Gangi Reddy, G. ; Nagabhushanam, T. ; Venkata Rao, K. ; Santappa, M. (1982) Oxygen-ascorbic acid-vanadyl ion initiating system. A kinetic study of the polymerization of methyl methacrylate and acrylonitrile in aqueous sulfuric acid Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 17 (8). pp. 1203-1224. ISSN 1060-1325
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Related URL: http://dx.doi.org/10.1080/00222338208074394
Abstract
The polymerization of methyl methacrylate (MMA) and acrylonitrile (AN) initiated by the oxygen-ascorbic acid (AA)-vanadyl ion (VO2+) system was studied at 40°C in dilute sulfuric acid medium. The rate of polymerization, Rp, was followed gravimetrically and found to be proportional to [MMA]1.3, [O2]0.6, and [VO2+]° at [VO2+]=4−8×10−4 M̲ in the polymerization of MMA. In the polymerization of AN, R was dependent on [AN]1.5, [O2]0.5, and [VO2+]° at[VO2+]=4−10×10−4 M̲, while at [VO2+]>10−3 M̲ it was proportional to [AN]1.7, [O2]0.7, and [VO2+]0.6. A slight dependence of Rp on [AA] and [H2SO4] was observed in both polymerizations. An increase of ionic strength had an accelerating effect on Rp. An initial increase in Rp and then a decrease with temperature was noticed. A plausible reaction mechanism with initiation by the primary radical R produced from the dissociation of the O2-AA-VO2+ complex and termination by mutual interaction with predominant oxidation of R by VO2+ was found to be consistent for the observed kinetic results at all [VO2+] for MMA and for AN at low [VO2+]. Linear termination was found to be operative at high [VO2+] in the polymerization of AN. The chain length of the polymers was determined viscometrically.
Item Type: | Article |
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Source: | Copyright of this article belongs to Taylor and Francis Group. |
ID Code: | 43407 |
Deposited On: | 11 Jun 2011 11:02 |
Last Modified: | 11 Jun 2011 11:02 |
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