CN106867256B - 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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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H05K2201/01—Dielectrics
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- H05K2201/0154—Polyimide
Abstract
The present invention relates to a kind of graphene fabric-modifying anisotropic thermal Kaptons, preparation method and application.Graphene fabric-modifying anisotropic thermal Kapton, it is using siliceous alicyclic diamine and aromatic series tetracid dianhydride as raw material, adding inorganic nano heat filling obtains polyamic acid-heat filling glue through polycondensation reaction simultaneously, then it disseminates in the graphene fabric laminated board with 3D reticular structure, is obtained through hot-imide.The high heat radiation aluminium-based copper-clad plate thermal conductivity with higher being prepared by above-mentioned anisotropic thermal Kapton, wherein lateral thermal coefficient is greater than 8.0W/mK, longitudinal thermal coefficient is greater than 5.0W/mK.Transmitting heat can be oriented as component circuit substrate, heat will not be made in component inner accumulation, to reduce cooling device.Aluminum-based copper-clad plate peel strength with higher, elevated temperature cohesiveness are good simultaneously.
Description
Technical field
Anisotropic thermal Kapton, preparation method are prepared the present invention relates to a kind of graphene fabric-modifying and are somebody's turn to do
Film in the application of high heat radiation aluminium-based copper-clad plate, mainly solve at present with category cannot be considered in terms of high-termal conductivity and manufacture at
The technical issues of sheet, low-dielectric energy and high-dimensional stability, it is mainly used on high cooling circuit board, belongs to high molecular material
Application field.
Background technique
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 mainstream substrate that sub- equipment uses compares FR-4 and common aluminum-based copper-clad plate, with nearly 10 times or more of thermal conductivity, high breakdown potential
Pressure, the excellent properties such as Gao Ti, table resistivity and excellent high temperature resistant meet the trend and demand of the development of high frequency microelectronics.
Great power LED is as lighting source with small in size, power consumption is small, fever is small, the service life is long, fast response time, safety
The advantages that 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 lamps and lanterns.But it is high-power
LED is heat-treated, and which greatly increases the costs of LED.In the design process, the additives of most expensive is exactly to radiate
Piece, cooling fin can be made by various metal materials, these materials had both included relatively cheap aluminium, also include that electric conductivity is more preferable
But more expensive material (such as copper and silver).And emerging high heat radiation aluminium-based copper-clad plate has radiating efficiency height, manufacture craft letter
The features such as single, at low cost, will there is vast potential for future development in great power LED.
It is that thermally conductive fill out is added in epoxy resin or Thermocurable polyimide used in current most of aluminum-based copper-clad plates
Material is used as conductive adhesive film, and CN102673048A reports a kind of epoxy resin conductive adhesive film, by epoxy resin (A-80), asphalt mixtures modified by epoxy resin
Rouge (E-51), mark, aluminium nitride, nitrile rubber, acetone, dimethylformamide, synthesize high thermal conductive resin, thermal resistance≤0.50
DEG C/W, thermal coefficient >=2.0W/mk, but poor in flexibility.It is thermally conductive that CN104708869A reports a kind of Thermocurable polyimide
Insulating layer, main component are made of thermoset polyimide resin and alumina fibre, obtain thermally conductive insulating layer, but thermally conductive effect
Great power LED requirement is still not achieved in fruit, and thermosetting resin mechanical energy is poor, if using meeting at high temperature for a long time
Decomposition is generated, service life is influenced.
Summary 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, is with siliceous alicyclic diamine and aromatic series four
Acid dianhydride is raw material, while adding inorganic nano heat filling and obtaining polyamic acid-heat filling glue through polycondensation reaction, then
It disseminates in the graphene fabric laminated board with 3D reticular structure, is obtained through hot-imide.
According to the above scheme, siliceous alicyclic diamine of the present invention includes silicone-containing diamines and silane-containing diamines, is divided
Sub- general formula is respectively such as formula 2,3, wherein R1For univalence hydrocarbyl or substituted hydrocarbon radical containing 1~14 carbon atom, such as methyl, ethyl, benzene
Base etc., R2For 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
Bis- aminopropyl tetramethyl disiloxane (GAPD) of 1,3-, two [4- (to phenoxy group)-phenoxy group] dimethylsilanes (APPMS), 1,
One of bis- aminophenyl tetramethyl disiloxane of 3- and the α containing multiple dimethyl siloxane chains, ω-diamino propyl derivatives
Or two or more mixtures.
According to the above scheme, aromatic series tetracid dianhydride monomer structure formula of the present invention is as shown in Equation 4, and R base represents in formula 4
Phenyl, xenyl, aromatic ether, aromatic ketone, preferably include pyromellitic acid anhydride (PMDA), bibenzene tetracarboxylic dianhydride (BPDA),
One or more of benzophenone tetracarboxylic dianhydride (BTDA), diphenyl ether tetracid dianhydride (ODPA) and hexafluorodianhydride (6FDA) (6FDA)
Mixture；
According to the above scheme, inorganic filler of the present invention is inorganic oxide or inorganic nitride, preferentially selects oxygen
Change one or more mixtures of aluminium (AlO), magnesia (MgO), boron nitride (BN), wherein partial size is 50~200nm.
According to the above scheme, polycondensation reaction prepares starting monomer aromatic tetracarboxylic acid two in polyamic acid-heat filling glue
Filler usage amount is 5%~30% by mass percentage in acid anhydride and siliceous alicyclic diamine and filler, preferably 10%~20%；
It is 5% that the starting monomer aromatic tetracarboxylic dianhydride and siliceous alicyclic diamine used, which accounts for solvent and the gross mass percentage of monomer,
~20%, preferably 10%~15%.
According to the above scheme, content percentage of the graphene fabric in Kapton is 1%~15%, preferably 5%
~10%.
According to the above scheme, the graphene fabric laminated board with 3D reticular structure is to do to grow with nickel wire reticulated
Substrate is layering by chemical vapor infiltration in the few graphene layer of its surface growth single layer or the number of plies.
According to the above scheme, the nickel wire reticulated selects 200 mesh~300 mesh nickel wire reticulateds；The graphene
Fabric laminated board includes 5~15 layers of graphene tissue layer.
According to the above scheme, the anisotropic thermal Kapton with a thickness of 20~50 μm.It is of the present invention
The method that graphene fabric-modifying prepares anisotropic thermal Kapton, which is characterized in that pass through in-situ polymerization first,
In aprotic polar solvent, using siliceous alicyclic diamine and aromatic series tetracid dianhydride, while adding a small amount of inorganic nano and leading
Hot filler, low temperature synthesize polyamic acid-heat filling glue that viscosity is greater than 40000mPas, and then dip dyeing is to 3D net
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 thermoplastic polyimide reaction equation is as shown in Equation 1.
According to the above scheme, in the preparation method of anisotropic thermal Kapton of the present invention, aromatic series four
The ratio between carboxylic acid dianhydride and the amount of substance of siliceous alicyclic diamine are 0.95~1.2:1, preferably 1.01~1.1:1.
According to the above scheme, aprotic polar solvent of the present invention is N-Methyl pyrrolidone (NMP), N, N- dimethyl
One of formamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), hexamethyl phosphoramide (HMP) or
Two or more mixtures.
According to the above scheme, polyamic acid of the present invention-heat filling glue synthetic method, it is characterised in that:
In reaction kettle, a certain amount of aprotic polar solvent is first added, adds a certain amount of siliceous alicyclic diamine under nitrogen protection again
With inorganic nano heat filling, 0.5~2h of high-speed stirred at room temperature sufficiently dissolves siliceous alicyclic diamine and by inorganic nano
Heat filling is uniformly dispersed；Reaction kettle is added in dianhydride in batches in 0.5~5h, specifically can be divided into 5~10 equal parts, and 0
It is stirred to react 5 at~5 DEG C~for 24 hours, polyamic acid-heat filling solution that viscosity is greater than 40000mPas is obtained, storage is put into
It deposits in tank, is stored under -10 DEG C of low temperature.
According to the above scheme, the preparation method of the graphene fabric laminated board: nickel wire reticulated is first through dilute hydrochloric acid table
Face removal of impurities processing, is then placed in H in quartz tube furnace2It is heated to 900~1100 DEG C of heat preservation a period of times under stream atmosphere, then will
Graphene growth catalyst is introduced into quartz ampoule, reacts after 0.5~1h to be cooled to room temperature rapidly, then etching removal Ni
Graphene fabric is obtained, graphene fabric is layering, the graphene fabric laminated board with 3D reticular structure is made.
According to the above scheme, the graphene growth catalyst is the CH that volume flow ratio is 4 ︰, 1~2 ︰ 14、H2Gaseous mixture；
The rate of temperature fall is 150~220 DEG C/min.
According to the above scheme, the heating rate for being heated to 900~1100 DEG C is 5~20 DEG C/min, and etching removal Ni is
The removal of etchant low-grade fever is immersed, etching agent is 5~15g CuSO4, 50ml nitric acid and hydrochloric acid mixed liquor and 50ml deionized water
Mixed liquor, etching temperature be 30~45 DEG C, etch period be 24~48h.
According to the above scheme, the hot-imide process is that 1~2h prolapse solvent is first kept the temperature 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 heat preservation makes its complete hot-imide, winds to obtain thermoplasticity anisotropic thermal through cutting edge after hot-imide
Kapton.
Above-mentioned graphene fabric-modifying anisotropic thermal Kapton is in preparing high heat radiation aluminium-based copper-clad plate
Using application method are as follows: 110~130 DEG C of anisotropic thermal Kapton are hot-pressed on aluminium sheet, and is 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 finish, cooling, take out, cut out by predetermined size.
High heat radiation aluminium-based copper-clad plate comprising above-mentioned graphene fabric-modifying anisotropic thermal Kapton.
Compared with prior art, present invention has an advantage that
(1) growth substrate for preparing graphene as vapor deposition method by Ni mesh-like fabric, so that graphene has
Identical reticular structure can obtain orderly three dimentional heat conduction network after being layering, and being added in polyimide resin can
It is laterally thermally conductive in face to realize.
(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 longitudinal direction after being prepared into Kapton, has good heating conduction, flexility, workability
Energy, heat resistance, dimensional stability and chemical-resistant.
(3) the high heat radiation aluminium-based copper-clad plate being prepared by thermoplasticity anisotropic thermal Kapton, have compared with
High thermal conductivity, wherein lateral thermal coefficient is greater than 8.0W/mK, longitudinal thermal coefficient is greater than 5.0W/mK.As component
Circuit substrate can orient transmitting heat, will not be heat in component inner accumulation, to reduce cooling device.The aluminium simultaneously
Base copper-clad plate peel strength with higher, elevated temperature cohesiveness are good.
Specific embodiment
Embodiment 1
(1) preparation of graphene fabric
The braided fabric that the size of mesh opening that the nickel wire that it is 45 μm that nickel wire mesh grid, which is by diameter, is made into is 70 × 70 μm.Having a size of
200 mesh.As gaseous phase deposition substrate.Twine impregnates 10min through dilute hydrochloric acid first, gets rid of impurity and surface oxide layer, then
It is put into quartz tube furnace, H21000 DEG C of heat preservations 10min, CH are heated to the 10 DEG C/min rate of heat addition under stream atmosphere4
(24sccm)、H2The gaseous mixture of (6sccm), which is introduced into quartz ampoule, is used as graphene growth catalyst, with 150 after reaction 30min
DEG C/min cools down 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 remove substrate Ni, can be obtained the graphene fabric laminated board with certain reticular structure.
(2) synthesis of polyamic acid and the preparation of polyimide composite film
In 2000ml reaction kettle, the aprotic polar solvent DMAc of 1000g is first added, then adds the siliceous alicyclic ring 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, sufficiently dissolution diamines are simultaneously evenly dispersed by needle inorganic nano heat filling.52.0g aromatic dianhydride PMDA is divided into 5
Equal part, point 5 addition reaction kettles in 0.5h, and it is stirred to react 5h at 0 DEG C, polyamic acid-heat filling glue is obtained, then
By glue dip dyeing to 10min between the graphene fabric laminated board in (1), graphene fabric/polyamic acid-heat filling is obtained
Impregnate plate.Then 2h prolapse solvent is first kept the temperature under 70 DEG C of vacuum, then in 110 DEG C, 140 DEG C, 170 DEG C of each 1h, 220 DEG C, 270
DEG C, 320 DEG C of each heat preservation 0.5h, make its complete hot-imide, the thermoplasticity for winding to obtain 20~50 μm through cutting edge after completion is each
The thermally conductive Kapton of anisotropy.
(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, it is covered with copper foil, is sent into hot press compacting, pressing process: 110 DEG C/0.5h, 140 DEG C, 170 DEG C, 220 DEG C of each 1h.It is complete
Finish, it is cooling, it takes 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, only each raw material type, quality and technological parameter are poor for the preparation method of embodiment 2~6
Different, the raw material of embodiment 2~6 is as shown in table 1, and the technological parameter of embodiment 2~6 is as shown in table 2.To obtained by embodiment 2~6
Polyimide composite film and high heat radiation aluminium-based copper-clad plate are tested for the property, and the results are shown in Table 3.
1 Examples 1 to 6 raw material of table
2 Examples 1 to 6 technological parameter of table
3 graphene fabric of table/Kapton and high heat radiation aluminium-based copper-clad plate the performance test results
Claims (9)
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 tetracid dianhydride, while adds inorganic nano heat filling and obtaining that polyamic acid-is thermally conductive to be filled out through polycondensation reaction
Expect glue, then disseminates in the graphene fabric laminated board with 3D reticular structure, obtained through hot-imide；Polycondensation reaction
Prepare starting monomer aromatic tetracarboxylic dianhydride and siliceous alicyclic diamine and inorganic nano in polyamic acid-heat filling glue
Inorganic nano heat filling usage amount is 5%~30% by mass percentage in heat filling；Graphene fabric is in polyimides
Content percentage in film is 1%~15%；The graphene fabric laminated board includes 5~15 layers of graphene tissue layer；Institute
The inorganic nano heat filling stated be one of inorganic oxide or inorganic nitride aluminium oxide, magnesia, boron nitride or
Two or more mixtures, wherein partial size is 50~200nm；The anisotropic thermal Kapton with a thickness of 20~50
μm；
The siliceous alicyclic diamine is selected from silicone-containing diamines and silane-containing diamines, general molecular formula respectively such as formula 2,3, wherein
R1For univalence hydrocarbyl or substituted hydrocarbon radical containing 1~14 carbon atom, R2For alkylidene, phenylene and substituted phenylene, n be greater than
Integer equal to 1,
。
2. graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that: institute
The aromatic series tetracid dianhydride monomer stated includes pyromellitic acid anhydride (PMDA), bibenzene tetracarboxylic dianhydride (BPDA), benzophenone
One or more mixtures of tetracid dianhydride (BTDA), diphenyl ether tetracid dianhydride (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 starting monomer aromatic tetracarboxylic dianhydride used in polyamic acid-heat filling glue and siliceous alicyclic two
It is 5%~20% that amine, which accounts for solvent and the gross mass percentage of monomer,.
4. graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that: institute
The polyamic acid stated-heat filling glue synthetic method are as follows: in a kettle, it is molten that a certain amount of aprotonic polar is first added
Agent adds a certain amount of siliceous alicyclic diamine and inorganic nano heat filling under nitrogen protection, at room temperature high-speed stirred again
0.5~2h sufficiently dissolves siliceous alicyclic diamine and inorganic nano heat filling is uniformly dispersed；Aromatic series tetracid dianhydride is existed
Reaction kettle is added in 0.5~5h in batches, and it is stirred to react at 0~5 DEG C 5~for 24 hours, viscosity is obtained greater than 40000mPas
Polyamic acid-heat filling solution, be put into holding vessel, stored under -10 DEG C of low temperature.
5. graphene fabric-modifying anisotropic thermal Kapton according to claim 4, it is characterised in that: institute
The ratio between amount of substance of aromatic tetracarboxylic dianhydride and siliceous alicyclic diamine is stated as 0.95~1.2:1；The non-proton pole
Property solvent be N-Methyl pyrrolidone (NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), diformazan
The mixture of one or more of sulfoxide (DMSO), hexamethyl phosphoramide (HMP).
6. graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that: institute
The preparation method for the graphene fabric laminated board stated: nickel wire reticulated is first handled through the removal of impurities of dilute hydrochloric acid surface, is then placed in stone
H in English tube furnace2It is heated to 900~1100 DEG C of heat preservation a period of times under stream atmosphere, then introduces graphene growth catalyst
To quartz ampoule, react after 0.5~1h to be cooled to room temperature rapidly, then graphene fabric can be obtained in etching removal Ni, by stone
Black alkene fabric is layering, and the graphene fabric laminated board with 3D reticular structure is made；
The graphene growth catalyst is the CH that volume flow ratio is 4 ︰, 1~2 ︰ 14、H2Gaseous mixture；The rate of temperature fall
For 150~220 DEG C/min.
7. graphene fabric-modifying anisotropic thermal Kapton according to claim 1, it is characterised in that: institute
The hot-imide process stated is that 1~2h prolapse solvent is first kept the temperature under 70~90 DEG C of vacuum, then in 110~130 DEG C, 140
Respectively keeping the temperature 0.5~1h at a temperature of~160 DEG C, 170~190 DEG C, 220~240 DEG C, 270~290 DEG C, 320~340 DEG C keeps its complete
Full hot-imide winds to obtain thermoplasticity anisotropic thermal Kapton through cutting edge after hot-imide.
8. graphene fabric-modifying anisotropic thermal Kapton described in claim 1 is preparing high heat radiation aluminium-based cover
Application in copper sheet, application method are as follows: graphene fabric-modifying anisotropic thermal polyimides described in claim 1 is thin
110~130 DEG C of film are hot-pressed on aluminium sheet, and are covered with copper foil, are then fed into hot press compacting, pressing process: 110~130 DEG C/0.
5~1 h, 140~160 DEG C, 170~190 DEG C, 220~240 DEG C of each 1~2 h, compacting finish, cooling, take out, by predetermined size
It cuts out.
9. including high heat radiation aluminium-based the covering of graphene fabric-modifying anisotropic thermal Kapton described in claim 1
Copper sheet.
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| CN108264766A (en) * | 2018-01-25 | 2018-07-10 | 无锡创彩光学材料有限公司 | A kind of preparation method of Kapton |
| TWI707906B (en) * | 2018-04-13 | 2020-10-21 | 安炬科技股份有限公司 | Graphene thermostatic fabric |
| US11049717B2 (en) * | 2018-12-21 | 2021-06-29 | National Chung-Shan Institute Of Science And Technology | Method for fabricating ultra-thin graphite film on silicon carbide substrate from siloxane-coupling-group-containing polyamic acid solution |
| CN109764321B (en) * | 2019-03-08 | 2020-06-26 | 南京理工大学 | Cooling structure of LED illuminating lamp and preparation method thereof |
| CN114349963A (en) * | 2021-12-30 | 2022-04-15 | 中国航空制造技术研究院 | In-situ polymerization preparation method of thermoplastic polyimide prepreg monomer |
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