CN101691363A - Method for preparing epoxy cyclohexane through catalytic epoxidation of cyclohexene - Google Patents
Method for preparing epoxy cyclohexane through catalytic epoxidation of cyclohexene Download PDFInfo
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- CN101691363A CN101691363A CN200910308578A CN200910308578A CN101691363A CN 101691363 A CN101691363 A CN 101691363A CN 200910308578 A CN200910308578 A CN 200910308578A CN 200910308578 A CN200910308578 A CN 200910308578A CN 101691363 A CN101691363 A CN 101691363A
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- epoxy cyclohexane
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Abstract
The invention relates to a method for preparing a fine chemical intermediate, in particular to a method for preparing epoxy cyclohexane through catalytic epoxidation of cyclohexene, which comprises the steps of: taking a synthetic Ti-Si molecular sieve as a catalyst, using an alkaline assistant, controlling the reaction temperature, stirring to react, reacting hydrogen peroxide and the cyclohexene in an organic solvent to obtain epoxy cyclohexane, and then carrying out separation and purification to obtain the epoxy cyclohexane. The reaction time of the invention is between 1 and 48 hours, the single pass conversion rate of the cyclohexene can reach over 40 percent, the selectivity of the epoxy cyclohexane can reach 96 percent, and the utilization rate of the hydrogen peroxide can reach 98 percent. The catalyst can be recovered for repeated use.
Description
Technical field
The present invention relates to the preparation method of fine-chemical intermediate, refer in particular to a kind of method of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene.
Background technology
Epoxy cyclohexane is a kind of important fine-chemical intermediate, has a wide range of applications in fields such as agricultural chemicals, medicine, materials.
As epoxy cyclohexane and the reaction of contraposition tert.-butyl phenol, generate 2-(4-tertiary butyl phenoxy group) hexalin, but react the organosulfur acaricide propargite of synthesizing efficient, low toxicity, wide spectrum, lasting period length, no teratogenesis carcinogenesis again with sulfur oxychloride and propiolic alcohol.
Epoxy cyclohexane and the reaction of contraposition tert.-butyl phenol, hydrogenation can generate 2-(4-tertiary butyl phenoxy group) hexalin then, in plastic working, have plasticising and fire retardation with the phosphoric acid ester made from phosphorus trichloride reaction again, can be used in zylonite, varnish, synthetic rubber, the thermosetting resin excellent property.
Epoxy cyclohexane can be used as the reactive thinner of Resins, epoxy in caking agent.This is to belong to reaction diluent, and in epoxy resin cure, itself also the epoxy group(ing) ring-opening polymerization can take place, and becomes the integral part in the network structure polymer.But epoxy cyclohexane and organic amine reaction synthetic epoxy resin solidifying agent except good curing performance, also have modifying function.
Adopted the distillatory method from the tankage of cyclohexane oxidation, to separate and obtained epoxy cyclohexane [CN1106784A], be domestic first release the epoxy cyclohexane product, but can not satisfy the demand of market development.From aspect the tetrahydrobenzene synthesis epoxy cyclohexane continuous exploration is being arranged in recent years.The characteristics that tetrahydrobenzene is produced method [CN1401640] description of epoxy cyclohexane with the reaction control phase transfer catalyst catalysis epoxidation are these class catalyst themselves, be insoluble in the reaction medium, but under the effect of hydrogen peroxide, can form the active specy that dissolves in the reaction medium, when hydrogen peroxide has been consumed, catalyzer promptly returns to initial structure and separates out from reaction system.The tertiary mixture that this method develops into benzene, hexanaphthene, tetrahydrobenzene arbitrary proportion is raw material [CN1880310] preparation epoxy cyclohexane.Production run finds that this catalyzer is difficult to guarantee steady running, the production cost height.
The employing tetrahydrobenzene is that raw material, molecular oxygen are intermediary [CN1542007] as oxygen source, valeraldehyde or isovaleric aldehyde or isobutyric aldehyde, aldehyde, alkene mole proportioning are 0.1～3: 1, adding is by one of oxide compound of manganese or iron or cobalt or nickel at least, one of oxide compound, the composite catalyzer that forms of one of oxygen acid of nitrogen or phosphorus or arsenic at least of molybdenum or tungsten at least, being under 30 ℃～80 ℃ of the temperature, reacted 2 hours～12 hours.Catalyst compounded peroxy acid, while catalysis peroxy acid and the tetrahydrobenzene of formoxy-can being turned in same reactor that this method is used reacts, and obtains epoxy cyclohexane.The catalyzer cost height of this method, the single of raw material changes low.
Be that the method that raw material is produced epoxy cyclohexane also is suggested [CN1724 524] with the hexanaphthene, this method becomes cyclohexyl hydroperoxide with cyclohexane oxidation earlier, add tetrahydrobenzene again and carry out epoxidation reaction, generate epoxy cyclohexane and hexalin, and dehydration of cyclohexanol generates tetrahydrobenzene, be used as one of raw material of epoxidation reaction, since the diversity of cyclohexane oxidation, the raw material consumption height of this method.There are problems such as the not high and aftertreatment of selectivity is loaded down with trivial details in someone's no-solvent process [CN101020 669] of metal-salt and consisting of phase-transferring agent composite catalyzing epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide that proposes to overuse in the recent period.
The classical chlorohydrination of relevant synthesizing epoxy compound, organo-peroxide oxidation style can be from the tetrahydrobenzene synthesis epoxy cyclohexanes, but exist Atom economy low and consume big shortcoming.
Summary of the invention
The objective of the invention is to be improved, innovate at shortcoming that exists in the background technology and problem, provide and utilize hydrogen peroxide catalyzed tetrahydrobenzene process for epoxidation, so that the production of epoxy cyclohexane further meets a kind of method of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene of the target call of Green Chemistry and cleaner production.
The inventive method is as follows:
Make catalyzer with the synthetic HTS, use alkaline assistant, control reaction temperature, stirring reaction makes the reaction of hydrogen peroxide and tetrahydrobenzene generate epoxy cyclohexane in organic solvent, and separating then purifies makes epoxy cyclohexane.
The HTS that the present invention uses has the MFI structure, and its preparation process is seen: CN1132699C.
Use alkaline assistant to comprise yellow soda ash in the reaction of the present invention, sodium bicarbonate, salt of wormwood, saleratus, sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, potassiumphosphate, inorganic salts such as dipotassium hydrogen phosphate and potassium primary phosphate compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, strontium hydroxide, inorganic base such as hydrated barta and calcium hydroxide compound, metal carboxylate such as sodium acetate and potassium acetate compound, urea, ethanamide, pyrazine, methylpyrazine, pyridine, picoline, ammonia, Monomethylamine, dimethylamine, Trimethylamine 99, monoethylamine, diethylamine, organic bases such as triethylamine and piperidines compounds uses one or more alkaline assistants in reaction.
The solvent that uses in the reaction of the present invention is alcoholic solvents such as methyl alcohol, ethanol, ketones solvents such as acetone, butanone, nitrile solvents such as acetonitrile, propionitrile, wherein a kind of or their mixture as solvent.
The solvent that uses in the reaction of the present invention and the volume ratio of tetrahydrobenzene are 1: 1 to 20: 1.
The amount ratio of hydrogen peroxide that uses in the reaction of the present invention and tetrahydrobenzene is 5: 1 to 1: 8, the concentration 10-50% of hydrogen peroxide.
In the reaction of the present invention hydrogen peroxide is added drop-wise in the reactor, the dropping time is 1-20 hour.
The reaction times of using in the reaction of the present invention is 1-48 hour.
The temperature of reaction of using in the reaction of the present invention is 0-100 ℃, is preferably 30-80 ℃.
It is that raw material, industrial hydrogen peroxide are oxygenant that the present invention adopts tetrahydrobenzene, in reaction, use one or more alkaline assistants, one or more that select alcohol, ketone, nitrile for use are solvent, the volume ratio of solvent and tetrahydrobenzene is 1: 1 to 20: 1, and the amount ratio of hydrogen peroxide and tetrahydrobenzene is 5: 1 to 1: 8, the concentration 10-50% of hydrogen peroxide, hydrogen peroxide is added drop-wise in the reactor, the dropping time is 1-20 hour, and temperature of reaction is 0-100 ℃, is preferably 30-80 ℃.Reaction times is 1-48 hour, and the tetrahydrobenzene per pass conversion can reach more than 40%, and the epoxy cyclohexane selectivity can reach 96%, and the hydrogen peroxide utilization ratio reaches 98%.The recyclable repeated use of catalyzer.
Embodiment
Embodiment 1:
800 milliliters of acetone and 1 mole of tetrahydrobenzene are mixed in reaction flask with 10 gram HTS, add Sodium phosphate dibasic 2 grams, be warmed up to 60 ℃ constant, with 2 hours 1 mole of hydrogen peroxide is dripped, reacted 6 hours.
Embodiment 2:
1200 milliliters of acetone and 1.5 moles of tetrahydrobenzene are mixed in reaction flask with 15 gram HTS, add yellow soda ash 2 grams, be warmed up to 50 ℃ constant, with 2 hours 1.5 moles of hydrogen peroxide are dripped, reacted 25 hours.
Embodiment 3:
1200 milliliters of acetone and 3.0 moles of tetrahydrobenzene are mixed in reaction flask with 15 gram HTS, add sodium bicarbonate 3 grams, be warmed up to 50 ℃ constant, with 2 hours 1.5 moles of hydrogen peroxide are dripped, reacted 8 hours.
Embodiment 4:
600 milliliters of acetone, 200 milliliters of acetonitriles and 1 mole of tetrahydrobenzene are mixed in reaction flask with 10 gram HTS, add Sodium phosphate dibasic 2 grams, be warmed up to 60 ℃ constant, with 2 hours 1 mole of hydrogen peroxide is dripped, reacted 8 hours.
Embodiment 5:
600 milliliters of butanone, 10 milliliters of diethylamine and 1 mole of tetrahydrobenzene are mixed in reaction flask with 10 gram HTS, be warmed up to 70 ℃ constant, with 2 hours 1 mole of hydrogen peroxide is dripped, reacted 8 hours.
Table one, epoxy cyclohexane compound experiment data
Embodiment of the present invention only is the description that preferred implementation of the present invention is carried out; be not that design of the present invention and scope are limited; do not breaking away under the preceding topic of design philosophy of the present invention; engineering technical personnel make technical scheme of the present invention in this area various modification and improvement; all should fall into protection scope of the present invention; the technology contents that the present invention asks for protection all is documented in claims.
Claims (8)
1. the method for a preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene, it is characterized in that: make catalyzer with the synthetic HTS, use alkaline assistant, control reaction temperature, stirring reaction, make the reaction of hydrogen peroxide and tetrahydrobenzene generate epoxy cyclohexane in organic solvent, separating then purifies makes epoxy cyclohexane.
2. the method for a kind of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene according to claim 1, it is characterized in that the alkaline assistant that uses including, but not limited to yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, potassiumphosphate, inorganic salts such as dipotassium hydrogen phosphate and potassium primary phosphate compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, strontium hydroxide, inorganic base such as hydrated barta and calcium hydroxide compound, metal carboxylate such as sodium acetate and potassium acetate compound, urea, ethanamide, pyrazine, methylpyrazine, pyridine, picoline, ammonia, Monomethylamine, dimethylamine, Trimethylamine 99, monoethylamine, diethylamine, organic bases such as triethylamine and piperidines compounds uses one or more alkaline assistants in reaction.
3. the method for a kind of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene according to claim 1, it is characterized in that employed solvent is including, but not limited to alcoholic solvents such as methyl alcohol, ethanol, ketones solvent such as acetone, butanone, nitrile solvents such as acetonitrile, propionitrile, wherein a kind of or their mixture as solvent.
4. the method for a kind of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene according to claim 1, the volume ratio that it is characterized in that employed solvent and tetrahydrobenzene is 1: 1 to 20: 1.
5. the method for a kind of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene according to claim 1, the amount ratio that it is characterized in that employed hydrogen peroxide and tetrahydrobenzene is 5: 1 to 1: 8, the concentration 10-50% of hydrogen peroxide.
6. the method for a kind of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene according to claim 1 is added drop-wise to hydrogen peroxide in the reactor in the reaction that it is characterized in that being carried out, and the dropping time is 1-20 hour.
7. the method for a kind of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene according to claim 1, the reaction times in it is characterized in that reacting is 1-48 hour.
8. the method for a kind of preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene according to claim 1, the temperature of reaction of using in it is characterized in that reacting is 0-100 ℃, is preferably 30-80 ℃.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675249A (en) * | 2012-05-07 | 2012-09-19 | 华东师范大学 | Method for synthesizing epoxide by catalysis of titanium-silicon molecular sieve |
| CN102766115A (en) * | 2012-07-03 | 2012-11-07 | 中国平煤神马能源化工集团有限责任公司 | Method for producing epoxycyclohexane with fixed bed reactor |
| CN103130749A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Method for preparing cyclohexene oxide through oxidation of cyclohexene |
| CN103554059A (en) * | 2013-11-05 | 2014-02-05 | 湖南化工职业技术学院 | Method for synthetizing 1,2-cyclopentene oxide by novel titanium silicalite (HTS)-1/ligand catalytic cyclopentene |
| CN103896880A (en) * | 2012-12-26 | 2014-07-02 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
| CN104803951A (en) * | 2015-05-15 | 2015-07-29 | 南京工业大学 | Method for preparing high-quality epoxy cyclohexane by adopting micro-flow field reaction technology |
| CN105523983A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Oxidation method for tert-butyl alcohol |
| CN105524023A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Cyclohexene oxidation method |
| CN106914274A (en) * | 2017-03-29 | 2017-07-04 | 西北大学 | With nanoscale twins from multi-stage porous HTS of delaminated structure and its preparation method and application |
-
2009
- 2009-10-21 CN CN200910308578A patent/CN101691363A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130749B (en) * | 2011-11-29 | 2015-12-02 | 岳阳昌德化工实业有限公司 | A kind of cyclohexene oxide prepares the method for epoxy cyclohexane |
| CN103130749A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Method for preparing cyclohexene oxide through oxidation of cyclohexene |
| CN102675249A (en) * | 2012-05-07 | 2012-09-19 | 华东师范大学 | Method for synthesizing epoxide by catalysis of titanium-silicon molecular sieve |
| CN102766115A (en) * | 2012-07-03 | 2012-11-07 | 中国平煤神马能源化工集团有限责任公司 | Method for producing epoxycyclohexane with fixed bed reactor |
| CN102766115B (en) * | 2012-07-03 | 2014-08-13 | 中国平煤神马能源化工集团有限责任公司 | Method for producing epoxycyclohexane with fixed bed reactor |
| CN103896880A (en) * | 2012-12-26 | 2014-07-02 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
| CN103896880B (en) * | 2012-12-26 | 2016-01-06 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
| CN103554059A (en) * | 2013-11-05 | 2014-02-05 | 湖南化工职业技术学院 | Method for synthetizing 1,2-cyclopentene oxide by novel titanium silicalite (HTS)-1/ligand catalytic cyclopentene |
| CN103554059B (en) * | 2013-11-05 | 2015-04-08 | 湖南化工职业技术学院 | Method for synthetizing 1,2-cyclopentene oxide by novel titanium silicalite (HTS)-1/ligand catalytic cyclopentene |
| CN105523983A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Oxidation method for tert-butyl alcohol |
| CN105524023A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Cyclohexene oxidation method |
| CN105524023B (en) * | 2014-09-29 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method of cyclohexene oxide |
| CN104803951A (en) * | 2015-05-15 | 2015-07-29 | 南京工业大学 | Method for preparing high-quality epoxy cyclohexane by adopting micro-flow field reaction technology |
| CN106914274A (en) * | 2017-03-29 | 2017-07-04 | 西北大学 | With nanoscale twins from multi-stage porous HTS of delaminated structure and its preparation method and application |
| CN106914274B (en) * | 2017-03-29 | 2019-08-02 | 西北大学 | With nanoscale twins from the multi-stage porous Titanium Sieve Molecular Sieve and its preparation method and application of delaminated structure |
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Open date: 20100407 |