CN110526882B - Furan tetramer and synthesis method thereof - Google Patents
Furan tetramer and synthesis method thereof Download PDFInfo
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- CN110526882B CN110526882B CN201910276781.XA CN201910276781A CN110526882B CN 110526882 B CN110526882 B CN 110526882B CN 201910276781 A CN201910276781 A CN 201910276781A CN 110526882 B CN110526882 B CN 110526882B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- 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
- C07D307/36—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
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Abstract
The invention discloses a method for preparing furan tetramer by catalyzing polymerization of 2-methylfuran and 5-hydroxymethylfurfural through solid acid, which comprises the following steps: 2-methyl furan, 5-hydroxymethyl furfural and solid acid are placed in a reaction device, dichloromethane is used as a solvent, the dosage of the solid acid catalyst is 5-60 mg, the reaction is carried out for 2-12 h at the temperature of 60-120 ℃, and after the reaction is finished, the catalyst and the product are separated through filtration to obtain the furan tetramer. In the method, the reaction condition is mild, the catalyst can be reused, and the preparation process is simple.
Description
Technical Field
The invention relates to a method for directly catalyzing and synthesizing furan tetramer, which specifically comprises the following steps: under mild condition, the solid acid catalyzes 2-methyl furan and 5-hydroxymethyl furfural to prepare furan tetramer through three condensation reactions.
Background
With the consumption of non-renewable energy sources, a series of environmental problems such as greenhouse effect and air pollution are raised. In recent years, the conversion of biomass derivatives to liquid fuels and fine chemicals has attracted attention by a large number of researchers in order to find ideal alternatives to fossil fuels. Therefore, the conversion of low-carbon furan derivative into high-carbon fuel precursor and the further ring opening of the high-carbon fuel are research hot spots in recent years. The furan tetramer derivative containing 21 carbon atoms can be obtained by three condensation reactions of 2-methyl furan and 5-hydroxymethyl furfural, and can be used as a precursor raw material of high-carbon fuel, in particular aviation kerosene. Therefore, the research of the method for directly catalyzing and synthesizing the furan tetramer derivative by taking 2-methyl furan and 5-hydroxymethyl furfural as the starting materials has very important significance.
At present, no report on preparing furan tetramer derivatives by three condensation reactions of 2-methyl furan and 5-hydroxymethyl furfural is reported. As a scheme with industrial development potential, the solid acid catalyst can be reused, the reaction condition required in the direct catalysis of the condensation reaction process of 2-methyl furan and 5-hydroxymethylfurfural is mild, the time consumption is short, and the preparation process of the solid phosphotungstic acid catalyst is simple and has high yield, thereby being more beneficial to industrial production.
Disclosure of Invention
The invention aims to solve the technical problems that: the method for preparing the furan tetramer by catalyzing the three condensation reactions of the 2-methyl furan and the 5-hydroxymethylfurfural is mild in reaction conditions, relates to one-pot multi-step reaction and is simple in catalyst preparation process.
The technical scheme of the invention is as follows: a furan tetramer having the structural formula:
the catalyst for preparing furan tetramer is 3-bromopyridine phosphotungstic acid.
In the method for preparing furan tetramer, under the condition of solvent, solid 3-bromopyridine phosphotungstic acid is used as a catalyst, and raw material 2-methyl furan and 5-hydroxymethylfurfural react for 2-12 hours at 60-120 ℃ to obtain furan tetramer.
The solvent is dichloromethane. The dosage of the catalyst is 5-60 mg.
The reaction temperature is preferably 100-120 ℃, and the reaction time is 8-12 h.
The invention has the beneficial effects that: the reaction time is moderate in the invention.
The solid acid catalyst used in the invention can be reused and is easy to recycle (the IR spectrum of the 3-bromopyridine phosphotungstic acid catalyst before and after use can be seen in figure 1).
Drawings
FIG. 1 is an IR spectrum of 3-bromopyridine phosphotungstic acid catalyst before and after use;
FIG. 2 is a mass spectrum of furan tetramer.
Detailed Description
Example 1
(1) And (3) preparing a 3-bromopyridine phosphotungstic acid catalyst. Firstly, adding 2.2mmol of phosphotungstic acid into a stainless steel autoclave provided with a 50 mL polytetrafluoroethylene reactor at normal temperature, and adding 30mL of absolute ethyl alcohol for dissolution; next, 2mmol of bromopyridine was added with stirring at room temperature and magnetically stirred for 1.5h. Aging the obtained precipitate at 90deg.C for 12 hr; finally, the solid acid catalyst was obtained by centrifugation and washing with absolute ethanol three times and drying overnight at 80 ℃.
(2) 3-bromopyridine phosphotungstic acid directly catalyzes polymerization of 2-methylfuran and 5-hydroxymethylfurfural to prepare furan tetramer. 20mg of 3-bromopyridine phosphotungstic acid, 3mmol of 2-methylfuran and 2mL of methylene chloride as a solvent were put into a pressure-resistant tube, and stirred at 100℃for 8 hours. After the reaction, the solid catalyst was separated by filtration, and the conversion of 2-methylfuran and the yield of tetramer in the reaction solution were measured by gas chromatography. The conversion of 2-methylfuran was 78.0% and the yield of furan tetramer was 37.1% as measured by standard curve method. The solid catalyst was washed with methylene chloride and dried, and then used for the next reaction (same reaction conditions), and the yield of the obtained furan tetramer was 35.5%.
Example 2
(1) And (3) preparing a 3-bromopyridine phosphotungstic acid catalyst. Firstly, adding 2.2mmol of phosphotungstic acid into a stainless steel autoclave provided with a 50 mL polytetrafluoroethylene reactor at normal temperature, and adding 30mL of absolute ethyl alcohol for dissolution; next, 2mmol of bromopyridine was added with stirring at room temperature and magnetically stirred for 1.5h. Aging the obtained precipitate at 90deg.C for 12 hr; finally, the solid acid catalyst was obtained by centrifugation and washing with absolute ethanol three times and drying overnight at 80 ℃.
(2) 3-bromopyridine phosphotungstic acid directly catalyzes polymerization of 2-methylfuran and 5-hydroxymethylfurfural to prepare furan tetramer. 60mg of 3-bromopyridine phosphotungstic acid, 3mmol of 2-methylfuran and 2mL of methylene chloride as solvents were put into a pressure-resistant tube, and stirred at 120℃for 10 hours. After the reaction, the solid catalyst was separated by filtration, and the conversion of 2-methylfuran and the yield of tetramer in the reaction solution were measured by gas chromatography. The conversion of 2-methylfuran was 85.0% and the yield of furan tetramer was 36.5% as measured by standard curve method. After washing and drying the solid catalyst with methylene chloride, it was used in the next reaction (same reaction conditions) to obtain a furan tetramer with a yield of 33.8%.
Example 3
(1) And (3) preparing a 3-bromopyridine phosphotungstic acid catalyst. Firstly, adding 2.2mmol of phosphotungstic acid into a stainless steel autoclave provided with a 50 mL polytetrafluoroethylene reactor at normal temperature, and adding 30mL of absolute ethyl alcohol for dissolution; next, 2mmol of bromopyridine was added with stirring at room temperature and magnetically stirred for 1.5h. Aging the obtained precipitate at 90deg.C for 12 hr; finally, the solid acid catalyst was obtained by centrifugation and washing with absolute ethanol three times and drying overnight at 80 ℃.
(2) 3-bromopyridine phosphotungstic acid directly catalyzes polymerization of 2-methylfuran and 5-hydroxymethylfurfural to prepare furan tetramer. 40mg of 3-bromopyridine phosphotungstic acid, 3mmol of 2-methylfuran and 2mL of methylene chloride as solvents were put into a pressure-resistant tube, and stirred at 60℃for 12 hours. After the reaction, the solid catalyst was separated by filtration, and the conversion of 2-methylfuran and the yield of tetramer in the reaction solution were measured by gas chromatography. The conversion of 2-methylfuran was 67.0% as measured by standard curve method and the yield of furan tetramer was 34.5%. After washing and drying the solid catalyst with methylene chloride, it was used in the next reaction (same reaction conditions) to obtain a furan tetramer with a yield of 33.7%.
Comparative example 1
(1) And (3) preparing a pyridine phosphotungstic acid catalyst.
1.1mmol of phosphotungstic acid was charged into a stainless steel autoclave equipped with a 50 mL polytetrafluoroethylene reactor at normal temperature, and 30mL of absolute ethanol was added for dissolution, and then 1mmol of pyridine was added with stirring at room temperature. The resulting precipitate was aged at 90℃for 12h. Finally, the solid acid catalyst pyridine phosphotungstic acid is obtained by centrifugal separation and washing with absolute ethyl alcohol three times and drying at 80 ℃ overnight.
(2) The pyridine phosphotungstic acid directly catalyzes the polymerization of 2-methyl furan and 5-hydroxymethylfurfural to prepare furan tetramer. 20mg of pyridylphospungstic acid, 3mmol of 2-methylfuran and 2mL of methylene chloride as a solvent were charged into the pressure-resistant tube, and the mixture was stirred at 100℃for 8 hours. After the reaction, the solid catalyst was separated by filtration, and the conversion of 2-methylfuran and the yield of tetramer in the reaction solution were measured by gas chromatography. The conversion of 2-methylfuran was 21.1% and the tetramer yield was 0.1% as measured by standard curve method.
Comparative example 2
The phosphotungstic acid directly catalyzes the polymerization of 2-methylfuran and 5-hydroxymethylfurfural to prepare furan tetramer. 5mg of phosphotungstic acid, 3mmol of 2-methylfuran were put into a pressure-resistant tube, stirred at 100℃for 8 hours, and after the completion of the reaction, sodium carbonate was added to neutralize the phosphotungstic acid, and the conversion of 2-methylfuran and the yield of tetramer in the reaction solution were measured by gas chromatography. The conversion of 2-methylfuran was 81.7% and the tetramer yield was 32.9% as measured by standard curve method.
Claims (4)
1. A method for preparing a furan tetramer, characterized by: the structural formula of the furan tetramer is as follows:
the preparation method comprises the following steps: under the condition of solvent, solid 3-bromopyridine phosphotungstic acid is used as a catalyst, and raw material 2-methyl furan and 5-hydroxymethylfurfural react for 2-12 hours at 60-120 ℃ to obtain furan tetramer.
2. A method for preparing furan tetramer according to claim 1, characterized in that: the solvent is dichloromethane.
3. A method for preparing furan tetramer according to claim 1, characterized in that: the dosage of the catalyst is 5-60 mg.
4. A method for preparing furan tetramer according to claim 1, characterized in that: the reaction temperature is 100-120 ℃, and the reaction time is 8-12 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762695A (en) * | 2009-12-11 | 2012-10-31 | 康斯乔最高科学研究公司 | Production of liquid fuels (sylvan liquid fuels) from 2-methylfuran |
| CN108947943A (en) * | 2018-08-27 | 2018-12-07 | 贵州大学 | A kind of method that solid phosphotungstic acid is directly catalyzed 5- methyl furfuryl alcohol dimerization |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762695A (en) * | 2009-12-11 | 2012-10-31 | 康斯乔最高科学研究公司 | Production of liquid fuels (sylvan liquid fuels) from 2-methylfuran |
| CN108947943A (en) * | 2018-08-27 | 2018-12-07 | 贵州大学 | A kind of method that solid phosphotungstic acid is directly catalyzed 5- methyl furfuryl alcohol dimerization |
Non-Patent Citations (3)
| Title |
|---|
| 3-Bromopyridine-Heterogenized Phosphotungstic Acid for Efficient Trimerization of Biomass-Derived 5-Hydroxymethylfurfural with 2-Methylfuran to C21Fuel Precursor;Yufei Xu，等;《Advances in Polymer Technology》;20200806;第1-12页 * |
| Saikat Dutta，等.Solventless C−C Coupling of Low Carbon Furanics to High Carbon Fuel Precursors Using an Improved Graphene Oxide Carbocatalyst.《ACS Catalysis》.2017, * |
| Solventless C−C Coupling of Low Carbon Furanics to High Carbon Fuel Precursors Using an Improved Graphene Oxide Carbocatalyst;Saikat Dutta，等;《ACS Catalysis》;20170421;第3906页Scheme 1 * |
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