HETEROGENEOUS CATALYST WITH MULTICATALYTIC ACTIVITY

Abstract

In this invention is described: a) the preparation of a new heterogeneous catalyst based on mesoporous silica with variable geometry of pore arrangement, covalently functionalized by an ionic liquid and as a counterion a tungsten polyoxometalate (Keggin acid); b) the application of this catalyst with dual action: Bronsted-Lowry acid and oxidizing agent; and c) its application in chemical reactions is described as: condensation, oxidation, polymerization, and esterification. This type of catalyst offers the following advantages in the chemical industry 1) reusable; 2) promotes different transformations in a single stage, attributed to their acidic and oxidizing characteristics (dual action); and 3) efficiency in the chemical transformations described, which allow to obtain precursors of homogeneous hydroprocessing catalysts, of interest for some projects of transformation of heavy crude oils in situ.

Claims

1. A heterogeneous catalyst with multicatalytic activity characterized by containing a group with an anionic character and another organic cationic, a combination of the anionic character group and the organic cationic group forming an ionic liquid which is integrated on a structured mesoporous silica support, with a structural chemical formula: ##STR00010## Where: R.sub.1 is a substituted alkyl, alkyl, aryl group or aryl substituted; R.sub.2 is a chain of 1 to 4 carbon atoms; X is a chemical element selected from the group consisting of Aluminum (Al), Silicon (Si), Phosphorus (P) or Sulfur (S); M is a chemical element of the type Molybdenum (Mo), Tungsten (W), Vanadium (V) Titanium (Ti) or Zirconium (Zr); OMM is a silica-based mesoporous support material; and n is the charge number.

2. The heterogeneous catalyst with multicatalytic activity in accordance with claim 1 wherein the organic cationic group R.sub.1 is a nitrogenous heterocyclic aromatic organic compound.

3. The heterogeneous catalyst with multicatalytic activity in accordance with claim 2, wherein the cationic component is an imidazolium type substituted with R.sub.1.

4. The heterogeneous catalyst with multicatalytic activity in accordance with claim 3 in which R.sub.1 is selected from the group consisting of a substituted alkyl, alkyl group, aryl group or substituted aryl group.

5. The heterogeneous catalyst with multicatalytic activity in accordance with claim 4, in which R.sub.1 is an alkyl containing from 1 to 6 carbon atoms.

6. The heterogeneous catalyst with multicatalytic activity in accordance with claim 1, in which 3-(R.sub.2 halide)trimethoxysilane is used to form the cationic group of the ionic liquid.

7. The heterogeneous catalyst with multicatalytic activity in accordance with claim 6, in which the halide of 3-(R.sub.2 halide)trimethoxysilane is a chlorine, bromine group, referred to as “A”.

8. The heterogeneous catalyst with multicatalytic activity in accordance with claim 7, in which the alkyl group R.sub.2 is a chain of 1 to 4 carbon atoms.

9. The heterogeneous catalyst with multicatalytic activity in accordance with claim 1, formed by the ionic liquid and the silica support, characterized by the latter presenting ordered arrangements of pores in the range of mesoporous materials.

10. The heterogeneous catalyst with multicatalytic activity in accordance with claim 9, consisting of an ionic liquid supported on mesoporous silica, characterized by the fact that the latter has networks of pores in one, two and three dimensions.

11. The heterogeneous catalyst with multicatalytic activity in accordance with claim 10, which further comprises a functionalized silica support, characterized by synthesis in the presence of an organic compound containing the cation of the ionic liquid.

12. The heterogeneous catalyst with multicatalytic activity in accordance with claim 1, in which ion exchange of anion A with a heteropolyacid of formula H.sub.3XM.sub.12O.sub.40, generates the heteropolyanion of polyoxometalate (POMs) of formula H.sub.2XM.sub.12O.sub.40.sup.n—.

13. The heterogeneous catalyst with multicatalytic activity in accordance with claim 12, in which the metal phase M of polyoxometalate (POMs) of formula H.sub.2XM.sub.12O.sub.40.sup.n—is selected from the group consisting of Molybdenum (Mo), Tungsten (W), Vanadium (V) Titanium (Ti) or Zirconium (Zr).

14. The heterogeneous catalyst with multicatalytic activity in accordance with claim 13 in which the X component of polyoxometalate (POMs) of formula H.sub.2XM.sub.12O.sub.40.sup.n—is selected from the group consisting of Aluminum (Al), Silicon (Si), Phosphorus (P) or Sulfur (S).

15. The heterogeneous catalyst with multicatalytic activity in accordance with claim 14 in which the polyoxometalate of formula XM.sub.12O.sub.40.sup.n—, includes a metallic phase in which M is Tungsten (W), X is Phosphorus (P) and n is an integer corresponding to the charge number generated from the acid H.sub.3PW.sub.12O.sub.40 that generates the acid of formula H.sub.2XM.sub.12O.sub.40.sup.n—.

16. A process to prepare the heterogeneous catalyst with multicatalytic activity that is part of the chemical structure of claim 1 consisting of the following steps: Reaction to obtain the ionic liquid derived from imidazolium and which has the following structural formula: ##STR00011## the ionic liquid integrated into a support to prepare the catalyst that is the subject of the present invention, as described below: covalently anchoring of the ionic liquid to a support that is based on mesoporous silica, to produce an ionic functional hybrid compound consisting of the functional chemical agent anchored to the porous silica support by means of an “oxygen bridge”, according to the scheme illustrated below: ##STR00012## followed by grafting of a metal phase to the support as follows: exchanging anion A via Ion exchange of anion A of the ionic functional hybrid compound with a polyoxometalate (POMs) of formula H.sub.2XM.sub.12O.sub.40.sup.n—.

17. The process for preparing the heterogeneous catalyst with multicatalytic activity in accordance with claim 16 where the order of addition of the reactants may be either as illustrated in (a) or (b) below: (a) (1) nitrogenous heterocyclic aromatic organic compound replaced with R.sub.1, (2) compound 3-(R halide.sub.2)trimethoxysilane, (3) mesoporous material with silica-based arrangement and (4) polyoxometalate acid or (b) (1) compound 3-(R.sub.2 halide)trimethoxysilane, (2) mesoporous material with silica-based arrangement, (3) the nitrogenous heterocyclic aromatic organic compound substituted with R.sub.1, and (4) polyoxometalate acid.

18. The process for preparing the heterogeneous catalyst with multicatalytic activity in accordance with claim 16, in which the temperature of the preparation in a single step is between 0° and +100° C.

19. The process for preparing the heterogeneous catalyst with multicatalytic activity in accordance with claim 16, in which the preparation time in a single step is between 10 to 100 hours.

20. The process for preparing the heterogeneous catalyst with multicatalytic activity in accordance with claim 16, in which the molar ratio of the compounds is 1:1:0.1 or 0.5 or 1:1 respectively, for: (a) (1) nitrogenous heterocyclic aromatic organic compound replaced with R.sub.1, (2) compound 3-(R halide.sub.2)trimethoxysilane, (3) mesoporous material with silica-based arrangement and ( )polyoxometalate acid or (b) (1) compound 3-(R.sub.2 halide)trimethoxysilane, (2) mesoporous material with silica-based arrangement, (3) the nitrogenous heterocyclic aromatic organic compound substituted with R.sub.1, and (4) the polyoxometalate acid is 1:0.1 or 0.5 or 1:1:1 respectively.

21. The process of preparing a heterogeneous catalyst with multicatalytic activity, the heterogeneous catalyst characterized by containing a group with an anionic character and another organic cationic, a combination of the anionic character group and the organic cationic group forming an ionic liquid which is integrated on a structured mesoporous silica support, with a structural chemical formula: ##STR00013## Where: R.sub.1 is a substituted alkyl, alkyl, aryl group or aryl substituted; R.sub.2 is a chain of 1 to 4 carbon atoms; X is a chemical element selected from the group consisting of Aluminum (Al), Silicon (Si), Phosphorus (P) or Sulfur (5); M is an active metal chemical element; OMM is a silica-based mesoporous support material; and n is the charge number; wherein the heterogeneous catalyst is prepared by a process in accordance with claim 16, and wherein the catalyst has dual acid characteristics of a Bronsted-Lowry acid with concentration of acid sites of 1.0 to 7 (meq/g) and oxidants.

22. The process of preparing a heterogeneous catalyst with multicatalytic activity, the heterogeneous catalyst characterized by containing a group with an anionic character and another organic cationic, a combination of the anionic character group and the organic cationic group forming an ionic liquid which is integrated on a structured mesoporous silica support, with a structural chemical formula: ##STR00014## Where: R.sub.1 is a substituted alkyl, alkyl, aryl group or aryl substituted; R.sub.2 is a chain of 1 to 4 carbon atoms; X is a chemical element selected from the group consisting of Aluminum (Al), Silicon (Si), Phosphorus (P) or Sulfur (S); M is an active metal chemical element; OMM is a silica-based mesoporous support material; and n is the charge number, wherein the heterogeneous catalyst is prepared by a process in accordance claim 16, and wherein the catalyst has the characteristic of being regenerable.

23. The process of preparing a heterogeneous catalyst with multicatalytic activity, the heterogeneous catalyst characterized by containing a group with an anionic character and another organic cationic, a combination of the anionic character group and the organic cationic group forming an ionic liquid which is integrated on a structured mesoporous silica support, with a structural chemical formula: ##STR00015## Where: R.sub.1 is a substituted alkyl, alkyl, aryl group or aryl substituted; R.sub.2 is a chain of 1 to 4 carbon atoms; X is a chemical element selected from the group consisting of Aluminum (Al), Silicon (Si), Phosphorus (P) or Sulfur (S); M is an active metal chemical element; OMM is a silica-based mesoporous support material; and n is the charge number, wherein the heterogeneous catalyst is prepared by a process in accordance claim 16 and wherein the catalyst has a specific area (S.sub.BET) between 70 and 310(m.sup.2/g).

24. The process of preparing a heterogeneous catalyst with multicatalytic activity, wherein the heterogeneous catalyst is characterized by containing a group with an anionic character and another organic cationic, a combination of the anionic character group and the organic cationic group forming an ionic liquid which is integrated on a structured mesoporous silica support, with a structural chemical formula: ##STR00016## Where: R.sub.1 is a substituted alkyl, alkyl, aryl group or aryl substituted; R.sub.2 is a chain of 1 to 4 carbon atoms; X is a chemical element selected from the group consisting of Aluminum (Al), Silicon (Si), Phosphorus (P) or Sulfur (S); M is an active metal chemical element; OMM is a silica-based mesoporous support material; and n is the charge number, wherein the heterogeneous catalyst is prepared by a process in accordance claim 16, and wherein the catalyst has a total pore volume (total V) between 0.99 to 0.3 (cm.sup.3/g).

25. A process of using the heterogeneous catalyst with multicatalytic activity in accordance with claim 1 for organic reactions, wherein these reactions are condensation to obtain 2-pyridones in a single reaction stage, oxidation reaction to obtain 2 pyridones from 4H-pyran, esterification reactions between alcohols and different carboxylic acids and polymerization reactions using phenol and formaldehyde derivatives.

Description

BRIEF DESCRIPTION OF THE FIGURES OF THE INVENTION

[0010] FIG. 1. Chromatogram of the esterification reaction (ESI) between polyethylene glycol with 200 UMA and sebacic acid; and

[0011] FIG. 2. Chromatogram of the polymerization reaction of nonylphenol with formaldehyde and a heterogeneous catalyst.

DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention consists first of the synthesis of mesoporous materials ordered based on silica and its functionalization by grafting an ionic liquid at the surface level and its subsequent metathesis process with a Keggin acid, to prepare heterogeneous catalysts with multicatalytic activity that promote hydroprocessing reactions, which has been tested by the different chemical reactions.

Example 1. Synthesis of Mesoporous Materials of the SBA-15 Type

[0013] In a polypropylene container with lid, 16.2 g of Pluronic P123 (Sigma-Aldrich, Mv=5800) were weighed, then dissolved in 375 mL of HCl 1.6 M solution (JT Baker, 37%). The reaction mixture was stirred at 35-40° C. for 4 h, keeping the temperature constant by oil bath. 37.0 mL of tetraethylortosilicate (TEOS, Sigma-Aldrich, 97%) were added by drip, by peristaltic pump with a flow of (0.9 mL/min). The polypropylene container is hermetically closed and stirred at the same temperature for 20 h (hydrolysis stage). Then the temperature is set to 80° C. and maintained for 24 h under static conditions (aging stage). The reaction mixture is cooled to room temperature and filtered under vacuum. The resulting solid is washed with 650 mL of distilled water. It dries at 60° C. by 12 h and calcines as follows: 120° C. (1 h, 5° C./min), 550 (6 h, 1° C./min), 50° C. (0.5 h, 5° C./min). The particle size is homogenized at 150 μm.

Example 2. Mesoporous Silica Synthesis with Ordered Pore Arrangements

[0014] The material based on porous silica is obtained by the following steps: a quantity of tri-block polymer EO/PO is dissolved in water, adding a solution of 1 to 5 molar containing hydrochloric or citric acid, to form a first mixture that is heated to 40-50° ° C., adding to that mixture 20 to 40 mmol of tetraethylortosilicate (TEOS: Sigma-Aldrich, Mv=5800), under constant stirring (at 35-40° C., 2 h at 750 rpm), by using a peristaltic pump, with a flow of 0.9 mL/min, to obtain the first reaction product. This is cooled to room temperature and filtered under vacuum, then washed with 650 mL of a mixture of EtOH: H2O (1:1). It is dried at 60° C. by 12 h before calcining the dry material in air or nitrogen atmosphere as follows: 120° C. (1 h, 5° C./min), 550 (6 h, 1° C./min), 50° C. (0.5 h, 5° C./min). The particle size is homogenized at 150 μm. This material has an average pore size between 3 and 30 nm, as well as a wall thickness between 1.5 and 2.5 nm and specific area between 500 and 1000 m.sup.2/g, specific areas greater than 800 m2/g and even greater than 1,000 m.sup.2/g are also obtained.

Example 3. Ordered Mesoporous Silica Synthesis with Variable Morphologies and Pore Arrangements

[0015] An aqueous solution of 4.5% p of structuring agents (CTAB or EO/PO tri-block) at concentrations of 0.49245×10.sup.−3 M, is prepared in demineralized and de-ionized water, (208.3×10-3 M), adding 60×10-3 M of co-solvents C.sub.2H.sub.5OH or C.sub.3H.sub.7OH and then added 6.47×10-3 M of ammonium hydroxide. Then 1.20×10-3 M of Tetraethyletoplasty (TEOS) is added. After a few minutes a translucent gel is formed that dries at 40° C. for 8 h, before calcining at 550° C. in nitrogen atmosphere, and then in air for 4 h. Reagent concentrations can be easily scaled to obtain higher production for the applications of interest. Thus, the structuring agent ratios (AEs) of CTAB/NH.sub.4OH or EO/PO-triblock/NH.sub.4OH of 0.076:1 and combinations of AE(CTAB or EO/PO)/Co-solvents (C.sub.2H.sub.5OH or C.sub.3H.sub.7OH) with molar ratios of 0.008211 lead to the obtaining of porous silica materials with particle morphologies and variable pore arrangements (sphere, ellipsoids, etc.) with one, two and three dimensions of pores or nanotubes in the same particle, of 3.5 nm of average diameter, which is verified by X-ray diffraction (XRD) and TEM techniques.

Example 4. Synthesis of Ionic Liquid

[0016] ##STR00001##

[0017] In a flask of 50 to 250 mL, 2.5-12.5 mL of N-methylimidazole (Sigma-Aldrich, 99%) and 2.5-12.5 mL of chloropropyltrimethoxysilane (CPTMS, Sigma-Aldrich, 97%) were placed. The reaction mixture was stirred at 70-90° C. with magnetic stirrer under nitrogen atmosphere for 12-24 h. Subsequently, it is cooled to room temperature and washed with Et.sub.2O anhydrous (3×20 mL). The liquid obtained was vacuum dried to generate the desired product (1). The ionic liquid was stored under nitrogen atmosphere.

Example 5. Synthesis of the Ionic Liquid Grafting Covalent in Two Steps

[0018] ##STR00002##

[0019] Reaction with CPTMS: In a 50 mL flask with agitator, 5.0 g of mesoporous silica, 15.6 mL of CPTMS (0.08 mol) and 75 mL of anhydrous PhMe are placed. The reaction mixture is brought to reflux and stirred for 24 h. It is cooled to room temperature, the solid is vacuum filtered and washed successively with 100 mL of PhMe and 100 mL of DCM.

[0020] Reaction with N-methylimidazole: In a 50 mL flask with agitator are placed 1.0 g of SBA-15-Cl (2), 0.97 mL of N-methylimidazole (0.08 mol, Sigma-Aldrich, 99%) and 25 mL of anhydrous PhMe. The reaction mixture is brought to reflux and stirred for 24 h. It is cooled to room temperature, the solid is vacuum filtered and washed successively with 100 mL of PhMe and 100 mL of DCM.

Example 6. Functionalization of Silica with Ionic Liquids in One Step

[0021] ##STR00003##

[0022] In a 50 mL flask with agitator are placed 1.0 g of mesoporous silica (SBA-15 or MCF, 16.7 mmol), 0.5 g of ionic liquid (1, 1.78 mmol) and 25 mL of anhydrous PhMe. The reaction mixture is brought to reflux and stirred for 24 h. It is cooled to room temperature, the solid is vacuum filtered and washed successively with 20 mL of PhMe and 20 mL of DCM. The solid is then washed with DCE in a Soxhlet extractor for 24 hours. The solid is vacuum dried to generate the product (2). Immobilization of Keggin's heteropolyacid, H.sub.3PW.sub.12O.sub.40 (HPW).

Example 7. Direct Impregnation

[0023] In a 50 mL dry flask with agitator, phosphotungstic acid (Sigma-Aldrich) is dissolved in 25 mL of absolute EtOH. 0.5 g of pure silica is added. The obtained suspension is stirred at room temperature for 12 h. The ethanol is evaporated and dried under vacuum (50 mbar, 40° C., 1 h). Catalysts with loads of 0.1, 0.5, and 1.0 mmol/g of HPW are prepared.

Example 8. Effect of Washing on Direct Impregnation

[0024] In a dry flask of 50 mL with agitator the phosphotungstic acid (Sigma-Aldrich) is dissolved in 25 mL of absolute EtOH. 0.5 g of pure silica is added. The obtained suspension is stirred at room temperature for 12 h. The solid is vacuum filtered and washed with absolute EtOH (3×20 mL). Finally, it is dried under vacuum (50 mbar, 40° C., 1 h). This is how catalysts are prepared with loads of 0.1, 0.5, 1.0 mmol/g of HPW.

Example 9. Chloride Ion Metathesis in Mesoporous Silicas Modified with Ionic Liquids

[0025] ##STR00004##

[0026] In a dry flask of 50 mL with agitator the phosphotungstic acid (Sigma-Aldrich) is dissolved in 25 mL of absolute EtOH. 0.5 g of functionalized silica is added (see reaction 2, structure 2). The obtained suspension is stirred at room temperature for 12 h. The ethanol is evaporated and dried under vacuum (50 mbar, 40° C., 1 h). This is how catalysts are prepared with loads of 0.1, 0.5, 1.0 mmol/g of HPW.

Example 10. Purification and Effect of Ethanol on the Metathesis Process

[0027] In a dry flask of 50 mL with agitator the phosphotungstic acid (Sigma-Aldrich) is dissolved in 25 mL of absolute EtOH. 0.5 g of functionalized silica is added (see reaction 2, structure 2). The obtained suspension is stirred at room temperature for 12 h. The solid is vacuum filtered and washed with absolute EtOH (3×20 mL). Finally, it is dried under vacuum (50 mbar, 40° C., 1 h). This is how catalysts are prepared with loads of 0.1, 0.5, 1.0 mmol/g of HPW.

Example 11. Use of Ultrasound in the Process of Metathesis in Modified Mesoporous Silicas

[0028] In a dry flask of 50 mL with agitator the phosphotungstic acid (Sigma-Aldrich) is dissolved in 25 mL of absolute EtOH. The solution is shaken sonically for 5 min and adicionan 0.5 g of functionalized silica (see reaction 2, structure 2). Again it is sonically shaken for an additional 5 min. The obtained suspension is stirred at room temperature for 12 h. The solid is vacuum filtered and washed with absolute EtOH (3×20 mL). Finally it is dried under vacuum (50 mbar, 40° C., 1 h). This is how catalysts are prepared with loads of 0.1, 0.5, 1.0 mmol/g of HPW.

[0029] Table 2 describes the characteristics of raw materials and the examples described, in order to analyze the most important properties of these materials and the relationship with their application.

TABLE-US-00002 TABLE 2 Physicochemical properties of different hpAs supported obtained by the methods of invention S.sub.BET V.sub.p D.sub.p C.sub.sa Material Description (m.sup.2/g) (cm.sup.3/g) (nm) (meq/g) RM H.sub.3PW.sub.12O.sub.40 Pure heteropolyacid NF NF NF NF RM SBA-15 Pure support 859 0.94 5.9 1.1 RM MCF Pure support 803 1.22 Window: 8.4 1.0 Cell: 18.6 1 MIM-SBA15 Support + IL 308 0.52 5.3 1.4 2 MIM-MCF Support + IL 259 0.99 Window: 7.3 2.2 Cell: 17.0 4 MIM-SBA-0.1 Support + IL + 0.1 mmol/g HPW 218 0.38 5.2 2.5 5 MIM-SBA-0.5 Support + IL + 0.5 mmol/g HPW 165 0.23 4.4 3.9 6 MIM-SBA-1.0 Support + IL + 1.0 mmol/g HPW 164 0.23 4.3 4.0 9 MIM-MCF-0.1 Support + IL + 0.1 mmol/g HPW 143 0.50 Window 6.6 4.6 Cell: 16.7 10 MIM-MCF-0.5 Support + IL + 0.5 mmol/g HPW 140 0.50 Window: 6.1 5.3 Cell: 15.3 11 MIM-MCF-1.0 Support + IL + 1.0 mmol/g HPW 72 0.29 Window: 6.1 6.2 Cell: 15.0 S.sub.BET = surface area; Total V: total volume. NF = not found, D.sub.p = Pore diameter, C.sub.sa = Concentration of acid sites; RM = Raw Material.

[0030] Analyzing the data in Table 1, it is observed that depending on the Keggin acid load (HPW), the specific area and volume decrease regardless of the material used (SBA and MCF). The acidity value is increased, but there are no bibliographic references to this value. The synthesis of mesoporous silica derivatives has been reported in the literature but materials with a composition involving the three components described based on silica, ionic liquid and keggin acid have not been described.

[0031] In contrast, the present invention describes the preparation of a new product, classified as a heterogeneous catalyst based on mesoporous silica covalently functionalized by an ionic liquid and as a counterion a tungsten polyoxometalate (Keggin acid) with unique properties such as specific area (S.sub.BET) between 72 and 308 (m.sup.2/g); with total pore volume (total v) between 0.99 to 0.29 (cm.sup.3/g) and concentration of acid sites (C.sub.sa) from 1.4 to 6.2 (meq/g).

[0032] The main advantages over the literature show that this product (catalyst) has a dual action: Bronsted-Lowry acid and oxidizing agent; In addition, this type of catalyst offers advantages for the chemical industry because it is reusable, carrying out different transformations in a single stage, attributed to its acidic and oxidizing characteristics (dual action), in addition to its efficiency to carry out chemical transformations.

Application Examples

[0033] This section describes the tests carried out to obtain organic molecules under different reaction conditions, demonstrating the tolerance and scope of this catalyst.

Example 12. REARRANGEMENT AND OXIDATION TO OBTAIN 2-PYRIDONES

[0034] ##STR00005##

[0035] There are reports of the synthesis of 2-pyridones in two reaction stages using 4H-pyranes as raw materials (Reaction 5).

[0036] Por what the present invention made an analysis on the scope of the catalysts developed. The results show the ability of the catalysts developed to generate desired products through a mechanism of acid rearrangement and subsequent oxidation, additionally the catalyst is recovered later, once washed with ethanol it is dried at 100° C. and reused for up to 6 times maintaining a similar performance.

[0037] In the present invention begins with the 4 H-piran 5 (see reaction 5) (1.50 mmol) to which the solvent and catalyst are added according to Table 3. The mixture is heated to the indicated temperature and times (Reaction 5 and Table 3). The progress of the reaction is monitored by thin layer chromatography (t/c) (hexane/EtOAc, 7:3) and purification is performed by recrystallization under an H.sub.2O/Et.sub.0H system (95/5).

TABLE-US-00003 TABLE 3 Application of the catalyst in rearrangement and oxidation reactions. Load Catalyst (% wt) Solvent T(° C.) t(h) Conc.(M) 2(%) 3(%) MIM-SBA-0.1 10 EtOH 120 12 0.1 n.d. n.d. MIM-SBA-0.1 25 EtOH 120 12 0.2 Trace n.d. MIM-SBA-1.0 25 EtOH 120 12 0.2 34 n.d. MIM-MCF-0.1 25 EtOH 120 12 0.2 Trace Trace MIM-MCF-1.0 25 EtOH 120 12 0.2 64 27 MIM-MCF-1.0 50 EtOH 120 12 0.1 25 18 MIM-MCF-1.0 25 EtOH:H.sub.2O 120 12 0.2 13 80 (1:1) MIM-MCF-1.0 25 MeCN 120 12 0.2 n.d. n.d. MIM-MCF-1.0 25 MeCN:H.sub.2O 120 12 0.2 24 72 (1:1) MIM-MCF-1.0 25 H.sub.2O 120 12 0.2 34 58 MIM-MCF-1.0 25 EtOH:H.sub.2O 120 24 0.2 n.d. 93 (88) (1:1) MIM-MCF-1.0 10 EtOH 80 12 0.1 73 25 nd: undetected

Example 13. Reaction of Multicomponents to Obtain 2-Pyridones

[0038] ##STR00006##

[0039] The present invention was proposed to obtain a catalyst that could favor the generation of 2-pyridones in a single reaction stage, and for this purpose aldehyde 10 (3.0 mmol), malononitrile 9 (3.0 mmol), ethyl acetoacetate 8 (see reaction 6) (3.0 mmol) and catalyst were used, which are placed in a 25 mL flask with a capacitor. The mixture reaches 120° C. by a conventional heating form for 24 h, in an EtOH/H.sub.2O mixture. The reaction is monitored by .sup.1H NMR or t/c. Once the reaction is finished, it is cooled and purified by recrystallization in a water/ethanol mixture, generating 2-pyridone with a 52% yield, which proves the versatility of the catalyst (Reaction 6).

Example 14. ESTERIFICATION REACTION

[0040] ##STR00007##

[0041] The esterification reaction between the alcohols and different carboxylic acids was carried out in a 1:1 ratio, with the MIM-MCF-1.0 catalyst, for which the reaction is monitored by the negative variation of the acid number (TAN), which has a value of 60 at the beginning of the reaction and this decays to 12, depending on the type of acid used (Table 4), for this, the percentage of catalyst was varied until the minimum acid number value (TAN) was achieved. This minimum value is achieved with the reaction time and with the heterogeneous catalyst MIM-MCF-1.0 at 10% wt. In almost all cases monoesterification and diesterification reactions are observed, while the recovery of the catalyst and its regeneration yield the same TAN value up to 5 times, after being washed and dried at 120° C. (Reaction 7).

TABLE-US-00004 TABLE 4 Products of the esterification reaction Alcohol Acid Catalyst TAN Isosorbide Stearic acid MIM-MCF-1.0 (10%) 38 PEG 200 Adipic acid MIM-MCF-1.0 (10%) 37 PEG 200 Adipic acid MIM-MCF-1.0 (20%) 29 PEG 200 Adipic acid MIM-MCF-1.0 (30%) 20 PEG 200 Sebacic acid MIM-MCF-1.0 (10%) 12

[0042] In a flask of two mouths of 100 ml the alcohol and the catalyst are placed. A Dean-Stark trap is adapted to a mouth, which is connected to a vacuum wrench, perfectly sealing the mouths with Teflon, then heated to 130° C. for 3 h, with periodic sampling to measure the acid number (TAN). The distribution of molecular weights is shown in FIG. 1 (see section of Figures), the study is carried out using the technique of mass spectrometry (El method) between polyethylene glycol of molecular weight of 200 m/z (PEG 200) and sebacic acid, where the molecular distribution indicates that monoesterification and diesterification reactions are carried out (Reaction 8).

##STR00008##

Example 15. POLYMERIZATION REACTION

[0043] Derived from the acidity of MIM-MCF catalysts at 0.1 (4.6 meq/g), 0.5 (5.3 meq/g), and 1 (6.2 meq/g) mmol/g HPW, its application in polymerization reactions using phenol and formaldehyde derivatives was tested. The importance of these products stems from their potential use for the formulation of crude oil dehydrating agents. In a two-mouth flask of 100 mL weigh 5 g of nonylphenol, 0.9 g of paraformaldehyde, 7.5 mL of toluene, adding 10% of the catalyst. One of the flask mouths adapts to a condenser and the other to a Dean-Stark trap, which is filled with toluene for the dragging of water generated during the condensation process. It is heated to 130° C. for 2-3 h, taking samples every 30 min, measuring the ISR value until the most appropriate one is achieved, e.g. 5.0. At the beginning of a test, the ISR of nonylphenol was measured, being equal to 0.8, so this value should be increased during the condensation process with the paraformaldehyde and the acid catalyst (Reaction 9). FIG. 2 shows the analysis by the technique of mass spectrometry (MALDI-TOF), the distribution of molecular weights of this reaction, which indicates that the maximum degree of polymerization was 4.5 and the lowest was equal to 2.

##STR00009##

[0044] The best mode for carrying out the invention has been described for purposes of illustrating the best mode known to the applicant at the time. The examples are illustrative only and not meant to limit the invention, as measured by the scope and merit of the claims. The invention has been described with reference to preferred and alternate embodiments. Obviously, modifications and alterations will occur to others upon the reading and understanding of the specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.