CN101205220A - Preparation method of methyl epichlorohydrin - Google Patents

Preparation method of methyl epichlorohydrin Download PDF

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Publication number
CN101205220A
CN101205220A CNA2006101349528A CN200610134952A CN101205220A CN 101205220 A CN101205220 A CN 101205220A CN A2006101349528 A CNA2006101349528 A CN A2006101349528A CN 200610134952 A CN200610134952 A CN 200610134952A CN 101205220 A CN101205220 A CN 101205220A
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Prior art keywords
methyl epichlorohydrin
reaction
hydrogen peroxide
catalyst
preparation
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高爽
赵公大
奚祖威
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CNA2006101349528A priority Critical patent/CN101205220A/en
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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 a methyl epichlorohydrin transferring the catalyst of epoxidation by using a Methallyl Chloride. The catalyst does not dissolve into a reaction medium, but under the effect of the hydrogen peroxide, the catalyst can dissolve into active species and further react with the Methallyl Chloride, thus leading to an epoxidation reaction under high selectivity. The Methallyl Chloride has a conversion rate of 96 percent for hydrogen peroxide, and the methyl epichlorohydrin has a selectivity of 95 percent for the Methallyl Chloride. 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 methyl epichlorohydrin 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 methyl epichlorohydrin.

Description

A kind of preparation method of methyl epichlorohydrin
Technical field
The present invention relates to the preparation method of methyl epichlorohydrin, by being catalyzer with the heteropolyacid salt compound, with the hydrogen peroxide is that oxygen source direct oxidation methylallyl chloride prepares methyl epichlorohydrin, the by product of reaction has only water, catalyzer is recyclable to be recycled, the technological line cleaning is simple, suitable industrial application.
Background technology
Methyl epichlorohydrin is a kind of important Organic Chemicals and intermediate, and its purposes is very extensive.Before and after the seventies in 20th century, the U.S., Japan and European many countries have all worked out this product in succession.Hypochlorination and saponification production technique that they adopt can produce a large amount of three wastes materials in the production process, cause environmental pollution, and the yield of product is very low, so there is not large-scale industrial production so far.Japanese Patent was once arranged, and (JP6388.44 573-575) has reported with the isopropyl benzene hydroperoxide to be the method that oxygenant is purchased methyl epichlorohydrin.Recently, one piece of Japanese Patent (JP05170,754) reported with the heteropolyacid to be catalyzer, hydrogen peroxide is an oxygen source, does in the system of solvent at toluene, obtained the optionally better result of 100% transformation efficiency and 92%, but catalyzer can't be turned one's head, and the economy of route is not high, therefore, develop a kind of eco-friendlyly, the synthetic route of the methyl epichlorohydrin of economical rationality is extremely important.
Summary of the invention
Having the object of the present invention is to provide a kind of is oxygen source with the hydrogen peroxide, with the heteropolyacid salt compounds is the method that the catalyst methylallyl chloride prepares methyl epichlorohydrin, this method can be converted into methyl epichlorohydrin with methylallyl chloride having under solvent or the solvent-free condition, catalyzer is recyclable and recycle, and methylallyl chloride is to the transformation efficiency height of hydrogen peroxide, and methyl epichlorohydrin is good to the selectivity of methylallyl chloride.
The present invention specifically provides a kind of preparation method of methyl epichlorohydrin, it is characterized in that: directly be raw material with the methylallyl chloride, with the metallic compound with reaction-controlled phase transfer catalysis effect is catalyzer, with the aqueous hydrogen peroxide solution is oxygen source, having under solvent or the condition of no solvent, methylallyl chloride is converted into methyl epichlorohydrin;
The reaction catalyst system therefor is the mixture with heteropllyacids compound of reaction control phase transition characteristics, and overall budget consists of Q mH nXM pO 4+3pWherein M is a central metal atom, is selected from 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 selected from P or As; 2≤m≤7, n=0 or 1; P=1～12;
Reaction conditions is: the molar ratio of alkene and hydrogen peroxide is 2: 1～1: 2, and the mol ratio of hydrogen peroxide and catalyzer is 50: 1～300: 1, and temperature of reaction is at 40 to 100 ℃.
Among the preparation method of methyl epichlorohydrin of the present invention, after reaction finished, catalyzer can Separation and Recovery recycle.
Among the preparation method of methyl epichlorohydrin of the present invention, employed oxygen source is the aqueous hydrogen peroxide solution of concentration between 25%～70%.
Among the preparation method of methyl epichlorohydrin of the present invention, reaction system can be solvent-free, can be solvent with halohydrocarbon, aromatic hydrocarbons also.
The preparation method of methyl epichlorohydrin of the present invention, with the hydrogen peroxide is oxygen source, with the heteropolyacid salt compounds is catalyzer, the catalysis methylallyl chloride prepares methyl epichlorohydrin, this method can be converted into methyl epichlorohydrin with methylallyl chloride having under solvent or the solvent-free condition, and catalyzer is recyclable and recycle.Methylallyl chloride reaches 96% to the transformation efficiency of hydrogen peroxide, and methyl epichlorohydrin is 95% to the selectivity of methylallyl chloride.
Embodiment
Give further instruction below by example to the present invention:
Embodiment 1
In 50mL jacketed reaction bottle, add 10g 30% aqueous hydrogen peroxide solution, the catalyzer [(n-C of 0.4g 8H 17) 4N] 3(PO 4) (MoO 3) 4], add the 15.7g methylallyl chloride,, under 65 ℃, react after 2 hours, the transformation efficiency of methylallyl chloride is 49.0%, the selectivity of methyl epichlorohydrin is 92%.This moment, catalyzer was separated out from reaction system, and catalyzer is reclaimed in centrifugal back.
Embodiment 2
In 50mL jacketed reaction bottle, add 10g 30% aqueous hydrogen peroxide solution, the catalyzer [(C of 0.4g 2H 5) 3NCH 2Ph] 2H (PO 4) (WO 3) 2.54], add the 15.7g methylallyl chloride, 15 milliliters of chloroforms, 55 ℃ of following high degree of agitation are after 4 hours, and the transformation efficiency of methylallyl chloride is 49.0%, and the selectivity of methyl epichlorohydrin is 95%.This moment, catalyzer was separated out from reaction system, and catalyzer is reclaimed in centrifugal back.
Embodiment 3
In 50mL jacketed reaction bottle, add 10g 30% aqueous hydrogen peroxide solution, the catalyzer [(n-C of 0.8g 4H 9) 4N] 3(PV 2O 16], add the 15.7g methylallyl chloride, 15 milliliters of chloroforms, 45 ℃ of following high degree of agitation are after 5 hours, and the transformation efficiency of methylallyl chloride is 47.0%, and the selectivity of methyl epichlorohydrin is 95%.This moment, catalyzer was separated out from reaction system, and catalyzer is reclaimed in centrifugal back.
Embodiment 4
In 50mL jacketed reaction bottle, add 10g 50% aqueous hydrogen peroxide solution, the catalyzer [(C of 0.6g 5H 5NC 12H 25] 3(AsO 4) (MoO 3) 11], add the 15.7g methylallyl chloride, 15 milliliters of toluene, 85 ℃ of following high degree of agitation are after 2 hours, and the transformation efficiency of methylallyl chloride is 49.0%, and the selectivity of methyl epichlorohydrin is 90%.This moment, catalyzer was separated out from reaction system, and catalyzer is reclaimed in centrifugal back.
Embodiment 5
In 50mL jacketed reaction bottle, add 10g 51.5% aqueous hydrogen peroxide solution, the catalyzer [(CH of 0.6g 3) 3C 16H 33N] 3(PO 4) (WO 3) 4], add the 15.9g methylallyl chloride, 15 milliliters of ethylene dichloride, 55 ℃ of following high degree of agitation are after 2.5 hours, and the transformation efficiency of methylallyl chloride is 49.0%, and the selectivity of methyl epichlorohydrin is 96.0%.This moment, catalyzer was separated out from reaction system, and catalyzer is reclaimed in centrifugal back.Catalyst recirculation is used 3 times the following table that the results are shown in.
Figure A20061013495200061
Above-mentioned example shows, adopt novel reaction control phase-transfer catalyst provided by the present invention, according to the condition that is provided is provided, can high-level efficiency, highly selective is converted into methyl epichlorohydrin with methylallyl chloride, catalyst reaction finishes separable the recycling in back, is an eco-friendly technological line.

Claims (4)

1. the preparation method of a methyl epichlorohydrin, it is characterized in that: directly be raw material with the methylallyl chloride, with the metallic compound with reaction-controlled phase transfer catalysis effect is catalyzer, with the aqueous hydrogen peroxide solution is oxygen source, having under solvent or the condition of no solvent, methylallyl chloride is converted into methyl epichlorohydrin;
The reaction catalyst system therefor is the mixture with heteropllyacids compound of reaction control phase transition characteristics, and overall budget consists of Q mH nXM pO 4+3pWherein M is a central metal atom, is selected from 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 selected from P or As; 2≤m≤7, n=0 or 1; P=1～12;
Reaction conditions is: the molar ratio of alkene and hydrogen peroxide is 2: 1～1: 2, and the mol ratio of hydrogen peroxide and catalyzer is 50: 1～300: 1, and temperature of reaction is at 40 to 100 ℃.
2. according to the preparation method of the described methyl epichlorohydrin of claim 1, it is characterized in that: after reaction finishes, the catalyst separating recycling use.
3. according to the preparation method of the described methyl epichlorohydrin of claim 1, it is characterized in that: employed oxygen source is the aqueous hydrogen peroxide solution of concentration between 25%～70%.
4. according to the preparation method of the described methyl epichlorohydrin of claim 1, it is characterized in that: solvent is chosen as halohydrocarbon, aromatic solvent.
CNA2006101349528A 2006-12-22 2006-12-22 Preparation method of methyl epichlorohydrin Pending CN101205220A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101987838A (en) * 2010-10-27 2011-03-23 中国石油化工股份有限公司 Method for producing epoxy chloropropane
CN101993423A (en) * 2010-10-27 2011-03-30 中国石油化工股份有限公司 Method for producing epoxy chloropropane
CN102101848A (en) * 2010-10-27 2011-06-22 中国石油化工股份有限公司 Method for producing epichlorohydrin
CN103788023A (en) * 2012-10-31 2014-05-14 中国科学院大连化学物理研究所 Method for preparing styrene oxide through epoxidation of styrene
WO2020082863A1 (en) * 2018-10-23 2020-04-30 江苏扬农化工集团有限公司 Method for preparing key intermediate of epoxy resin
CN114702463A (en) * 2022-03-29 2022-07-05 浙江皇马科技股份有限公司 Method for preparing methyl epichlorohydrin
CN116143727A (en) * 2023-02-09 2023-05-23 浙江皇马科技股份有限公司 Refining method of methyl epoxy chloropropane

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101987838A (en) * 2010-10-27 2011-03-23 中国石油化工股份有限公司 Method for producing epoxy chloropropane
CN101993423A (en) * 2010-10-27 2011-03-30 中国石油化工股份有限公司 Method for producing epoxy chloropropane
CN102101848A (en) * 2010-10-27 2011-06-22 中国石油化工股份有限公司 Method for producing epichlorohydrin
CN103788023A (en) * 2012-10-31 2014-05-14 中国科学院大连化学物理研究所 Method for preparing styrene oxide through epoxidation of styrene
CN103788023B (en) * 2012-10-31 2016-03-16 中国科学院大连化学物理研究所 A kind of method of epoxidation of styrene Styryl oxide
WO2020082863A1 (en) * 2018-10-23 2020-04-30 江苏扬农化工集团有限公司 Method for preparing key intermediate of epoxy resin
CN114702463A (en) * 2022-03-29 2022-07-05 浙江皇马科技股份有限公司 Method for preparing methyl epichlorohydrin
CN116143727A (en) * 2023-02-09 2023-05-23 浙江皇马科技股份有限公司 Refining method of methyl epoxy chloropropane

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