将一系列酸性、碱性和中性的功能化离子液体用于催化甘油和尿素合成甘油碳酸酯。结果表明,中性离子液体表现出更高的催化活性。离子液体阳离子和阴离子的协同效应促进了反应的进行,离子液体阳离子的正电性活化尿素,阴离子的负电性活化甘油,并且催化剂酸碱位点的平衡对催化反应过程也有一定的影响。此外,离子液体可以实现回收利用至少五次,且催化活性基本不变。采用功能化离子液体替代传统金属催化剂,减少了不可再生资源的利用,且所用原料为廉价易得的生物基原料,过程中也不使用有机溶剂,环境友好。
Acidic, basic and neutral ionic liquids (ILs) have been used as catalysts in the carbonylation of glyc‐erol with urea. The results show that neutral ILs have high catalytic activity in the reaction. The excellent performance of the catalysts can be attributed to the synergistic effect of the cation and anion. We speculated that the cation with positive charge activates urea, and the anion with nega‐tive charge activates glycerol. In addition, the well balanced acid‐basic properties of the catalysts are necessary for good catalytic performance. The ILs can be reused at least five times without loss of activity. Using ILs, instead of the traditional metal catalysts, reduces the use of non‐renewable re‐sources. It is eco‐friendly that two inexpensive and bio‐based raw materials were used and the catalytic reaction was carried out without solvent.
参考文献
[1] | Ma F R;Hanna M A .[J].Bioresource Technology,1999,70:1. |
[2] | Behr A;Eilting J;Irawadi K;Leschinski J;Lindner F .Improved utilisation of renewable resources: New important derivatives of glycerol[J].Green chemistry,2008(1):13-30. |
[3] | Zhou C H;Beltramini J N;Fan Y X;Lu G Q .[J].CHEMICAL SOCIETY REVIEWS,2008,37:527. |
[4] | Sonnati M O;Amigoni S;de Givenchy E P T;Darmanin T Choulet O Guittard F .[J].Green Chemistry,2013,15:283. |
[5] | Hu J L;Li J J;Gu Y L;Guan Z H Mo W L Ni Y M Li T Li G X .[J].Applied Catalysis A:General,2010,386:188. |
[6] | Lim Y N;Lee C;Jang H Y.[J].EUROPEAN JOURNAL OF ORGANIC CHEMISTRY,2014:1823. |
[7] | Strain F .[P].US Patent 2 446 145,1948. |
[8] | Patel Y;George J;Pillai S M;Munshi P .[J].Green Chemistry,2009,11:1056. |
[9] | Kim S C;Kim Y H;Lee H;Yoon D Y Song B K .[J].JOURNAL OF MOLECULAR CATALYSIS B:ENZYMATIC,2007,49:75. |
[10] | Climent, M.J.;Corma, A.;De Frutos, P.;Iborra, S.;Noy, M.;Velty, A.;Concepción, P. .Chemicals from biomass: Synthesis of glycerol carbonate by transesterification and carbonylation with urea with hydrotalcite catalysts. The role of acid-base pairs[J].Journal of Catalysis,2010(1):140-149. |
[11] | Wang L G;Ma Y B;Wang Y;Liu S M Deng Y Q .[J].CATALYSIS COMMUNICATIONS,2011,12:1458. |
[12] | Turney T W;Patti A;Gates W;Shaheen U Kulasegaram S .[J].Green Chemistry,2013,15:1925. |
[13] | Rahim M H A;He Q;Lopez-Sanchez J A;Hammond C Dimitratos N Sankar M Carley A F Kiely C J Knight D W Hutchings G J .[J].Catal Sci Technol,2012,2:1914. |
[14] | Jagadeeswaraiah K;Kumar C R;Prasad P S S;Loridant S Lingaiah N .[J].Applied Catalysis A:General,2014,469:165. |
[15] | Fujita, S.-I.;Yamanishi, Y.;Arai, M..Synthesis of glycerol carbonate from glycerol and urea using zinc-containing solid catalysts: A homogeneous reaction[J].Journal of Catalysis,2013:137-141. |
[16] | Sandesh S;Shanbhag G V;Halgeri A B .[J].RSC Adv,2014,4:974. |
[17] | Claude S;Mouloungui Z;Yoo J W;Gaset A .[P].US Patent 6 025 504,2000. |
[18] | Lee M S;Baek J H .[P].US Patent 2 013 026 771 5A1,2013. |
[19] | Buzzeo M C;Evans R G;Compton R G .[J].CHEMPHYSCHEM,2004,5:1106. |
[20] | Macfarlane D R;Forsyth M;Howlett P C;Pringle J M Sun J Annat G Neil W Izgorodina E I .[J].Accounts of Chemical Research,2007,40:1165. |
[21] | Liu H T;Liu Y;Li J H .[J].Physical Chemistry Chemical Physics,2010,12:1685. |
[22] | Mulik A;Chandam D;Patil P;Patil D Jagdale S Deshmukh M .[J].Journal of Molecular Liquids,2013,179:104. |
[23] | Welton T .[J].CHEMICAL REVIEWS,1999,99:2071. |
[24] | Cole A C;Jensen J L;Ntai I;Tran K L T Weaver K J Forbes D C Davis J H .[J].Journal of the American Chemical Society,2002,124:5962. |
[25] | Forbes DC;Weaver KJ .Bronsted acidic ionic liquids: the dependence on water of the Fischer esterification of acetic acid and ethanol[J].Journal of molecular catalysis, A. Chemical,2004(1):129-132. |
[26] | Gu Y L;Shi F;Deng Y Q .[J].CATALYSIS COMMUNICATIONS,2003,4:597. |
[27] | Nockemann P;Thijs B;Parac-Vogt TN;Van Hecke K;Van Meervelt L;Tinant B;Hartenbach I;Schleid T;Ngan VT;Nguyen MT .Carboxyl-Functionalized Task-Specific Ionic Liquids for Solubilizing Metal Oxides[J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,2008(21):9987-9999. |
[28] | Bates E D;Mayton R D;Ntai I;Davis J H .[J].Journal of the American Chemical Society,2002,124:926. |
[29] | Sarkar, A.;Roy, S.R.;Parikh, N.;Chakraborti, A.K. .Nonsolvent application of ionic liquids: Organo-catalysis by 1-alkyl-3-methylimidazolium cation based room-temperature ionic liquids for chemoselective N-tert-butyloxycarbonylation of amines and the influence of the C-2 hydrogen on catalytic efficiency[J].The Journal of Organic Chemistry,2011(17):7132-7140. |
[30] | Sarkar, A.;Roy, S.R.;Chakraborti, A.K. .Ionic liquid catalysed reaction of thiols with α,β-unsaturated carbonyl compounds-remarkable influence of the C-2 hydrogen and the anion[J].Chemical communications,2011(15):4538-4540. |
[31] | Park D W;Mun N Y;Kim K H;Kim I Park S W .[J].Catalysis Today,2006,115:130. |
[32] | Tharun J;Kathalikkattil A C;Roshan R;Kang D H Woo H C Park D W .[J].CATALYSIS COMMUNICATIONS,2014,54:31. |
[33] | Ju H Y;Manju M D;Kim K H;Park S W Park D W .[J].Journal of Industrial and Engineering Chemistry,2008,14:157. |
[34] | Kim D W;Roshan R;Tharun J;Cherian A Park D W .[J].Korean Journal of Chemical Engineering,2013,30:1973. |
[35] | Kim M I;Choi S J;Kim D W;Park D W .[J].Journal of Industrial and Engineering Chemistry,2014,20:3102. |
[36] | Kim D W;Kim C W;Koh J C;Park D W .[J].Journal of Industrial and Engineering Chemistry,2010,16:474. |
[37] | Saravanamurugan S;Riisager A .[J].Catalysis Today,2013,200:94. |
[38] | Fukumoto K;Yoshizawa M;Ohno H .[J].Journal of the American Chemical Society,2005,127:2398. |
[39] | Wang C;Liu X M;Yang M;Ma H Y Yan P F Slattery J M Gao Y A .[J].RSC Adv,2013,3:8796. |
[40] | Wang C;Liu J;Leng W G;Gao Y A .[J].INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES,2014,15:1284. |
[41] | Singh, A.;Kumar, A. .Probing the mechanism of Baylis-Hillman reaction in ionic liquids[J].The Journal of Organic Chemistry,2012(19):8775-8779. |
[42] | Zhang S G;Qi X J;Ma X Y;Lu L J Deng Y Q .[J].Journal of Physical Chemistry B,2010,114:3912. |
[43] | Matsumoto K;Hagiwara R;Yoshida R;Ito Y,Mazej Z,Benki?P,?emva B,Tamada O,Yoshino H,Matsubara S.[J].DALTON TRANSACTIONS,2004:144. |
[44] | Srour H;Rouault H;Santini C C;Chauvin Y .[J].Green Chemistry,2013,15:1341. |
[45] | Cull S G;Holbrey J D;Vargas-Mora V;Seddon K R Lye G J .[J].Biotech-nol Bioeng,2000,69:227. |
[46] | Schaber P M;Colson J;Higgins S;Thielen D Anspach B Brauer J .[J].Thermochimica Acta,2004,424:131. |
[47] | Li Q B;Zhang W Y;Zhao N;Wei W Sun Y H .[J].Catalysis Today,2006,115:111. |
[48] | Cláudio A F M;Swift L;Hallett J P;Welton T Coutinho J A P Freire M G .[J].Physical Chemistry Chemical Physics,2014,16:6593. |
[49] | Roy, S.R.;Chakraborti, A.K. .Supramolecular assemblies in ionic liquid catalysis for aza-michael reaction[J].Organic letters,2010(17):3866-3869. |
[50] | Chakraborti A K;Roy S R .[J].Journal of the American Chemical Society,2009,131:6902. |
[51] | Chakraborti A K;Roy S R;Kumar D;Chopra P .[J].Green Chemistry,2008,10:1111. |
[52] | Lungwitz R;Strehmel V;Spange S .[J].New Journal of Chemistry,2010,34:1135. |
- 下载量()
- 访问量()
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%