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Reactivity ratios for the terpolymerization of methyl methacrylate, vinyl acetate, and molecular oxygen

De, Priyadarsi and Sathyanarayana, DN (2002) Reactivity ratios for the terpolymerization of methyl methacrylate, vinyl acetate, and molecular oxygen. In: Journal of Polymer Science, 40 (4). pp. 564-572.

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Abstract

The copolymerization of methyl methacrylate (MMA) and vinyl acetate (VAc) under high oxygen pressure was investigated. Copolyperoxides of various compositions were synthesized by the free-radical-initiated oxidative copolymerization of NMIA and VAc monomers. The copolyperoxide compositions obtained from H-1 and C-13 NMR spectra were used for determining the reactivity ratios of the monomers. The reactivity ratios indicated a larger proportion of MMA units statistically placed in the copolyperoxides. A theoretical analysis based on semiempirical AM1 calculations was performed to support the reactivity ratios. NMR studies showed irregularities in the copolyperoxide chain due to the cleavage reactions of the propagating peroxide radical. Thermal analyses of the copolyperoxides by differential scanning calorimetry gave evidence for the presence of alternating peroxide units in the copolyperoxide chain, The activation energies of thermal degradation suggested that degradation was controlled by the dissociation of the peroxide (-O-O-) bond in the backbone of the copolyperoxide chain.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to John Wiley and Sons.
Keywords: copolyperoxides;reactivity ratios;chain irregularities;low molecular weight;differential scanning calorimetry (DSC); exothermic degradation
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 19 Nov 2009 08:23
Last Modified: 19 Sep 2010 05:00
URI: http://eprints.iisc.ernet.in/id/eprint/18190

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