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Journal ArticleDOI

Redox polymerization of acrylonitrile. Kinetics of the reaction initiated by systems based on cyanoacetic acid/Mn(III) complexes in dimethylsulphoxide

01 Jan 1982-European Polymer Journal (Pergamon)-Vol. 18, Iss: 6, pp 501-505
TL;DR: The kinetics of polymerization of acrylonitrile initiated by the redox systems cyanoacetic acid/Mn(OAc) 3 and tris(benzoylacetonato)manganese(III) in dimethylsulphoxide as solvent have been investigated over the range 20-35°.
About: This article is published in European Polymer Journal.The article was published on 1982-01-01. It has received 1 citations till now. The article focuses on the topics: Cyanoacetic acid & Polymerization.
Citations
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Journal ArticleDOI
TL;DR: In this paper, the photodegradation of thin poly(para-tert-butylstyrene) with 265 nm radiation in the presence of oxygen, and as a function of irradiation time, has been studied using fluorescence, Fourier transform-infrared spectroscopy, and ultraviolet visible spectrograms.
Abstract: The photodegradation of thin films of poly(para-tert-butylstyrene) with 265 nm radiation in the presence of oxygen, and as a function of irradiation time, has been studied using fluorescence, Fourier transform-infrared spectroscopy, and ultraviolet-visible spectroscopy. The influence of phthalate and terephthalate plasticizers on photo-oxidative degradation was also investigated. Blending with phthalate plasticizers was found to cause a higher efficiency of degradation than that obtained for doping with terephthalate plasticizers. The intensity of absorption was also found to increase with time of irradiation and in the intensity of a new absorption band at longer wavelength, thus indicating a possibility of photodegradation of polymer films. The analysis of the Fourier transform-infrared spectra of the irradiated and non-irradiated samples showed an increase in the intensities of the carbonyl and hydroxyl regions of the Fourier transform-infrared spectra providing evidence for the photodegradation as well as the photo-oxidation of polymeric chains. The increase in the analyzed ranges is attributed to the formation of alcohols, aliphatic ketones and to the increase in the number of polyene structures that resulted from hydrogen abstraction during photodegradation reactions.

11 citations

References
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Journal ArticleDOI
TL;DR: In this article, the authors investigated the kinetics of the polymerization of acrylonitrile, methyl methacrylate, and acrylamide initiated by the redox system cyanoacetic acid/manganese triacetate in dimethylformamide solution.
Abstract: The kinetics of the polymerization of acrylonitrile, methyl methacrylate, and acrylamide initiated by the redox system cyanoacetic acid/manganese triacetate in dimethylformamide solution were investigated in the temperature range of 25 – 40°C. It was found that an initial complexation between the reactants followed by an electron transfer yields radicals. In contrast to acrylamide, acrylonitrile and methyl methacrylate effectively suppress further oxidation of the primary radicals. Exclusively the mutual termination accounts for the kinetics of these polymerizations. Data on the average degrees of the polymerizations support the suggested mechanisms. Rate and equilibrium constants were evaluated and their significance is discussed.

7 citations

Journal ArticleDOI
TL;DR: In this article, the polymerization of methyl methacrylate initiated by ferric salt and thiourea in dimethyl sulfoxide solution was studied and the results were discussed on the basis of the IR and NMR data.
Abstract: The polymerization of methyl methacrylate initiated by ferric salt and thiourea in dimethyl sulfoxide solution was studied. By the substitution of hydrogen by an alkyl or aryl group in the thiourea, the rate of the polymerization decreases. The logarithm of the rate is proportional to the σ* value of Taft's equation. The results are discussed on the basis of the IR and NMR data. It was confirmed that the polymerization is initiated by a radical produced by the reaction of the ferric ion with the isothiourea which is formed from the thiourea by tautomerization. The termination of the polymerization is also discussed based on the results of kinetic studies with different kinds and concentrations of the ferric salt.

3 citations

Journal ArticleDOI
TL;DR: In this article, the authors investigated the thermodynamic properties of acrylonitrile and methyl methacrylate in aqueous sulfuric acid and propanedinitrile-Mn(OAc)3 in DMF and glacial acetic acid in the temperature range 20-40°C.
Abstract: Polymerization of acrylonitrile and methyl methacrylate by the redox systems propanedinitrile-Mn(III) in aqueous sulfuric acid and propanedinitrile-Mn(OAc)3 in DMF and glacial acetic acid was investigated in the temperature range 20–40°C. The kinetics are consistent with the formation of an intermediate complex whose irreversible decomposition yields the initiating radical. With both monomers mutual termination predominates. The main difference between aqueous H2SO4 and acetic acid compared with DMF lies in the ease of oxidation of the primary radicals by the oxidant. Rate and equilibrium parameters were estimated and their significance discussed.

3 citations

Journal ArticleDOI
TL;DR: In this paper, the authors investigated the polymerisation of acrylonitrile and methyl methacrylate initiated by the system cyanoacetic acid-Mn(III)(acac)3 in DMF and in DMSO at 25-35°C.
Abstract: Polymerisation of acrylonitrile and methyl methacrylate initiated by the system cyanoacetic acid-Mn(III)(acac)3 is investigated in DMF and in DMSO at 25–35°C. Kinetics of reduction of the complex by cyanoacetic acid shows the formation of a mixed ligand complex whose decomposition yields the primary radicals. Efficient initiation of polymerisation by these radicals followed by exclusive mutual termination accounts for the kinetics of polymerisation. Rate and equilibrium parameters are evaluated and their significance discussed.

3 citations