CN1019015B - Process for producing catalyzer of olefin epoxidation reaction - Google Patents
Process for producing catalyzer of olefin epoxidation reactionInfo
- Publication number
- CN1019015B CN1019015B CN 89108700 CN89108700A CN1019015B CN 1019015 B CN1019015 B CN 1019015B CN 89108700 CN89108700 CN 89108700 CN 89108700 A CN89108700 A CN 89108700A CN 1019015 B CN1019015 B CN 1019015B
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- reaction
- molybdenum
- catalysts
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- imido grpup
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a process for preparing organic soluble catalysts of epoxides from the reaction of olefin with alkyl hydrogen peroxide. The present invention has a structural formula disclosed in the specification. The catalyst has the advantages of easy and economic preparation; in addition, epoxidation reaction can be carried out under the condition that the feeding ratio of propene to tert-butyl hydroperoxide is 1.5: 1 (weight ratio); the conversion rate of the tert-butyl hydroperoxide is 100%, and the selectivity of generated epoxy propane is 94%.
Description
The present invention relates to class alkene and alkyl peroxide reaction system epoxy compounds catalyzer and preparation method.
Kollar is at its patent of invention U.S.3,351, the process that the reaction of propylene and unsaturated homologue thereof and alkyl peroxide generates propylene oxide and other epoxide has been described in 635, in this process, propylene or other alkene and alkyl peroxide are in the presence of the metallic compound (as the complex compound of molybdenum) of-solubility, and propylene oxide or other epoxy compoundss are produced in reaction in liquid phase.The transformation efficiency of alkyl peroxide is the highest can to reach 100%, and simultaneously, the selectivity that generates propylene oxide also can reach 95%, but this result obtains when reacting in varsol.Usually increase the propylene consumption to replace other varsols, propylene and reinforcedization of alkyl peroxide (weight ratio) will just can obtain result preferably above 2: 1 simultaneously, here the activity of molybdenum catalyst and other performances, as the solubility property in reaction medium and stability with decisive role.
About the catalyzer of alkene and alkyl peroxide reaction system epoxy compounds had many patent reports.For example, Haystron etc. (U.S.3,991,090) make the catalyzer that solubility contains molybdenum with molybdic oxide and the reaction of adjacent glycol,
It is compared with other catalyzer, has improved moving character and the productive rate that has improved product, and it can strengthen stabilization of peroxide and improve generating product selectivity greatly, and weak point is the less stable of catalyzer.
(U.S.4 such as Shun, 607,113) disclose another and removed a kind of novel soluble complex compound catalyst that makes under the condition of anhydrating by molybdic oxide and two (glycol ether) ether, the stability of its catalyzer is better relatively, active high, but preparation catalyzer process is complicated, and the preparation of part is also complicated, and price is more expensive.In addition, also have other various types of molybdenum catalysts, their general all unstable depositions of easily decomposing in reaction medium, perhaps the solubleness in reaction medium is very low, those molybdenum content height particularly, dissolve in the more difficult realization industrialization of Preparation of catalysts of organic solvent, and cost an arm and a leg, and the feed molar ratio (weight ratio) that has alkene in catalytic epoxidation and alkyl peroxide only is higher than 2: 1 and just can obtains high transformation efficiency and selectivity.
The objective of the invention is to avoid the weak point of above-mentioned prior art and provide a kind of alkene and alkyl peroxide to react make epoxy compounds Preparation of catalysts method, with the catalyzer of present method preparation solubleness height in organic solvent, active good not only, the content of molybdenum component is also higher, and is difficult for decomposing deposition in reaction medium.
Catalyzer of the present invention has following structure:
R wherein
1, R
2, R
3, R
4, R
6, R
7, R
8, R
9, R
10, R
11, R
12, R
13In each group can be identical, also can be different, can be hydrogen atom, also can be the alkyl that contains 1-6 carbon atom, R
5Can be hydrogen atom or the alkyl that contains 1-10 carbon atom.In structure formula I and (II), R wherein
1, R
6And R
10Be alkyl, substituted alkyl or the aryl that contains 1-6 carbon, all the other groups can be hydrogen atoms, also can be the alkyl that contains 1-6 carbon.If R
1, R
6, R
10Be methyl, all the other groups are hydrogen atom, are β, β-imines dipropoxy molybdenum dioxide and β, β, β-nitrilo base tripropoxy hydroxyl oxidize molybdenum (VI).
In structure formula I and (II), R wherein
1-R
13All groups also can be hydrogen atom, are β, β-imines diethoxy dioxy base molybdenum and β, β, β nitrilo base triethoxy hydroxyl oxidize molybdenum (VI).
In structure formula I and (II), R wherein
5Be methyl, all the other groups are hydrogen atom, i.e. N-methyl-β, β-imido grpup diethoxy molybdenum dioxide.
In the structure formula I, R wherein
1, R
5And R
6All be methyl, all the other groups are hydrogen atom, i.e. N-methyl-β, β-imido grpup dipropoxy molybdenum dioxide.
Above-mentioned Preparation of catalysts process is an epoxide and primary amine (methylamine, ethamine, propylamine, butylamine) that is easy to get etc. or ammonia react make β, β-pure and mild the β of imido grpup dialkyl group, β, β-parts such as nitrilo base trialkyl alcohol, these parts are 20-200 ℃ with molybdic oxide temperature in the presence of solvent-free respectively again, or at benzene, N, dinethylformamide, reaction promptly obtains β, β-imines dialkoxy molybdenum dioxide, β under the following 20-200 ℃ of temperature of the arbitrary organic solvent existence of tetrahydrofuran (THF) or dioxane, β, β-nitrilo base tri-alkoxy hydroxyl oxidize molybdenum (VI).In suitability for industrialized production, epoxide (propylene oxide) raw material sources can be directly from alkene and alkyl peroxide react product get it because its consumption only accounts for the very small proportion of product production.
The present invention adopts above-mentioned complex compound to be used for alkene (as propylene, tetrahydrobenzene, vinylbenzene) and alkyl peroxide epoxidation reaction and produces corresponding epoxide (as propylene oxide, 1,2-epoxidation hexanaphthene, phenyl ethylene oxide).Promptly under 40 normal atmosphere, in the time of 100 ℃, propylene and tertbutyl peroxide in the trimethyl carbinol (weight ratio 1.5: 1), at β, there are reaction down two hours in β-imido grpup-propoxy-molybdenum dioxide, and tertbutyl peroxide is transformed fully, and the selectivity that generates propylene oxide can reach 94%.Above-mentioned catalyst for reaction is by β, β, and when β-nitrilo base tripropoxy hydroxyl oxidize molybdenum (VI) substituted, the transformation efficiency of tertbutyl peroxide can reach 100%, and generating the propylene oxide selectivity is 78%.
Advantage of the present invention is, catalyst preparation process is simple, economical, in EPOXIDATION OF ALKENES CATALYZED BY, even is lower than in the weight ratio of feed molar ratio alkene and alkyl peroxide under 2: 1 the condition, reaches very high transformation efficiency and selectivity.For further narration the present invention, the following embodiment of special proposition.Obviously embodiments of the present invention are not limited to following embodiment.
Example 1:
1.5 mixture stirring reaction certain hour in the time of 80 ℃ of gram diisopropanolamine (DIPA) and 1.5 gram molybdic oxides, the color of reactant becomes blue grey by yellow gradually, when stopped reaction, the color of reactant is the sticking shape of white, be cooled to solid, get white crystal with recrystallizing methanol, productive rate is 80%, and the molecular formula of compound is:
The ultimate analysis value is: calculated value: C, 27.81%; H, 5.02%; N, 5.40%.
Measured value: C, 28.16%; H, 5.52%; N, 4.93%.
In a stainless autoclave that has a reciprocating type stirring, the tertbutyl peroxide that adds 13.2 grams 89%, the 13 gram trimethyl carbinols and 18 gram propylene, and with the above-mentioned catalyzer β that makes, β-imido grpup dipropoxy molybdenum dioxide adds 0.04 gram, then at 100 ℃, 40 normal atmosphere are reaction down, the transformation efficiency of tertbutyl peroxide is 100%, under 640mmHg air pressure, steams propylene oxide (29 ℃ of boiling points).The productive rate of propylene oxide is 94%.
Example 2:
1.5 gram diisopropanolamine (DIPA) and 1.5 gram molybdic oxides back flow reaction 10 hours in 10 milliliters, molybdic oxide all dissolves, and stopped reaction, cooling add diethyl ether, and obtain β, the white solid of β-imines propoxy-molybdenum dioxide.Use recrystallizing methanol again, obtain white crystal.Productive rate is 75%.
Example 3:
1.5 gram diisopropanolamine (DIPA) and 1.5 gram molybdic oxides back flow reaction 10 hours in 10 milliliters of benzene, reactant becomes white ex vivo through yellow, light grey, after having reacted, cooling is with the solid recrystallizing methanol, obtain β, the white crystal of β-imido grpup dipropoxy molybdenum dioxide.Productive rate is 73%.
Example 4:
1.5 gram diisopropanolamine (DIPA) and 1.5 gram molybdic oxides back flow reaction 8 hours in 10 milliliters of tetrahydrofuran (THF)s, molybdic oxide all dissolves, and cooling adularescent solid is separated out, with this solid recrystallizing methanol, obtain β, the white crystal of β-imido grpup diisopropoxy molybdenum dioxide.Productive rate is 75%.
Example 5:
2.6 restrain two (β-propyl alcohol base) methylamines and 1.5 gram molybdic oxides at 10 milliliters of N, back flow reaction is ten hours in the dinethylformamide, molybdic oxide all dissolves, stopped reaction, cooling adds a small amount of ether, obtain white solid, use recrystallizing methanol again, obtain N-methyl-β, the white crystal of β-imido grpup dipropoxy molybdenum dioxide.Productive rate is 83%.
Example 6:
2.4 restrain two (β-ethanol based) methylamines and 1.5 gram molybdenum dioxide at 10 milliliters of N, back flow reaction is 10 hours in the dinethylformamide, molybdic oxide all dissolves, stopped reaction, cooling, add a small amount of ether, obtain N-methyl-β, the white solid of β-imido grpup diethoxy molybdenum dioxide is used recrystallizing methanol again, obtain N-methyl-β, the white crystal of β-imido grpup diethoxy molybdenum dioxide.Productive rate is 85%.
Example 7:
3.2 gram β, β-imino-diacetic butanols and 1.5 gram molybdic oxides are at N, back flow reaction is 10 hours in the dinethylformamide, and molybdic oxide all dissolves, cooling, add ether, obtain white solid, use recrystallizing methanol, obtain β, the white crystal of β-imines dibutoxy molybdenum dioxide, productive rate is 80%.
Example 8:
3.8 gram tri-isopropanolamine and 1.5 gram molybdic oxides, reflux and stir certain hour in the dinethylformamide at 10 milliliters of N, molybdic oxide all dissolves, and solution is shallow yellow transparent solution.Remove solvent under reduced pressure, the solid recrystallizing methanol obtains β, β, and β-nitrilo base tripropoxy hydroxyl oxidize molybdenum (VI), productive rate is 90%.Molecular formula is:
In the autoclave of the reciprocating type stirring of a stainless steel, the tertbutyl peroxide that adds 13.2 grams 89%, the 13 gram trimethyl carbinols and 18 gram propylene, and with the above-mentioned catalyzer β that makes, β, β-nitrilo base tripropoxy hydroxyl oxidize molybdenum (VI) add 0.04 gram, then at 100 ℃, 40 normal atmosphere are the reaction certain hour down, and the transformation efficiency of tertbutyl peroxide is 100%, and the productive rate of propylene oxide is 78%.
Example 9:
4.0 gram β, β, β-nitrilo base three butanols and 1.5 gram molybdic oxides are at N, back flow reaction is 10 hours in the dinethylformamide, molybdic oxide all dissolves, and cooling adds ether sedimentation, obtain white solid, use recrystallizing methanol, obtain β, β, the white crystal of β-nitrilo base three butoxy hydroxyl oxidize molybdenums (VI), productive rate is 85%.
Example 10:
In a glass reactor; under the nitrogen protection; 3.0 tertbutyl peroxide (0.78 grams per milliliter) and 4.0 milliliters of tetrahydrobenzene of milliliter; 20 milligrams of β; β-imido grpup dipropoxy molybdenum dioxide reacts certain hour in the time of 80 ℃ in 10 milliliters of benzene, the transformation efficiency of tertbutyl peroxide is 100%; 1, the productive rate of 2-epoxy cyclohexane is 97%.
Example 11:
In a glass reactor; under the nitrogen protection; 3.0 the tertbutyl peroxide (0.78 grams per milliliter) of milliliter and 4.0 milliliters cyclic ethylene; 20 milligrams of β, β, β-nitrilo base tripropoxy hydroxyl oxidize molybdenum (VI) is in 10 milliliters of benzene; reaction certain hour in the time of 80 ℃; the transformation efficiency of tertbutyl peroxide is 85%, generates 1, and the selectivity of 2-epoxy cyclohexane is 98%.
Claims (7)
1, the preparation method who is used for the organic soluble catalysts containing molybdenum of epoxidation reaction of olefines, it is characterized in that epoxide and ammonia or comprise its part of primary amine reaction system of one of methylamine, ethamine, propylamine, butylamine, at solvent-free or benzene, W, W-dimethylformamide, tetrahydrofuran (THF), the arbitrary organic solvent of dioxane exist down, temperature of reaction is 20-200 ℃, with resulting glycol amine and molybdic oxide mixture reaction, obtain the catalyzer of following structure:
R wherein
1-R
4, R
6-R
13In each group can be identical, also can be different, can be hydrogen atom, also can be the alkyl that contains 1-6 carbon atom, R
5Can be hydrogen atom, also can be the alkyl of 1-10 carbon atom.
2, Preparation of catalysts method as claimed in claim 1 is characterized in that the temperature of reacting is 70-120 ℃.
3, Preparation of catalysts method as claimed in claim 1 is characterized in that R
1-R
13All groups are hydrogen atom.
4,, it is characterized in that (I) and (II) is respectively β, β-imido grpup dipropoxy molybdenum dioxide, β, β, β-nitrilo base tripropoxy hydroxyl oxidize molybdenum (VI) as claim 1 or 3 described Preparation of catalysts methods.
5,, it is characterized in that (I) and (II) is respectively β, β-imido grpup dibutoxy molybdenum dioxide, β, β, β-nitrilo base three butoxy hydroxyl oxidize molybdenums (VI) as claim 1 or 3 described Preparation of catalysts methods.
6,, it is characterized in that (I) is N-methyl-β, β-imido grpup diethoxy molybdenum dioxide as claim 1 or 3 described Preparation of catalysts methods.
7,, it is characterized in that (I) is N-methyl-β, β-imido grpup dipropoxy molybdenum dioxide as claim 1 or 3 described Preparation of catalysts methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108700 CN1019015B (en) | 1989-11-18 | 1989-11-18 | Process for producing catalyzer of olefin epoxidation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108700 CN1019015B (en) | 1989-11-18 | 1989-11-18 | Process for producing catalyzer of olefin epoxidation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1046906A CN1046906A (en) | 1990-11-14 |
| CN1019015B true CN1019015B (en) | 1992-11-11 |
Family
ID=4857703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89108700 Expired CN1019015B (en) | 1989-11-18 | 1989-11-18 | Process for producing catalyzer of olefin epoxidation reaction |
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| Country | Link |
|---|---|
| CN (1) | CN1019015B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448857C (en) * | 2006-06-12 | 2009-01-07 | 北京科技大学 | Method for preparing epoxide by selectively catalyzing alkene epoxidation |
| CN103012485B (en) * | 2011-09-22 | 2015-10-21 | 中国石油化工股份有限公司 | Acetylacetone shrinkage benzoyl hydrazine molybdenum complex and preparation method thereof |
| CN103012486B (en) * | 2011-09-22 | 2015-10-21 | 中国石油化工股份有限公司 | Acetylacetone shrinkage isonicotinyl hydrazine molybdenum complex and preparation method thereof |
| CN103012487B (en) * | 2011-09-22 | 2016-05-18 | 中国石油化工股份有限公司 | 2-acetylpyridine contracting o-aminophenol molybdenum complex and preparation method thereof |
-
1989
- 1989-11-18 CN CN 89108700 patent/CN1019015B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN1046906A (en) | 1990-11-14 |
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