CN107774331A - A kind of Metal Supported MOFs catalyst and preparation method thereof and the application in PMDPTA synthesis - Google Patents
A kind of Metal Supported MOFs catalyst and preparation method thereof and the application in PMDPTA synthesis Download PDFInfo
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- CN107774331A CN107774331A CN201711015304.5A CN201711015304A CN107774331A CN 107774331 A CN107774331 A CN 107774331A CN 201711015304 A CN201711015304 A CN 201711015304A CN 107774331 A CN107774331 A CN 107774331A
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- 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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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
Application the invention provides a kind of Metal Supported MOFs catalyst and preparation method thereof and in PMDPTA synthesis, more particularly to catalyst technical field, the catalyst includes carrier and active component, and the carrier is MOFs materials, and the active component is single metal or composite metal particles.The catalyst uses excessive infusion process, and at least one of metal chloride or metal nitrate solution and MOFs materials are stirred at room temperature into 24h, filters, obtains catalyst precursor；Catalyst precursor acts on obtaining Metal Supported MOFs catalyst with reducing agent.The preparation method of the catalyst has the advantages that preparation process is simple, Stability Analysis of Structures.The catalyst is used to synthesize PMDPTA by the present invention, has cost low, and product yield is high, it is green the advantages that.
Description
Technical field
The present invention relates to catalyst technical field, is specifically related to a kind of Metal Supported MOFs catalyst and preparation method thereof
With synthesized in PMDPTA in application.
Background technology
Polyurethane (PU) is a kind of high molecular polymer for containing carbamate groups (- NH-CO-O-) in molecule,
The numerous areas such as ship, building, electromechanics, light industry occupy an important position.Most of common polyurethane material is with foams
Form is present.Polyurethane foam is progressively polymerize under catalyst action by binary or multicomponent isocyanate and polyol compound
What reaction formed.Wherein, catalyst can not only accelerate to react, and can control the speed of reaction, influence reactant mixture
Mobility and product physicochemical properties, thus vital effect is played in the formation to polyurethane foam.At present
More conventional catalyst includes organo-metallic compound and organic amine compound.Organo-metallic compound is with organic tin
Based on compound, industrially it is mainly used in being catalyzed polyurethane resin；This kind of catalyst harm to the human body is larger and produces serious
Environmental pollution, do not meet environmental requirement.Therefore, organic amine catalyst just turns into the main research of current catalysts for polyurethanes
Direction.
Organic amine catalyst often based on tertiary amine catalyst, is mainly used in being catalyzed polyurethane foam.Conventional tertiary amines
Catalyst has triethylene diamine (TMDA), diethylenetriamine (DMTA) and N, N, N ', N ', N "-pentamethyl dipropylenetriamine
(PMDPTA).PMDPTA traditional synthesis is in the presence of formic acid 3, and 3 '-imido grpup is double (N, N- dimethyl propylene amine)
Occur what methylation reaction obtained with formalin.Not only cost is high for this process route, low yield, and inevitable real estate
Raw environmental pollution and severe corrosive.In order to reduce cost, yield and green is improved, improved technique is with methylamine solution
It is raw material with acrylonitrile, by Michael's addition, hydrogenation, the three-step reaction that methylates obtains PMDPTA in high yield, and used urges
Agent is W-3 type Raney Ni.Chemical equation is as follows：
However, W-3 type Raney Ni catalyst is also complicated there is building-up process, it is easy to aoxidize and store difficulty etc. scarce
Fall into.And metal load type catalyst can be efficiently against drawbacks described above.MOFs materials are by inorganic metal center (metal ion
Or metal cluster) formed one kind is connected with each other by self assembly with the organic ligand of bridging there is the crystalline substance of periodic network structure
State porous material.Compared with other inorganic porous materials, MOFs materials have that specific surface area is big, and structure is adjustable and is easy to function
The features such as change.Therefore, MOFs materials are by as excellent carrier, applied to all kinds of reactions.
Therefore urgent need offer is a kind of replaces the Metal Supported MOFs of W-3 type Raney Ni catalyst to urge in PMDPTA synthesis
Agent and preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of Metal Supported MOFs catalyst and preparation method thereof and in PMDPTA synthesis
Application.The advantages of catalyst has that preparation method is simple, Stability Analysis of Structures, and yield is high and green.
To achieve the above object, technical scheme is as follows：
A kind of Metal Supported MOFs catalyst, including carrier and active component, the carrier are that (metal is organic for MOFs materials
Framework material), the active component is single metal or composite metal particles.
Preferably, active component mass content is 0.1-20% in Metal Supported MOFs catalyst.
The preparation method of Metal Supported MOFs catalyst, including following preparation process：
(1) at least one of metal chloride or metal nitrate are dissolved in certain solvent and obtain solution；
(2) 24h is stirred at room temperature by excessive infusion process in the solution obtained in step (1) and MOFs materials, obtained
Catalyst precursor；
(3) catalyst precursor obtained in step (2) and reducing agent are acted on obtaining Metal Supported MOFs catalyst.
Preferably, the raw material of active component is palladium bichloride, nickel chloride, palladium nitrate, chlorination in Metal Supported MOFs catalyst
Copper, copper nitrate, chromium chloride, at least one of zinc chloride and iron chloride.The namely preparation side of Metal Supported MOFs catalyst
The metal chloride described in step (1) in method includes palladium bichloride, nickel chloride, copper chloride, chromium chloride, zinc chloride or chlorination
Iron, the metal nitrate described in step (1) include palladium nitrate or copper nitrate.
Preferably, the solvent described in the step (1) in the preparation method of Metal Supported MOFs catalyst be water, methanol,
At least one of ethanol or acetone.
Preferably, the carrier of catalyst i.e. MOFs materials include zeolite imidazole skeleton material, carry out Wa Xier skeleton materials
At least one of material, UiO-66 or UiO-67.
Preferably, zeolite imidazole skeleton material includes ZIF-8 and ZIF-67, and carrying out Wa Xier framework materials includes MIL-101
And MIL-100, that is to say, that described MOFs materials are ZIF-8, ZIF-67, UiO-66, UiO-67, MIL-101 and MIL-100
At least one of.
Preferably, the preparation process of MOFs materials is as follows：The methanol solution of zinc nitrate or cobalt nitrate respectively with it is a certain amount of
The methanol solution of 2-methylimidazole is stirred at room temperature 24h and obtains ZIF-8 or ZIF-67；A certain amount of zirconium chloride and terephthaldehyde
Acid or the methanol solution to naphthalenedicarboxylic acid, 120 DEG C of reaction 24h obtain UiO-66 or UiO-67 in water heating kettle；A certain amount of nitre
Sour chromium or the ferric nitrate DMF solution with terephthalic acid (TPA) respectively, 220 DEG C of reaction 8h obtain MIL-101 in water heating kettle；It is a certain amount of
Chromic nitrate or the ferric nitrate DMF solution with trimesic acid respectively, 150 DEG C of reaction 24h obtain MIL-100 in water heating kettle.
Preferably, reducing agent is hydrazine hydrate in the step (3) in the preparation method of Metal Supported MOFs catalyst, hydroboration
One kind in sodium or hydrogen.
Application of the prepared Metal Supported MOFs catalyst in synthesis of polyurethane catalyst-PMDPTA, specific steps
It is as follows：
(1) methanol solution of methylamine reacts with acrylonitrile at 25 DEG C obtains N, N- bis- (2- cyanoethyls) methylamine；
(2) N, N- bis- (2- cyanoethyls) methylamine, ethanol, sodium hydroxide, Metal Supported MOFs catalyst are in Hydrogen Vapor Pressure
2.0-3.0MPa, temperature stop reaction after 6h is reacted under the conditions of 80-100 DEG C, and mixture filters after being down to room temperature, filtrate concentration
Obtain N, N- bis- (3- aminopropyls) methylamine, wherein, it is preferred that (2- cyanoethyls) methylamine of N, N- bis- and solvent are 1 by volume:3-
9；The mass ratio of amount and N, N- bis- (2- cyanoethyls) methylamine of the catalyst is 1:3-7；
(3) N, N- bis- (3- aminopropyls) methylamine, methanol, metallic particles load MOFs catalyst, formalin (37wt%)
It is 2.5-4.0MPa in Hydrogen Vapor Pressure, temperature stops reaction after 5h is reacted under the conditions of 90-110 DEG C, is down to mixture after room temperature
Filter, filtrate is concentrated to give PMDPTA.
Preferably, (3- aminopropyls) methylamine of N, N- bis- and solvent are 1 by volume:6-12；N, N- bis- (3- aminopropyls) first
The mol ratio of amine and formalin is 1:4-8；The mass ratio of amount and N, N- bis- (3- aminopropyls) methylamine of the catalyst is 1:
4-12。
The beneficial effects of the invention are as follows：The preparation method has the advantages of preparation method is simple, Stability Analysis of Structures.The catalyst
For synthesizing PMDPTA, there is the advantages that cost is low, and yield is high and green.
Embodiment
A kind of Metal Supported MOFs catalyst, including carrier and active component, the carrier are that (metal is organic for MOFs materials
Framework material), the active component is single metal or composite metal particles.
The preparation method of Metal Supported MOFs catalyst and PMDPTA synthesis in application it is as follows：
Embodiment 1
0.016g palladium bichlorides, which are dissolved in, prepares homogeneous palladium bichloride acetone soln in 5mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H20.1%Pd/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 2
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and embodiment 1 are made
Standby catalyst (6g) is added in 300mL autoclaves, and air in the closed rear nitrogen displacement kettle of autoclave is used again after displacement three times
Hydrogen is replaced three times.Reactant mixture reacts 6h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 2.0MPa.It is down to room
Mixture filters after temperature, and filtrate is concentrated to give 13.5g N, N- bis- (3- aminopropyls) methylamine, yield 45.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 1
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 3.0MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 7.3g product PMDPTA, yield 55.0%.
Embodiment 3
0.16 palladium nitrate, which is dissolved in, prepares homogeneous palladium nitrate acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H21%Pd/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 4
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and embodiment 3 are made
Standby catalyst (6g) is added in 300mL autoclaves, and air in the closed rear nitrogen displacement kettle of autoclave is used again after displacement three times
Hydrogen is replaced three times.Reactant mixture reacts 6h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 2.0MPa.It is down to room
Mixture filters after temperature, and filtrate is concentrated to give 27.3g N, N- bis- (3- aminopropyls) methylamine, yield 91.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 3
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 3.0MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 14.8g product PMDPTA, yield 89.0%.
Embodiment 5
0.22g palladium bichlorides, which are dissolved in, prepares homogeneous palladium bichloride acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H21%Pd/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 6
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and embodiment 5 are made
Standby catalyst (6g) is added in 300mL autoclaves, and air in the closed rear nitrogen displacement kettle of autoclave is used again after displacement three times
Hydrogen is replaced three times.Reactant mixture reacts 6h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 2.0MPa.It is down to room
Mixture filters after temperature, and filtrate is concentrated to give 26.4g N, N- bis- (3- aminopropyls) methylamine, yield 88.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 5
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 3.0MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 17.5g product PMDPTA, yield 87.0%.
Embodiment 7
0.22g palladium bichlorides, which are dissolved in, prepares homogeneous palladium bichloride acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, and adds 0.18g sodium borohydrides, is continued after stirring 6h,
Filter, drying obtains 1%Pd/MIL-101 catalyst.
Embodiment 8
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and embodiment 7 are made
Standby catalyst (6g) is added in 300mL autoclaves, and air in the closed rear nitrogen displacement kettle of autoclave is used again after displacement three times
Hydrogen is replaced three times.Reactant mixture reacts 6h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 2.0MPa.It is down to room
Mixture filters after temperature, and filtrate is concentrated to give 27.0g N, N- bis- (3- aminopropyls) methylamine, yield 90.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 7
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 3.0MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 17.7g product PMDPTA, yield 88.0%.
Embodiment 9
0.22g palladium bichlorides, which are dissolved in, prepares homogeneous palladium bichloride ethanol solution in 25mL ethanol；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL ethanol, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H21%Pd/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 10
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and embodiment 9 are made
Standby catalyst (6g) is added in 300mL autoclaves, and air in the closed rear nitrogen displacement kettle of autoclave is used again after displacement three times
Hydrogen is replaced three times.Reactant mixture reacts 6h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 2.0MPa.It is down to room
Mixture filters after temperature, and filtrate is concentrated to give 27.3g N, N- bis- (3- aminopropyls) methylamine, yield 91.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 9
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 3.0MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 14.8g product PMDPTA, yield 89.0%.
Embodiment 11
0.80g palladium bichlorides, which are dissolved in, prepares homogeneous palladium bichloride acetone soln in 50mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Pd/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 12
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 11
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 2.0MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 27.4g N, N- bis- (3- aminopropyls) methylamine, yield 91.2%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 11
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 90 DEG C, stops reaction in pressure 3.0MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 18.1g product PMDPTA, yield 90.0%.
Embodiment 13
0.41g nickel chlorides, which are dissolved in, prepares homogeneous nickel chloride acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H21%Ni/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 14
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 13
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 18.0g N, N- bis- (3- aminopropyls) methylamine, yield 60.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 13
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 14.3g product PMDPTA, yield 71.0%.
Embodiment 15
2.05g nickel chlorides, which are dissolved in, prepares homogeneous nickel chloride acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Ni/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 16
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 15
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 26.3g N, N- bis- (3- aminopropyls) methylamine, yield 87.5%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 15
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 16.3g product PMDPTA, yield 81.0%.
Embodiment 17
8.20g nickel chlorides, which are dissolved in, prepares homogeneous nickel chloride acetone soln in 100mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H220%Ni/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 18
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 17
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 26.4g N, N- bis- (3- aminopropyls) methylamine, yield 88.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 17
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 16.5g product PMDPTA, yield 82.0%.
Embodiment 19
2.05g nickel chlorides, which are dissolved in, prepares homogeneous nickel chloride acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The UiO-66 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Ni/UiO-66 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 20
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 19
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 27.0g N, N- bis- (3- aminopropyls) methylamine, yield 85.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 19
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 14.3g product PMDPTA, yield 71.0%.
Embodiment 21
2.05g nickel chlorides, which are dissolved in, prepares homogeneous nickel chloride acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The UiO-67 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Ni/UiO-67 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 22
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 21
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 24.6g N, N- bis- (3- aminopropyls) methylamine, yield 82.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 21
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 14.1g product PMDPTA, yield 70.0%.
Embodiment 23
2.05g nickel chlorides, which are dissolved in, prepares homogeneous nickel chloride acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The MIL-100 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Ni/MIL-100 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 24
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 23
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 24.0g N, N- bis- (3- aminopropyls) methylamine, yield 80.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 23
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 13.1g product PMDPTA, yield 65.0%.
Embodiment 25
2.05g copper chlorides, which are dissolved in, prepares homogeneous copper chloride acetone soln in 25mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Cu/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 26
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 25
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 24.6g N, N- bis- (3- aminopropyls) methylamine, yield 82.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 25
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 15.3g product PMDPTA, yield 76.0%.
Embodiment 27
2.56g chromium chlorides, which are dissolved in, prepares homogeneous chromium chloride acetone soln in 100mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Cr/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 28
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 27
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 21.6g N, N- bis- (3- aminopropyls) methylamine, yield 72.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 27
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 14.1g product PMDPTA, yield 70.0%.
Embodiment 29
2.05g zinc chloride, which are dissolved in, prepares homogeneous zinc chloride acetone soln in 100mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Zn/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 30
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 29
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 21.0g N, N- bis- (3- aminopropyls) methylamine, yield 70.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 29
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 9.3g product PMDPTA, yield 46.0%.
Embodiment 31
1.45g iron chloride, which is dissolved in, prepares homogeneous iron chloride acetone soln in 100mL acetone；Solution is added drop-wise to dropwise
The MIL-101 of 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz boat
In, in H25%Fe/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 32
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 31
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 22.8g N, N- bis- (3- aminopropyls) methylamine, yield 76.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 31
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 14.7g product PMDPTA, yield 73.0%.
Embodiment 33
1.02g nickel chlorides and 1.02g copper chlorides, which are dissolved in 100mL acetone, prepares homogeneous phase solution；Solution is added dropwise dropwise
MIL-101 to 10g activation is distributed in 50mL acetone, and 24h is stirred at room temperature, filters to obtain presoma；Presoma is placed in quartz
In boat, in H25%NiCu/MIL-101 catalyst is obtained under atmosphere after reductase 12 h.
Embodiment 34
By N, N- bis- (2- cyanoethyls) methylamine (30mL), ethanol (150mL), sodium hydroxide (0.18g) and the institute of embodiment 33
The catalyst (6g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 6h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 2.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 24.3g N, N- bis- (3- aminopropyls) methylamine, yield 81.0%.
By N, N- bis- (3- aminopropyls) methylamine (14.5g), methanol (150mL), formalin (40.6g) and the institute of embodiment 33
The catalyst (3g) of preparation is added in 300mL autoclaves, by autoclave it is closed after air in nitrogen displacement kettle, after displacement three times again
With hydrogen displacement three times.Reactant mixture reacts 5h at rotating speed 500rpm and 100 DEG C, stops reaction in pressure 3.5MPa.It is down to
Mixture filters after room temperature, and filtrate is concentrated to give 15.7g product PMDPTA, yield 78.0%.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, although with reference to foregoing reality
Apply example the present invention is described in detail, for those skilled in the art, it still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic.All essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (10)
1. a kind of Metal Supported MOFs catalyst, it is characterised in that including carrier and active component, the carrier is MOFs materials
Material, the active component is single metal or composite metal particles.
2. Metal Supported MOFs catalyst according to claim 1, it is characterised in that the active component mass content is
0.1-20%.
3. the preparation method of the Metal Supported MOFs catalyst described in claim 1 or 2, it is characterised in that including following preparation
Step：
(1) at least one of metal chloride or metal nitrate are dissolved in certain solvent and obtain solution；
(2) 24h is stirred at room temperature by excessive infusion process in the solution obtained in step (1) and MOFs materials, is catalyzed
Agent presoma；
(3) catalyst precursor obtained in step (2) and reducing agent are acted on obtaining Metal Supported MOFs catalyst.
4. the preparation method of Metal Supported MOFs catalyst according to claim 3, it is characterised in that institute in step (1)
The metal chloride stated includes palladium bichloride, nickel chloride, copper chloride, chromium chloride, zinc chloride or iron chloride, described in step (1)
Metal nitrate includes palladium nitrate or copper nitrate.Solvent described in step (1) be in water, methanol, ethanol or acetone at least
It is a kind of.
5. the preparation method of Metal Supported MOFs catalyst according to claim 3, it is characterised in that institute in step (2)
The MOFs materials stated are at least one of ZIF-8, ZIF-67, UiO-66, UiO-67, MIL-101 and MIL-100.
6. the preparation method of Metal Supported MOFs catalyst according to claim 5, it is characterised in that the MOFs materials
It is prepared as follows to obtain：
ZIF-8 and ZIF-67 materials be by the methanol solution of zinc nitrate or cobalt nitrate respectively with a certain amount of 2-methylimidazole
Methanol solution is stirred at room temperature 24h and obtained；
MIL-101 is by a certain amount of chromic nitrate or the ferric nitrate DMF solution with terephthalic acid (TPA) respectively, in water heating kettle
220 DEG C of reaction 8h are obtained；
MIL-100 is by a certain amount of chromic nitrate or the ferric nitrate DMF solution with trimesic acid respectively, in water heating kettle
150 DEG C of reaction 24h are obtained；
UiO-66 and UiO-67 is by a certain amount of zirconium chloride and terephthalic acid (TPA) or the methanol solution to naphthalenedicarboxylic acid, in water
120 DEG C of reaction 24h are obtained in hot kettle.
7. the preparation method of Metal Supported MOFs catalyst according to claim 3, it is characterised in that in step (3)
Described reducing agent is one kind in hydrazine hydrate, sodium borohydride or hydrogen.
8. application of the Metal Supported MOFs catalyst in PMDPTA synthesis described in claim 1 or 2, it is characterised in that
(1) methanol solution of methylamine reacts with acrylonitrile at 25 DEG C obtains N, N- bis- (2- cyanoethyls) methylamine；
(2) N that will be obtained in step (1), N- bis- (2- cyanoethyls) methylamine are catalyzed with ethanol, sodium hydroxide and Metal Supported MOFs
Agent is 2.0-3.0MPa in Hydrogen Vapor Pressure, and temperature stops reaction after 6h is reacted under the conditions of being 80-100 DEG C, mixed after being down to room temperature
Thing filters, and filtrate is concentrated to give N, N- bis- (3- aminopropyls) methylamine；
(3) N that will be obtained in step (2), N- bis- (3- aminopropyls) methylamine and methanol, Metal Supported MOFs catalyst and formaldehyde are molten
Liquid (37wt%) is 2.5-4.0MPa in Hydrogen Vapor Pressure, and temperature stops reaction after 5h is reacted under the conditions of being 90-110 DEG C, is down to room
Mixture filters after temperature, and filtrate is concentrated to give PMDPTA.
9. application of the Metal Supported MOFs catalyst according to claim 8 in PMDPTA synthesis, it is characterised in that step
Suddenly (2- cyanoethyls) methylamine of the N described in (2), N- bis- and ethanol are 1 by volume:3-9；The Metal Supported MOFs catalyst
Amount and step (2) described in N, the mass ratio of N- bis- (2- cyanoethyls) methylamine is 1:3-7.
10. application of the Metal Supported MOFs catalyst according to claim 8 in PMDPTA synthesis, it is characterised in that
N described in step (3), N- bis- (3- aminopropyls) methylamine and methanol are 1 by volume:6-12；N described in step (3), N- bis-
The mol ratio of (3- aminopropyls) methylamine and formalin is 1:4-8；In the amount and step (3) of the Metal Supported MOFs catalyst
The mass ratio of described N, N- bis- (3- aminopropyls) methylamine is 1:4-12.
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