Hydrogenation of natural rubber in the presence of OsHCL(CO)(O2)(PCY3)2: Kinetics and mechanism

• Published in: Journal of applied polymer science Vol. 100; no. 6; pp. 4499 - 4514
• Main Authors: Hinchiranan, N., Prasassarakich, P., Rempel, G. L.
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 15-06-2006; Wiley
• Subjects: Applied sciences; catalyst; Exact sciences and technology; hydrogenation; kinetics; Natural polymers; Natural rubber; osmium complex; Physicochemistry of polymers; Propylene copolymer; Olefin copolymer; Osmium Complexes; Natural rubber; Experimental study; Property processing relationship; Hydrogenation; Optimization; Thermal stability; Thermal properties; osmium complex; Chemical modification; catalyst; Homogeneous catalysis; Ethylene copolymer; Reaction mechanism; Alternating copolymer; Kinetics; Catalyst activity; Activation energy
• ISSN: 0021-8995; 1097-4628
• DOI: 10.1002/app.22125

The homogeneous catalyst precursor, OsHCl(CO)(O2)(PCy3)2, was utilized for the hydrogenation of natural rubber to convert the unsaturated structure to a saturated form, providing an alternating ethylene‐propylene copolymer. A detailed kinetic investigation was carried out by monitoring the amount of hydrogen consumption during the reaction using a gas‐uptake apparatus. 1H NMR spectroscopy was used to determine the final olefin conversion to the hydrogenated product. Kinetic data, collected according to a statistical design framework, defined the influence of catalyst and polymer concentration, hydrogen pressure, and reaction temperature on the catalytic activity. The kinetic results indicated that the hydrogenation rate exhibited a first‐ shifted to zero‐order dependence on hydrogen at lower hydrogen pressure, which then decreased toward an inverse behavior at pressures higher than 41.4 bar. The hydrogenation was also observed to be first‐order with respect to catalyst concentration, and an apparent inverse dependence on rubber concentration was observed due to the impurities in the rubber. The hydrogenation rate was dependent on reaction temperature, and the apparent activation energy over the temperature range of 125–145°C was found to be 122.76 kJ/mol. Mechanistic aspects of the hydrogenation of natural rubber in the presence of OsHCl(CO)(O2)(PCy3)2 were proposed on the basis of the observed kinetic results. The addition of some acids and certain nitrogen containing materials showed an effect on the hydrogenation rate. The thermal properties of hydrogenated natural rubber indicated that the thermal stability increased with increasing % hydrogenation of the rubber. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4499–4514, 2006