Study of the polymerization mechanisms of methacrylonitrile under cathodic polarization on a nickel electrode

Tanguy, J.; Deniau, Guy; Augé, C.; Zalczer, G.; Lecayon, G.

doi:10.1016/0022-0728(94)03449-4

Cited by 32 publications

(33 citation statements)

References 20 publications

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“…that decrease the local concentration of the monomer in the double layer (where the polymerization is initiated), must have a detrimental effect on the occurrence of the electrografting reaction. Since most of the experiments reported so far have been conducted only in ACN, this might explain why changing the only monomer (and not the solvent), as well as only a few monomers such as acrylonitrile [3], p-chlorostyrene [19] and methacrylonitrile [20] have been successfully grafted. As an indication of this, Tanguy et al [20,25] have recently reported that the appearance of the so-called prepeak (the signature of the grafting reaction) of methacrylonitrile in ACN occurs only at very high concentrations.…”

Section: Discussionmentioning

confidence: 99%

“…The possibility of extending the electrografting of AN to commonly used metals such as copper and steel [16,17], and to functionalize [18] the polymer coating have also been investigated. Hitherto, electrografting onto metals has been reported only for a few monomers, AN being the most representative one [3,19,20]. The purpose of the present paper is to report two distinct effects of the solvent on the electrografting reaction: (i) the effect of the polymer solvation on the electrochemical signature and the characteristics of the deposited film, and (ii) the influence of solvent polarity on the inhibition peak, the potential and intensity of which are directly related to the grafting reaction.…”

Section: Introductionmentioning

confidence: 99%

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Solvent effect on the electrografting of acrylonitrile on nickel

Mertens

Calberg

Baute

et al. 1998

Journal of Electroanalytical Chemistry

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The effect of solvent on the reductive electrografting of acrylonitrile (AN) onto nickel cathodes has been studied in dimethylformamide (DMF), a solvent for polyacrylonitrile (PAN), and in non-solvents that include acetonitrile (ACN), propylene carbonate (PC) and pyridine (PY). Electrografting responsible for the cathode inhibition has been observed for the first time in PC and PY. Not only the polymer-solvent interactions but also the intrinsic polarity of the solvent have an effect on the intensity of the inhibition peak which is the signature of the electrografting reaction. Concentration of the monomer in the electrode double layer appears to decrease as the solvent polarity is increased, consistently with a more efficient displacement of the monomer by a more polar compound. That such a competition occurs is also supported by the effect of the nature and concentration of the conducting salt. The best quality films are formed in DMF, which is a solvent for PAN. Quarts: microbalance experiments have emphasized the crucial importance of the potential range used for the AN electroreduction, particularly in a solvent of the polymer.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Solvent effect on the electrografting of acrylonitrile on nickel

Mertens

Calberg

Baute

et al. 1998

Journal of Electroanalytical Chemistry

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“…Displacement of solvent molbiguous, since this polymer is known to be soluble in the reaction medium (ACN). Furthermore, according to these ecules by an electroactive molecule is the rule [25] and competitive adsorption of different species is a phenomenon authors, infrared spectra did not show any structural modification indicating cross-linking [11] . Nevertheless, they commonly observed in these experiments [26] .…”

Section: Introductionmentioning

confidence: 95%

“…The important role played by the solvent in interfacial adence of the deposited film. The case of polymethacrylonitrile, recently reported by Tanguy et al [11] [12] , is less am-sorption processes has been known for a long time in electrochemical experiments [24] . Displacement of solvent molbiguous, since this polymer is known to be soluble in the reaction medium (ACN).…”

Section: Introductionmentioning

confidence: 96%

Electrografting of Acrylic and Methacrylic Monomers onto Metals: Influence of the Relative Polarity and Donor–Acceptor Properties of the Monomer and the Solvent

Baute

Teyssié

Martinot

et al. 1998

Eur. J. Inorg. Chem.

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The possibility of grafting a series of alkyl polyacrylates and polymethacrylates onto a nickel cathode by electropolymerization of the parent monomers has been investigated and has emphasized the critical importance of the solvent used. Indeed, the intensity of the inhibition peak, which is the electrochemical mark of the cathode passivation as result of the polymer grafting, clearly depends on both the polarity and the donor‐acceptor properties of the solvent. The Gutmann concept is used to account for these experimental results. An increase in the donicity of the solvent used for the electrochemical medium has allowed, for the very first time, several polyacrylates and polymethacrylates [such as poly(ethyl acrylate), poly(methyl methacrylate), and poly(2‐trimethylsilyloxyethyl methacrylate)] to be electrografted onto Ni. This observation is consistent with a competition process between the monomer and the solvent for being adsorbed on the cathode and amassing in its very close vicinity. The outcome of this competition is controlled by the relative polarity (in case of low donicity) and the relative donor‐acceptor properties (when the difference is high enough) of the monomer/solvent pair, and by the monomer concentration (in case of weak competition). A semi‐quantitative relationship has also been observed between the monomer ability to be electrografted and the electron‐accepting character of the vinyl β‐carbon atom as measured by 13C NMR.

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“…Until recently, the choice of the monomer to be grafted was restricted to AN and methacrylonitrile (MAN) [12], which would constitute a severe limitation to the practical use of this technique. In an effort to understand the origin of this restriction, dependence of the electrochemical reaction on the composition of the conducting solution (mainly conducting salt and solvent) has been studied [8].…”

mentioning

confidence: 99%

Electrodeposition of mixed adherent thin films of poly(ethyl acrylate) and polyacrylonitrile onto nickel

et al. 2004

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Adherent thin polymer films have been prepared by sequential electrodeposition of ethyl acrylate (EA) and acrylonitrile (AN) onto nickel. Their composition has been studied by IR spectroscopy and time of flight -secondary ion mass spectrometry. Morphology and thickness have been analyzed by atomic force microscopy and ellipsometry, respectively, and compared to single component films of PEA and PAN. No microphase separation was detected in the mixed PEA/ PAN films. These show a granular morphology comparable to that of PAN films. The grains contain the two constitutive polymers, as confirmed by the selective thermal degradation of PEA.

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Study of the polymerization mechanisms of methacrylonitrile under cathodic polarization on a nickel electrode

Cited by 32 publications

References 20 publications

Solvent effect on the electrografting of acrylonitrile on nickel

Solvent effect on the electrografting of acrylonitrile on nickel

Electrografting of Acrylic and Methacrylic Monomers onto Metals: Influence of the Relative Polarity and Donor–Acceptor Properties of the Monomer and the Solvent

Electrodeposition of mixed adherent thin films of poly(ethyl acrylate) and polyacrylonitrile onto nickel

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