CN103012324B - Propylene epoxidation reaction method - Google Patents
Propylene epoxidation reaction method Download PDFInfo
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- CN103012324B CN103012324B CN201110369127.7A CN201110369127A CN103012324B CN 103012324 B CN103012324 B CN 103012324B CN 201110369127 A CN201110369127 A CN 201110369127A CN 103012324 B CN103012324 B CN 103012324B
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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
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a propylene epoxidation reaction method, which mainly solves the problem that methods for catalyzing epoxidation of propylene by adopting a molybdenum Schiff alkali compound are undisclosed in the previous literatures. According to the method, tert-butyl hydroperoxide and propylene are taken as raw materials and are in contact with a catalyst for 1-12 hours to generate propylene epoxide under the conditions that the reaction temperature is 40-120 DEG C, the reaction pressure is 0.5-5 Mpa and the molar ratio of the tert-butyl hydroperoxide to the propylene is 1:(1-10), wherein the catalyst is an acetylacetone isonicotinic acid hydrazide molybdenum complex, the chemical structural formula of the acetylacetone isonicotinic acid hydrazide molybdenum complex is shown in the specification, and the technical scheme that R1 is selected from -OHR2 or R2 is CnH2n+1, and n is 2-10 better solves the problem. The method can be applied to the industrial production of propylene epoxide prepared through propylene epoxidation reaction.
Description
Technical field
The present invention relates to a kind of method of propylene ring oxidation reaction.
Background technology
Schiff alkali refers to a class organic compound that contains imines or azomethine characteristic group (RC=N-), and it is to be generated by the carbonyl of aldehyde ketone and amino condensation under certain conditions.Due to the hyperconjugation of C=N key and phenyl ring, this compounds is generally all more stable.Contain-OH of phenyl ring and-the Schiff alkali of the coordination functional groups such as N, intramolecular hydrogen bond effect makes it have rigid structure, very easily as polydentate ligand and high-valency metal formation complex compound.Therefore, Schiff alkali occupies critical role in coordination chemistry.
Schiff alkali is important organic synthesis reagent and intermediate of a class.Schiff alkaloid compound and metal complexes thereof have important application at catalytic field.Document CN1651472A discloses a kind of Schiff JianIVB family title complex containing olefin oxy, and it take the product of the salicylic aldehyde condensation p-aminophenyl alkylene ether that alkyl replaces is part, take titanium or zirconium as active centre, prepares the catalyzer for vinyl polymerization.Document CN1814645A discloses a kind of Schiff alkali Al catalysts preparation method for rac-Lactide ring-opening polymerization, it is characterized in that take that beta-diketon class Schiff alkali reacts the product and the derivative thereof that generate with aluminium triethyl be catalyzer, for rac-Lactide ring-opening polymerization.Document CN101108367A discloses a kind of catalyzer for the synthesis of phenyl aldehyde and preparation method, it is characterized in that take that chromium is as active centre, O-Phenylene Diamine salicylaldehyde is part, make chromium Schiff alkali title complex, take silica gel as carrier, as catalyst benzyl alcohol oxidation synthesizing benzaldehyde again.Document CN101020747A discloses a kind of catalyzer for the synthesis of polycarbonate, and salicylic aldehyde condensation diamines or three aminated compounds products that it be take containing quaternary ammonium salt or quaternary alkylphosphonium salt group are part, and cobalt, chromium or aluminium are active centre.But have no up to now, the report of molybdenum Schiff alkali complex compound.
Propylene oxide (PO), is the third-largest derivative that in acryloyl derivative, output is only second to polypropylene and vinyl cyanide, is very important basic organic chemical industry raw material.At present, PO, except for the production of polyether glycol, propylene glycol and urethane, also can be used for producing propylene glycol, nonionogenic tenside, oil field demulsifier, farm chemical emulgent, softening agent, fire retardant and wetting agent etc.PO derivative is widely used in the industries such as automobile, building, food, tobacco, weaving, chemical industry, medicine and makeup, and nearly hundred kinds of the derived product of having produced, are the important source material of fine chemical product.At present, the catalyzer for preparing epoxypropane by epoxidation of propene mainly contains three classes: HTS class, precious metal (comprising gold and silver, copper etc.) and molybdenum, tungsten, vanadium class.HTS synthetic method exists the shortcoming of synthesis material costliness, severe reaction conditions, has seriously hindered the process of industrialization of HTS.And this province of precious metal is expensive, with them, make catalyzer, cost is also high.The Wang Xiaohan of Industrial Catalysis institute of East China University of Science and Lu Guanzhong be take ethylene glycol as part, and ammonium molybdate is molybdenum source, have prepared molybdenum-ol title complex, and as catalyzer, hydrogen phosphide cumene is oxygenant, and ethanol is solvent, has studied the reaction of propylene oxidation step propylene oxide processed.At 100 ℃, under the condition of 0.5MPa, react 2h, the transformation efficiency of hydrogen phosphide cumene is 65.0%, the selectivity of propylene oxide is 70.4%.Chinese Academy of Sciences's Lanzhou chemical physics Lv Zhengrong etc. to take acetyl acetone (MoO2 (acac) 2) be catalyzer, tertbutyl peroxide is oxygenant, the mol ratio of propylene and tertbutyl peroxide is 3: 1, under 100 ℃ and 0.8MPa condition, the transformation efficiency of tertbutyl peroxide is 100%, and the selectivity of propylene oxide is 70%.But we are by identical condition test acetyl acetone catalytic epoxidation of propone reaction, and the transformation efficiency of gained tertbutyl peroxide is 45.8%, and the selectivity of propylene oxide is 95%.
Summary of the invention
Technical problem to be solved by this invention is the problem of unexposed employing molybdenum Schiff alkali complex catalysis epoxidation of propylene in prior art, and a kind of method of new propylene ring oxidation reaction is provided.It is simple that the method has method for preparing catalyst, and cost is low, and reaction conditions is gentle, workable feature.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of propylene ring oxidation reaction, take tertbutyl peroxide and propylene as raw material, under solvent exists, in temperature of reaction, it is 40～120 ℃, reaction pressure is 0.5～5MPa, and the mol ratio of tertbutyl peroxide and propylene is 1: under (1～10) condition, reaction raw materials contacts 1～12 hour and generates propylene oxide with catalyzer; Wherein catalyzer used is methyl ethyl diketone contracting Isonicotinoylhydrazine molybdenum complex, and its chemical structural formula is as follows:
Wherein, R
1be selected from-OHR
2or
r
2for C
nh
2n+1, n=2～10.
In technique scheme, R
1be selected from-OHC
2h
5or
In technique scheme, described solvent is selected from least one in n-propyl alcohol, Virahol, methyl alcohol, the trimethyl carbinol or oil of mirbane, and the mol ratio of solvent and propylene is (1～10): 1.Temperature of reaction preferable range is 80～120 ℃, and reaction pressure preferable range is 0.5～3.5MPa, and reaction times preferable range is 1～4 hour, and the mol ratio preferable range of tertbutyl peroxide and propylene is 1: (1.5～5).
The preparation method of catalyzer methyl ethyl diketone contracting Isonicotinoylhydrazine molybdenum complex used in the present invention, comprise the following steps: Isonicotinoylhydrazine reacts after 10～360 minutes in 10～100 ℃ in solvent with methyl ethyl diketone, add molybdenum presoma, at 10～100 ℃, continue reaction 30～360 minutes, precipitate is dry through separation, obtains described methyl ethyl diketone contracting Isonicotinoylhydrazine molybdenum complex complex compound; Wherein, the mol ratio of Isonicotinoylhydrazine, solvent, methyl ethyl diketone and molybdenum presoma is 1: (8.6～800): (0.25～4): (0.1～10).Described molybdenum presoma is selected from acetyl acetone; Described solvent is selected from
or C
nh
2n+2, n=2～10 wherein; Preferred version is for being selected from C
2h
5oH.
Methyl ethyl diketone contracting Isonicotinoylhydrazine molybdenum complex preparation method technique in the present invention is simple; Reaction conditions is gentle, simple to operate, safety; With acetyl acetone MoO
2(acac)
2as cheap molybdenum presoma, cost is low, and environmental protection, environmentally friendly; The methyl ethyl diketone contracting Isonicotinoylhydrazine molybdenum complex stability of preparation is better; The oxidation of alkene is shown to excellent catalytic performance.Adopt the inventive method, mol ratio at 100 ℃, 3.2MPa, tertbutyl peroxide and propylene is 1: under (2～3) condition, tertbutyl peroxide transformation efficiency can reach 55.0%, and the selectivity of propylene oxide can reach 95%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the infrared analysis spectrum of the methyl ethyl diketone contracting Isonicotinoylhydrazine molybdenum complex in the present invention.
In Fig. 1, concrete IR absorption band is allocated as follows:
Note: Vs is symmetrical stretching vibration, and Vas is asymmetric stretching vibration.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Take 10 mmole Isonicotinoylhydrazine, put into the round-bottomed flask (50 milliliters) containing 20 milliliters of dehydrated alcohols, 75 ℃ of heated and stirred, after Isonicotinoylhydrazine dissolves completely, add 12 mmole methyl ethyl diketones, stir after 2 hours and add 10 mmole acetyl acetones, have orange red powder to separate out, continuation heated and stirred suction filtration after 2 hours, 40 ℃ of washing with alcohol final vacuums are dry to obtain orange red powdered product, and its structural formula is as follows, and its infrared analysis spectrum is shown in Fig. 1.
[embodiment 2]
Take 10 mmole Isonicotinoylhydrazine, put into the round-bottomed flask (50 milliliters) containing 20 milliliters of pyridines, 75 ℃ of heated and stirred, after Isonicotinoylhydrazine dissolves completely, add 12 mmole methyl ethyl diketones, stir after 2 hours and add 10 mmole acetyl acetones, have orange red powder to separate out, continuation heated and stirred suction filtration after 2 hours, pyridine washs 40 ℃ of dry products that to obtain of final vacuum, and its structural formula is as follows, and its infrared analysis spectrum is similar to Fig. 1.
[embodiment 3]
Get tertbutyl peroxide, n-propyl alcohol and [embodiment 1] synthetic methyl ethyl diketone contracting Isonicotinoylhydrazine molybdenum complex and put into autoclave, after sealed reactor, start heated and stirred.When reaching default 100 ℃, high-pressure pump pumps into propylene, and propylene amount is determined by pumping into volume.Reaction timing, arrives and takes off reactor after 2 hours, with frozen water, is cooled to 10～15 ℃, gets liquid phase to freezing sampler.Sampler is outwarded winding after continuing freezing 30 minutes at subzero 20 ℃ purging valve, opens sampler after the propylene in sampler is slowly emitted, and seals after fast remaining liq being transferred to chromatogram sample injection bottle, carries out stratographic analysis.
Reaction conditions: 100 ℃ of temperature of reaction, 2 hours reaction times, rotating speed 540rpm, tertbutyl peroxide (TBHP) add-on 70 mmoles, n-propyl alcohol add-on 50 mmoles, catalyzer add-on 0.1 mmole, 60 milliliters of reactors, passing into propylene to pressure is 3.2MPa.
Reaction result: tertbutyl peroxide transformation efficiency can reach 55.0%, the selectivity of propylene oxide can reach 95%.
Claims (3)
1. the method for a propylene ring oxidation reaction, take tertbutyl peroxide and propylene as raw material, under solvent exists, in temperature of reaction, it is 40～120 ℃, reaction pressure is 0.5～5MPa, the mol ratio of tertbutyl peroxide and propylene is 1:(1～10) under condition, reaction raw materials contacts 1～12 hour and generates propylene oxide with catalyzer; Wherein catalyzer used is methyl ethyl diketone contracting Isonicotinoylhydrazine molybdenum complex, and its chemical structural formula is as follows:
Wherein, R
1be selected from-OHC
2h
5or
2. the method for propylene ring oxidation reaction described in claim 1, is characterized in that described solvent is selected from least one in n-propyl alcohol, Virahol, methyl alcohol, the trimethyl carbinol or oil of mirbane, and the mol ratio of solvent and propylene is (1～10): 1.
3. the method for propylene ring oxidation reaction described in claim 1, is characterized in that temperature of reaction is 80～120 ℃, and reaction pressure is 0.5～3.5MPa, and the reaction times is 1～4 hour, and the mol ratio of tertbutyl peroxide and propylene is 1:(1.5～5).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223631A (en) * | 1992-06-30 | 1993-06-29 | National Science Council | Bimetallic complexes as catalysts in an oxidation process |
| CN1161963A (en) * | 1996-04-08 | 1997-10-15 | 武汉大学 | Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide |
| WO1999051546A1 (en) * | 1998-04-02 | 1999-10-14 | President And Fellows Of Harvard College | Parallel combinatorial approach to the discovery and optimization of catalysts and uses thereof |
| CN1534033A (en) * | 2003-03-28 | 2004-10-06 | 浙江大学 | Preparation method of 3-methylfuran |
-
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- 2011-11-18 CN CN201110369127.7A patent/CN103012324B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223631A (en) * | 1992-06-30 | 1993-06-29 | National Science Council | Bimetallic complexes as catalysts in an oxidation process |
| CN1161963A (en) * | 1996-04-08 | 1997-10-15 | 武汉大学 | Method for catalyzing expoxidation of olefines by imino-dialkoxyl molybdenum dioxide |
| WO1999051546A1 (en) * | 1998-04-02 | 1999-10-14 | President And Fellows Of Harvard College | Parallel combinatorial approach to the discovery and optimization of catalysts and uses thereof |
| CN1534033A (en) * | 2003-03-28 | 2004-10-06 | 浙江大学 | Preparation method of 3-methylfuran |
Non-Patent Citations (6)
| Title |
|---|
| )配合物合成、表征.《高等学校化学学报》.2003,第24卷(第11期),第2099～2102页. * |
| Icirc * |
| Matsunaga, Shigeki等.Catalytic Asymmetric 1,4-Addition Reactions Using α,β-Unsaturated N-Acylpyrroles as Highly Reactive Monodentate α,β-Unsaturated Ester Surrogates.《Journal of the American Chemical Society》.2004,第126卷(第24期),第7559-7570页. * |
| 章亚东等.聚苯乙烯负载席夫碱Mo(& * |
| 章亚东等.聚苯乙烯负载席夫碱Mo(Î |
| 隋岩等.THAM衍生席夫碱双氧MO(Vl)配合物催化环己烯环氧化.《中国化学会第九届全国络合催化学术讨论会论文集》.2005,第233页. * |
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