CN104888855A - Molybdenyl acetylacetonate solid catalyst used for alkene epoxidation reaction and preparation method thereof - Google Patents
Molybdenyl acetylacetonate solid catalyst used for alkene epoxidation reaction and preparation method thereof Download PDFInfo
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- CN104888855A CN104888855A CN201510159121.5A CN201510159121A CN104888855A CN 104888855 A CN104888855 A CN 104888855A CN 201510159121 A CN201510159121 A CN 201510159121A CN 104888855 A CN104888855 A CN 104888855A
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Abstract
The invention discloses a molybdenyl acetylacetonate solid catalyst used for an alkene epoxidation reaction and a preparation method thereof. According to the invention, divinyl benzene and allyl amine are subjected to a free radical polymerization to obtain an organic macromolecule polymer, then a molybdenyl acetylacetonate organic ligand and amino on a polymer frame are subjected to a chemical bond effect to prepare the loaded molybdenyl acetylacetonate solid catalyst. The catalyst preparation method has the advantages of simple and easy operation, high catalysis efficiency, repeatedly usable performance and reduced production cost, and is expected to become a cleaning epoxidation technology route having competitiveness.
Description
Technical field
The present invention relates to a kind of preparation method of epoxidation reaction of olefines Novel solid-catalyst, adopt organic high molecular polymer load acetylacetone,2,4-pentanedione oxygen molybdenum to prepare solid epoxidation catalyst DVB-NH
2-MoO
2(acac)
2, belong to meticulous field of chemical technology.
Background technology
The epoxidation reaction of alkene all has in theory study or in actual production to be studied 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.In order to overcome a series of equipment corrosions that traditional employing peroxycarboxylic acid method EPOXIDATION OF ALKENES CATALYZED BY is brought, the shortcoming and defect such as energy consumption is high, or adopt precious metals ag etc. to limit to as the industry application that catalyst is adjoint, in recent years, sight has more been invested with transition metal (as Mo by people, 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.
Molybdenum (Mo) is demonstrated excellent catalytic performance in the epoxidation reaction of organometallic complex alkene.But this kind of complex result in homogeneous catalysis system mostly, catalyst is difficult to reclaim and reuse.Traditional solution is that organo-metallic compound is immobilized on the carrier such as molecular sieve and active carbon by coupling agent (as triethoxysilane etc.), obtained loaded catalyst, but these carrying methods of having reported for work, not only preparation process is loaded down with trivial details, single carrying capacity of active component is not high, and there is active component and easily block the shortcoming such as duct and solution-off.
In order to solve the problem, the present invention adopts radical polymerization to obtain organic polymer immobilized acetylacetone,2,4-pentanedione oxygen molybdenum catalysis of solid catalyst epoxidation reaction of olefines, and this method has not yet to see report.
Summary of the invention
The present invention be directed to the deficiency that traditional liquid carboxylic acid catalyst exists in epoxidation reaction of olefines, a kind of method preparing support type acetylacetone,2,4-pentanedione oxygen molybdenum solid catalyst that technique is simple, easy and simple to handle is provided, and be applied to the epoxidation reaction of catalyzed alkene, achieve good catalytic effect.
Technical scheme of the present invention: adopt a kind of organic polymer of free-radical polymerized preparation immobilized acetylacetone,2,4-pentanedione oxygen molybdenum solid catalyst DVB-NH
2-MoO
2(acac)
2preparation method, it is characterized in that comprising following process:
Be that 1:0.2 ~ 1:2 joins in 20 ~ 50mL alcohol solvent by divinylbenzene and allylamine according to mol ratio, add a certain amount of initator azodiisobutyronitrile AIBN, its quality is 0.5% ~ 3% of reactant gross mass, 24 ~ 48h is stirred at 60 ~ 100 DEG C, filter to isolate solid product, wash three times with ethanol, vacuum drying 8 ~ 24h at 60 ~ 80 DEG C, obtains organic high molecular polymer DVB-NH
2, by gained DVB-NH
2be that 1:1 ~ 2:1 joins in 30 ~ 50mL alcohol solvent with acetylacetone,2,4-pentanedione oxygen molybdenum according to mol ratio, at 80 ~ 120 DEG C of magnetic agitation 24 ~ 48h, filter to isolate solid product, wash three times with ethanol, 60 DEG C of vacuum drying 8 ~ 24h, obtain solid catalyst DVB-NH
2-MoO
2(acac)
2.
Above-mentioned solid catalyst DVB-NH
2-MoO
2(acac)
2the application of EPOXIDATION OF ALKENES CATALYZED BY, it is characterized in that: be that 1:1 ~ 1:4 adds in reactor by alkene and TBHP according to mol ratio, then add 3% ~ 15% solid catalyst DVB-NH that the dichloromethane solvent of 20 ~ 50mL and quality are reactant gross mass
2-MoO
2(acac)
2, be 60 DEG C ~ 90 DEG C in reaction temperature, stirring reaction 2 ~ 10h, obtains the mixture containing alkene epoxidation product.
Above-mentioned synthesis technique, is characterized in that, alkene is the one in cyclo-octene, cyclohexene, citrene, 1-octene and styrene.
Compared with prior art, advantage of the present invention is: catalyst preparing is simple, catalytic activity is high, catalyst simple filtration can reclaim and reuse, and catalyst reuses 4 times, and catalytic activity is without obvious reduction.
Accompanying drawing explanation
Support type acetylacetone,2,4-pentanedione oxygen molybdenum solid catalyst DVB-NH prepared by Fig. 1 the present invention
2-MoO
2(acac)
2infared spectrum.
Detailed description of the invention
Below by specific embodiment, the present invention is further illustrated, but do not limited the present invention.
[embodiment 1]
In 100mL round-bottomed flask, the divinylbenzene of 0.05mol and 0.05mol allylamine are joined in 50mL alcohol solvent, add the initator azodiisobutyronitrile AIBN of 0.18g, 24h is stirred at 80 DEG C, filter to isolate solid product, wash three times with ethanol, vacuum drying 10h at 60 DEG C, obtains organic high molecular polymer DVB-NH
2, by the DVB-NH of 0.02mol
2join in 50mL alcohol solvent with 0.01mol acetylacetone,2,4-pentanedione oxygen molybdenum, at 80 DEG C of magnetic agitation 48h, filter to isolate solid product, wash three times with ethanol, 60 DEG C of vacuum drying 10h, obtain solid catalyst DVB-NH
2-MoO
2(acac)
2.
[embodiment 2]
In 50mL round-bottomed flask, add 0.01mol cyclo-octene, 0.02mol TBHP and 20mL carrene, then the solid catalyst DVB-NH adding 0.2g
2-MoO
2(acac)
2, be 70 DEG C in reaction temperature, stirring reaction 4h, through chromatography, cyclo-octene conversion ratio is 95%, and epoxide ring octane is selective is 98%.
[embodiment 3]
In 50mL round-bottomed flask, add 0.01mol cyclic ethylene, 0.02mol TBHP and 20mL carrene, then the solid catalyst DVB-NH adding 0.2g
2-MoO
2(acac)
2, be 70 DEG C in reaction temperature, stirring reaction 4h, through chromatography, cyclic ethylene conversion ratio is 89%, and 7-oxa-bicyclo[4.1.0 is selective is 94%.
[embodiment 4]
In 50mL round-bottomed flask, add 0.01mol citrene, 0.02mol TBHP and 20mL carrene, then the solid catalyst DVB-NH adding 0.2g
2-MoO
2(acac)
2, be 70 DEG C in reaction temperature, stirring reaction 5h, through chromatography, citrene conversion ratio is 88%, and epoxidation product is selective is 92%.
[embodiment 5]
In 50mL round-bottomed flask, add 0.01mol 1-octene, 0.02mol TBHP and 20mL carrene, then the solid catalyst DVB-NH adding 0.2g
2-MoO
2(acac)
2, be 70 DEG C in reaction temperature, stirring reaction 8h, through chromatography, 1-octene conversion is 55%, and epoxidation product is selective is 90%.
[embodiment 6]
In 50mL round-bottomed flask, add 0.01mol styrene, 0.02mol TBHP and 20mL carrene, then the solid catalyst DVB-NH adding 0.2g
2-MoO
2(acac)
2, be 70 DEG C in reaction temperature, stirring reaction 8h, through chromatography, styrene conversion rate is 56%, and epoxidation product is selective is 72%.
[embodiment 7]
The Reusability performance of solid catalyst.
In 50mL round-bottomed flask, add 0.01mol cyclo-octene, 0.02mol TBHP and 20mL carrene, then the solid catalyst DVB-NH adding 0.2g
2-MoO
2(acac)
2, be 70 DEG C in reaction temperature, stirring reaction 4h, after reaction terminates, filter out solid catalyst, 60 DEG C of dry 2h, use this catalyst recycle, and gained reactivity worth is as shown in table 1.
The result of table 1 support type acetylacetone,2,4-pentanedione oxygen molybdenum catalyst catalysis cyclo-octene epoxidation reaction
Claims (3)
1. macromolecule loading acetylacetone,2,4-pentanedione oxygen molybdenum solid catalyst for epoxidation reaction of olefines and preparation method thereof, is characterized in that comprising following process:
Be that 1:0.2 ~ 1:2 joins in 20 ~ 50mL alcohol solvent by divinylbenzene and allylamine according to mol ratio, add a certain amount of initator azodiisobutyronitrile AIBN, its quality is 0.5% ~ 3% of reactant gross mass, 24 ~ 48h is stirred at 60 ~ 100 DEG C, filter to isolate solid product, wash three times with ethanol, vacuum drying 8 ~ 24h at 60 ~ 80 DEG C, obtains organic high molecular polymer DVB-NH
2, by gained DVB-NH
2be that 1:1 ~ 2:1 joins in 30 ~ 50mL alcohol solvent with acetylacetone,2,4-pentanedione oxygen molybdenum according to mol ratio, at 80 ~ 120 DEG C of magnetic agitation 24 ~ 48h, filter to isolate solid product, wash three times with ethanol, 60 DEG C of vacuum drying 8 ~ 24h, obtain solid catalyst DVB-NH
2-MoO
2(acac)
2.
2. by solid catalyst DVB-NH prepared by method described in claim 1
2-MoO
2(acac)
2the application of EPOXIDATION OF ALKENES CATALYZED BY, it is characterized in that: be that 1:1 ~ 1:4 adds in reactor by alkene and TBHP according to mol ratio, then add 3% ~ 15% solid catalyst DVB-NH that the dichloromethane solvent of 20 ~ 50mL and quality are reactant gross mass
2-MoO
2(acac)
2, be 60 DEG C ~ 90 DEG C in reaction temperature, stirring reaction 2 ~ 10h, obtains the mixture containing alkene epoxidation product.
3. synthesis technique according to claim 2, is characterized in that, alkene is the one in cyclo-octene, cyclohexene, citrene, 1-octene and styrene.
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|---|---|---|---|
| CN201510159121.5A CN104888855B (en) | 2015-04-03 | 2015-04-03 | A kind of acetylacetone,2,4-pentanedione oxygen molybdenum solid catalyst for epoxidation reaction of olefines and preparation method thereof |
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| CN201510159121.5A CN104888855B (en) | 2015-04-03 | 2015-04-03 | A kind of acetylacetone,2,4-pentanedione oxygen molybdenum solid catalyst for epoxidation reaction of olefines and preparation method thereof |
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| CN104888855B CN104888855B (en) | 2017-03-01 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143847A (en) * | 2019-06-06 | 2019-08-20 | 南京焕然生物科技有限公司 | A kind of 1S, 4R-1- methyl -4-(1- methyl ethylene) -2- cyclohexene -1- alcohol preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0326392A1 (en) * | 1988-01-28 | 1989-08-02 | Eastman Chemical Company | Selective epoxidation of olefins |
| CN1437590A (en) * | 2000-06-09 | 2003-08-20 | 国际壳牌研究有限公司 | Process for operating the epoxidation of ethylene |
| CN102464632A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane |
| CN103272644A (en) * | 2013-06-09 | 2013-09-04 | 江南大学 | Schiff base metal catalyst used in liquid phase epoxidation reaction and preparation method of schiff base metal catalyst |
-
2015
- 2015-04-03 CN CN201510159121.5A patent/CN104888855B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0326392A1 (en) * | 1988-01-28 | 1989-08-02 | Eastman Chemical Company | Selective epoxidation of olefins |
| CN1437590A (en) * | 2000-06-09 | 2003-08-20 | 国际壳牌研究有限公司 | Process for operating the epoxidation of ethylene |
| CN102464632A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing epoxy chloropropane |
| CN103272644A (en) * | 2013-06-09 | 2013-09-04 | 江南大学 | Schiff base metal catalyst used in liquid phase epoxidation reaction and preparation method of schiff base metal catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143847A (en) * | 2019-06-06 | 2019-08-20 | 南京焕然生物科技有限公司 | A kind of 1S, 4R-1- methyl -4-(1- methyl ethylene) -2- cyclohexene -1- alcohol preparation method |
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Effective date of registration: 20210430 Address after: 313000 room 1020, science and Technology Pioneer Park, 666 Chaoyang Road, Nanxun Town, Nanxun District, Huzhou, Zhejiang. Patentee after: Huzhou You Yan Intellectual Property Service Co.,Ltd. Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province Patentee before: Jiangnan University |