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Kinetic study on the carbonylation of methyl acetate to acetic anhydride catalyzed by partially quaternized poly(4‐vinylpyridine) bound rhodium complexes
Author(s) -
Wang Enlai,
Li Xiabao,
Jiang Dazhi
Publication year - 1997
Publication title -
polymers for advanced technologies
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.61
H-Index - 90
eISSN - 1099-1581
pISSN - 1042-7147
DOI - 10.1002/(sici)1099-1581(199711)8:11<644::aid-pat695>3.0.co;2-z
Subject(s) - carbonylation , acetic anhydride , methyl acetate , rhodium , methyl iodide , catalysis , iodide , chemistry , carbon monoxide , lithium iodide , organic chemistry , polymer chemistry , medicinal chemistry , electrode , electrolyte
The carbonylation of methyl acetate to acetic anhydride catalyzed by a partially quaternized poly(4‐vinylpyridine) bound rhodium complex with methyl iodide as the promotor has been investigated. The reaction was verified to be first order with respect to both rhodium and methyl iodide in the presence of lithium acetate and provided that the partial pressure of carbon monoxide was above 1.5 MPa. The oxidative addition of methyl iodide to the active rhodium species and the subsequent reaction of acetyl iodide with methyl acetate to produce acetic anhydride were discovered to be the two rate‐determining steps, of which the latter depended on the concentration of lithium acetate. A possible reaction mechanism was suggested. The activation parameters were determined and revealed that a higher catalytic activity of the partially quaternized poly(4‐vinylpyridine) bound rhodium complex for the carbonylation of methyl acetate to acetic anhydride was essentially due to the reduction of activation energy. © 1997 John Wiley & Sons, Ltd.