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Hydroformylation of high-molecular-weight cis-1,4-polybutadiene catalyzed by HRH(CO)(PPh3)3



The kinetics of the hydroformylation of high-molecular-weight cis-1,4-polybutadiene in the presence of HRh(CO)(PPh3)3 and monochlorobenzene as a solvent were studied. The degree of conversion was examined by spectroscopic characterization with Fourier transform infrared and 1H-NMR analysis. According to the 24-factorial experimental design, the temperature, catalyst concentration, and pressure appear to be significant factors for the hydroformylation of cis-1,4-polybutadiene. The kinetic studies indicated that the hydroformylation was first-order with respect to the catalyst and carbon–carbon double-bond concentrations and H2/CO pressure (1:1 ratio). The effects of the H2/CO ratio in the synthesis gas and added triphenyl phosphine were also studied. The apparent activation energy for the hydroformylation of cis-1,4-polybutadiene over the temperature range of 60–80°C was estimated to be 41 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 854–869, 2004