CN106083046A - A kind of preparation method of Graphene/polyimides copolymerization heat conducting film - Google Patents
A kind of preparation method of Graphene/polyimides copolymerization heat conducting film Download PDFInfo
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
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Abstract
The invention discloses the preparation method of a kind of Graphene/polyimides copolymerization heat conducting film, this method not only overcomes the problem that cost that high energy consumption causes is high, and Graphene can well disperse in the base, improve the compatibility between matrix, reduce the heat conduction of the impact of thermal resistance, beneficially composite film material between interface.
Description
Technical field
The invention belongs to Graphene Heat Conduction Material field, be specifically related to a kind of Graphene/polyimides copolymerization heat conducting film
Preparation method.
Background technology
Along with development and the progress of science and technology, electronic product is increasingly intelligent and complicates, its interiors of products electronics unit
Part gets more and more, and integrated level improves constantly.A lot of heats can be produced, easily accumulation formation high temperature in running, and high temperature
Generation will reduce the performance of electronic product, reliability and service life.Therefore, Current electronic industry is for as thermal control system
The heat sink material of system core component proposes the highest requirement, and in the urgent need to a kind of high-efficiency heat conduction, light material can
Heat is promptly passed, to ensure the properly functioning of electronic equipment.Graphite is cheap, wide material sources, heat-conducting effect
Good, it is now widely used composite heat conducting material.But in use there is certain problem, owing to graphite divides in the material
Dissipating uneven, cause the heat conducting film surface irregularity of preparation, heat conductivility is low, do not reach theoretical thermal conductivity values.Therefore, relatively stone is sought
Ink preferably Heat Conduction Material is extremely urgent.
Graphene has perfect two dimensional crystal structure, and it is a kind of hexagonal being made up of with sp2 hybrid orbital carbon atom
Shape is the flat film of honeycomb lattice, the two-dimensional material of only one of which carbon atom thickness.It is that known world is the thinnest, the hardest
Nano material.Heat conductivity is up to 5300W/m K, and higher than CNT and diamond, under room temperature, its electron mobility exceedes
15000cm2/ v s, again ratio CNT or silicon wafer height, and resistivity only about 10-6Ω cm, lower than copper or silver, for
The material that resistivity is minimum in the world.Exactly because its this resistivity is extremely low, the characteristic that the speed of electron transfer is exceedingly fast, it is expected to
It is used for developing thinner, conduction speed a new generation's electronic component or transistor faster.And Graphene also has high intensity
(1100GPa), the specific surface area (2630m of high fracture strength (125GPa), super large2/g).The performance of these excellences makes graphite
Alkene mobile device, Aero-Space, new forms of energy field of batteries etc. have light application prospect, attracted vast researcher and
The favor of industrial quarters.The thermal conductivity of Graphene is 2.3 times of graphite guide heating rate (2200W/m K), and has lower line expansion
Coefficient, therefore Graphene fin is one the most potential high-efficiency heat conduction material, is preferable graphite heat conducting material
Upgraded product.
Graphite film and manufacture method thereof disclosed in Chinese patent CN103080005A, this technology passes through high temperature carbonization and high temperature
Graphitization macromolecule membrane prepares composite membrane, and this heat dissipation film material thickness can design, and radiating effect is preferable, and density is less, energy
Meet the requirement that electronic product is frivolous well, but this kind of composite membrane high temperature carbonization in the fabrication process and graphitization need to disappear
Consuming big energy, cause high cost, every thousands of unit of square meter, causes holding at high price of heat dissipation film material easily.
Chinese patent CN104085143A reports " preparation method of Graphene composite heat conduction film and product ", and it led to before this
The method crossing spraying prepares graphene oxide film, and the graphene film obtained after being reduced carries out covering treatment and answered
The heat conducting film closed.The method is that Graphene is incorporated into substrate material surface, and heat conduction is mainly carried out by Graphene, two interfaces
Between there is bigger thermal resistance, affect the transmission of energy between interface, be unfavorable for play material conducts heat performance.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the present invention provides a kind of simple method to carry out synthesizing graphite alkene/polyimides
Copolymerization heat conducting film, this method not only overcomes the problem that cost that high energy consumption causes is high, and Graphene can well disperse
In the base, improve the compatibility between matrix, reduce leading of the impact of thermal resistance, beneficially composite film material between interface
Heat.
The present invention is achieved through the following technical solutions: the system of a kind of Graphene/polyimides copolymerization heat conducting film material
Preparation Method, comprises the following steps:
Step 1: by the Hummers method synthesis graphene oxide improved;
Step 2: then prepared the Graphene of amino functional by amidation process;
Step 3: the Graphene of the amino functional obtained in step 2 and pyromellitic dianhydride are carried out condensation reaction, system
Standby compound polyimide precursor;
Step 4: utilize the presoma compacting film forming that step 3 is obtained by the method for hot pressing film forming, and at high temperature burn
Knot, obtains Graphene/polyimides copolymerization heat conducting film.
Further, the Hummers method concrete grammar of the improvement of described step 1 is as follows,
(1) it is graphite by mass ratio: the ratio of potassium permanganate=1:6 joins in concentrated sulphuric acid strong phosphoric acid mixed liquor, 50
Stirring reaction 12 hours under the conditions of DEG C, wherein concentrated sulphuric acid is 9:1 with the volume ratio of strong phosphoric acid;
(2) above-mentioned reactant liquor is mixed with frozen water 1:1 by volume, add and account for the double of above-mentioned mixeding liquid volume 3~4 ‰
Oxygen water, after temperature reaches 24~26 degrees Celsius, puts in the centrifuge that rotating speed is 3500-5500rpm and is centrifuged 4 hours;
(3) successively with distilled water, 30% hydrochloric acid, washing with alcohol said mixture, every time after washing all 4000 revs/min from
Scheming separates 4 hours, is subsequently adding ether, sucking filtration, and is at room temperature vacuum dried, prepare graphene oxide.
Further, in described step 2, the graphene oxide of amino functional is prepared by the following method, will step
200 milligrams of graphene oxide powder ultrasonics of rapid 1 are dispersed in 200 milliliters of DMF solvents, supersound process 0~
3 hours, obtain graphene oxide suspension;Then 30 grams of 4,4 '-diaminodiphenyl ethers and 5 grams of dicyclohexyl phosphinylidynes it are added thereto to
Imines, ultrasonic 5 minutes, reacts 24~72 hours at 120 DEG C, adds 60 milliliters of dehydrated alcohol, stand overnight;Then filter and use
Ethanol and deionized water wash, gained sample is dried at 70 DEG C, is obtained the Graphene of amino functional.
Further, the polyimide precursor in described step 3 is prepared by the following method, and step 2 is obtained
To the Graphene of amino functional be dissolved in DMF solvent, supersound process, be passed through nitrogen deoxygenation, then divide
The most successional addition pyromellitic dianhydride, is stirred overnight under nitrogen protection, then filters and under 50 DEG C of vacuum conditions
It is dried, prepares compound polyimide precursor.
Further, in described step 4, Graphene/polyimides copolymerization heat conducting film is prepared by the following method,
By compound polyimide presoma hot pressing film forming on hot press of step 3, obtain Graphene/polyimides copolymer membrane, then by stone
Ink alkene/polyimides copolymer membrane sintering processes in high temperature reaction stove, obtains Graphene/polyimides copolymerization heat conducting film.
Preferably, in described step 3, the consumption of the Graphene of amino functional is 0.1%~10%.
Preferably, in described step 4, hot pressing temperature is 200~550 DEG C.
Preferably, in described step 4, sintering temperature is 700~2500 DEG C.
Further, the DMF solvent described in step 2 can also be water, ethanol, ethyl acetate, third
One or more in ketone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide.
The present invention compared to existing technology, has the advantages that
(1) present invention is by increasing the consumption of potassium permanganate, and the volume ratio that system changes into dense H2SO4 with H3PO4 is
9:1, improves tradition Hummers method and prepares graphene oxide, improve Hummers method not only technique simple to operation, and
And prepared graphene oxide not only possesses greater number of hydroxyl and carboxyl, and containing a number of epoxide group, same
Time interlamellar spacing relatively big, more convenient after ultrasonic stripping, prepare the less graphene oxide of the number of plies.
(2) Graphene that the present invention is modified can be dispersed in polyimide matrix, reduces interface resistance, contributes to multiple
The energy transmission of condensation material, thus the heat conductivility improving composite that can be bigger.
(3) preparation method of the present invention is conducive to playing other premium properties that substrate itself is had, and meets industry raw
Demand to high-performance heat conducting film in product, can be advantageously applied in the electronic product of a lot of golf calorific value, lead existing film
Hot material has the most substituting.
Detailed description of the invention
Below by example, technical scheme is described in further detail.
Embodiment 1:
By the Hummers method synthesis graphene oxide improved, specific as follows: by 3.0 grams of graphite, 18.0 grams of potassium permanganate
Join concentrated sulphuric acid: in strong phosphoric acid (360:40 milliliter) mixed liquor, 50 DEG C of stirring reactions 12 hours.Reactant liquor is poured into
+ 3 milliliters of hydrogen peroxide of 400 milliliters of frozen water, 4000 revs/min of centrifugations 4 hours after temperature is down to room temperature, successively with 200 millis
Rise distilled water, 200 milliliter of 30% hydrochloric acid, 200 milliliters of ethanol, every time all 4000 revs/min of centrifugations 4 hours after washing, so
Rear addition ether, sucking filtration, and be at room temperature vacuum dried, prepare graphene oxide.
The graphene oxide of 4,4 '-diaminodiphenyl ether chemical modification is prepared: 200 milligrams aoxidize stones by amidation process
Ink alkene powder ultrasonic is dispersed in 200 milliliters of DMF solvents, and supersound process 2.5 hours obtains graphene oxide
Suspension;Then 30 gram 4 it is added thereto to, 4 '-diaminodiphenyl ether, 5 grams of Dicyclohexylcarbodiimide, ultrasonic 5 minutes,
120 DEG C are reacted 48 hours, add 60 milliliters of dehydrated alcohol, stand overnight;Then filter and with ethanol and deionized water wash, institute
Obtain sample to dry at 70 DEG C, obtain the Graphene of amino functional.
The Graphene of amino functional and pyromellitic dianhydride are carried out condensation reaction, the polyimides forerunner that preparation is compound
Body: by the graphene dispersion of 20 milligrams of amino functionals in 100 milliliters of DMF solvents, supersound process, logical
Enter nitrogen deoxygenation, 4 grams of pyromellitic dianhydrides of the most successional addition, be stirred overnight under nitrogen protection, then mistake
Filter is also dried under 50 DEG C of vacuum conditions, prepares compound polyimide precursor.
Polyimide precursor is pressed into finished product composite membrane by the method utilizing hot pressing film forming: before 1 gram of above-mentioned acquisition
Drive body to be placed in a punching block, heat to 260 DEG C with the speed of 4 DEG C/min, be maintained at lower 10 points of the pressure of 1-2 MPa
Clock, then proceedes to be warmed up to 320 DEG C, is maintained at lower 1 hour of the pressure of 5-10 MPa, is cooled to 100 DEG C under the pressure of application
Hereinafter, from punching block, finally remove finished film, obtain functionalization graphene/polyimides copolymer membrane.
Sintered processing to obtain copolymerization heat conducting film, average thickness is 120 ± 10 microns, and heat conductivity is 670W/m K.
Embodiment 2:
By the Hummers method synthesis graphene oxide improved, specific as follows: by 3.0 grams of graphite, 18.0 grams of potassium permanganate
Join concentrated sulphuric acid: in strong phosphoric acid (360:40 milliliter) mixed liquor, 50 DEG C of stirring reactions 12 hours.Reactant liquor is poured into
+ 3 milliliters of hydrogen peroxide of 400 milliliters of frozen water, 4000 revs/min of centrifugations 4 hours after temperature is down to room temperature, successively with 200 millis
Rise distilled water, 200 milliliter of 30% hydrochloric acid, 200 milliliters of ethanol, every time all 4000 revs/min of centrifugations 4 hours after washing, so
Rear addition ether, sucking filtration, and be at room temperature vacuum dried, prepare graphene oxide.
The graphene oxide of 4,4 '-diaminodiphenyl ether chemical modification is prepared: 200 milligrams aoxidize stones by amidation process
Ink alkene powder ultrasonic is dispersed in 200 milliliters of DMF solvents, and supersound process 2.5 hours obtains graphene oxide
Suspension;Then 30 gram 4 it is added thereto to, 4 '-diaminodiphenyl ether, 5 grams of Dicyclohexylcarbodiimide, ultrasonic 5 minutes,
120 DEG C are reacted 48 hours, add 60 milliliters of dehydrated alcohol, stand overnight;Then filter and with ethanol and deionized water wash, institute
Obtain sample to dry at 70 DEG C, obtain the Graphene of functionalization.
The Graphene of amino functional and pyromellitic dianhydride are carried out condensation reaction, the polyimides forerunner that preparation is compound
Body: by the graphene dispersion of 40 milligrams of amino functionals in 100 milliliters of DMF solvents, supersound process, logical
Enter nitrogen deoxygenation, 4 grams of pyromellitic dianhydrides of the most successional addition, be stirred overnight under nitrogen protection, then mistake
Filter is also dried under 50 DEG C of vacuum conditions, prepares compound polyimide precursor.
Polyimide precursor is pressed into finished product composite membrane by the method utilizing hot pressing film forming: before 1 gram of above-mentioned acquisition
Drive body to be placed in a punching block, heat to 260 DEG C with the speed of 4 DEG C/min, be maintained at lower 10 points of the pressure of 1-2 MPa
Clock, then proceedes to be warmed up to 320 DEG C, is maintained at lower 1 hour of the pressure of 5-10 MPa, is cooled to 100 DEG C under the pressure of application
Hereinafter, from punching block, finally remove finished film, obtain functionalization graphene/polyimides copolymer membrane.
Sintered processing to obtain copolymerization heat conducting film, average thickness is 120 ± 10 microns, and heat conductivity is 800W/m K.
Embodiment 3:
By the Hummers method synthesis graphene oxide improved, specific as follows: by 3.0 grams of graphite, 18.0 grams of potassium permanganate
Join concentrated sulphuric acid: in strong phosphoric acid (360:40 milliliter) mixed liquor, 50 DEG C of stirring reactions 12 hours.Reactant liquor is poured into
+ 3 milliliters of hydrogen peroxide of 400 milliliters of frozen water, 4000 revs/min of centrifugations 4 hours after temperature is down to room temperature, successively with 200 millis
Rise distilled water, 200 milliliter of 30% hydrochloric acid, 200 milliliters of ethanol, every time all 4000 revs/min of centrifugations 4 hours after washing, so
Rear addition ether, sucking filtration, and be at room temperature vacuum dried, prepare graphene oxide.
The graphene oxide of 4,4 '-diaminodiphenyl ether chemical modification is prepared: 200 milligrams aoxidize stones by amidation process
Ink alkene powder ultrasonic is dispersed in 200 milliliters of DMF solvents, and supersound process 2.5 hours obtains graphene oxide
Suspension;Then 30 gram 4 it is added thereto to, 4 '-diaminodiphenyl ether, 5 grams of Dicyclohexylcarbodiimide, ultrasonic 5 minutes,
120 DEG C are reacted 48 hours, add 60 milliliters of dehydrated alcohol, stand overnight;Then filter and with ethanol and deionized water wash, institute
Obtain sample to dry at 70 DEG C, obtain the Graphene of functionalization.
The Graphene of amino functional and pyromellitic dianhydride are carried out condensation reaction, the polyimides forerunner that preparation is compound
Body: by the graphene dispersion of 80 milligrams of amino functionals in 100 milliliters of DMF solvents, supersound process, logical
Enter nitrogen deoxygenation, 4 grams of pyromellitic dianhydrides of the most successional addition, be stirred overnight under nitrogen protection, then mistake
Filter is also dried under 50 DEG C of vacuum conditions, prepares compound polyimide precursor.
Polyimide precursor is pressed into finished product composite membrane by the method utilizing hot pressing film forming: before 1 gram of above-mentioned acquisition
Drive body to be placed in a punching block, heat to 260 DEG C with the speed of 4 DEG C/min, be maintained at lower 10 points of the pressure of 1-2 MPa
Clock, then proceedes to be warmed up to 320 DEG C, is maintained at lower 1 hour of the pressure of 5-10 MPa, is cooled to 100 DEG C under the pressure of application
Hereinafter, from punching block, finally remove finished film, obtain functionalization graphene/polyimides copolymer membrane.
Sintered processing to obtain copolymerization heat conducting film, average thickness is 120 ± 10 microns, and heat conductivity is 1220W/m K.
Embodiment 4:
By the Hummers method synthesis graphene oxide improved, specific as follows: by 3.0 grams of graphite, 18.0 grams of potassium permanganate
Join concentrated sulphuric acid: in strong phosphoric acid (360:40 milliliter) mixed liquor, 50 DEG C of stirring reactions 12 hours.Reactant liquor is poured into
+ 3 milliliters of hydrogen peroxide of 400 milliliters of frozen water, 4000 revs/min of centrifugations 4 hours after temperature is down to room temperature, successively with 200 millis
Rise distilled water, 200 milliliter of 30% hydrochloric acid, 200 milliliters of ethanol, every time all 4000 revs/min of centrifugations 4 hours after washing, so
Rear addition ether, sucking filtration, and be at room temperature vacuum dried, prepare graphene oxide.
The graphene oxide of 4,4 '-diaminodiphenyl ether chemical modification is prepared: 200 milligrams aoxidize stones by amidation process
Ink alkene powder ultrasonic is dispersed in 200 milliliters of DMF solvents, and supersound process 2.5 hours obtains graphene oxide
Suspension;Then 30 gram 4 it is added thereto to, 4 '-diaminodiphenyl ether, 5 grams of Dicyclohexylcarbodiimide, ultrasonic 5 minutes,
120 DEG C are reacted 48 hours, add 60 milliliters of dehydrated alcohol, stand overnight;Then filter and with ethanol and deionized water wash, institute
Obtain sample to dry at 70 DEG C, obtain the Graphene of functionalization.
The Graphene of amino functional and pyromellitic dianhydride are carried out condensation reaction, the polyimides forerunner that preparation is compound
Body: by the graphene dispersion of 200 milligrams of amino functionals in 100 milliliters of DMF solvents, supersound process, logical
Enter nitrogen deoxygenation, 4 grams of pyromellitic dianhydrides of the most successional addition, be stirred overnight under nitrogen protection, then mistake
Filter is also dried under 50 DEG C of vacuum conditions, prepares compound polyimide precursor.
Polyimide precursor is pressed into finished product composite membrane by the method utilizing hot pressing film forming: before 1 gram of above-mentioned acquisition
Drive body to be placed in a punching block, heat to 260 DEG C with the speed of 4 DEG C/min, be maintained at lower 10 points of the pressure of 1-2 MPa
Clock, then proceedes to be warmed up to 320 DEG C, is maintained at lower 1 hour of the pressure of 5-10 MPa, is cooled to 100 DEG C under the pressure of application
Hereinafter, from punching block, finally remove finished film, obtain functionalization graphene/polyimides copolymer membrane.
Sintered processing to obtain copolymerization heat conducting film, average thickness is 120 ± 10 microns, and heat conductivity is 1360W/m K.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, still the present invention can be carried out
Some improvement and modification, these improve and modify also by the protection domain falling into the claims in the present invention.The present invention will not
Can be intended to be limited to the embodiments shown herein, but meet consistent with principles disclosed herein and features of novelty
Wide scope.
Claims (9)
1. a preparation method for Graphene/polyimides copolymerization heat conducting film material, comprises the following steps:
Step 1:: by the Hummers method synthesis graphene oxide improved;
Step 2: then prepared the Graphene of amino functional by amidation process;
Step 3: the Graphene of the amino functional obtained in step 2 and pyromellitic dianhydride carry out condensation reaction, preparation is multiple
The polyimide precursor closed;
Step 4: utilize the presoma compacting film forming that step 3 is obtained by the method for hot pressing film forming, and be at high temperature sintered,
Graphene/polyimides copolymerization heat conducting film.
The preparation method of Graphene the most according to claim 1/polyimides copolymerization heat conducting film material, it is characterised in that:
The Hummers method concrete grammar of the improvement of described step 1 is as follows,
(1) it is graphite by mass ratio: the ratio of potassium permanganate=1:6 joins in concentrated sulphuric acid strong phosphoric acid mixed liquor, 50 DEG C of conditions
Lower stirring reaction 12 hours, wherein concentrated sulphuric acid is 9:1 with the volume ratio of strong phosphoric acid;
(2) above-mentioned reactant liquor is mixed with frozen water 1:1 by volume, adds the hydrogen peroxide accounting for above-mentioned mixeding liquid volume 3 ~ 4 ‰,
After temperature reaches 24 ~ 26 degrees Celsius, put in the centrifuge that rotating speed is 3500-5500rpm and be centrifuged 4 hours;
(3) successively with distilled water, 30% hydrochloric acid, washing with alcohol said mixture, every time all at 4000 revs/min of centrifuges after washing
Middle separation 4 hours, is subsequently adding ether, sucking filtration, and is at room temperature vacuum dried, and prepares graphene oxide.
The preparation method of Graphene the most according to claim 1/polyimides copolymerization heat conducting film material, it is characterised in that:
In described step 2, the graphene oxide of amino functional is prepared by the following method,
The 200 of step 1 milligrams of graphene oxide powder ultrasonics are dispersed in 200 milliliters of DMF solvents, super
Sonication 0 ~ 3 hour, obtains graphene oxide suspension;Then 30 grams of 4,4 '-diaminodiphenyl ethers and 5 grams of bicyclo-it are added thereto to
Hexyl carbimide, ultrasonic 5 minutes, reacts 24 ~ 72 hours at 120 DEG C, adds 60 milliliters of dehydrated alcohol, stand overnight;Then
Filtering and use ethanol and deionized water wash, gained sample is dried at 70 DEG C, obtains the Graphene of amino functional.
The preparation method of Graphene the most according to claim 1/polyimides copolymerization heat conducting film material, it is characterised in that:
Polyimide precursor in described step 3 is prepared by the following method,
The Graphene of amino functional step 2 obtained is dissolved in DMF solvent, and supersound process is passed through nitrogen
Gas deoxygenation, the most successional addition pyromellitic dianhydride, it is stirred overnight under nitrogen protection, then filters and 50
It is dried under DEG C vacuum condition, prepares compound polyimide precursor.
The preparation method of Graphene the most according to claim 1/polyimides copolymerization heat conducting film material, it is characterised in that:
In described step 4, Graphene/polyimides copolymerization heat conducting film is prepared by the following method,
By compound polyimide presoma hot pressing film forming on hot press of step 3, obtain Graphene/polyimides copolymer membrane, then
By Graphene/polyimides copolymer membrane sintering processes in high temperature reaction stove, obtain Graphene/polyimides copolymerization heat conducting film.
The preparation method of Graphene the most according to claim 4/polyimides copolymerization heat conducting film material, it is characterised in that:
In described step 3, the consumption of the Graphene of amino functional is 0.1% ~ 10%.
The preparation method of Graphene the most according to claim 5/polyimides copolymerization heat conducting film material, it is characterised in that:
In described step 4, hot pressing temperature is 200 ~ 550 DEG C.
The preparation method of Graphene the most according to claim 5/polyimides copolymerization heat conducting film material, it is characterised in that:
In described step 4, sintering temperature is 700 ~ 2500 DEG C.
The preparation method of Graphene the most according to claim 3/polyimides copolymerization heat conducting film, it is characterised in that: step 2
Described in N,N-dimethylformamide solvent can also be water, ethanol, ethyl acetate, acetone, N,N-dimethylformamide, N,
One or more in N-dimethyl acetylamide, dimethyl sulfoxide.
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CN110903505A (en) * | 2019-11-22 | 2020-03-24 | 桂林电器科学研究院有限公司 | Graphene-enhanced polyimide composite film, preparation method thereof and artificial graphite film |
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CN108727962A (en) * | 2018-06-27 | 2018-11-02 | 南京林业大学 | A kind of aqueous polyurethane coating and graphene oxide composite coating interface ultrabranching polyamide adhering method |
CN110776737A (en) * | 2018-07-31 | 2020-02-11 | 天津大学 | Graphene-polyimide resin heat-conducting composite material and preparation method thereof |
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CN111261833B (en) * | 2020-01-19 | 2021-06-22 | 中南大学 | Self-supporting lithium metal cathode and preparation and application thereof |
CN115073056A (en) * | 2022-07-01 | 2022-09-20 | 苏州恩多科石墨烯科技有限公司 | Graphene high-thermal-conductivity material and preparation method thereof |
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