CN110423467A - A kind of superthick polyimide film and preparation method thereof and graphite flake - Google Patents
A kind of superthick polyimide film and preparation method thereof and graphite flake Download PDFInfo
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Abstract
The invention discloses a kind of superthick polyimide films and preparation method thereof, should be the preparation method comprises the following steps: the modified carbon nanotube in surface, inorganic filler to be dissolved in organic solvent and stir evenly；Then diamine monomer is added, dianhydride monomer is added in batches after diamine monomer dissolution, is eventually adding cross-linking type end-capping reagent, defoams, obtains polyamic acid resin；Add dehydrating agent, catalyst is uniformly mixed and obtains presoma resin, formed through salivation, high temperature imidization and crosslinking, annealing thermal finalization.The superthick polyimide film obtains the graphite flake that thickness in monolayer is 45~130 μm by carbonization, graphitization, calendering process, it solves superthick PI film in current industry and generates excessive expansion during high temperature graphitization, be unable to get the technical problem of single layer thicker graphite flake.
Description
Technical field
The invention belongs to polyimides technical field more particularly to a kind of superthick polyimide film and preparation method thereof and
Graphite flake.
Background technique
As microelectric technique rapidly develops, especially mechanics of communication is upgraded to " 5G " by " 4G ", high-frequency to introduce, is hard
Part integrated level is continuously improved, chip continuous miniaturization and networked devices and antenna amount are doubled and redoubled, and leads to the function of equipment
Consumption constantly increases, and calorific value also increases severely therewith, and the heat dissipation of component has become the bottle that " 5G " epoch communication terminal equipment faces
Neck problem.
After high-performance PI film is graphitized by high temperature cabonization, available thermal conductivity is several times as much as the heat conductive graphite piece of copper, is
Electronic product solves the core material of heat dissipation problem at present.But current graphite flake is limited only to production thickness with PI film manufacturing technology
90 μm of degree or less product, can only prepare the heat conductive graphite piece within 40 μm, including 17 microns, 25 microns, 32 microns and 40 microns
Equal-specification, single layer heat dissipation flux are low, it is necessary to increase graphite linings thickness by multi-laminate Calais, improve heat flux, be temporarily applied to
The electronic product in " 4G " stage.Moreover, current this heat conductive graphite blade technolgy making technology is complicated, furthermore higher cost is folded
The use of added-time glue-line will form thermal resistance effect, significantly reduces heat diffusion capabilities, is unable to satisfy " 5G " technology to high heat storage ability
With the dual requirements of heat fast transfer ability.Therefore, 90 μm of thickness or more are prepared, is suitable for firing the super of heat conductive graphite piece
Thicker PI film is the preferred plan for solving " 5G " epoch heat dissipation problem.
However thickness increase can bring a series of problems to the production of PI film, firstly, traditional PI film precursor resin exists
At the end of polymerization process, amido, the acid anhydrides at strand both ends still will be slow reaction, cause the difficult to control of reaction end, storage and
The molecular weight of resin generates fluctuation when conveying, influences quality stability, general after polymerization reaction to reduce the change of molecular weight
Save resin using -20 DEG C or so of ultralow temperature, but to will cause resin apparent viscosity excessive for too low temperature, reduces coating
When resin levelability so that curtain coating non-uniform film thickness, defect increase；Secondly, the resin of ultra low temperature state is to catalyst activity
Harshness is required with dosage, is difficult to prepare superthick PI film；Finally, more than 90 μ m thicks PI film in high temperature graphitization process
Middle degrees of expansion especially Z-direction is difficult to control, it is easy to be generated foaming excessively, can not be rolled to obtain high density product, show
Writing reduces heating conduction, while excessively expansion will also result in many open defects such as graphite flake appearance layering, picking, rupture, shadow
Ring the surface quality and technique application of final products.
Patent CN201610825198.6 discloses one kind, and by hot imidization to prepare aqueous carbon black modified polyimides thin
Film；Patent CN201810206525.9 provides the device that a kind of hot imidization technique prepares thick polyimide film or super thick film；
Patent CN102093715A discloses the hot imidization preparation method of a kind of carbon nanotube enhancing PI film and fiber, use 10~
10000 microns of length of carbon nanotube are too long, can generate a large amount of winding, influence the comprehensive performance of film.Above-mentioned patent uses
The preparation of hot imidization method carrys out PI film, can not obtain the film being orientated in the uniform and high face of structure, is not suitable for being applied to heat conductive graphite
Piece, the especially preparation of thicker graphite flake.
Patent CN201510409013.9 and CN201610726723.9 use blending method by nothings such as oxide, inorganic acid salts
Machine particle is scattered in resin, prepares polyimide film by chemical imidization, final high temperature handles to obtain graphite flake, this side
The PI film of method production is unable to control the excessive expansion of normal direction in graphitizing process, therefore film thickness is usually no more than 90 μm, can not obtain
To the thicker graphite flake haveing excellent performance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind superthick polyimide film and preparation method thereof and graphite flake.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of superthick polyimide film, with a thickness of 90~250 μm.
The inventive concept total as one, the present invention also provides a kind of preparation sides of above-mentioned superthick polyimide film
Method, comprising the following steps:
(1) the modified carbon nanotube in surface, inorganic filler are dissolved in organic solvent and are stirred evenly；
(2) diamine monomer is first added in the solution that step (1) stirs evenly, is added in batches after diamine monomer dissolution
Dianhydride monomer is eventually adding end-capping reagent, defoaming, obtains polyamic acid resin, 0-20 DEG C of storage；
(3) polyamic acid resin for obtaining step (2) is uniformly mixed in dehydrating agent, catalyst, then through salivation, imines
Change, high temperature thermal finalization, superthick polyimide film is prepared.
Cross-linking type end-capping reagent is introduced during preparation method of the invention, reduces the active site of molecular chain-end, is reacted
Terminal is controllable, guarantees that resin viscosity is stablized, is not necessarily to cryopreservation, reduces apparent viscosity when stream film, improves thick film
Levelability improves apparent mass, and on the other hand, the requirement to catalytic activity reduces, it is possible to reduce catalyst amount is adopted
With the catalyst of milder, the selection face of catalyst system is improved.In addition, end-capping reagent can crosslink reaction at high temperature,
The molecule chain end " latching " of polyimides can be reduced the locomitivity of strand, improve molecular structure regularity, be more suitable for
In preparation heat conductive graphite piece.
Above-mentioned preparation method, it is preferred that in the step (1), the modified carbon nanotube in surface refers to surface by carboxylic
The carbon nanotube of base, amination and any one of fluorine processing.Carbon nanotube can with PI matrix because chemical bonding or
Person's hydrogen bond action forms good interface interaction, produces appropriately crosslinked effect, effectively increases the effect between strand
Power effectively inhibits the excessive foaming of the expansion of graphite film, especially Z-direction, improves pressure during high temperature graphitization
The carbon density for delaying graphite flake improves the heating conduction of graphite flake.By carboxylated, amination and fluorine treated carbon
Nanotube and resin system compatibility are more preferable, and binding force is stronger, can more inhibit excessively to expand.
Above-mentioned preparation method, it is preferred that in the step (1), the modified carbon nanotube (CNTs) in the surface it is straight
10~200nm of diameter, length are 0.5~50 μm；The additive amount of the modified carbon nanotube in surface is the 0.1% of polyimides film quality
~1%.
Above-mentioned preparation method, it is preferred that in the step (1), inorganic filler be selected from silica, silicon carbide, silicon nitride,
One or more of boron nitride, calcium phosphate, calcium monohydrogen phosphate, calcium pyrophosphate, calcium carbonate and calcium bicarbonate；The inorganic filler
Partial size is 50nm~5 μm, and additive amount is the 0.1%~1% of polyimides film quality.
Above-mentioned preparation method, it is preferred that in the step (1), organic solvent is dimethylformamide (DMF), diformazan
Any one of yl acetamide (DMAc) and N-Methyl pyrrolidone (NMP)；
In the step (2), 4,4 '-diaminodiphenyl ether of diamine monomer (4,4 '-ODA), 3,4 '-diaminodiphenyl ethers
One or more of (3,4 '-ODA), p-phenylenediamine (1,4-PDA), bis- (4- amino-benzene oxygen) benzene (BAPP) of 2,2-；Dianhydride
Monomer is pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (s-BPDA), 2,3,3 ', 4- biphenyl tetracarboxylic acid
Acid dianhydride (α-BPDA), 3,3 ', 4,4- benzophenone tetracarboxylic dianhydride (BTDA), in 4,4 '-biphenyl ether dianhydrides (4,4 '-ODPA)
One or more；The moles total number ratio of the diamines and the dianhydride is 1:(0.85~1.15).
Above-mentioned preparation method, it is preferred that in the step (2), cross-linking type end-capping reagent is 4- phenylacetylene benzoic anhydride (4-
PEPA), the one or more of 4- acetenyl phthalic anhydride (EPA), 4- acetylenylaniline, the additive amount of cross-linking type end-capping reagent
It is the 0.1%~1% of polyamic acid resin quality.
In the step (3), dehydrating agent is selected from least one of chloroacetic chloride, acetic anhydride, propionic andydride, benzoyl oxide, takes off
Aqua additive amount is the 10~30% of polyamic acid resin quality；Further preferably 20~30%；
The catalyst is selected from least one of pyridine and its derivatives, imidazoles, quinoline, isoquinolin, catalyst addition
Amount is the 0.05~1% of polyamic acid resin quality.
Above-mentioned preparation method, it is preferred that in the step (2), the solid content for the polyamic acid resin being prepared is
15%~35%.
Above-mentioned preparation method, it is preferred that in the step (3), salivation temperature is the temperature of 100~200 DEG C, imidization
It is 200~450 DEG C；High temperature thermal finalization refers to thermal finalization of annealing at 250~350 DEG C.Added in salivation using 100~200 DEG C
The quick solvent flashing of heat obtains polyamic acid gel mould, then passes through 200~450 DEG C of imidization furnace, realization imidization, while
End-capping reagent realizes chemical crosslinking at 400 DEG C~450 DEG C, further increases film performance, then will be carried out by 250~350 DEG C
Stress concentration phenomenon is unfolded and eliminated to annealing, strand, to be uniformly directed, be suitble to fire the polyamides of high thermal conductivity graphite flake
Imines film.
The inventive concept total as one, the present invention also provides a kind of graphite flakes, by above-mentioned superthick polyimide film
Or the superthick polyimide film that above-mentioned preparation method is prepared is obtained by carbonization, graphitization, calendering process.
Above-mentioned graphite flake, it is preferred that the thickness in monolayer of the graphite flake is 45~130 μm.
Compared with the prior art, the advantages of the present invention are as follows:
(1) present invention introduces cross-linking type end-capping reagent in polyamic acid resin raw material, and cross-linking type end-capping reagent can be reduced point
The active site at subchain end keeps reaction end controllable, and resin viscosity is stablized, relative to traditional chemical imidization filming technology, nothing
Cryopreservation is needed, resin storage temperature is improved；Also avoid that ultralow temperature resin surface viscosity is larger simultaneously, levelling is difficult
Disadvantage improves the levelability of resin when preparing thick film, improves surface quality；On the other hand, the chemistry used in the present invention is sub-
Amine method also reduces requirement of the resin to catalytic activity, it is possible to reduce catalyst amount or the catalyst using milder mention
The high selection face of catalyst system；In addition, cross-linking type end-capping reagent can crosslink reaction at high temperature, it can be by polyimides
Molecule chain end " latching " reduces the locomitivity of strand, improves molecular structure regularity, more suitable for preparing heat conductive graphite
Piece.
(2) present invention employs 10~200nm of diameter, 0.5~50 μm of length of surface-modified carbon nanotubes (CNTs) work
It is generated for one of the modified filler of PI film with PI matrix because chemical bonding or hydrogen bond action form good interface interaction
Appropriately crosslinked effect, effectively increases the active force between strand, during high temperature graphitization, effectively inhibits graphite
The excessive foaming of the expansion of film, especially Z-direction improves the carbon density of graphite flake after calendering, improves leading for graphite flake
Hot property.
(3) thickness in monolayer of graphite flake prepared by the present invention is 45~130 μm, when graphite flake overall thickness is suitable, single layer
Thicker graphite flake has higher heat flux than multiple-layer stacked graphite flake, because the latter is in superposition by the double-sided adhesive shadow used
The resistance of pilot's pyrogenicity increases, such as 47 μm of thickness in monolayer of thicker graphite flake, compared with double-deck 25 μm of superposition graphite flakes, the former has
Better thermal coefficient and heat flux, equally, 65 μm of single layer of thicker graphite flake heating conduction is also above double-deck 32 μm of superposition stones
Ink sheet, therefore the present invention solves superthick PI film in current industry and generates excessive expansion during high temperature graphitization, it can not
Obtain the technical problem of single layer thicker graphite flake.
(4) the present invention provides a kind of 90~250 μm of superthick PI films and the preparation method of chemical imidization, it can be used for thickness
The production of type heat conductive graphite piece, is more suitably applied to the application of 5G epoch high cooling requirements communicating terminal.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with preferred embodiment and more comprehensively, is meticulously retouched
It states, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Comparative example 1:
The preparation method of the graphite flake of this comparative example, comprising:
(1) prepared by resin: first by 0.39kg, 1 μm of partial size of Ca3(PO4)2It dissolves in the DMAc of 280.14kg, stirs evenly
4, the Isosorbide-5-Nitrae-PDA of 4 '-ODA and 5.2kg of 30.3kg are added afterwards, is added 43.51kg's in batches after dissolving to diamines
PMDA, resin viscosity reach 1560 pools, and simultaneously -20 DEG C of storages are stand-by for defoaming；
(2) PI film preparation: the polyamic acid resin of step (1) preparation and 71.83kg acetic anhydride, 25.77kg pyridine is mixed
It closes uniformly, then through 100~190 DEG C of gradient increased temperature salivation film forming, 210~400 DEG C of high temperature imidizations are prepared with a thickness of 90 μm
Polyimide film；
(3) prepared by graphite flake: the polyimide film with a thickness of 90 μm being sequentially placed into retort and graphitizing furnace carries out height
Temperature processing, then rolls, obtains high thermal conductivity graphite flake.
Comparative example 2:
The preparation method of the graphite flake of this comparative example, comprising:
(1) prepared by resin: first that 1 μm of 0.4kg, diameter 30nm, length surface carboxylation is modified CNTs and 0.6kg, grain
The CaCO that 0.6 μm of diameter3It dissolves in the DMF of 453.55kg, is stirring evenly and then adding into the 3 of 35.5kg, the 4 of 4 '-ODA and 10.0kg,
The PMDA of 54.06kg is added in 4 '-ODA in batches after dissolving to diamines, resin viscosity reaches 1780 pools, defoams simultaneously -18 DEG C
Storage is stand-by；
(2) PI film preparation: the polyamic acid resin of step (1) preparation and 138.27kg propionic andydride, 50.83kg quinoline is mixed
Uniformly, then through 100~180 DEG C of gradient increased temperatures salivation film forming, 220~380 DEG C of high temperature imidizations, last 270 DEG C of annealing is hot to be determined for conjunction
The polyimide film with a thickness of 90 μm is prepared in type；
(3) prepared by graphite flake: polyimide film being sequentially placed into retort and graphitizing furnace carries out high-temperature process, is then pressed
Prolong, obtains high thermal conductivity graphite flake.
Comparative example 3:
The preparation method of the graphite flake of this comparative example, comprising:
(1) resin prepare: first 0.19kg, 1.4 μm of partial size of SiC are dissolved in the DMF of 510.3kg, after mixing evenly plus
Enter the 4 of 45kg, PMDA the and 12.14kg s-BPDA of 40.06kg is added, finally in 4 '-ODA in batches after dissolving to diamines
The aniline sealing end of 3.04kg is added, resin viscosity reaches 1600 pools, defoams and 3 DEG C of storages are stand-by.
(2) PI film preparation: resin is uniformly mixed with 72.9kg benzoyl oxide, 1.82kg triethylamine, then through 130~160
90 μm of polyamides Asia is made in DEG C gradient increased temperature salivation film forming, 200~410 DEG C of high temperature imidizations, last 290 DEG C of annealing thermal finalization
Amine film.
(3) prepared by graphite flake: PI film being sequentially placed into retort and graphitizing furnace carries out high-temperature process, then calendering obtains
High thermal conductivity graphite flake.
Comparative example 4:
It is superimposed on two layers using commercially available with a thickness of 25 μm of heat conductive graphite pieces, centre is glued using 5 μm of double-sided adhesive
It connects, obtains compound heat conductive graphite piece.
Comparative example 5:
It is superimposed on two layers using commercially available with a thickness of 32 μm of heat conductive graphite pieces, centre is glued using 5 μm of double-sided adhesive
It connects, obtains compound heat conductive graphite piece.
Comparative example 6:
Using the commercially available PI film (prepared by traditional chemical imines method) with a thickness of 125 μm, it is sequentially placed into retort and graphite
Change furnace and carry out high-temperature process, then rolls, obtain heat conductive graphite piece.
Comparative example 7:
Using the commercially available PI film (prepared by hot imines method) with a thickness of 125 μm, it is sequentially placed into retort and graphitizing furnace carries out
Then high-temperature process is rolled, heat conductive graphite piece is obtained.
Embodiment 1:
A kind of preparation method of graphite flake of the invention, comprising:
(1) prepared by resin: first by 0.88kg, diameter 100nm, 0.6 μm of length of carboxylated modified CNTs and 0.19kg, grain
The Ca that 0.2 μm of diameter2P2O7It dissolves in the DMF of 486.05kg, is stirring evenly and then adding into the Isosorbide-5-Nitrae-PDA's and 15.6kg of 21.6kg
The 4,4-ODPA of the PMDA and 11.78kg of 43.6kg are added in batches, are eventually adding 5.2kg by BAPP after dissolving to diamines
4-PEPA sealing end, reach 1920 pools to resin viscosity, defoam and 4 DEG C store stand-by (solid content is about 17%)；
(2) PI film preparation: resin prepared by step (1) is uniformly mixed with 163.44kg propionic andydride, 1.75kg pyridine, then
Through 120~190 DEG C of gradient increased temperature salivation film forming, 225~440 DEG C of high temperature imidizations, last 310 DEG C of annealing thermal finalization processing, system
It is standby to obtain the polyimide film with a thickness of 90 μm；
(3) prepared by graphite flake: polyimide film being sequentially placed into retort and graphitizing furnace carries out high-temperature process, is then pressed
Prolong to obtain high thermal conductivity graphite flake.
Embodiment 2:
A kind of preparation method of graphite flake of the invention, comprising:
(1) prepared by resin: first by 0.25kg, diameter 15nm, 15 μm of length amination modified CNTs and 0.52kg, partial sizes
4 μm of SiO2It dissolves in the NMP of 313.2kg, is stirring evenly and then adding into the 4 of 43.2kg, 4 '-ODA divide after dissolving to diamines
The PMDA of 54.4kg is added in batch, is then added the 3 of 6.8kg, and the reaction was continued by 4 '-ODA, is eventually adding the EPA sealing end of 2.92kg,
Reach 1820 pools to resin viscosity, defoams and 12 DEG C of storages are stand-by；
(2) PI film preparation: resin prepared by step (1) is uniformly mixed with 116.52kg acetic anhydride, 4kg pyridine, then passed through
105~185 DEG C of gradient increased temperature salivation film forming, 230~435 DEG C of high temperature imidizations, last 340 DEG C of annealing thermal finalization are prepared
With a thickness of 125 μm of polyimide film；
(3) prepared by graphite flake: polyimide film being sequentially placed into retort and graphitizing furnace carries out high-temperature process, is then pressed
Prolong to obtain high thermal conductivity graphite flake.
Embodiment 3:
A kind of preparation method of graphite flake of the invention, comprising:
(1) prepared by resin: first that 2 μm of 0.23kg, diameter 150nm, length carboxylated is modified CNTs and 0.94kg, partial size
4.2 μm of CaHPO4It dissolves in the DMAc of 369.3kg, is stirring evenly and then adding into the 4 of 36.2kg, the PDA of 4 '-ODA, 5.8kg, to
The PMDA of 57.11kg is added in diamines in batches after dissolving, the BAPP that 11.2kg is then added adjusts viscosity, is eventually adding
The 4PEPA of 0.96kg is blocked, and reaches 1950 pools to resin viscosity, defoams and 2 DEG C of storages are stand-by；
(2) PI film preparation: resin prepared by step (1) is uniformly mixed with 57.55kg benzoyl oxide, 2.55kg imidazoles,
Again through 110~175 DEG C of gradient increased temperature salivation film forming, 235~415 DEG C of high temperature imidizations, last 300 DEG C of annealing thermal finalization, preparation
Obtain the polyimide film with a thickness of 150 μm；
(3) prepared by graphite flake: PI film being sequentially placed into retort and graphitizing furnace carries out high-temperature process, then rolls, obtains
To high thermal conductivity graphite flake.
Embodiment 4:
A kind of preparation method of graphite flake of the invention, comprising:
(1) resin prepare: first by 0.98kg, diameter 70nm, 35 μm of fluorine modifications of length CNTs and 0.91kg, partial size
1.5 μm of CaCO3It dissolves in the DMAc of 477.94kg, is stirring evenly and then adding into the 4 of 51.5kg, 4 '-ODA have been dissolved to diamines
The s-BPDA of the PMDA and 18.45kg of 42.16kg is added after finishing in batches, is eventually adding the 4- acetylenylaniline envelope of 3.54kg
End, resin viscosity reach 1690 pools, defoam and 10 DEG C of storages are stand-by；
(2) PI film preparation: resin prepared by step (1) is uniformly mixed with 88.5kg acetic anhydride, 1.77kg quinoline, then passed through
125~190 DEG C of gradient increased temperature salivation film forming, 240~420 DEG C of high temperature imidizations, last 265 DEG C of annealing thermal finalization are prepared
With a thickness of 175 μm of polyimide film；
(3) prepared by graphite flake: PI film being sequentially placed into retort and graphitizing furnace carries out high-temperature process, then rolls, obtains
To high thermal conductivity graphite flake.
Embodiment 5:
A kind of preparation method of graphite flake of the invention, comprising:
(1) prepared by resin: first by 0.18kg, diameter 30nm, 1 μm of length amination modified CNTs and 0.19kg, partial size
0.8 μm of boron nitride dissolves in the DMAc of 372.11kg, is stirring evenly and then adding into the 4 of 46.5kg, and 4 '-ODA have been dissolved to diamines
Finish after be added in batches 42kg PMDA and 24.69kg ODPA, then be added 4.3kg Isosorbide-5-Nitrae-PDA adjust viscosity, finally plus
The EPA sealing end for entering 2.45kg, reaches 1790 pools to resin viscosity, defoams and 5 DEG C of storages are stand-by；
(2) PI film preparation: resin prepared by step (1) is uniformly mixed with 132.68kg acetic anhydride, 2.84kg quinoline, then
Through 130~185 DEG C of gradient increased temperature salivation film forming, 205~405 DEG C of high temperature imidizations, last 305 DEG C of annealing thermal finalization is prepared into
To the polyimide film with a thickness of 200 μm；
(3) prepared by graphite flake: polyimide film being sequentially placed into retort and graphitizing furnace carries out high-temperature process, is then pressed
Prolong to obtain high thermal conductivity graphite flake.
Embodiment 6:
A kind of preparation method of graphite flake of the invention, comprising:
(1) prepared by resin: first by 0.77kg, diameter 175nm, 45 μm of length amination modified CNTs and 0.25kg, grains
2 μm of diameter of Ca (HCO3)2It dissolves in the DMF of 404.6kg, is stirring evenly and then adding into the 4 of 48.6kg, 4 '-ODA have been dissolved to diamines
The PMDA of 51.8kg is added after finishing in batches, is eventually adding the 4-PEPA sealing end of 3.2kg, reaches 1850 pools to resin viscosity, disappear
It steeps and 15 DEG C of storages is stand-by；
(2) PI film preparation: resin is uniformly mixed with 75.67kg propionic andydride, 0.75kg isoquinolin, then through 115~165 DEG C
Gradient increased temperature salivation film forming, 240~445 DEG C of high temperature imidizations, last 325 DEG C of annealing thermal finalization are prepared with a thickness of 250 μm
Polyimide film；
(3) prepared by graphite flake: polyimide film being sequentially placed into retort and graphitizing furnace carries out high-temperature process, is then pressed
Prolong to obtain high thermal conductivity graphite flake.
The performance for the polyamic acid resin being prepared in embodiment 1-6 and comparative example 1-3 is as shown in table 1.
The resin property comparison of each embodiment and comparative example of table 1 preparation
From the data in table 1 it can be found that having used the resin of cross-linking type end-capping reagent, when in reaction end with storage,
Viscosity fluctuation is smaller, and the storage temperature of resin is relatively high so that coating when resin apparent viscosity it is lower, levelability compared with
It is good.
The performance of the polyimide film and graphite flake that are prepared in embodiment 1-6 and comparative example 1-3 is as shown in table 2.
The PI film and graphite flake performance comparison of each embodiment and comparative example of table 2 preparation
It can analyze from 2 result of table, the resin levelability without termination process is poor, causes film surface quality bad, such as
Comparative example 2；PI film without annealing, in-plane stress are concentrated, and thermal coefficient is low after graphite flake is made, such as comparative example 1；Not plus
The film for entering surface-modified carbon nanotubes, the graphite flake thickness after carbonized graphite significantly increase, and calendering rear surface quality is not
Good, heating conduction is poor.The film of response type end-capping reagent and modified carbon nano-tube is added, surface quality is good, fills after being graphitized
Divide and inhibit excessive foaming, graphite flake thickness is low, good heat conductivity.
Note:
(1) polyamic acid resin viscosity is tested using rotational viscometer；
(2) PI film surface quality refers to:
By visual observation, breadth 1.5m is had rated according to following standard, the PI film of length 10m:
The defects of well (√): thickness, uniform color, any surface finish is smooth, pin-free, bubble；
The defects of bad (×): thickness, uneven color are even, rough surface out-of-flatness, and there are pin holes, bubble.
(3) graphite flake surface quality refers to after rolling:
By visual observation, breadth 0.25m is had rated according to following standard, the heat conductive graphite piece of length 2m:
Well (√): thickness, uniform color, no layering, picking, rupture the defects of.
The defects of bad (×): thickness, uneven color are even, and there are layering, picking, ruptures.
Claims (10)
1. a kind of superthick polyimide film, which is characterized in that the superthick polyimide film with a thickness of 90~250 μm.
2. a kind of preparation method of superthick polyimide film as described in claim 1, which is characterized in that including following step
It is rapid:
(1) the modified carbon nanotube in surface, inorganic filler are dissolved in organic solvent and are stirred evenly；
(2) diamine monomer is first added in the solution that step (1) stirs evenly, dianhydride is added in batches after diamine monomer dissolution
Monomer is eventually adding cross-linking type end-capping reagent, and defoaming obtains polyamic acid resin；
(3) by step (2), polyamic acid resin is uniformly mixed in dehydrating agent, catalyst and obtains presoma resin afterwards, then through salivation,
Imidization, high temperature thermal finalization, are prepared superthick polyimide film.
3. preparation method as claimed in claim 2, which is characterized in that in the step (1), the modified carbon nanotube in surface is
Refer to carbon nanotube of the surface by carboxylated, amination and any one of fluorine processing.
4. preparation method as claimed in claim 2, which is characterized in that in the step (1), the modified carbon nanotube in surface
10~200nm of diameter, length are 0.5~50 μm；The additive amount of the modified carbon nanotube in surface is polyimides film quality
0.1%~1%.
5. preparation method as claimed in claim 2, which is characterized in that in the step (1), inorganic filler be selected from silica,
One or more of silicon carbide, silicon nitride, boron nitride, calcium phosphate, calcium monohydrogen phosphate, calcium pyrophosphate, calcium carbonate and calcium bicarbonate；
The partial size of the inorganic filler is 50nm~5 μm, and additive amount is the 0.1%~1% of polyimides film quality.
6. preparation method as claimed in claim 2, which is characterized in that in the step (1), organic solvent is dimethyl formyl
Any one of amine, dimethyl acetamide and N-Methyl pyrrolidone；
In the step (2), 4,4 '-diaminodiphenyl ether of diamine monomer (4,4 '-ODA), 3,4 '-diaminodiphenyl ethers (3,
4 '-ODA), p-phenylenediamine (1,4-PDA), one or more of bis- (4- amino-benzene oxygen) benzene (BAPP) of 2,2-；Dianhydride monomer
For pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (s-BPDA), 2,3,3 ', 4- biphenyltetracarboxyacid acid two
Acid anhydride (α-BPDA), 3,3 ', 4,4- benzophenone tetracarboxylic dianhydride (BTDA), one in 4,4 '-biphenyl ether dianhydrides (4,4 '-ODPA)
Kind is several；The moles total number ratio of the diamines and the dianhydride is 1:(0.85~1.15).
7. preparation method as claimed in claim 2, which is characterized in that in the step (2), cross-linking type end-capping reagent is 4- benzene second
The one or more of alkynes phthalic anhydride (4-PEPA), 4- acetenyl phthalic anhydride (EPA), 4- acetylenylaniline, cross-linking type sealing end
The additive amount of agent is the 0.1%~1% of polyamic acid resin quality；
In the step (3), dehydrating agent is selected from least one of chloroacetic chloride, acetic anhydride, propionic andydride, benzoyl oxide, dehydrating agent
Additive amount is the 10~30% of polyamic acid resin quality；
The catalyst is selected from least one of pyridine and its derivatives, imidazoles, quinoline, isoquinolin, and catalyst loading is
The 0.05~1% of polyamic acid resin quality.
8. preparation method as claimed in claim 2, which is characterized in that in the step (2), the polyamic acid tree that is prepared
The solid content of rouge is 15%~35%.
9. a kind of graphite flake, which is characterized in that it is by the superthick polyimide film or claim 2~8 in claim 1
In the superthick polyimide film that is prepared of any preparation method obtained by carbonization, graphitization, calendering process.
10. graphite flake as claimed in claim 9, which is characterized in that the thickness in monolayer of the graphite flake is 45~130 μm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982102A (en) * | 2019-12-23 | 2020-04-10 | 宁波长阳科技股份有限公司 | Polyimide film, preparation method thereof, artificial graphite sheet and electronic product |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798076A (en) * | 2010-04-02 | 2010-08-11 | 上海交通大学 | Method for preparing composite thin plate based on glass carbon and carbon nanotube |
| CN103889196A (en) * | 2014-04-11 | 2014-06-25 | 江苏悦达新材料科技有限公司 | Manufacturing method of high thermal conductivity artificial graphite film |
| CN105255177A (en) * | 2014-07-11 | 2016-01-20 | 杜邦-东丽株式会社 | Polyimide film for graphite sheet and manufacture method thereof |
| CN105566630A (en) * | 2014-10-14 | 2016-05-11 | 株洲时代电气绝缘有限责任公司 | Polyimide film and preparation method thereof |
| CN106832923A (en) * | 2016-12-16 | 2017-06-13 | 深圳瑞华泰薄膜科技有限公司 | A kind of Kapton for preparing electrographite film and preparation method thereof |
| CN109929129A (en) * | 2019-04-04 | 2019-06-25 | 长安大学 | A kind of carboxylic carbon nano-tube/polyimide composite film and preparation method thereof |
| CN110172151A (en) * | 2019-06-11 | 2019-08-27 | 慧迈材料科技(广东)有限公司 | A kind of preparation method of graphene/carbon nano-tube/polyimide composite film |
| CN110172168A (en) * | 2019-05-16 | 2019-08-27 | 长安大学 | A kind of aminated carbon nano tube/polyimide composite film and preparation method thereof |
| WO2020262765A1 (en) * | 2019-06-28 | 2020-12-30 | 피아이첨단소재 주식회사 | Polyimide film for graphite sheet and manufacturing method therefor |
-
2019
- 2019-09-04 CN CN201910833194.6A patent/CN110423467B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798076A (en) * | 2010-04-02 | 2010-08-11 | 上海交通大学 | Method for preparing composite thin plate based on glass carbon and carbon nanotube |
| CN103889196A (en) * | 2014-04-11 | 2014-06-25 | 江苏悦达新材料科技有限公司 | Manufacturing method of high thermal conductivity artificial graphite film |
| CN105255177A (en) * | 2014-07-11 | 2016-01-20 | 杜邦-东丽株式会社 | Polyimide film for graphite sheet and manufacture method thereof |
| CN105566630A (en) * | 2014-10-14 | 2016-05-11 | 株洲时代电气绝缘有限责任公司 | Polyimide film and preparation method thereof |
| CN106832923A (en) * | 2016-12-16 | 2017-06-13 | 深圳瑞华泰薄膜科技有限公司 | A kind of Kapton for preparing electrographite film and preparation method thereof |
| CN109929129A (en) * | 2019-04-04 | 2019-06-25 | 长安大学 | A kind of carboxylic carbon nano-tube/polyimide composite film and preparation method thereof |
| CN110172168A (en) * | 2019-05-16 | 2019-08-27 | 长安大学 | A kind of aminated carbon nano tube/polyimide composite film and preparation method thereof |
| CN110172151A (en) * | 2019-06-11 | 2019-08-27 | 慧迈材料科技(广东)有限公司 | A kind of preparation method of graphene/carbon nano-tube/polyimide composite film |
| WO2020262765A1 (en) * | 2019-06-28 | 2020-12-30 | 피아이첨단소재 주식회사 | Polyimide film for graphite sheet and manufacturing method therefor |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111002668A (en) * | 2019-12-19 | 2020-04-14 | 宁波长阳科技股份有限公司 | Artificial graphite composite membrane and preparation method thereof |
| CN110982102A (en) * | 2019-12-23 | 2020-04-10 | 宁波长阳科技股份有限公司 | Polyimide film, preparation method thereof, artificial graphite sheet and electronic product |
| CN110982102B (en) * | 2019-12-23 | 2022-06-28 | 宁波长阳科技股份有限公司 | Polyimide film, preparation method thereof, artificial graphite sheet and electronic product |
| CN112456484B (en) * | 2019-12-27 | 2021-08-03 | 中天电子材料有限公司 | Graphite heat-conducting film and preparation method thereof |
| CN112456484A (en) * | 2019-12-27 | 2021-03-09 | 中天电子材料有限公司 | Graphite heat-conducting film and preparation method thereof |
| CN111017921A (en) * | 2019-12-27 | 2020-04-17 | 深圳烯湾科技有限公司 | Preparation method of polyimide graphite film |
| CN111470876A (en) * | 2020-03-16 | 2020-07-31 | 中山大学 | High-graphitization polyimide-based graphite thick film and preparation method thereof |
| CN111470876B (en) * | 2020-03-16 | 2021-10-19 | 中山大学 | High-graphitization polyimide-based graphite thick film and preparation method thereof |
| CN112591743A (en) * | 2020-12-28 | 2021-04-02 | 碳元科技股份有限公司 | Super-thick foamed graphite, preparation method thereof and conductive heating material |
| CN113788478A (en) * | 2021-09-03 | 2021-12-14 | 中天电子材料有限公司 | Ultra-thick graphite heat-conducting film and preparation method and application thereof |
| CN113788478B (en) * | 2021-09-03 | 2023-05-23 | 中天电子材料有限公司 | Super-thick graphite heat conducting film, and preparation method and application thereof |
| CN114956068A (en) * | 2022-06-23 | 2022-08-30 | 中天电子材料有限公司 | Artificial graphite heat-conducting film and preparation method thereof |
| CN114956068B (en) * | 2022-06-23 | 2023-09-08 | 中天电子材料有限公司 | Artificial graphite heat conducting film and preparation method thereof |
| CN115627073A (en) * | 2022-10-31 | 2023-01-20 | 安徽碳华新材料科技有限公司 | Wide artificial graphite high-conductivity film structure for communication base station |
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