CN109097859A - A kind of polyimide-based heat-conductive composite material and preparation method thereof - Google Patents
A kind of polyimide-based heat-conductive composite material and preparation method thereof Download PDFInfo
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- CN109097859A CN109097859A CN201810792279.XA CN201810792279A CN109097859A CN 109097859 A CN109097859 A CN 109097859A CN 201810792279 A CN201810792279 A CN 201810792279A CN 109097859 A CN109097859 A CN 109097859A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
The present invention provides a kind of polyimide-based heat-conductive composite materials, include polyimides, graphene and silver nano-grain, the graphene dispersion is in polyimide matrix, and the silver nano-grain load is on the surface of graphene.By embodiment result it is found that the thermal conductivity of polyimide-based heat-conductive composite material provided by the invention can reach 2.12W/mK, glass transition temperature is 205.8~216.1 DEG C, and heat-resistance index is 275.4~298.6 DEG C.The present invention also provides the preparation methods of the polyimide-based heat-conductive composite material.The present invention can effectively prevent graphene to reunite by modifying silver nano-grain on graphene, while silver nano-grain has constructed the thermal conducting path of graphene film interlayer as " bridge ", be conducive to the heating conduction for increasing graphene film interlayer；The method combined using in-situ polymerization-spinning is improved the dispersion situation of modified by silver graphene in the base, is more conducive to construct graphene heat conduction network.
Description
Technical field
The present invention relates to polymer matrix Heat Conduction Material technical field more particularly to a kind of polyimide-based heat-conductive composite materials
And preparation method thereof.
Background technique
In recent years, electronics and energy field achieve huge progress in the aspect of performance for meeting requirements at the higher level, such as
The power and integrated level of LEDs, energy storage material and organic solar batteries etc. are continuously improved.However, mentioning with performance
It rises, the said goods can generate more heats during the work time, if can not in time conduct these heats, meeting
The aging and damage for aggravating product, to reduce the performance of product, reliability and service life.Therefore, Current electronic and energy field
Requirement higher and higher is proposed for the heating conduction of material.
Traditional metal or ceramic material has been unable to satisfy height since density is big, weatherability is poor, thermal expansion coefficient is big
Imitate thermally conductive, light, easy processing requirement.Therefore, the polymer matrix composite with high thermal conductivity receives more and more
Concern and research.Such as the developed countries such as U.S., thermal conductive polymer based composites have just been put into work in the mid-1970s
In industryization application, and the demand of Polymer Composites with High Thermal Conductivity is still increased with annual 20~30% speed.
Polyimides (PI) is one of optimal high-molecular organic material of comprehensive performance, low, the resistance to height with thermal expansion coefficient
Temperature, the excellent property such as radiation-resistant property is good, mechanical performance is excellent, are widely used in aerospace, extraordinary electric appliance, resistance to height
The fields such as warm printed circuit substrate.But PI itself poor thermal conductivity (thermal conductivity λ is about 0.20W/mK) limits it in extraordinary electricity
Device, aerospace, great power LED s etc. have the application in high thermal conductivity requirement field.Therefore, the PI composite material tool of high thermal conductivity
There are huge demand and application market.Chinese patent (CN101168598) discloses a kind of aluminium nitride (AlN) raising PI composite wood
The method of the heating conduction of material, when AlN additional amount is 3~8% mass percent, the λ of PI composite material is 0.6~0.8W/
MK, heating conduction are simultaneously bad.United States Patent (USP) (US2006/0127686 (A1)) discloses a kind of inorganic with core-shell structure and fills out
The method that material improves the heating conduction of PI composite material, when the additive amount of inorganic filler is 40~85% mass percent, PI
The λ of composite material improves unobvious again smaller than 1W/mK, heating conduction.
Summary of the invention
The purpose of the present invention is to provide a kind of polyimide-based heat-conductive composite material and preparation method thereof, the polyamides is sub-
Amido heat-conductive composite material has high thermal conductivity when adding a small amount of heat filling.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of polyimide-based heat-conductive composite materials, include polyimides, graphene and silver nanoparticle
Grain, the graphene dispersion is in polyimide matrix, and the silver nano-grain load is on the surface of graphene.
Preferably, the mass ratio of the polyimides, graphene and silver nano-grain is 100:(0.5~15): (0.1~
4)。
The present invention provides the preparation methods of the polyimide-based heat-conductive composite material, comprise the following steps:
(1) reduction reaction is carried out after mixing graphene oxide dispersion, silver ammino solution and reducing agent, obtains modified by silver stone
Black alkene；
(2) under an inert atmosphere, after the modified by silver graphene, diamine monomer, dianhydride monomer and organic solvent being mixed
Polymerization reaction is carried out, spinning solution is obtained；
(3) spinning solution is subjected to spinning, obtains spinning fibre；
(4) spinning fibre is subjected to hot imidization, obtains polyimide-based heat-conductive composite material.
Preferably, the mass concentration of the graphene oxide dispersion is 9~50%, and the concentration of the silver ammino solution is
0.01~0.5mol/L；
The mass ratio of the graphene oxide dispersion, silver ammino solution and reducing agent is (200~1100): (1.5~10):
(50~100).
Preferably, the temperature of the reduction reaction is 100~150 DEG C, and the time of the reduction reaction is 8~15h.
Preferably, the molar ratio of the diamine monomer and dianhydride monomer is 1:(0.5~1.5)；
The mass ratio of the modified by silver graphene, diamine monomer and organic solvent is (2.5~52): 100:(722~
1512)。
Preferably, the temperature of the polymerization reaction is -10~10 DEG C, and the time of the polymerization reaction is 3~8h.
Preferably, the voltage of the spinning is 10~30KV, and the temperature of the spinning is 15~35 DEG C, the ring of the spinning
Border humidity is 20~50%, and the speed of injecting of the spinning is 0.2~1mm/min.
Preferably, the hot imidization include sequentially carry out the first hot imidization processing, the second hot imidization processing and
The processing of third hot imidization；
The temperature of the first hot imidization processing is 110~130 DEG C, and the time of the first hot imidization processing is 1
~3h；
The temperature of the second hot imidization processing is 190~210 DEG C, and the time of the second hot imidization processing is 1
~3h；
The temperature of the third hot imidization processing is 240~260 DEG C, and the time of the third hot imidization processing is 1
~3h；
The heating rate for being warming up to the first hot imidization treatment temperature is 1~5 DEG C/min；
By the first hot imidization treatment temperature be warming up to the second hot imidization treatment temperature heating rate be 1~5 DEG C/
min；
By the second hot imidization treatment temperature be warming up to third hot imidization treatment temperature heating rate be 1~5 DEG C/
min。
Preferably, the poly- of specific modality is obtained also comprising carrying out hot pressing to hot imidization product after the hot imidization
Imide heat-conductive composite material；
The temperature of the hot pressing is 300~350 DEG C, and the pressure of the hot pressing is 5~25MPa, and the time of the hot pressing is
15~60min.
The present invention provides a kind of polyimide-based heat-conductive composite materials, include polyimides, graphene and silver nanoparticle
Grain, the graphene dispersion is in polyimide matrix, and the silver nano-grain load is on the surface of graphene.It is provided by the invention
Polyimide-based heat-conductive composite material is improved by adding a small amount of graphene and Nano silver grain in polyimide matrix
The heating conduction of material.By embodiment result it is found that the thermal conductivity of polyimide-based heat-conductive composite material provided by the invention can
Reach 2.12W/mK, glass transition temperature is 205.8~216.1 DEG C, and heat-resistance index is 275.4~298.6 DEG C.
The present invention also provides the preparation method of the polyimide-based heat-conductive composite material, (1) divides graphene oxide
Reduction reaction is carried out after dispersion liquid, silver ammino solution and reducing agent mixing, obtains modified by silver graphene；(2) under an inert atmosphere, by institute
Polymerization reaction is carried out after stating modified by silver graphene, diamine monomer, dianhydride monomer and organic solvent mixing, obtains spinning solution；(3)
The spinning solution is subjected to spinning, obtains spinning fibre；(4) spinning fibre is subjected to hot imidization, obtains polyamides Asia
Amido heat-conductive composite material.The present invention can effectively prevent graphene to reunite, together by modifying silver nano-grain on graphene
When silver nano-grain the thermal conducting path of graphene film interlayer has been constructed as " bridge ", be conducive to increase leading for graphene film interlayer
Hot property；The method combined using in-situ polymerization-spinning improves the dispersion situation of modified by silver graphene in the base, more
Help to construct graphene heat conduction network.Preparation method provided by the invention is easy to operate, easy to implement.
Specific embodiment
The present invention provides a kind of polyimide-based heat-conductive composite materials, include polyimides, graphene and silver nanoparticle
Grain, the graphene dispersion is in polyimide matrix, and the silver nano-grain load is on the surface of graphene.
In the present invention, the mass ratio of the polyimides, graphene and silver nano-grain be preferably 100:(0.5~
15): (0.1~4), more preferably 100:(0.81~14.12): (0.2~3.53), most preferably 100:(3~10): (0.5~
3), can also be preferably 100:(5~8): (1~2).In the present invention, the mass ratio of the graphene and silver nano-grain is excellent
It is selected as 4:1.
In the present invention, the partial size of the silver nano-grain is preferably 50~120nm, more preferably 80~100nm.
The present invention also provides the preparation methods of the polyimide-based heat-conductive composite material, comprise the following steps:
(1) reduction reaction is carried out after mixing graphene oxide dispersion, silver ammino solution and reducing agent, obtains modified by silver stone
Black alkene；
(2) under an inert atmosphere, after the modified by silver graphene, diamine monomer, dianhydride monomer and organic solvent being mixed
Polymerization reaction is carried out, spinning solution is obtained；
(3) spinning solution is subjected to spinning, obtains spinning fibre；
(4) spinning fibre is subjected to hot imidization, obtains polyimide-based heat-conductive composite material.
The present invention carries out reduction reaction after mixing graphene oxide dispersion, silver ammino solution and reducing agent, obtains silver and repairs
Adorn graphene.In the present invention, the mass concentration of the graphene oxide dispersion is preferably 9~50%, more preferably 15~
40%, most preferably 20~30%；The concentration of the silver ammino solution is preferably 0.01~0.5mol/L, more preferably 0.1~
0.4mol/L, most preferably 0.2~0.3mol/L；The mass ratio of the graphene oxide dispersion, silver ammino solution and reducing agent
Preferably (200~1100): (1.5~10): (50~100), more preferably (300~1000): (1.85~9.27): (60~
90), most preferably (400~800): (2~8): (70~80), it can also preferably (500~600): (4~6): (75~78).
Graphene oxide dispersion and silver ammino solution are preferably first uniformly mixed by the present invention, are then mixed again with reducing agent
It closes, can guarantee that graphene oxide dispersion and silver ammino solution are uniformly dispersed in this way, keep silver nano-grain uniform in reduction
Distribution is on the surface of graphene.
In the present invention, the graphene oxide dispersion is the dispersion for being dispersed in water graphene oxide
System；The present invention does not have any particular/special requirement to the embodiment of the dispersion, using well-known to those skilled in the art point
Method is dissipated to carry out.
In the present invention, the graphene oxide preferably uses made products, and the preparation method of the graphene oxide is excellent
Choosing comprises the following steps:
Oxidation reaction is carried out after crystalline flake graphite, the concentrated sulfuric acid and potassium permanganate are mixed, obtains oxidation product system；
The oxidation product system and water are mixed, diluted system is obtained；
The diluted system and hydrogen peroxide are mixed and reacted, second order reaction system is obtained；
Washing and centrifugal treating are sequentially carried out to the second order reaction system, obtain graphene oxide.
The present invention carries out oxidation reaction after preferably mixing crystalline flake graphite, the concentrated sulfuric acid and potassium permanganate, obtains oxidation product
System.In the present invention, the crystalline flake graphite is preferably the crystalline flake graphite for being purchased from 325 mesh of AlfaAesar company production；It is described
The mass concentration of the concentrated sulfuric acid is preferably 97~98%.
The present invention preferably first mixes crystalline flake graphite and the concentrated sulfuric acid, then mixes again with potassium permanganate.The present invention is first by squama
Piece graphite and concentrated sulfuric acid mixing enable to sulfate ion intercalation into the lamella of crystalline flake graphite, are added after then making
Potassium permanganate dissolves in concentrated sulfuric acid, realizes oxidation purpose in the lamella of crystalline flake graphite；Permanganic acid is preferably slowly added dropwise in the present invention
Potassium avoids that heat accumulation is excessively caused to cause explosion because of additional amount.
In the present invention, the mass ratio of the crystalline flake graphite, the concentrated sulfuric acid and potassium permanganate be preferably 100:(1000~
4000): (10~500), more preferably 100:(2000~3500): (100~400), most preferably 100:(2500~3000):
(200~300).
In the present invention, the temperature of the oxidation reaction is preferably 0~40 DEG C, and more preferably 10~30 DEG C, most preferably
15~25 DEG C；The time of the oxidation reaction is preferably 2~6h, more preferably 3~4h.
Oxidation process of the present invention is mainly potassium permanganate and strong sulfuric acid response, generates manganese heptoxide, seven oxidations two
Aoxidize to manganese reselection the unsaturated aliphatic double bond on crystalline flake graphite.
KMnO4+3H2SO4→K++MnO3 ++H3O++3HSO4 -
MnO3 ++MnO4 --→Mn2O7
The present invention preferably mixes the oxidation product system and water, obtains diluted system.In the present invention, the scale
The mass ratio of graphite and water is preferably 100:(10000~30000), more preferably 100:(15000~25000), most preferably
100:(20000~22000).Dilution of the present invention discharges heat primarily to dilute the excessive concentrated sulfuric acid.
The present invention, which preferably mixes the diluted system and hydrogen peroxide, to react, and obtains second order reaction system.In this hair
In bright, the hydrogen peroxide uses the hydrogen peroxide of commercially available normal concentration well-known to those skilled in the art, described
The mass ratio of crystalline flake graphite and hydrogen peroxide is preferably 100:(500~1500), more preferably 100:(700~1300), most preferably
For 100:(900~1000).Reaction of the present invention is the reaction carried out between hydrogen peroxide and excessive potassium permanganate.
The present invention is preferably sequentially washed to the second order reaction system and centrifugal treating, obtains graphene oxide.This
It is preferable to use distilled water to carry out the washing for invention；The revolving speed of the centrifugal treating is preferably 3000~10000 revs/min, more excellent
It is selected as 5000~8000 revs/min, most preferably 6000~7000 revs/min；The time of the centrifugal treating is preferably 5~5min,
More preferably 10~12min.The present invention preferably reads the washing and centrifugal treating operation again repeatedly, until at last time centrifugation
The pH value for managing supernatant is 6~7.The sediment that the present invention preferably obtains centrifugal treating, which is dried, obtains graphite oxide
Alkene.
In the present invention, the reducing agent is preferably one or more of citric acid, glucose and hydrazine hydrate.
In the present invention, the temperature of the reduction reaction is preferably 100~150 DEG C, more preferably 110~140 DEG C, optimal
It is selected as 120~130 DEG C；The time of the reduction reaction is preferably 8~15h, more preferably 10~12h.
In the present invention, silver ion is reduced to Nano silver grain, simultaneous oxidation graphene during the reduction reaction
Also it is reduced agent and is reduced to graphene.
C6H12O6+H2O+Ag+→C6H12O7+Ag+2H+
After the reduction reaction, product system is preferably naturally cooling to room temperature by the present invention, then again to product body
System is sequentially filtered, washed and is dried, and the modified by silver graphene of clean dry is obtained.
After obtaining modified by silver graphene, the present invention under an inert atmosphere, by the modified by silver graphene, diamine monomer, two
Polymerization reaction is carried out after anhydride monomer and organic solvent mixing, obtains spinning solution.The present invention is preferably first by modified by silver graphene, two
Amine monomers and organic solvent mixing, ultrasonic treatment dissolve diamine monomer sufficiently so that modified by silver graphene dispersion is uniform,
Obtain dispersion liquid.In the present invention, the power of the ultrasonic treatment is preferably 250~350W, more preferably 300~320W；Institute
The time for stating ultrasonic treatment is preferably 20~40min, more preferably 30~35min.
Dianhydride monomer is preferably added in the present invention under an inert atmosphere.Since dianhydride monomer is hygroscopic, the inert atmosphere energy
It enough prevents dianhydride monomer from absorbing the moisture in air, while oxygen and moisture can also be avoided in air to the shadow of polymerization reaction
It rings.In the present invention, the inert atmosphere is preferably nitrogen and/or argon gas.
In the present invention, the diamine monomer is preferably 1,3- bis- (4- phenalgin oxygroup) benzene；The dianhydride monomer is preferably
4,4 '-biphenyl ether dianhydrides.In the present invention, the molar ratio of the diamine monomer and dianhydride monomer is preferably 1:(0.5~1.5),
More preferably 1:(1~1.2).
In the present invention, the organic solvent is preferably n,N-dimethylacetamide (DMAc) and tetrahydrofuran (THF)
Mixed solvent, the mass ratio of the n,N-dimethylacetamide (DMAc) and tetrahydrofuran (THF) are preferably (1~2): 1, it is more excellent
It is selected as (1.2~1.5): 1.The mixed organic solvents that the present invention uses enable to spinning to be not susceptible to adhesion.In this hair
In bright, the mass ratio of the modified by silver graphene, diamine monomer and organic solvent is preferably (2.5~52): 100:(722~
1512), more preferably (2.58~51.53): 100:(722.46~1511.9), most preferably (20~40): 100:(100~
1200)。
Polymerization reaction of the present invention is that dianhydride monomer and diamine monomer polymerization generate polyamic acid；Since the present invention first will
Diamine monomer and the mixing of modified by silver graphene, modified by silver graphene film interlayer can have diamine monomer, so having one when polymerization
A little molecular chain growths are conducive to the dispersion of modified by silver graphene in modified by silver graphene film interlayer.In the present invention, the polymerization
The temperature of reaction influences to be -10~10 DEG C, more preferably -5~5 DEG C, most preferably 0~2 DEG C；The time of the polymerization reaction is excellent
It is selected as 3~8h, more preferably 4~5h.
After obtaining spinning solution, the spinning solution is carried out spinning by the present invention, obtains spinning fibre.In the present invention,
The spinning is preferably electrostatic spinning, and the voltage of the spinning is preferably 10~30KV, more preferably 15~25KV, most preferably
20~22KV；The temperature of the spinning is preferably 15~35 DEG C, more preferably 20~30 DEG C, most preferably 25~28 DEG C；It is described
The ambient humidity of spinning is preferably 20~50%, and more preferably 25~45%, most preferably 30~40%；The spinning is injected
Speed is preferably 0.2~1mm/min, more preferably 0.5~1.5mm/min, most preferably 0.8~1.2mm/min.
The diameter for the spinning fibre that the present invention obtains is preferably 500~1500nm, more preferably 800~1300nm, optimal
It is selected as 100~1200nm.After the spinning, the spinning fibre of obtained dry solidification is mixed and disorderly staggered row column-shaped, similar
In nonwoven fabric construct.
After obtaining spinning fibre, the spinning fibre is carried out hot imidization by the present invention, is obtained polyimide-based thermally conductive multiple
Condensation material.In the present invention, the hot imidization preferably comprises the first hot imidization processing sequentially carried out, the second hot imidization
Processing and the processing of third hot imidization；
The temperature of the first hot imidization processing is preferably 110~130 DEG C, and more preferably 115~120 DEG C；Described
The time of one hot imidization processing is preferably 1~3h, more preferably 2h；
The temperature of the second hot imidization processing is preferably 190~210 DEG C, and more preferably 195~200 DEG C；Described
The time of two hot imidizations processing is preferably 1~3h, more preferably 2h；
The temperature of the third hot imidization processing is preferably 240~260 DEG C, and more preferably 245~250 DEG C；Described
The time of three hot imidizations processing is preferably 1~3h, more preferably 2h；
The heating rate for being warming up to the first hot imidization treatment temperature is preferably 1~5 DEG C/min, more preferably 2~4 DEG C/
min；
The heating rate that the second hot imidization treatment temperature is warming up to by the first hot imidization treatment temperature is preferably 1~5
DEG C/min, more preferably 2~4 DEG C/min；
The heating rate that third hot imidization treatment temperature is warming up to by the second hot imidization treatment temperature is preferably 1~5
DEG C/min, more preferably 2~4 DEG C/min.
System is preferably naturally cooling to room temperature after third hot imidization processing by the present invention.
The present invention enables to the more abundant of imidization progress using the processing of three step hot imidizations；The imidization
It is that the carboxyl and imido grpup on polyamic acid strand occur under heat effect for the process of polyamic acid intramolecular cyclization dehydration
Reaction forms imide bond.
The present invention, also comprising carrying out hot pressing to hot imidization product, obtains the poly- of specific modality after the hot imidization
Imide heat-conductive composite material；The hot pressing is specially to cut hot imidization product, be laminated and be placed on compression molding
Melting sizing is carried out in machine.In the present invention, the temperature of the hot pressing is preferably 300~350 DEG C, more preferably 320~330
℃；The pressure of the hot pressing is preferably 5~25MPa, more preferably 10~20MPa；The time of the hot pressing is preferably 15~
60min, more preferably 30~40min.The present invention carries out 3~5 exhausts preferably in the hot pressing.
Polyimide-based heat-conductive composite material provided by the invention and preparation method thereof is carried out below with reference to embodiment detailed
Thin explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The crystalline flake graphite of 100 parts by weight is added in 98% concentrated sulfuric acid of 4000 parts by weight, is stirred evenly, then will
The potassium permanganate of 200 parts by weight is added in above-mentioned concentrated sulfuric acid solution, is stirred to react under the conditions of 4 DEG C 2 hours.By above-mentioned reaction solution
It is mixed with the distilled water of 15000 parts by weight, then the hydrogen peroxide of 500 parts by weight is added in above-mentioned mixed solution.It is washed with distillation
Above-mentioned mixed solution is washed, each time after washing, is all centrifuged 10 minutes in the centrifuge that revolving speed is 8000 revs/min, until last
The pH of supernatant after secondary centrifugation is 6~7, and the drying precipitate after centrifugation is then obtained graphene oxide.
The graphene oxide of 100 parts by weight is taken to be added in the distilled water of 100 parts by weight, ultrasonic treatment makes graphene oxide
It is uniformly dispersed, obtains graphene oxide dispersion.The silver ammino solution of 1.85 parts of 0.1mol/L and graphene oxide dispersion are mixed
It closes uniformly, then the glucose of 100 parts by weight is added in mixed liquor.At a temperature of hydro-thermal reaction by above-mentioned mixed liquor at 100 DEG C
It 12 hours, is cooled to room temperature to temperature, filters, washs, dries, obtain modified by silver graphene.
The modified by silver graphene of (the 4- phenalgin oxygroup) benzene of 1,3- bis- of 100 parts by weight and 2.08 parts by weight is added to
DMAc and the THF in the mixed solvent (mass ratio DMAc:THF=1.5) of 940.00 parts by weight, ultrasonic (power 300W, time
Make modified by silver graphene dispersion uniform for the above-mentioned solvent of 30min), and make 1, the dissolution of (the 4- phenalgin oxygroup) benzene of 3- bis- is complete.?
Under nitrogen gas protection, the 4 of 106.12 parts by weight, 4 '-biphenyl ether dianhydrides are added in above-mentioned solution, are stirred at a temperature of 10 DEG C
It mixes 4 hours, obtains modified by silver graphene/polyamic acid solution.
Then resulting modified by silver graphene/polyamic acid solution is transferred in the syringe with metal needle, it will
Said syringe is fixed in the infusing device of electrospinning device, and injecting speed is 0.20mm/min.By electrospinning device
In positive high voltage collet be fixed to syringe metal needle on, and by the negative high voltage in electrospinning device be fixed to Static Spinning
In roller reception device in silk equipment, adjusting voltage is 20kV.Meanwhile adjusting the temperature in electrostatic spinning apparatus is 25 DEG C,
Relative humidity is 25%, and modified by silver graphene/polyamic acid fiber can be obtained.
Modified by silver graphene/polyamic acid fiber obtained above is placed in hot imidization in baking oven, the step of hot imidization
Suddenly are as follows: the temperature of baking oven is warming up to 120 DEG C by room temperature with the heating rate of 1 DEG C/min, then keeps the temperature 1 hour for 120 DEG C.Again with
The heating rate of 1 DEG C/min is warming up to 200 DEG C, then keeps the temperature 1 hour for 200 DEG C.It is warming up to again with the heating rate of 1 DEG C/min
250 DEG C, then keep the temperature 1 hour for 250 DEG C.Then room temperature is naturally cooling to get modified by silver graphene/polyimide fiber.
Resulting modified by silver graphene/polyimide fiber is finally cut to the square sample of 1.50cm*1.50cm,
It is put into mold, is then put into mold in 320 DEG C of vulcanizing press, the retention time after said sample is successively superimposed
30min, pressure 10MPa are vented 5 times, and then pressure is naturally cooling to room temperature, obtaining thickness is about the polyimide-based of 2mm
Heat-conductive composite material.
After tested, the thermal conductivity of made polyimide-based heat-conductive composite material is 0.35W/mK, and glass transition temperature is
205.8 DEG C, heat-resistance index is 275.4 DEG C.
Embodiment 2
The crystalline flake graphite of 100 parts by weight is added in 98% concentrated sulfuric acid of 4000 parts by weight, is stirred evenly, then will
The potassium permanganate of 200 parts by weight is added in above-mentioned concentrated sulfuric acid solution, is stirred to react under the conditions of 40 DEG C 2 hours.By above-mentioned reaction
Liquid is mixed with the distilled water of 15000 parts by weight, then the hydrogen peroxide of 500 parts by weight is added in above-mentioned mixed solution.Use distilled water
Above-mentioned mixed solution is washed, each time after washing, is all centrifuged 10 minutes in the centrifuge that revolving speed is 8000 revs/min, until last
The pH of supernatant after primary centrifugation is 6~7, and the drying precipitate after centrifugation is then obtained graphene oxide.
The graphene oxide of 100 parts by weight is taken to be added in the distilled water of 100 parts by weight, ultrasonic treatment makes graphene oxide
It is uniformly dispersed, obtains graphene oxide dispersion.The silver ammino solution of 9.27 parts of 0.1mol/L and graphene oxide dispersion are mixed
It closes uniformly, then the hydrazine hydrate of 100 parts by weight is added in mixed liquor.At a temperature of hydro-thermal reaction by above-mentioned mixed liquor at 150 DEG C
It 12 hours, is cooled to room temperature to temperature, filters, washs, dries, obtain modified by silver graphene.
The modified by silver graphene of (the 4- phenalgin oxygroup) benzene of 1,3- bis- of 100 parts by weight and 10.85 parts by weight is added to
DMAc and the THF in the mixed solvent (mass ratio DMAc:THF=1.5) of 1085.14 parts by weight, ultrasound (power 300W, when
Between be 30min) above-mentioned solvent makes modified by silver graphene dispersion uniform, and makes 1, the dissolution of (the 4- phenalgin oxygroup) benzene of 3- bis- is complete.
Under nitrogen gas protection, the 4 of 106.12 parts by weight, 4 '-biphenyl ether dianhydrides are added in above-mentioned solution, at a temperature of -4 DEG C
Stirring 4 hours, obtains modified by silver graphene/polyamic acid solution.
Then resulting modified by silver graphene/polyamic acid solution is transferred in the syringe with metal needle, it will
Said syringe is fixed in the infusing device of electrospinning device, and injecting speed is 0.20mm/min.By electrospinning device
In positive high voltage collet be fixed to syringe metal needle on, and by the negative high voltage in electrospinning device be fixed to Static Spinning
In roller reception device in silk equipment, adjusting voltage is 25kV.Meanwhile adjusting the temperature in electrostatic spinning apparatus is 25 DEG C,
Relative humidity is 25%, and modified by silver graphene/polyamic acid fiber can be obtained.
Modified by silver graphene/polyamic acid fiber obtained above is placed in hot imidization in baking oven, the step of hot imidization
Suddenly are as follows: the temperature of baking oven is warming up to 120 DEG C by room temperature with the heating rate of 1 DEG C/min, then keeps the temperature 1 hour for 120 DEG C.Again with
The heating rate of 1 DEG C/min is warming up to 200 DEG C, then keeps the temperature 1 hour for 200 DEG C.It is warming up to again with the heating rate of 1 DEG C/min
250 DEG C, then keep the temperature 1 hour for 250 DEG C.Then room temperature is naturally cooling to get modified by silver graphene/polyimide fiber.
Resulting modified by silver graphene/polyimide fiber is finally cut to the square sample of 1.50cm*1.50cm,
It is put into mold, is then put into mold in 320 DEG C of vulcanizing press, the retention time after said sample is successively superimposed
30min, pressure 10MPa are vented 5 times, and then pressure is naturally cooling to room temperature, obtaining thickness is about the polyimide-based of 2mm
Heat-conductive composite material.
After tested, the thermal conductivity of made polyimide-based heat-conductive composite material is 0.92W/mK, and glass transition temperature is
212.5 DEG C, heat-resistance index is 289.5 DEG C.
Embodiment 3
The crystalline flake graphite of 100 parts by weight is added in 98% concentrated sulfuric acid of 4000 parts by weight, is stirred evenly, then will
The potassium permanganate of 200 parts by weight is added in above-mentioned concentrated sulfuric acid solution, is stirred to react under the conditions of 15 DEG C 2 hours.By above-mentioned reaction
Liquid is mixed with the distilled water of 15000 parts by weight, then the hydrogen peroxide of 500 parts by weight is added in above-mentioned mixed solution.Use distilled water
Above-mentioned mixed solution is washed, each time after washing, is all centrifuged 10 minutes in the centrifuge that revolving speed is 8000 revs/min, until last
The pH of supernatant after primary centrifugation is 6~7, and the drying precipitate after centrifugation is then obtained graphene oxide.
The graphene oxide of 100 parts by weight is taken to be added in the distilled water of 100 parts by weight, ultrasonic treatment makes graphene oxide
It is uniformly dispersed, obtains graphene oxide dispersion.The silver ammino solution of 5 parts of 0.3mol/L and graphene oxide dispersion are mixed equal
It is even, then the sodium citrate of 100 parts by weight is added in mixed liquor.At a temperature of hydro-thermal reaction 12 by above-mentioned mixed liquor at 130 DEG C
Hour, it is cooled to room temperature to temperature, filters, washs, dries, obtain modified by silver graphene.
The modified by silver graphene of (the 4- phenalgin oxygroup) benzene of 1,3- bis- of 100 parts by weight and 39.46 parts by weight is added to
DMAc and the THF in the mixed solvent (mass ratio DMAc:THF=1.5) of 1266.18 parts by weight, ultrasound (power 300W, when
Between be 30min) above-mentioned solvent makes modified by silver graphene dispersion uniform, and makes 1, the dissolution of (the 4- phenalgin oxygroup) benzene of 3- bis- is complete.
Under nitrogen gas protection, the 4 of 106.12 parts by weight, 4 '-biphenyl ether dianhydrides are added in above-mentioned solution, at a temperature of 4 DEG C
Stirring 4 hours, obtains modified by silver graphene/polyamic acid solution.
Then resulting modified by silver graphene/polyamic acid solution is transferred in the syringe with metal needle, it will
Said syringe is fixed in the infusing device of electrospinning device, and injecting speed is 0.20mm/min.By electrospinning device
In positive high voltage collet be fixed to syringe metal needle on, and by the negative high voltage in electrospinning device be fixed to Static Spinning
In roller reception device in silk equipment, adjusting voltage is 25kV.Meanwhile adjusting the temperature in electrostatic spinning apparatus is 25 DEG C,
Relative humidity is 25%, and modified by silver graphene/polyamic acid fiber can be obtained.
Modified by silver graphene/polyamic acid fiber obtained above is placed in hot imidization in baking oven, the step of hot imidization
Suddenly are as follows: the temperature of baking oven is warming up to 120 DEG C by room temperature with the heating rate of 1 DEG C/min, then keeps the temperature 1 hour for 120 DEG C.Again with
The heating rate of 1 DEG C/min is warming up to 200 DEG C, then keeps the temperature 1 hour for 200 DEG C.It is warming up to again with the heating rate of 1 DEG C/min
250 DEG C, then keep the temperature 1 hour for 250 DEG C.Then room temperature is naturally cooling to get modified by silver graphene/polyimide fiber.
Resulting modified by silver graphene/polyimide fiber is finally cut to the square sample of 1.50cm*1.50cm,
It is put into mold, is then put into mold in 320 DEG C of vulcanizing press, the retention time after said sample is successively superimposed
30min, pressure 10MPa are vented 5 times, and then pressure is naturally cooling to room temperature, obtaining thickness is about the polyimide-based of 2mm
Heat-conductive composite material.
After tested, the thermal conductivity of made polyimide-based heat-conductive composite material is 2.12W/mK, and glass transition temperature is
216.1 DEG C, heat-resistance index is 298.6 DEG C.
As seen from the above embodiment, the present invention provides a kind of polyimide-based heat-conductive composite material, comprising polyimides,
Graphene and silver nano-grain, for the graphene dispersion in polyimide matrix, the silver nano-grain is supported on graphene
Surface.Polyimide-based heat-conductive composite material provided by the invention by added in polyimide matrix a small amount of graphene and
Nano silver grain improves the heating conduction of material.It is by embodiment result it is found that provided by the invention polyimide-based thermally conductive multiple
The thermal conductivity of condensation material can reach 2.12W/mK, and glass transition temperature is 205.8~216.1 DEG C, and heat-resistance index is 275.4~
298.6℃。
The present invention also provides the preparation method of the polyimide-based heat-conductive composite material, (1) divides graphene oxide
Reduction reaction is carried out after dispersion liquid, silver ammino solution and reducing agent mixing, obtains modified by silver graphene；(2) under an inert atmosphere, by institute
Polymerization reaction is carried out after stating modified by silver graphene, diamine monomer, dianhydride monomer and organic solvent mixing, obtains spinning solution；(3)
The spinning solution is subjected to spinning, obtains spinning fibre；(4) spinning fibre is subjected to hot imidization, obtains polyamides Asia
Amido heat-conductive composite material.The present invention can effectively prevent graphene to reunite, together by modifying silver nano-grain on graphene
When silver nano-grain the thermal conducting path of graphene film interlayer has been constructed as " bridge ", be conducive to increase leading for graphene film interlayer
Hot property；The method combined using in-situ polymerization-spinning improves the dispersion situation of modified by silver graphene in the base, more
Help to construct graphene heat conduction network.Preparation method provided by the invention is easy to operate, easy to implement.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of polyimide-based heat-conductive composite material includes polyimides, graphene and silver nano-grain, the graphene point
It dissipates in polyimide matrix, the silver nano-grain load is on the surface of graphene.
2. polyimide-based heat-conductive composite material according to claim 1, which is characterized in that the polyimides, graphite
The mass ratio of alkene and silver nano-grain is 100:(0.5~15): (0.1~4).
3. the preparation method of polyimide-based heat-conductive composite material as claimed in claim 1 or 2, comprises the following steps:
(1) reduction reaction is carried out after mixing graphene oxide dispersion, silver ammino solution and reducing agent, obtains modified by silver graphite
Alkene；
(2) under an inert atmosphere, it is carried out after the modified by silver graphene, diamine monomer, dianhydride monomer and organic solvent being mixed
Polymerization reaction obtains spinning solution；
(3) spinning solution is subjected to spinning, obtains spinning fibre；
(4) spinning fibre is subjected to hot imidization, obtains polyimide-based heat-conductive composite material.
4. preparation method according to claim 3, which is characterized in that the mass concentration of the graphene oxide dispersion is
9~50%, the concentration of the silver ammino solution is 0.01~0.5mol/L；
The mass ratio of the graphene oxide dispersion, silver ammino solution and reducing agent is (200~1100): (1.5~10): (50
~100).
5. preparation method according to claim 3 or 4, which is characterized in that the temperature of the reduction reaction is 100~150
DEG C, the time of the reduction reaction is 8~15h.
6. preparation method according to claim 3, which is characterized in that the molar ratio of the diamine monomer and dianhydride monomer is
1:(0.5~1.5)；
The mass ratio of the modified by silver graphene, diamine monomer and organic solvent is (2.5~52): 100:(722~1512).
7. the preparation method according to claim 3 or 6, which is characterized in that the temperature of the polymerization reaction is -10~10
DEG C, the time of the polymerization reaction is 3~8h.
8. preparation method according to claim 3, which is characterized in that the voltage of the spinning is 10~30KV, the spinning
The temperature of silk is 15~35 DEG C, and the ambient humidity of the spinning is 20~50%, and the speed of injecting of the spinning is 0.2~1mm/
min。
9. the preparation method according to claim 3 or 8, which is characterized in that the hot imidization includes the sequentially carried out
The processing of one hot imidization, the processing of the second hot imidization and the processing of third hot imidization；
The temperature of the first hot imidization processing is 110~130 DEG C, and the time of the first hot imidization processing is 1~3h；
The temperature of the second hot imidization processing is 190~210 DEG C, and the time of the second hot imidization processing is 1~3h；
The temperature of the third hot imidization processing is 240~260 DEG C, and the time of the third hot imidization processing is 1~3h；
The heating rate for being warming up to the first hot imidization treatment temperature is 1~5 DEG C/min；
It is 1~5 DEG C/min by the heating rate that the first hot imidization treatment temperature is warming up to the second hot imidization treatment temperature；
It is 1~5 DEG C/min by the heating rate that the second hot imidization treatment temperature is warming up to third hot imidization treatment temperature.
10. preparation method according to claim 9, which is characterized in that also comprising to hot imines after the hot imidization
Change product and carry out hot pressing, obtains the polyimide-based heat-conductive composite material of specific modality；
The temperature of the hot pressing is 300~350 DEG C, and the pressure of the hot pressing is 5~25MPa, the time of the hot pressing is 15~
60min。
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