Synthesis of dimethyl carbonate from CO2 and ethylene oxide catalyzed by K2CO3-based binary salts in the presence of H2O

We systematically screened binary catalysts for synthesis of dimethyl carbonate (DMC) from CO2, CH3OH and ethylene oxide (EO) in the presence of H2O by two-step transesterification process, and found the commercial quaternary ammonium salts/K2CO3, pyridinium salts/K2CO3 and KI/K2CO3 were effective binary catalysts for two-step synthesis of DMC with no need for separation of ethylene carbonate (EC). Near 100% conversion of EO and 82% yield of DMC were obtained under mild reaction conditions. However, the imidazolium salts were not compatible with inorganic alkaline possibly because of the reactive C(2)–H in the imidazolium ring. Furthermore, the KI/K2CO3 could be easily recovered and reused 12 times without obvious loss of its catalytic activity. The process avoids EC separation, and represents a simple, ecologically safer, cost-effective and energy-saving route for synthesis of DMC with high product quality, as well as easy catalyst recycling.

[1]  Jian Sun,et al.  Efficient acid-base bifunctional catalysts for the fixation of CO(2) with epoxides under metal- and solvent-free conditions. , 2011, ChemSusChem.

[2]  G. Hutchings,et al.  Synthesis of glycerol carbonate from glycerol and urea with gold-based catalysts. , 2011, Dalton transactions.

[3]  Liang‐Nian He,et al.  Carbon Dioxide in Heterocyclic Synthesis , 2011 .

[4]  Liguo Wang,et al.  Quaternary Ammonium Ionic Liquids as Bi-functional Catalysts for One-step Synthesis of Dimethyl Carbonate from Ethylene Oxide, Carbon Dioxide and Methanol , 2011 .

[5]  Tao Jiang,et al.  Highly efficient synthesis of cyclic carbonates from CO2 and epoxides over cellulose/KI. , 2011, Chemical communications.

[6]  Charlotte K. Williams,et al.  A bimetallic iron(III) catalyst for CO2/epoxide coupling. , 2011, Chemical communications.

[7]  James A. Lee,et al.  One-pot conversions of olefins to cyclic carbonates and secondary allylic and homoallylic amines to cyclic carbamates. , 2010, The Journal of organic chemistry.

[8]  A. Kleij,et al.  Efficient carbonate synthesis under mild conditions through cycloaddition of carbon dioxide to oxiranes using a Zn(salphen) catalyst. , 2010, Chemical communications.

[9]  M. Sankar,et al.  Transesterification of cyclic carbonates to dimethyl carbonate using solid oxide catalyst at ambient conditions: environmentally benign synthesis. , 2010, ChemSusChem.

[10]  T. Endo,et al.  Amidine-mediated delivery of CO2 from gas phase to reaction system for highly efficient synthesis of cyclic carbonates from epoxides , 2010 .

[11]  Suojiang Zhang,et al.  Reusable and efficient polymer-supported task-specific ionic liquid catalyst for cycloaddition of epoxide with CO2 , 2009 .

[12]  Dae-Won Park,et al.  Selective production of cyclic carbonate over polycarbonate using a double metal cyanide–quaternary ammonium salt catalyst system , 2009 .

[13]  K. Tomishige,et al.  Low pressure CO(2) to dimethyl carbonate by the reaction with methanol promoted by acetonitrile hydration. , 2009, Chemical communications.

[14]  B. Han,et al.  MOF-5/n-Bu4NBr: an efficient catalyst system for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions , 2009 .

[15]  M. North,et al.  One-component catalysts for cyclic carbonate synthesis. , 2009, Chemical communications.

[16]  J. Pérez‐Ramírez,et al.  Synthesis of dimethyl carbonate by transesterification of ethylene carbonate over activated dawsonites. , 2009, ChemSusChem.

[17]  T. Sakakura,et al.  The synthesis of organic carbonates from carbon dioxide. , 2009, Chemical communications.

[18]  S. Yin,et al.  Synthesis and structure of bismuth compounds bearing a sulfur-bridged bis(phenolato) ligand and their catalytic application to the solvent-free synthesis of propylene carbonate from CO2 and propylene oxide. , 2009, Chemical communications.

[19]  Suojiang Zhang,et al.  Water as an efficient medium for the synthesis of cyclic carbonate , 2009 .

[20]  B. Lu,et al.  Studies on synthesis of dimethyl carbonate from methanol and carbon dioxide , 2009 .

[21]  A. Perosa,et al.  Sequential Coupling of The Transesterification of Cyclic Carbonates with The Selective N-Methylation of Anilines Catalysed by Faujasites , 2008 .

[22]  Mi-Kyung Lee,et al.  Moderate route for the utilization of CO2-microwave induced copolymerization with cyclohexene oxide using highly efficient double metal cyanide complex catalysts based on Zn3[Co(CN)6] , 2008 .

[23]  Jian Sun,et al.  Hydroxyl-functionalized ionic liquid: a novel efficient catalyst for chemical fixation of CO2 to cyclic carbonate , 2008 .

[24]  Mai Xu,et al.  Fixation of CO2 by electrocatalytic reduction and electropolymerization in ionic liquid-H2O solution. , 2008, ChemSusChem.

[25]  Liang‐Nian He,et al.  Bifunctional metal-salen complexes as efficient catalysts for the fixation of CO2 with epoxides under solvent-free conditions. , 2008, ChemSusChem.

[26]  Dae-Won Park,et al.  Synthesis of cyclic carbonate from vinyl cyclohexene oxide and CO2 using ionic liquids as catalysts , 2008 .

[27]  Wing‐Leung Wong,et al.  A robust ionic liquid as reaction medium and efficient organocatalyst for carbon dioxide fixation. , 2008, ChemSusChem.

[28]  Hiroyuki Yasuda,et al.  Transformation of carbon dioxide. , 2007, Chemical reviews.

[29]  Liang‐Nian He,et al.  Efficient synthesis of dimethyl carbonate from methanol, propylene oxide and CO2 catalyzed by recyclable inorganic base/phosphonium halide-functionalized polyethylene glycol , 2007 .

[30]  B. Bhanage,et al.  Silica supported polyvinyl pyridine as a highly active heterogeneous base catalyst for the synthesis of cyclic carbonates from carbon dioxide and epoxides , 2007 .

[31]  M. Sankar,et al.  Transesterification of cyclic carbonates with methanol at ambient conditions over tungstate-based solid catalysts , 2006 .

[32]  Liang‐Nian He,et al.  One-pot synthesis of dimethyl carbonate catalyzed by n-Bu4NBr/n-Bu3N from methanol, epoxides, and supercritical CO2 , 2006 .

[33]  Yuan Li,et al.  Synthesis of dimethyl carbonate from methanol, propylene oxide and carbon dioxide over KOH/4A molecular sieve catalyst , 2005 .

[34]  Y. Kishimoto,et al.  Amine-catalyzed, one-pot coproduction of dialkyl carbonates and 1,2-diols from epoxides, alcohols, and carbon dioxide , 2004 .

[35]  Weize Wu,et al.  One-pot synthesis of dimethyl carbonate and glycols from supercritical CO2, ethylene oxide or propylene oxide, and methanol , 2004 .

[36]  M. Arai,et al.  Transesterification of urea and ethylene glycol to ethylene carbonate as an important step for urea based dimethyl carbonate synthesis , 2003 .

[37]  Tao Wang,et al.  One-pot synthesis of dimethyl carbonate using ethylene oxide, methanol, and carbon dioxide under supercritical conditions , 2003 .

[38]  Yuhan Sun,et al.  Synthesis of dimethyl carbonate by transesterification over CaO/carbon composites , 2003 .

[39]  M. Arai,et al.  Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides and methanol using heterogeneous Mg containing smectite catalysts: effect of reaction variables on activity and selectivity performance , 2003 .

[40]  K. Kunimori,et al.  Catalytic and direct synthesis of dimethyl carbonate starting from carbon dioxide using CeO2-ZrO2 solid solution heterogeneous catalyst: effect of H2O removal from the reaction system , 2002 .

[41]  A. Bell,et al.  Effects of Catalyst Phase Structure on the Elementary Processes Involved in the Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide over Zirconia , 2002 .

[42]  Hiroyuki Yasuda,et al.  Selective and high yield synthesis of dimethyl carbonate directly from carbon dioxide and methanol , 2002 .

[43]  Masahiko Arai,et al.  Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides, and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity , 2001 .

[44]  P. Tundo.  New developments in dimethyl carbonate chemistry , 2001 .

[45]  M. Arai,et al.  Synthesis of dimethyl carbonate from carbon dioxide and methanol in the presence of methyl iodide and base catalysts under mild conditions: effect of reaction conditions and reaction mechanism , 2001 .

[46]  Takakazu Yamamoto,et al.  Poly(pyridine-2,5-diyl)–CuCl2 catalyst for synthesis of dimethyl carbonate by oxidative carbonylation of methanol: catalytic activity and corrosion influence , 2000 .

[47]  Paul T. Anastas,et al.  Life cycle assessment and green chemistry: the yin and yang of industrial ecology , 2000 .

[48]  James H. Clark,et al.  Green chemistry: challenges and opportunities , 1999 .

[49]  Christopher L. Marshall,et al.  Review of Dimethyl Carbonate (DMC) Manufacture and Its Characteristics as a Fuel Additive , 1997 .