Polmerization of Vinyl Monomers Initiated by Aquopentaamminecobalt(III)Complex

富久男, 竹村; 礼子, 松山; 克恵, 森; 丸子, 永井

doi:10.1246/nikkashi1948.92.1102

Cited by 5 publications

(2 citation statements)

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“…+TEAt (4) Ru(bpy)j +TEAt +TEA (5) TEAt +TEA-(C 2 H 5 hNH+ . +(C 2 H 5 )zNCHCH 3 (6) In CH 3 CN and DMF, the accumulation of Ru(bpy)j, which had an absorption band located about 510 nm, was observed as shown in Figure 1, since TEAt reacted with TEA ( eq 6) 13 irreversively.…”

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confidence: 99%

Tris(2,2′-bipyridine)Ruthenium(II)-Sensitized Photopolymerization of Acrylamide

Iwai

Uesugi

Takemura

1985

Polym J

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ABSTRACT:Photopolymerization of vinyl monomers sensitized by tris(2,2'-bipyridine)-ruthenium(II) complex was studied in polar solvents. No vinyl monomer tested was photopolymerized in the presence of sensitizer + alone under irradiation of visible light. Acrylamide (AA) was found to be photopolymerized in the presence of both the sensitizer and an electron donor triethylamine. The photopolymerization of AA did not occur in the presence of the sensitizer and methylviologen as an electron acceptor, but did in the coexistence of KSCN. In these systems the photosensitizer + was not consumed during the polymerization. The photopolymerization mechanisms for the +-sensitized systems are discussed.

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Section: + *mentioning

confidence: 99%

Tris(2,2′-bipyridine)Ruthenium(II)-Sensitized Photopolymerization of Acrylamide

Iwai

Uesugi

Takemura

1985

Polym J

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“…[8][9][10][11][12][13][14] In a previous paper, 13 we reported the photopolymerization of AA sensitized by the [Co(NH 3 ) 6 ]Cl 3 or [Co(enh]Cl 3 (en: ethylenediamine)-KSCN system in aqueous medium. These metal complexes alone could not initiate the photopolymerization of AA, but could sensitize the polymerization markedly in the presence of KSCN.…”

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confidence: 99%

Effects of Inorganic Anions on the Photopolymerization of Acrylamide Sensitized by 2,3-Butanedione in Aqueous Solutions

Takemura

Iwai

Ikesu

et al. 1988

Polym J

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ABSTRACT:In aqueous solutions, 2,3-butanedione (biacetyl: BA) served as a sensitizer for the photopolymerization of acrylamide (AA). The presence of inorganic salts such as KSCN, KSeCN, and NaN3 increased not only the rate of polymerization but also the molecular weight of the polymer. On the other hand, Na2SeO3 increased the rate of polymerization markedly with apparently normal kinetic behavior. In the absence of any salt, the triplet excited state of BA was shown to act as a degradative chain transfer agent as well as a photo-sensitizer. The mechanism of this characteristic photosensitized polymerization is discussed. KEY WORDSPhotopolymerization / Sensitizer / Acrylamide / 2,3-Butanedione / Biacetyl / Triplet Excited State / Inorganic Anion / Degradative Chain Transfer / The photopolymerization of vinyl monomers sensitized by organic carbonyl compounds has been investigated by many workers.1 Most of these studies were carried out in organic solvents. 2,3-Butanedione (Biacetyl: BA), an a-diketone soluble both in water and organic media, was used as an efficient sensitizer for the polymerizations of monomers such as styrene and methyl methacrylate. 2 -5 But there has been little study on BA-sensitized polymerization in an aqueous medium. Recently, Encina and his coworkers 6 reported that in the polymerization of N-vinyl-2-pyrrolidone and vinyl acetate, BA was a poor initiator and relatively high photoinitiation efficiencies were achieved only in the presence of methanol or water, by which BA was solvated giving a hydroxy-substituted alkanone effective at 300 nm irradiation.We studied the photopolymerizations of vinyl monomers such as acrylonitrile, styrene, methyl methacrylate, and acrylamide (AA) sensitized by organic dyes 7 and metal complexes.8-14 In a previous paper, 13 we reported the photopolymerization of AA sensitized by the [Co(NH 3 ) 6 ]Cl 3 or [Co(enh]Cl 3 (en: ethylenediamine)-KSCN system in aqueous medium. These metal complexes alone could not initiate the photopolymerization of AA, but could sensitize the polymerization markedly in the presence of KSCN.We thus studied such effects of inorganic salts on the photopolymerizations in aqueous solutions. BA is soluble in water and has a relatively unique property of exhibiting phosphorescence as well as fluorescence in a fluid solution at room temperature. Then, the effects of inorganic salts on the photopolymerization of AA sensitized by BA were studied kinetically and spectroscopically.Contrary to the normal kinetic behavior of radical polymerization, 15 the addition of some 565

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Catalytic action of metallic salts in autoxidation and polymerization. IX. Polymerization of methyl methacrylate with sodium hexanitrocobaltate(III) in mixed solvent of acetone and water

Osawa¹,

Sorimachi²,

Kanazawa³

et al. 1973

J. Polym. Sci. Polym. Chem. Ed.

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Polymerization of methyl methacrylate with some cobalt (III) complexes was carried out in various solvents and in mixed solvents of acetone and water or alcohols. Sodium hexanitrocobaltate(III) was found to be an effective initiator in mixed solvent of water and acetone. The kinetic study on the polymerization of methyl methacrylate with Na3[Co(NO2)6] in a water‐acetone mixed solvent gave the following over‐all rate equation: Rp = 8.04 × 104 exp{ −13,500/RT} [I]1/2[M]2 (mol/1.−sec). The effects of various additives on polymerization rate and the copolymerization curve with styrene suggest that polymerization proceeds via a radical mechanism. The dependence of the polymerization rate on the square of monomer concentration and the spectroscopic data were indicative of the formation of a complex between initiator and monomer.

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Polmerization of Vinyl Monomers Initiated by Aquopentaamminecobalt(III)Complex

Cited by 5 publications

References 0 publications

Tris(2,2′-bipyridine)Ruthenium(II)-Sensitized Photopolymerization of Acrylamide

Tris(2,2′-bipyridine)Ruthenium(II)-Sensitized Photopolymerization of Acrylamide

Effects of Inorganic Anions on the Photopolymerization of Acrylamide Sensitized by 2,3-Butanedione in Aqueous Solutions

Catalytic action of metallic salts in autoxidation and polymerization. IX. Polymerization of methyl methacrylate with sodium hexanitrocobaltate(III) in mixed solvent of acetone and water

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