CN110358123A - A kind of high thermal conductivity graphene composite film and preparation method thereof - Google Patents
A kind of high thermal conductivity graphene composite film and preparation method thereof Download PDFInfo
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- CN110358123A CN110358123A CN201910655793.3A CN201910655793A CN110358123A CN 110358123 A CN110358123 A CN 110358123A CN 201910655793 A CN201910655793 A CN 201910655793A CN 110358123 A CN110358123 A CN 110358123A
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Abstract
The present invention provides a kind of high thermal conductivity graphene composite films and preparation method thereof, graphene oxide is first carried out to lift-off processing and organically-modified respectively with hexagonal boron nitride, then methyl acrylate is added together, crosslinking agent, photoinitiator, in the premixed liquid that acetone is mixed, it is uniformly mixed and obtains mixed liquor, vacuum defoamation, on even spread to Kapton, polymerization is finally heated under the conditions of nitrogen protection and ultraviolet light, dry winding, form coiled material, reduction, washing, it dries again, resulting graphene composite film thermal conductivity is high, production cost is low, it is worth with great commercial introduction.The organically-modified processing of graphene oxide, hexagonal boron nitride introduces carbon-carbon double bond, polymerization reaction occurs with the methyl acrylate in premixed liquid, plays the role of similar bridge joint, is conducive to heat transfer, further improves thermal conductivity.
Description
Technical field
The present invention relates to grapheme material technical fields, particularly, be related to a kind of high thermal conductivity graphene composite material and its
Preparation method.
Background technique
With the continuous integrated and high power of microelectronics system, chip heat flow density increases sharply, and gives chip cooling
Great challenge is brought, the heat dissipation of integrated chip and equipment becomes the fields such as limitation electronic product, high-power electrical, aerospace
The bottleneck of development.Graphene heat conducting film is a kind of novel heat-conducting heat sink material developed in recent years, has high thermal conductivity coefficient and low
Thermal resistance, it is light, it is widely used in many fields such as electronics, communication, illumination, aviation and defence and military.In addition, graphene is thermally conductive
The surface of film can be combined with other materials such as metal, plastic cement, adhesive stickers to meet more design functions and needs, Ke Yigen
It needs to carry out cutting cutting to it according to true form.
At present the preparation method of graphene film be mainly there are two types of, one is the graphite oxides for first preparing nanoscale
Then alkene prepares graphene oxide film, finally reduction obtains graphene film；Another kind is directly to prepare graphene film.
Indirect method mainly has vacuum filtration method, spin-coating method, self-assembly method, electrophoresis, electrochemical process, spray coating method；The direct system of graphene
Have adhesive tape stripping method, silicon carbide or metal surface epitaxial growth method and chemical vapour deposition technique (CVD).In first kind graphene
In the preparation process of film, graphite will be not sufficiently stable through two processes of peroxidating and reduction, the performance of obtained graphene, this is right
Follow-up study has a certain impact.Second class chemical vapour deposition technique can obtain the single-layer graphene of large-area high-quality, but set
Standby to require height, obtained film also tends to need to be transferred in other substrates.But existing method for preparing graphene membrane is raw
Produce at high cost, thermal conductivity is not able to satisfy higher and higher high-grade, precision and advanced domain requirement.
Summary of the invention
It is an object of that present invention to provide a kind of high thermal conductivity graphene composite films and preparation method thereof, to solve production cost
The high, technical problems such as product thermal conductivity is low.
To achieve the above object, the present invention provides a kind of preparation methods of high thermal conductivity graphene composite film, first by oxygen
Graphite alkene carries out lift-off processing and organically-modified with hexagonal boron nitride respectively, be then added together methyl acrylate, crosslinking agent,
In the premixed liquid that photoinitiator, acetone are mixed, it is uniformly mixed and obtains mixed liquor, vacuum defoamation, even spread to polyamides Asia
On amine film, polymerization is finally heated under the conditions of nitrogen protection and ultraviolet light, dry winding forms coiled material, and reduction is washed
It washs, dries again to get a kind of high thermal conductivity graphene composite film；Wherein, organically-modified specific method is: oxidation
Graphene, hexagonal boron nitride are reacted with methacryloxypropyl trimethoxy silane respectively introduces carbon-carbon double bond, with third
Polymerization reaction occurs for e pioic acid methyl ester；The mass ratio of graphene oxide and hexagonal boron nitride is 1:0.1~0.2.
Preferably, the graphene oxide is prepared using improved Hummers method.
Preferably, the process conditions of lift-off processing are as follows: graphene oxide or hexagonal boron nitride are added in isopropanol, voltage
3.1~3.3kV, 0.3~0.6mA of electric current are handled the time 40~50 minutes, and 30~32 DEG C for the treatment of temperature, revolving removes isopropanol
?；The mass volume ratio of graphene oxide or hexagonal boron nitride and isopropanol is 1g:20~30mL.
Preferably, organically-modified specific method is: by after lift-off processing graphene oxide or hexagonal boron nitride be added
It impregnates 12 hours, filters, i.e., in the methacryloxypropyl trimethoxy silane of volume ratio 1:9 and the mixed solution of toluene
?.
It is further preferred that the mass volume ratio of graphene oxide or hexagonal boron nitride and mixed solution be 1g:20~
30mL。
Preferably, premixed liquid the preparation method comprises the following steps: by methyl acrylate, crosslinking agent and photoinitiator adding into acetone, surpass
Sonication 30~40 minutes to get.The crosslinking agent is more preferably 2-hydroxyethyl acrylate, and photoinitiator is into one
Step is preferably photoinitiator 651.
Preferably, mixed liquor the preparation method is as follows: by lift-off processing and organically-modified graphene oxide and six side's nitrogen
Change boron to be added in premixed liquid together, supersonic oscillations 30~40 minutes to obtain the final product.
Preferably, vacuum defoamation is realized using vacuum degasing machine, so that bubble of the diameter greater than 0.2mm is not allow for, directly
Air bubble content of the diameter less than 0.2mm is less than 0.02mL/L.
Preferably, the coating of mixed liquor is realized using electrostatic spraying, specific method is: Kapton connects in drying tunnel
Reforwarding turns, and EFI coating head is spread over inside entire drying tunnel, is sprayed to mixed liquor on Kapton using EFI coating head.Often
The spray rate of a EFI coating head is still more preferably 10~15g/ minutes.The thickness of gained coiled material is still more preferably 10
~15 μm.
Preferably, the specific method that polymerization is heated under the conditions of nitrogen protection and ultraviolet light is: protecting full of nitrogen
Under the wavelength 365nm ultraviolet lamp of shield, 65~75 DEG C of heating temperature, handle the time 20~30 minutes.
Preferably, the process conditions of dry winding are as follows: 200~250 DEG C drying 8~10 hours.
Preferably, it is restored using the hydrazine hydrate solution of mass concentration 50~60%, graphene oxide is molten with hydrazine hydrate
2~3g:1L of mass volume ratio of liquid.Reduction reaction is still more preferably to carry out 2~3 hours under reflux conditions.
Preferably, it adopts and is washed with deionized.
Preferably, dry process conditions again are as follows: 200~250 DEG C drying 8~10 hours.
The present invention also provides a kind of high thermal conductivity graphene composite films that above-mentioned preparation method obtains.
The invention has the following advantages:
Graphene oxide is first carried out lift-off processing and organically-modified by the present invention respectively with hexagonal boron nitride, then together plus
Enter in the premixed liquid that methyl acrylate, crosslinking agent, photoinitiator, acetone are mixed, be uniformly mixed and obtain mixed liquor, vacuum is de-
It steeps, on even spread to Kapton, polymerization is finally heated under the conditions of nitrogen protection and ultraviolet light, it is dry to receive
Volume forms coiled material, restores, and washing is dried again, and resulting graphene composite film thermal conductivity is high, and production cost is low, has pole
Big commercial introduction value.The organically-modified processing of graphene oxide, hexagonal boron nitride introduces carbon-carbon double bond, with premixed liquid
In methyl acrylate polymerization reaction occurs, play the role of similar bridge joint, be conducive to heat transfer, further improve thermally conductive
Rate.
The amount ratio of graphene oxide and hexagonal boron nitride is very crucial.The lattice of graphene oxide reduction gained graphene
Structure is simultaneously imperfect, and there are lattice defects.Hexagonal boron nitride has the surface of atomically flating and has certain energy gap, table
Face also without dangling bonds, can carry out hydridization with graphene, and the present invention exactly utilizes this feature of hexagonal boron nitride to graphene
Lattice defect is filled, and facilitates the perfect of thermal conducting path, improves heating conduction.The dosage of hexagonal boron nitride is very little, can not
Realization is sufficient filling with graphene lattice defect, and the dosage of hexagonal boron nitride is too many, due to hexagonal boron nitride and graphite alkenes
As layer structure, be unfavorable for the formation of film instead.
It is organically-modified again that graphene oxide first carries out lift-off processing with hexagonal boron nitride, and lift-off processing forms single layer structure,
Be conducive to the modification of methacryloxypropyl trimethoxy silane, and then occur with the methyl acrylate in premixed liquid
Photopolymerization reaction forms thermal conducting path, improves heating conduction.On the other hand, modification promotes oxygen under the conditions of organic solvent
Graphite alkene it is evenly dispersed, with the uniform film of forming properties, guarantee preferable heating conduction.
Mixed liquor is coated again after wanting vacuum defoamation, to reduce the formation of bubble, avoids the reduction of heating conduction.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
The present invention is further detailed explanation below.
Specific embodiment
The embodiment of the present invention is described in detail below, but the present invention can be limited and be covered according to claim
Multitude of different ways implement.
Embodiment 1:
A kind of preparation method of high thermal conductivity graphene composite film first carries out graphene oxide with hexagonal boron nitride respectively
Lift-off processing is simultaneously organically-modified, and the premix that methyl acrylate, crosslinking agent, photoinitiator, acetone are mixed then is added together
In liquid, it is uniformly mixed and obtains mixed liquor, vacuum defoamation, on even spread to Kapton, finally in nitrogen protection and purple
Polymerization is heated under the conditions of the irradiation of outer light, dry winding forms coiled material, restores, washing, is dried again to get described a kind of high
Thermal conductivity graphene laminated film；Wherein, organically-modified specific method is: graphene oxide, hexagonal boron nitride respectively with methyl
Acryloyloxypropyltrimethoxysilane reaction introduces carbon-carbon double bond, polymerization reaction occurs with methyl acrylate；Aoxidize stone
The mass ratio of black alkene and hexagonal boron nitride is 1:0.1.
The process conditions of lift-off processing are as follows: graphene oxide or hexagonal boron nitride are added in isopropanol, voltage 3.1kV,
Electric current 0.3mA is handled the time 40 minutes, and 30 DEG C for the treatment of temperature, revolving removes isopropanol；Graphene oxide or six sides nitridation
The mass volume ratio of boron and isopropanol is 1g:20mL.
Organically-modified specific method is: by after lift-off processing graphene oxide or hexagonal boron nitride be added volume ratio 1:
Impregnated 12 hours in 9 methacryloxypropyl trimethoxy silane and the mixed solution of toluene, filter to get.Oxidation
The mass volume ratio of graphene or hexagonal boron nitride and mixed solution is 1g:20mL.
Premixed liquid the preparation method comprises the following steps: by methyl acrylate, crosslinking agent and photoinitiator adding into acetone, supersonic oscillations
30 minutes to get.Crosslinking agent is 2-hydroxyethyl acrylate, and photoinitiator is photoinitiator 651.
Mixed liquor the preparation method is as follows: by lift-off processing and organically-modified graphene oxide and hexagonal boron nitride together
It is added in premixed liquid, supersonic oscillations 30 minutes to obtain the final product.
Vacuum defoamation is realized using vacuum degasing machine, so that bubble of the diameter greater than 0.2mm is not allow for, diameter is less than
The air bubble content of 0.2mm is less than 0.02mL/L.
The coating of mixed liquor is realized using electrostatic spraying, specific method is: Kapton is continuously run in drying tunnel,
EFI coating head is spread over inside entire drying tunnel, is sprayed to mixed liquor on Kapton using EFI coating head.Each EFI
The spray rate of coating head is 10g/ minutes.Gained coiled material with a thickness of 10 μm.
The specific method that polymerization is heated under the conditions of nitrogen protection and ultraviolet light is: in the wavelength for being full of nitrogen protection
Under 365nm ultraviolet lamp, 65 DEG C of heating temperature, handle the time 20 minutes.
The process conditions of dry winding are as follows: 200 DEG C drying 8 hours.
It is restored using the hydrazine hydrate solution of mass concentration 50%, the quality volume of graphene oxide and hydrazine hydrate solution
Compare 2g:1L.Reduction reaction is to carry out 2 hours under reflux conditions.
It adopts and is washed with deionized.
Dry process conditions again are as follows: 200 DEG C drying 8 hours.
Embodiment 2:
A kind of preparation method of high thermal conductivity graphene composite film first carries out graphene oxide with hexagonal boron nitride respectively
Lift-off processing is simultaneously organically-modified, and the premix that methyl acrylate, crosslinking agent, photoinitiator, acetone are mixed then is added together
In liquid, it is uniformly mixed and obtains mixed liquor, vacuum defoamation, on even spread to Kapton, finally in nitrogen protection and purple
Polymerization is heated under the conditions of the irradiation of outer light, dry winding forms coiled material, restores, washing, is dried again to get described a kind of high
Thermal conductivity graphene laminated film；Wherein, organically-modified specific method is: graphene oxide, hexagonal boron nitride respectively with methyl
Acryloyloxypropyltrimethoxysilane reaction introduces carbon-carbon double bond, polymerization reaction occurs with methyl acrylate；Aoxidize stone
The mass ratio of black alkene and hexagonal boron nitride is 1:0.2.
The process conditions of lift-off processing are as follows: graphene oxide or hexagonal boron nitride are added in isopropanol, voltage 3.3kV,
Electric current 0.6mA is handled the time 50 minutes, and 32 DEG C for the treatment of temperature, revolving removes isopropanol；Graphene oxide or six sides nitridation
The mass volume ratio of boron and isopropanol is 1g:30mL.
Organically-modified specific method is: by after lift-off processing graphene oxide or hexagonal boron nitride be added volume ratio 1:
Impregnated 12 hours in 9 methacryloxypropyl trimethoxy silane and the mixed solution of toluene, filter to get.Oxidation
The mass volume ratio of graphene or hexagonal boron nitride and mixed solution is 1g:30mL.
Premixed liquid the preparation method comprises the following steps: by methyl acrylate, crosslinking agent and photoinitiator adding into acetone, supersonic oscillations
40 minutes to get.Crosslinking agent is 2-hydroxyethyl acrylate, and photoinitiator is photoinitiator 651.
Mixed liquor the preparation method is as follows: by lift-off processing and organically-modified graphene oxide and hexagonal boron nitride together
It is added in premixed liquid, supersonic oscillations 40 minutes to obtain the final product.
Vacuum defoamation is realized using vacuum degasing machine, so that bubble of the diameter greater than 0.2mm is not allow for, diameter is less than
The air bubble content of 0.2mm is less than 0.02mL/L.
The coating of mixed liquor is realized using electrostatic spraying, specific method is: Kapton is continuously run in drying tunnel,
EFI coating head is spread over inside entire drying tunnel, is sprayed to mixed liquor on Kapton using EFI coating head.Each EFI
The spray rate of coating head is 15g/ minutes.Gained coiled material with a thickness of 15 μm.
The specific method that polymerization is heated under the conditions of nitrogen protection and ultraviolet light is: in the wavelength for being full of nitrogen protection
Under 365nm ultraviolet lamp, 75 DEG C of heating temperature, handle the time 30 minutes.
The process conditions of dry winding are as follows: 250 DEG C drying 10 hours.
It is restored using the hydrazine hydrate solution of mass concentration 60%, the quality volume of graphene oxide and hydrazine hydrate solution
Compare 3g:1L.Reduction reaction is to carry out 3 hours under reflux conditions.
It adopts and is washed with deionized.
Dry process conditions again are as follows: 250 DEG C drying 10 hours.
Embodiment 3:
A kind of preparation method of high thermal conductivity graphene composite film first carries out graphene oxide with hexagonal boron nitride respectively
Lift-off processing is simultaneously organically-modified, and the premix that methyl acrylate, crosslinking agent, photoinitiator, acetone are mixed then is added together
In liquid, it is uniformly mixed and obtains mixed liquor, vacuum defoamation, on even spread to Kapton, finally in nitrogen protection and purple
Polymerization is heated under the conditions of the irradiation of outer light, dry winding forms coiled material, restores, washing, is dried again to get described a kind of high
Thermal conductivity graphene laminated film；Wherein, organically-modified specific method is: graphene oxide, hexagonal boron nitride respectively with methyl
Acryloyloxypropyltrimethoxysilane reaction introduces carbon-carbon double bond, polymerization reaction occurs with methyl acrylate；Aoxidize stone
The mass ratio of black alkene and hexagonal boron nitride is 1:0.1.
The process conditions of lift-off processing are as follows: graphene oxide or hexagonal boron nitride are added in isopropanol, voltage 3.3kV,
Electric current 0.3mA is handled the time 50 minutes, and 30 DEG C for the treatment of temperature, revolving removes isopropanol；Graphene oxide or six sides nitridation
The mass volume ratio of boron and isopropanol is 1g:30mL.
Organically-modified specific method is: by after lift-off processing graphene oxide or hexagonal boron nitride be added volume ratio 1:
Impregnated 12 hours in 9 methacryloxypropyl trimethoxy silane and the mixed solution of toluene, filter to get.Oxidation
The mass volume ratio of graphene or hexagonal boron nitride and mixed solution is 1g:20mL.
Premixed liquid the preparation method comprises the following steps: by methyl acrylate, crosslinking agent and photoinitiator adding into acetone, supersonic oscillations
40 minutes to get.Crosslinking agent is 2-hydroxyethyl acrylate, and photoinitiator is photoinitiator 651.
Mixed liquor the preparation method is as follows: by lift-off processing and organically-modified graphene oxide and hexagonal boron nitride together
It is added in premixed liquid, supersonic oscillations 30 minutes to obtain the final product.
Vacuum defoamation is realized using vacuum degasing machine, so that bubble of the diameter greater than 0.2mm is not allow for, diameter is less than
The air bubble content of 0.2mm is less than 0.02mL/L.
The coating of mixed liquor is realized using electrostatic spraying, specific method is: Kapton is continuously run in drying tunnel,
EFI coating head is spread over inside entire drying tunnel, is sprayed to mixed liquor on Kapton using EFI coating head.Each EFI
The spray rate of coating head is 15g/ minutes.Gained coiled material with a thickness of 10 μm.
The specific method that polymerization is heated under the conditions of nitrogen protection and ultraviolet light is: in the wavelength for being full of nitrogen protection
Under 365nm ultraviolet lamp, 75 DEG C of heating temperature, handle the time 20 minutes.
The process conditions of dry winding are as follows: 250 DEG C drying 8 hours.
It is restored using the hydrazine hydrate solution of mass concentration 60%, the quality volume of graphene oxide and hydrazine hydrate solution
Compare 2g:1L.Reduction reaction is to carry out 3 hours under reflux conditions.
It adopts and is washed with deionized.
Dry process conditions again are as follows: 200 DEG C drying 10 hours.
Embodiment 4:
A kind of preparation method of high thermal conductivity graphene composite film first carries out graphene oxide with hexagonal boron nitride respectively
Lift-off processing is simultaneously organically-modified, and the premix that methyl acrylate, crosslinking agent, photoinitiator, acetone are mixed then is added together
In liquid, it is uniformly mixed and obtains mixed liquor, vacuum defoamation, on even spread to Kapton, finally in nitrogen protection and purple
Polymerization is heated under the conditions of the irradiation of outer light, dry winding forms coiled material, restores, washing, is dried again to get described a kind of high
Thermal conductivity graphene laminated film；Wherein, organically-modified specific method is: graphene oxide, hexagonal boron nitride respectively with methyl
Acryloyloxypropyltrimethoxysilane reaction introduces carbon-carbon double bond, polymerization reaction occurs with methyl acrylate；Aoxidize stone
The mass ratio of black alkene and hexagonal boron nitride is 1:0.2.
The process conditions of lift-off processing are as follows: graphene oxide or hexagonal boron nitride are added in isopropanol, voltage 3.1kV,
Electric current 0.6mA is handled the time 40 minutes, and 32 DEG C for the treatment of temperature, revolving removes isopropanol；Graphene oxide or six sides nitridation
The mass volume ratio of boron and isopropanol is 1g:20mL.
Organically-modified specific method is: by after lift-off processing graphene oxide or hexagonal boron nitride be added volume ratio 1:
Impregnated 12 hours in 9 methacryloxypropyl trimethoxy silane and the mixed solution of toluene, filter to get.Oxidation
The mass volume ratio of graphene or hexagonal boron nitride and mixed solution is 1g:30mL.
Premixed liquid the preparation method comprises the following steps: by methyl acrylate, crosslinking agent and photoinitiator adding into acetone, supersonic oscillations
30 minutes to get.Crosslinking agent is 2-hydroxyethyl acrylate, and photoinitiator is photoinitiator 651.
Mixed liquor the preparation method is as follows: by lift-off processing and organically-modified graphene oxide and hexagonal boron nitride together
It is added in premixed liquid, supersonic oscillations 40 minutes to obtain the final product.
Vacuum defoamation is realized using vacuum degasing machine, so that bubble of the diameter greater than 0.2mm is not allow for, diameter is less than
The air bubble content of 0.2mm is less than 0.02mL/L.
The coating of mixed liquor is realized using electrostatic spraying, specific method is: Kapton is continuously run in drying tunnel,
EFI coating head is spread over inside entire drying tunnel, is sprayed to mixed liquor on Kapton using EFI coating head.Each EFI
The spray rate of coating head is 10g/ minutes.Gained coiled material with a thickness of 15 μm.
The specific method that polymerization is heated under the conditions of nitrogen protection and ultraviolet light is: in the wavelength for being full of nitrogen protection
Under 365nm ultraviolet lamp, 65 DEG C of heating temperature, handle the time 30 minutes.
The process conditions of dry winding are as follows: 200 DEG C drying 10 hours.
It is restored using the hydrazine hydrate solution of mass concentration 50%, the quality volume of graphene oxide and hydrazine hydrate solution
Compare 3g:1L.Reduction reaction is to carry out 2 hours under reflux conditions.
It adopts and is washed with deionized.
Dry process conditions again are as follows: 250 DEG C drying 8 hours.
Embodiment 5:
A kind of preparation method of high thermal conductivity graphene composite film first carries out graphene oxide with hexagonal boron nitride respectively
Lift-off processing is simultaneously organically-modified, and the premix that methyl acrylate, crosslinking agent, photoinitiator, acetone are mixed then is added together
In liquid, it is uniformly mixed and obtains mixed liquor, vacuum defoamation, on even spread to Kapton, finally in nitrogen protection and purple
Polymerization is heated under the conditions of the irradiation of outer light, dry winding forms coiled material, restores, washing, is dried again to get described a kind of high
Thermal conductivity graphene laminated film；Wherein, organically-modified specific method is: graphene oxide, hexagonal boron nitride respectively with methyl
Acryloyloxypropyltrimethoxysilane reaction introduces carbon-carbon double bond, polymerization reaction occurs with methyl acrylate；Aoxidize stone
The mass ratio of black alkene and hexagonal boron nitride is 1:0.15.
The process conditions of lift-off processing are as follows: graphene oxide or hexagonal boron nitride are added in isopropanol, voltage 3.2kV,
Electric current 0.4mA is handled the time 45 minutes, and 31 DEG C for the treatment of temperature, revolving removes isopropanol；Graphene oxide or six sides nitridation
The mass volume ratio of boron and isopropanol is 1g:25mL.
Organically-modified specific method is: by after lift-off processing graphene oxide or hexagonal boron nitride be added volume ratio 1:
Impregnated 12 hours in 9 methacryloxypropyl trimethoxy silane and the mixed solution of toluene, filter to get.Oxidation
The mass volume ratio of graphene or hexagonal boron nitride and mixed solution is 1g:25mL.
Premixed liquid the preparation method comprises the following steps: by methyl acrylate, crosslinking agent and photoinitiator adding into acetone, supersonic oscillations
35 minutes to get.Crosslinking agent is 2-hydroxyethyl acrylate, and photoinitiator is photoinitiator 651.
Mixed liquor the preparation method is as follows: by lift-off processing and organically-modified graphene oxide and hexagonal boron nitride together
It is added in premixed liquid, supersonic oscillations 35 minutes to obtain the final product.
Vacuum defoamation is realized using vacuum degasing machine, so that bubble of the diameter greater than 0.2mm is not allow for, diameter is less than
The air bubble content of 0.2mm is less than 0.02mL/L.
The coating of mixed liquor is realized using electrostatic spraying, specific method is: Kapton is continuously run in drying tunnel,
EFI coating head is spread over inside entire drying tunnel, is sprayed to mixed liquor on Kapton using EFI coating head.Each EFI
The spray rate of coating head is 12g/ minutes.Gained coiled material with a thickness of 12 μm.
The specific method that polymerization is heated under the conditions of nitrogen protection and ultraviolet light is: in the wavelength for being full of nitrogen protection
Under 365nm ultraviolet lamp, 70 DEG C of heating temperature, handle the time 25 minutes.
The process conditions of dry winding are as follows: 220 DEG C drying 9 hours.
It is restored using the hydrazine hydrate solution of mass concentration 55%, the quality volume of graphene oxide and hydrazine hydrate solution
Compare 2.5g:1L.Reduction reaction is to carry out 2.5 hours under reflux conditions.
It adopts and is washed with deionized.
Dry process conditions again are as follows: 220 DEG C drying 9 hours.
Comparative example 1
Hexagonal boron nitride is omitted, remaining is the same as embodiment 1.
Comparative example 2
Premixed liquid is replaced with acetone, remaining is the same as embodiment 1.
Comparative example 3
Vacuum defoamation step is omitted, remaining is the same as embodiment 1.
Comparative example 4
Methacryloxypropyl trimethoxy silane is replaced with vinyltriethoxysilane, remaining is the same as embodiment 1.
Test example
Examples 1 to 5 and 1~4 gained graphene composite film of comparative example are tested for the property, the results are shown in Table 1.
1. the performance test results of table
As shown in Table 1, graphene composite film obtained by Examples 1 to 5 all have in the horizontal direction and the vertical direction compared with
High thermal conductivity, mechanical performance are excellent.Comparative example 1 omits hexagonal boron nitride, since there are lattice defect, gained for graphene itself
The thermal conductivity of film product is obviously deteriorated；Comparative example 2 replaces premixed liquid, unpolymerized formation access structure, gained film with acetone
The thermal conductivity of product is obviously deteriorated, and mechanical strength is also obviously deteriorated；Comparative example 3 omits vacuum defoamation step, deposits in gained film
In bubble, the thermal conductivity of product is influenced, and will affect the mechanical strength of product；Comparative example 4 uses vinyltriethoxysilane
Methacryloxypropyl trimethoxy silane is replaced, although being also introduced into double bond, leading for access is formed after polymerization reaction
Hot property is obviously deteriorated, and mechanical strength is also obviously deteriorated.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high thermal conductivity graphene composite film, which is characterized in that first nitrogenize graphene oxide and six sides
Boron carries out lift-off processing and organically-modified, then addition methyl acrylate, crosslinking agent, photoinitiator, acetone mixing together respectively
In manufactured premixed liquid, it is uniformly mixed and obtains mixed liquor, vacuum defoamation, on even spread to Kapton, finally in nitrogen
Polymerization is heated under the conditions of gas shielded and ultraviolet light, dry winding forms coiled material, restores, and washing is dried again to get institute
A kind of high thermal conductivity graphene composite film stated；Wherein, organically-modified specific method is: graphene oxide, hexagonal boron nitride
It is reacted respectively with methacryloxypropyl trimethoxy silane and introduces carbon-carbon double bond, to polymerize instead with methyl acrylate
It answers；The mass ratio of graphene oxide and hexagonal boron nitride is 1:0.1~0.2.
2. preparation method according to claim 1, which is characterized in that the process conditions of lift-off processing are as follows: by graphite oxide
Alkene or hexagonal boron nitride are added in isopropanol, and 3.1~3.3kV of voltage, 0.3~0.6mA of electric current are handled the time 40~50 minutes,
30~32 DEG C for the treatment of temperature, revolving removes isopropanol；The quality volume of graphene oxide or hexagonal boron nitride and isopropanol
Than for 1g:20~30mL.
3. preparation method according to claim 1, which is characterized in that organically-modified specific method is: by lift-off processing
The methacryloxypropyl trimethoxy silane and toluene of volume ratio 1:9 is added in graphene oxide or hexagonal boron nitride afterwards
Mixed solution in impregnate 12 hours, filter to get.
4. preparation method according to claim 1, which is characterized in that premixed liquid the preparation method comprises the following steps: by methyl acrylate,
Crosslinking agent and photoinitiator adding into acetone, supersonic oscillations 30~40 minutes to get.
5. preparation method according to claim 1, which is characterized in that mixed liquor the preparation method is as follows: by lift-off processing
And organically-modified graphene oxide and hexagonal boron nitride are added in premixed liquid together, supersonic oscillations 30~40 minutes to obtain the final product.
6. preparation method according to claim 1, which is characterized in that vacuum defoamation is realized using vacuum degasing machine, so that
Bubble of the diameter greater than 0.2mm is not allow for, and air bubble content of the diameter less than 0.2mm is less than 0.02mL/L.
7. preparation method according to claim 1, which is characterized in that realize the coating of mixed liquor, tool using electrostatic spraying
Body method is: Kapton is continuously run in drying tunnel, and EFI coating head is spread over inside entire drying tunnel, utilizes EFI coating head
Mixed liquor is sprayed on Kapton.
8. preparation method according to claim 1, which is characterized in that heated under the conditions of nitrogen protection and ultraviolet light
The specific method of polymerization is: under the wavelength 365nm ultraviolet lamp full of nitrogen protection, 65~75 DEG C of heating temperature, handling the time
20~30 minutes.
9. preparation method according to claim 1, which is characterized in that the process conditions of dry winding are as follows: 200~250 DEG C
It is 8~10 hours dry.
10. a kind of high thermal conductivity graphene composite film that preparation method described in any one of claim 1~9 obtains.
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