TW200400954A - Manufacture of 3-methyl-tetrahydrofuran from alpha-methylene-gamma-butyrolactone in a direct process - Google Patents

Abstract

Disclosed is a single step continuous hydrogenation process for the preparation of 3-methyl-tetrahydrofuran from alpha-methylene-gamma-butyrolactone, in the presence of a catalytic metal.

Description

200400954 玖 玖, description of the invention (the description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and a brief description of the drawings) TECHNICAL FIELD This case discloses a continuous method, which consists of A single chemical step for the preparation of 3-fluorenyl-tetrahydrofuran from γ-butyrolactone. Prior art Substituted tetrahydrofuran (such as 3-methyl-tetrahydrofuran of the present invention) is generally used in the field in which tetrahydrofuran is used. Examples include polymerization reactions to make fibers and use as solvents. Poly (tetramethylene ether glycol) is polymerized to obtain tetrahydrofuran. This polymer is used as a chain block in polyurethanes and polyesters. Polyurethane based on poly (tetramethylene ether glycol) soft block has improved hydrolytic stability / abrasion resistance and elastomeric properties. Other advantages include strength, toughness, durability, low compression set properties and high water vapor permeability. The largest end use range for these polyurethanes is as spandex fibers for apparel. Poly (tetramethylene.¾diol) -containing products are also used in wheels, high-speed rollers, vehicle parts, bushings, special hoses, cable covers, covers and coatings, pipeline liners, and roof and floor coatings. The 3-methyl-tetrahydrofuran monomer can be used as a comonomer for modified poly (tetramethylene ether glycol), resulting in better elastomer properties. In the case where tetrahydrofuran is used as a solvent (where lower volatility is necessary), 3-methyl-tetrahydrofuran is advantageous because tetrahydrofuran boils at 66 ° C, while 3-methyl- Tetrahydrofuran boils at 86 ° C. Methods for producing 3-methyl-tetrahydrofuran by hydrogenating itaconic acid ester or 3-methylfluorenyl-2-methylpropionate and by hydrogenating methyl-succinate are disclosed in Japanese Patent Applications 219981/1994 and 217768/1996. Together with the target 3-methyl-200400954 Description of the invention continued ⑺ Tetrahydrocondensation, these reactions produce alcohols (must be separated in another step). 3-methyl-tetrahydrofuran forms an azeotropic mixture with mainly lower alcohols (for example, methanol with an azeotropic point of 64.5 ° C) and is composed of 25% by weight of 3-methyl-tetrahydrofuran and 75% by weight of methanol An azeotropic composition. The presence of this azeotropic mixture requires expensive, energy-intensive separation steps to produce pure 3-methyl-tetrahydrofuran. Specifically, the 3-methyl-tetrahydrofuran used to modify the poly (tetramethylene ether glycol) can tolerate an alcohol purity of less than 0.2%. Similarly, U.S. Patent No. 5,990,324 discloses a method for producing 3-methyl-tetrahydrofuran, which is carried out by hydrogenating β-formyl isobutyrate having the general formula ROOC-CH (CH3) -CH2-CHO, Wherein R is an alkyl group having 1 to 3 carbon atoms, and the formamyl group may exist as a condensate having an alkanol having 1 to 8 carbon atoms. In this method, the alcohol product is separated from 2-methyl-γ-butyrolactone in the second step. This separation can be performed by simple distillation. Although azeotropic distillation is not necessary, alcohol separation is still a necessary step in the process for producing 3-methyl-tetrahydrofuran. The α-methylene-γ-butyrolactone system is a reactive monomer. Attempts have been made in the past to directly catalyze the conversion of α-methylene-γ-butyrolactone to 3-methyl-tetrahydrofuran. However, because the catalytic reaction requires high temperatures (greater than 150 ° C), the conversion reaction results in the polymerization of α-fluorenyl-γ-butyrolactone. Therefore, the problem to be solved is to provide a simple and economical one-step method for producing 3-methyl-tetrahydrofuran. The single-step method of the present invention reveals a more efficient way to produce 3-methyl-tetrahydroρ-loss from α-methylene-γ-butyrolactone using a novel catalyst system (without any alcohols). Generated) to exclude common beaches or other types of separation steps. 200400954 (3) Description of the Invention Continued Summary of the Invention The present invention relates to a method for producing 3-methyl-tetrahydrofuran, which comprises a step of hydrogenating α-methylene-γ-butyrolactone represented by a compound of formula (I) to Production of 3-methyl-tetrahydrofuran (II) as a product (in the presence of a catalytic metal)

(0 (ID implementation

"Ct-methylene-γ-butyrolactone" represents a compound represented by the following formula., _ / Η2

"Acid promoter" refers to a compound that is acidic in nature and is added to enhance the physical or chemical function of the catalyst. "Metal accelerator" refers to a metal compound added to enhance the physical or chemical function of the catalyst. Acid and metal accelerators are chemical accelerators commonly used to enhance the activity of catalyst agents. The accelerator can be incorporated into the catalyst during any step of the chemical treatment of the catalyst component. The present invention relates to a method for synthesizing 3-methyl-tetrahydrofuran from α-methylene-γ-butyrolactone. More specifically, the present invention relates to a method for synthesizing 3-methyl-tetrahydrofuran from α-methylene-γ-butyrolactone in a single chemical step. Chemical method 200400954 Description of the invention continued (4) Alcohols are produced as by-products. The final product does not require isolation or purification of alcohols. Due to the high temperature of the catalytic reaction (greater than 150 ° C), previous attempts to directly convert α-methylene-γ-butyrolactone to 3-methyl-tetrahydrofuran have caused α-methylene-γ-butyrolactone monomers Polymer formation. This method involves a hydrogenation reaction of α-methylene-γ-butyrolactone to 3-methyl-tetrahydromalan as a product. Metal catalysts (with or without support) may be present for the hydrogenation reaction. Optionally, an acidic material may be used to promote the sword to assist the reaction. Optionally, metals can be used as accelerators to assist the reaction. The method of the present invention can be carried out in any of the apparatuses commonly used in the continuous method, in a batch, continuous batch (i.e., a series of batch reactor), or continuous mode. If necessary, remove condensed water from the main part of the reaction with the help of inert gas removal. In order to achieve high yields of 3-methyl-tetrahydrofuran, the process temperature needs to be controlled. The temperature range for the reaction is about 100 ° C to about 250 ° C. A temperature range of about 200 ° C to about 250 ° C is preferred. A more preferred temperature range is from about 220 ° C to about 230 ° T. The pressure used in the reaction ranges from about 3.4 MPa to about 14.0 MPa. A pressure range of about 5.1 MPa to about 10.4 MPa is preferred. A better pressure range is about 5.1 MPa to about 6.9 MPa. The catalyst used here is a substance (chemically unchanged) that can affect the reaction rate but does not affect the reaction equilibrium and is formed by the self-made process. Chemical accelerators usually increase catalyst activity. The accelerator can be incorporated into the catalyst during any step of the chemical treatment of the catalyst component. Chemical accelerators usually enhance the physical or chemical function of the catalyst, but they can also be added to block unwanted side reactions. The hydrogenation reaction of α-methylene-γ-butyrolactone into 3-methyl-tetrahydrocran is carried out in (5) (5) 200400954 Description of the invention continued on the presence of a catalytic catalyst. The main component of the catalyst is a group consisting of palladium, ten, rhodium, rhodium, iridium, platinum, compounds or combinations thereof. — The catalytic metal used in the method disclosed in this case may be a catalyst that is either cross-supported or unsupported. Supported catalysts are those in which the active catalyst agent is sprayed, impregnated, or physically mixed, followed by drying, sintering, and, if necessary, deposition on a carrier material 41 by activation such as reduction or oxidation. . Materials often used as carriers are porous materials with a high total surface area (external and internal), which can provide a high concentration of activation area per unit weight of catalyst. Dazzle may enhance the function of catalyst agents. Catalysts not supported on the catalyst carrier are unsupported catalysts. The support material is selected from the group consisting of carbon, aluminum oxide, silicon dioxide, silicon oxide-alumina, titanium dioxide, and combinations thereof. Furthermore, the supported catalytic metals can have the same support material: people make needles or different temple materials. The preferred support is carbon. The carbon may be a commercially available carbon such as cahka c, Sibunit C, or Calgon c (trade name Centaui: (R)). The preferred catalytic metal content in the catalyst supported by rhenium is in the range of about 0 to about 15%. A more preferred catalytic metal content range is from about 1% to about yet a still more preferred catalytic metal content range is from about 1% to about 5%. The preferred combination of catalytic metal and support system comprises palladium / merged on carbon ' on carbon and rhodium / merged on carbon / on carbon. Acid promoters can be used in the reactions of the present invention. Suitable accelerators include acids having a pKa of 4 (preferably having a pKa of less than about 2) 'containing inorganic acids, organic continuous acid acids, perfluoroalkylsulfonic acids, and mixtures thereof. Also suitable are metal salts with acids having a pKa of less than about 4, metal sulfonates, metal trifluoroacetates, metal triflates and mixtures thereof (containing salts 200400954 (6) Invention Explain that the continuation sheet and its co-acid mixture) ° Specific examples of accelerators include sulfuric acid, fluoric acid, '' scale acid, p-toluenesulfonic acid, benzoic acid, arsenic acid, loamic acid, trifluoromethane Burning acid, 1,1,2,2-tetrafluorohexanoic acid: ^ acid, 1,2,3,2,3,3-hexapropane acid, bismuth trifluoromethanesulfonate, trifluoro ^ Slope acid period, trifluoromethane sulfonium acid, titanium trifluoromethanesulfonate, trifluoromethane * lanthanum acid, lanthanum trifluoromethanesulfonate, and trifluoromethane 'zirconium sulfonate. The preferred accelerator is selected from the group consisting of Zn (BF4) 2, CBV_3020E zeolite, and 20-Αίphorite. The acid accelerator is at a concentration of 0.1 to 5% by weight. use. A better concentration range is 0.250 /. To 2,5. /. . Appropriate heterogeneous acid promoters are zeolites, fluorinated alumina, acid-treated silica, fatigued silica-alumina, acid-treated white clay, heterogeneous heteropoly acids And sulfated zirconia. Metal accelerators can optionally be used in the method of the invention with acid accelerators. Suitable metal accelerators include tin, zinc, copper, gold, silver, and combinations thereof. A preferred metal accelerator is tin. The following abbreviations are used in the ESCAT Calsicat Carbon Sibunit Carbon JM-A11108 Carbon Calgon Carbon example: Catalyst series provided by Engelhard Corp. Catalyst support provided by Engelhard Corp. Provided by Inst, of Technical Carbon, Omsk (Russia) The catalyst carrier was provided by Johnson Matthey, Inc. The catalyst carrier was provided by Calgon Corp. under the brand name Centaur (R) CBV-3020E Zeolite type acid accelerator 20-A Zeolite type acid accelerator Commercially available carriers such as carbon, alumina, silicon dioxide, di-oxo-ox-oxide, hafnium dioxide (available from Engelhard Corp. (E. Windsor, -10- 200400954 ⑺ Description of the Invention Continued CT)) , Penetrating into metal salts. The precursors used were NiCl2.6H20 (Alfa Chemical Co.), Re207 (Alfa Chemical Co.), PdCl2 (Alfa Chemical Co.), RuC13.XH2O (Aldrich Chemical Co.), H2PtCl6 (Johnson Matthey, W. Deptford, NJ), CrCl3. 6H20 (Mallinckrodt Baker, Inc.), 5% Rh (using RhCl3. XH20 (Alfa Chemical Co.)). The samples were dried and reduced in H2 at 300-450 ° C for 2 hours. The carbon used is commercially available Calsicat Carbon, Sibunit Carbon or Calgon Carbon (Centaur (R)). Calsicat Carbon is lot number S-96-140 available from Engelhard Corp, Beachwood, OH. Sibunit Carbon is Sibunit-2 available from Inst, of Technical Carbon, 5th Kordnaya, Omsk 64418 (Russia). Calgon Carbon is a PCB Carbon available from Calgon Corp. (ΊMain Bookmark is Centaur (R)). Example-1 Preparation of Catalyst 5% Pt on Pickled Calsicat Carbon In a 150 ml beaker, 4.5 ml of 0.3 M H2PtCl6 and 4.0 ml of deionized osmium 20 were used to form a solution. Add 4.75 grams of pickled Calsicat Carbon (12 X 20 mesh, dried overnight at 120 ° C) to a beaker. Allow the slurry to stand at room temperature for 1 hour (with occasional stirring), and with frequent stirring, dry at 120 ° C overnight (until free flowing) in an alumina boat, in a quartz-lined furnace, and at It was cleared at room temperature with 500 SCCM (standard cubic centimeters per minute) N2 for 15 minutes, and then at room temperature with 100 SCCM He for 15 minutes. The catalyst was heated to 15 °. (3, and kept at 150 ° C for 1 hour under He. At this moment, add 100 SCCM H2, and kept at 150 ° C for 1 hour under He and H2. Increase the temperature to 300t, and make contact under He-H2 The medium was reduced at 300 ° C for 8 hours. The H2 was stopped, and the sample was kept at 400400954 under He. Description of the invention continued at 300 ° C for 30 minutes, and then cooled to room temperature in flowing He. Finally, the solution was allowed to stand at room temperature. The catalyst was passivated in 1.5% 02 (in N2) at 500 SCCM for 1 hour and weighed 4.93 grams when unloaded. Example 1-36: α-Methylene-γ-butyrolactone becomes 3-methyl -Hydrogenation of tetrahydrofuran Add 50% MBL (in dihumane) (1000.6 mg, 5.1 mmol) and appropriate amount of catalyst and carrier (as shown in the table below) to a 2 ml pressure reactor. Closed reactor And filled with H2 of 6.89 MPa and heated to a reaction temperature of 225 ° C. After a predetermined period of time, the reaction was stopped and cooled within 10 to 15 minutes. An internal standard (2-methoxyethyl ether) was added to the reaction The mixture was analyzed by GC on a HP-6890 GC with a Chrompack column (CP-WAX 58, 25 m x 25 mm). Do not list the reaction conditions, catalysts, acid promoters, and conversion and selectivity of reactants and products. All tests are performed with 50% α-methylene-γ-butyrolactone (in dihumane) Table 1 Test number time (hours) Catalytic acid accelerator MBL conversion rate (%) 3-Me-THF selectivity (%) MeGBL selectivity (%) 1.2 5% Pd / C (ESCAT 140) 99.21 0.23 83.53 2. 2 5% Pd / C (ESCAT 142) 85.57 0.28 93.72 3 2 5% Pd / C (ESCAT 143) 99.49 0.19 96.94 4. 2 5% Pd / C (ESCAT 148) 86.71 0.33 97.80 5. 2 5% Pd / C (ESCAT 149) 99.92 0.14 94.36 6. 2 5% Pd / C (ESCAT 160) 95.05 0.24 97.80 7. 2 5% Pd / C (ESCAT 162) 97.87 0.15 88.55 8. 2 l% Ru / 6% Re / C 99.44 0.16 90.27 9. 2 l% Ru / 6% Re / C Zn (BF4) 2 91.31 0.57 63.14 200400954 (9) Description of the invention Continuation test number (hours) Catalyst acid accelerator MBL conversion rate (%) 3-Me-THF selectivity (%) MeGBL selectivity (%) 10. 2 l% Ru / 6% Re / C CBV-3020 94.25 0.87 71.79 11. 2 l% Ru / 6% Re / C 20A 93.15 1.05 64.49 12. 2 1,87% Ru / 5.65% Re / 0.77% Sn / C Zn (BF4) 2 78.25 0.46 51.03 13. 2 1.87% Ru / 5.65% Re / 0.77% Sn / C CBV-3020 96.76 0.06 1.14 14. 4 5% Pd / C JM-A11108-5 + 5% Re / Sibunit C 100.00 1.68 95.62 15. 4 5% Pd / C JM-A11108-5 + 5% Re / Calsicat C 100.00 2.58 95.43 16. 4 5% Pd / CJM-Al 1108-5 + 5% Re / Calgon C 100.00 0.59 61.23 17. 4 5% Pd / C JM-A11108-5 + 5% Re / Calsicat C (400C) 100.00 1.94 94.34 18. 4 5% Pd / C JM-A11108-5 + 10% Re / Calsicat C (400C) 100.00 94.79 19. 4 5% Pd / C + 20% Re / Calsicat C (400C) 100.00 5.10 93.84 20 . 4 5% Pd / C JM-A11108-5 + 5% Re / Sibunit C 100.00 8.22 90.04 21. 4 5% Pd / C JM-A11108-5 + 5% Re / Calsicat C 100.00 12.66 82.70 22. 4 5% Pd / C JM-A11108-5 + 5% Re / Calgon C 100.00 2.93 92.38 23. 4 5% Pd / C JM-A11108-5 + 5% Re / Calsicat C (400C) 100.00 10.14 85.15 24. 4 5% Pd / CJM-Al 1108-5 + 10% Re / Calsicat C (400C) 100.00 12.35 83.89 25. 4 5% Pd / Calsicat C + 5% Ir / Calsicat C 100.00 1.25 89.34

-13-200400954 (10) Description of the invention Continuation page test number time (hours) Catalytic acid accelerator MBL conversion rate (%) 3-Me-THF selectivity (%) MeGBL selectivity (%) 26. 4 5% Rh / Calsicat C + 5% Ir / Calsicat C 100.00 1.84 87.45 27. 4 5% Ru / Calsicat C + 5% Ir / Calsicat C 100.00 2.91 81.53 28. 4 5% Ru / A1203 + 5% Ir / Calsicat C 98.41 0.51 80.21 29. 4 5% Pd / Calsicat C + 5% Ir / A1203 100.00 0.67 90.74 30. 4 5% Rh / Calsicat C + 5% Ir / A1203 100.00 0.55 86.61 31. 4 5% Ru / Calsicat C + 5% Ir / A1203 98.50 0.51 62.70 32. 4 5% Ru / A1203 + 5% Ir / A1203 98.33 0.17 68.52 4 5% Pd / Calsicat C + 5% Re / Cal. C 98.74 5.96 77.39 34. 4 5% Rh / Calsicat C + 5% Re / Cal. C 99.63 21.42 60.41 35. 4 5% Ru / Calsicat C + 5% Re / Cal. C 86.95 5.58 55.00 36. 4 5% Ru / A1203 + 5% Re / Cal. C 94.14 5.56 68.68

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Claims (1)

200400954 Patent application scope 1. A method for preparing 3-methyl-tetrahydrofuran of formula (11), which comprises hydrogenating α-methylene-γ-butyrolactone of compound of formula (I) in the presence of a catalytic metal. 2. The method according to item 1 of the scope of patent application, wherein the catalytic metal is selected from the group consisting of exemption, tetrahydrofuran, baht, rhodium, watch, starter, compounds and combinations thereof. 3. The method of claim 1 in which the catalytic metal is supported on a catalyst carrier. 4. The method of claim 3, wherein the catalyst carrier is selected from the group consisting of carbon, aluminum oxide, silicon dioxide, silicon dioxide-alumina, titanium dioxide, compounds thereof, and combinations thereof. 5. The method of claim 1 in which the reaction is performed in the presence of a metal accelerator. 6. The method of claim 5 in which the metal accelerator is selected from the group consisting of tin, zinc, pins, gold, silver, and combinations thereof. 7. The method of claim 5 in which the metal accelerator is tin. 8. The method of claim 1 in which the reaction is performed in the presence of an acid promoter. 9. The method according to item 8 of the patent application, wherein the acid accelerator is an acid having a pKa of less than 4 or a metal salt thereof. 200400954 Application for Patent Continued 10. The method as described in Item 9 of the Patent Scope, wherein the acid accelerator is selected from the group consisting of inorganic acids, organic continuous acids, heteropolyacids, perfluoroalkanoic acids and metal salts thereof. . 11. The method of claim 10, wherein the acid promoter is selected from the group consisting of sulfuric acid, fluorosulfonic acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, phosphotungstic acid, phosphomolybdic acid, and trifluoromethanesulfonic acid. Acid, 1,1,2,2-tetrafluoroethanesulfonic acid, 1,1,1,2,3,4-hexapropanesulfonic acid, bismuth trifluoromethanesulfonate, yttrium trifluoromethanesulfonate, trifluoro A group of thorium methanesulfonate, titanium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, thallium trifluoromethanesulfonate and trifluoromethanesulfonate files. 12. The method according to item 8 of the patent application, wherein the acid accelerator is selected from the group consisting of zeolite, fluorinated alumina, sulfuric acid-treated silicon dioxide, sulfuric acid-treated silicon dioxide-alumina, and support for oxidation. A group of heteropolyacids on zirconium, titanium dioxide, aluminum oxide and / or silicon dioxide. 13. The method according to item 8 of the patent application, wherein the acid accelerator is Zn (BF4) 2. 14. The method as claimed in claim 8 wherein the acid accelerator is zeolite CBV-3020E. 15. The method according to item 8 of the patent application, wherein the acid accelerator is zeolite CBV-20 A. 16. The method of claim 1 in which the reaction is performed in the presence of an acid accelerator and a metal accelerator. 17. The method according to item 1 of the patent application range, wherein the method is performed at a temperature of 100 ° C to 250 ° C. 18. The method according to item 1 of the scope of patent application, wherein the method is performed at a temperature of 200,400,954. 19. The method according to item 1 of the patent application range, wherein the method is performed at a temperature of 220 ° C to 230 ° C. 20. The method according to item 1 of the patent application range, wherein the method is performed under a pressure of 3.4 MPa to 14.0 MPa. 21. The method according to item 1 of the patent application range, wherein the method is performed under a pressure of 5.1 MPa to 10.4 MPa. 22. The method according to item 1 of the patent application range, wherein the method is performed under a pressure of 5.1 MPa to 6.9 MPa. 23. The method according to item 1 of the patent application range, wherein the method is performed at a temperature of 220 ° C to 230 ° C and a pressure of 5.1 MPa to 6.9 MPa. 24. The method of claim 1 in which the catalytic metal is supported, and the catalytic metal support is palladium / merged on carbon / bath on carbon. 25. The method of claim 1 in which the catalytic metal is supported and the catalytic metal support is rhodium / merged on carbon / bath on carbon. 26. The method of claim 24, wherein the palladium / on carbon is present at a content of 5% and the baht / on carbon is present at a content of 5%. 27. The method of claim 24, wherein the palladium / carbon is present at a content of 5% and the baht / carbon is present at a content of 10%. 28. The method as claimed in claim 25, wherein the rhodium / carbon is present as 5%, and the baht / carbon is present as 5%. 29. The method of claim 25, wherein the rhodium / carbon is present at a content of 5%, and the baht / carbon is present at a content of 10%. 200400954 Lu, (a), the designated representative of this case is: Figure _ (b), a brief description of the element representative symbols of this representative: