CN107903399A - A kind of MOF material preparation methods for being catalyzed amidation process - Google Patents
A kind of MOF material preparation methods for being catalyzed amidation process Download PDFInfo
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- CN107903399A CN107903399A CN201710969134.8A CN201710969134A CN107903399A CN 107903399 A CN107903399 A CN 107903399A CN 201710969134 A CN201710969134 A CN 201710969134A CN 107903399 A CN107903399 A CN 107903399A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/06—Formation or introduction of functional groups containing nitrogen of amide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/40—Acylated substituent nitrogen atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention provides a kind of preparation method of heterogeneous Zr MOF catalyst and its application in amidation process is catalyzed, and belongs to synthesis and the catalytic field of catalyst.Using aromatic carboxylic acid as organic ligand and zirconium oxychloride in N, in N dimethylformamides and acetum, metal-organic framework material is obtained through solvent thermal reaction, the Zr MOF have the three-D pore structure that octahedra cage and the tetrahedron cage being alternately arranged is formed, and there is the carboxylic acid functional for not participating in coordination,, can be as the catalyst of amidation process with certain acidity.The Zr MOF catalyst shows very high activity in terms of amidation process is catalyzed, and catalyst is highly stable in catalyst system and catalyzing and easy to recycling and recycling, and being repeated 5 times reactivity does not substantially reduce.
Description
Technical field
Synthesis and catalytic field the invention belongs to catalyst, and in particular to a kind of heterogeneous Zr-MOF catalyst and catalysis
Amidation process.
Background technology
The formation reaction of amido link is that a kind of important reaction, amido link are widely present in medicine intermediate in organic synthesis
In biochemical substances.The method of conventional synthesis acid amides is usually directed to the use of activated acylating reagent, such as acetic anhydride and chloroacetic chloride.Though
These right reagents are cheap, but its toxicity and hygroscopicity prevent them from making preferable acylating agent.Many methods are also using heterogeneous
With homogeneous metallic catalyst, this is usually costly, and needs purification step.Therefore, a kind of high catalytic efficiency, service life are developed
Long heterogeneous catalysis has great importance.
Metal-organic framework materials (MOFs) are one be self-assembly of by organic ligand and metal ion or ion cluster
Class has the porous crystalline material of net structure, gas absorption with separating, heterogeneous catalysis etc. with wide application before
Scape.The unsaturated coordination site of metal ion can be with as the activated centre of catalytic reaction, on its skeleton in MOFs materials
Introduce a variety of organic ligands with catalytic performance；MOFs skeletons pore size can micropore and it is mesoporous between adjust, compare table greatly
Area can also load the nano metal active component of high dispersive, therefore MOFs materials have and are different from the only of other catalyst materials
Special architectural feature.
A series of Zr-MOF materials are synthesized, Zr-MOF stable structure, the acidic site as conditioning agent using acetic acid herein
It is more, still show good catalytic performance after being used repeatedly, therefore the MOF catalyst is a kind of good heterogeneous
Catalyst, has a good application prospect in Industrial Catalysis amidation process.
The content of the invention
It is an object of the invention to provide a kind of preparation of heterogeneous Zr-MOF catalyst and its in catalysis amidation process
In application.
A kind of heterogeneous Zr-MOF catalyst, it is characterised in that the heterogeneous Zr-MOF catalyst, which has, not to be participated in largely
The carboxylic acid functional (- COOH) of coordination.
The preparation method of above-mentioned heterogeneous Zr-MOF catalyst, comprises the following steps：
Eight hydration zirconium oxychlorides, aromatic carboxylic acids, N,N-dimethylformamide and acetic acid mixing ultrasound is taken to obtain for 10 minutes
Bright solution, mixed solution is placed in round-bottomed flask, and when 80~150 DEG C of agitating and heatings 10~48 are small, natural cooling is down to room temperature
Afterwards, white solid is centrifugally separating to obtain, is first washed three times with n,N-Dimethylformamide, again with methanol washing activates three times, very
Sky is dry (when vacuum drying 24 is small at 60 DEG C), obtains white powder, i.e. Zr-MOF materials.
In above-mentioned steps, the molar ratio of eight hydration zirconium oxychlorides and aromatic carboxylic acids is preferably 1:0.5~1:3；N, N- diformazan
The volume ratio of base formamide and acetic acid is 1:1~10:1；Aromatic carboxylic acids is selected from terephthalic acid (TPA), trimesic acid, 1,2,4- benzene
One kind in tricarboxylic acid, 1,2,4,5- benzene tertacarbonic acids.
The Zr-MOF materials of above-mentioned synthesis may be used as the heterogeneous catalysis of amidation process, should after reaction is completed
Heterogeneous catalysis can be repeated several times use and catalytic activity does not substantially reduce.
The present invention is conditioning agent using acetic acid, uses solvent-thermal method to be prepared for the MOF materials using Zr as metallic site, is led to
The catalytic activity of MOF can be adjusted by crossing change ligand.The catalyst heat endurance and chemical stability of the present invention is high, wherein hot steady
It is qualitative to can reach 500 DEG C, chemical stability show in high-temperature catalytic system can holding structure it is constant and can recycle 5 times with
On.The Zr-MOF materials have the-COOH for not participating in coordination.Therefore heterogeneous catalysis table in amidation process is catalyzed
Reveal very high catalytic activity.
Brief description of the drawings
Fig. 1 is the thermal multigraph of heterogeneous Zr-MOF catalyst in present example.
Fig. 2 is the infrared figure of heterogeneous Zr-MOF catalyst in present example.
Fig. 3 is the equation of Zr-MOF catalysis amidation process
Fig. 4 is X-ray powder diffraction (XRD) figure of Zr-MOF catalyst after different number recyclings in example.
Fig. 5 is the repetition result of the test of heterogeneous Zr-MOF catalysts amidation process in present example.
Embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
This conjunction implement in use eight hydration zirconium oxychlorides, aromatic carboxylic acids, N,N-dimethylformamide, acetic acid, benzene methanamine,
Ethyl acetate etc. is all that analysis is pure.
Embodiment 1
The hydrations of organic ligand trimesic acid 1mmol and eight zirconium oxychloride 3mmol is added to 30ml N, N- dimethyl
In the mixed solution of formamide and 15ml acetic acid, ultrasound 10 minutes, obtains clear transparent solutions.Mixed liquor is moved into single-necked flask
In, when 120 DEG C of oil bath heatings 24 are small, cooled to room temperature, centrifugation removes reaction solution, with n,N-Dimethylformamide and first
Alcoholic solution respectively 3 times (100ml/ time) of washing, activate in methanol 24 it is small when.Upper strata methanol solution is outwelled after centrifugation, will be precipitated
When being put into that 60 DEG C of dryings 24 are small in vacuum drying oven, white powder is obtained.
Embodiment 2
The hydrations of organic ligand trimesic acid 1mmol and eight zirconium oxychloride 3mmol is added to 35ml N, N- dimethyl
In the mixed solution of formamide and 10ml acetic acid, ultrasound 10 minutes, obtains clear transparent solutions.Mixed liquor is moved into single-necked flask
In, when 120 DEG C of oil bath heatings 24 are small, cooled to room temperature, centrifugation removes reaction solution, with n,N-Dimethylformamide and first
Alcoholic solution respectively 3 times (100ml/ time) of washing, activate in methanol 24 it is small when.Upper strata methanol solution is outwelled after centrifugation, will be precipitated
When being put into that 60 DEG C of dryings 24 are small in vacuum drying oven, white powder is obtained.
Embodiment 3
The hydrations of organic ligand trimesic acid 1mmol and eight zirconium oxychloride 3mmol is added to 40ml N, N- dimethyl
In the mixed solution of formamide and 5ml acetic acid, ultrasound 10 minutes, obtains clear transparent solutions.Mixed liquor is moved into single-necked flask
In, when 120 DEG C of oil bath heatings 24 are small, cooled to room temperature, centrifugation removes reaction solution, with n,N-Dimethylformamide and first
Alcoholic solution respectively 3 times (100ml/ time) of washing, activate in methanol 24 it is small when.Upper strata methanol solution is outwelled after centrifugation, will be precipitated
When being put into that 60 DEG C of dryings 24 are small in vacuum drying oven, white powder is obtained.
Embodiment 4
The hydrations of organic ligand terephthalic acid (TPA) 1mmol and eight zirconium oxychloride 1mmol is added to 30ml N, N- dimethyl
In the mixed solution of formamide and 15ml acetic acid, ultrasound 10 minutes, obtains clear transparent solutions.Mixed liquor is moved into single-necked flask
In, when 120 DEG C of oil bath heatings 24 are small, cooled to room temperature, centrifugation removes reaction solution, with n,N-Dimethylformamide and first
Alcoholic solution respectively 3 times (100ml/ time) of washing, activate in methanol 24 it is small when.Upper strata methanol solution is outwelled after centrifugation, will be precipitated
When being put into that 60 DEG C of dryings 24 are small in vacuum drying oven, white powder is obtained.
Embodiment 5
The hydrations of organic ligand 1,2,4 benzenetricarboxylic acid 1mmol and eight zirconium oxychloride 1mmol is added to 30ml N, N- diformazans
In the mixed solution of base formamide and 15ml acetic acid, ultrasound 10 minutes, obtains clear transparent solutions.Mixed liquor is moved into single port to burn
In bottle, when 120 DEG C of oil bath heatings 24 are small, cooled to room temperature, centrifugation removes reaction solution, with n,N-Dimethylformamide and
Methanol solution respectively 3 times (100ml/ time) of washing, activate in methanol 24 it is small when.Upper strata methanol solution is outwelled after centrifugation, will be heavy
When shallow lake is put into that 60 DEG C of dryings 24 are small in vacuum drying oven, white powder is obtained.
Embodiment 6
The hydrations of organic ligand 1,2,4,5- benzene tertacarbonic acids 1mmol and eight zirconium oxychloride 1mmol is added to 30ml N, N- bis-
In the mixed solution of methylformamide and 15ml acetic acid, ultrasound 10 minutes, obtains clear transparent solutions.Mixed liquor is moved into single port
In flask, when 120 DEG C of oil bath heatings 24 are small, cooled to room temperature, centrifugation removes reaction solution, uses n,N-Dimethylformamide
Respectively washed with methanol solution 3 times (100ml/ times), when activation 24 is small in methanol.Upper strata methanol solution is outwelled after centrifugation, will
When precipitation is put into that 60 DEG C of dryings 24 are small in vacuum drying oven, white powder is obtained.
The Zr-MOF catalyst of above-mentioned synthesis and benzene methanamine are added in ethyl acetate, mixed liquor is put into reaction kettle,
When reaction 12 is small at 80 DEG C.The amount of wherein each reactant is benzene methanamine 1mmol, ethyl acetate 2ml, catalyst 25mg respectively.Instead
Centrifuged after the completion of answering, take supernatant, CDCl3For solvent, use1H NMR carry out product analysis.Heterogeneous catalysis after reaction
Agent is washed 3 times with methanol, is put into 60 DEG C of drying of vacuum drying oven, is reused next time.The acyl of benzene methanamine and ethyl acetate
Aminating reaction equation is as follows：
In the amidation process of above-mentioned benzene methanamine and ethyl acetate, the conversion ratio of benzene methanamine>99%, product N- acetyl
The yield of benzylamine is up to 98%.
Heterogeneous Zr-MOF catalyst has higher heat endurance as shown in Figure 1, up to 500 DEG C.It is non-equal as shown in Figure 2
There is-the COOH for not participating in coordination in phase Zr-MOF catalyst.
Fig. 3 represents the equation of heterogeneous Zr-MOF catalysis amidation process.
The change of heterogeneous Zr-MOF catalyst crystal structure after reusing 5 times is understood by Fig. 4 XRD test results
Change, as can be seen that after being reused many times from figure, the crystal structure of Zr-MOF catalyst illustrates the catalysis without significant change
Agent has good heat endurance, may be reused.
As shown in Figure 5, which has good reusing, after recycling 5 times, the conversion ratio of benzene methanamine
>98%.
Table 1 shows that under the effect of heterogeneous Zr-MOF catalysts with ethyl acetate acyl occurs for different aromatic amines
The product yield of aminating reaction.As can be seen that the catalyst is generally applicable to the amidation process of aromatic amine and ethyl acetate.
Table 1
Claims (6)
1. a kind of preparation method of heterogeneous Zr-MOF catalyst, it is characterised in that comprise the following steps：Take eight hydration dichloro oxygens
Zirconium, aromatic carboxylic acids, n,N-Dimethylformamide and ultrasonic extraction with acetic acid obtain clear solution, and mixed solution is placed in round-bottomed flask,
For a period of time, natural cooling is cooled to room temperature agitating and heating, is centrifugally separating to obtain white solid, is first used n,N-Dimethylformamide
Three times, three times, vacuum drying, obtains white powder, i.e. Zr-MOF for again with methanol washing activation for washing.
2. according to the preparation method of claim 1, it is characterised in that the molar ratio of eight hydration zirconium oxychlorides and aromatic carboxylic acids is preferred
For 1:0.5~1:3.
3. according to the preparation method of claim 1, it is characterised in that n,N-Dimethylformamide and the volume ratio of acetic acid are 1:1
~10:1.
4. according to the preparation method of claim 1, it is characterised in that the aromatic carboxylic acids is selected from terephthalic acid (TPA), equal benzene three
One kind in formic acid, 1,2,4 benzenetricarboxylic acid, 1,2,4,5- benzene tertacarbonic acids.
5. the heterogeneous Zr-MOF catalyst being prepared according to claim 1-4 any one of them preparation methods.
6. the heterogeneous Zr-MOF catalyst being prepared according to claim 1-5 any one of them preparation methods is used to be catalyzed
The purposes of amidation process.
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Cited By (3)
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| CN110668963A (en) * | 2019-09-05 | 2020-01-10 | 湖南恒泰生物医药有限公司 | Method for synthesizing dichloroacetamide |
| CN116715600A (en) * | 2023-08-07 | 2023-09-08 | 广州宏度精细化工有限公司 | Preparation process of fatty acyl amino acid surfactant |
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| US20170291912A1 (en) * | 2014-09-26 | 2017-10-12 | Universitetet I Oslo | Process for preparing a zirconium-based metal organic framework |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498928A (en) * | 2018-06-04 | 2019-11-26 | 北京工业大学 | A kind of pair of Minim Benzene in Gas Phase system object has the metal-organic framework material of efficient absorption removal capacity |
| CN110668963A (en) * | 2019-09-05 | 2020-01-10 | 湖南恒泰生物医药有限公司 | Method for synthesizing dichloroacetamide |
| CN116715600A (en) * | 2023-08-07 | 2023-09-08 | 广州宏度精细化工有限公司 | Preparation process of fatty acyl amino acid surfactant |
| CN116715600B (en) * | 2023-08-07 | 2023-10-03 | 广州宏度精细化工有限公司 | Preparation process of fatty acyl amino acid surfactant |
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