CN103977839A - Ionic organic metal tungstate epoxidation catalyst and preparation method thereof - Google Patents
Ionic organic metal tungstate epoxidation catalyst and preparation method thereof Download PDFInfo
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- CN103977839A CN103977839A CN201410250012.XA CN201410250012A CN103977839A CN 103977839 A CN103977839 A CN 103977839A CN 201410250012 A CN201410250012 A CN 201410250012A CN 103977839 A CN103977839 A CN 103977839A
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Abstract
The invention relates to an ionic organic metal tungstate epoxidation catalyst for liquid-phase epoxidation reaction and a preparation method of the catalyst, and belongs to the technical field of fine organic chemical industry and catalyst preparation. The invention discloses an ionic organic multi-phase epoxidation catalyst based on organometallic complexes and tungstic acid and a preparation method of the ionic organic multi-phase epoxidation catalyst. Active components are the organometallic complexes and tungstic acid anions (WO42-), wherein organic components are acetylacetone functional ironic liquid cations, ironic liquid is selected from imidazole, pyridine or triethylamine, and metal centers are Mo, V, Ni, Cu, Co, Fe, Mn and Ti; the preparation method comprises synthesizing the ionic organic metal tungstate epoxidation catalyst containing different metal centers by taking 2-bromoethylam, organic amine, acetylacetone metallic compound and tungstate as raw materials. The catalyst can be used for epoxidation reactions of various olefins, the reaction conditions are mild without the problems of equipment corrosion, polluted wastewater discharge and the like, and the catalyst has the advantages of high activity and selectivity, simple and convenient recycling and repeated use, and is an environment-friendly novel solid catalyst.
Description
Technical field
The invention relates to a kind of solid oxide catalyst and preparation and application thereof, specifically, about a kind of composition structure, preparation method and the application of this catalyst in epoxidation reaction of olefines of ionic organic metal tungstate catalysts, belong to Minute Organic Synthesis and catalyst preparation technical field.
Background technology
The epoxidation reaction of alkene is in theory study or in actual production, all have research widely, because epoxides is as the important organic chemical industry's intermediate of a class, has been widely used in Minute Organic Synthesis and organic chemical industry's process.The a series of equipment corrosions that bring in order to overcome traditional employing peroxycarboxylic acid method EPOXIDATION OF ALKENES CATALYZED BY, the shortcoming and defect such as energy consumption height, or the industry application limitation that adopts precious metals ag etc. to follow as catalyst, in recent years, people have more invested sight with transition metal (as Mo, V, Ni, Cu, Co, Mn, Fe and Ti etc.) be catalyst, hydrogen peroxide (H
2o
2), TBHP (TBHP) or oxygen (O
2) be the new epoxy catalytic process of oxidant.
Organometallic complex as a class important containing the oxidation reduction catalyst of transition metal, there is the physical and chemical performances such as unique optical, electrical, magnetic due to it and be subject to people's extensive concern.The more important thing is, some organo-metallic catalysts have demonstrated excellent catalytic performance in the epoxidation reaction of alkene.But organic ligand is conventionally expensive, and synthetic yield is not high; In addition, current reported organo-metallic catalyst has caused homogeneous catalysis system mostly, and catalyst is difficult to reclaim and reuse.Traditional solution be by immobilized organo-metallic compound in porous carrier (as silica gel, macromolecule, molecular sieve etc.) upper, make loaded catalyst, but these methods inevitably exist resistance to mass tranfer to strengthen, the shortcoming that the easy solution-off of active component etc. is difficult for overcoming.
Ionic liquid has been widely used in all kinds of organic synthesis as the novel green solvent of the class catalyst of holding concurrently.In recent years, cation or anion by catalytic active component functionalization to ionic liquid, preparation becomes to the ionic solids catalyst that ionic liquid has similar composition structure the focus that people study gradually, for example, by to the cationic functionalized design of ionic liquid, organo-metallic compound can be incorporated in the cation of ionic liquid; In addition, by anion exchange effect, can be by larger some volumes, the metal oxygen cluster compound (as polyoxometallate and metal oxide etc.) that valence state is higher is incorporated in the anion of ionic liquid, forms the ionic solids catalyst with redox catalysis performance.But people's research at present also mainly concentrates on the simple cation to ionic liquid or anion carries out functionalized design; And simultaneously the cation to ionic liquid and anion to carry out the solid catalyst of redox functionalized design also very rare.
Summary of the invention
The object of the invention is to the deficiency existing for catalyst in current epoxidation reaction of olefines, provide a kind of building-up process simple, and the preparation method of cheap ionic organic metal tungstates solid catalyst, and the application of this catalyst in liquid phase olefin epoxidation reaction.
Technical scheme of the present invention:
A. By Amine Solutions and 2-bromine ethylamine hydrobromide ethanolic solution are mixed according to stoichiometric, at 50～160 DEG C, stirring reaction 1～3 day, then cooling, through washing, filtration and the dry ionic liquid presoma that obtains functional amido;
B. after the ionic liquid presoma of above-mentioned synthetic functional amido and metallo-organic compound being mixed according to stoichiometric, stir 1～2 day at 50～140 DEG C, then the desolvation that reduces pressure, through washing and the dry ionic liquid presoma that obtains organic metal functionalization;
C. the ionic liquid presoma of above-mentioned synthetic organic metal functionalization and tungstates are made into respectively to the aqueous solution, after again two kinds of solution being mixed according to stoichiometric, stirring at room temperature 1～2 day, after filtration, washing and the dry ionic organic metal tungstate catalysts that obtains.
Described organic amine is N-alkyl imidazole, pyridine or triethylamine; Described organo-metallic compound be acetylacetone,2,4-pentanedione oxygen molybdenum, acetylacetone,2,4-pentanedione vanadyl, nickel acetylacetonate, acetylacetone copper, acetylacetone cobalt, ferric acetyl acetonade, manganese acetylacetonate with or acyl acetone oxygen titanium; Described tungstates is sodium tungstate or potassium tungstate.
The above-mentioned ionic organic metal tungstate catalysts making, for the method for epoxidation reaction of olefines, is characterized in that comprising following process:
(1) olefin reactant is joined in reactor, adding quality is 0.01～5% catalyst of reactant gross mass, adding mole is the oxidant of 0.5～6 times of reactant mole again, it is 30～90 DEG C in reaction temperature, reaction time is 0.2～24h, obtains the mixed liquor of epoxidation reaction.Adopt gas-chromatography or liquid chromatogram to detect analysis to mixed liquor.
(2) after having reacted, go out solid catalyst by filtration or centrifugation, after ethanol washs, is dried, can be directly used in reaction next time.
Above-mentioned synthesis technique, is characterized in that, alkene can be the one in cyclic olefin, chain alkene, unsaturated enol, unsaturated fat compounds of group, unsaturated aromatic compound.
Ionic organic metal tungstate catalysts provided by the present invention, synthesis technique is simple, and yield is high; While being applied to epoxidation reaction of olefines, have activity and selectivity high, reclaim the convenient and stable feature of repeat performance.
Detailed description of the invention
Below by specific embodiment, the present invention is further described, but does not limit the present invention.
[embodiment 1]
In 100mL round-bottomed flask, add 50mL ethanol, 8.20g N-methylimidazole and 20.50g2-bromine ethylamine hydrobromide stir 24h under 80 DEG C of conditions.After reaction finishes, revolve to steam and remove ethanol, cooling, in ethanol, recrystallization obtains white solid.White solid is dissolved in to 10mL water, is adjusted to neutrality with the KOH aqueous solution, then revolve and steam except anhydrating.In mixture, add 20mL methyl alcohol and 2mL CHCl
3after, adularescent solid appears at drag, after filtration, revolves steaming, obtains functional amido ionic liquid 1-methyl-3-aminopropyl imidazoles bromine salt.Nuclear-magnetism characteristic peak (300MHz, D
2o, TMS) δ (ppm)=3.47 (m, 2H ,-CH
2), 4.58 (m, 2H ,-CH
2), 5.40 (dd, 1H ,-CH), 5.81 (dd, 1H ,-CH), 7.13 (m, 1H ,-CH), 7.66 (s, 1H ,-CH), 7.81 (s, 1H ,-CH), 9.18 (s, 1H ,-CH).
In 100mL round-bottomed flask, add 50mL ethanol, 4.12g1-methyl-3-aminopropyl imidazoles bromine salt and 3.26g acetylacetone,2,4-pentanedione oxygen molybdenum stir 24h under 80 DEG C of conditions.After reaction finishes, after filtration, wash, after being dried, obtain the ionic liquid presoma of acetylacetone,2,4-pentanedione oxygen molybdenum functionalization.
In 100mL there-necked flask, add 30mL ethanol, 20mL water, the ionic liquid presoma of 1.00g acetylacetone,2,4-pentanedione oxygen molybdenum functionalization and slightly excessive Disodium tungstate (Na2WO4) dihydrate or potassium tungstate (0.94g), mechanical agitation 24h under 80 DEG C of conditions.After reaction finishes, after filtration, washing, the dry imidazol ion type organic-molybdenum tungstate catalysts that obtains.
[embodiment 2]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only change the N-methylimidazole in preparation method into pyridine, obtain pyridinium ion type organic-molybdenum tungstate catalysts.
[embodiment 3]
Under the preparation condition and the identical situation of embodiment 1 of catalyst, only change the N-methylimidazole in preparation method into triethylamine, obtain quaternary amine ionic organic-molybdenum tungstate catalysts.
[reaction embodiment 4-6]
Be equipped with in magnetic stir bar and spherical condensation tube round-bottomed flask at 50mL, add 0.06g catalyst, 15mL acetonitrile solvent, 5mmol cyclo-octene and 12.5mmol hydrogen peroxide (H
2o
2), warming-in-water to 60 DEG C, reaction 4h.After reaction finishes, carry out GC analysis.Taking conversion ratio and selective as catalyst performance evaluation index, gained reactivity worth is as shown in table 1.
Table 1 catalyst activity evaluation result
[reaction embodiment 7]
The catalytic effect of catalyst to epoxidation of cyclohexene reaction, taking catalyst synthetic in embodiment 1 as example:
Be equipped with in magnetic stir bar and spherical condensation tube round-bottomed flask at 50mL, add 0.06g catalyst, 15mL acetonitrile solvent, 5mmol cyclo-octene and 12.5mmol hydrogen peroxide (H
2o
2), warming-in-water to 60 DEG C, reaction 6h.After reaction finishes, carry out GC analysis.Taking conversion ratio and selective as catalyst performance evaluation index, gained reactivity worth is as shown in table 2.
[reaction embodiment 8]
The catalytic effect of catalyst to leaf-alcohol epoxidation reaction, taking catalyst synthetic in embodiment 1 as example:
Method of operating, with embodiment 7, just changes epoxidation reaction thing cyclohexene into leaf-alcohol, and gained reactivity worth is as shown in table 2.[reaction embodiment 9]
The catalytic effect of catalyst to 1-hexene epoxidation reaction, taking catalyst synthetic in embodiment 1 as example:
Method of operating, with embodiment 7, just changes reactant cyclohexene into 1-hexene, and gained reactivity worth is as shown in table 2.
[reaction embodiment 10]
The catalytic effect of catalyst to 1-octene epoxidation reaction, taking catalyst synthetic in embodiment 1 as example:
Method of operating, with embodiment 7, just changes reactant cyclohexene into 1-octene, and gained reactivity worth is as shown in table 2.
[reaction embodiment 11]
The catalytic effect of catalyst to epoxidation of styrene reaction, taking catalyst synthetic in embodiment 1 as example:
Method of operating, with embodiment 7, just changes reactant cyclohexene into styrene, and gained reactivity worth is as shown in table 2.
The catalytic effect of table 2 ionic organic metal tungstate catalysts to different rings oxidation reaction
[embodiment 12]
Catalyst is reused stability experiment, taking catalyst synthetic in embodiment 1 as example:
The experiment of investigating catalytic activity with fresh catalyst is as embodiment 4.After reaction finishes, thing to be mixed is chilled to room temperature, and centrifugation goes out solid powder th-1 catalyst, and with ethanol washing three times, 80 DEG C of dry 2h, add 15mL acetonitrile solvent, 5mmol cyclo-octene and 12.5mmol hydrogen peroxide (H
2o
2), warming-in-water to 60 DEG C, reaction 4h, then carries out GC analysis.So, catalyst recovery is also reused 4 times, and the repeat performance of gained catalyst is as shown in table 3.
Table 3 ionic organic metal tungstate catalysts reuse result
Claims (9)
1. an ionic organic metal tungstates epoxidation catalyst, is characterized in that having following general formula:
Wherein: R represents ionic liquid cation, can be selected from glyoxaline cation, pyridylium, quaternary ammonium cation; M can be transition metal molybdenum, vanadium, nickel, copper, cobalt, iron, manganese and titanium; X can be oxygen atom, the integer that n is 0-2.
Described in a claim 1 for the preparation method of the ionic organic metal tungstate catalysts of epoxidation reaction, it is characterized in that forming with acetylacetone metallic compound and functional amido ionic liquid cation sites the ionic liquid presoma of organic metal function, by obtaining ionic organic metal tungstate catalysts with tungstates anion exchange effect, its concrete steps are as follows again:
A. By Amine Solutions and 2-bromine ethylamine hydrobromide ethanolic solution are mixed according to stoichiometric, at 50～160 DEG C, stirring reaction 1～3 day, then cooling, through washing, filtration and the dry ionic liquid presoma that obtains functional amido;
B. after the ionic liquid presoma of above-mentioned synthetic functional amido and metallo-organic compound being mixed according to stoichiometric, stir 1～2 day at 50～140 DEG C, then the desolvation that reduces pressure, through washing and the dry ionic liquid presoma that obtains organic metal functionalization;
C. the ionic liquid presoma of above-mentioned synthetic organic metal functionalization and tungstates are made into respectively to the aqueous solution, after again two kinds of solution being mixed according to stoichiometric, stir 1～2 day, after filtration, washing and the dry ionic organic metal tungstate catalysts that obtains.
3. preparation method according to claim 2, is characterized in that, described organic amine is N-alkyl imidazole, pyridine or quaternary ammonium salt.
4. preparation method according to claim 2, it is characterized in that, described metal source compound is in acetylacetone,2,4-pentanedione oxygen molybdenum, acetylacetone,2,4-pentanedione vanadyl, nickel acetylacetonate, acetylacetone copper, acetylacetone cobalt, ferric acetyl acetonade, manganese acetylacetonate and acetylacetone,2,4-pentanedione oxygen titanium.
5. preparation method according to claim 2, is characterized in that, described tungstates is sodium tungstate or potassium tungstate.
6. be used for a liquid phase olefin epoxidation reaction with the prepared catalyst of claim 1, it is characterized in that comprising following process:
A certain amount of olefin reactant is joined in reactor, adding volume is the solvent of 3～20 times of reactant volume, then adding quality is 0.01～5% solid catalyst of reactant gross mass, adding mol ratio is the oxidant of 0.5～5 times of reaction volume again, it is 30～90 DEG C in reaction temperature, reaction time is 0.2～24h, obtain the mixed liquor of epoxidation reaction, adopt gas-chromatography or liquid chromatogram to detect analysis to mixed liquor, go out solid catalyst by filtration or centrifugation, after washing, being dried, can be directly used in reaction next time.
7. catalytic reaction technique according to claim 6, is characterized in that, reaction substrate alkene can be cyclic olefin, chain alkene, unsaturated enol, unsaturated aromatic compound, long-chain unsaturated fat compounds of group.
8. catalytic reaction technique according to claim 6, is characterized in that, solvent can be acetonitrile, acetonitrile/water mixed solvent, water, carbon tetrachloride, chloroform, carrene, 1,2-dichloroethanes, ethyl acetate, acetone, ethanol, methyl alcohol.
9. catalytic reaction technique according to claim 6, is characterized in that, oxidant can be hydrogen peroxide, TBHP, clorox.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341297A (en) * | 2014-09-16 | 2015-02-11 | 浙江恒丰新材料有限公司 | Method for preparing polyol by using bio-oil and application |
| CN106423278A (en) * | 2016-08-19 | 2017-02-22 | 中国科学院福建物质结构研究所 | Method for preparing ionic catalyst and carrying out catalytic conversion on carbon dioxide |
| CN112808306A (en) * | 2021-01-13 | 2021-05-18 | 华东理工大学 | Preparation method and application of metal oxygen cluster catalyst with stable organic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503893A (en) * | 2011-11-07 | 2012-06-20 | 华东师范大学 | Ionic liquid of alkyl imidazole metal oxysalt and preparation method thereof |
| CN103172777A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Method for preparing polybutadiene epoxy resin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503893A (en) * | 2011-11-07 | 2012-06-20 | 华东师范大学 | Ionic liquid of alkyl imidazole metal oxysalt and preparation method thereof |
| CN103172777A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Method for preparing polybutadiene epoxy resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341297A (en) * | 2014-09-16 | 2015-02-11 | 浙江恒丰新材料有限公司 | Method for preparing polyol by using bio-oil and application |
| CN104341297B (en) * | 2014-09-16 | 2016-06-15 | 浙江恒丰新材料有限公司 | A kind of bio oil prepares method and the application of polyhydric alcohol |
| CN106423278A (en) * | 2016-08-19 | 2017-02-22 | 中国科学院福建物质结构研究所 | Method for preparing ionic catalyst and carrying out catalytic conversion on carbon dioxide |
| CN106423278B (en) * | 2016-08-19 | 2019-01-15 | 中国科学院福建物质结构研究所 | A kind of method of the preparation and catalyzed conversion carbon dioxide of ionized catalyst |
| CN112808306A (en) * | 2021-01-13 | 2021-05-18 | 华东理工大学 | Preparation method and application of metal oxygen cluster catalyst with stable organic acid |
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