CN106008972B - A kind of preparation method of carbon nano pipe array/polyimide alignment heat-conductive composite material - Google Patents
A kind of preparation method of carbon nano pipe array/polyimide alignment heat-conductive composite material Download PDFInfo
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- CN106008972B CN106008972B CN201610349900.6A CN201610349900A CN106008972B CN 106008972 B CN106008972 B CN 106008972B CN 201610349900 A CN201610349900 A CN 201610349900A CN 106008972 B CN106008972 B CN 106008972B
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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
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
Abstract
The present invention relates to a kind of preparation methods of carbon nano pipe array/polyimide alignment heat-conductive composite material；Diamine monomer and dianhydride monomer are dissolved in polar solvent, is stirred to react 15~40 hours in nitrogen protection and under room temperature, then obtains polyimide precursor solution；On a silicon substrate, using dimethylbenzene as carbon source, ferrocene prepares directional carbon nanotube array as catalyst using chemical gas-phase method；Carbon nano pipe array is infiltrated into polyamic acid solution, 80 DEG C~250 DEG C step-up temperatures cure for 5~6 hours in Muffle furnace obtains carbon nano pipe array/polyimide alignment heat-conductive composite material.After tested, thermal conductivity reaches 30W/ (mK) or more to the composite material obtained in an axial direction.
Description
Technical field
The present invention relates to a kind of preparation methods of carbon nano pipe array/polyimide alignment heat-conductive composite material, specifically
Say it is that directional carbon nanotube array is prepared using chemical gas-phase method, the carbon nano pipe array of orientation is infiltrated into polyimide precursor
Solution, cured acquisition carbon nano pipe array/polyimides heat-conductive composite material.
Background technology
With the high speed development of science and technology, efficient heat conduction and heat dissipation become the critical issue of field of heat management and by people
Extensive concern.With the fast development of microelectronics integrated technology and package technique, the volume of logic circuit and electronic component
It is smaller and smaller, and working frequency sharply increases the heat abruptly increase for making system generate, if without sufficient heat management guarantee, easily
Lead to related device premature aging or damage.Microelectronic chip surface temperature must be maintained at lower temperature (such as silicon device
100 DEG C of part ﹤) it just can ensure that its high performance operation, many electronic unit needs could work normally at a temperature of 40~60 DEG C,
For ensure electronic component can for a long time reliably work normally, heat-sinking capability just become its service life length restriction because
Element.Therefore the performances such as excellent heat conductivility, high-fire resistance and high flame retardant be must assure that when preparing Heat Conduction Material.Compared to
Traditional metal thermal conductive material, carbon nano pipe array have lower density, low thermal coefficient of expansion, excellent mechanical performance and compared with
The many advantages such as high thermal conductivity, in addition, its orientation heat conductivility having becomes has application prospect very much in recent years
A kind of Heat Conduction Material, cause the extensive concern of people.
Polyimide material not only possesses excellent high temperature resistance, also has good physical property, electrical property and power
Performance is learned, mechanical performance is excellent, and dimensional stability is strong, and temperature resistant range is wide, and resistant to chemical etching and electrical insulation capability is excellent, exactly
It due to a series of this excellent performance, is used widely in industrial circle, some mandates or openly similar to patent also occurs.In
Magnificent State Intellectual Property Office of people's republic grant number is that the patents of invention such as CN102093715B, CN103588985B disclose profit
Enhance the method for polyimides or other polymer composites with carbon nanotube.
Above-described patent of invention is that the composite polyimide material enhanced about carbon nanotube is improving machinery mostly
The application of aspect of performance, there is no the applications about composite polyimide material in heat conduction field.Based on heat filling enhancing
Flexible polymer thermal interfacial material is since there are great anisotropic heat conductivities for heat filling itself, along the heat conduction of vertical crystal plane direction
Coefficient is less than 10W/mK, while its random orientation in a polymer matrix, causes to be difficult to be formed between heat filling effectively to lead
The passage of heat and there are prodigious interface resistance, strongly limit thermal conductivity of composite materials raising (Vivek Goyal,
Alexander A.Balandin.Thermal properties of thehybrid graphene—metal nano-
micro—composites:Applicat1ns in thermal interfacematerials.Applied Physics
Letters 100(2012):073113).Therefore, for the heat dissipation feature of existing electronic component, in conjunction with the resistance to height of polyimides
The excellent properties such as temperature develop a kind of composite material, only have high thermal conductivity coefficient and can be by device heating face along specific direction
Heat efficiently and directionally dredge cooling surface and be particularly important.
Invention content
The present invention for existing heat conduction carbon/polymer composites capacity of heat transmission anisotropy and thermal coefficient it is low lack
It falls into, carbon nano pipe array/polyimides that a kind of through-thickness i.e. carbon nano tube growth direction has high thermal conductivity is provided
Composite material and preparation method.Through-thickness thermal conductivity reaches the thermally conductive sheet of 30W/ (mK).
The present invention uses following technical scheme：
A kind of through-thickness has the preparation method of high thermal conductivity coefficient carbon nano pipe array/composite polyimide material,
Steps are as follows：
1) at room temperature, in polar solvent, diamine monomer is added and is uniformly mixed, adds equimolar dianhydride monomer,
It is small to be stirred to react 15~40 10~20% under nitrogen protection for the solution solid content mass concentration that monomer addition makes
When, then obtain polyimide solution, i.e. polyamic acid；
2) on a silicon substrate, using dimethylbenzene as carbon source, a concentration of 0.02~0.05g/ml is made as catalyst in ferrocene
Complex catalyst precursor liquid substrate will be reacted and is placed in the flat-temperature zone of vacuum tube furnace, after being evacuated to 0~10Pa through ultrasonic vibration
Argon gas is passed through as protection gas, is controlled and is heated up by tube furnace program, be at the uniform velocity warming up to 700~800 DEG C with 10~15 DEG C/min, reach
To after set temperature, complex catalyst precursor liquid is pushed into vacuum tube furnace, the growth of carbon nano pipe array is oriented；
3) polyamic acid solution made from the carbon nano pipe array immersion step one for obtaining step 2), it is solid in Muffle furnace
Change, condition of cure is 80 DEG C~250 DEG C step-up temperatures 5~6 hours to get to carbon nano pipe array/composite polyimide material.
The polar solvent used in the step 1) is DMAc (dimethylacetylamide) or NMP (N- crassitudes
Ketone).
In the step 1) using diamine monomer be TFDB (4,4 '-diamino -2,2 '-bis trifluoromethyl biphenyl) or
BAPB (4,4'- bis- (4- phenalgins oxygroup) biphenyl), the dianhydride monomer used are 6FDA (hexafluorodianhydride (6FDA)) or BPDA (3,3', 4,4'-
Bibenzene tetracarboxylic dianhydride).
Complex catalyst precursor liquid is pushed into vacuum tube furnace and is stablized with 0.2~0.6ml/min speed in the step 2)
Heat preservation 5~80 minutes.
It is characterized in that the growth length of directional carbon nanotube array is 20~80 μm in the step 2), array density is
2 × 108~2 × 109cm-2, obtained carbon nano pipe array scanning electron microscopic picture is as shown in Figure 1.
Carbon nano pipe array obtained is infiltrated into polyimide precursor solution in the step 3), to control leaching in right amount
Profit degree, makes carbon nano pipe array be wrapped up by solution, as shown in Figure 2；
Since the thermal coefficient of polyimides is poor, so the amount of suitable control polyamic acid, what both be ensure that answers
The condensation material capacity of heat transmission, and maintain the excellent performance of polyimides；
By the heat cure of above step carbon nano pipe array and polyamic acid, realizes polyimides and have in an axial direction
The carbon nano pipe array of high thermal conductivity it is compound, obtain thermal conductivity through-thickness be more than 30W/ (mK) orientation heat conduction carbon
Nanotube/composite polyimide material.
Beneficial effects of the present invention：The matrix material polyamic acid of the present invention is easy to get, the growth of directional carbon nanotube array
It is simple controllable.The composite material that the present invention obtains both had maintained the excellent properties of polyimides, further through compound with carbon nanotube
Realize orientation heat conduction.
Description of the drawings：
Fig. 1 is the scanning electron microscopic picture of carbon nano pipe array；
Fig. 2 is carbon nano pipe array/composite polyimide material schematic diagram of the present invention.
Specific implementation mode
5 embodiments of the present invention are given below, is the further explanation to the present invention, rather than limits the model of the present invention
It encloses.
Embodiment 1
1) it selects TFDB and 6FDA as the monomer (each 0.01mol) for preparing polyimides, solvent is made with DMAc (30ml),
It is stirred to react 15h at room temperature, polyamic acid solution is made；
2) on a silicon substrate, using dimethylbenzene as carbon source, the catalysis of a concentration of 0.02g/ml is made as catalyst in ferrocene
Reaction substrate is placed in the flat-temperature zone of vacuum tube furnace, argon is passed through after being evacuated to 0~10Pa by agent precursor liquid through ultrasonic vibration
Gas is controlled by tube furnace program and is heated up as protection gas, is at the uniform velocity warming up to 700 DEG C, after reaching set temperature with 10 DEG C/min, is used
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace simultaneously by injector for medical purpose under the action of delicate flow pumps with 0.2ml/min
Stablize heat preservation 10 minutes, is oriented the growth of carbon nano pipe array；
3) obtained carbon nano pipe array is infiltrated into polyamic acid, cured in Muffle furnace, solid conditions are 2 small at 80 DEG C
When, each half an hour at 100 DEG C, 150 DEG C, 200 DEG C, 2 hours at 250 DEG C.Test obtained composite material through-thickness heat conduction
Rate is 32.4W/ (mK).
Embodiment 2
1) it selects TFDB and 6FDA as the monomer (each 0.01mol) for preparing polyimides, solvent is made with DMAc (30ml),
It is stirred to react 20h at room temperature, polyamic acid solution is made；
2) on a silicon substrate, using dimethylbenzene as carbon source, the catalysis of a concentration of 0.03g/ml is made as catalyst in ferrocene
Reaction substrate is placed in the flat-temperature zone of vacuum tube furnace, argon is passed through after being evacuated to 0~10Pa by agent precursor liquid through ultrasonic vibration
Gas is controlled by program and is heated up, be at the uniform velocity warming up to 800 DEG C, after reaching set temperature with 12 DEG C/min, use medical injection as protection gas
Complex catalyst precursor liquid is at the uniform velocity pushed into 0.3ml/min in vacuum tube furnace under the action of delicate flow pumps and is stablized and protected by emitter
Temperature 30 minutes, is oriented the growth of carbon nano pipe array；
3) obtained carbon nano pipe array is infiltrated into polyamic acid, cured in Muffle furnace, solid conditions are 2 small at 80 DEG C
When, each half an hour at 100 DEG C, 150 DEG C, 200 DEG C, 2 hours at 250 DEG C.Test obtained composite material through-thickness heat conduction
Rate is 33.7W/ (mK).
Embodiment 3
1) it selects TFDB and 6FDA as the monomer (each 0.01mol) for preparing polyimides, solvent is made with DMAc (40ml),
It is stirred to react 25h at room temperature, polyamic acid solution is made；
2) on a silicon substrate, using dimethylbenzene as carbon source, the catalysis of a concentration of 0.05g/ml is made as catalyst in ferrocene
Reaction substrate is placed in the flat-temperature zone of vacuum tube furnace, argon is passed through after being evacuated to 0~10Pa by agent precursor liquid through ultrasonic vibration
Gas is controlled by tube furnace program and is heated up as protection gas, is at the uniform velocity warming up to 800 DEG C, after reaching set temperature with 15 DEG C/min, is used
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace simultaneously by injector for medical purpose under the action of delicate flow pumps with 0.5ml/min
Stablize heat preservation 60 minutes, is oriented the growth of carbon nano pipe array；
3) by obtained carbon nano pipe array infiltrate polyamic acid, cure in Muffle furnace, solid conditions be 80 DEG C, 100
DEG C, 150 DEG C, at 200 DEG C 2 hours at each 1 hour, 250 DEG C.Testing obtained composite material through-thickness thermal conductivity is
31.6W/(m·K)。
Embodiment 4
1) it selects TFDB and 6FDA as the monomer (each 0.01mol) for preparing polyimides, solvent is made with DMAc (60ml),
It is stirred to react 40h at room temperature, polyamic acid solution is made；
2) on a silicon substrate, using dimethylbenzene as carbon source, the catalysis of a concentration of 0.05g/ml is made as catalyst in ferrocene
Reaction substrate is placed in the flat-temperature zone of vacuum tube furnace, argon is passed through after being evacuated to 0~10Pa by agent precursor liquid through ultrasonic vibration
Gas is controlled by tube furnace program and is heated up as protection gas, is at the uniform velocity warming up to 800 DEG C, after reaching set temperature with 12 DEG C/min, is used
Complex catalyst precursor liquid is at the uniform velocity pushed into vacuum tube furnace simultaneously by injector for medical purpose under the action of delicate flow pumps with 0.5ml/min
Stablize heat preservation 80 minutes, is oriented the growth of carbon nano pipe array；
3) by obtained carbon nano pipe array infiltrate polyamic acid, cure in Muffle furnace, solid conditions be 80 DEG C, 100
DEG C, 150 DEG C, at 200 DEG C 2 hours at each 1 hour, 250 DEG C.Testing obtained composite material through-thickness thermal conductivity is
32.3W/(m·K)。
Embodiment 5
1) it selects BAPB and BPDA as the monomer (each 0.01mol) for preparing polyimides, solvent is made with NMP (30ml),
It is stirred to react 20h at room temperature, polyamic acid solution is made；
2) on a silicon substrate, using dimethylbenzene as carbon source, the catalysis of a concentration of 0.05g/ml is made as catalyst in ferrocene
Reaction substrate is placed in the flat-temperature zone of vacuum tube furnace, argon is passed through after being evacuated to 0~10Pa by agent precursor liquid through ultrasonic vibration
Gas is controlled by program and is heated up, be at the uniform velocity warming up to 800 DEG C, after reaching set temperature with 12 DEG C/min, use medical injection as protection gas
Complex catalyst precursor liquid is at the uniform velocity pushed into 0.5ml/min in vacuum tube furnace under the action of delicate flow pumps and is stablized and protected by emitter
Temperature 30 minutes, is oriented the growth of carbon nano pipe array；
3) obtained carbon nano pipe array is infiltrated into polyamic acid, cured in Muffle furnace, solid conditions are 2 small at 80 DEG C
When, each half an hour at 100 DEG C, 150 DEG C, 200 DEG C, 2 hours at 250 DEG C.Test obtained composite material through-thickness heat conduction
Rate is 32.6W/ (mK).
Claims (7)
1. the preparation method of a kind of carbon nano pipe array/polyimide alignment heat-conductive composite material, it is characterized in that steps are as follows：
1) at room temperature, in polar solvent, diamine monomer is added and is uniformly mixed, adds equimolar dianhydride monomer, controls
Monomer addition makes solution solid content monomer mass concentration 10~20%, is stirred to react under nitrogen protection 15~40 hours,
Then polyimide solution is obtained；
2) on a silicon substrate, using dimethylbenzene as carbon source, urging for a concentration of 0.02~0.05g/ml is made as catalyst in ferrocene
Reaction substrate is placed in the flat-temperature zone of vacuum tube furnace, is passed through after being evacuated to 0~10Pa by agent precursor liquid through ultrasonic vibration
Argon gas is controlled by tube furnace program and is heated up, be at the uniform velocity warming up to 700~800 DEG C with 10~15 DEG C/min, reach and set as protection gas
After constant temperature degree, complex catalyst precursor liquid is pushed into vacuum tube furnace, the growth of carbon nano pipe array is oriented；
3) the carbon nano pipe array immersion step 1 for obtaining step 2)) made from polyamic acid solution, cure in Muffle furnace,
Condition of cure is 80 DEG C~250 DEG C step-up temperatures 5~6 hours to get to carbon nano pipe array/composite polyimide material.
2. the method as described in claim 1, it is characterized in that the polar solvent used in the step 1) is dimethylacetamide
Amine or N-Methyl pyrrolidone.
3. the method as described in claim 1, it is characterized in that the diamine monomer is 4,4 '-diamino -2,2 '-bis- fluoroforms
Base biphenyl or bis- (the 4- phenalgins oxygroup) biphenyl of 4,4'-.
4. the method as described in claim 1, it is characterized in that the dianhydride monomer is hexafluorodianhydride (6FDA) or 3,3', 4,4'- biphenyl
Tetracarboxylic acid dianhydride.
5. the method as described in claim 1, it is characterized in that complex catalyst precursor liquid is with 0.2~0.6ml/ in the step 2)
Min speed is pushed into vacuum tube furnace and stablizes heat preservation 5~80 minutes.
6. the method as described in claim 1, it is characterized in that in the step 2) directional carbon nanotube array growth length
It it is 20~80 μm, array density is 2 × 108~2 × 109cm-2。
7. the method as described in claim 1 is gathered it is characterized in that infiltrating carbon nano pipe array obtained in the step 3)
Acid imide precursor solution, makes carbon nano pipe array be wrapped up by solution.
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| CN108504096B (en) * | 2018-04-19 | 2020-02-18 | 天津大学 | Preparation method of carbon nano tube/polymer composite material |
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Address after: 300350 Haijing garden, Haihe Education Park, Jinnan, Tianjin, 135, Tianjin University. Patentee after: Tianjin University Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92, Tianjin University Patentee before: Tianjin University |