CN101205221A - Method for preparing p-vinyl epoxy cyclohexane - Google Patents
Method for preparing p-vinyl epoxy cyclohexane Download PDFInfo
- Publication number
- CN101205221A CN101205221A CNA2006101349443A CN200610134944A CN101205221A CN 101205221 A CN101205221 A CN 101205221A CN A2006101349443 A CNA2006101349443 A CN A2006101349443A CN 200610134944 A CN200610134944 A CN 200610134944A CN 101205221 A CN101205221 A CN 101205221A
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- CN
- China
- Prior art keywords
- epoxy cyclohexane
- vinyl
- vinyl epoxy
- catalyst
- cyclohexene
- Prior art date
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to novel method for obtaining an Vinyl-1-Cyclohexene 1,2-Epoxide transferring the catalyst of epoxidation by using an ethenyl-Cyclohexene. The catalyst does not dissolve into a reaction medium, but under the effect of the hydrogen peroxide, the catalyst can be formed into active species which can dissolve into the reaction medium and further reacts with the ethenyl-Cyclohexene, thus leading to an epoxidation reaction under high selectivity. The ethenyl-Cyclohexene has a conversion rate of 96 per cent for hydrogen peroxide, and the Vinyl-1-Cyclohexene 1,2-Epoxide has a selectivity of 98 per cent for the cyclohexene. When the hydrogen peroxide is fully consumed, the catalyst is precipated from the reaction system. Through a simple separation, the catalyst can be recycled and reused again. The separation of the catalyst, compared with the multi-phase catalyst, fully presents the characteristics of the even-phase catalyst in the reaction process. The invention has the advantages of easy recycling and simple reaction system. The product is a single Vinyl-1-Cyclohexene 1,2-Epoxide which is environmentally-friendly and has a low cost which meets the request for economical technology; therefore the invention is a novel method which is suitable for lager-scale industrial production of the Vinyl-1-Cyclohexene 1,2-Epoxide.
Description
Technical field
The present invention relates to catalytic epoxidation, specifically provided one vinyl cyclohexene produced new reaction process to vinyl epoxy cyclohexane with the reaction control phase transfer catalyst catalysis epoxidation.
Background technology
To vinyl epoxy cyclohexane is a kind of important intermediate that is used to prepare the efficiency light solidifying agent in recent years.Along with continually developing of its purposes, to demand also will grow with each passing day.
At present, also do not have the operational path of a suitable production to vinyl epoxy cyclohexane, tradition is used for the acid system of crossing of synthesizing epoxy compound, because to very easily hydrolysis of vinyl epoxy cyclohexane, so can not be applicable to its production.And, have potential safety hazard simultaneously because peroxy acid self costs an arm and a leg, be difficult to industrialized value.In addition, synthetic low to the selectivity of vinyl epoxy cyclohexane with chlorohydrination, while chlorohydrination itself is with regard to there being a lot of urgency problem to be solved, and is serious as equipment corrosion, the production process complexity, and environmental pollution is serious etc.
Summary of the invention
The object of the present invention is to provide and a kind of vinyl cyclohexene is produced method and epoxidization reaction process thereof to vinyl epoxy cyclohexane with the reaction control phase transfer catalyst catalysis epoxidation, such catalyzer shows the characteristics of homogeneous catalyst fully in reaction process, the catalytic activity height, is 96% to vinyl cyclohexene to the transformation efficiency of hydrogen peroxide, is 98% to vinyl epoxy cyclohexane to the selectivity of vinyl cyclohexene; And after entire reaction finished, the separation of catalyzer was then similar to heterogeneous catalyst, and the catalyzer after reclaiming can recycle, and the effect that recycles is suitable with the reaction effect of raw catalyst.This method catalyst recovery is easy, and reaction system is simple, and post-reaction treatment is easy, and product is single to vinyl epoxy cyclohexane, and production cost is low, and the no hidden danger of safety is relatively more friendly to environment.
The present invention specifically provides a kind of preparation method to vinyl epoxy cyclohexane, it is characterized in that: with the metallic compound with reaction-controlled phase transfer catalysis effect is catalyzer, with the aqueous hydrogen peroxide solution is oxygen source, in organic solvent, make to vinyl cyclohexene optionally catalysis epoxidation produce vinyl epoxy cyclohexane;
Described catalyzer is the mixture with heteropllyacids compound of reaction control phase transition characteristics, and overall budget consists of Q
mH
nXM
pO
4+3p, M is a central metal atom, is Mo, W or V atoms metal; Q is a cationic moiety, with [R
1R
2R
3R
4N
+] expression, wherein R
1, R
2, R
3, R
4Be alkyl, cycloalkyl, the benzyl that H-, carbon number are no more than 18 straight or branched, or R
1R
2R
3N is pyridine and homologue thereof; X is a heteroatoms, is P or As; 2≤m≤7, n=0 or 1; P=1～12;
Reaction conditions is: the molar ratio of substrate and oxygen source is 3: 1～1: 3, and oxygen source and molecular proportion of catalyst are 100: 1～500: 1, and the temperature of reaction is at 30 to 70 ℃.
Among the preparation method of the present invention to vinyl epoxy cyclohexane, described reaction control phase transfer catalyst recycles through Separation and Recovery.
Among the preparation method of the present invention to vinyl epoxy cyclohexane, employed organic solvent comprises alkane solvents, aromatic hydrocarbon solvent, halogenated hydrocarbon solvent, esters solvent, one or more the mixing of alcoholic solvent matter.Alkane solvents is straight-chain paraffin, branched paraffin or naphthenic hydrocarbon.Aromatic hydrocarbon solvent is benzene, toluene, ethylbenzene, or other single replacement or polysubstituted alkylbenzene.Halogenated hydrocarbon solvent is a halogenated alkane, or halogenated aryl hydrocarbon.Esters solvent is fatty acid ester, aromatic esters, or trialkylphosphate.Alcoholic solvent is methyl alcohol, ethanol, or the trimethyl carbinol.
Oxygen source used in the present invention is that concentration is 25%～70% hydrogen peroxide (H
2O
2) aqueous solution.
Among the preparation method of the present invention to vinyl epoxy cyclohexane, employed catalyst themselves is insoluble in the reaction medium, but under the effect of hydrogen peroxide, can form the active specy that dissolves in the reaction medium, and then with to the vinyl cyclohexene effect, make it optionally carry out epoxidation reaction; Be consumed and work as hydrogen peroxide, catalyzer is just separated out from reaction system.By simple separation, catalyzer just can reclaim, and the catalyzer after the recovery can recycle, and the effect that recycles is suitable with the reaction effect of raw catalyst.
The reaction conditions gentleness of the present invention in epoxidation reaction, epoxidization reaction process is simple, can high-level efficiency, the highly selective preparation is to vinyl epoxy cyclohexane, catalyzer can separate and reclaim easily, and can be recycled, what consumed in the whole process is to vinyl cyclohexene, hydrogen peroxide, with low cost, product is single to vinyl epoxy cyclohexane, do not have joint product, aftertreatment is simple, and is relatively more friendly to environment, can satisfy the requirement of Technological Economy, be a new way that is suitable for large-scale commercial production to vinyl epoxy cyclohexane.
Reaction formula is as follows:
Embodiment
Give further instruction below by example to the present invention.
Embodiment 1
40mmol is dissolved in 40mL to vinyl cyclohexene and mixes in the trimethylbenzene, adds 30% aqueous hydrogen peroxide solution (w/W) of 20mmol, the catalyzer [(CH of 0.2mmol
3)
3C
8H
17N]
3(PO
4) (WO
3)
4], under 65 ℃, react after 1 hour, be 49.0% to the transformation efficiency of vinyl cyclohexene, be 95.2% to the selectivity of vinyl epoxy cyclohexane.This moment, catalyzer was separated out from reaction system, and catalyzer is reclaimed in centrifugal back.
Embodiment 2
40mmol is dissolved in the 40mL chloroform vinyl cyclohexene, adds 30% aqueous hydrogen peroxide solution (w/W) of 20mmol, the catalyzer [(C of 0.2mmol
2H
5)
3C
16H
33N]
2H (PO
4) (MoO
3)
2.54], under 50 ℃, react after 3 hours, be 47.0% to the transformation efficiency of vinyl cyclohexene, be 93.2% to the selectivity of vinyl epoxy cyclohexane.This moment, catalyzer was separated out from reaction system, and catalyzer is reclaimed in centrifugal back.
Embodiment 3
40mmol is dissolved in 60mL toluene and the tributyl phosphate (volume ratio 3: 1) vinyl cyclohexene, adds 30% aqueous hydrogen peroxide solution (w/W) of 20mmol, the catalyzer [(n-C of 0.2mmol
8H
17]
4N]
3(AsO
4) (WO
3)
12], under 35 ℃, react after 5 hours, be 45.0% to the transformation efficiency of vinyl cyclohexene, be 94.2% to the selectivity of vinyl epoxy cyclohexane.This moment, catalyzer was separated out from reaction system, and catalyzer is reclaimed in centrifugal back.
Embodiment 4
40mmol is dissolved in 40mL to vinyl cyclohexene and mixes in the trimethylbenzene, adds 25% aqueous hydrogen peroxide solution (w/W) of 20mmol, the catalyzer [(C of 0.2mmol
2H
5]
3NCH
2Ph]
2HPV
2O
16, under 65 ℃, react after 1 hour, be 49.0% to the transformation efficiency of vinyl cyclohexene, be 95.2% to the selectivity of vinyl epoxy cyclohexane.This moment, catalyzer was separated out from reaction system, and catalyzer, vacuum-drying are reclaimed in centrifugal back.Distill out in the organic layer unreacted raw material to vinyl cyclohexene and product to vinyl epoxy cyclohexane.At the bottom of the resulting distillation liquid add the epoxidation catalyst of recovery again, to vinyl cyclohexene and hydrogen peroxide, the same circulating reaction, reaction result is as shown in the table.
Embodiment 5
40mmol is dissolved in the 40mL different solvents vinyl cyclohexene, adds 35% aqueous hydrogen peroxide solution (w/W) of 20mmol, the catalyzer [(CH of 0.2mmol
3)
3C
16H
33]
3PMoO
16, under 55 ℃, reacting after 2 hours, reaction result sees the following form.
Claims (9)
1. preparation method to vinyl epoxy cyclohexane, it is characterized in that: with the metallic compound with reaction-controlled phase transfer catalysis effect is catalyzer, with the aqueous hydrogen peroxide solution is oxygen source, in organic solvent, make to vinyl cyclohexene optionally catalysis epoxidation produce vinyl epoxy cyclohexane;
Described catalyzer is the mixture with heteropllyacids compound of reaction control phase transition characteristics, and overall budget consists of Q
mH
nXM
pO
44+3p, M is a central metal atom, is Mo, W or V atoms metal; Q is a cationic moiety, with [R
1R
2R
3R
4N
+] expression, wherein R
1,, R
2,, R
3, R
4Be alkyl, cycloalkyl, the benzyl that H-, carbon number are no more than 18 straight or branched, or R
1R
2R
3N is pyridine and homologue thereof; X is a heteroatoms, is P or As; 2≤m≤7, n=0 or 1; P=1～12;
Reaction conditions is: the molar ratio of substrate and oxygen source is 3: 1～1: 3, and oxygen source and molecular proportion of catalyst are 100: 1～500: 1, and the temperature of reaction is at 30 to 70 ℃.
2. according to the described preparation method to vinyl epoxy cyclohexane of claim 1, it is characterized in that: described reaction control phase transfer catalyst recycles through Separation and Recovery.
3. according to the described preparation method to vinyl epoxy cyclohexane of claim 1, it is characterized in that: employed organic solvent comprises alkane solvents, aromatic hydrocarbon solvent, halogenated hydrocarbon solvent, esters solvent, one or more the mixing of alcoholic solvent matter.
4. according to the described preparation method to vinyl epoxy cyclohexane of claim 1, it is characterized in that: employed alkane solvents is straight-chain paraffin, branched paraffin or naphthenic hydrocarbon.
5. according to the described preparation method to vinyl epoxy cyclohexane of claim 1, it is characterized in that: employed aromatic hydrocarbon solvent is benzene, toluene, ethylbenzene, or other single replacement or polysubstituted alkylbenzene.
6. according to the described preparation method to vinyl epoxy cyclohexane of claim 1, it is characterized in that: employed halogenated hydrocarbon solvent is a halogenated alkane, or halogenated aryl hydrocarbon.
7. according to the described preparation method to vinyl epoxy cyclohexane of claim 1, it is characterized in that: employed esters solvent is fatty acid ester, aromatic esters, or trialkylphosphate.
8. according to the described preparation method to vinyl epoxy cyclohexane of claim 1, it is characterized in that: employed alcoholic solvent is methyl alcohol, ethanol, or the trimethyl carbinol.
9. according to the described preparation method to vinyl epoxy cyclohexane of claim 1, it is characterized in that: employed oxygen source is that concentration is 25%～70% aqueous hydrogen peroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101349443A CN101205221A (en) | 2006-12-22 | 2006-12-22 | Method for preparing p-vinyl epoxy cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101349443A CN101205221A (en) | 2006-12-22 | 2006-12-22 | Method for preparing p-vinyl epoxy cyclohexane |
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| Publication Number | Publication Date |
|---|---|
| CN101205221A true CN101205221A (en) | 2008-06-25 |
Family
ID=39565719
Family Applications (1)
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|---|---|---|---|
| CNA2006101349443A Pending CN101205221A (en) | 2006-12-22 | 2006-12-22 | Method for preparing p-vinyl epoxy cyclohexane |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870658A (en) * | 2010-05-14 | 2010-10-27 | 东北师范大学 | Keggin polyoxometallate-based ion liquid and synthesis method thereof |
| CN101671318B (en) * | 2008-09-10 | 2011-07-20 | 山东鲁抗立科药物化学有限公司 | Cycloaliphatic epoxy resin and preparation method thereof |
| CN102393123A (en) * | 2011-09-15 | 2012-03-28 | 无锡市超群自动化设备有限公司 | Inner rail for refrigerator sliding rail |
| CN101734996B (en) * | 2009-12-29 | 2012-12-19 | 岳阳昌德化工实业有限公司 | Method for recycling and utilizing waste liquor containing 4-vinyl cyclohexene |
| CN108250163A (en) * | 2018-01-16 | 2018-07-06 | 江苏泰特尔新材料科技有限公司 | A kind of method prepared with micro passage reaction to vinyl epoxy cyclohexane |
| CN108993581A (en) * | 2018-07-13 | 2018-12-14 | 浙江大学 | Load type metal polyoxy hydrochlorate hybrid catalyst and its preparation method and application |
-
2006
- 2006-12-22 CN CNA2006101349443A patent/CN101205221A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671318B (en) * | 2008-09-10 | 2011-07-20 | 山东鲁抗立科药物化学有限公司 | Cycloaliphatic epoxy resin and preparation method thereof |
| CN101734996B (en) * | 2009-12-29 | 2012-12-19 | 岳阳昌德化工实业有限公司 | Method for recycling and utilizing waste liquor containing 4-vinyl cyclohexene |
| CN101870658A (en) * | 2010-05-14 | 2010-10-27 | 东北师范大学 | Keggin polyoxometallate-based ion liquid and synthesis method thereof |
| CN101870658B (en) * | 2010-05-14 | 2013-02-13 | 东北师范大学 | Keggin polyoxometallate-based ion liquid and synthesis method thereof |
| CN102393123A (en) * | 2011-09-15 | 2012-03-28 | 无锡市超群自动化设备有限公司 | Inner rail for refrigerator sliding rail |
| CN108250163A (en) * | 2018-01-16 | 2018-07-06 | 江苏泰特尔新材料科技有限公司 | A kind of method prepared with micro passage reaction to vinyl epoxy cyclohexane |
| CN108993581A (en) * | 2018-07-13 | 2018-12-14 | 浙江大学 | Load type metal polyoxy hydrochlorate hybrid catalyst and its preparation method and application |
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Open date: 20080625 |