CN109096743A - A kind of graphene film aligned and preparation method thereof and composite radiating film - Google Patents

A kind of graphene film aligned and preparation method thereof and composite radiating film Download PDF

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CN109096743A
CN109096743A CN201810927932.9A CN201810927932A CN109096743A CN 109096743 A CN109096743 A CN 109096743A CN 201810927932 A CN201810927932 A CN 201810927932A CN 109096743 A CN109096743 A CN 109096743A
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film
graphene
graphene film
hydrogen atom
parts
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CN109096743B (en
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林菊香
邝许平
矦亚茹
陈斌
郭辉
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Shenzhen Selen Science & Technology Co Ltd
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Shenzhen Selen Science & Technology Co Ltd
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Abstract

The present invention provides a kind of graphene films, the graphene film includes the component of following mass fraction: 100 parts of modified graphenes, 250~450 parts of solvents, 15~50 parts of film forming agents, 0.5~1.5 part of curing agent, 0.25~15 part of modifying agent, 3~10 parts of auxiliary agents, the graphene film with a thickness of 10 μm -80 μm, the graphene film aligns, heat dissipation area is larger, thermal conductivity with higher, thermal emissivity rate and good flexibility, bending resistance and impact resistance, it is not easy to lose powder, machinability is good.The present invention also provides a kind of composite radiating films, the graphene film that the composite radiating film is from bottom to top followed successively by ultra-thin thermal conductive silicon rubber mat, aligns, the composite radiating film can be contacted directly with heat source, without double-sided adhesive, substantially reduce thermal contact resistance, with good heating conduction and mechanical performance, can be widely used in the field of radiating of electronic product.

Description

A kind of graphene film aligned and preparation method thereof and composite radiating film
Technical field
The present invention relates to heat dissipation film fields, and in particular to a kind of graphene film and composite radiating film.
Background technique
In recent years, as industry and the continuous promotion of consumer electronics product performance, the heating problem of each electronic device are got over Come more serious, heat dissipation is particularly important.The theoretical thermal conductivity of graphene is 3000~5000W/ (mK), can be applied to electronics The field of radiating of product.However, biggish bedding void can be generated after graphene sheet layer assembling film forming in practice, it is empty Gap not only forms thermal resistance, but also influences the density of graphene film, to reduce the whole heat transfer efficiency of graphene heat conducting film.Cause This, will obtain the graphene film of high heat conductance, need to solve the clearance issues of graphene sheet layer, prepare the stone of highly directional arrangement Black alkene film.
Prior art discloses the preparation methods of some graphene films aligned, but have certain problems.As in State's patent 201410146002.1 discloses a kind of method of the graphene film of liquid phase method beam system for highly conductive high thermal conductivity, i.e., will Graphene oxide vacuum temp control, vacuum filtration prepare the graphene oxide membrane of orientated deposition, then are restored by chemical vapor deposition, The graphene film of orientated deposition is obtained, this method step is complicated, the high requirements on the equipment, and graphene film obtained is deposited on copper On foil or other substrates, it is difficult to graphene film easy to damage when shifting, and shifting, while this method is using the preparation of hummer method Graphene oxide obtains graphene film as presoma, by reduction treatment, is difficult to realize thoroughly reduction, graphene is caused to deposit In segmental defect, the high thermal conductivity characteristic for causing graphene intrinsic is difficult to fully demonstrate, obtained graphene film thermal coefficient highest 800W/ (mK) is only reached, still there is a big difference with its theoretical thermal conductivity.Chinese patent 201410331358.2 discloses one kind Ammonium hydroxide, i.e., be added in graphene oxide solution by the preparation method of N doping oriented graphite alkene, carries out hydro-thermal reaction, will aoxidize Graphene is reduced into graphene, is then oriented vacuumize process, and the graphene film that this method obtains is simple powder Overlap joint film forming, easily loses powder, mechanical performance is poor, flexible fracture, it is difficult to process, and directly shift from filter paper and be relatively stranded The thickness of graphene film can be increased to a millimeter rank, be unable to satisfy electronics by difficulty in order to reduce destruction of the transfer process to film layer The lightening requirement of apparatus field.
Summary of the invention
Unless otherwise specified, " part " in the present invention refers both to " mass parts ".
In view of the problems of the existing technology, the present invention provides a kind of graphene film, which aligns, heat dissipation Area is larger, thermal conductivity with higher and thermal emissivity rate, the graphene film have simultaneously good flexibility, bending resistance and Impact resistance is not easy to lose powder, and machinability is good: the present invention also provides a kind of composite radiating film, which has good Heating conduction and mechanical performance.
A kind of graphene film, the graphene film include the component of following mass fraction: 100 parts of modified graphenes, 250~ 450 parts of solvents, 15~50 parts of film forming agents, 0.5~1.5 part of curing agent, 0.25~15 part of modifying agent, 3~10 parts of auxiliary agents, it is described at The solidification temperature of film be 40 DEG C~120 DEG C, the graphene film with a thickness of 10 μm~80 μm.
The graphene film is the graphene film aligned.
Shown in the structural formula of the modifying agent such as formula (1),
In formula (1), R1For the alkyl or hydrogen atom of C1~C3, R2For hydrogen atom or methyl, R3For straight chained alkyl, R4、R5、 R6、R7、R8In at least 3 be polar group, remaining is hydrogen atom, the polar group be sulfonic group and/or carboxyl, n 1 ~3 integer.
In the formula (1), R1For hydrogen atom, R2For hydrogen atom or methyl, R3For the alkyl of C1~C3, R4, R5, R6, R7, R8 It is sulfonic group, the integer that n is 1~3.
In the formula (1), R1For hydrogen atom, R2For hydrogen atom or methyl, R3For the alkyl of C1~C3, R4, R5, R6, R7, R8 It is carboxyl, the integer that n is 1~3.
In the formula (1), R1For hydrogen atom, R2For methyl, R3For methyl, R4, R5, R6, R7, R8It is carboxyl, n=1.
In the formula (1), R1For hydrogen atom, R2For hydrogen atom, R3For propyl, R4, R5, R6, R7, R8It is carboxyl, n=3.
The modified graphene includes graphene and carbon nanotube, and the quality of the carbon nanotube accounts for the total matter of modified graphene The 5%~50% of amount, the number of plies of the graphene is within 10 layers；The not oxidised reduction approach processing of modified graphene, The modified graphene is by mechanical force stripping method, chemical vapour deposition technique, high-temperature cracking method, intercalation stripping method or liquid phase stripping method Preparation, the preferably described modified graphene are prepared by mechanical force stripping method, and the mechanical stripping method includes medium milling stripping method, surpasses One of sound stripping method, water jet stripping method, homogenizer stripping method and airslide disintegrating mill stripping method are a variety of.
It is preferred that the carbon nanotube include one of single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube or A variety of, the caliber of the carbon nanotube is 5~50nm, and length is 5~35 μm, and the preferably described carbon nanotube is hydroxylating or carboxyl The carbon nanotube of change.
For the modified graphene through surfactant-modified, the surfactant contains polar hydrophilic group, the pole Property hydrophilic radical includes one of carboxylic acid, sulfonic acid, sulfuric acid, amino or amido and its salt, hydroxyl, amide groups, ehter bond or a variety of. It is preferred that the surfactant includes one of polyvinylpyrrolidone, polyvinyl alcohol, kayexalate or a variety of.
The solvent be one of deionized water, dehydrated alcohol, N-Methyl pyrrolidone, n,N-Dimethylformamide or It is a variety of.
The film forming agent is one or both of polyvinyl alcohol emulsions, acrylic resin and polyaminoester emulsion；It is preferred that at Film is acrylic acid modified aqueous polyurethane emulsion, and solid content is 25%~40%, and viscosity is 100cps~500cps；Into one Walking the preferably film forming agent includes self-crosslinking aqueous acrylic acid modified polyurethane resin, aqueous acrylic modified aliphatic polyurethane One or both of resin.
The curing agent be self-emulsifying polyisocyanate ,-NCO content be 16%-48%, viscosity be 500~ 6500cps。
The auxiliary agent includes one of defoaming agent, levelling agent, coalescing agent, polyethylene wax or a variety of；The levelling Agent is polyether polyurethane levelling agent, preferably levelling agent RM-2020；The defoaming agent is water-based system defoaming agent, preferably TEGO Foamex 810 or BYK-019；The coalescing agent includes propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono butyl It is one or more in ether, isopropanol etc.；The polyethylene wax be aqueous high density polyethylene waxes lotion, viscosity be 50~ 200cps, solid content are 34~36%, and pH-value is 7.5~9.5.
The preparation method of the above-mentioned graphene film aligned comprising the steps of:
(1) it prepares modified graphene: being according to mass ratio with mill pearl by graphite powder, carbon nanotube, surfactant, solvent (10~30): 5: (0.15~0.3): be placed in ball-grinding machine at 250: 100, with the rate ball milling of 1000r/min~4000r/min Gained slurry is centrifuged under the revolving speed of 1500~2500rpm 10~30min, upper liquid is collected, by upper liquid by 1~6h, discharging It is freeze-dried, obtains modified graphene；
(2) compounding, mixing: by 100: (250~450): (15~50): (0.5~1.5): (0.25~15): (3~10) Mass ratio successively weigh modified graphene, solvent, film forming agent, curing agent, modifying agent and auxiliary agent, in high-speed mixer with After the revolving speed of 1500~4000rpm stirs 5~120min, slurry is taken out, then with the rotation speed pair of 1000~10000rpm 10~30min of pulp centrifuged processing collects upper layer uniform sizing material；
(3) it is filtered by vacuum: slurry described in step (2) is filtered by vacuum, heat is added in discontinuity while filtering Solution auxiliary filters, the graphene film aligned.
Graphite powder includes crystalline graphite powder, expanded graphite powder, ball-type graphite, micro powder graphite, artificial stone in the step (1) One of ink, the partial size of the graphite powder are 400~8000 mesh；The ball-grinding machine includes grinder, vibromill, high-speed stirring Mix one of machine, sand mill, homogenizer；
Hot solution includes deionized water, dehydrated alcohol, toluene, N-Methyl pyrrolidone, N, N- diformazan in the step (3) One of base formamide is a variety of；The temperature of the hot solution is 40~100 DEG C；
The graphene film that the composite radiating film is from bottom to top respectively ultra-thin thermal conductive silicon rubber mat, aligns is described super Thin thermal conductive silicon rubber mat with a thickness of 5~50 μm, thermal coefficient is 5~17W/ (mK), the graphene film aligned With a thickness of 10~80 μm, thermal coefficient is 1500~1780W/ (mK).
The structure of the composite radiating film is as shown in Figure 1:
The composite radiating film can also be bonded PET protection film, from bottom to top be followed successively by PET protection film, ultra-thin heat conductive silica gel The graphene film that pad, aligns, PET protection film.The PET protection film with a thickness of 0.012mm~0.25mm, ultra-thin thermally conductive Silicagel pad with a thickness of 5~50 μm, the graphene film that aligns with a thickness of 10~80 μm, PET protection film with a thickness of 0.012mm~0.125mm.
The structure of the composite radiating film is as shown in Figure 2:
The preparation method of above-mentioned composite radiating film, comprising the following steps:
(1) it prepares the paste material of ultra-thin thermal conductive silicon rubber mat: weighing 10~28 parts of vinyl silicone oils, 0.5~3 part by mass parts Containing hydrogen silicone oil, 0.10~0.25 part of platinum catalyst, 0.02~0.05 part of inhibitor, 1~3 part of titanate esters silane coupling agent and 50 ~80 parts of nano carbon microspheres and 100 parts of ball-aluminium oxides be placed in planetary stirring machine be stirred uniformly after, then with 5~15 parts Raw rubber carries out mill in open mill together, obtains paste material.
(2) calendering formation: the paste material of ultra-thin thermal conductive silicon rubber mat is coated on to the one side of graphene film, then in graphene PET protection film is enclosed on the two sides of film, after calender calender lamination, is gone in vulcanizer, in 120 DEG C and 150 DEG C of two warm areas Vulcanized, the vulcanization time of every section of warm area is respectively 10min~20min, makes the complete heat cure of the paste material of thermal conductive silicon rubber mat Molding, forms ultra-thin thermal conductive silicon rubber mat, finally obtains the composite radiating film that can be used directly.
The thermal coefficient of ultra-thin thermal conductive silicon rubber mat paste material is 5~17 (W/mK) in the step (1)；
The partial size of ball-aluminium oxide is 10~35nm in the step (1), and the partial size of the nano carbon microsphere is 15~30nm, The viscosity of the vinyl silicone oil is 1500~3000cps, and the mass fraction of medium vinyl is 0.14%, the Silicon Containing Hydrogen The hydrogen content of oil is 0.16%~0.36%, and the inhibitor is ethynylcyclohexanol, and the raw rubber is raw for east rank of nobility 110-2S Glue.
Beneficial effects of the present invention:
(1) modified graphene of the present invention includes graphene and carbon nanotube, and carbon nanotube rises between the lamella of graphene To bridging act on, overcome Mechanical Method preparation graphene film diameter size it is inhomogenous, it is mutual overlap joint there are problems that gap, realize Line face contact and plane-plane contact form heat conduction network, are conducive to the high thermal conductivity characteristic for giving full play to graphene.In addition, this hair Bright that modifying agent is added to during preparing graphene film, graphene film has good bending resistance, flexibility, impact resistance Property and higher thermal conductivity and thermal emissivity rate, are not easy to lose powder, machinability is strong.In addition, graphene film is in align, thermal conductivity Rate is up to 1780 (W/mK), and heat dissipation performance is excellent, 100 DEG C of heat source temperature can be reduced to 48.8 DEG C or so.
(2) graphene film that composite radiating film of the invention includes ultra-thin thermal conductive silicon rubber mat, aligns, ultra-thin thermal conductive silicon Rubber mat has good thermal conductivity, insulating properties, compressibility and viscoplasticity, may replace traditional double-sided adhesive, with graphene film, heat source It directly contacts, greatly reduces the thermal contact resistance between heat dissipation film and heat source, realize the quick transmitting of heat, the composite radiating film Structure is simple, has good thermal conductivity, flexibility, insulating properties.
Detailed description of the invention
Fig. 1 composite radiating film (1) expression aligns graphene film；(2) ultra-thin thermal conductive silicon rubber mat is indicated
Fig. 2 composite radiating film (1) indicates PET protection film；(2) it indicates to align graphene film；(3) indicate ultra-thin thermally conductive Silicagel pad；(4) PET protection film is indicated
The SEM picture for the graphene film that Fig. 3 is aligned
Specific embodiment
Below with reference to embodiment, the invention will be further described, but following embodiments, only present pre-ferred embodiments , the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to the invention patent scope and specification content made by it is equivalent Variation and modification, should still be within the scope of the present invention.
The test method of the graphene film and composite radiating film that align:
(1) bending resistance is tested: sample both ends being fixed on HM-8666 bend resistance testing machine with the power of 0.98N, curved Bilge radius is that 5mm starts bend test under conditions of bending angle is 180 °, and can test sample bend 10000 times or more.
(2) impact resistance is tested:
Impact resistance refers to that rapid deformation occurs in the case where being subjected to high speed gravity for paint film without cracking and the ability to fall off.With The weight of certain mass is fallen on film test plate (panel) from different height, and paint film is made to be subjected to elongation strain without cracking and falling off most Big height, the maximum height indicate the impact resistance of the paint film, usually indicate with centimetre (cm) that the quality of weight is 1kg.
(3) flexibility is tested:
It is tested using flexible analyzer according to the standard of GB1731 " paint film flexibility measuring method ", i.e., with the rigid of 1mm Roller is axle center, and by sample doubling 1 time, whether observation sample cracks or peel off.
(4) thickness is tested: thickness is tested using film thickness gauge, unit: μm
(5) heat emissivity coefficient is tested:
It is 23 ± 2 DEG C in environment temperature, under conditions of humidity is 50 ± 5%R.H, is surveyed using SR-5000 infrared Fourier It tries instrument (Israel SR-5000), according to examination criteria GJB 5023.2-2003, " material and coating reflectivity and emissivity are tested Method part 2: emissivity " it is detected.
(6) thermal conductivity is tested:
It is 23 ± 2 DEG C in environment temperature, under conditions of humidity is 50 ± 5%R.H, uses laser heat conduction coefficient tester (the resistance to LFA 467 that speeds), differential scanning calorimeter (the resistance to DSC214 that speeds) are surveyed according to examination criteria ASTM E1461-13 with flicker method The standard test method for determining thermal diffusivity is detected.
Sample is prepared into the geomery of fixture requirement, and (transverse test is the disk of diameter 25.4mm, and testing longitudinal is The disk of diameter 12.7mm).It is tested using calibrator and records sample thickness.Sample is smoothly placed on correspondence by adjusting instrument Sample tray in, stablize sample vertically, be placed in laser heat conducting instrument furnace body.Detection parameters and fixed warm program are set, opened Begin to detect, measures its thermal diffusion coefficient α.Using balance, drainage measures sample rate ρ, is measured using differential scanning calorimeter Sample specific heat capacity Cp。
According to the calculation formula K=α * C of thermal conductivityp* the thermal conductivity K of sample is calculated in ρ.
(7) heat dissipation performance is tested:
Heat dissipation test is carried out using thermal management stimulation tester TT-SIM, thermal management stimulation tester is by platform warm The composition such as source, programmable power limitation control system, data processing system, data management system, by simulating different electronic devices State in actual operation, precise measurement under different operation power, in different thermal management scheme electronic device practical temperature Degree, to assess the performance of heat sink material or heat sink conception in practical applications.I.e. according to the temperature of the pyrotoxin under the conditions of invariable power Degree measurement, obtains the data that influence on device self-temperature bring of heat sink material, to the heat dissipation performance quantitative of material Assessment.Testing procedure is as follows:
A. composite radiating film being fitted on heat source first, is then turned on power supply and by may be programmed power limitation control system System carries out parameter setting, inputs required watt level and testing time etc.；
B. testing button is clicked, starts to be tested by the power and time of setting, data processing system will supervise in real time Control and record environment temperature T0And heat source temperature T, stablize to heat source temperature, test terminates, and closes power supply.
C. temperature rise Δ T=T-T is calculated0, temperature rise value is smaller, indicates that the heat dissipation effect of composite radiating film is better.
The embodiment of the present invention and material used in comparative example are as follows:
A indicates that graphite powder, A-1 are crystalline graphite powder, and partial size is 8000 mesh；A-2 is expanded graphite powder, partial size 4000 Mesh；A-3 is artificial graphite, and partial size is 400 mesh.
B indicates carbon nanotube, and B-1 is the hydroxyl carbon nano tube that caliber is 5nm, length is 5 μm, and B-2 is that caliber is 50nm, the carboxylic carbon nano-tube that length is 35 μm.
C indicates surfactant, and C-1 is polyvinylpyrrolidone, and C-2 is polyvinyl alcohol, and C-3 is polystyrolsulfon acid Sodium.
D indicates solvent, and D-1 is deionized water, and D-2 is dehydrated alcohol.
F indicates mill pearl.
G indicates modified graphene, and ' -1 G-1, G-2, G-3, G respectively indicates the modified graphene of different condition preparation.
H indicates solvent, and H-1 is deionized water, H-2 N ' dinethylformamide.
I indicates film forming agent, and I-1 is that solid content is 25%, viscosity 100cps, and the partial size of emulsion particle is the propylene of 50nm The modified aqueous polyurethane of acid；I-2 is that solid content is 40%, viscosity 500cps, and the partial size of emulsion particle is the propylene of 10nm The modified aqueous polyurethane of acid；I-3 is acrylic emulsion.
J indicates that curing agent, J-1 are-NCO content is 16%, viscosity is 500cps self-emulsifying polyisocyanate；J-2 be- The self-emulsifying polyisocyanate that NCO content is 48%, viscosity is 6500cps.
K indicates modifying agent, shown in structural formula such as formula (1),
In formula (1), R1For the alkyl or hydrogen atom of C1~C3, R2For hydrogen atom or methyl, R3For straight chained alkyl, R4、R5、 R6、R7、R8In at least 3 be polar group, remaining is hydrogen atom, the polar group be sulfonic group and/or carboxyl, n 1 ~3 integer.
Shown in the structural formula of K-1 such as formula (1), wherein R1For hydrogen atom, R2、R3It is methyl, R4, R5, R6, R7, R8It is Carboxyl, n=1.
Shown in the structural formula of K-2 such as formula (1), wherein R1For hydrogen atom, R2For hydrogen atom, R3For propyl, R4, R5, R6, R7, R8It is carboxyl, n=3.
Shown in the structural formula of K-3 such as formula (1), wherein R1For hydrogen atom, R2、R3It is methyl, R4, R5, R6, R7, R8It is Sulfonic group, n=1.
L indicates auxiliary agent, and L-1 includes levelling agent RM-2020, non-silicon class water-based system defoaming agent BYK-019, dipropylene glycol list The aqueous high density polyethylene waxes of methyl ether, viscosity 100cps, PH=8, four mass ratioes are 1.5: 1: 7: 0.5；L-2 includes disappearing Infusion TEGO Foamex 810, Dipropylene glycol mono-n-butyl Ether and viscosity be 50cps, the aqueous high density polyethylene waxes of PH=7.5, Three's mass ratio is 1.5: 0.5: 1.
M indicates hot solution, and M-1 is the deionized water that temperature is 40 DEG C, and M-2 is the deionized water that temperature is 80 DEG C；M-3 is The N-Methyl pyrrolidone that temperature is 100 DEG C.
Table 1 prepares the formula and technological parameter (unit: kg) of modified graphene
Table 2 prepares the formula and technological parameter (unit: kg) of the graphene film aligned
Prepare the graphene film aligned
(1) prepare modified graphene: by weighed according to the formula in table 1 with dosage graphite powder, carbon nanotube, surfactant, Solvent and mill pearl, are placed in ball-grinding machine, with rate 1~6h of ball milling of 1000r/min~4000rpm, discharging, by gained slurry It is centrifuged 10~30min under the revolving speed of 1500~2500rpm, collects upper liquid, upper liquid is freeze-dried, is respectively obtained ' -1 modified graphene G-1, G-2, G-3, G.
(2) modified graphene, solvent, film forming agent, curing agent, modification compounding, mixing: are weighed by the formula and dosage of table 2 Agent and auxiliary agent, in high-speed mixer with revolving speed be 1500~4000rpm under the conditions of, stir 5~120min after, take out slurry Then material carries out 10~30min of centrifugal treating to slurry under the revolving speed of 1000~10000rpm, collect upper layer uniform sizing material.
(3) it is filtered by vacuum: slurry described in step (2) is filtered by vacuum, heat is added in discontinuity while filtering Solution auxiliary filters, the graphene film aligned.
The preparation method of composite radiating film:
(1) it prepares the paste material of ultra-thin thermal conductive silicon rubber mat: weighing the vinyl silicone oil 28 that viscosity is 3000cps by mass parts Part, hydrogen content be 0.16% 1.2 parts of containing hydrogen silicone oil, 0.10 part of platinum catalyst, 0.025 part of ethynylcyclohexanol inhibitor, 100 parts of ball-aluminium oxide that 80 parts of the nano carbon microsphere and partial size that 3 parts of titanate esters silane coupling agent and partial size are 15nm are 30nm, It is placed in planetary stirring machine after being stirred uniformly, then is opened in open mill together with 10 parts of eastern rank of nobility 110-2S raw rubbers Refining finally collects and obtains paste material.
(2) ultra-thin thermal conductive silicon rubber mat is fitted in graphite heat radiation fin: paste material made from above-mentioned steps is respectively coated In the one side of the graphene film aligned prepared by Examples 1 to 5 and comparative example 1-1,1-2,1-3,1-4 and 1-5, two PET protection film is enclosed in face, after calender calender lamination, is gone in 120 DEG C and 150 DEG C of two warm area vulcanizer immediately and is carried out sulphur Change, every section of warm area carries out 20min vulcanizing treatment respectively, and heat conductive silica gel is made to pad now complete heat cure molding to get PET protection Graphene film/ultra-thin heat conductive silica gel the gasket for film/align/PET protection film composition composite radiating film.At this point, ultra-thin lead Hot silicagel pad is with a thickness of 10 μm, compression ratio 40%, thermal conductivity 7W/mK
The performance for the graphene film that table 3 aligns
The heat dissipation effect of 4 composite radiating film of table is tested
As can be seen from Figure 3, in the form of sheets, parallel orientation close-packed arrays, film layer has biggish specific surface area to graphene film.From table 3 as can be seen that the thickness of graphene film that aligns of the present invention between 10~80 μm, has excellent bending resistance, resistance to Impact and flexibility and higher thermal emissivity rate and thermal conductivity；As can be seen from Table 4, the graphene film that will be aligned It is bonded with ultra-thin thermal conductive silicon rubber mat, prepares composite radiating film, composite radiating film has excellent heat dissipation performance.From embodiment 1 ~3 and comparative example 1-1,2-1 and 3-1 comparison in it is not difficult to find out that, be added in the preparation process of graphene film such as formula (1) after modifying agent shown in, bending resistance, impact resistance, flexibility, thermal emissivity rate and thermal conductivity of graphene film etc. are every Performance is obviously improved；Under conditions of not adding modifying agent, the mechanical performance of obtained graphene film is poor, thermal conductivity Rate and thermal emissivity rate are lower, and heat dissipation performance is poor.
In formula (1), R1For the alkyl or hydrogen atom of C1~C3, R2For hydrogen atom or methyl, R3For straight chained alkyl, R4、R5、 R6、R7、R8In at least 3 be polar group, remaining is hydrogen atom, the polar group be sulfonic group and/or carboxyl, n 1 ~3 integer.
Illustrate: ultra-thin heat conductive silica gel mat thickness be 5 μm~50 μm, compression ratio be 30%~80%, thermal conductivity be 5~ 17W/mK is also able to achieve the purpose of the present invention；The ultra-thin thermal conductive silicon rubber mat of the present invention is commercially available, such as Fujipoly richness The models such as scholar Sarcon XR-E, XR-HE meet requirement.

Claims (12)

1. a kind of graphene film, which is characterized in that the graphene film includes the component of following mass fraction: 100 parts of modified stones Black alkene, 250~450 parts of solvents, 15~50 parts of film forming agents, 0.5~1.5 part of curing agent, 0.25~15 part of modifying agent, 3~10 parts Auxiliary agent, the graphene film with a thickness of 10 μm~80 μm.
2. graphene film according to claim 1, which is characterized in that shown in the structural formula of the modifying agent such as formula (1),
In formula (1), R1For the alkyl or hydrogen atom of C1~C3, R2For hydrogen atom or methyl, R3For straight chained alkyl, R4、R5、R6、R7、 R8In at least 3 be polar group, remaining is hydrogen atom, and the polar group is sulfonic group and/or carboxyl, and n is 1~3 Integer.
3. graphene film according to claim 2, which is characterized in that in the formula (1), R1For hydrogen atom, R2For hydrogen atom Or methyl, R3For the alkyl of C1~C3, R4, R5, R6, R7, R8It is sulfonic group, the integer that n is 1~3.
4. graphene film according to claim 2, which is characterized in that in the formula (1), R1For hydrogen atom, R2For hydrogen atom Or methyl, R3For the alkyl of C1~C3, R4, R5, R6, R7, R8It is carboxyl, the integer that n is 1~3.
5. graphene film according to claim 4, which is characterized in that in the formula (1), R1For hydrogen atom, R2For methyl, R3For methyl, R4, R5, R6, R7, R8It is carboxyl, n=1.
6. graphene film according to claim 4, which is characterized in that in the formula (1), R1For hydrogen atom, R2For hydrogen original Son, R3For propyl, R4, R5, R6, R7, R8It is carboxyl, n=3.
7. graphene film according to claim 1, which is characterized in that the modified graphene group containing polar hydrophilic, The polar hydrophilic group includes one of carboxyl, sulfonic group, sulfate, amino, amido, hydroxyl, amide groups, ehter bond or more Kind.
8. graphene film according to claim 1, which is characterized in that the film forming agent is polyvinyl alcohol emulsions, acrylic acid One or both of resin and polyaminoester emulsion.
9. described in any item graphene films according to claim 1~8, which is characterized in that the graphene film is to align Graphene film.
10. the preparation method of graphene film according to any one of claims 1 to 9, which is characterized in that comprise the steps of:
(1) prepare modified graphene: by graphite powder, carbon nanotube, surfactant, solvent and mill pearl according to mass ratio be (10 ~30): 5: (0.15~0.3): be placed in ball-grinding machine at 250: 100, with the rate ball milling 1 of 1000r/min~4000r/min~ Gained slurry be centrifuged 10~30min by 6h, discharging under the revolving speed of 1500~2500rpm, collection upper liquid, by upper liquid into Row freeze-drying, obtains modified graphene powder；
(2) compounding, mixing: by 100: (250~450): (15~50): (0.5~1.5): (0.25~15): the matter of (3~10) Amount ratio successively weighs modified graphene, solvent, film forming agent, curing agent, modifying agent and auxiliary agent, high-speed mixer with 1500~ After the revolving speed of 4000rpm stirs 5~120min, take out slurry, then with the rotation speed of 1000~10000rpm to slurry from The heart handles 10~30min, collects upper layer uniform sizing material；
(3) it is filtered by vacuum: slurry described in step (2) is filtered by vacuum, hot solution is added in discontinuity while filtering Auxiliary filters, the graphene film aligned, and the temperature range of the hot solution is 40~100 DEG C.
11. a kind of composite radiating film, which is characterized in that the composite radiating film from bottom to top be respectively ultra-thin thermal conductive silicon rubber mat, The graphene film aligned.
12. a kind of composite radiating film described in claim 11, which is characterized in that the heat dissipation composite membrane is from bottom to top followed successively by PET protection film, ultra-thin thermal conductive silicon rubber mat, the graphene film aligned, PET protection film.
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