CN103880779B - A kind of method of heteropolyacid quaternary ammonium salt catalyzing expoxidation of olefines - Google Patents
A kind of method of heteropolyacid quaternary ammonium salt catalyzing expoxidation of olefines Download PDFInfo
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- CN103880779B CN103880779B CN201210559384.1A CN201210559384A CN103880779B CN 103880779 B CN103880779 B CN 103880779B CN 201210559384 A CN201210559384 A CN 201210559384A CN 103880779 B CN103880779 B CN 103880779B
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Abstract
The present invention provides a kind of method of heteropolyacid quaternary ammonium salt catalyzing expoxidation of olefines, its technical scheme is: alkene, oxygenant react under heteropolyacid quaternary ammonium salt catalyst, reductibility auxiliary agent and organic solvent exist, temperature of reaction 50 ~ 80 DEG C, reaction times 2 ~ 10h, reaction precipitates out catalyzer after terminating and can be separated and re-use, and reaction solution obtains target epoxide by distillation. Technique of the present invention is simple, and mild condition, catalyzer are easy to separation and recovery, environmental protection, have very big prospects for commercial application.
Description
Technical field
The invention belongs to chemical catalysis field, in particular, provide a kind of method of heteropolyacid quaternary ammonium salt catalyzing expoxidation of olefines.
Background technology
Alkene epoxidation is one of reaction the most important in chemical industry, and its epoxidation product is the raw material preparing multiple important Chemicals, is widely used in the various fields such as organic synthesis, fine chemistry industry and petrochemical complex. It is chlorohydrination and conjugated oxidation that tradition prepares the method for epoxy compounds, and they all exist more serious problem of environmental pollution. People are devoted to develop that flow process is simple, by product is few and free of contamination olefin epoxidation process always for many years, at present report taking green oxygen source hydrogen peroxide as, in the olefin epoxidation catalysts of oxygen source, the heteropolyacid quaternary ammonium salt with reaction-controlled phase-transfer characteristic is the catalyzer of a class compared with tool industrial prospect. This type of document report has:
Document: XiZW, ZhouN, SunY, LiKL.Reaction-ControlledPhase-TransferCatalysisforPropyl eneEpoxidationtoPropyleneOxide [J] .Science, 2001,292:1139
Document: GaoS, LiM, LvY, ZhouN, XiZW.EpoxidationofPropylenewithAqueousHydrogenPeroxideon aReaction-ControlledPhase-TransferCatalyst [J] .OrganicProcessResearch&Development, 2004,8:131
Document: LiJ, XiZW, GaoS, Anenvironmentallybenignrouteforepichlorohydrinfromallylc hlorideepoxidationcatalyzedbyheteropolyphosphatotungstat e [J] .ResearchonChemicalIntermediates, 2007,33:523
Document: CN101045716B, CN101205219B and CN100532371C etc.
In above-mentioned document is reported, alkene needs excessive more, to ensure the completely consumed of H2O2 so that catalyzer can efficiently precipitate out and cycling and reutilization, but which has limited the application of this catalyst system. The present invention is by adding the mode of reductibility auxiliary agent, H2O2 can be consumed completely, reduce the charging capacity of olefin substrate, successfully the catalysis epoxidation of a series of alkene, this technique has higher olefin conversion, selectivity and cyclical stability, and application prospect is huge.
Summary of the invention
Alkene, oxygenant react under heteropolyacid quaternary ammonium salt catalyst, reductibility auxiliary agent and organic solvent exist, temperature of reaction 50 ~ 80 DEG C, in the reaction times 2 ~ 10h, reaction precipitates out catalyzer after terminating and can be separated and re-use, and reaction solution obtains target epoxide by distillation.
Heteropolyacid quaternary ammonium salt catalyst molecule composition QmHnPMxOyQ is quaternary ammonium salt cationic, quaternary ammonium salt is at least one in 4-butyl ammonium, trimethyl amine salt, cetyl trimethyl amine salt, Octadecyl trimethylamine salt or two octadecyldimethylamine salt, metal M is W and/or Mo, 1��m��7,1��x��12,0��n��4,10��y��40.
The hydrogen peroxide that oxygenant can be aqueous hydrogen peroxide solution or be dissolved in organic solvent. Wherein the hydrogen peroxide in organic solvent can obtain by steaming water pretreatment, and it steams water pretreatment process and condition is: add a certain amount of organic solvent and aqueous hydrogen peroxide solution in the there-necked flask of 250ml. Flask is installed condensation reflux device and water trap, start to stir at normal temperatures and pressures, slow raised temperature to 30 ~ 50 DEG C, pressure drops to 0.005 ~ 0.01MPa, system starts boiling and steams water, no longer raise to the water layer in water trap, stop heating decompression, obtain the H2O2-oxidation in organic solvent agent of colourless equal.
Organic solvent is at least one in chloroform, ethylene dichloride, tetracol phenixin, benzene, toluene, dimethylbenzene, heavy aromatics, acetonitrile, butylacetate, dimethyl formamide, tributyl phosphate, tetrabutyl urea, chlorallylene or ethyl acetate.
Reductibility auxiliary agent is at least one of Sulfothiorine, xitix, alkene, Sodium Nitrite, S-WAT, nitrogen protoxide or sodium borohydride. Alkene in reductibility auxiliary agent is at least one of propylene, chlorallylene, 1-butylene, 2-butylene. Reductibility auxiliary agent can add before the reaction together with reactant, it is also possible to adds in reaction process.
In reaction solution, the content of oxidants hydrogen peroxide is 30 ~ 100 grams per liter reaction solutions, the content of quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is 2 ~ 60 grams per liter reaction solutions, the content of reductibility auxiliary agent is 1 ~ 250 grams per liter reaction solution, the content of substrate alkene is 30 ~ 150 grams per liter reaction solutions, the content of water is 1 ~ 200 grams per liter reaction solution, and all the other are organic solvent.
Substrate alkene is the chain shape of C3 ~ C15 or the alkene of ring-type, it is possible to is monoolefine, or has the polyene hydrocarbon of more than 2 ethylene linkages.
Embodiment
Further instruction is given to the present invention below by embodiment:
Embodiment 1: the styrene catalyzed epoxidation of heteropolyacid quaternary ammonium salt
(1) heteropolyacid quaternary ammonium salt catalyst is prepared: reference JournalofMolecularCatalysisA, 2001,166:219..
Weigh 2.50g wolframic acid and join the H that 10ml mass concentration is 30%2O2In, it is heated to 60 DEG C while stirring, after 60 minutes, obtains colourless transparent solution. In this dissolving, add the phosphoric acid that 0.29g mass concentration is 85%, add 20ml distilled water and continue to stir 30min. Weighing 2.5g palmityl trimethyl ammonium chloride is dissolved in the ethylene dichloride of 40ml, is added drop-wise in above-mentioned hydrogen peroxide solution fast by this solution, continues to stir 60min, is precipitated. The PH being precipitated to filtrate with distilled water wash about equals 4. Filtrate vacuum-drying at 50 ~ 60 DEG C, obtains phosphorus heteropoly tungstic acid quaternary amine catalyzer.
(2) epoxidation reaction of vinylbenzene: in 100ml glass reaction bottle, add heteropolyacid quaternary ammonium salt catalyst 0.3g obtained above, ethylene dichloride 30ml, vinylbenzene 3.3g, concentration is the H of 50%2O22.1g, after stirring 5h, adds 0.5g xitix at temperature of reaction 60 DEG C, then continues reaction 0.5h, and cooling is solid catalyst also, and catalyst recovery yield is 97%. Reaction solution is by gas chromatographic analysis, and Styryl oxide is to H2O2Product rate be 90%.
Embodiment 2: heteropolyacid quaternary ammonium salt catalysis epoxidation of cyclohexene
(1) heteropolyacid quaternary ammonium salt catalyst is prepared: with embodiment 1
(2) epoxidation reaction of tetrahydrobenzene: in 100ml glass reaction bottle, add heteropolyacid quaternary ammonium salt catalyst 0.6g, ethylene dichloride 30ml, tetrahydrobenzene 5.6g, concentration is the H of 50%2O24.2g, after stirring 4h, adds 0.5g S-WAT at temperature of reaction 50 DEG C, then continues reaction 0.5h, and cooling is solid catalyst also, and catalyst recovery yield is 98%. Reaction solution is by gas chromatographic analysis, and epoxy cyclohexane is to H2O2Product rate be 92%.
Embodiment 3: heteropolyacid quaternary ammonium salt catalysis cyclopentenes epoxidation
(1) heteropolyacid quaternary ammonium salt catalyst is prepared: with embodiment 1
(2) epoxidation reaction of cyclopentenes: in 100ml glass reaction bottle, add heteropolyacid quaternary ammonium salt catalyst 0.6g, ethylene dichloride 40ml, vinylbenzene 4.5g, concentration is the H of 50%2O24.2g, after stirring 2h, adds 0.5g Sulfothiorine at temperature of reaction 50 DEG C, then continues reaction 0.5h, and cooling is solid catalyst also, and catalyst recovery yield is 95%. Reaction solution is by gas chromatographic analysis, and cyclopentane epoxide is to H2O2Product rate be 93%.
Embodiment 4: heteropolyacid quaternary ammonium salt catalysis ��-pinene epoxidation
(1) heteropolyacid quaternary ammonium salt catalyst is prepared: with embodiment 1
(2) epoxidation reaction of ��-pinene: in 100ml glass reaction bottle, add heteropolyacid quaternary ammonium salt catalyst 0.3g, H2O2Concentration is the toluene-tributyl phosphate reaction solution 50ml, ��-pinene 6.0g, chlorallylene 11.0g of 1.0mmol/g, 0.1g pyridine, after stirring 6h at temperature of reaction 50 DEG C, and cooling solid catalyst. Reclaim catalyzer and carry out circulation experiment.
Technique of the present invention is simple, and mild condition, catalyzer are easy to separation and recovery, environmental protection, have very big prospects for commercial application.
Claims (9)
1. the method for a heteropolyacid quaternary ammonium salt catalyzing expoxidation of olefines, it is characterized in that: alkene, oxygenant react under heteropolyacid quaternary ammonium salt catalyst, reductibility auxiliary agent and organic solvent exist, temperature of reaction 50��80 DEG C, reaction times 2��10h, reaction precipitates out catalyzer after terminating and can be separated and re-use, and reaction solution obtains target epoxide by distillation; Reductibility auxiliary agent is at least one of xitix, alkene, Sodium Nitrite, nitrogen protoxide or sodium borohydride or more than two kinds; Alkene in reductibility auxiliary agent is propylene, chlorallylene, 1-butylene, at least one of 2-butylene or more than two kinds, and the alkene in described reductibility auxiliary agent is different from substrate alkene.
2. method according to claim 1, it is characterised in that: heteropolyacid quaternary ammonium salt catalyst molecule composition QmHnPMxOy, Q is quaternary ammonium salt cationic, and quaternary ammonium salt is at least one in 4-butyl ammonium, trimethyl amine salt, cetyl trimethyl amine salt, Octadecyl trimethylamine salt or two octadecyldimethylamine salt or more than two kinds; Metal M is W and/or Mo, 1��m��7,1��x��12,0��n��4,10��y��40.
3. method according to claim 1, it is characterised in that: the hydrogen peroxide that oxygenant can be aqueous hydrogen peroxide solution or be dissolved in organic solvent.
4. method according to claim 1, it is characterised in that: reductibility auxiliary agent can add before the reaction together with reactant, it is also possible to adds in reaction process;
Organic solvent is at least one in chloroform, ethylene dichloride, tetracol phenixin, benzene, toluene, dimethylbenzene, heavy aromatics, acetonitrile, butylacetate, dimethyl formamide, tributyl phosphate, tetrabutyl urea, chlorallylene or ethyl acetate or more than two kinds.
5. method according to claim 1 and 2, it is characterised in that: the content of quaternary ammonium salt phosphor-tungstic heteropoly acid catalyzer is 2��60 grams per liter reaction solutions.
6. method according to claim 1, it is characterised in that: the content of oxidants hydrogen peroxide is 30��100 grams per liter reaction solutions.
7. method according to claim 1 or 4, it is characterised in that: the content of reductibility auxiliary agent is 1��250 grams per liter reaction solution.
8. method according to claim 1, it is characterised in that: the content of substrate alkene is 30��150 grams per liter reaction solutions; Substrate alkene is the chain shape of C3��C15 or the alkene of ring-type.
9. method according to claim 1, it is characterised in that: the content of water is 1��200 grams per liter reaction solution.
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| CN104098531B (en) * | 2014-07-25 | 2016-11-23 | 南京红太阳新材料有限公司 | A kind of synthetic method of 1,2-epoxy butane |
| CN105618138B (en) * | 2014-10-29 | 2018-01-09 | 中国科学院大连化学物理研究所 | Solid-carrying type phosphorus heteropoly tungstic acid catalyzer and its application |
| CN109046452B (en) * | 2018-05-29 | 2022-02-08 | 南京大学 | Immobilized heteropolyacid catalyst and preparation method and application thereof |
| CN111253342A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for catalyzing olefin epoxidation by heteropoly acid quaternary ammonium salt |
| CN109603890A (en) * | 2019-01-23 | 2019-04-12 | 中国天辰工程有限公司 | A kind of regeneration method of polyoxometallate |
| CN110833866A (en) * | 2019-11-14 | 2020-02-25 | 江苏扬农化工集团有限公司 | Method for improving recovery rate of epoxidation catalyst |
| CN111036293A (en) * | 2020-01-02 | 2020-04-21 | 江苏扬农化工集团有限公司 | Preparation method of heteropoly acid catalyst |
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