Glycerol was reacted with CO2 (5 MPa) at 450 K in presence of Sn-catalysts (n-Bu2Sn(OMe)(2) 1, n-Bu2SnO 2 or Sn(OMe)(2) 3), using either glycerol or tetraethylene glycol dimethyl ether (tedmg) as reaction medium. 1 was much more active than 2. 1 was demonstrated to convert into n-Bu2Sn(glycerol-2H) 4 upon reaction with glycerol and elimination of MeOH. Monomeric 4 is proposed to be the active species in catalysis. It converted into a polymeric material with time with consequent reduction of its catalytic activity. Also, after the first catalytic cycle 4 was converted into an oligomeric material that did not contain glycerol. This also caused the reduction of the catalytic activity. 3 was able to uptake CO2 but was not able to promote the carboxylation of glycerol. 1 and 2 also promoted the trans-esterification of dimethylcarbonate (DMC) with glycerol to afford glycerol carbonate, but at a lower rate than the direct carboxylation of glycerol. This fact seems to rule out that the carboxylation of glycerol may proceed through the preliminary formation of DMC and its subsequent trans-esterification.

A study on the carboxylation of glycerol to glycerol carbonate with carbon dioxide: the role of the catalyst, solvent and reaction conditions

DIBENEDETTO, Angela;F. NOCITO;
2006

Abstract

Glycerol was reacted with CO2 (5 MPa) at 450 K in presence of Sn-catalysts (n-Bu2Sn(OMe)(2) 1, n-Bu2SnO 2 or Sn(OMe)(2) 3), using either glycerol or tetraethylene glycol dimethyl ether (tedmg) as reaction medium. 1 was much more active than 2. 1 was demonstrated to convert into n-Bu2Sn(glycerol-2H) 4 upon reaction with glycerol and elimination of MeOH. Monomeric 4 is proposed to be the active species in catalysis. It converted into a polymeric material with time with consequent reduction of its catalytic activity. Also, after the first catalytic cycle 4 was converted into an oligomeric material that did not contain glycerol. This also caused the reduction of the catalytic activity. 3 was able to uptake CO2 but was not able to promote the carboxylation of glycerol. 1 and 2 also promoted the trans-esterification of dimethylcarbonate (DMC) with glycerol to afford glycerol carbonate, but at a lower rate than the direct carboxylation of glycerol. This fact seems to rule out that the carboxylation of glycerol may proceed through the preliminary formation of DMC and its subsequent trans-esterification.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11586/49324
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