Preparation of Well‐Defined PVOH/C60 Nanohybrids by Cobalt‐Mediated Radical Polymerization of Vinyl Acetate

Detrembleur, Christophe; Stoilova, Olya; Bryaskova, Rayna; Debuigne, Antoine; Mouithys-Mickalad, Ange; Jérôme, Robert

doi:10.1002/marc.200500871

Cited by 36 publications

(41 citation statements)

References 24 publications

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“…[29][30][31][32] Well-defined statistical copolymers [33,34] could also be prepared and fullerene was successfully grafted by PVAc and PVOH. [35] Until recently, CMRP was explained by a reversible termination mechanism based on the homolytic cleavage of the terminal CoÀC bond. [26] However, recent studies proposed that a degenerative chain transfer would operate, at least under certain conditions.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Cobalt‐Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(III) Adducts as Initiators

Debuigne

Champouret

Jérôme

et al. 2008

Chemistry A European J

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Over the past few years, cobalt-mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the reason for this success and the intimate mechanism remained basically speculative. Herein, two mechanisms are shown to coexist: the reversible termination of the growing poly(vinyl acetate) chains by the Co(acac)2 complex (acac: acetylacetonato), and a degenerative chain-transfer process. The importance of one contribution over the other strongly depends on the polymerization conditions, including complexation of cobalt by ligands, such as water and pyridine. This significant progress in the CMRP mechanism relies on the isolation and characterization of the very first cobalt adducts formed in the polymerization medium and their use as CMRP initiators. The structure proposed for these adducts was supported by DFT calculations. Beyond the control of the VAc polymerization, which is the best ever achieved by CMRP, extension to other monomers and substantial progress in macromolecular engineering are now realistic forecasts.

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Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into the Cobalt‐Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(III) Adducts as Initiators

Debuigne

Champouret

Jérôme

et al. 2008

Chemistry A European J

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181

318

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“…9 However, polymer chains can be directly grafted onto the CNT surfaces by employing radical addition reactions between the free radicals of the polymer chain ends and the π-bonds of the CNT surfaces, which is a more convenient method to prepare polymer-functionalized CNTs. Detrembleur et al 21 synthesized photoactive PVA-grafted fullerenes (C60) via direct grafting of PVAc to C60 and subsequent hydrolysis of the PVAc. They first synthesized welldefined PVAc-Co(acac) 2 via bulk CMRP of VAc.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of water-soluble poly(vinyl alcohol)-grafted multi-walled carbon nanotubes

Jeon

Youk

2010

Macromol. Res.

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A facile method for preparing waster-soluble poly(vinyl alcohol)-grafted multi-walled carbon nanotubes (PVA-grafted MWNTs) was developed. Well-defined poly(vinyl acetate) chains end-capped by a cobalt(II) acetylacetonate (Co(acac) 2 ) complex [PVAc-Co(acac) 2 ] were synthesized by the cobalt-mediated radical polymerization (CMRP) of vinyl acetate. PVAc macroradicals generated by the homolytic cleavage of the carbon-cobalt (C-Co) bonds of PVAc-Co(acac) 2 chains were then grafted directly to the MWNTs via radical addition reactions in dimethyl sulfoxide (DMSO) at 50 o C. The amount of the PVAc grafted onto the surface of the MWNTs decreased with increasing molecular weight of PVAc-Co(acac) 2 . Hydrolysis of the grafted PVAc finally yielded PVA-grafted MWNTs, which showed good solubility in water. Surface functionalization of the MWNTs was confirmed by 1 H NMR spectroscopy, FTIR spectroscopy and TEM.

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“…As a rule, the treatment of polymers prepared by CMRP with nitroxides and thiols produced cobalt-free polymers that were terminated by an alkoxyamine and hydrogen, respectively [44]. Both, fullerenes [45,46] and nanotubes [47], which are prone to radical addition, were similarly used as radical traps, leading to carbon nanoobjects grafted with polymers.…”

Section: Macromolecular Engineeringmentioning

confidence: 99%

Cobalt‐Mediated Radical Polymerization

Debuigne

Jérôme

et al. 2012

Materials Science and Technology

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Controlled radical polymerization driven by cobalt complexes has emerged over the past decades as a powerful tool for the design of precision polymers. This so‐called Cobalt‐Mediated Radical Polymerization (CMRP) relies on the temporary deactivation of the radical chains by a cobalt complex, which strongly decreases the probability of bimolecular termination reactions. CMRP imparts control to industrially important monomers and allows formation of polymers with predictable molecular weights and well‐defined architectures. This book chapter describes general mechanistic principles, key parameters and synthetic progress of CMRP as well as remaining challenges.

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Preparation of Well‐Defined PVOH/C60 Nanohybrids by Cobalt‐Mediated Radical Polymerization of Vinyl Acetate

Cited by 36 publications

References 24 publications

Mechanistic Insights into the Cobalt‐Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(III) Adducts as Initiators

Mechanistic Insights into the Cobalt‐Mediated Radical Polymerization (CMRP) of Vinyl Acetate with Cobalt(III) Adducts as Initiators

Synthesis of water-soluble poly(vinyl alcohol)-grafted multi-walled carbon nanotubes

Cobalt‐Mediated Radical Polymerization

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