CN103788023B - A kind of method of epoxidation of styrene Styryl oxide - Google Patents
A kind of method of epoxidation of styrene Styryl oxide Download PDFInfo
- Publication number
- CN103788023B CN103788023B CN201210428828.8A CN201210428828A CN103788023B CN 103788023 B CN103788023 B CN 103788023B CN 201210428828 A CN201210428828 A CN 201210428828A CN 103788023 B CN103788023 B CN 103788023B
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- CN
- China
- Prior art keywords
- reaction
- edta
- vinylbenzene
- styrene
- styryl oxide
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
The invention provides a kind of novel method of styrene oxidation Styryl oxide, with H
2o
2for oxygen source, application response control phase transfer catalysis system, using toluene, tributyl phosphate, acetonitrile, ethylene dichloride, ethyl acetate wherein one or both mixing as solvent, using ethylenediamine tetraacetic acid (EDTA) (EDTA) as auxiliary agent and stablizer.The method flow process is simple, and environmental protection is gentle, is the novel environment-friendly process of a high reactivity, highly selective.
Description
Technical field
The present invention relates to catalyzed oxidation field, be specifically related to a kind of method of catalyzed oxidation vinylbenzene Styryl oxide.
Background technology
Styrene oxide 98min., also known as Styryl oxide, is a kind of important organic synthesis intermediate, is widely used in organic synthesis, medicine preparation and production of flavor etc.Can be used as epoxy resin diluent, UV-absorption agent, sweetener etc.And Styryl oxide can prepare bata-phenethyl alcohol with hydrogen addition further under catalyst action, its effect widely, can be used for, in floral type daily essence, also can be used in food; The important intermediate of Styryl oxide or synthetic hydrochloric acid LEVAMISOLE HCL, R-12564 is all spendable broad spectrum anthelmintic of a kind of humans and animals.Be that the market requirement increases year after year to Styryl oxide, therefore, the suitability for industrialized production of Styryl oxide receives much attention.
The production method of conventional epoxy phenylethane is bromohydrin method, and it is serious that this method exists equipment corrosion, produces the problems such as a large amount of brominated waste water, is a kind of urgency production technique to be modified.
In recent years, mainly start with in oxygen source, catalyzer etc. in research epoxidation of styrene process.Wherein, H
2o
2a kind of ideal oxygen source, cheap and easy to get comparatively speaking as oxygenant using it, and also " active oxygen " content is high, and reacted by product is only water, non-environmental-pollution.Therefore, with H
2o
2for the vinylbenzene catalysis epoxidation research of oxygen source constantly comes into one's own, the catalyst system developed is divided into even phase system and heterogeneous system two class substantially.[document 1: Ding Liqin, Zhang Juntao, Liang Shengrong, Wang little Quan, the Research advance in catalysts for production of Styrene oxide 98min. is prepared in epoxidation of styrene reaction.Xi'an Petroleum University's journal, 2011, Vol.26, No.4,71-77.] and there is active low, the problem such as selectivity is not high in heterogeneous catalytic system; And there is separation aftertreatment difficulty in even phase reaction system, this seminar of problem such as be difficult to recycle and research and develop a class reaction control phase transfer catalyst in calendar year 2001, this catalyzer is even phase in reaction process, separate out with the form of heterogeneous catalyst again after reaction, have the feature of even phase catalyst high-activity high-selectivity and the easily separated recycling use of heterogeneous catalyst concurrently.[document 2:Xi, Z.W; Zhou, N.; Sun, Y.; Li, K.L., Reaction-controlledphase-transfercatalysisforpropyleneep oxidationtopropyleneoxide.Science2001,292,1139-1141.] with H
2o
2for oxygen source, under the reaction-controlled phase transfer catalysis system condition that this seminar develops, the research of Styrene oxide 98min. synthesizing epoxy phenylethane, has been reported [document 3: Liu Junhui, Li Jun, Zhang Aiping, Liu Junlong, invigorating, reaction-controlled phase transfer catalysis epoxidation vinyl benzene.Applied chemistry, 2010, Vol.27, No.7,769-772.] and, the feature of such reaction is that catalytic activity is good, non-environmental-pollution produce raw, and reaction conditions is gentle, meets the requirement of green chemistry.But the feature that vinylbenzene is easily polymerized, makes cinnamic add-on in reaction process too greatly, otherwise easily can not produce a large amount of by products in reaction process, and makes troubles to aftertreatment.Further, the easy open loop of product Styryl oxide and polymerization in reaction process, also make selectivity can not reach the requirement of industrial applications.Institute in this approach, needs to study further.
Summary of the invention
The object of the invention is the deficiency overcoming the styrene catalyzed Styryl oxide processed of above-mentioned reaction-controlled phase-transfer system.There is provided a kind of novel method of styrene oxidation Styryl oxide, application response controls phase transfer catalysis system, with H
2o
2for oxygen source, with ethylenediamine tetraacetic acid (EDTA) (EDTA) for auxiliary agent and stablizer.The method flow process is simple, and environmental protection is gentle, is the novel environment-friendly process of a high reactivity, highly selective.
In order to achieve the above object, technical scheme of the present invention is: with H
2o
2for oxygen source, be mixed into solvent catalysis styrene oxidation Styryl oxide with one or both in toluene, tributyl phosphate, acetonitrile, ethylene dichloride, ethyl acetate.
Temperature of reaction of the present invention is 30 ° of C ~ 90 ° C, and the reaction times is 2 ~ 8 hours.Preferred temperature of reaction is 40 ° of C ~ 80 ° C, and the preferred reaction times is 3 ~ 6 hours.
Auxiliary agent of the present invention and stablizer are ethylenediamine tetraacetic acid (EDTA) (EDTA), wherein vinylbenzene: EDTA=30:1 ~ 3:1(mol ratio).
Inventory of the present invention, wherein vinylbenzene: H2O2=3:1 ~ 1:1(mol ratio).
Hydrogen peroxide of the present invention, its mass concentration is 30% ~ 50%.
After reaction terminates, by reaction system cool to room temperature, centrifugation goes out catalyzer, and catalyzer is capable of circulation to be reused.Further, stable high reactivity is kept.
Due to the utilization of above-mentioned technology, the present invention compared with prior art has following advantages:
1, use reaction control phase transfer catalyst, make the catalyzer applying small amount can reach very high reactive behavior and can be recycled, have the advantage of heterogeneous and even phase catalyst concurrently.
2, make used additives and stablizer, make the larger raising of Styryl oxide selectivity.
3, H is used
2o
2for oxygen source, under the effect of auxiliary agent and stablizer, make vinylbenzene and H
2o
2material ratio, when 1 ~ 3 mole: 1 mole, obtains very high activity, more meets Atom economy requirement.
Embodiment
Specific embodiment of the invention step is described in detail below by some embodiments, should by these embodiments as scope of the invention restriction.
The catalyzer used in embodiment is the phosphorus heteropoly tungstic acid compounds catalyzer mentioned in the patent ZL01123653.1 of Dalian Chemical Physics Research Institute's independent research, and its composition can be expressed as (Q
mh
nxM
po
4+3p), Q is cationic moiety, available [R
1r
2r
3r
4n
+] represent, wherein R
1, R
2, R
3, R
4for H-, C
1-C
20alkyl, cycloalkyl, the benzyl of straight or branched; Or R
1r
2r
3r
4n is pyridine and homologue thereof.Atom centered by M is Mo, W or V atoms metal.X is heteroatoms, is P or As.2≤m≤7, n=0 or 1, P=2,3,4.
[embodiment 1] different solvents reaction result
In 100ml single port flask, add vinylbenzene 15mmol, H
2o
210mmol(hydrogen peroxide mass concentration is 50%), solvent 20ml, catalyzer [(C
2h
5)
3nCH
2ph]
2hAsMo
2o
100.1mmol and EDTA5mmol, stirring reaction at 70 ° of C temperature, reaction 6h, centrifugation goes out solid catalyst, obtains product Styryl oxide, and organic phase carries out GC Qualitative and quantitative analysis, and reaction result is in table one.(transformation efficiency is based on H
2o
2add-on calculates)
Table one different solvents reaction result
As can be seen from Table I, under the effect of EDTA auxiliary agent, for the solvent in table, catalyzer all maintains higher activity, and has higher catalyst recovery yield.
[embodiment 2]
In 100ml single port flask, add vinylbenzene 30mmol, H
2o
210mmol(hydrogen peroxide mass concentration is 50%), solvent ethyl acetate 20ml, catalyzer [(CH
3)
3nCH
2ph]
7pV
4o
160.1mmol and EDTA1mmol, stirring reaction at 70 ° of C temperature, reaction 6h, centrifugation goes out solid catalyst, obtains product Styryl oxide, and organic phase carries out GC Qualitative and quantitative analysis, and reaction result is in table two.(transformation efficiency is based on H
2o
2add-on calculates)
[embodiment 3]
In 100ml single port flask, add vinylbenzene 10mmol, H
2o
210mmol(hydrogen peroxide mass concentration is 30%), solvent ethylene dichloride 20ml, catalyzer [(C
2h
5)
3nCH
2ph]
2hAsMo
2o
100.09mmol and EDTA2mmol, stirring reaction at 60 ° of C temperature, reaction 7h, centrifugation goes out solid catalyst, obtains product Styryl oxide, and organic phase carries out GC Qualitative and quantitative analysis, and reaction result is in table two.(transformation efficiency is based on H
2o
2add-on calculates)
[embodiment 4]
In 100ml single port flask, add vinylbenzene 20mmol, H
2o
210mmol(hydrogen peroxide mass concentration is 50%), solvent ethyl acetate 20ml, catalyzer [(CH
3)
3nCH
2ph]
7pV
4o
160.09mmol and EDTA3mmol, stirring reaction at 70 ° of C temperature, reaction 6h, centrifugation goes out solid catalyst, obtains product Styryl oxide, and organic phase carries out GC Qualitative and quantitative analysis, and reaction result is in table two.(transformation efficiency is based on H
2o
2add-on calculates)
Table two
| Embodiment | Transformation efficiency | Selectivity | The Cat rate of recovery |
| Embodiment 2 | 93% | 97% | 91% |
| Embodiment 3 | 90% | 92% | 90% |
| Embodiment 4 | 94% | 95% | 92% |
As can be seen from Table II, under EDTA effect, the change of vinylbenzene add-on, and the change of hydrogen peroxide mass concentration, all little on the impact of reaction result.Not because cause the decomposition of epoxy product because hydrogen peroxide mass concentration reduces the more water yield of introducing, or bring other side reaction because concentration of styrene increases.
[embodiment 5]
In 100ml single port flask, add vinylbenzene 15mmol, H
2o
210mmol(hydrogen peroxide mass concentration is 50%), solvent ethyl acetate 20ml, catalyzer [(CH
3)
3nCH
2ph]
7pV
4o
160.1mmol and EDTA2mmol, stirring reaction at 70 ° of C temperature, reaction 6h, obtain product Styryl oxide, centrifugal rear organic phase carries out GC Qualitative and quantitative analysis, isolates solid catalyst, carries out five circulating reactions.Reaction result is in table three.(transformation efficiency is based on H
2o
2add-on calculates)
Table three circulating reaction result
| Reaction times | Transformation efficiency | Selectivity | The Cat rate of recovery |
| Fresh reactant | 96% | 95% | 90% |
| Circulating reaction 1 time | 95% | 97% | 92% |
| Circulating reaction 2 times | 95% | 95% | 90% |
| Circulating reaction 3 times | 94% | 95% | 91% |
| Circulating reaction 4 times | 94% | 94% | 90% |
| Circulating reaction 5 times | 92% | 94% | 89% |
As can be seen from Table III, by adding EDTA, not only serving the effect of auxiliary agent, in circulating reaction process, also serving the effect of stablizer, stabilize the activity of catalyzer, make catalyzer in circulating reaction still keep high reactivity and highly selective.
[comparative example 1]
In 100ml single port flask, add vinylbenzene 30mmol, H
2o
210mmol(hydrogen peroxide mass concentration is 30%), solvent ethyl acetate 20ml and catalyzer [(CH
3)
3nCH
2ph]
7pV
4o
160.1mmol, stirring reaction at 65 ° of C temperature, reaction 5h, centrifugation goes out solid catalyst, obtains product Styryl oxide, and organic phase carries out GC Qualitative and quantitative analysis, and reaction result is in table four.(transformation efficiency is based on H
2o
2add-on calculates)
[comparative example 2]
In 100ml single port flask, add vinylbenzene 10mmol, H
2o
210mmol(hydrogen peroxide mass concentration is 30%), solvent ethylene dichloride 20ml and catalyzer [(C
2h
5)
3nCH
2ph]
2hAsMo
2o
100.09mmol, stirring reaction at 65 ° of C temperature, reaction 5h, centrifugation goes out solid catalyst, obtains product Styryl oxide, and organic phase carries out GC Qualitative and quantitative analysis, and reaction result is in table four.(transformation efficiency is based on H
2o
2add-on calculates)
Table four comparative example reaction result
| Embodiment | Transformation efficiency | Selectivity | The Cat rate of recovery |
| Comparative example 1 | 84% | 84% | 82% |
| Comparative example 2 | 85% | 86% | 80% |
Can be found out by comparative example, when not adding EDTA as auxiliary agent and stablizer, reaction result significantly reduces.Thus EDTA vital role is in the reaction described.
Claims (8)
1. a method for epoxidation of styrene Styryl oxide, with H
2o
2for oxygen source, application response controls phase transfer catalysis system, under organic solvent exists, using edta edta as auxiliary agent and stablizer; Styrene catalyzed oxidation Styryl oxide processed;
Described reaction-controlled phase transfer catalysis system is phosphorus heteropoly tungstic acid compounds Q
mh
nxM
po
4+3p, Q is cationic moiety, with [R
1r
2r
3r
4n
+] represent, wherein R
1, R
2, R
3, R
4for H-, C
1-C
20alkyl, cycloalkyl, the benzyl of straight or branched; Or, R
1r
2r
3n is pyridine and homologue thereof;
Atom centered by M is Mo, W or V atoms metal; X is heteroatoms, is P or As; 2≤m≤7, n=0 or 1, P=2,3,4.
2. in accordance with the method for claim 1, it is characterized in that: be wherein auxiliary agent and stablizer with edta edta, the mol ratio=30:1 ~ 3:1 of vinylbenzene: EDTA.
3. in accordance with the method for claim 1, it is characterized in that: wherein said organic solvent is one or more mixing in toluene, tributyl phosphate, acetonitrile, ethylene dichloride, ethyl acetate.
4. according to the method described in claim 1, it is characterized in that: wherein said temperature of reaction 30 DEG C ~ 90 DEG C, the reaction times is 2 ~ 8 hours.
5. in accordance with the method for claim 4, it is characterized in that: preferred temperature of reaction is 40 DEG C ~ 80 DEG C, and the preferred reaction times is 3 ~ 6 hours.
6. in accordance with the method for claim 1, it is characterized in that: wherein vinylbenzene: H
2o
2mol ratio=3:1 ~ 1:1.
7. according to the method described in claim 1 or 6, it is characterized in that: the hydrogen peroxide mass concentration wherein used is 30% ~ 50%.
8. according to the method described in claim 1 or 3, it is characterized in that: as vinylbenzene 10-50mmol, the consumption 10 ~ 100ml of organic solvent.
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|---|---|---|---|
| CN201210428828.8A CN103788023B (en) | 2012-10-31 | 2012-10-31 | A kind of method of epoxidation of styrene Styryl oxide |
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|---|---|---|---|
| CN201210428828.8A CN103788023B (en) | 2012-10-31 | 2012-10-31 | A kind of method of epoxidation of styrene Styryl oxide |
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| CN103788023B true CN103788023B (en) | 2016-03-16 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315307A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院大连化学物理研究所 | Method for catalytically synthesizing L-cis-1,2-epoxypropylphosphonic acid-D-alpha-phenylethylamine by using phosphotungstic heteropoly acid phase transfer catalyst |
| CN105618138B (en) * | 2014-10-29 | 2018-01-09 | 中国科学院大连化学物理研究所 | Solid-carrying type phosphorus heteropoly tungstic acid catalyzer and its application |
| CN104817097B (en) * | 2015-05-05 | 2017-05-10 | 南通市海圣药业有限公司 | Recycling and reusing method of sodium bromide in synthesis process of styrene oxide |
| CN106631887B (en) * | 2016-10-19 | 2018-03-20 | 杨绮红 | A kind of preparation technology of (1R, 2S) 1 cyano group 2 (3,4 difluorophenyl) cyclopropane |
| CN113117755B (en) * | 2021-04-14 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method and application of molybdenum catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3248404A (en) * | 1962-08-11 | 1966-04-26 | Dehydag Deutsche Hydriewerke G | Novel epoxidation process |
| CN1197069A (en) * | 1997-04-18 | 1998-10-28 | 林德股份公司 | Method of preparing epoxide from olefines |
| CN1401425A (en) * | 2001-08-27 | 2003-03-12 | 中国科学院大连化学物理研究所 | Phase-transfer catalyst for control of oxidizing reaction and oxidizing reaction procedure |
| CN101205220A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of methyl epichlorohydrin |
| CN101205219A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of epoxypropane |
-
2012
- 2012-10-31 CN CN201210428828.8A patent/CN103788023B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3248404A (en) * | 1962-08-11 | 1966-04-26 | Dehydag Deutsche Hydriewerke G | Novel epoxidation process |
| CN1197069A (en) * | 1997-04-18 | 1998-10-28 | 林德股份公司 | Method of preparing epoxide from olefines |
| CN1401425A (en) * | 2001-08-27 | 2003-03-12 | 中国科学院大连化学物理研究所 | Phase-transfer catalyst for control of oxidizing reaction and oxidizing reaction procedure |
| CN101205220A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of methyl epichlorohydrin |
| CN101205219A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Preparation method of epoxypropane |
Non-Patent Citations (2)
| Title |
|---|
| Reaction-Controlled Phase Transfer Catalysis for Styrene Epoxidation to Styrene Oxide with Aqueous Hydrogen Peroxide;Xiaoge Yang et al;《Organic Process Research & Development》;20050326;第9卷(第3期);第294-296页 * |
| 反应控制相转移催化环氧化苯乙烯;刘军辉 等;《应用化学》;20100710;第27卷(第7期);第769-771页 * |
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