24 Another milestone was attributed to Jérôme et al who used cobalt(II) acetylacetonate [Co II (acac) 2 , Scheme 1(d)] to control the VAc polymerization. 25 Afterward, several cobalt complexes were then applied to mediate controlled/living radical polymerization.…”

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confidence: 99%

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Cobalt(II) phenoxy‐imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

Chen

et al. 2019

Journal of Polymer Science

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A series of cobalt(II) phenoxy‐imine complexes (CoII(FI)2) have been synthesized to mediate the radical polymerization of vinyl acetate (VAc) and methyl acrylate (MA) to evaluate the influence of chelating atoms and configuration to the control of polymerization. The VAc polymerizations showed the properties of controlled/living radical polymerization (C/LRP) with complexes 1a and 3a, but the catalytic chain transfer (CCT) behaviors with complexes 2a, 1b, 2b, and 3b. The control of VAc polymerization mediated by complex 1a could be improved by decreasing the reaction temperature to approach the molecular weights that not only linearly increased with conversions but also matched the theoretical values and relatively narrow molecular weight distributions. The catalytic chain transfer polymerizations (CCTP) mediated by complexes 2a, 1b, 2b, and 3b were characterized by Mayo plots and the polymer chain end double bonds were observed by 1H NMR spectra. The tendency toward C/LRP or CCTP in VAc polymerization mediated by CoII(FI)2 could be determined by the ligand structure. Cobalt complex coordinated by the ligand with more steric hindered and less electron‐donating substituents favored the controlled/living radical polymerization. In contrast, the efficiency of CCT process could be enhanced by less steric hindered, more electron‐donating ligands. The controlled/living radical polymerization of MA, however, could not be achieved by the mediation of these cobalt(II) phenoxy‐imine complexes. Associated with the results of polymerization mediated by other cobalt complexes, this study implied that the configuration and spin state of cobalt complexes were more critical than the chelating atoms to the control behavior of radical polymerization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 101–113

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Cobalt(II) phenoxy‐imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

Chen

et al. 2019

Journal of Polymer Science

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“…Recently, inspired by the progress of CMRP for less activated monomers, such as vinyl acetate (VAc), [20] our group explored the polymerization of VDF mediated by cobalt acetylacetonate complexes. [18,19] Thanks to the more efficient reactivation of PVDF T À X (when X=Co III (acac) 2 ) chains [21] observed under these CMRP conditions, it led to an enhanced control of the polymerization.…”

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confidence: 98%

“…ITP, [6][7][8][9][10][11] RAFT, [12][13][14][15][16][17] and CMRP [18][19] polymerizations have proven to be the most suitable methods for the polymerization of VDF. In 1979, VDF was polymerized by ITP method, [6] but the effective activation of the HH addition product (PVDFÀ CF 2 À CH 2 À I) was not reported until the Asandei's group introduced metal carbonyl photoactivators such as Mn 2 (CO) 10 .…”

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PhotoRAFT Polymerization of Vinylidene Fluoride Using a Household White LED as Light Source at Room Temperature

2019

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The photoRAFT (RAFT = reversible addition-fragmentation radical transfer) polymerization of vinylidene fluoride (VDF) mediated by O-ethyl-S-(1-methoxycarbonyl)ethyl dithiocarbonate using a household white LED as light source at room temperature is presented. PVDFs with molar masses up to ca. 8000 g mol À 1 and low dispersities (1.11-1.49) were obtained. Kinetic experiments revealed that the use of Ir(ppy) 3 as photoredox catalyst lead to faster polymerization. A slowdown of the chain equilibration process was observed during the polymerization, attributed to the accumulation of the less reactivatable CF 2 À CH 2 À Xa terminated chains.

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Fluoropolymers for Automotive and Aerospace Industries

Bouharras

Raihane

Lopez³

et al. 2022

Macromolecular Engineering

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The usefulness of fluoropolymers (PFs) in various items for vehicles, shuttles, and space‐crafts is presented, considering their synthesis, properties, applications, and recycling. The advantages of FPs are first supplied, including outstanding properties (chemical, oxidative, and thermal resistances, and excellent weatherability and durability to avoid obsolescence), as well as their synthesis usually achieved by conventional radical copolymerization of fluoromonomers. They can be composites and shape memory polymers or specific copolymers produced on demand. Applications of specific FPs are discussed in various areas: (i) high‐performance thermoplastic elastomers (composed of central soft blocks and external hard sequences as triblock copolymers) involved as cross‐linked O‐rings or shafts, (ii) flame retardant coatings and liners for planes; (iii) for energy related‐materials (e.g. fuel cell membranes for the next generation of clean energy‐vehicles, reliable components for safer Lithium ion batteries for hybrid vehicles, electroactive devices, etc.).

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Straightforward Synthesis of Well-Defined Poly(vinylidene fluoride) and Its Block Copolymers by Cobalt-Mediated Radical Polymerization

Abstract: The organometallic-mediated radical polymerization (OMRP) of vinylidene fluoride (VDF) using an alkyl cobalt(III) compound as initiator was recently proven successful for the controlled synthesis of PVDF (Angew.

Cited by 36 publications

References 57 publications

Cobalt(II) phenoxy‐imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

Cobalt(II) phenoxy‐imine complexes in radical polymerization of vinyl acetate: The interplay of catalytic chain transfer and controlled/living radical polymerization

PhotoRAFT Polymerization of Vinylidene Fluoride Using a Household White LED as Light Source at Room Temperature

Fluoropolymers for Automotive and Aerospace Industries

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