CN115286598B - Synthesis method of 2, 5-furandicarboxylic acid diester compound - Google Patents
Synthesis method of 2, 5-furandicarboxylic acid diester compound Download PDFInfo
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- CN115286598B CN115286598B CN202210765803.0A CN202210765803A CN115286598B CN 115286598 B CN115286598 B CN 115286598B CN 202210765803 A CN202210765803 A CN 202210765803A CN 115286598 B CN115286598 B CN 115286598B
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- furandicarboxylic acid
- furancarboxylate
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- -1 2, 5-furandicarboxylic acid diester compound Chemical class 0.000 title claims abstract description 31
- CHTHALBTIRVDBM-UHFFFAOYSA-N dehydromucic acid Natural products OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 26
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- INULFORHAGYOGB-UHFFFAOYSA-N dipropyl furan-2,5-dicarboxylate Chemical compound CCCOC(=O)C1=CC=C(C(=O)OCCC)O1 INULFORHAGYOGB-UHFFFAOYSA-N 0.000 claims description 8
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 claims description 7
- NHXSTXWKZVAVOQ-UHFFFAOYSA-N Ethyl furoate Chemical compound CCOC(=O)C1=CC=CO1 NHXSTXWKZVAVOQ-UHFFFAOYSA-N 0.000 claims description 6
- PAMQYEWNNPDBLM-UHFFFAOYSA-N butyl furan-2-carboxylate Chemical compound CCCCOC(=O)C1=CC=CO1 PAMQYEWNNPDBLM-UHFFFAOYSA-N 0.000 claims description 6
- NLHUMZUNLXZWNW-UHFFFAOYSA-N dibutyl furan-2,5-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)O1 NLHUMZUNLXZWNW-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- ZKHQSQYLKSSYIP-UHFFFAOYSA-N methyl furan-3-carboxylate Chemical compound COC(=O)C=1C=COC=1 ZKHQSQYLKSSYIP-UHFFFAOYSA-N 0.000 claims description 4
- HSCVIIISAAEVQT-UHFFFAOYSA-N Propyl 2-furoate Chemical compound CCCOC(=O)C1=CC=CO1 HSCVIIISAAEVQT-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 12
- 238000007599 discharging Methods 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- SXULPFQMFZDBIC-UHFFFAOYSA-N 3,4-dibutylfuran-2,5-dicarboxylic acid Chemical compound CCCCC1=C(C(O)=O)OC(C(O)=O)=C1CCCC SXULPFQMFZDBIC-UHFFFAOYSA-N 0.000 description 1
- JODJLOUEMNZRNF-UHFFFAOYSA-N 3,4-diethylfuran-2,5-dicarboxylic acid Chemical compound CCC1=C(C(O)=O)OC(C(O)=O)=C1CC JODJLOUEMNZRNF-UHFFFAOYSA-N 0.000 description 1
- NVWMHICCPUEWLL-UHFFFAOYSA-N 3,4-dimethylfuran-2,5-dicarboxylic acid Chemical compound CC=1C(C)=C(C(O)=O)OC=1C(O)=O NVWMHICCPUEWLL-UHFFFAOYSA-N 0.000 description 1
- NDCKJSSRIIGRNF-UHFFFAOYSA-N 3,4-dipropylfuran-2,5-dicarboxylic acid Chemical compound CCCC1=C(C(O)=O)OC(C(O)=O)=C1CCC NDCKJSSRIIGRNF-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000193448 Ruminiclostridium thermocellum Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004334 oxygen containing inorganic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention provides a synthesis method of a2, 5-furandicarboxylic acid diester compound, which comprises the steps of dissolving alkyl furancarboxylate in a solvent to obtain a raw material solution; uniformly stirring and mixing the raw material solution and the metal supported catalyst in a reaction kettle container, sealing the container, replacing air in the sealed container with carbon dioxide, and keeping the gas pressure of the carbon dioxide in the sealed container to be 1-6 MPa; opening a stirring device, a heating device and an axial cooling device of the automatic reaction kettle; filtering the reaction product, adding the filtered reaction product into a vacuum rectifying tower, discharging 2, 5-furandicarboxylic acid diester compounds from the bottom of the vacuum rectifying tower, condensing the gas discharged from the top of the vacuum rectifying tower after entering a recovery tank, and drying and rectifying the collected condensed liquid for reuse. The invention opens up a novel synthetic route, uses gaseous carbon dioxide as raw material, has environment-friendly production process, and has high catalytic efficiency, good stability and high total product yield.
Description
Technical Field
The invention belongs to the field of organic synthesis, and in particular relates to a novel synthesis method for preparing a2, 5-furandicarboxylic acid diester compound by using a metal supported catalyst.
Background
Polyethylene terephthalate (PET) is one of the main polyester materials at present, the yield of the PET in 2020 reaches 1 hundred million tons, the yield of the PET is over 7000 ten thousand tons, and the PET is widely applied to the fields of packaging, fibers, engineering plastic stools, but the PET has the defect that the gas barrier property cannot meet the requirement when being applied to the fields of packaging of wines, medicines, cosmetics and the like. The furan polyester material polyethylene 2, 5-furandicarboxylate (PEF) synthesized by using the 2, 5-furandicarboxylate compound as a monomer has higher gas barrier property than PET, the gas barrier property to CO 2 is twice that of PET, the gas barrier property to O 2 is 10 times that of PET, and the gas barrier property to water vapor is 2 times that of PET. PEF has the further advantage of biodegradability, which has been shown to be hydrolysable by recombinant clostridium thermocellum cutinase. It is seen that PEF is more applicable than PET in the packaging field, and as PEF is more and more emphasized, research on monomers of PEF is also being pursued, and PEF is one of the mainstream polyester materials that can replace PET in the future.
The 2, 5-furandicarboxylic acid diester compound used for synthesizing PEF generally refers to short-chain dibasic esters including dimethyl 2, 5-furandicarboxylic acid, diethyl 2, 5-furandicarboxylic acid, dipropyl 2, 5-furandicarboxylic acid and di-n-butyl 2, 5-furandicarboxylic acid, which are generally colorless or white crystals. The main function of the 2, 5-furandicarboxylic acid diester compound is to synthesize chiral catalyst, molecular recognition receptor and high molecular material, especially in the aspects of manufacturing polyester, polyamide and polyurethane.
The main synthesis method of the 2, 5-furandicarboxylic acid diester compound is esterification of 2, 5-furandicarboxylic acid and alcohol compounds. The esterification reaction is an organic chemical reaction, is a reaction of alcohol and carboxylic acid or oxygen-containing inorganic acid to generate ester and water, and is widely applied to the field of organic synthesis. The esterification reaction is a reversible reaction, and is not generally thorough, and according to the principle of reaction equilibrium, in order to increase the yield of esters, it is necessary to separate one component from the product or to make one component of the reactants excessive so that the reaction proceeds in the forward direction, and therefore, the esterification synthesis of 2, 5-furandicarboxylic acid diester compounds has low yield and low atomic economy. The invention utilizes the metal supported catalyst to catalyze the raw materials to synthesize the 2, 5-furandicarboxylic acid diester compound, and can effectively find a synthesizing route with high economy and environmental protection.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a synthesis method of a2, 5-furandicarboxylic acid diester compound. In the process of the invention, the inventor determines a novel synthetic route for synthesizing 2, 5-furandicarboxylic acid diester compounds by using metal supported catalyst from raw material alkyl furancarboxylate: the route firstly develops a high-efficiency and stable metal supported catalyst which provides an active site for 5-hydrogen protons of raw materials, and synthesizes a2, 5-furandicarboxylic acid diester compound with carbon dioxide and a solvent, the reaction is carried out in an automatic reaction kettle, and a reaction product is further dried and rectified to obtain a target product.
The reaction equation of this reaction is as follows:
In order to achieve the above purpose, the present invention adopts the following technical scheme:
Dissolving alkyl furancarboxylate in a solvent to obtain a raw material solution with the molar concentration of 0.5-3 mol/L; uniformly stirring and mixing the raw material solution and the metal supported catalyst in a reaction kettle container, sealing the container, replacing air in the sealed container with carbon dioxide, and keeping the gas pressure of the carbon dioxide in the sealed container to be 1-6 MPa; opening a stirring device, a heating device and an axial cooling device of the automatic reaction kettle, setting the reaction temperature to be 140-250 ℃ and the rotating speed to be 300-500 r/min;
The automatic reaction kettle device stops reacting after operating for 6-10 hours under the above conditions, the reaction product is filtered and then added into a vacuum rectifying tower, the 2, 5-furandicarboxylic acid diester compound is discharged from the bottom of the vacuum rectifying tower, the gas discharged from the top of the vacuum rectifying tower enters a recovery tank and is condensed, and the collected condensed liquid can be reused after drying and rectifying.
The alkyl furancarboxylate used as a raw material in the present invention includes methyl furancarboxylate, ethyl furancarboxylate, propyl furancarboxylate, or n-butyl furancarboxylate.
The solvent corresponding to the raw material used in the present invention includes methanol, ethanol, propanol or n-butanol.
The 2, 5-furandicarboxylic acid diester compound synthesized by the invention comprises 2, 5-furandicarboxylic acid dimethyl ester, 2, 5-furandicarboxylic acid diethyl ester, 2, 5-furandicarboxylic acid dipropyl ester or 2, 5-furandicarboxylic acid di-n-butyl ester.
Alkyl furancarboxylate used as a synthetic method of the 2, 5-furandicarboxylic acid diester compound in the present invention: the molar ratio of the metal supported catalyst is 10-30:1.
The metal-supported catalyst used as the synthesis method of the 2, 5-furandicarboxylic acid diester compound in the present invention includes cobalt (Co), manganese (Mn), rhodium (Rh), or palladium (Pd).
The metal supported catalyst carrier used as the synthesis method of the 2, 5-furandicarboxylic acid diester compound in the invention comprises ZSM-5 type molecular sieve, 4A type molecular sieve, X type molecular sieve, Y type molecular sieve, alumina or silicon dioxide.
As the synthesis method of the 2, 5-furandicarboxylic acid diester compound, the mass ratio of metal to carrier in the metal supported catalyst is 0.7-3:10.
Preferred combinations of metals and supports for the metal supported catalysts of the present invention include Co/alumina type catalysts, pd/ZSM-5 type catalysts, rh/X type molecular sieves or Mn/4A type molecular sieves.
In the present invention, the metal-supported catalyst used in the present invention is commercially purchased or prepared.
In the invention, the reduced pressure heating temperature of the reduced pressure rectifying tower is 140-170 ℃ and the pressure is 0.01MPa
The synthesis method of the invention opens up a novel synthesis route of 2, 5-furandicarboxylic acid diester compound, uses gaseous carbon dioxide as raw material in the production process of the product, has high atomic economy and environment-friendly production process, and simultaneously has high catalytic efficiency, good stability and high total yield of the product.
Compared with the prior art, the invention has the following advantages:
1. The method has the advantages of simple reaction conditions, convenient operation, easily obtained reaction raw materials, extracted products and potential industrial application prospect.
2. The method can effectively utilize carbon dioxide, the reaction process is environment-friendly, and meanwhile, the solvent used in the reaction process can be reused after rectification, so that the atomic economy is high, and meanwhile, the method meets the requirements of green chemical processes.
Drawings
FIG. 1 is a diagram showing the analysis of 1 H-NMR of dimethyl 2, 5-furandicarboxylate.
FIG. 2 is a chart showing C-NMR analysis of dimethyl 2, 5-furandicarboxylate 13.
FIG. 3 is a chart of the analysis of diethyl 2, 5-furandicarboxylate 1 H-NMR.
FIG. 4 is a C-NMR analysis chart of diethyl 2, 5-furandicarboxylate 13.
FIG. 5 is a chart of the analysis of dipropyl 2, 5-furandicarboxylate 1 H-NMR.
FIG. 6 is a C-NMR analysis chart of dipropyl 2, 5-furandicarboxylate 13.
FIG. 7 is a chart of the analysis of dibutyl 2, 5-furandicarboxylate 1 H-NMR.
FIG. 8 is a chart showing C-NMR analysis of dibutyl 2, 5-furandicarboxylate 13.
The specific embodiment is as follows:
the present invention will be described in further detail with reference to the following specific examples.
The automatic reaction kettle used in the invention is of a common reaction kettle type in the market, the use temperature is 10-350 ℃, and the bearable pressure is less than or equal to 10MPa.
The following examples all employ automated reactor apparatus.
The purity of the furandicarboxylic acid diester compound obtained in the following examples is more than 98%
Example 1:
⑴ A methyl furancarboxylate solution with a molar concentration of 0.5mol/L was prepared in 1L of methanol solution, to which 48g of commercially available Co/alumina catalyst was added, the mass ratio of Co to alumina in the catalyst was 0.7:10, methyl furancarboxylate: the molar ratio of the metal supported catalyst is 10:1, a stirrer is started, the rotating speed is set to 300r/min, and substances in a reaction kettle container are uniformly stirred and mixed; sealing the container, replacing air in the sealed container with carbon dioxide, and pressurizing and keeping the gas pressure of the carbon dioxide in the container to reach 4MPa; opening a stirring shaft cooling device and a heating device of the reaction kettle, and setting the reaction temperature to be 200 ℃; the reaction vessel apparatus was operated under the above conditions for 10 hours and then stopped.
⑵ Cooling to room temperature, evacuating the container, taking out the reaction product, filtering out solid impurities, introducing into a vacuum rectifying tower, heating under reduced pressure (the temperature of the top of the tower is 180 ℃ and the pressure is 0.01 MPa), collecting the gas at the bottom of the tower into a recovery tank, and discharging the product of the dimethyl 2, 5-furandicarboxylate at the bottom of the tower. The yield of 176.68g of dimethyl 2, 5-furandicarboxylate was about 96%, and the analysis spectra of 1 H-NMR and 13 C-NMR of dimethyl 2, 5-furandicarboxylate were shown in FIGS. 1 and 2.
Example 2:
⑴ A solution of ethyl furancarboxylate with a molar concentration of 1mol/L is prepared in 1L of ethanol solution, 55.3g of commercially available Pd/ZSM-5 molecular sieve catalyst is added, and the mass ratio of the catalyst Pd to the ZSM-5 molecular sieve is 1:10, wherein the catalyst Pd is ethyl furancarboxylate: the molar ratio of the metal supported catalyst is 15:1, a stirrer is started, the rotating speed is set to 400r/min, and substances in a reaction kettle container are uniformly stirred and mixed; sealing the container, replacing air in the sealed container with carbon dioxide, and pressurizing and keeping the gas pressure of the carbon dioxide in the container to reach 3MPa; opening a stirring shaft cooling device and a heating device of the reaction kettle, and setting the reaction temperature to 140 ℃; the reaction vessel apparatus was operated under the above conditions for 6 hours and then stopped.
⑵ Cooling to room temperature, evacuating the container, taking out the reaction product, filtering out solid impurities, feeding the reaction product into a vacuum rectifying tower, heating under reduced pressure, wherein the temperature of the tower top is 170 ℃, the pressure is 0.01MPa, collecting tower bottom gas into a recovery tank, and discharging the product diethyl 2, 5-furandicarboxylate from the tower bottom. The total yield of 201.1g of diethyl 2, 5-furandicarboxylate was about 94.7%, and the analysis spectra of 1 H-NMR and 13 C-NMR of diethyl 2, 5-furandicarboxylate were shown in FIGS. 3 and 4. .
Example 3:
⑴ A solution of ethyl furancarboxylate with a molar concentration of 3mol/L is prepared in 1L of ethanol solution, 55.3g of commercially available Pd/ZSM-5 molecular sieve catalyst is added, and the mass ratio of the catalyst Pd to the ZSM-5 molecular sieve is 2:10, wherein the catalyst Pd is ethyl furancarboxylate: the molar ratio of the metal supported catalyst is 20:1, a stirrer is started, the rotating speed is set to be 450r/min, and substances in a reaction kettle container are uniformly stirred and mixed; sealing the container and replacing air in the sealed container with carbon dioxide, and pressurizing and keeping the gas pressure of the carbon dioxide in the container to reach 3.5MPa; opening a stirring shaft cooling device and a heating device of the reaction kettle, and setting the reaction temperature to 160 ℃; the reaction vessel apparatus was operated under the above conditions for 7 hours and then stopped.
⑵ Cooling to room temperature, evacuating the container, taking out the reaction product, filtering out solid impurities, feeding the reaction product into a vacuum rectifying tower, heating under reduced pressure, wherein the temperature of the tower top is 170 ℃, the pressure is 0.01MPa, collecting tower bottom gas into a recovery tank, and discharging the product diethyl 2, 5-furandicarboxylate from the tower bottom. The total yield of 203.8g of diethyl 2, 5-furandicarboxylate was about 96%, and the analysis spectra of 1 H-NMR and 13 C-NMR of diethyl 2, 5-furandicarboxylate were shown in FIGS. 3 and 4.
Example 4:
⑴ Preparing Rh/X type molecular sieve catalyst by an impregnation method: 6.4g of rhodium chloride is dissolved in 100mL of water, the rhodium chloride is fully dispersed and dissolved, 45g of X-type molecular sieve is fully dispersed in the water, the two are fully stirred and mixed for 3h, the mixture is kept stand for 2h, and the mixture is dried and then baked for 5h at 450 ℃, 48g of Rh/X-type molecular sieve catalyst can be obtained, and the mass ratio of the Rh to the X-type molecular sieve in the catalyst is 2:10.
⑵ To a 1L propanol solution was added a 48gRh/X type aluminum catalyst to a 1.5mol/L solution of propyl furancarboxylate: the molar ratio of the metal supported catalyst is 25:1, a stirrer is started, the rotating speed is set to be 500r/min, and substances in a reaction kettle container are uniformly stirred and mixed; sealing the container, replacing air in the sealed container with carbon dioxide, and pressurizing and keeping the gas pressure of the carbon dioxide in the container to reach 2MPa; opening a stirring shaft cooling device and a heating device of the reaction kettle, and setting the reaction temperature to 220 ℃; the reaction vessel apparatus was operated under the above conditions for 10 hours and then stopped.
⑶ Cooling to room temperature, evacuating the container, taking out the reaction product, filtering out solid impurities, feeding the reaction product into a vacuum rectifying tower, heating under reduced pressure, wherein the temperature of the tower top is 170 ℃, the pressure is 0.01MPa, collecting tower bottom gas into a recovery tank, and discharging the product of 2, 5-dipropyl furandicarboxylate from the tower bottom. As a result, 228.1g of dipropyl 2, 5-furandicarboxylate was obtained, and the yield was about 95%, and the analysis spectra of 1 H-NMR and 13 C-NMR of dipropyl 2, 5-furandicarboxylate were shown in FIGS. 5 and 6.
Example 5:
⑴ Preparing Mn/4A type molecular sieve catalyst by an impregnation method: 8.2g of manganese dichloride is dissolved in 100mL of water, and the solution is fully dispersed; simultaneously, 38g of 4A type molecular sieve is fully dispersed in water, the two are fully stirred and mixed for 3 hours, and the mixture is stood for 2 hours, dried and burned for 5 hours at 450 ℃ to obtain 46.3g of Mn/4A type molecular sieve catalyst, wherein the mass ratio of Mn to 4A type molecular sieve in the catalyst is 3:10
⑵ Preparing n-butyl furancarboxylate solution with the molar concentration of 1mol/L into 1L of n-butanol solution, and adding 44.3gMn/4A molecular sieve catalyst into the n-butyl furancarboxylate solution: the molar ratio of the metal supported catalyst is 30:1, a stirrer is started, the rotating speed is set to be 450r/min, and substances in a reaction kettle container are uniformly stirred and mixed; sealing the container, replacing air in the sealed container with carbon dioxide, and pressurizing and keeping the gas pressure of the carbon dioxide in the container to reach 6MPa; opening a stirring shaft cooling device and a heating device of the reaction kettle, and setting the reaction temperature to be 250 ℃; the reaction vessel apparatus was operated under the above conditions for 8 hours and then stopped.
⑶ Cooling to room temperature, evacuating the container, taking out the reaction product, filtering out solid impurities, feeding the reaction product into a vacuum rectifying tower, heating under reduced pressure, wherein the temperature of the tower top is 164 ℃, the pressure is 0.01MPa, collecting tower bottom gas into a recovery tank, and discharging the product of di-n-butyl 2, 5-furandicarboxylate from the tower bottom. The total yield of n-dibutyl 2, 5-furandicarboxylate was 257.27g, and about 96% was obtained, and the analysis spectra of dipropyl 2, 5-furandicarboxylate in 1 H-NMR and 13 C-NMR were shown in FIGS. 7 and 8.
Example 6:
⑴ Preparing Mn/4A type molecular sieve catalyst by an impregnation method: 8.2g of manganese dichloride is dissolved in 100mL of water, and the solution is fully dispersed; meanwhile, 38g of the 4A type molecular sieve is fully dispersed in water, the two are fully stirred and mixed for 3 hours, the mixture is kept stand for 2 hours, and the mixture is dried and then baked for 5 hours at 450 ℃, so that 46.3g of Mn/4A type molecular sieve catalyst can be obtained, and the mass ratio of Mn of the catalyst to the 4A type molecular sieve is 3:10.
⑵ Preparing n-butyl furancarboxylate solution with the molar concentration of 2mol/L into 1L of n-butanol solution, and adding 44.3gMn/4A molecular sieve catalyst into the n-butyl furancarboxylate solution: the molar ratio of the metal supported catalyst is 20:1, a stirrer is started, the rotating speed is set to 400r/min, and substances in a reaction kettle container are uniformly stirred and mixed; sealing the container, replacing air in the sealed container with carbon dioxide, and pressurizing and keeping the gas pressure of the carbon dioxide in the container to reach 2MPa; opening a stirring shaft cooling device and a heating device of the reaction kettle, and setting the reaction temperature to be 180 ℃; the reaction vessel apparatus was operated under the above conditions for 10 hours and then stopped.
⑶ Cooling to room temperature, evacuating the container, taking out the reaction product, filtering out solid impurities, feeding the reaction product into a vacuum rectifying tower, heating under reduced pressure, wherein the temperature of the tower top is 164 ℃, the pressure is 0.01MPa, collecting tower bottom gas into a recovery tank, and discharging the product of di-n-butyl 2, 5-furandicarboxylate from the tower bottom. The total yield of n-dibutyl 2, 5-furandicarboxylate was 254.6g, and the yield was about 95%, and the analysis spectra of the dipropyl 2, 5-furandicarboxylate were 1 H-NMR and 13 C-NMR in FIGS. 7 and 8.
It should be noted that the above list is a few specific embodiments of the invention, of course the invention is not limited to the above embodiments. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (5)
1. The synthesis method of the 2, 5-furandicarboxylic acid diester compound is characterized by comprising the following steps of:
Dissolving alkyl furancarboxylate in a solvent to obtain a raw material solution with the molar concentration of 0.5-3 mol/L; uniformly stirring and mixing the raw material solution and the metal supported catalyst in a reaction kettle container, sealing the container, replacing air in the sealed container with carbon dioxide, and keeping the gas pressure of the carbon dioxide in the sealed container to be 1-6 MPa; opening a stirring device, a heating device and an axial cooling device of the automatic reaction kettle, setting the reaction temperature to be 140-250 ℃ and the rotating speed to be 300-500 r/min;
The automatic reaction kettle device stops reacting after operating for 6-10 hours under the above conditions, the reaction product is filtered and then added into a vacuum rectifying tower, the 2, 5-furandicarboxylic acid diester compound is discharged from the bottom of the vacuum rectifying tower, the gas discharged from the top of the vacuum rectifying tower enters a recovery tank and is condensed, and the collected condensed liquid can be reused after drying and rectifying;
the solvent is selected from methanol, ethanol, propanol or n-butanol; the metal supported catalyst is selected from Co/alumina type catalyst, pd/ZSM-5 type catalyst, rh/X type molecular sieve or Mn/4A type molecular sieve.
2. The synthesis method according to claim 1, wherein: the alkyl furancarboxylate used as raw material is selected from methyl furancarboxylate, ethyl furancarboxylate, propyl furancarboxylate or n-butyl furancarboxylate.
3. The synthesis method according to claim 1, wherein: the generated 2, 5-furandicarboxylic acid diester compound is selected from 2, 5-furandicarboxylic acid dimethyl ester, 2, 5-furandicarboxylic acid diethyl ester, 2, 5-furandicarboxylic acid dipropyl ester or 2, 5-furandicarboxylic acid di-n-butyl ester.
4. The synthesis method according to claim 1, wherein: alkyl furancarboxylate: the molar ratio of the metal supported catalyst is 10-30:1.
5. The synthesis method according to claim 1, wherein: the mass ratio of the metal to the carrier in the metal supported catalyst is 0.7-3.0:10.
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