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
- Authority
- CN
- China
- Prior art keywords
- reaction
- molybdenum
- catalysts
- preparation
- imido grpup
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 14
- 150000001336 alkenes Chemical class 0.000 title abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- -1 alkyl hydrogen peroxide Chemical compound 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 235000016768 molybdenum Nutrition 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- BGFRQORRILMEQK-UHFFFAOYSA-N C(CC)O[Mo](OCCC)(=O)=O Chemical compound C(CC)O[Mo](OCCC)(=O)=O BGFRQORRILMEQK-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- BVUADLDFPQMIDJ-UHFFFAOYSA-N C(C)O[Mo](OCC)(=O)=O Chemical compound C(C)O[Mo](OCC)(=O)=O BVUADLDFPQMIDJ-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims 1
- YFGBWQALYZWDMZ-UHFFFAOYSA-N C(CCC)O[Mo](OCCCC)(=O)=O Chemical compound C(CCC)O[Mo](OCCCC)(=O)=O YFGBWQALYZWDMZ-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 10
- 150000002924 oxiranes Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 abstract 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 8
- 229940043276 diisopropanolamine Drugs 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000003956 methylamines Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BXKUNJKPCWCLRZ-UHFFFAOYSA-N C(C)(C)O[Mo](OC(C)C)(=O)=O Chemical compound C(C)(C)O[Mo](OC(C)C)(=O)=O BXKUNJKPCWCLRZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Epoxy Compounds (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 |
Country Status (1)
| 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 | A kind of method of selective catalytic olefin epoxidation to prepare epoxide |
| 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 |
| 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 |
| 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN1046906A (en) | 1990-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1093138C (en) | Polyalkylaluminoxane compositions formed by non-hydrolytic means | |
| CN1134937A (en) | Integrated process for epoxidation | |
| SU1662996A1 (en) | Method of producing butene-1 | |
| Harthun et al. | Proof of chiral dihydride complexes including catalyst and substrate during the bis (phosphinite) rhodium (I)‐catalyzed hydrogenation of dimethyl itaconate | |
| RU2183637C2 (en) | Method of combined synthesis of 1-ethyl-2- alkylidenealumacyclopentanes and 1-ethyl-2- methylene-3- alkylalumacyclopentanes | |
| CN1019015B (en) | Process for producing catalyzer of olefin epoxidation reaction | |
| CN1062523A (en) | The method for preparing diether | |
| RU2245885C1 (en) | Method of jointly preparing 2-alkylidenemagnesiumcyclopentanes and 2-alkyl-3-methylidenemagnesiumcyclopentanes | |
| RU2290406C1 (en) | Method for preparing 2,3,4,5-tetraalkylmagnesa-cyclopenta-2,4-dienes | |
| CN1401640A (en) | Process for preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene | |
| CN86104037A (en) | Hydrolysis of olefin oxides generates the method for glycol | |
| CN109721066B (en) | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method | |
| EP0485985A1 (en) | Organosilicon compounds and methods of manufacturing thereof | |
| US3506722A (en) | Di(hydroxymethyl)methyl-cyclopentanes | |
| CN108329191B (en) | Method for processing cyclohexane oxidation liquid | |
| CN1120320A (en) | Catalyst for conversion of methane to ethylene, preparation thereof and method for producing ethylene with said catalyst | |
| RU2130024C1 (en) | Method of combined preparation of 1-(alkoxy)-2,3,4,5- tetraalkyl-(aryl) alumacyclopentadienes and 1-(alkoxy)- 2,3-dialkyl (aryl)alumacyclopropenes | |
| RU2381230C2 (en) | Method of producing tricyclo[4.2.1.02,5]nonane-3-spiro (3'-ethyl-3'-aluminacyclopentane) | |
| CN107986295B (en) | Silicon-containing molecular sieve and preparation method thereof | |
| CN114702396A (en) | Preparation method of PEG-6 glycerol polyoxyethylene ether quaternary ammonium salt | |
| CN108117087B (en) | Silicon-containing molecular sieve and preparation method thereof | |
| CN109721069B (en) | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method | |
| RU2191192C1 (en) | Method of synthesis of substituted 1-ethylalumo-cyclopentanes | |
| CN1161963A (en) | Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide | |
| US20230112595A1 (en) | Production of allyl alcohol from glycerol using a reusable catalyst made from rhenium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |