Electrogenerated aromatic radical cations as initiators of cationic polymerization of styrene

Turcot, Luce; Glasel, Arnold; Funt, B. Lionel

doi:10.1002/pol.1974.130121204

Cited by 10 publications

(5 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this latter case, the oxidation of DPA is confirmed by the appearance of a blue color in the electrode vicinity which may be attributed to the presence of the DPA' + radical cation. Thus it may be considered that C104" and DPA '+ radicals initiate the THF polymerization, a very likely hypothesis as we know that DPA is very often used for cationic polymerization (18). This hypothesis is also confirmed by the work of Nakahama et al (8) but is in opposition to the mechanism proposed by Dey et al (10), who assume that the polymerization is initiated by the THF electrooxidation.…”

Section: Resultsmentioning

confidence: 77%

“…Under certain experimental conditions the amount of charge that the Ir surface can store in the oxide region increases during cycling. The electrode activation depends on the limits of the potential excursion, on the rate of the potential perturbation, and on the electrolyte composition (8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23).…”

Section: Introductionmentioning

confidence: 99%

“…Various explanations have been advanced for the electrochemical behavior of Ir in aqueous solutions such as an expanded lattice theory for oxide growth on noble metals (5), an irreversible oxide formation with subsequent stoichiometry changes (16), oxide-filled pitting formation, and formation of a polymeric layer of oxygen-bridged hydrated oxy-hydroxo species (18,19). These attempts, however, are only qualitative and * Electrochemical Society Active Member.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Polaromicrotribometric (PMT) and Spectroscopic (Infrared‐XPS) Study of the Formation and Modifications of Films Formed on a Polarized Platinum Electrode in THF ‐ LiClO4 Medium: II . Anodic Polarization

Tourillon

Dubois

Lacaze

1978

J. Electrochem. Soc.

View full text Add to dashboard Cite

The surface changes occurring when a platinum electrode is anodieally polarized in THF-LiC104 or in THF-LiCIO~-9,10 dip'henylanthracene (DPA) are detected and investigated by means of polaromicrotribometry (PMT). The formation of a 'homogeneous film on the metal surface is associated with a very small value of the friction coefficient. The thickness of this film, designated by the general symbol PtITHF, LiC104, Oxl, may be adjusted from 100 to 5000A. It appears as a very pure variety of polyTHF, uncontaminated by the electrolyte. Multiple-reflection infrared spectroscopy and x-ray photoelectron spectroscopy (XPS) are used to determine its structure. Its formation results from the polymerization of THF via an ionic mechanism initiated by C104" or DPA" + radicals. It only occurs if the water content is less than 250 ppm. This film has well-defined physical properties: a marked hydrophobicity, very strong adherence on the platinum surface, and great homogeneity; although it is a nonconductor out of the solution, its porous structure makes it a conductor in electrolyte solution.The development of the technology in the area in microelectronics and, more recently, in that of integrated optics is more and more dependent on different methods of elaborating organic or mineral films (1). In the case of organic films, numerous techniques for deposition on metallic surfaces have been described. The most common methods are based on vapor deposition or sublimation (1), adsorption (2) or polymerization of an organic vapor subjected to electronic bombardment (3) or to an electric discharge (4). Electrochemical techniques can also be used for the elaboration of mineral or organic films, applicable to the previous areas. The film quality (purity, adherence, and homogeneity) depends on the Chemical system chosen, on the polarization conditions, and also on the choice of the chemical medium in which the electrode reaction is occurring. Generally speaking, it is possible to obtain an organic polymer film adsorbed on a metallic surface by oxidizing or reducing a compound which produces polymerizable radical or ionic species. The chosen reagent may either be a monomer dissolved in a solvent, or the solvent itself. The THF example belongs to this latter case, and in a previous work (5) we show that several mineral films are formed on the electrode under cathodic polarization.The polymerization of THF by chemical (6) or electrochemical (7-10) means has already been described in the literature, but it is only related to the formation of the dissolved polymer in solution. As far as we know, no study has been devoted to the phenomena which occur on the electrode surface for an anodic polarization.By using the PMT technique (11, 12), we have been a~ble to show important modifications of the platinum surface in the anodic zone. These are related to the appearance of a deposit which could not be detected * Electrochemical Society Active Member. by analysis of the i-E curves alone. This first observation is confirmed by means of other analytica...

show abstract

Section: Resultsmentioning

confidence: 77%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Polaromicrotribometric (PMT) and Spectroscopic (Infrared‐XPS) Study of the Formation and Modifications of Films Formed on a Polarized Platinum Electrode in THF ‐ LiClO4 Medium: II . Anodic Polarization

Tourillon

Dubois

Lacaze

1978

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…Most published work deals with kinetic aspects of the cation radical monomer interaction and shows that the rates of cation radical decay, of monomer reaction and of polymer formation do not always parallel one another (8,9). This point means that if practical interest is involved in the use of cation radicals, specific experiments demonstrating the feasibility of polymer synthesis must be performed, as was reported for DPA" , which effectively polymerizes styrene with both the generation techniques mentioned above (9).…”

Section: Introductionmentioning

confidence: 99%

Perylene cation radical as initiator of cationic polymerization

Oberrauch

Salvatori

Cesca

1978

J. Polym. Sci. B Polym. Lett. Ed.

View full text Add to dashboard Cite

“…In this paper we present a comparison of the reactivity of a number of radical cations formed by the electrolysis of their polyaromatic hydrocarbon parent molecules some of which are shown in the form of the basic compounds including the numbering in the following scheme. 1 5 10 4 Anthracene Perylene 6 5 Pyrene 2 I Triphenylene Rubrene (5,6,11,12-tetraphenylnaphthacene) An equal initial (mole) concentration of radical cation was formed in each case, and the rate of cation reaction was measured from the time of monomer addition. We also report on electropolymerization studies in which the parent hydrocarbon and monomer are electrolyzed "in situ" at controlled potential.…”

mentioning

confidence: 99%

Comparative reactivities of electrogenerated radical cations in cationic polymerization

1976

Self Cite

View full text Add to dashboard Cite

Persistent radical cations were produced electrochemically from the parent hydrocarbons 9,lO-diphenylanthracene (DPA), 9-phenylanthracene (9-PA), 9,l O-dimethylanthracene (DMA), rubrene (Ru), triphenylene (TP), 1,3,6&tetraphenylpyrene (TPP), and perylene (P). The stabilities of these cations in the absence of monomer wereThe rates of decay of DPA? increased with the dielectric constant of the solvent and were 4 to 5 times greater in CH3CN than in CH2CI2 or C6H5N02.The kinetics of the reaction of the radical cation with monomer were investigated for styrene and isobutyl vinyl ether. For styrene and P + or DPA f a first order dependence on the radical cation concentration was found. However, R u t decay was unaffected by the addition of styrene and polymerization was not initiated. With R u t and isobutyl vinyl ether a first order dependence on cation was observed and polymers were obtained. Electropolymerizations were also conducted with the generation of radical cations in situ and the rates of monomer consumption and polymer production were measured. The passage ofthe same electric charge in Faradays (1 Faraday = 96496 coulomb) resulted in the polymerization of different amounts of the monomer and generally paralleled the reactivities found for the various radical cations. ZUSAMMENFASSUNG:Bestandige Radikalkationen wurden elektrochemisch erzeugt, ausgehend von den Kohlenwasserstoffen 9,lO-Diphenylanthracen (DPA), 9-Phenylanthracen (9-PA), 9,lO-Dimethylanthracen (DMA), Rubren (Ru), Triphenylen (TP), 1,3,6&Tetraphenylpyrene (TP), und Perylen (P). Die Stabilitaten dieser Kationen in Abwesenheit nahmen in der folgenden Reihenfolge ab: 3345

show abstract

Electrogenerated aromatic radical cations as initiators of cationic polymerization of styrene

Cited by 10 publications

References 14 publications

Polaromicrotribometric (PMT) and Spectroscopic (Infrared‐XPS) Study of the Formation and Modifications of Films Formed on a Polarized Platinum Electrode in THF ‐ LiClO4 Medium: II . Anodic Polarization

Polaromicrotribometric (PMT) and Spectroscopic (Infrared‐XPS) Study of the Formation and Modifications of Films Formed on a Polarized Platinum Electrode in THF ‐ LiClO4 Medium: II . Anodic Polarization

Perylene cation radical as initiator of cationic polymerization

Comparative reactivities of electrogenerated radical cations in cationic polymerization

Contact Info

Product

Resources

About