CN110483797A - The method of carbon material surface in-situ preparation polyimide type covalent organic frame material - Google Patents
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material Download PDFInfo
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- CN110483797A CN110483797A CN201910806125.6A CN201910806125A CN110483797A CN 110483797 A CN110483797 A CN 110483797A CN 201910806125 A CN201910806125 A CN 201910806125A CN 110483797 A CN110483797 A CN 110483797A
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 45
- 229920001721 polyimide Polymers 0.000 title claims abstract description 45
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 58
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000002086 nanomaterial Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000012043 crude product Substances 0.000 claims description 21
- 238000007789 sealing Methods 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical group C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical class C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 239000002041 carbon nanotube Substances 0.000 abstract description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000009102 absorption Effects 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000002604 ultrasonography Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000002679 ablation Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses the methods of carbon material surface in-situ preparation polyimide type covalent organic frame material, using pyromellitic dianhydride, the monomer and carbon nanomaterial of three-functionality-degree amine, the covalent organic frame of polyimide type and C constructed by solvent-thermal method one-step synthesis based on pyromellitic dianhydride60Or carbon nanotube in-situ composite.Preparation process of the present invention is simple, and the cost of raw material is cheap, high yield no coupling product, not high to equipment requirement, is easy to industrial mass into production.And the covalent organic frame of polyimide type prepared has many advantages, such as large specific surface area, fine heat-resisting performance.The composite material of synthesis has the features such as pore structure is flourishing, thermal stability and good chemical stability, with important application prospects in fields such as electrochemistry, temperature-resistant material, gas absorptions.
Description
Technical field
The invention belongs to covalent organic frame material preparation fields, and in particular to carbon material surface in-situ preparation polyimides
The method of type covalent organic frame material.
Background technique
Covalent organic frame material be it is a kind of be made of lightweight elements such as C, N, H there is high crystalline, high-specific surface area
Organic porous polymer, have the characteristics that duct is regular, chemical property is stable, thermal stability is high, gas absorption and storage,
Photoelectric field, catalytic field, biology carry the fields such as medicine with important researching value and application prospect.Such material was from 2005
So far, had numerous relevant reports since reporting for the first time, but be mostly the research for new topological structure and new monomer, but
It is that the application field of covalent organic frame material itself is also more limited to.Composite material can greatly enhance covalent organic frame material
The relevant nature of material, therefore the preparation of composite material is for widening the application field of covalent organic frame material and developing potential answer
With value, there are significances.
Carbon nanotube and C60It is common nano-carbon material.Wherein, carbon nanotubes is that the nanoscale graphite of a kind of tubulose is brilliant
Body is that single-layer or multi-layer graphite flake surrounds central axis by seamless nanoscale pipe made of certain helical angle curling；C60It is a kind of
The stabilization molecule being made of 60 carbon atoms merely is similar to football also known as football alkene.Both carbon nanomaterials, because it is special
Structure and properties, therefore since being found i.e. cause pay close attention to and discuss warmly, have important answer in fields such as photoelectricity, heatproof, sensings
Use prospect.
The covalent organic frame of polyimide type is a kind of material with excellent heat stability and chemical stability, and by
In the carbonyl functional group of its surface exposure, therefore the oxidation-reduction quality having by it has in fields such as electrochemistry and widely grinds
Study carefully value；But since covalent organic frame is made of the lightweight element of electric conductivity difference, its development is limit, still
Such issues that composite material being combined with carbon material be able to solve.
Summary of the invention
Goal of the invention: for the deficiency of current existing technical solution, the object of the present invention is to provide carbon material surface originals
The method that position generates polyimide type covalent organic frame material.Pyromellitic dianhydride is based on by the preparation of one step of solvent thermal process
The covalent organic frame of the polyimide type constructed and C60Or carbon nanotube in-situ composite.The composite material of preparation has high
Specific surface area and excellent heatproof and electrical property, and preparation method is simple, it is low in cost, it is easy to accomplish industrialized mass production.
Technical solution: in order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, includes the following steps:
1) it by pyromellitic dianhydride, the monomer and carbon nanomaterial of three-functionality-degree amine, is uniformly mixed and is placed on reaction unit
In, catalyst, solvent are added in reaction unit, ultrasonic mixing is uniform, liquid nitrogen frozen, vacuumizes and flame sealing, heating are anti-
It answers, the crude product of composite material is obtained after being cooled to room temperature；Specific reaction equation is as follows:
2) crude product of above-mentioned composite material is washed in organic solvent, it is covalently organic to obtain polyimide type after dry
Frame and carbon nanomaterial in-situ composite.
In step 1), the monomer of three-functionality-degree amine, including three (4- aminophenyl) amine, 1,3,5- tri- (4- aminophenyl) benzene,
2,4,6- tri- (4- aminophenyl) -1,3,5-triazines；Carbon nanomaterial includes C60, single-walled carbon nanotube, multi-walled carbon nanotube；Instead
Answering device is glass tube sealing or water heating kettle.
In step 1), the molar ratio of pyromellitic dianhydride and three-functionality-degree amine is 3: 2；Pyromellitic dianhydride and carbon nanometer material
The mass ratio of material is 1: 0.02-15.5.
In step 1), catalyst is isoquinolin, and dosage is 0.05 ‰ -3 ‰ (mass concentrations)；Solvent is mesitylene, N-
At least one of methyl pyrrolidone, n,N-Dimethylformamide, toluene, dioxane.
In step 1), reaction temperature is 160-240 DEG C, and the reaction time is -120h for 24 hours.
In step 2), washing is methanol, n,N-dimethylacetamide, tetrahydrofuran, N, N- dimethyl methyl with organic solvent
At least one of amide, acetone.
In step 2), drying means is boulton process, supercritical CO2Seasoning, freeze-drying.
Boulton process drying condition is dried in vacuo 6h-12h under the conditions of being 60-150 DEG C；Supercritical CO2Seasoning is dry
Condition is 45-70 DEG C, 8-20MP, gas flow rate keep 1-5h under being 20-200mL/min；Freeze-drying drying condition be -
35 DEG C -- 30 DEG C of vacuum drying 6-12h.
Polyimide type covalent organic frame material made from above-mentioned preparation method.
The present invention has following advantage and application prospect:
1) cost of material selected of the present invention is low, and synthetic method is simple, can one-step synthesis yield it is high, reaction condition is more warm
With easily prepared and industrialized mass production.
2) composite material prepared by the present invention has high crystalline, high-specific surface area and higher thermal stability and chemistry steady
It is qualitative, there is researching value in multiple application fields such as combination electrode material, gas absorption and storage, temperature-resistant material.
Detailed description of the invention
Fig. 1 is the covalent organic frame of polyimide type and C that pyromellitic dianhydride is constructed60The X-ray of in-situ composite
Polycrystalline diffraction phenogram；
Fig. 2 is the covalent organic frame of polyimide type and C that pyromellitic dianhydride is constructed60The nitrogen of in-situ composite is inhaled
Attached and desorption curve figure；
Fig. 3 is the covalent organic frame of polyimide type and C that pyromellitic dianhydride is constructed60The TEM of in-situ composite schemes；
In figure, a C60Transmission electron microscope picture, b be composite material TEM scheme；
Fig. 4 is the covalent organic frame of polyimide type and carbon nanotube in-situ composite that pyromellitic dianhydride is constructed
X-ray polycrystalline diffraction phenogram；
Fig. 5 is the covalent organic frame of polyimide type and carbon nanotube in-situ composite that pyromellitic dianhydride is constructed
Nitrogen adsorption and desorption curve figure；
Fig. 6 is the covalent organic frame of polyimide type and carbon nanotube in-situ composite that pyromellitic dianhydride is constructed
TEM figure；In figure, a is that the TEM of multi-walled carbon nanotube schemes, and b is that the TEM of composite material schemes.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several modifications and improvements can also be made, these belong to the present invention
Protection scope.
Following embodiment master instrument to be used and reagent are as follows: transmission electron microscope (JEM-1011, JEOL, Japan)；
X-ray polycrystalline diffractometer；Specific surface and Porosimetry (JW-BK200B, JWGB SCI.&TECH., China).Master used
Want reagent purchased from Mike woods or An Naiji Reagent Company.
Embodiment 1
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride, 58.0mg1,3,5- tri- (4- aminophenyl) amine, 50mgC are weighed60, pass through beforehand research
Mill is uniformly mixed, and is added in glass tube sealing, the isoquinolin and 0.5mL mesitylene and N- methylpyrrole of 1 ‰ mass concentrations of addition
The mixed solvent that alkanone volume ratio is 1: 1, makes to be uniformly mixed by ultrasound, reaction system is taken out under the conditions of liquid nitrogen frozen true
Sky is repeated 3 times, and is allowed to seal by alcohol blast burner ablation glass tube sealing, and reaction system is warming up to 200 DEG C, reacts 72h, cold
But the crude product of composite material is obtained afterwards.
2) by the crude product of the composite material of above-mentioned synthesis, sufficiently washing removes unreacted list in tetrahydrofuran solvent
Body, heat drying 12h under the conditions of vacuum, 120 DEG C, obtains constructing based on pyromellitic dianhydride after being cooled to room temperature poly- later
The covalent organic frame of imide-type and C60In-situ composite 1.
X-ray polycrystalline diffraction phenogram characteristic peak shows that composite material has in 3.2 °, 5.5 °, 6.6 °, 17.7 ° in Fig. 1
The feature of covalent organic frame, and there is good crystallinity；Fig. 2 is the nitrogen adsorption and desorption curve figure of composite material,
The specific surface area of the composite material of synthesis is 874m2/g；A is C in Fig. 360TEM figure, b be composite material TEM scheme, contrast table
Bright, the covalent organic frame of polyimide type is uniformly compounded in carbon material surface, obtains one kind and is constructed based on pyromellitic dianhydride
The covalent organic frame of polyimide type and C60In-situ composite.
Embodiment 2
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride, 58.0mg1,3,5- tri- (4- aminophenyl) amine, 50mg multi-wall carbon nano-tube are weighed
Pipe, by pre-grinding be uniformly mixed, be added glass tube sealing in, be added 2 ‰ mass concentrations isoquinolin and 0.5mL mesitylene with
The mixed solvent that N-Methyl pyrrolidone volume ratio is 1: 1, makes to be uniformly mixed, by reaction system in liquid nitrogen frozen item by ultrasound
It vacuumizes, is repeated 3 times under part, be allowed to seal by alcohol blast burner ablation glass tube sealing, reaction system be warming up to 200 DEG C, instead
72h is answered, obtains the crude product of composite material after cooling.
2) crude product of the composite material of above-mentioned synthesis is sufficiently washed in tetrahydrofuran solvent unreacted to remove
Monomer passes through supercritical CO later2Seasoning is dry, condition be 20mL/min in 50 DEG C, 10MP, gas flow rate under keep
3h obtains the covalent organic frame of the polyimide type constructed based on pyromellitic dianhydride and multi-walled carbon nanotube after being cooled to room temperature
In-situ composite 2.
X-ray polycrystalline diffraction phenogram characteristic peak shows composite wood in 3.3 °, 5.5 °, 6.3 °, 8.7 °, 26.9 ° in Fig. 4
Expect the feature with covalent organic frame, and there is good crystallinity；Fig. 5 is the nitrogen adsorption and desorption song of composite material
Line chart, the specific surface area of the composite material of synthesis are 1124m2/g；A is that the TEM of multi-walled carbon nanotube schemes in Fig. 6, and b is composite wood
The TEM of material schemes, and comparison shows that the covalent organic frame of polyimide type is uniformly compounded in carbon material surface, obtains one kind and be based on
The covalent organic frame of the polyimide type that pyromellitic dianhydride is constructed and multi-walled carbon nanotube in-situ composite.
Embodiment 3
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride, 58.0mg1,3,5- tri- (4- aminophenyl) amine, 200mg single are weighed
Pipe is uniformly mixed by pre-grinding, is added in water heating kettle, and the isoquinolin and 1mL mesitylene solvent of 3 ‰ mass concentrations is added,
Make to be uniformly mixed by ultrasound, reaction system is vacuumized under the conditions of liquid nitrogen frozen, is repeated 3 times, passes through alcohol blast burner ablation
Glass tube sealing is allowed to seal, and reaction system is warming up to 160 DEG C, reacts 120h, obtains the crude product of composite material after cooling.
2) crude product of the composite material of above-mentioned synthesis is sufficiently washed in methanol agent to remove unreacted monomer, it
Dry 12h is freeze-dried under the conditions of vacuum, -30 DEG C afterwards, obtains constructing based on pyromellitic dianhydride after being cooled to room temperature poly-
The covalent organic frame of imide-type and single-walled carbon nanotube in-situ composite 3.
Embodiment 4
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride, 70.2mg1,3,5- tri- (4- aminophenyl) benzene, 1.5mgC are weighed60, by pre-
Ground and mixed is uniform, is added in glass tube sealing, and the isoquinolin and 0.2mLN of 0.05 ‰ mass concentrations, dinethylformamide is added
Solvent makes to be uniformly mixed by ultrasound, and reaction system is vacuumized under the conditions of liquid nitrogen frozen, is repeated 3 times, passes through alcohol blast burner
Ablation glass tube sealing is allowed to seal, and reaction system is warming up to 240 DEG C, reaction for 24 hours, obtains the thick production of composite material after cooling
Object.
2) crude product of the composite material of above-mentioned synthesis is sufficiently washed in methanol solvate to remove unreacted monomer,
Heat drying 6h under the conditions of vacuum, 150 DEG C later obtains the polyamides constructed based on pyromellitic dianhydride Asia after being cooled to room temperature
The covalent organic frame of amine type and C60In-situ composite 4.
Embodiment 5
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride, 70.2mg1,3,5- tri- (4- aminophenyl) benzene, 100mg multi-wall carbon nano-tube are weighed
Pipe is uniformly mixed by pre-grinding, is added in glass tube sealing, and the isoquinolin and 2mL toluene solvant of 1 ‰ mass concentrations is added, and is led to
Crossing ultrasound makes to be uniformly mixed, and reaction system is vacuumized under the conditions of liquid nitrogen frozen, is repeated 3 times, alcohol blast burner ablation glass is passed through
Glass tube sealing is allowed to seal, and reaction system is warming up to 240 DEG C, reacts 120h, obtains the crude product of composite material after cooling.
2) crude product of the composite material of above-mentioned synthesis is sufficiently washed in N-N dimethylacetamide solvent to remove not
The monomer of reaction, passes through supercritical CO later2Seasoning is dry, and condition is in the case where 70 DEG C, 20MP, gas flow rate are 20mL/min
1h is kept, the covalent organic frame of the polyimide type constructed based on pyromellitic dianhydride is obtained after being cooled to room temperature and is received with multi wall carbon
Mitron in-situ composite 5.
Embodiment 6
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride is weighed, 70.2mg1,3,5- tri- (4- aminophenyl) benzene, 1000mg single wall carbon receives
Mitron is uniformly mixed by pre-grinding, is added in water heating kettle, and isoquinolin and the 5mL dioxane that 3 ‰ mass concentrations are added are molten
Agent makes to be uniformly mixed by ultrasound, and reaction system is vacuumized under the conditions of liquid nitrogen frozen, is repeated 3 times, is burnt by alcohol blast burner
Erosion glass tube sealing is allowed to seal, and reaction system is warming up to 240 DEG C, reacts 120h, obtains the crude product of composite material after cooling.
2) crude product of the composite material of above-mentioned synthesis is sufficiently washed in N-N solvent dimethylformamide to remove not
The monomer of reaction is freeze-dried dry 12h under the conditions of vacuum, -30 DEG C later, is obtained after being cooled to room temperature based on equal benzene tetramethyl
The covalent organic frame of the polyimide type that acid anhydrides is constructed and single-walled carbon nanotube in-situ composite 6.
Embodiment 7
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride is weighed, 70.8mg2,4,6- tri- (4- aminophenyl) -1,3,5-triazines,
1000mgC60, it is uniformly mixed, is added in glass tube sealing by pre-grinding, the isoquinolin and the equal front three of 5mL of 3 ‰ mass concentrations is added
Benzene makes to be uniformly mixed by ultrasound, and reaction system is vacuumized under the conditions of liquid nitrogen frozen, is repeated 3 times, is burnt by alcohol blast burner
Erosion glass tube sealing is allowed to seal, and reaction system is warming up to 180 DEG C, reacts 96h, obtains the crude product of composite material after cooling.
2) crude product of the composite material of above-mentioned synthesis is sufficiently washed in acetone solvent to remove unreacted monomer,
Dry 6h is freeze-dried under the conditions of vacuum, -35 DEG C later, obtains constructing based on pyromellitic dianhydride after being cooled to room temperature poly-
The covalent organic frame of imide-type and C60In-situ composite 7.
Embodiment 8
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride, 70.8mg2,4,6- tri- (4- aminophenyl) -1,3,5-triazines, 500mg are weighed
Multi-walled carbon nanotube is uniformly mixed by pre-grinding, is added in water heating kettle, and the isoquinolin and 4mLN- of 2.5 ‰ mass concentrations is added
Methyl pyrrolidone makes to be uniformly mixed by ultrasound, and reaction system is vacuumized under the conditions of liquid nitrogen frozen, is repeated 3 times, passes through
Alcohol blast burner ablation glass tube sealing is allowed to seal, and reaction system is warming up to 220 DEG C, reacts 72h, obtains composite material after cooling
Crude product.
2) crude product of the composite material of above-mentioned synthesis is sufficiently washed in acetone solvent to remove unreacted monomer,
Pass through supercritical CO later2Seasoning is dry, condition be 200mL/min in 45 DEG C, 8MP, gas flow rate under keep 5h, it is cooling
The covalent organic frame of the polyimide type constructed based on pyromellitic dianhydride is obtained after to room temperature and multi-walled carbon nanotube is multiple in situ
Condensation material 8.
Embodiment 9
The method of carbon material surface in-situ preparation polyimide type covalent organic frame material, steps are as follows:
1) 65.4mg pyromellitic dianhydride, 70.8mg2,4,6- tri- (4- aminophenyl) -1,3,5-triazines, 150mg are weighed
Single-walled carbon nanotube is uniformly mixed by pre-grinding, is added in glass tube sealing, and the isoquinolin and 3mL of 0.5 ‰ mass concentrations is added
The mixed solvent that dioxane and volume of toluene ratio are 1: 1, makes to be uniformly mixed, by reaction system in liquid nitrogen frozen item by ultrasound
It vacuumizes, is repeated 3 times under part, be allowed to seal by alcohol blast burner ablation glass tube sealing, reaction system be warming up to 160 DEG C, instead
120h is answered, obtains the crude product of composite material after cooling.
2) crude product of the composite material of above-mentioned synthesis is sufficiently washed in methanol solvate to remove unreacted monomer,
Heat drying 12h under the conditions of vacuum, 60 DEG C later obtains the polyamides constructed based on pyromellitic dianhydride Asia after being cooled to room temperature
The covalent organic frame of amine type and single-walled carbon nanotube in-situ composite 9.
Claims (9)
1. the method for carbon material surface in-situ preparation polyimide type covalent organic frame material, which is characterized in that including as follows
Step:
1) it by pyromellitic dianhydride, the monomer and carbon nanomaterial of three-functionality-degree amine, is uniformly mixed and is placed in reaction unit, In
Catalyst, solvent are added in reaction unit, ultrasonic mixing is uniform, liquid nitrogen frozen, vacuumizes and flame sealing, heating reaction are cold
But to obtaining the crude product of composite material after room temperature；Specific reaction equation is as follows:
2) crude product of above-mentioned composite material is washed in organic solvent, obtains the covalent organic frame of polyimide type after dry
With carbon nanomaterial in-situ composite.
2. the method for carbon material surface in-situ preparation polyimide type covalent organic frame material according to claim 1,
It is characterized in that, in step 1), the monomer of three-functionality-degree amine, including three (4- aminophenyl) amine, 1,3,5- tri- (4- aminophenyls)
Benzene, 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines；Carbon nanomaterial includes C60, single-walled carbon nanotube, multi-wall carbon nano-tube
Pipe；Reaction unit is glass tube sealing or water heating kettle.
3. the method for carbon material surface in-situ preparation polyimide type covalent organic frame material according to claim 1,
It is characterized in that, the molar ratio of pyromellitic dianhydride and three-functionality-degree amine is 3: 2 in step 1)；Pyromellitic dianhydride is received with carbon
The mass ratio of rice material is 1: 0.02-15.5.
4. the method for carbon material surface in-situ preparation polyimide type covalent organic frame material according to claim 1,
It is characterized in that, catalyst is isoquinolin in step 1), mass concentration is 0.05 ‰ -3 ‰；Solvent is mesitylene, N- methyl
At least one of pyrrolidones, n,N-Dimethylformamide, toluene, dioxane.
5. the method for carbon material surface in-situ preparation polyimide type covalent organic frame material according to claim 1,
It is characterized in that, reaction temperature is 160-240 DEG C in step 1), the reaction time is -120h for 24 hours.
6. the method for carbon material surface in-situ preparation polyimide type covalent organic frame material according to claim 1,
It is characterized in that, washing is methanol, n,N-dimethylacetamide, tetrahydrofuran, N, N- dimethyl with organic solvent in step 2)
At least one of formamide, acetone.
7. the method for carbon material surface in-situ preparation polyimide type covalent organic frame material according to claim 1,
It is characterized in that, drying means is boulton process, supercritical CO in step 2)2Seasoning, freeze-drying.
8. the method for carbon material surface in-situ preparation polyimide type covalent organic frame material according to claim 7,
It is characterized in that, boulton process drying condition is dried in vacuo 6h-12h under the conditions of being 60-150 DEG C；Supercritical CO2Seasoning is dry
Dry condition is 45-70 DEG C, 8-20MP, gas flow rate keep 1-5h under being 20-200mL/min；Freeze-drying drying condition is
At -35 DEG C -- 30 DEG C of vacuum drying 6-12h.
9. polyimide type covalent organic frame material made from claim 1-8 either method.
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