CN111253342A - Method for catalyzing olefin epoxidation by heteropoly acid quaternary ammonium salt - Google Patents
Method for catalyzing olefin epoxidation by heteropoly acid quaternary ammonium salt Download PDFInfo
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- CN111253342A CN111253342A CN201811455222.7A CN201811455222A CN111253342A CN 111253342 A CN111253342 A CN 111253342A CN 201811455222 A CN201811455222 A CN 201811455222A CN 111253342 A CN111253342 A CN 111253342A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C07—ORGANIC CHEMISTRY
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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Abstract
The invention provides a method for catalyzing olefin epoxidation by heteropoly acid quaternary ammonium salt, which comprises the step of reacting olefin and an oxidant in the presence of heteropoly acid quaternary ammonium salt catalyst, an auxiliary agent and an organic solvent, wherein the organic solvent is 3-chloropropene, the reaction temperature is 25-80 ℃, the reaction time is 0.5-10 h, the catalyst is solid after the reaction is finished, the catalyst can be simply separated and recycled, and the reaction liquid is distilled to obtain a target epoxide. The method has the advantages of simple process, mild conditions, easy separation, recovery and reuse of the catalyst, environmental protection and great industrial application prospect.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly provides a method for catalyzing olefin epoxidation by heteropoly acid quaternary ammonium salt.
Background
Olefin epoxidation is one of the most important reactions in the chemical industry, and the epoxidation product is a raw material for preparing various important chemical products and is widely applied to numerous fields such as organic synthesis, fine chemical industry, petrochemical industry and the like. The traditional methods for preparing epoxy compounds are a chlorohydrin method and an oxidation method, which have serious environmental pollution problems. People have been dedicated to develop olefin epoxidation process with simple flow, less by-products and no pollution for many years, and in the olefin epoxidation catalyst taking green oxygen source hydrogen peroxide as the oxygen source reported at present, heteropoly acid quaternary ammonium salt with reaction control phase transfer characteristic is a catalyst with better industrial prospect. Such documents report:
the literature: xi Z W, Zhou N, Sun Y, Li K L.reaction-Controlled Phase-transfer catalysis for the oxidation of a Propylene Oxide [ J ]. Science,2001,292:1139
The literature: gao S, Li M, Lv Y, Zhou N, Xi Z W. oxidation of Propylene with aqueous Hydrogen Peroxide on a Reaction-Controlled Phase-Transfer Catalyst [ J ]. Organic Process Research & Development,2004,8:131
The literature: li J, Xi Z W, Gao S, An environmental sensitivity pencil route for An aerobic chloride oxidation catalyzed bya hecteofluoropropylphosphate [ J ]. Research on Chemical Intermediates,2007,33:523
The literature: CN101045716B, CN101205219B, CN100532371C and the like
In the above-mentioned reports, the substrate olefin needs to be excessive to ensure the complete consumption of H2O2, so that the heteropolyacid salt catalyst can be efficiently precipitated as a solid and recycled after the reaction, but this limits the application of the catalytic system.
Disclosure of Invention
The invention uses 3-chloropropene as solvent, so that H2O2 can be completely consumed, the dosage of substrate olefin is reduced, a series of catalytic epoxidation reactions of olefin are successfully realized, the process has high olefin conversion rate, selectivity and circulation stability, and the application prospect is huge.
The method for catalyzing olefin epoxidation by using the heteropoly acid quaternary ammonium salt comprises the step of reacting olefin and an oxidant in the presence of a heteropoly acid quaternary ammonium salt catalyst, an auxiliary agent and an organic solvent, wherein the organic solvent is 3-chloropropene, the reaction temperature is 25-80 ℃, the reaction time is 0.5-10 h, the catalyst is solid after the reaction is finished and can be separated for reuse, and the reaction liquid is distilled to obtain a target epoxide.
Wherein the heteropoly acid quaternary ammonium salt catalyst molecule forms QmHnPMxOyQ is quaternary ammonium salt cation, and the quaternary ammonium salt is at least one of tetrabutylammonium salt, dodecyl trimethyl amine salt, hexadecyl trimethyl amine salt, octadecyl trimethyl amine salt or dioctadecyl dimethyl amine salt; m is metal tungsten, M is more than or equal to 1 and less than or equal to 7，1≤x≤12，0≤n≤4，10≤y≤40。
The substrate olefin molecular formula is:
the substrate olefin is non-chiral olefin, chiral olefin or enantiomer olefin, wherein R1, R2, R3 and R4 are hydrogen and straight-chain alkyl (C)nH2n+1N is 1 to 10), branched alkyl (C)nH2n+1N is 1 to 10), and a cyclic alkyl group (C)nH2nN is 3 to 8), aryl, a linear substituent containing one carbonyl group (C)nH2n-1O, n-3 to 10) and a branched substituent containing one carbonyl group (C)nH2n-1O, n is 3 to 10) and a cyclic substituent (C) containing a carbonyl groupnH2n-2O, n-3 to 8) and a linear substituent containing one epoxy group (C)nH2n-1O, n-3 to 10) and a branched substituent (C) having one epoxy groupnH2n-1O, n-3 to 10) and a cyclic substituent (C) containing one epoxy groupnH2n-2O，n＝3～8)。
The oxidant is aqueous hydrogen peroxide solution with the mass concentration of 10-80%.
The auxiliary agent is at least one of sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, phosphoric acid, hydrochloric acid, sulfuric acid, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and sodium phosphate.
The content of the heteropoly acid quaternary ammonium salt catalyst is 2-80 g/L of reaction liquid, the content of hydrogen peroxide is 30-100 g/L of reaction liquid, the content of the auxiliary agent is 0.5-10 g/L of reaction liquid, the content of the substrate olefin is 30-150 g/L of reaction liquid, the content of water is 7-200 g/L of reaction liquid, and the balance is solvent 3-chloropropene.
The catalyst is solid after the reaction is finished, the catalyst can be simply separated and recycled, and the target epoxide can be obtained by distilling the reaction liquid. The method has the advantages of simple process, mild conditions, easy separation, recovery and reuse of the catalyst, environmental protection and great industrial application prospect.
Detailed Description
The invention is further illustrated by the following examples:
example 1: heteropoly quaternary ammonium salt catalyzed styrene epoxidation
Preparing heteropoly acid quaternary ammonium salt catalyst: reference Journal of Molecular Catalysis A,2001,166:219.
2.50g of tungstic acid were weighed into 10ml of 30% by mass H2O2While stirring, the mixture was heated to 60 ℃ for 60 minutes to give a colorless transparent solution. To this solution was added 0.29g of 85% strength phosphoric acid, 20ml of distilled water and stirring was continued for 30 min. 2.5g of cetyltrimethylammonium chloride was weighed and dissolved in 40ml of dichloroethane, and this solution was quickly dropped into the above-mentioned hydrogen peroxide solution at normal temperature, and stirred for 60min continuously to obtain a precipitate. The precipitate was washed with distilled water until the filtrate had a pH of about 4. And drying the filtrate in vacuum at 50-60 ℃ to obtain the phosphotungstic heteropoly acid quaternary ammonium salt catalyst.
(II) epoxidation of styrene: 0.3g of the obtained heteropoly acid quaternary ammonium salt catalyst, 10ml of 3-chloropropene, 3.7g of styrene and 50 percent of H are added into a 100ml glass reaction bottle2O22.5g and 0.02g of disodium hydrogen phosphate, sealing the reaction bottle, stirring for 3 hours at the reaction temperature of 60 ℃, cooling, opening the bottle and separating the solid catalyst, wherein the recovery rate of the catalyst is 96%. The reaction oil phase was analyzed by gas chromatography, and styrene oxide was added to H2O2The yield of (A) is 75%, and the co-product epichlorohydrin is p-H2O2The yield of (a) was 16%.
Example 2: epoxidation of cyclohexene by heteropoly acid quaternary ammonium salt catalysis
Preparing heteropoly acid quaternary ammonium salt catalyst: same as example 1 (one)
(II) epoxidation of cyclohexene: adding 0.5g of heteropoly acid quaternary ammonium salt catalyst, 15ml of 3-chloropropene, 4.6g of cyclohexene and 50 percent of H into a 100ml glass reaction bottle2O24.0g of sodium bicarbonate and 0.02g of sodium bicarbonate, sealing the reaction bottle, stirring for 4 hours at the reaction temperature of 50 ℃, cooling, opening the bottle, separating the solid catalyst, and recovering the catalystThe ratio was 97%. The reaction oil phase is analyzed by gas chromatography, and the epoxy cyclohexane is opposite to H2O2The yield of (A) is 80%, and the co-product epichlorohydrin is p-H2O2The yield of (3) was 17%.
Example 3: heteropoly quaternary ammonium salt catalyzed cyclopentene epoxidation
Preparing heteropoly acid quaternary ammonium salt catalyst: same as example 1 (one)
Epoxidation of cyclopentene (di): in a 100ml glass reaction bottle, 0.6g of heteropoly acid quaternary ammonium salt catalyst, 20ml of 3-chloropropene, 6.5g of cyclopentene and 50% H are added2O25.2g of phosphoric acid with the mass concentration of 85 percent, 0.01g of phosphoric acid, closing the reaction bottle, stirring for 2 hours at the reaction temperature of 50 ℃, cooling, opening the bottle and separating the solid catalyst, wherein the recovery rate of the catalyst is 95 percent. Analysis of the oil phase by gas chromatography of the reaction, cyclopentane epoxide vs. H2O2The yield of (A) is 72%, and the co-product epichlorohydrin is p-H2O2The yield of (2) was 20%.
Example 4: heteropolyacid quaternary ammonium salt catalysis 1-octene epoxidation
Preparing heteropoly acid quaternary ammonium salt catalyst: same as example 1 (one)
(II) epoxidation of 1-octene: in a 100ml glass reaction bottle, 0.5g of heteropoly acid quaternary ammonium salt catalyst, 15ml of 3-chloropropene, 5.5g of 1-octene and 30% H are added2O23.4g and 0.03g of sodium dihydrogen phosphate, the reaction flask is closed, the mixture is stirred for 3.5 hours at the reaction temperature of 65 ℃, and then the solid catalyst is cooled, opened and separated, and the catalyst recovery rate is 94 percent. The reaction oil phase is analyzed by gas chromatography, and 1, 2-epoxyoctane is opposite to H2O2The yield of (A) is 65%, and the co-product epichlorohydrin is p-H2O2The yield of (3) was 30%.
Example 5: heteropoly quaternary ammonium salt catalyzed propylene epoxidation
Preparing heteropoly acid quaternary ammonium salt catalyst: same as example 1 (one)
(II) epoxidation of propylene: in a 50ml stainless steel pressure kettle, 0.8g of heteropoly acid quaternary ammonium salt catalyst and 10ml of 3-chloropropene are sequentially added, and H with the concentration of 50 percent is added2O22.2g and 0.03g of disodium hydrogen phosphate, and 5.2g of propylene is filled into the reaction kettle. Stirring for 3.5H at the reaction temperature of 50 ℃, placing the pressure kettle into an ice water bath for cooling for 0.5H after reaction, slowly releasing gas to normal pressure, opening the reaction kettle, separating the solid catalyst, wherein the recovery rate of the catalyst is 94%, and the reaction oil phase is analyzed by gas chromatography, and propylene oxide is used for H2O2The yield of (A) is 45 percent, and the coproduct epichlorohydrin is p-H2O2The yield of (3) was 31%. The aqueous phase was analyzed by gas chromatography and the by-product 1, 2-propanediol was p-H2O2The yield of (a) was 16%.
Example 6 heteropolyacid quaternary ammonium salt catalyzed epoxidation of α -pinene
Preparing heteropoly acid quaternary ammonium salt catalyst: same as example 1 (one)
α -epoxidation of pinene, adding heteropoly acid quaternary ammonium salt catalyst 0.6g, 3-chloropropene 40ml, α -pinene 6.0g and H with concentration of 50% into 100ml glass reaction bottle2O23.2g of sodium bicarbonate 0.05g, the reaction flask was closed, stirred at a reaction temperature of 50 ℃ for 4 hours, cooled and the solid catalyst was isolated. The catalyst was recovered and subjected to a cycle test, and the cycle test was carried out 3 times, and the results of the cycle reaction are shown in Table 1.
TABLE 1
Claims (6)
1. A method for catalyzing olefin epoxidation by heteropoly acid quaternary ammonium salt is characterized in that: olefin and oxidant react in the presence of a heteropoly acid quaternary ammonium salt catalyst, an auxiliary agent and an organic solvent, wherein the organic solvent is 3-chloropropene, the reaction temperature is 25-80 ℃, the reaction time is 0.5-10 h, the catalyst is solid after the reaction is finished, the catalyst can be recycled through simple separation, and the target epoxide is obtained through distillation of reaction liquid.
2. A method according to claim 1, characterized in that: heteropolyacid quaternary ammonium salt catalyst molecule composition QmHnPMxOyQ is quaternary ammonium salt cation, and the quaternary ammonium salt is at least one of tetrabutylammonium salt, dodecyl trimethyl amine salt, hexadecyl trimethyl amine salt, octadecyl trimethyl amine salt or dioctadecyl dimethyl amine salt; m is metal tungsten, M is more than or equal to 1 and less than or equal to 7, x is more than or equal to 1 and less than or equal to 12, n is more than or equal to 0 and less than or equal to 4, and y is more than or equal to 10 and less than or equal to 40.
3. A method according to claim 1, characterized in that: the substrate olefin molecular formula is:
the substrate olefin is non-chiral olefin, chiral olefin or enantiomer olefin, wherein R1, R2, R3 and R4 are respectively hydrogen and straight-chain alkyl (C)nH2n+1N is 1 to 10), branched alkyl (C)nH2n+1N is 1 to 10), and a cyclic alkyl group (C)nH2nN is 3 to 8), aryl, a linear substituent containing one carbonyl group (C)nH2n-1O, n-3 to 10) and a branched substituent containing one carbonyl group (C)nH2n-1O, n is 3 to 10) and a cyclic substituent (C) containing a carbonyl groupnH2n-2O, n-3 to 8) and a linear substituent containing one epoxy group (C)nH2n-1O, n-3 to 10) and a branched substituent (C) having one epoxy groupnH2n-1O, n-3 to 10) and a cyclic substituent (C) containing one epoxy groupnH2n-2O，n＝3～8)。
4. A method according to claim 1, characterized in that: the oxidant is aqueous hydrogen peroxide solution with the mass concentration of 10-80%.
5. A method according to claim 1, characterized in that: the auxiliary agent is at least one of sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, phosphoric acid, hydrochloric acid, sulfuric acid, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and sodium phosphate.
6. The method according to any one of claims 1 to 5, characterized in that: the content of the heteropoly acid quaternary ammonium salt catalyst is 2-80 g/L of reaction liquid, the content of hydrogen peroxide is 30-100 g/L of reaction liquid, the content of the auxiliary agent is 0.5-10 g/L of reaction liquid, the content of the substrate olefin is 30-150 g/L of reaction liquid, the content of water is 7-200 g/L of reaction liquid, and the balance is solvent 3-chloropropene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115888828A (en) * | 2023-01-06 | 2023-04-04 | 陕西煤业化工技术研究院有限责任公司 | Phosphorus-boron-doped tungsten-molybdenum-containing catalyst, preparation method thereof and method for synthesizing epoxy compound |
| CN116063251A (en) * | 2023-01-06 | 2023-05-05 | 陕西煤业化工技术研究院有限责任公司 | Method for preparing epoxy compound by utilizing microchannel reactor |
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| CN103880782A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxy propane |
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| CN115888828A (en) * | 2023-01-06 | 2023-04-04 | 陕西煤业化工技术研究院有限责任公司 | Phosphorus-boron-doped tungsten-molybdenum-containing catalyst, preparation method thereof and method for synthesizing epoxy compound |
| CN116063251A (en) * | 2023-01-06 | 2023-05-05 | 陕西煤业化工技术研究院有限责任公司 | Method for preparing epoxy compound by utilizing microchannel reactor |
| CN116063251B (en) * | 2023-01-06 | 2024-05-14 | 陕西煤业化工技术研究院有限责任公司 | Method for preparing epoxy compound by utilizing microchannel reactor |
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