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High-pressure kinetics of oxidative copolymerization of styrene with alpha-methyl styrene

De, Priyadarsi and Sathyanarayana, DN (2002) High-pressure kinetics of oxidative copolymerization of styrene with alpha-methyl styrene. In: Macromolecular Chemistry and Physics, 203 (15). pp. 2218-2224.

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/1521-39...


This is the first report on the study carried out on high-pressure free-radical initiated oxidated copolymerization of styrene (STY) with alpha-methylstyrene (AMS) at various temperatures (45-65degreesC) at constant pressure (100 psi) and then at various pressures (50-300 psi) keeping the temperature (50degreesC) constant. The compositions of the copolyperoxides obtained from the H-1 NMT spectra were utilized to determine the reactivity ratios of the monomers. The reactivity ratios indicate that STY forms an ideal copolyperoxide with AMS and the copolyperoxide is richer in AMS. The effect of temperature and oxygen pressure in the reactivity ratios of the monomers was studied. The rates of copolymerization (R-p) were used to determine the overall activation energies (E-a) and activation volume (DeltaV(#)) of copolymerization. The unusually higher values of the DeltaV(#) may be due to the pressurizing fluid oxygen which itself is a reactant in the copolymerization, the side reactions, and the chain-transfer reactions occuring during copolymerizations.

Item Type: Journal Article
Publication: Macromolecular Chemistry and Physics
Publisher: John Wiley and Sons
Additional Information: Copyright of this article belongs to John Wiley and Sons.
Keywords: copolymerization;free-radical polymerization;kinetics;-methylstyrene
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 19 Jul 2011 04:46
Last Modified: 19 Jul 2011 04:46
URI: http://eprints.iisc.ac.in/id/eprint/39230

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