Synthesis of 1,2-glycerol carbonate from carbon dioxide: the role of methanol in fluid phase equilibrium

S. Podila, L. Plasseraud, H. Cattey, D. Ballivet-Tkatchenko, G. V. S. M. Carrera, M. Nunes Da Ponte, S. Neuberg, A. Behr

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Abstract

The effect of methanol on the synthesis of 1,2-glycerol carbonate from CO2 and glycerol is studied in the presence of Bu 2Sn(OCH3)2, n-Bu2SnO, and tert-Bu2SnO. At 423 K, up to 2.7 mol% yield in glycerol carbonate, based on glycerol, could be obtained in the pressure range 14-20 MPa. Addition of acetonitrile promotes notably the yield to 7 mol%. Fluid phase equilibrium experiments with the ternary mixture CO2/glycerol/methanol show that the reaction takes place in a liquid phase where methanol dissolves glycerol, CO2, and the tin complexes. Above ∼0.6 mole fraction, CO 2 behaves as an anti-solvent, separating methanol from glycerol, thus inhibiting the formation of 1,2-glycerol carbonate. Dimethyl carbonate is a sideproduct of glycerol carbonation resulting mainly from transesterification between glycerol carbonate and methanol. Glycerol coordination to tin center is evidenced by the isolation of di-tert-Bu2Sn(1,2-glycerolate) complex. Its structure determination by single-crystal X-ray diffraction shows that the remaining OH group of glycerol promotes the formation of onedimensional polymeric chain.

Original languageEnglish
Pages (from-to)1330-1338
Number of pages9
JournalIndian Journal of Chemistry - Section A Inorganic, Physical, Theoretical and Analytical Chemistry
Volume51
Issue number9-10(SI)
Publication statusPublished - Sep 2012

Keywords

  • Carbon dioxide
  • Dibutyltin glycerolate
  • Fluid phase equilibrium
  • Glycerol
  • Glycerol carbonate
  • Methanol
  • Vapour-liquid equilibrium
  • X-ray structure

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