23-May-2013
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NISCAIR ONLINE PERIODICALS REPOSITORY (NOPR) >
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Indian Journal of Chemistry -Section A (IJC-A) >
IJC-A Vol.51A [2012] >
IJC-A Vol.51A(09-10) [September-October 2012] >
| Title: | Synthesis of 1,2-glycerol carbonate from carbon dioxide: The role of methanol in fluid phase equilibrium |
| Authors: | Podila, S
Plasseraud, L
Cattey, H
Ballivet-Tkatchenko, D
Carrera, G V S M
Nunes da Ponte, M
Neuberg, S
Behr, A |
| Keywords: | Glycerol
Glycerol carbonate
Carbon dioxide
Methanol
Fluid phase equilibrium
Vapour-liquid equilibrium
Dibutyltin glycerolate
X-ray structure |
| Issue Date: | Sep-2012 |
| Publisher: | NISCAIR-CSIR, India |
| Abstract: | The effect of methanol on the synthesis of
1,2-glycerol carbonate from CO2 and glycerol is studied in the
presence of Bu2Sn(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, CO2 behaves as an
anti-solvent, separating methanol from glycerol, thus inhibiting the formation
of 1,2-glycerol carbonate. Dimethyl carbonate is a side-product 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
one-dimensional polymeric chain. |
| Page(s): | 1330-1338 |
| CC License: |  CC Attribution-Noncommercial-No Derivative Works 2.5 India |
| ISSN: | 0975-0975(Online); 0376-4710(Print) |
| Source: | IJC-A Vol.51A(09-10) [September-October 2012]
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