H3PW12O40 supported on MCM-41 molecular sieves: An effective catalyst for acetal formation

Abstract Mesoporous Si-MCM-41 and Al-MCM-41 molecular sieves in four Si/Al ratios: 25, 50, 75 and 100, were synthesized under hydrothermal conditions. Ten weight percent, 15 wt.% and 20 wt.% H 3 PW 12 O 40 (PW) was supported on Si-MCM-41. They were characterized using powder X-ray diffraction (XRD), FT-IR, BET and TEM. The catalytic activity of these materials were tested for the acetalization of carbonyl compounds with 2,2-bis(hydroxymethyl)propane-1,3-diol at refluxing temperature using a Dean–Stark apparatus. The hydrophobic properties of catalyst and alcohols, and the steric properties of carbonyl compounds were suggested to play important roles in the acetalization. Fifteen weight percent PW/MCM-41 was found to be more active than other catalysts used and to have similar activity to that of HPA. TEM studies show that the high dispersion of HPA units, which was maintained through out the reaction, was lost when recycled even for shorter reaction cycle. The reaction was also studied over commercially available heteropolyacids, and zeolites (Hβ, HY, HM and ZSM-5). Occurrence of the reaction mainly within the pores was confirmed by running the reaction over the HPA loaded on an as-prepared catalyst that provides less product yield than the calcined material.

[1]  D. Sauer,et al.  Application of palladium-catalyzed [3 + 2] cycloaddition technology to the elaboration of kempane diterpenes. Stereocontrolled synthesis of (.+-.)-3.alpha.-hydroxy-7.beta.-kemp-8(9)-en-6-one and (.+-.)-3.beta.-hydroxykemp-7(8)-en-6-one , 1992 .

[2]  W. Cheng,et al.  NMR study of the adsorption of phosphomolybdates on alumina , 1988 .

[3]  Y. Shan,et al.  Immobilization of the heteropoly acid (HPA) H4SiW12O40 (SiW12) on mesoporous molecular sieves (HMS and MCM-41) and their catalytic behavior , 1996 .

[4]  A. Jentys,et al.  Catalytic activity of Pt and tungstophosphoric acid supported on MCM-41 for the reduction of NOx in the presence of water vapor , 2000 .

[5]  Tong‐Shuang Li,et al.  Synthesis Of Diacetals By Condensation Of Carbonyl Compounds With Bis(Hydrox Ymethyl)-1,3-Propanediol Catalysed By Expansive Graphite , 1999 .

[6]  A. Corma,et al.  Supported heteropolyacid (HPW) catalysts for the continuous alkylation of isobutane with 2-butene: The benefit of using MCM-41 with larger pore diameters , 1998 .

[7]  S. Uemura,et al.  Ce{sup 3+}-exchanged montmorillonite (Ce{sup 3+}-mont) as a useful substrate-selective acetalization catalyst , 1995 .

[8]  K. Hidajat,et al.  Improvement of the hydrothermal stability of fluorinated MCM-41 material , 2000 .

[9]  D. Ponde,et al.  Natural kaolinitic clay: A remarkable reusable solid catalyst for the selective functional protection of aldehydes and ketones , 1996 .

[10]  Catalysis of organic reactions by inorganic solids , 1986 .

[11]  J. S. Beck,et al.  Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism , 1992, Nature.

[12]  E. Taylor,et al.  Trimethyl Orthoformate Absorbed on the Montmorillonite Clay K-10; an Effective Reagent for Acetal Formation , 1977 .

[13]  J. Kula,et al.  Efficient Electrocatalytical Acetalization of Aliphatic Aldehydes , 1986 .

[14]  K. Hidajat,et al.  Structure, acidity, and catalytic activity of mesoporous acid catalysts for the gas-phase synthesis of MTBE from MeOH and ButOH , 2002 .

[15]  M. Kubota,et al.  SCANDIUM TRIFLUOROMETHANESULFONIMIDE AND SCANDIUM TRIFLUOROMETHANESULFONATE AS EXTREMELY ACTIVE ACETALIZATION CATALYSTS , 1996 .

[16]  K. Hidajat,et al.  Synthesis of SO42−/ZrO2/MCM-41 as a new superacid catalyst , 2000 .

[17]  A. Steigel,et al.  Stereochemistry of cyclic compounds—I : Synthesis and configurational assignment of diastereomeric 2,4-dioxaspiro[5.5]undec-8-enes , 1979 .

[18]  K. Nowiǹska,et al.  Catalytic activity of supported heteropoly acids for reactions requiring strong acid centres , 1991 .

[19]  M. Misono,et al.  Catalytic Chemistry of Heteropoly Compounds , 1996 .

[20]  I. Kozhevnikov,et al.  New acid catalyst comprising heteropoly acid on a mesoporous molecular sieve MCM-41 , 1994 .

[21]  P. K. Sinha,et al.  Comparison of mesoporous Al-MCM-41 molecular sieves in the production of p-cymene for isopropylation of toluene , 2002 .

[22]  B. R. Jermy,et al.  Catalytic application of Al-MCM-41 in the esterification of acetic acid with various alcohols , 2005 .

[23]  W. Scott,et al.  1,3-Dioxolane formation via Lewis acid-catalyzed reaction of ketones with oxiranes , 1993 .

[24]  N. Essayem,et al.  H3PW12O40 supported on Cs modified mesoporous silica: catalytic activity in n-butane isomerisation and in situ FTIR study: Comparison with microporous CsxH3−xPW12O40 , 2002 .

[25]  S. F. Marrian.  The chemical reactions of pentaerythritol and its derivatives. , 1948, Chemical reviews.

[26]  A. Al-Arfaj,et al.  Rhodium(I) and rhodium(III)–heteropolyacids supported on MCM-41 for the catalytic hydroformylation of styrene derivatives , 2005 .

[27]  R. Gobetto,et al.  Solid state NMR and IR studies of phosphomolybdenum and phosphotungsten heteropoly acids supported on SiO2, γ-Al2O3, and SiO2Al2O3 , 1989 .

[28]  V. Terskikh,et al.  1H, 31P NMR MAS, infrared and catalytic studies of heteropolyacid H3PW12O40 supported on MgF2 , 1995 .

[29]  C. Ching,et al.  Comparative studies on alkylation of phenol with tert-butyl alcohol in the presence of liquid or solid acid catalysts in ionic liquids , 2004 .

[30]  O. Terasaki,et al.  Structural elucidation of microporous and mesoporous catalysts and molecular sieves by high-resolution electron microscopy. , 2001, Accounts of chemical research.

[31]  J. B. Montón,et al.  Hydrocracking of Vacuum Gasoil on the Novel Mesoporous MCM-41 Aluminosilicate Catalyst , 1995 .

[32]  I. Kozhevnikov,et al.  Study of catalysts comprising heteropoly acid H3PW12O40 supported on MCM-41 molecular sieve and amorphous silica , 1996 .

[33]  A. Clearfield,et al.  Synthesis of aluminum rich MCM-41 , 1995 .

[34]  P. Laszlo,et al.  Clay-Supported Reagents; II1. Quaternary Ammonium-Exchanged Montmorillonite as Catalyst in the Phase-Transfer Preparation of Symmetrical Formaldehyde Acetals , 1982 .