Photopolymerization of Vinyl acetate sensitized by Acriflavine and l-Ascorbic acid

Takayama, Gozo

doi:10.1295/koron1944.17.644

Kobunshi Kagaku

1960

DOI: 10.1295/koron1944.17.644

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Photopolymerization of Vinyl acetate sensitized by Acriflavine and l-Ascorbic acid

Gozo Takayama¹

Abstract: Effect of acriflavine concentration on the dye-sensitized photopolymerization of vinyl acetate 30•Ž, methanol 23% (vol), l-ascorbic acid 0.191 g/dl, air/VAc-CH3OH 0.62(vol ratio)

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Cited by 10 publications

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Photosensitized polymerization of acrylic monomers. II. Kinetics of polymerization in the presence of oxygen

Delzenne¹,

Dewinter²,

Toppet³

et al. 1964

J. Polym. Sci. A Gen. Pap.

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The kinetics of the photopolymerization of acrylamide and methacrylic acid in aqueous and semi‐organic solutions have been examined; the initiating redox system used in the presence of oxygen were eosin‐thiourea, eosin‐1‐ascorbic acid, or in some cases riboflavine. The rates of photopolymerization were determined by measuring the thermal rise of the reaction cell using a thermistor technique. In aqueous and in semi‐organic solutions, the rate is proportional to the square of the monomer concentration in both cases. Below a critical concentration of sensitizer the rate of polymerization of monomers is proportional to the square root of sensitizer concentration (acrylamide in the presence of riboflavine, methacrylic acid in the presence of eosin‐ascorbic acid); above it, the rate becomes inversely proportional to the square root of the sensitizer concentration. With respect to the reducing agent concentration, the exponent for thiourea is located between 0.5 and 1 in the case of acrylamide and 0.5 for methacrylic acid. Finally with respect to the oxygen concentration the rates are proportional to the square root of its concentration, at least below a given oxygen‐concentration where the induction period becomes predominant. These results are interpreted assuring a participation of the monomer in the initiation step, and a low initiation efficiency of the primary radicals (cage recombination). A kinetic scheme is presented and the experimental results discussed on the basis of it.

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Photosensitized polymerization of acrylic monomers. II. Kinetics of polymerization in the presence of oxygen

Delzenne¹,

Dewinter²,

Toppet³

et al. 1964

J. Polym. Sci. A Gen. Pap.

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Dye‐sensitized polymerization of vinyl monomers in aqueous solution

Santappa

1965

J. Polym. Sci. A Gen. Pap.

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The kinetics of the polymerization of the vinyl monomers methyl methacrylate, methyl acrylate, and acrylonitrile sensitized by dye‐reducing agent systems have been studied systematically. The systems were irradiated with light of 350–450 mμ wavelength. The induction period before the onset of polymerization was kept to a minimum by suitable experimental conditions. All the experiments were conducted in the presence of oxygen. The redox system sodium fluorescein (Uranine)–ascorbic acid was used for polymerization. The systems were buffered with phosphate buffer. The effects of temperature, viscosity, etc., on the reaction system were studied. The course of the reactions was followed by the measurements of rate of monomer disappearance (gravimetrically), rate of dye disappearance (spectrophotometrically) and the chain length of the polymer formed (viscometrically). Light intensity, wavelength, monomer concentration, dye concentration, reducing agent concentration, temperature, etc., were variable. The tentative kinetic scheme proposed is examined in the light of the experimental results. The values for the specific rate constants for the various steps have been evaluated.

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Dye‐sensitized photopolymerization of vinyl monomers in the presence of ascorbic acid–sodium hydrogen orthophosphate complex

Nagabhushanam

Santappa

1972

J. Polym. Sci. A‐1 Polym. Chem.

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The kinetics of photopolymerization of vinyl monomers (methyl methacrylate, methylacrylate, and acrylonitrile) sensitized by the dyes acridine orange, dahlia violet, rose bengal and Pyronine G have been studied systematically. Systems containing dye, reducing agent, and monomer were irradiated with light of wavelengths 365 mμ, 546 mμ, and 405 mμ. The induction period was kept to a minimum by suitable experimental conditions. All experiments were conducted under deaerated conditions. The complex, AA–B, formed between ascorbic acid and sodium hydrogen orthophosphate (of the buffer) and reported earlier from our laboratory, played an important role in the production of the free radicals. The course of the polymerization reaction was followed by the measurements of rate of monomer disappearance −d[M]/dt (gravimetrically), rate of dye disappearance −d[D]/dt (spectrophotometrically), and the chainlengths n, of the polymer formed (viscometrically); light intensity, light wavelength, and concentrations of the dye, reducing agent, and monomer were the various variables for these measurements. A tentative scheme based on the excitation of the dye in the primary photochemical act and the interaction of the excited dye with the complex AA–B in the dark resulting in radicals (from ascorbic acid) which initiate vinyl polymerization is proposed, and the experimental results are found to conform to such a scheme. The values of various ratios of rate constants such as kp/kt½, kr/k7, ki/k6 were calculated and are discussed.

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Photopolymerization of Vinyl acetate sensitized by Acriflavine and l-Ascorbic acid

Abstract: Effect of acriflavine concentration on the dye-sensitized photopolymerization of vinyl acetate 30•Ž, methanol 23% (vol), l-ascorbic acid 0.191 g/dl, air/VAc-CH3OH 0.62(vol ratio)

Cited by 10 publications

References 0 publications

Photosensitized polymerization of acrylic monomers. II. Kinetics of polymerization in the presence of oxygen

Photosensitized polymerization of acrylic monomers. II. Kinetics of polymerization in the presence of oxygen

Dye‐sensitized polymerization of vinyl monomers in aqueous solution

Dye‐sensitized photopolymerization of vinyl monomers in the presence of ascorbic acid–sodium hydrogen orthophosphate complex

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