CN106867256A - A kind of Graphene fabric-modifying anisotropic thermal Kapton, preparation method and application - Google Patents
A kind of Graphene fabric-modifying anisotropic thermal Kapton, preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of Graphene fabric-modifying anisotropic thermal Kapton, preparation method and application.Graphene fabric-modifying anisotropic thermal Kapton, it is with siliceous alicyclic diamine and aromatic series tetracarboxylic dianhydride as raw material, inorganic nano heat filling is added simultaneously obtains polyamic acid heat filling glue through polycondensation reaction, then contaminate in the Graphene fabric laminated board with 3D network structures, obtained through hot-imide.The high heat radiation aluminium-based copper-clad plate prepared by above-mentioned anisotropic thermal Kapton has thermal conductivity higher, wherein horizontal thermal conductivity factor is more than 8.0W/mK, longitudinal thermal conductivity factor is more than 5.0W/mK.Transmission heat can be oriented as component circuit substrate, heat will not be made in component inner accumulation, so as to reduce cooling device.The aluminum-based copper-clad plate has peel strength higher simultaneously, and elevated temperature cohesiveness is good.
Description
Technical field
Anisotropic thermal Kapton, preparation method are prepared the present invention relates to a kind of Graphene fabric-modifying and be somebody's turn to do
Film mainly solves to take into account high-termal conductivity and be manufactured into category at present in the application of high heat radiation aluminium-based copper-clad plate
Originally, the technical problem of low-dielectric energy and high-dimensional stability, is mainly used on high cooling circuit board, belongs to macromolecular material
Application field.
Background technology
High heat radiation aluminium-based copper-clad plate (TCCAS) will be large power supply, military electronic and the micro- electricity of high frequency as emerging substrate
The main flow substrate that sub- equipment is used, compared to FR-4 and common aluminum-based copper-clad plate, with nearly more than 10 times of thermal conductivity, breakdown potential high
The excellent properties such as pressure, Gao Ti, table resistivity, and excellent high temperature resistant, meet the trend and demand of high frequency microelectronics development.
Great power LED has that small volume, power consumption are small, heating is small, long lifespan, fast response time, safety as lighting source
The advantages of low-voltage, good weatherability, good directionality, the special industries such as oil field, petrochemical industry, railway, mine, army, decor,
Landscape light in city, display screen and stadiums etc., being with a wide range of applications in Special Work light fixture.But it is high-power
LED needs to be heat-treated, which greatly increases the cost of LED.In the design process, the additives of most expensive is exactly to radiate
Piece, fin can be made by various metal materials, and these materials both include relatively cheap aluminium, also more preferable including electric conductivity
But more expensive material (such as copper and silver).And emerging high heat radiation aluminium-based copper-clad plate has radiating efficiency high, manufacture craft letter
The features such as list, low cost, will there is vast potential for future development in great power LED.
The addition heat conduction in epoxy resin or Thermocurable polyimide is used to fill out in current most of aluminum-based copper-clad plates
Used as conductive adhesive film, CN102673048A reports a kind of epoxy resin conductive adhesive film to material, by epoxy resin (A-80), asphalt mixtures modified by epoxy resin
Fat (E-51), mark, aluminium nitride, nitrile rubber, acetone, dimethylformamide, synthesize high thermal conductive resin, its thermal resistance≤0.50
DEG C/W, thermal conductivity factor >=2.0W/mk, but poor in flexibility.CN104708869A reports a kind of Thermocurable polyimide heat conduction
Insulating barrier, its main component is made up of thermoset polyimide resin with alumina fibre, obtains thermally conductive insulating layer, but heat conduction is imitated
Fruit does not reach great power LED use requirement still, and thermosetting resin mechanical energy is poor, if using meeting at high temperature for a long time
Decomposition is produced, service life is influenceed.
The content of the invention
It is an object of the present invention to provide a kind of Graphene fabric-modifying anisotropic thermal Kapton, preparation method and
Application of the film in high heat radiation aluminium-based copper-clad plate.
Graphene fabric-modifying anisotropic thermal Kapton, it is with siliceous alicyclic diamine and aromatic series four
Acid dianhydride is raw material, while add inorganic nano heat filling obtains polyamic acid-heat filling glue through polycondensation reaction, then
Contaminate in the Graphene fabric laminated board with 3D network structures, obtained through hot-imide.
By such scheme, siliceous alicyclic diamine of the present invention includes silicone-containing diamines and silane-containing diamines, point
Sub- formula is respectively such as formula 2,3, wherein R1It is containing 1~14 univalence hydrocarbyl or substituted hydrocarbon radical of carbon atom, such as methyl, ethyl, benzene
Base etc., R2It is alkyl, phenylene and substituted phenylene etc., n is the integer more than or equal to 1, it is generally preferable to less than 10.It is preferential to select
The aminopropyl tetramethyl disiloxanes (GAPD) of 1,3- bis-, two [4- (to phenoxy group)-phenoxy group] dimethylsilanes (APPMS), 1,
One kind in the aminophenyl tetramethyl disiloxanes of 3- bis- and the α containing multiple dimethyl siloxane chains, ω-diamino propyl derivatives
Or two or more mixtures.
By such scheme, as shown in Equation 4, R bases are represented aromatic series tetracarboxylic dianhydride monomer structure formula of the present invention in formula 4
Phenyl, xenyl, aromatic ether, aromatic ketone, preferably include pyromellitic acid anhydride (PMDA), bibenzene tetracarboxylic dianhydride (BPDA),
One or more in benzophenone tetracarboxylic dianhydride (BTDA), oxydiphthalic (ODPA) and hexafluorodianhydride (6FDA) (6FDA)
Mixture；
By such scheme, inorganic filler of the present invention is inorganic oxide or inorganic nitride, preferentially from oxygen
Change one or more mixtures in aluminium (AlO), magnesia (MgO), boron nitride (BN), wherein particle diameter is 50~200nm.
By such scheme, polycondensation reaction prepares starting monomer aromatic tetracarboxylic acid two in polyamic acid-heat filling glue
Acid anhydride is by mass percentage 5%~30%, preferably 10%~20% with filler usage amount in siliceous alicyclic diamine and filler；
The gross mass percentage that the starting monomer aromatic tetracarboxylic acid dianhydride for using accounts for solvent and monomer with siliceous alicyclic diamine is 5%
~20%, preferably 10%~15%.
By such scheme, content percentage of the Graphene fabric in Kapton is 1%~15%, preferably 5%
~10%.
By such scheme, the Graphene fabric laminated board with 3D network structures is to do to grow with nickel wire reticulated
Substrate, is layering what is obtained by chemical vapor infiltration in its superficial growth individual layer or the few graphene layer of the number of plies.
By such scheme, the nickel wire reticulated selects 200 mesh~300 mesh nickel wire reticulateds；Described Graphene
Fabric laminated board includes 5~15 layer graphene tissue layers.
By such scheme, the thickness of the anisotropic thermal Kapton is 20~50 μm.It is of the present invention
The method that Graphene fabric-modifying prepares anisotropic thermal Kapton, it is characterised in that first by in-situ polymerization,
In aprotic polar solvent, using siliceous alicyclic diamine and aromatic series tetracarboxylic dianhydride, while add a small amount of inorganic nano leading
Hot filler, low temperature polyamic acid-heat filling glue of the synthesis viscosity more than 40000mPas, then contaminates to 3D nets
In the Graphene fabric laminated board of shape structure, Graphene fabric/polyamic acid-heat filling dipping thin plate is obtained, then through hot acyl
Imidization obtains anisotropic thermal Kapton.
The TPI reaction equation is as shown in Equation 1.
By such scheme, in the preparation method of anisotropic thermal Kapton of the present invention, aromatic series four
The ratio between carboxylic acid dianhydride and amount of material of siliceous alicyclic diamine are 0.95~1.2：1, preferably 1.01~1.1：1.
By such scheme, aprotic polar solvent of the present invention is 1-METHYLPYRROLIDONE (NMP), N, N- dimethyl
One kind in formamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), hexamethyl phosphoramide (HMP) or
Two or more mixtures.
By such scheme, the synthetic method of polyamic acid of the present invention-heat filling glue, it is characterised in that：
In reactor, a certain amount of aprotic polar solvent is first added, a certain amount of siliceous alicyclic diamine is added again under nitrogen protection
With inorganic nano heat filling, 0.5~2h of high-speed stirred at room temperature fully dissolves siliceous alicyclic diamine and by inorganic nano
Heat filling is uniformly dispersed；Dianhydride is added into reactor in batches in 0.5~5h, 5~10 equal parts are specifically divided into, and 0
5~24h of stirring reaction at~5 DEG C, obtains polyamic acid-heat filling solution of the viscosity more than 40000mPas, is put into storage
Deposit in tank, stored under -10 DEG C of low temperature.
By such scheme, the preparation method of described Graphene fabric laminated board：Nickel wire reticulated is first through watery hydrochloric acid table
Face removal of impurities treatment, is then placed in H in quartz tube furnace2900~1100 DEG C of insulation a period of times are heated under stream atmosphere, then will
Graphene growth catalyst is incorporated into quartz ampoule, and to be cooled to room temperature rapidly after 0.5~1h of reaction, then etching removes Ni
Graphene fabric is obtained, Graphene fabric is layering, the Graphene fabric laminated board with 3D network structures is obtained.
By such scheme, described graphene growth catalyst is CH that volume flow ratio is the ︰ 1 of 4 ︰ 1~24、H2Gaseous mixture；
Described rate of temperature fall is 150~220 DEG C/min.
By such scheme, the heating rate for being heated to 900~1100 DEG C is 5~20 DEG C/min, and etching removal Ni is
The low-grade fever removal of immersion etchant, etching agent is 5~15g CuSO4, 50ml nitric acid and hydrochloric acid mixed liquor and 50ml deionized waters
Mixed liquor, etching temperature be 30~45 DEG C, etch period be 24~48h.
By such scheme, described hot-imide process deviates from solvent to be first incubated 1~2h under 70~90 DEG C of vacuum,
Then at a temperature of 110~130 DEG C, 140~160 DEG C, 170~190 DEG C, 220~240 DEG C, 270~290 DEG C, 320~340 DEG C
0.5~1h of each insulation makes its complete hot-imide, and thermoplasticity anisotropic thermal is obtained through cutting edge winding after hot-imide
Kapton.
Above-mentioned Graphene fabric-modifying anisotropic thermal Kapton is in high heat radiation aluminium-based copper-clad plate is prepared
Using application process is：By anisotropic thermal Kapton, 110~130 DEG C are hot-pressed onto on aluminium sheet, and are covered with Copper Foil,
It is then fed into hot press compacting, pressing process：110~130 DEG C/0.5~1h, 140~160 DEG C, 170~190 DEG C, 220~240
DEG C each 1~2h, compacting is finished, and is cooled down, and is taken out, and is cut out by given size.
High heat radiation aluminium-based copper-clad plate comprising above-mentioned Graphene fabric-modifying anisotropic thermal Kapton.
Compared with prior art, advantage of the invention is that：
(1) growth substrate of Graphene is prepared as vapor deposition method by Ni mesh-likes fabric so that Graphene has
Identical network structure, can obtain orderly three dimentional heat conduction network after being layering, and being added in polyimide resin can
To realize horizontal heat conduction in face.
(2) a certain amount of inorganic heat filling is added during preparing polyamic acid by situ aggregation method so that thin
Film insulating heat-conductive in the vertical, after being prepared into Kapton, with good heat conductivility, flexility, workability
Energy, heat resistance, dimensional stability and chemical-resistant.
(3) the high heat radiation aluminium-based copper-clad plate prepared by thermoplasticity anisotropic thermal Kapton, with compared with
Thermal conductivity high, wherein horizontal thermal conductivity factor is more than 8.0W/mK, longitudinal thermal conductivity factor is more than 5.0W/mK.As component
Circuit substrate can orient transmission heat, will not be heat in component inner accumulation, so as to reduce cooling device.While the aluminium
Base copper-clad plate has peel strength higher, and elevated temperature cohesiveness is good.
Specific embodiment
Embodiment 1
(1) preparation of Graphene fabric
Nickel wire mesh grid is the braid that the size of mesh opening being made into by a diameter of 45 μm of nickel wire is 70 × 70 μm.Size is
200 mesh.As gaseous phase deposition substrate.Twine soaks 10min through watery hydrochloric acid first, gets rid of impurity and surface oxide layer, then
It is put into quartz tube furnace, H2With 10 DEG C/min heating rates to 1000 DEG C of insulations 10min, CH under stream atmosphere4
(24sccm)、H2The gaseous mixture of (6sccm) is incorporated into quartz ampoule as graphene growth catalyst, with 150 after reaction 30min
DEG C/min lowers the temperature rapidly.Then reactant is put into etchant (copper nitrate 100g+ hydrochloric acid 500ml+ water 500ml) and is heated to
35 DEG C of immersion 1h, removal substrate Ni, you can obtain the Graphene fabric laminated board with certain network structure.
(2) synthesis of polyamic acid and the preparation of polyimide composite film
In 2000ml reactors, the aprotic polar solvent DMAc of 1000g is first added, then add the siliceous alicyclic rings of 59.0g
The needle inorganic nano heat filling boron nitride of race diamines GAPD and 12.5g, nitrogen charging gas shielded, the high-speed stirred at 10 DEG C
0.5h, fully dissolving diamines are simultaneously dispersed by needle inorganic nano heat filling.52.0g aromatic dianhydrides PMDA is divided into 5
Equal part, point 5 addition reactors in 0.5h, and the stirring reaction 5h at 0 DEG C, obtain polyamic acid-heat filling glue, then
The glue is contaminated to 10min between the Graphene fabric laminated board in (1), Graphene fabric/polyamic acid-heat filling is obtained
Dipping plate.Then 2h abjection solvents, then in 110 DEG C, 140 DEG C, 170 DEG C of each 1h, 220 DEG C, 270 are first incubated under 70 DEG C of vacuum
DEG C, 320 DEG C of each insulation 0.5h, make its complete hot-imide, the thermoplasticity for obtaining 20~50 μm through cutting edge winding after completion is each
Anisotropy heat conduction Kapton.
(3) preparation of high heat radiation aluminium-based copper-clad plate
Graphene fabric/polyamic acid-heat filling laminated film in (2) is hot-pressed onto 10 × 15cm's at 110 DEG C
On aluminium sheet, Copper Foil, feeding hot press compacting, pressing process are covered with：110 DEG C/0.5h, 140 DEG C, 170 DEG C, 220 DEG C of each 1h.It is complete
Finish, cooling is taken out.Obtain the high heat radiation aluminium-based copper-clad plate that polyimides is heat-conducting layer.
Embodiment 2~6
In the same manner as in Example 1, simply each raw material type, quality and technological parameter are poor for the preparation method of embodiment 2~6
Different, as shown in table 1, the technological parameter of embodiment 2~6 is as shown in table 2 for the raw material of embodiment 2~6.To obtained by embodiment 2~6
Polyimide composite film and high heat radiation aluminium-based copper-clad plate carry out performance test, as a result as shown in table 3.
The raw material of 1 embodiment of table 1~6
The technological parameter of 2 embodiment of table 1~6
The Graphene fabric of table 3/Kapton and high heat radiation aluminium-based copper-clad plate the performance test results
Claims (12)
1. Graphene fabric-modifying anisotropic thermal Kapton, it is characterised in that：It is with siliceous alicyclic diamine
It is raw material with aromatic series tetracarboxylic dianhydride, is filled out while adding inorganic nano heat filling and obtaining polyamic acid-heat conduction through polycondensation reaction
Material glue, then contaminates in the Graphene fabric laminated board with 3D network structures, is obtained through hot-imide.
2. Graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that：Institute
The siliceous alicyclic diamine stated includes silicone-containing diamines and silane-containing diamines, and general molecular formula is respectively such as formula 2,3, wherein R1Be containing
1~14 univalence hydrocarbyl or substituted hydrocarbon radical of carbon atom, R2It is alkyl, phenylene and substituted phenylene etc., n is more than or equal to 1
Integer,
As shown in Equation 4, R bases represent phenyl, xenyl, aromatic ether, virtue to described aromatic series tetracarboxylic dianhydride monomer structure formula in formula 4
Ketone musk, preferably includes pyromellitic acid anhydride (PMDA), bibenzene tetracarboxylic dianhydride (BPDA), benzophenone tetracarboxylic dianhydride
(BTDA), one or more mixtures in oxydiphthalic (ODPA) and hexafluorodianhydride (6FDA) (6FDA),
3. Graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that：Contracting
Poly- reaction prepares in polyamic acid-heat filling glue starting monomer aromatic tetracarboxylic acid dianhydride and siliceous alicyclic diamine and fills out
Filler usage amount is by mass percentage 5%~30% in material；The starting monomer aromatic tetracarboxylic acid dianhydride for using with it is siliceous
The gross mass percentage that alicyclic diamine accounts for solvent is 5%~20%.
4. Graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that：Stone
Content percentage of the black alkene fabric in Kapton is 1%~15%；The Graphene with 3D network structures is knitted
Thing laminated board is to do growth substrate with nickel wire reticulated, few in its superficial growth individual layer or the number of plies by chemical vapor infiltration
Graphene layer be layering what is obtained.
5. Graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that：Institute
Nickel wire reticulated is stated from 200 mesh~300 mesh nickel wire reticulateds；Described Graphene fabric laminated board includes 5~15 layers
Graphene tissue layer；Described inorganic filler is inorganic oxide or inorganic nitride, and wherein particle diameter is 50~200nm；Institute
The thickness for stating anisotropic thermal Kapton is 20~50 μm.
6. the Graphene fabric-modifying described in claim 1 prepares the preparation method of anisotropic thermal Kapton, its
It is characterised by：First by in-situ polymerization, in aprotic polar solvent, siliceous alicyclic diamine and aromatic series tetracid two are used
Acid anhydride, while adding a small amount of inorganic nano heat filling, low temperature polyamic acid-heat conduction of the synthesis viscosity more than 40000mPas is filled out
Material glue, in then contaminating the Graphene fabric laminated board with 3D network structures, obtain Graphene fabric/polyamic acid-
Heat filling impregnates thin plate, then obtains anisotropic thermal Kapton through hot-imide.
7. the preparation method of Graphene fabric-modifying anisotropic thermal Kapton according to claim 6, its
It is characterised by：In the preparation method of described anisotropic thermal Kapton, aromatic tetracarboxylic acid's dianhydride with contain silicone grease
The ratio between amount of material of ring race diamines is 0.95~1.2：1；Described aprotic polar solvent is 1-METHYLPYRROLIDONE
(NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), hexamethyl phosphinylidyne
One or more mixture in amine (HMP).
8. Graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that：Institute
The synthetic method of the polyamic acid stated-heat filling glue, it is characterised in that：In a kettle., a certain amount of non-matter is first added
Sub- polar solvent, adds a certain amount of siliceous alicyclic diamine and inorganic nano heat filling, at room temperature again under nitrogen protection
0.5~2h of high-speed stirred, fully dissolves siliceous alicyclic diamine and inorganic nano heat filling is uniformly dispersed；By aromatic series four
Acid dianhydride adds reactor, and 5~24h of stirring reaction at 0~5 DEG C in batches in 0.5~5h, obtains viscosity and is more than
The polyamic acid of 40000mPas-heat filling solution, is put into holding vessel, is stored under -10 DEG C of low temperature.
9. Graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that：Institute
The preparation method of the Graphene fabric laminated board stated：Nickel wire reticulated is first processed through the removal of impurities of watery hydrochloric acid surface, is then placed in stone
H in English tube furnace2900~1100 DEG C of insulation a period of times are heated under stream atmosphere, then graphene growth catalyst is introduced
To quartz ampoule, to be cooled to room temperature rapidly after 0.5~1h of reaction, then etching removal Ni is that can obtain Graphene fabric, by stone
Black alkene fabric is layering, and the Graphene fabric laminated board with 3D network structures is obtained；
Described graphene growth catalyst is CH that volume flow ratio is the ︰ 1 of 4 ︰ 1~24、H2Gaseous mixture；Described rate of temperature fall
It is 150~220 DEG C/min.
10. Graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that：
Described hot-imide process for first under 70~90 DEG C of vacuum be incubated 1~2h abjection solvent, then 110~130 DEG C,
140~160 DEG C, 170~190 DEG C, 220~240 DEG C, 270~290 DEG C, 0.5~1h of each insulation makes it at a temperature of 320~340 DEG C
Complete hot-imide, thermoplasticity anisotropic thermal Kapton is obtained after hot-imide through cutting edge winding.
Graphene fabric-modifying anisotropic thermal Kapton described in 11. claims 1 prepare it is high heat radiation aluminium-based
Application in copper-clad plate, application process is：By anisotropic thermal Kapton, 110~130 DEG C are hot-pressed onto on aluminium sheet, and
Copper Foil is covered with, hot press compacting, pressing process is then fed into：110~130 DEG C/0.5~1h, 140~160 DEG C, 170~190
DEG C, 220~240 DEG C of each 1~2h, compacting finishes, and cools down, and takes out, and is cut out by given size.
12. include the high heat radiation aluminium-based of the Graphene fabric-modifying anisotropic thermal Kapton described in claim 1
Copper-clad plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710107734.3A CN106867256B (en) | 2017-02-27 | 2017-02-27 | A kind of graphene fabric-modifying anisotropic thermal Kapton, preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710107734.3A CN106867256B (en) | 2017-02-27 | 2017-02-27 | A kind of graphene fabric-modifying anisotropic thermal Kapton, preparation method and application |
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| Publication Number | Publication Date |
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| CN106867256A true CN106867256A (en) | 2017-06-20 |
| CN106867256B CN106867256B (en) | 2019-10-18 |
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