CN106179503A - The catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene - Google Patents

The catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene Download PDF

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CN106179503A
CN106179503A CN201610535119.8A CN201610535119A CN106179503A CN 106179503 A CN106179503 A CN 106179503A CN 201610535119 A CN201610535119 A CN 201610535119A CN 106179503 A CN106179503 A CN 106179503A
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catalyst
hexamethylene
silica gel
ketohexamethylene
reflux
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王晓丽
吴功德
刘浩
吕小笛
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Nanjing Institute of Technology
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Nanjing Institute of Technology
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
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    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
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    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
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    • B01J2531/845—Cobalt
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01J2531/847—Nickel

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Abstract

The present invention is the catalyst of a kind of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene, described catalyst is with transition metal Schiff base complex as active constituent, with silica gel as carrier, silica gel: chromium Schiff base complex=1 g:0.05 0.5 mmol.The present invention has the advantage that compared with existing catalyst (1) method for preparing catalyst is simple, easily operates；(2) in Hexalin synthetic reaction, cyclohexane conversion is high, and product Hexalin selectivity is good；(3) catalyst repeat performance is good.(4) low cost, reaction condition is gentle, green.

Description

The catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene
Technical field
The present invention relates to a kind of new catalyst for hexamethylene high-selectivity oxidation synthesizing cyclohexanol and preparation side thereof Method.
Background technology
Cyclohexanol/cyclohexanone is collectively referred to as KA oil, is the important source material of synthesis of caprolactam, adipic acid and nylon66 fiber.At present, work Main employing cyclohexane oxidation synthesis technique in industry, with soluble cobalt as catalyst, with O2For oxidant.Because of hexamethylene C-H Key is highly stable, for improving oxidizing reaction rate, often need to add organic solvent or initiator, and carry out under high temperature, high pressure, but This can increase target product deep oxidation simultaneously and generate polyprotic acid and the chance of ester so that by-products content is higher.Therefore, industry The upper selectivity for ensureing cyclohexanol/cyclohexanone, can only allow reaction at relatively mild bar with sacrifice cyclohexane conversion as cost (160 are carried out under partoC, 2 MPa).Now cyclohexane conversion is only 4%, but can control Hexalin+Ketohexamethylene selectivity and be About 80%.This process energy consumption is high, efficiency is low, and because using homogeneous metallic catalyst, causes a large amount of metal ion pollution.Can See, it would be highly desirable to develop the novel of clean environment firendly, high energy efficiency, height optionally hexamethylene green oxidation synthesizing cyclohexanol/Ketohexamethylene Catalytic oxidation system.
O2As oxidant, inexpensively, being easy to get, oxidized byproduct is only water, and applicable industrialized production.O2Oxidation system is normal Catalyst include metalloporphyrin, solid supported type metal coordination compound, molecular sieve, oxide etc..Wherein, solid supported type metal coordination compound Catalyst system and catalyzing reaction condition is gentle, reactivity preferably (cyclohexane conversion about 35%), the higher (Hexalin/hexamethylene of selectivity Ketone selectivity about 95%), catalyst easily separates with product.But course of reaction often need to be added initiator, promoter or use Organic solvent, so that purify product.And catalyst efficiency and stability wait to improve further, can be only achieved work The requirement that industry produces, energy consumption, material consumption are the most serious.
Summary of the invention
In order to solve the problems referred to above, the invention provides a kind of new for hexamethylene high-selectivity oxidation synthesizing cyclohexanol Type catalyst and preparation method thereof.
In order to achieve the above object, the present invention is achieved by the following technical solutions:
The present invention is the catalyst of a kind of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene, described catalyst with Transition metal Schiff base complex is active constituent, with silica gel as carrier, silica gel: chromium Schiff base complex=1 g: 0.05-0.5 mmol。
The preparation method of the catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene includes walking as follows Rapid:
(1) a certain amount of silica gel is joined in the cyclohexane solution of certain density organic coupling agent, coupling agent, hexamethylene and The mass ratio of silica gel is 10:50-200:5-9, and after being heated to reflux 10-12 h, reduce pressure sucking filtration, gained solid sample toluene Soxhlet Extracting 8-12 h, 80-100 DEG C of vacuum drying 6-10 h, obtain the silica gel that organic coupling group is modified；
(2) ethanol solution dissolved with a certain amount of organic diamine is added drop-wise in the anhydrous alcohol solution dissolved with a certain amount of aldehyde, Reflux at 80 DEG C 2-5 h, adds a certain amount of transition metal salt, the quality of aldehyde, organic diamine, ethanol and transition metal salt Than being 1:0.6:60-150:1.5-2.5, continue to be stirred at reflux 3-6 h, cool down, reduce pressure sucking filtration, obtains transition metal Schiff Coordination compound；
(3) silica gel modified for a certain amount of organic coupling group and transition metal Schiff base complex are joined a certain amount of In hexamethylene, the mass ratio of silica gel, transition metal Schiff base complex and thiacyclohexane that coupling group is modified is 1:0.5-2: 50-100, is stirred at reflux 6-10 h, toluene extracting sample 8-10 h, 80-100 DEG C of vacuum drying 8-12h, obtains supported on silica-gel Transition metal Schiff base complex catalyst.
Preferred: organic coupling agent is 3-aminopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-anilino- One or both in trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
Preferred: machine diamine is the one in ethylenediamine, diethylenetriamine, cyclohexanediamine, o-phenylenediamine, binaphthyl diamidogen Or two kinds.
Preferred: aldehyde is salicylide, 3-sodium sulfonate salicylide, 5-sodium sulfonate salicylide, 3-nitrosalicylaldehyde, 5-nitro water One or both in poplar aldehyde.
Preferred: transition metal salt can be vanadium oxysulfate, Chlorizate chromium, manganese chloride, iron chloride, cobaltous chloride, Nickel dichloride., chlorine Change in copper, zinc chloride one or both.
The catalyst of the present invention is used for synthesizing cyclohexanol, and method is by hexamethylene, and consumption is reactant gross weight 0.5- The catalyst of 3.0 % adds in stainless steel cauldron together, is filled with the oxygen of 0.5 ~ 2.0 MPa, under agitation, is warming up to 60-120 DEG C, react 4-48 h, after being performing centrifugal separation on out catalyst, obtain product.
Product analysis: product with Agilent 6890 gas chromatograph (capillary column: 30 mm × 320um × 0.25um) analyzing, chromatographic condition is as follows: column temperature 100 DEG C, temperature programming: initial temperature 50 DEG C, is raised to 220 with 10 DEG C/min DEG C, continue 5 min.Carrier gas is N2, flow velocity 40 mL/min, hydrion flame detector, hand sampling, sample size 0.2 μ L is logical Cross normalization method and each product is carried out quantitative analysis.
The present invention has the advantage that compared with existing catalyst
(1) method for preparing catalyst is simple, easily operates.
(2) in Hexalin synthetic reaction, cyclohexane conversion is high, and product Hexalin selectivity is good.
(3) catalyst repeat performance is good.
(4) low cost, reaction condition is gentle, green.
Detailed description of the invention
In order to deepen the understanding of the present invention, being described in further detail the present invention below in conjunction with embodiment, this is real Execute example and be only used for explaining the present invention, protection scope of the present invention is not constituted and limit.
As shown in the Examples, the present invention is urging of a kind of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene Agent, described catalyst is with transition metal Schiff base complex as active constituent, with silica gel as carrier, silica gel: chromium Schiff Alkali coordination compound=1 g:0.05-0.5 mmol.
The preparation method of the catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene, including walking as follows Rapid:
(1) a certain amount of silica gel is joined in the cyclohexane solution of certain density organic coupling agent, be heated to reflux 10-12 h After, reduce pressure sucking filtration, gained solid sample toluene soxhlet type 8-12 h, 80-100 DEG C of vacuum drying 6-10 h, obtains organic The silica gel that coupling group is modified, wherein said organic coupling agent is 3-aminopropyl triethoxysilane, 3-mercapto propyl trimethoxy One or both in silane, 3-anilino-trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane；
(2) ethanol solution dissolved with a certain amount of organic diamine is added drop-wise in the anhydrous alcohol solution dissolved with a certain amount of aldehyde, Reflux at 80 DEG C 2-5 h, adds a certain amount of transition metal salt, continues to be stirred at reflux 3-6 h, cools down, reduce pressure sucking filtration, i.e. Obtaining transition metal Schiff base complex, wherein machine diamine is ethylenediamine, diethylenetriamine, cyclohexanediamine, o-phenylenediamine, connection How one or both in diamidogen, aldehyde is salicylide, 3-sodium sulfonate salicylide, 5-sodium sulfonate salicylide, 3-nitrosalicylaldehyde, 5- One or both in nitrosalicylaldehyde；Transition metal salt can be vanadium oxysulfate, Chlorizate chromium, manganese chloride, iron chloride, chlorination One or both in cobalt, Nickel dichloride., copper chloride, zinc chloride；
(3) silica gel modified for a certain amount of organic coupling group and transition metal Schiff base complex are joined a certain amount of In hexamethylene, it is stirred at reflux 6-10 h, toluene extracting sample 8-10 h, 80-100 DEG C of vacuum drying 8-12h, obtains silica gel solid The transition metal Schiff base complex catalyst carried.
Embodiment 1
5.0 g 3-aminopropyl triethoxysilanes are joined in 50 g hexamethylene and is configured to solution, after stirring wherein Adding 3.5 g silica gel, be heated to reflux 10 h, cooling, sucking filtration, solid sample toluene extracts 8h, is vacuum dried 8h, i.e. at 80 DEG C Obtain the silica gel that aminopropyl is modified.Then by the 25 g ethanol solutions dissolved with 0.25 g ethylenediamine and 0.25 g diethylenetriamine Being added drop-wise to dissolved with in 25 g anhydrous alcohol solution of 1.1g salicylic aldehyde, reflux at 80 DEG C 2 h, adds the vanadium oxysulfate of 1.5g, continues Continuous 3 h that are stirred at reflux, cooling, sucking filtration, both homogeneous Schiff vanadium complex.By silica gel modified for 1.5 g aminopropyls and 0.5 g homogeneous Schiff vanadium complex joins in 50 g hexamethylene, after being stirred at reflux 6 h, and cooling, sucking filtration, solid sample Extract 8 h with toluene, at 80 DEG C, be vacuum dried 8 h, obtain the catalyst of the Schiff coordination compound of final supported on silica-gel.
Embodiment 2
5.0 g 3-mercaptopropyl trimethoxysilanes are joined in 100 g hexamethylene and are configured to solution, stir backward its Middle addition 4.0 g silica gel, is heated to reflux 12 h, cooling, sucking filtration, and solid sample toluene extracts 12 h, is vacuum dried at 100 DEG C 8h, obtains the silica gel that mercapto is modified.Then by the 25 anhydrous second of g dissolved with 0.3 g o-phenylenediamine and 0.25 g diethylenetriamine Alcoholic solution is added drop-wise in the 25 g anhydrous alcohol solution dissolved with 1.5 g 3-sodium sulfonate salicylides, and reflux at 80 DEG C 3 h, adds The Chlorizate chromium of 1.7 g, continues to be stirred at reflux 4 h, cooling, sucking filtration, both homogeneous Schiff chromic compound.By 2.0 g mercaptos third Silica gel and 1.0 g homogeneous Schiff chromic compound that base is modified join in 50 g hexamethylene, after being stirred at reflux 6 h, cold But, sucking filtration, solid sample toluene extracts 12 h, is vacuum dried 8 h at 80 DEG C, obtains the Schiff of final supported on silica-gel The catalyst of coordination compound.
Embodiment 3
5.0 g 3-anilino-trimethoxy silanes are joined in 70 g hexamethylene and is configured to solution, after stirring wherein Adding 3.5 g silica gel, be heated to reflux 10 h, cooling, sucking filtration, solid sample toluene extracts 10h, is vacuum dried 10 at 100 DEG C H, obtains the silica gel that anilino-is modified.Then by dissolved with 0.3 g o-phenylenediamine and 25 g dehydrated alcohol of 0.25 g binaphthyl diamidogen Solution is added drop-wise in the 25 g anhydrous alcohol solution dissolved with 1.5 g 5-sodium sulfonate salicylides, and reflux at 80 DEG C 5 h, adds 1.5 The manganese chloride of g, continues to be stirred at reflux 6 h, cooling, sucking filtration, both homogeneous Schiff manganese complex.2.0 g anilino-s are changed Silica gel and the 1.2 g homogeneous Schiff manganese complex of property join in 50 g hexamethylene, after being stirred at reflux 8 h, cool down, take out Filter, solid sample toluene extracts 10 h, is vacuum dried 10 h at 80 DEG C, obtains the Schiff coordination compound of final supported on silica-gel Catalyst.
Embodiment 4
5.0 g N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane is joined in 80 g hexamethylene and is configured to solution, stir Mixing after uniformly and be added thereto to 3.0 g silica gel, be heated to reflux 9 h, cooling, sucking filtration, solid sample toluene extracts 10 h, and 90 It is vacuum dried 10 h at DEG C, obtains the silica gel that N-(β-aminoethyl)-γ-aminopropyl is modified.Then will be dissolved with 0.3 g o-phenylenediamine It is added drop-wise to the 30 g anhydrous alcohol solution dissolved with 1.8 g 3-nitrosalicylaldehydes with 50 g ethanol solutions of 0.3 g cyclohexanediamine In, reflux at 80 DEG C 6 h, adds the iron chloride of 2.0 g, continues to be stirred at reflux 6 h, cooling, sucking filtration, both homogeneously Schiff iron complex.The silica gel modified by 2.0 g N-(β-aminoethyl)-γ-aminopropyl and the homogeneous Schiff of 1.5 g Iron complex joins in 80 g hexamethylene, after being stirred at reflux 10 h, and cooling, sucking filtration, solid sample toluene extracts 10 h, and 80 It is vacuum dried 10 h at DEG C, obtains the catalyst of the Schiff coordination compound of final supported on silica-gel.
Embodiment 5
5.0 g N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane is joined in 100 g hexamethylene and is configured to solution, Being added thereto to 4.0 g silica gel after stirring, be heated to reflux 10 h, cooling, sucking filtration, solid sample toluene extracts 9 h, It is vacuum dried 10 h at 100 DEG C, obtains the silica gel that N-(β-aminoethyl)-γ-aminopropyl is modified.Then will be dissolved with 0.5 g neighbour's benzene 50 g ethanol solutions of diamidogen are added drop-wise in the 30 g anhydrous alcohol solution dissolved with 1.8 g 5-nitrosalicylaldehydes, at 80 DEG C Reflux 6 h, adds the cobaltous chloride of 2.0 g, continues to be stirred at reflux 6 h, cooling, sucking filtration, both the cooperation of homogeneous Schiff cobalt Thing.The silica gel modified by 2.0 g N-(β-aminoethyl)-γ-aminopropyl and 1.5 g homogeneous Schiff cobalt complex join In 80 g hexamethylene, after being stirred at reflux 10 h, cooling, sucking filtration, solid sample toluene extracts 10 h, is vacuum dried 10 at 80 DEG C H, obtains the catalyst of the Schiff coordination compound of final supported on silica-gel.
Embodiment 6
3.0 g 3-anilino-trimethoxy silanes and 2.0 g N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane are added Enter and be configured to solution in 100 g hexamethylene, be added thereto to after stirring..0 g silica gel, is heated to reflux 12 h, cool down, Sucking filtration, solid sample toluene extracts 10 h, is vacuum dried 10 h at 100 DEG C, obtain anilino-and N-(β-aminoethyl)-γ- The silica gel that aminopropyl is jointly modified.Then will drip dissolved with 50 g ethanol solutions of 0.3 g o-phenylenediamine and 0.2 g ethylenediamine Being added to dissolved with in 30 g anhydrous alcohol solution of 2.0 g salicylic aldehydes, reflux at 80 DEG C 6 h, adds the Nickel dichloride. of 2.0 g, continues Be stirred at reflux 5 h, cooling, sucking filtration, both homogeneous Schiff nickel complex.By 2.0 g anilino-s and N-(β-aminoethyl)- Silica gel and 1.5 g homogeneous Schiff cobalt complex that γ-aminopropyl is jointly modified join in 100 g hexamethylene, stir back After flowing 10 h, cooling, sucking filtration, solid sample toluene extracts 12 h, is vacuum dried 12 h at 80 DEG C, obtains silica gel solid finally The catalyst of the Schiff coordination compound carried.
Embodiment 7
3.0 g 3-anilino-trimethoxy silanes and 2.0 g 3-aminopropyl triethoxysilanes are joined 80 g hexamethylene In be configured to solution, be added thereto to 3.0 g silica gel after stirring, be heated to reflux 10 h, cooling, sucking filtration, solid sample is used Toluene extracts 12 h, is vacuum dried 8 h at 100 DEG C, obtains anilino-and the silica gel of aminopropyl modification jointly.Then will be dissolved with 80 g ethanol solutions of 0.3 g o-phenylenediamine and 0.3 g diethylenetriamine are added drop-wise to dissolved with 1.0 g salicylic aldehydes and 1.0 g In 60 g anhydrous alcohol solution of 5-nitrosalicylaldehyde, reflux at 80 DEG C 4 h, adds the copper chloride of 2.0 g, continues to stir back Flow 6 h, cooling, sucking filtration, both homogeneous Schiff copper complex.By silica gel jointly modified to 2.0 g anilino-s and aminopropyl Join in 80 g hexamethylene with 1.5 g homogeneous Schiff cobalt complex, after being stirred at reflux 10 h, cooling, sucking filtration, solid Sample toluene extracts 10 h, is vacuum dried 10 h at 80 DEG C, obtains the catalysis of the Schiff coordination compound of final supported on silica-gel Agent.
Embodiment 8
2.0 g 3-mercaptopropyl trimethoxysilanes and 3.0 g 3-aminopropyl triethoxysilanes are joined 100 g hexamethylene In be configured to solution, be added thereto to 2.8 g silica gel after stirring, be heated to reflux 11 h, cooling, sucking filtration, solid sample is used Toluene extracts 12 h, is vacuum dried 10 h at 100 DEG C, obtains mercapto propyl group and the silica gel of aminopropyl modification jointly.Then will be dissolved with 80 g ethanol solutions of 0.2 g cyclohexanediamine and 0.4 g diethylenetriamine are added drop-wise to dissolved with 1.5 g 5-sodium sulfonate bigcatkin willows In 80 g anhydrous alcohol solution of aldehyde and 1.0 g 5-nitrosalicylaldehydes, reflux at 80 DEG C 6 h, adds the zinc chloride of 2.5 g, Continue to be stirred at reflux 6 h, cooling, sucking filtration, both homogeneous Schiff Zn complex.By common to 2.5 g mercapto propyl group and aminopropyl Modified silica gel and 1.5 g homogeneous Schiff cobalt complex join in 100 g hexamethylene, after being stirred at reflux 8 h, cooling, Sucking filtration, solid sample toluene extracts 10 h, is vacuum dried 12 h at 80 DEG C, and the Schiff obtaining supported on silica-gel finally coordinates The catalyst of thing.

Claims (6)

1. the catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene, it is characterised in that: described catalysis Agent is with transition metal Schiff base complex as active constituent, with silica gel as carrier, and silica gel: chromium Schiff base complex=1 g: 0.05-0.5 mmol。
2. produce the preparation of the catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene described in claim 1 Method, it is characterised in that: described preparation method comprises the steps:
(1) being joined by silica gel in the cyclohexane solution of organic coupling agent, after being heated to reflux 10-12 h, reduce pressure sucking filtration, and gained is solid Body sample toluene soxhlet type 8-12 h, 80-100 DEG C of vacuum drying 6-10 h, obtain the silicon that organic coupling group is modified Glue；
(2) being added drop-wise to by the ethanol solution dissolved with organic diamine dissolved with in the anhydrous alcohol solution of aldehyde, reflux at 80 DEG C 2- 5 h, add transition metal salt, continue to be stirred at reflux 3-6 h, cool down, reduce pressure sucking filtration, obtain transition metal Schiff and coordinate Thing；
(3) silica gel modified for organic coupling group and transition metal Schiff base complex are joined a certain amount of hexamethylene In, it is stirred at reflux 6-10 h, toluene extracting sample 8-10 h, 80-100 DEG C of vacuum drying 8-12h, obtains the mistake of supported on silica-gel Cross metal Schiff base complex catalyst.
The preparation of the catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene the most according to claim 2 Method, it is characterised in that: described organic coupling agent is 3-aminopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3- One or both in anilino-trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.
The preparation of the catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene the most according to claim 2 Method, it is characterised in that: machine diamine is in ethylenediamine, diethylenetriamine, cyclohexanediamine, o-phenylenediamine, binaphthyl diamidogen Plant or two kinds.
The preparation of the catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene the most according to claim 2 Method, it is characterised in that: aldehyde is salicylide, 3-sodium sulfonate salicylide, 5-sodium sulfonate salicylide, 3-nitrosalicylaldehyde, 5-nitro One or both in salicylide.
The preparation of the catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene the most according to claim 2 Method, it is characterised in that: transition metal salt can be vanadium oxysulfate, Chlorizate chromium, manganese chloride, iron chloride, cobaltous chloride, Nickel dichloride., One or both in copper chloride, zinc chloride.
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