CN110172168A - A kind of aminated carbon nano tube/polyimide composite film and preparation method thereof - Google Patents
A kind of aminated carbon nano tube/polyimide composite film and preparation method thereof Download PDFInfo
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a kind of aminated carbon nano tube/polyimide composite films and preparation method thereof, belong to imide membrane preparation technical field.A kind of preparation method of aminated carbon nano tube/polyimide composite film, comprising the following steps: 1) in a solvent by aminated carbon nano tube and polyamic acid dispersion, stirred under ice bath, obtain polyamic acid/aminated carbon nano tube mixed solution；2) polyamic acid/aminated carbon nano tube mixed solution is formed a film using casting method or pulling method, and the mixed solution on supporter is subjected to hot imidization, obtain aminated carbon nano tube/polyimide composite film.The preparation method solves the problems, such as to exist in polyimide composite film and is easy to reunite, disperses unevenness.Aminated carbon nano tube/polyimide composite film prepared by the present invention, aminated carbon nano tube are uniformly dispersed, and thermal conductivity is high.
Description
Technical field
The present invention relates to Kapton preparation technical field more particularly to a kind of aminated carbon nano tube/polyamides are sub-
Amine laminated film and preparation method thereof.
Background technique
Polyimides is the Typical Representative having in the high-molecular organic material of good comprehensive performance, has resistance to height outstanding
Cryogenic property, without apparent fusing point, insulation performance is especially prominent, is usually used as product in the form of a film.Utilize polyimides
The excellent high temperature insulation of film, will be such that it applies in motor in early days, its presence can be improved the high-temperature thermal stability of motor
Property, and Kapton has been widely used in Aeronautics and Astronautics, microelectronics, nanotechnology, liquid crystal technology, seperation film skill at present
The fields such as art and laser technology further increase its comprehensive performance as polyimides with the expansion of application field
The emphasis of thin film study.
Carbon nanotube can be formed by one layer or multilayer mono-layer graphite according to the curling of some helical angle, diameter is nanometer
The cylindrical shell of magnitude, has that good electricity, mechanical, heat and magnetic performance, intensity are high, elasticity is big, density is low, specific surface area
The advantages that height, chemical property are stable, hydrophobicity is strong is a kind of very valuable heat filling.
Carbon nanotube is applied to there is a problem of being easy reunion in polyimide composite film, disperses unevenness, while thermally conductive
Property is relatively low, these defects limit application of the carbon nanotube in Kapton.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, it is sub- to provide a kind of aminated carbon nano tube/polyamides
Amine laminated film and preparation method thereof.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of preparation method of aminated carbon nano tube/polyimide composite film, comprising the following steps:
1) in a solvent by aminated carbon nano tube and polyamic acid dispersion, polyamic acid/aminated carbon nano tube is obtained
Mixed solution；
2) polyamic acid/aminated carbon nano tube mixed solution is formed a film using casting method or pulling method, and will branch
Liquid film on support body carries out hot imidization, obtains aminated carbon nano tube/polyimide composite film.
Further, in step 1) in polyamic acid/aminated carbon nano tube mixed solution aminated carbon nano tube matter
Amount score is 0.15%-0.25%, and the mass fraction of polyamic acid is 8%-12%.
Further, the solvent in step 1) is n,N-dimethylacetamide, n,N-Dimethylformamide, N- methyl
Pyrrolidones or dimethyl sulfoxide.
Further, the hot imidization in step 2) carries out in vacuum or inert gas.
Further, in step 2) by supporter mixed solution carry out hot imidization specifically includes the following steps:
201) temperature is warming up to 50~60 DEG C, and the mixed solution on supporter is obtained in 3~4h of this temperature
The first film；
202) temperature is risen to 100~120 DEG C, and the first film is kept the temperature into 1~2h at this temperature, it is thin to obtain second
Film；
203) temperature is risen to 200~210 DEG C, and the second film is kept the temperature into 1~2h at this temperature, obtain amination carbon
Nanotube/polyimide composite film.
Further, step 202) and 203) in heating rate be 2~3 DEG C/min.
Further, the amino source of aminated carbon nano tube and the synthesis material diamine monomer of polyamic acid are identical.
Further, the diamine monomer is 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ether, 4,4 '-diamino
Base -3,3 '-dimethyl diphenyl, p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diamino -3,3 '-two (trifluoromethyl) biphenyl, 2- (4-
Aminophenyl) -5- aminopyrimidine, 2- amino -5 (4- aminophenyl)-pyrimidine, 2- (4- aminophenyl) -5- aminopyridine, 2,5-
One of two (4- aminophenyl) pyrimidines and 2,5- bis- (4- aminophenyl) pyridine are a variety of.
A kind of amination carbon that the preparation method using above-mentioned aminated carbon nano tube/polyimide composite film obtains is received
Mitron/polyimide composite film.
Compared with prior art, the invention has the following advantages:
Aminated carbon nano tube/polyimide composite film preparation method of the invention, during hot imidization
The compound of aminated carbon nano tube and polyimides is completed, easy to operate, the aminated carbon nano tube in film is uniformly dispersed；Into
One step, multi-solvents can use, and the range of choice of raw material is wide；Hot imidization can be into one in vacuum or inert gas progress
The mechanical property of film after the enhancing film forming of step；The amino source of aminated carbon nano tube and the synthesis material two of polyamic acid
Amine monomers are identical, and the further aminated carbon nano tube that improves is in the dispersibility of polyamic acid.
The amination being prepared using aminated carbon nano tube/polyimide composite film preparation method of the invention
Carbon nano-tube/polyimide laminated film, aminated carbon nano tube is uniformly dispersed in film, and film has excellent heating conduction
Good, when aminated carbon nano tube content is 4%, polyimide composite film thermal conductivity can 0.6289W/mK.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of Kapton section；
Polyimides/aminated carbon nano tube laminated film section that Fig. 2 is aminated carbon nano tube content when being 3%
Scanning electron microscope diagram；
Fig. 3 is that polyimides/aminated carbon nano tube laminated film that the carbon nanotube of different content is prepared is led
Heating rate；
Fig. 4 is polyimides/aminated carbon nano tube laminated film drawing that the carbon nanotube of different content is prepared
Stretch intensity.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work
It encloses.
It should be noted that description and claims of this specification and term " first " in above-mentioned attached drawing, "
Two " etc. be to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that using in this way
Data be interchangeable under appropriate circumstances, so as to the embodiment of the present invention described herein can in addition to illustrating herein or
Sequence other than those of description is implemented.In addition, term " includes " and " having " and their any deformation, it is intended that cover
Cover it is non-exclusive include, for example, the process, method, system, product or equipment for containing a series of steps or units are not necessarily limited to
Step or unit those of is clearly listed, but may include be not clearly listed or for these process, methods, product
Or other step or units that equipment is intrinsic.
The invention will be described in further detail with reference to the accompanying drawing:
Embodiment 1
1) amino multi-wall carbon nanotube of 0.15g is taken to be put into beaker, by 91.85gN, N- dimethyl acetamide is poured into
In the beaker, it is ultrasonically treated 1h at room temperature, the polyamic acid that 8g is added continues ultrasound 0.5h；
Mixed solution after ultrasonic treatment is stirred into 30min under condition of ice bath, obtains aminated carbon nano tube/polyamide
Acid solution；
2) a piece of clean glass plate is taken, on a glass by aminated carbon nano tube/polyamic acid solution, adjustment is scraped
The height of diaphragm plate scratches solution even uniform on a glass with diaphragm plate is scraped, is placed in vacuum drying oven and vacuumizes later, temperature
Degree is set as 50 DEG C and keeps 3h, is warming up to 100 DEG C of holding 1h later, is finally warming up to 200 DEG C of holding 1h, heating rate setting
For 2 DEG C/min, aminated carbon nano tube/Kapton is obtained；
Aminated carbon nano tube in embodiment 1 the preparation method is as follows:
2g multi-walled carbon nanotube is poured into beaker, mix acid liquor (concentrated sulfuric acid and concentrated nitric acid that volume ratio is 3:1) is added
Enter into the beaker, is ultrasonically treated multi-walled carbon nanotube 1h at room temperature；
By the suspension after ultrasonic treatment 70 DEG C at a temperature of be vigorously stirred for 24 hours, pour into deionized water, staticly settle；
It washs, be centrifuged, be dried to obtain functionalized multi-wall carbonnanotubes, specifically, clear liquid above removal suspension, by lower layer
Suspension is centrifuged twice, and the solid of centrifuge tube is washed with deionized.It is put into vacuum drying oven or electric drying oven with forced convection
Middle evaporation deionized water, then washed with n,N-dimethylacetamide, it is centrifuged, the solid n,N-dimethylacetamide in centrifuge tube
Washing is got off, and is put into drying 8h in vacuum drying oven and is obtained functionalized multi-wall carbonnanotubes；
0.4g carboxylic carbon nano-tube is poured into three-necked flask, monomer (ODA), 2g dehydrating agent that 4g contains amino is added
(DCC), 1.2g catalyst (DMAP) and 40mL solvent (DMF), by magnetic agitation 96h under mixed solution again 70 DEG C of oil baths；Finally
Centrifugation obtains amino multi-wall carbon nanotube, specifically, pour out suspension is centrifuged 10min in centrifuge tube, pours out suspension later
Lower layer's suspension is continued to be centrifuged by clear liquid above liquid, and the solid in centrifuge tube is got off with ethanol washing.Be put into vacuum drying oven or
Ethanol evaporation in electric drying oven with forced convection, obtains amino multi-wall carbon nanotube.
The polyamic acid synthetic method of embodiment 1 is as follows:
4, the 4'- diaminodiphenyl ether (ODA) and 45mL n,N-dimethylacetamide of 2.27g are placed in three-necked flask,
30min is stirred under conditions of ice-water bath, 2.53g pyromellitic dianhydride (PMDA) is added in above-mentioned solution, temperature several times
Control is at 5 DEG C or less；Continue to react 1h at 5 DEG C later, has obtained polyamic acid solution；
4,4'- diaminodiphenyl ethers (ODA) are used as diamine monomer, and diamine monomer can also be 3,4 '-diaminodiphenyl ethers
4,4 '--3,3 '-dimethyl diphenyls of diamino, p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diamino -3,3 '-two (trifluoromethyl) connection
Benzene, 2- (4- aminophenyl) -5- aminopyrimidine, 2- amino -5 (4- aminophenyl)-pyrimidine, 2- (4- aminophenyl) -5- amino
One of pyridine, (4- aminophenyl) pyrimidine of 2,5- bis- and 2,5- bis- (4- aminophenyl) pyridine are a variety of；Benzene tetracarboxylic acid acid anhydride
It (PMDA) is as dianhydride monomer, dianhydride monomer can also be pyromellitic dianhydride, 3,4,3 ', 4 '-bibenzene tetracarboxylic dianhydrides, 2,
3,3 ', 4 '-bibenzene tetracarboxylic dianhydrides, 3,4,3 ', 4 '-diphenyl thio-ether tetrformate dianhydrides, 3,4,3 ', 4 '-triphen bis ether tetracarboxylic acids
Dianhydride, 4,4 '-(hexafluoroisopropyli,ene)-two anhydride phthalic acids, 3,4,3 ', 4 '-benzophenone tetracarboxylic dianhydrides, 3,4,3 ', 4 '-hexichol
Ether dianhydride and 4,4 '-is to one of two ether dianhydride of benzene or a variety of；
The polyamic acid solution of synthesis is dissolved in acetone under agitation, the polyamic acid of precipitation is dried to obtain polyamides
Amino acid solid.
Embodiment 2
1) it takes the aminated carbon nano tube of 0.25g in beaker, 87.75g n,N-Dimethylformamide is poured into the beaker
In, it is ultrasonically treated 1h at room temperature, the polyamic acid of 12g, ultrasonic 0.5h is added；
By the mixed solution after ultrasonic treatment, 30min is stirred at room temperature, it is molten to obtain aminated carbon nano tube/polyamic acid
Liquid；
2) a piece of clean glass plate is taken, on a glass by aminated carbon nano tube/polyamic acid solution, adjustment is scraped
The height of diaphragm plate scratches solution even uniform on a glass with diaphragm plate is scraped, is placed in vacuum drying oven and vacuumizes later, temperature
Degree is set as 60 DEG C and keeps 4h, is warming up to 120 DEG C of holding 2h later, is finally warming up to 210 DEG C of holding 2h, heating rate setting
For 3 DEG C/min, aminated carbon nano tube/Kapton is obtained.
Aminated carbon nano tube in embodiment 2 the preparation method is as follows:
4g multi-walled carbon nanotube is poured into beaker, by 300mL mix acid liquor (volume ratio of the concentrated sulfuric acid and concentrated nitric acid be 3:
1) it is added in the beaker, ultrasonic 1h obtains suspension；
By the suspension after ultrasonic treatment 70 DEG C at a temperature of be vigorously stirred for 24 hours, pour into deionized water, staticly settle；
It washs, be centrifuged, be dried to obtain functionalized multi-wall carbonnanotubes, specifically, clear liquid above removal suspension, by lower layer
Suspension is centrifuged twice, and the solid of centrifuge tube is washed with deionized.It is put into vacuum drying oven or electric drying oven with forced convection
Middle evaporation deionized water, then washed with n,N-dimethylacetamide, it is centrifuged, the solid n,N-dimethylacetamide in centrifuge tube
Washing is got off, and is put into drying 8h in vacuum drying oven and is obtained functionalized multi-wall carbonnanotubes；
0.4g carboxylic carbon nano-tube is poured into three-necked flask, addition 4g 2- amino -5 (4- aminophenyl)-pyrimidine,
2g DCC, 1.2g DMAP and 40mL DMF, by magnetic agitation 96h under mixed solution again 70 DEG C of oil baths；Finally centrifugation obtains amino
Multi-walled carbon nano-tube pours out clear liquid above suspension specifically, pour out suspension is centrifuged 10min in centrifuge tube later, will
Lower layer's suspension continues to be centrifuged, and the solid in centrifuge tube is got off with ethanol washing.It is put into vacuum drying oven or electric heating forced air drying
Ethanol evaporation in case, obtains amino multi-wall carbon nanotube.
Polyamic acid synthetic method in embodiment 2 is as follows:
(4- the aminophenyl)-pyrimidine of 2- amino -5 and 45mL DMAC N,N' dimethyl acetamide of 2.27g are placed in three-necked flask
In, 30min is stirred under conditions of ice-water bath, 2.53g pyromellitic dianhydride (PMDA) is added several times in above-mentioned solution,
Temperature is controlled at 5 DEG C or less；Continue to react 1h under the conditions of ice-water bath later, has obtained polyamic acid solution；
The polyamic acid solution of synthesis is dissolved in acetone under agitation, the polyamic acid of precipitation is dried to obtain polyamides
Amino acid solid.
Embodiment 3
1) take the aminated carbon nano tube of 0.2g in beaker, by 89.8gN, N-N- methyl pyrrolidone pours into the beaker
In, it is ultrasonically treated 1h at room temperature, the polyamic acid of 10g is added；
By the mixed solution after ultrasonic treatment, 30min is stirred at room temperature, it is molten to obtain aminated carbon nano tube/polyamic acid
Liquid；
2) a piece of clean glass plate is taken, on a glass by aminated carbon nano tube/polyamic acid solution, adjustment is scraped
The height of diaphragm plate scratches solution even uniform on a glass with diaphragm plate is scraped, is placed in vacuum drying oven and vacuumizes later, temperature
Degree is set as 55 DEG C and keeps 3.5h, is warming up to 110 DEG C of holding 1.5h later, is finally warming up to 205 DEG C of holding 1.5h, heating speed
Rate is set as 2.5 DEG C/min, obtains aminated carbon nano tube/Kapton.
Aminated carbon nano tube in embodiment 3 the preparation method is as follows:
4g carbon nanotube is poured into beaker, 300mL mix acid liquor (volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1) is added
Enter into the beaker, ultrasonic 1h obtains suspension；
By the suspension after ultrasonic treatment 70 DEG C at a temperature of be vigorously stirred for 24 hours, pour into deionized water, staticly settle；
It washs, be centrifuged, be dried to obtain functionalized multi-wall carbonnanotubes, specifically, clear liquid above removal suspension, by lower layer
Suspension is centrifuged twice, and the solid of centrifuge tube is washed with deionized.It is put into vacuum drying oven or electric drying oven with forced convection
Middle evaporation deionized water, then washed with n,N-dimethylacetamide, it is centrifuged, the solid n,N-dimethylacetamide in centrifuge tube
Washing is got off, and is put into drying 8h in vacuum drying oven and is obtained functionalized multi-wall carbonnanotubes；
0.4g carboxylic carbon nano-tube is poured into three-necked flask, be added total amount be 4g p-phenylenediamine and m-phenylene diamine (MPD),
2g DCC, 1.2g DMAP and 40mL DMF, by magnetic agitation 96h under mixed solution again 70 DEG C of oil baths；Finally centrifugation obtains amino
Multi-walled carbon nano-tube pours out clear liquid above suspension specifically, pour out suspension is centrifuged 10min in centrifuge tube later, will
Lower layer's suspension continues to be centrifuged, and the solid in centrifuge tube is got off with ethanol washing.It is put into vacuum drying oven or electric heating forced air drying
Ethanol evaporation in case, obtains amino multi-wall carbon nanotube.
Polyamic acid synthetic method in embodiment 3 is as follows:
P-phenylenediamine and m-phenylene diamine (MPD) and 45mL DMAC N,N' dimethyl acetamide that total amount is 2.27g are placed in three-necked flask
In, 30min is stirred under conditions of ice-water bath, 2.53g pyromellitic dianhydride (PMDA) is added several times in above-mentioned solution,
Temperature is controlled at 5 DEG C or less；Continue to react 1h under the conditions of ice-water bath later, has obtained polyamic acid solution；
The polyamic acid solution of synthesis is dissolved in acetone under agitation, the polyamic acid of precipitation is dried to obtain polyamides
Amino acid solid.
Embodiment 4
1) it takes the aminated carbon nano tube of 0.15g in beaker, 88.85g dimethyl sulfoxide is poured into the beaker, in room
Temperature is lower to be ultrasonically treated 1h, and the polyamic acid of 11g is added；
By the mixed solution after ultrasonic treatment, 30min is stirred at room temperature, it is molten to obtain aminated carbon nano tube/polyamic acid
Liquid；
2) a piece of clean glass plate is taken, on a glass by aminated carbon nano tube/polyamic acid solution, adjustment is scraped
The height of diaphragm plate scratches solution even uniform on a glass with diaphragm plate is scraped, is placed in vacuum drying oven and vacuumizes later, temperature
Degree is set as 58 DEG C and keeps 4h, is warming up to 115 DEG C of holding 1h later, is finally warming up to 200 DEG C of holding 1.5h, heating rate is set
It is set to 2 DEG C/min, obtains aminated carbon nano tube/Kapton.
Aminated carbon nano tube in embodiment 4 the preparation method is as follows:
4g carbon nanotube is poured into beaker, 300mL mix acid liquor (volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1) is added
Enter into the beaker, ultrasonic 1h obtains suspension；
By the suspension after ultrasonic treatment 70 DEG C at a temperature of be vigorously stirred for 24 hours, pour into deionized water, staticly settle；
It washs, be centrifuged, be dried to obtain functionalized multi-wall carbonnanotubes, specifically, clear liquid above removal suspension, by lower layer
Suspension is centrifuged twice, and the solid of centrifuge tube is washed with deionized.It is put into vacuum drying oven or electric drying oven with forced convection
Middle evaporation deionized water, then washed with n,N-dimethylacetamide, it is centrifuged, the solid n,N-dimethylacetamide in centrifuge tube
Washing is got off, and is put into drying 8h in vacuum drying oven and is obtained functionalized multi-wall carbonnanotubes；
0.4g carboxylic carbon nano-tube is poured into three-necked flask, 3, the 4 '-diaminodiphenyl ethers 4 that total amount is 4g are added,
4 '--3,3 '-dimethyl diphenyls of diamino, 4,4 '-diamino -3,3 '-two (trifluoromethyl) biphenyl, 2- (4- aminophenyl) -5-
Aminopyrimidine and (4- aminophenyl) pyrimidine of 2,5- bis- and 2,5- bis- (4- aminophenyl) pyridine, 2g DCC, 1.2g DMAP and
40mL DMF, by magnetic agitation 96h under mixed solution again 70 DEG C of oil baths；Finally centrifugation obtains amino multi-wall carbon nanotube, has
Body, pour out suspension and be centrifuged 10min in centrifuge tube, pour out clear liquid above suspension later, by lower layer's suspension continue from
The heart, the solid in centrifuge tube are got off with ethanol washing.It is put into ethanol evaporation in vacuum drying oven or electric drying oven with forced convection, is obtained
Amino multi-wall carbon nanotube.
Polyamic acid synthetic method in embodiment 4 is as follows:
3,4 '--3,3 '-dimethyl diphenyls of 4,4 '-diamino of diaminodiphenyl ether, the 4,4 '-diaminos for being 2.27g by total amount
Base -3,3 '-two (trifluoromethyl) biphenyl, 2- (4- aminophenyl) -5- aminopyrimidine and (4- aminophenyl) pyrimidine of 2,5- bis- and
2,5- bis- (4- aminophenyl) pyridines and 45mL n,N-dimethylacetamide are placed in three-necked flask, under conditions of ice-water bath
2.53g pyromellitic dianhydride (PMDA) is added in above-mentioned solution stirring 30min several times, and temperature is controlled at 5 DEG C or less；It
After continue to react 1h under the conditions of ice-water bath, obtained polyamic acid solution；
The polyamic acid solution of synthesis is dissolved in acetone under agitation, the polyamic acid of precipitation is dried to obtain polyamides
Amino acid solid.
Referring to Fig. 1 and Fig. 2, Fig. 1 and Fig. 2 is respectively the scanning electron microscope diagram and amination of Kapton section
Polyimides/aminated carbon nano tube laminated film section scanning electron microscope diagram when content of carbon nanotubes is 3%；Figure
Section in 2 becomes coarse relative to the section of Fig. 1, this is because aminated carbon nano tube there are the reason of.
Referring to Fig. 3, Fig. 3 is polyimides/amination carbon nanometer that the aminated carbon nano tube of different content is prepared
The thermal conductivity of pipe laminated film, the percentage composition of aminated carbon nano tube is the quality and polyamide of aminated carbon nano tube herein
The mass ratio of acid, the compound after aminated carbon nano tube is added on the whole is not than adding the thermally conductive of aminated carbon nano tube
Rate wants high, and the amount with addition aminated carbon nano tube increases, and aminated carbon nano tube increases with it.
Referring to fig. 4, Fig. 4 is the polyimides/aminated carbon nano tube THIN COMPOSITE being prepared with the carbon nanotube of content
The tensile strength of film, the percentage composition of aminated carbon nano tube is the quality of aminated carbon nano tube and the matter of polyamic acid herein
The ratio between amount, it can be seen from the figure that the amount for the aminated carbon nano tube being added is not to be exceeded 3%, when additional amount is less than 3%, with
The increase tensile strength of additive amount increase with it, and more than 3% after, tensile strength sharply declines.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press
According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention
Protection scope within.
Claims (9)
1. a kind of preparation method of aminated carbon nano tube/polyimide composite film, which comprises the following steps:
1) polyamic acid/aminated carbon nano tube mixing in a solvent by aminated carbon nano tube and polyamic acid dispersion, is obtained
Solution；
2) polyamic acid/aminated carbon nano tube mixed solution is formed a film using casting method or pulling method, and by supporter
On liquid film carry out hot imidization, obtain aminated carbon nano tube/polyimide composite film.
2. the preparation method of aminated carbon nano tube/polyimide composite film according to claim 1, feature exist
In the mass fraction of aminated carbon nano tube is 0.15%- in polyamic acid/aminated carbon nano tube mixed solution in step 1)
0.25%, the mass fraction of polyamic acid is 8%-12%.
3. the preparation method of aminated carbon nano tube/polyimide composite film according to claim 1, feature exist
In the solvent in step 1) is n,N-dimethylacetamide, n,N-Dimethylformamide, N-Methyl pyrrolidone or diformazan
Base sulfoxide.
4. the preparation method of aminated carbon nano tube/polyimide composite film according to claim 1, feature exist
In the hot imidization in step 2) carries out in vacuum or inert gas.
5. the preparation method of aminated carbon nano tube/polyimide composite film according to claim 1 or 4, feature
Be, in step 2) by supporter mixed solution carry out hot imidization specifically includes the following steps:
201) temperature is warming up to 50~60 DEG C, and the mixed solution on supporter is obtained first in 3~4h of this temperature
Film；
202) temperature is risen to 100~120 DEG C, and the first film is kept the temperature into 1~2h at this temperature, obtain the second film；
203) temperature is risen to 200~210 DEG C, and the second film is kept the temperature into 1~2h at this temperature, obtain amination carbon nanometer
Pipe/polyimide composite film.
6. the preparation method of aminated carbon nano tube/polyimide composite film according to claim 5, feature exist
In, step 202) and 203) heating rate in is 2~3 DEG C/min.
7. the preparation method of aminated carbon nano tube/polyimide composite film according to claim 1, feature exist
In the amino source of aminated carbon nano tube and the synthesis material diamine monomer of polyamic acid are identical.
8. the preparation method of aminated carbon nano tube/polyimide composite film according to claim 7, feature exist
In the diamine monomer is 4,4 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ether, 4,4 '-diamino -3,3 '-dimethyl connection
Benzene, p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diamino -3,3 '-two (trifluoromethyl) biphenyl, 2- (4- aminophenyl) -5- amino
Pyrimidine, 2- amino -5 (4- aminophenyl)-pyrimidine, 2- (4- aminophenyl) -5- aminopyridine, 2,5- bis- (4- aminophenyl) are phonetic
One of pyridine and 2,5- bis- (4- aminophenyl) pyridine are a variety of.
9. a kind of preparation side of aminated carbon nano tube/polyimide composite film according to claim 1-8
Aminated carbon nano tube/polyimide composite film that method obtains.
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| CN114106385A (en) * | 2021-11-12 | 2022-03-01 | 江苏天奈科技股份有限公司 | Flexible heating film and preparation method thereof |
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