CN106480533A - A kind of polymide dielectric heat-conductive composite material and preparation method thereof - Google Patents
A kind of polymide dielectric heat-conductive composite material and preparation method thereof Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- 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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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
Abstract
The invention provides a kind of polymide dielectric heat-conductive composite material and preparation method thereof, with 1,3,4 triphenyl, two ether diamine APB, 4, the double phthalic anhydride 6FDA and 1 of 4 (hexafluoro isopropyl), 3 diaminopropyl tetramethyl disiloxane GAPD are raw material, cubic boron nitride hBN is heat filling, hBN/ polyamic acid heat conduction composite fiber is prepared using in-situ polymerization method of electrostatic spinning, then cuts out, through hot imidization, the hBN/PI dielectric heat-conductive composite material that stacking die press technology for forming prepares high heat conduction, low dielectric.HBN/PI dielectric heat-conductive composite material prepared by the present invention has the advantages that high heat conduction, low dielectric and excellent heat resistance.
Description
Technical field
The present invention relates to a kind of dielectric heat-conductive composite material, particularly a kind of polymide dielectric heat-conductive composite material, also
It is related to the preparation method of this polymide dielectric heat-conductive composite material.
Background technology
Polyimides (PI) has prominent heat resistance, excellent chemical stability, good electrical insulating property and excellent
Many advantages, such as mechanical performance, have wide practical use in high-technology fields such as Aeronautics and Astronautics, optics and electronic equipments.
However, PI itself heat conductivility poor (thermal conductivity factor λ is 0.174W/mK) so as to which application is limited.In order to expand PI further in electricity
The high heat transfer such as sub- components and parts and integrated circuit and the application of radiating occasion, the heat conductivility for improving PI matrix is key problem in technology.
The research of PI dielectric heat-conductive composite material is relatively fewer both at home and abroad, mostly using the single high heat conduction of filling, low Jie
The inorganic filler of electricity is preparing PI heat-conductive composite material.Boron nitride is because having high thermal conductivity factor (λ), low dielectric constant (ε)
Many advantages, such as with dielectric loss angle tangent (tan δ), excellent non-oxidizability and corrosion resistance so as to become preparation PI and be situated between
The preferable property-modifying additive of electric heat-conductive composite material.
Content of the invention
In order to overcome the deficiencies in the prior art, the present invention provides a kind of polyimides heat-conductive composite material, with 1,3,4- tri-
Two ether diamines of phenyl (APB), 4,4- (hexafluoro isopropyl) double phthalic anhydride (6FDA) and 1,3- diaminopropyl tetramethyl
Disiloxane (GAPD) is raw material, and cubic boron nitride (hBN) is heat filling, is prepared using in-situ polymerization-method of electrostatic spinning
HBN/ polyamic acid (hBN/PAA) heat conduction composite fiber felt, then prepare through hot imidization-die press technology for forming, hBN/ gathers
Acid imide acid (hBN/PI) dielectric heat-conductive composite material has the advantages that high heat conduction, low dielectric.
The technical solution adopted for the present invention to solve the technical problems is：A kind of polymide dielectric heat-conductive composite material,
If being formed using dried layer heat conduction composite fiber felt superposition lamination, the component of every layer of heat conduction composite fiber felt includes 70～95 weight portions
Polyimides and 5～30 weight portions cubic boron nitride.
The present invention also provides a kind of preparation method of polymide dielectric heat-conductive composite material, comprises the following steps：
A two ether diamine of 1,3,4- triphenyl of 6.5～7.5 weight portions is mixed 75～86 weight under the conditions of ice-water bath by ()
The DMAC N,N' dimethyl acetamide of part；After treating that 1,3,4- triphenyl, two ether diamine is completely dissolved, then divide several times add 10.6～
The double phthalic anhydrides of 4,4- (hexafluoro isopropyl) of 12.3 weight portions；Treat that the double phthalic anhydrides of 4,4- (hexafluoro isopropyl) are complete
After portion adds and dissolves, 1, the 3- diaminopropyl tetramethyl disiloxane of 0.29～0.34 weight portion, mechanical agitation are added
30min；The cubic boron nitride of 5～30 weight portions is added, continues 30～60min of stirring, in-situ polymerization obtains cubic boron nitride/polyamides
Amino acid solution；
B cubic boron nitride/polyamic acid solution is carried out electrostatic spinning by (), obtain cubic boron nitride/polyamic acid heat conduction
Composite fibrofelt；
C () cubic boron nitride/polyamic acid heat conduction composite fiber felt is removed at 60 DEG C of vacuum solvent 4h；Then with 1 DEG C/
The heating rate of min is heated to 120 DEG C of insulation 1h, is heated to 200 DEG C of insulation 1h with the heating rate of 1 DEG C/min, with 1 DEG C/min
Heating rate be heated to 250 DEG C insulation 1h, carry out hot imidization；Take out after being down to room temperature, obtain cubic boron nitride/polyimides
Heat conduction composite fiber felt；
If d () is by dried layer cubic boron nitride/polyimides heat conduction composite fiber felt compression molding, obtain cubic boron nitride/
Polyimides heat conduction composite fiber felt dielectric heat-conductive composite material；The temperature of the compression molding is 290～320 DEG C, and pressure is 5
～10MPa, time are 10～15min.
In described step (a), after the double phthalic anhydrides of 4,4- (hexafluoro isopropyl) of interpolation are completely dissolved every time again
Add the double phthalic anhydrides of 4,4- (hexafluoro isopropyl) of next batch.
In described step (a), the weight of the double phthalic anhydrides of 4,4- (hexafluoro isopropyl) for adding every time is less than
0.2g.
In described step (b), cubic boron nitride/polyamic acid solution is loaded the injection needle for being furnished with metal needle
In, then injection needle is horizontally fixed on injection apparatus, by the high voltage power supply positive electrode of electrostatic spinning machine and metal needle
It is connected, tinfoil paper is collected paper bag and overlayed on cylinder shape negative electrode, injection needle aligns with drum center, keeps the work of electrostatic spinning machine
Room is sealing state, and keeps work room temperature for 18～25 DEG C, and envionmental humidity is 50%～60%, high-voltage power voltage
For 15kV～25kV, the distance of syringe needle to centre of the drum is 15～20cm, and the rotating speed of cylinder is 40m/min.
In described step (d), cubic boron nitride/polyimides heat conduction composite fiber felt 2g is weighed, is cut into a size of
The sample of 20 × 20mm loads in mould, compression molding on tablet vulcanizer.
The invention has the beneficial effects as follows：Method due to being combined using in-situ polymerization, electrostatic spinning and compression molding, real
Show the dispersed of PI intrinsic silicon hBN and aligned, obtain the thermal conductivity factor λ of hBN/PI dielectric heat-conductive composite material
Significantly improve, dielectric constant (ε) and dielectric loss angle tangent (tan δ) are relatively low.Thermal conductivity factor λ is by prior art
0.174W/mK bring up to 0.233W/mK～0.696W/mK；Dielectric constant (ε) value between 3.21～3.77, dielectric loss
Angle tangent value (tan δ) is between 0.0038～0.0070.
Specific embodiment
With reference to embodiment, the present invention is further described, and the present invention includes but are not limited to following embodiments.
The present invention prepares a kind of polymide dielectric heat-conductive composite material using " hot imidization-compression molding " method, and which is special
Point is prepared from by the polyimides (PI) of 70%～95% weight and the cubic boron nitride (hBN) of 5%～30% weight.Its
Middle PI is two ether diamines of 1,3,4- triphenyl (APB) by 6.5%～7.5% weight, the 4,4- of 10.6%～12.3% weight
(hexafluoro isopropyl) double phthalic anhydrides (6FDA), two silicon of 1,3- diaminopropyl tetramethyl of 0.29%～0.34% weight
The DMAC N,N' dimethyl acetamide (DMAc) of oxygen alkane (GAPD) and 75%～86% weight is prepared from through two-step method.
A kind of preparation method of polymide dielectric heat-conductive composite material, comprises the steps：
A the APB of 6.5%～7.5% weight is put in the there-necked flask for being furnished with agitator and nitrogen conduit by (), ice-water bath
Under the conditions of add 75%～86% weight DMAc, after APB is completely dissolved, by the 6FDA of 10.6%～12.3% weight in batches
Add (every batch of 6FDA weight is less than 0.2000g, adds down and criticize after upper crowd of 6FDA is completely dissolved).Treat that 6FDA is all added
And after dissolving, add the GAPD of 0.29%～0.34% weight.Mechanical agitation 30min, adds the hBN of 5%～30% weight, continues
30～60min of continuous stirring, in-situ polymerization obtain hBN/ polyamic acid (hBN/PAA) solution；
B () is furnished with the hBN/PAA solution loading through step (a) in the 8ml injection needle of metal needle, then will injection
Needle tubing is horizontally fixed on injection apparatus, and the high voltage power supply positive electrode tab of electrostatic spinning machine is connected with metal needle, tinfoil paper
Collect paper bag to overlay on cylinder shape negative electrode, the center of injection needle aligns with drum, the operating room for keeping electrostatic spinning machine is close
Envelope state, and keep work room temperature for 18～25 DEG C, high voltage power supply is 15kV～25kV, and the distance of syringe needle to centre of the drum is
15cm～20cm, envionmental humidity are 50%～60%, and the rotating speed of cylinder is 40m/min, and electrostatic spinning obtains hBN/PAA heat conduction
Composite fibrofelt；
(c) will be through step (b) hBN/PAA heat conduction composite fiber felt in vacuum drying oven 60 DEG C remove solvent 4h, by 120
DEG C/1h+200 DEG C/1h+250 DEG C/1h, heating rate is that the program of 1 DEG C/min carries out hot imidization, takes out, obtain after being down to room temperature
HBN/ polyimides (hBN/PI) heat conduction composite fiber felt；
D () weighs the hBN/PI heat conduction composite fiber felt 2.00g through step (c), be cut to the loading of 20mm × 20mm sample
In mould, compression molding on tablet vulcanizer prepares hBN/PI dielectric heat-conductive composite material, molding temperature 290 DEG C～320
DEG C, pressure is 5MPa～10MPa, and clamp time is 10～15min.
Embodiment 1：The APB of 1.6078g is put in the there-necked flask for being furnished with agitator and nitrogen conduit, ice-water bath condition
The DMAc of lower addition 13.5200g, is dividedly in some parts the 6FDA of 2.6656g after APB is completely dissolved, then treats that 6FDA is all added simultaneously
The GAPD of 0.0745g after dissolving, is added, the hBN of 0.1527g after mechanical agitation 30min, is added, continue stirring 30min, in situ poly-
Close to obtain hBN/PAA solution；HBN/PAA solution is loaded and is furnished with the 8ml injection needle of metal needle, then by injection needle water
Put down and be fixed on injection apparatus, the high voltage power supply positive electrode tab of electrostatic spinning machine is connected with metal needle, paper collected by tinfoil paper
It is coated on cylinder shape negative electrode, the center of injection needle aligns with drum, the operating room for keeping electrostatic spinning machine is sealing state,
And keeping work room temperature for 18 DEG C, electrostatic positive voltage is 15kV, and operating distance is 15cm, and envionmental humidity is 50%, connects
Receipts rotating speed is 40m/min, and electrostatic spinning obtains hBN/PAA heat conduction composite fiber felt, in vacuum drying oven 60 DEG C except solvent 4h after
By 120 DEG C/1h+200 DEG C/1h+250 DEG C/1h, heating rate carries out hot imidization for the program of 1 DEG C/min, takes after being down to room temperature
Go out, obtain hBN/PI heat conduction composite fiber felt；2.00g hBN/PI heat conduction composite fiber felt is cut to 20mm × 20mm sample dress
Enter in mould, compression molding on tablet vulcanizer prepares hBN/PI dielectric heat-conductive composite material, 290 DEG C of molding temperature, pressure
Power is 5MPa, and clamp time is 10min.
After tested, the λ of made hBN/PI dielectric heat-conductive composite material be 0.233W/mK, ε be 3.21, tan δ be 0.0038.
Embodiment 2：The APB of 1.6078g is put in the there-necked flask for being furnished with agitator and nitrogen conduit, ice-water bath condition
The DMAc of lower addition 22.3600g, is dividedly in some parts the 6FDA of 2.6656g after APB is completely dissolved, then treats that 6FDA is all added simultaneously
The GAPD of 0.0745g after dissolving, is added, the hBN of 1.2437g after mechanical agitation 30min, is added, continue stirring 60min, in situ poly-
Close to obtain hBN/PAA solution；HBN/PAA solution is loaded and is furnished with the 8ml injection needle of metal needle, then by injection needle water
Put down and be fixed on injection apparatus, the high voltage power supply positive electrode tab of electrostatic spinning machine is connected with metal needle, paper collected by tinfoil paper
It is coated on cylinder shape negative electrode, the center of injection needle aligns with drum, the operating room for keeping electrostatic spinning machine is sealing state,
And keeping work room temperature for 25 DEG C, electrostatic positive voltage is 25kV, and operating distance is 20cm, and envionmental humidity is 60%, connects
Receipts rotating speed is 40m/min, and electrostatic spinning obtains hBN/PAA heat conduction composite fiber felt, in vacuum drying oven 60 DEG C except solvent 4h after
By 120 DEG C/1h+200 DEG C/1h+250 DEG C/1h, heating rate carries out hot imidization for the program of 1 DEG C/min, takes after being down to room temperature
Go out, obtain hBN/PI heat conduction composite fiber felt；2.00g hBN/PI heat conduction composite fiber felt is cut to 20mm × 20mm sample dress
Enter in mould, compression molding on tablet vulcanizer prepares hBN/PI dielectric heat-conductive composite material, 320 DEG C of molding temperature, pressure
Power is 10MPa, and clamp time is 15min.
After tested, the λ of made hBN/PI dielectric heat-conductive composite material be 0.696W/mK, ε be 3.77, tan δ be 0.0070.
Embodiment 3：The APB of 1.6078g is put in the there-necked flask for being furnished with agitator and nitrogen conduit, ice-water bath condition
The DMAc of lower addition 14.7900g, is dividedly in some parts the 6FDA of 2.6656g after APB is completely dissolved, then treats that 6FDA is all added simultaneously
The GAPD of 0.0745g after dissolving, is added, the hBN of 0.3224g after mechanical agitation 30min, is added, continue stirring 35min, in situ poly-
Close to obtain hBN/PAA solution；HBN/PAA solution is loaded and is furnished with the 8ml injection needle of metal needle, then by injection needle water
Put down and be fixed on injection apparatus, the high voltage power supply positive electrode tab of electrostatic spinning machine is connected with metal needle, paper collected by tinfoil paper
It is coated on cylinder shape negative electrode, the center of injection needle aligns with drum, the operating room for keeping electrostatic spinning machine is sealing state,
And keeping work room temperature for 20 DEG C, electrostatic positive voltage is 20kV, and operating distance is 18cm, and envionmental humidity is 55%, connects
Receipts rotating speed is 40m/min, and electrostatic spinning obtains hBN/PAA heat conduction composite fiber felt, in vacuum drying oven 60 DEG C except solvent 4h after
By 120 DEG C/1h+200 DEG C/1h+250 DEG C/1h, heating rate carries out hot imidization for the program of 1 DEG C/min, takes after being down to room temperature
Go out, obtain hBN/PI heat conduction composite fiber felt；2.00g hBN/PI heat conduction composite fiber felt is cut to 20mm × 20mm sample dress
Enter in mould, compression molding on tablet vulcanizer prepares hBN/PI dielectric heat-conductive composite material, 300 DEG C of molding temperature, pressure
Power is 5MPa, and clamp time is 10min.
After tested, the λ of made hBN/PI dielectric heat-conductive composite material be 0.264W/mK, ε be 3.38, tan δ be 0.0043.
Embodiment 4：The APB of 1.6078g is put in the there-necked flask for being furnished with agitator and nitrogen conduit, ice-water bath condition
The DMAc of lower addition 20.0000g, is dividedly in some parts the 6FDA of 2.6656g after APB is completely dissolved, then treats that 6FDA is all added simultaneously
The GAPD of 0.0745g after dissolving, is added, the hBN of 0.9673g after mechanical agitation 30min, is added, continue stirring 50min, in situ poly-
Close to obtain hBN/PAA solution；HBN/PAA solution is loaded and is furnished with the 8ml injection needle of metal needle, then by injection needle water
Put down and be fixed on injection apparatus, the high voltage power supply positive electrode tab of electrostatic spinning machine is connected with metal needle, paper collected by tinfoil paper
It is coated on cylinder shape negative electrode, the center of injection needle aligns with drum, the operating room for keeping electrostatic spinning machine is sealing state,
And keeping work room temperature for 22 DEG C, electrostatic positive voltage is 25kV, and operating distance is 20cm, and envionmental humidity is 60%, connects
Receipts rotating speed is 40m/min, and electrostatic spinning obtains hBN/PAA heat conduction composite fiber felt, in vacuum drying oven 60 DEG C except solvent 4h after
By 120 DEG C/1h+200 DEG C/1h+250 DEG C/1h, heating rate carries out hot imidization for the program of 1 DEG C/min, takes after being down to room temperature
Go out, obtain hBN/PI heat conduction composite fiber felt；2.00g hBN/PI heat conduction composite fiber felt is cut to 20mm × 20mm sample dress
Enter in mould, compression molding on tablet vulcanizer prepares hBN/PI dielectric heat-conductive composite material, 320 DEG C of molding temperature, pressure
Power is 10MPa, and clamp time is 12min.
After tested, the λ of made hBN/PI dielectric heat-conductive composite material be 0.546W/mK, ε be 3.66, tan δ be 0.0060.
Embodiment 5：The APB of 1.6078g is put in the there-necked flask for being furnished with agitator and nitrogen conduit, ice-water bath condition
The DMAc of lower addition 16.2700g, is dividedly in some parts the 6FDA of 2.6656g after APB is completely dissolved, then treats that 6FDA is all added simultaneously
The GAPD of 0.0745g after dissolving, is added, the hBN of 0.5122g after mechanical agitation 30min, is added, continue stirring 40min, in situ poly-
Close to obtain hBN/PAA solution；HBN/PAA solution is loaded and is furnished with the 8ml injection needle of metal needle, then by injection needle water
Put down and be fixed on injection apparatus, the high voltage power supply positive electrode tab of electrostatic spinning machine is connected with metal needle, paper collected by tinfoil paper
It is coated on cylinder shape negative electrode, the center of injection needle aligns with drum, the operating room for keeping electrostatic spinning machine is sealing state,
And keeping work room temperature for 20 DEG C, electrostatic positive voltage is 20kV, and operating distance is 18cm, and envionmental humidity is 55%, connects
Receipts rotating speed is 40m/min, and electrostatic spinning obtains hBN/PAA heat conduction composite fiber felt, in vacuum drying oven 60 DEG C except solvent 4h after
By 120 DEG C/1h+200 DEG C/1h+250 DEG C/1h, heating rate carries out hot imidization for the program of 1 DEG C/min, takes after being down to room temperature
Go out, obtain hBN/PI heat conduction composite fiber felt；2.00g hBN/PI heat conduction composite fiber felt is cut to 20mm × 20mm sample dress
Enter in mould, compression molding on tablet vulcanizer prepares hBN/PI dielectric heat-conductive composite material, 300 DEG C of molding temperature, pressure
Power is 5MPa, and clamp time is 12min.
After tested, the λ of made hBN/PI dielectric heat-conductive composite material be 0.346W/mK, ε be 3.48, tan δ be 0.0050.
Embodiment 6：The APB of 1.6078g is put in the there-necked flask for being furnished with agitator and nitrogen conduit, ice-water bath condition
The DMAc of lower addition 17.9800g, is dividedly in some parts the 6FDA of 2.6656g after APB is completely dissolved, then treats that 6FDA is all added simultaneously
The GAPD of 0.0745g after dissolving, is added, the hBN of 0.7255g after mechanical agitation 30min, is added, continue stirring 45min, in situ poly-
Close to obtain hBN/PAA solution；HBN/PAA solution is loaded and is furnished with the 8ml injection needle of metal needle, then by injection needle water
Put down and be fixed on injection apparatus, the high voltage power supply positive electrode tab of electrostatic spinning machine is connected with metal needle, paper collected by tinfoil paper
It is coated on cylinder shape negative electrode, the center of injection needle aligns with drum, the operating room for keeping electrostatic spinning machine is sealing state,
And keeping work room temperature for 22 DEG C, electrostatic positive voltage is 25kV, and operating distance is 20cm, and envionmental humidity is 60%, connects
Receipts rotating speed is 40m/min, and electrostatic spinning obtains hBN/PAA heat conduction composite fiber felt, in vacuum drying oven 60 DEG C except solvent 4h after
By 120 DEG C/1h+200 DEG C/1h+250 DEG C/1h, heating rate carries out hot imidization for the program of 1 DEG C/min, takes after being down to room temperature
Go out, obtain hBN/PI heat conduction composite fiber felt；2.00g hBN/PI heat conduction composite fiber felt is cut to 20mm × 20mm sample dress
Enter in mould, compression molding on tablet vulcanizer prepares hBN/PI dielectric heat-conductive composite material, 310 DEG C of molding temperature, pressure
Power is 10MPa, and clamp time is 15min.
After tested, the λ of made hBN/PI dielectric heat-conductive composite material be 0.479W/mK, ε be 3.60, tan δ be 0.0056.
Claims (6)
1. a kind of polymide dielectric heat-conductive composite material, it is characterised in that：If using dried layer heat conduction composite fiber felt superimposed layer
Pressure is formed, the component of every layer of heat conduction composite fiber felt include the polyimides of 70～95 weight portions and 5～30 weight portions cube
Boron nitride.
2. the preparation method of polymide dielectric heat-conductive composite material described in a kind of claim 1, it is characterised in that including following
Step：
A two ether diamine of 1,3,4- triphenyl of 6.5～7.5 weight portions is mixed 75～86 weight portions under the conditions of ice-water bath by ()
DMAC N,N' dimethyl acetamide；After treating that 1,3,4- triphenyl, two ether diamine is completely dissolved, then divide 10.6～12.3 weights of addition several times
The double phthalic anhydrides of 4,4- (hexafluoro isopropyl) of amount part；Treat that the double phthalic anhydrides of 4,4- (hexafluoro isopropyl) are all added
And after dissolving, 1, the 3- diaminopropyl tetramethyl disiloxane of 0.29～0.34 weight portion of addition, mechanical agitation 30min；Plus
Enter the cubic boron nitride of 5～30 weight portions, continue 30～60min of stirring, it is molten that in-situ polymerization obtains cubic boron nitride/polyamic acid
Liquid；
B cubic boron nitride/polyamic acid solution is carried out electrostatic spinning by (), obtain cubic boron nitride/polyamic acid heat conduction and be combined
Fibrofelt；
C () cubic boron nitride/polyamic acid heat conduction composite fiber felt is removed at 60 DEG C of vacuum solvent 4h；Then with 1 DEG C/min
Heating rate be heated to 120 DEG C insulation 1h, with the heating rate of 1 DEG C/min be heated to 200 DEG C insulation 1h, with 1 DEG C/min's
Heating rate is heated to 250 DEG C of insulation 1h, carries out hot imidization；Take out after being down to room temperature, obtain cubic boron nitride/polyimides and lead
Hot composite fibrofelt；
If d dried layer cubic boron nitride/polyimides heat conduction composite fiber felt compression molding is obtained cubic boron nitride/polyamides by ()
Imines heat conduction composite fiber felt dielectric heat-conductive composite material；The temperature of the compression molding be 290～320 DEG C, pressure be 5～
10MPa, time are 10～15min.
3. the preparation method of polymide dielectric heat-conductive composite material according to claim 2, it is characterised in that：Described
In step (a), the double phthalic anhydrides of 4,4- (hexafluoro isopropyl) of interpolation add next batch after being completely dissolved every time
The double phthalic anhydrides of 4,4- (hexafluoro isopropyl).
4. the preparation method of polymide dielectric heat-conductive composite material according to claim 2, it is characterised in that：Described
In step (a), the weight of the double phthalic anhydrides of 4,4- (hexafluoro isopropyl) for adding every time is less than 0.2g.
5. the preparation method of polymide dielectric heat-conductive composite material according to claim 2, it is characterised in that：Described
In step (b), cubic boron nitride/polyamic acid solution is loaded and is furnished with the injection needle of metal needle, then by injection needle
Pipe is horizontally fixed on injection apparatus, and the high voltage power supply positive electrode of electrostatic spinning machine is connected with metal needle, and paper collected by tinfoil paper
It is coated on cylinder shape negative electrode, injection needle aligns with drum center, the operating room for keeping electrostatic spinning machine is sealing state, and
It is 18～25 DEG C to keep work room temperature, and envionmental humidity is 50%～60%, and high-voltage power voltage is 15kV～25kV, pin
Head is 15～20cm to the distance of centre of the drum, and the rotating speed of cylinder is 40m/min.
6. the preparation method of polymide dielectric heat-conductive composite material according to claim 2, it is characterised in that：Described
In step (d), cubic boron nitride/polyimides heat conduction composite fiber felt 2g is weighed, is cut into a size of sample of 20 × 20mm
Load in mould, compression molding on tablet vulcanizer.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750296A (en) * | 2017-03-20 | 2017-05-31 | 西北工业大学 | A kind of modified graphene/polyimides heat-conductive composite material and preparation method thereof |
| CN108239399A (en) * | 2018-01-29 | 2018-07-03 | 铜陵四通环境科技有限公司 | A kind of preparation method of high temperature resistant glass fibre reinforced plastic |
| CN108997754A (en) * | 2018-08-28 | 2018-12-14 | 武汉理工大学 | A kind of polyimides high-temperature dielectric composite membrane and preparation method thereof |
| CN109487630A (en) * | 2018-11-15 | 2019-03-19 | 东华大学 | A kind of polyimides extrusion coating paper of nano silicon nitride boron modification and its preparation and application |
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| CN110129994A (en) * | 2019-05-24 | 2019-08-16 | 东华大学 | Micro nanometer fiber film and preparation method thereof with efficient absorbent cooling function |
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| CN114750491A (en) * | 2022-05-24 | 2022-07-15 | 陕西科技大学 | Polydopamine modified boron nitride nanosheet/polyimide heat-conducting and insulating composite film and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277648A (en) * | 2011-05-30 | 2011-12-14 | 中国科学院青岛生物能源与过程研究所 | Inorganic/organic composite polyimide nanometer fibrous film, preparation method thereof and application thereof |
| KR101416614B1 (en) * | 2013-08-01 | 2014-07-08 | (주)에프티이앤이 | Polyimide nanofiber filter with excellent heat-resisting property and its method |
| CN104892968A (en) * | 2015-07-02 | 2015-09-09 | 河北工业大学 | Preparation method of high-heat-conduction hexagonal boron nitride/polyimide composite material |
-
2016
- 2016-10-09 CN CN201610880285.1A patent/CN106480533B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277648A (en) * | 2011-05-30 | 2011-12-14 | 中国科学院青岛生物能源与过程研究所 | Inorganic/organic composite polyimide nanometer fibrous film, preparation method thereof and application thereof |
| KR101416614B1 (en) * | 2013-08-01 | 2014-07-08 | (주)에프티이앤이 | Polyimide nanofiber filter with excellent heat-resisting property and its method |
| CN104892968A (en) * | 2015-07-02 | 2015-09-09 | 河北工业大学 | Preparation method of high-heat-conduction hexagonal boron nitride/polyimide composite material |
Non-Patent Citations (4)
| Title |
|---|
| PENGGANG LI ET AL: "Thermal and dielectric properties of electrospun fiber membranes from polyimides with different structural units", 《J.APPL.POLYM.SCI》 * |
| 李博弘等: "静电纺丝法制备聚酰亚胺/聚苯胺导电复合纤维膜", 《化学与粘合》 * |
| 杨娜等: "聚酰亚胺/氮化硼导热复合薄膜的制备与性能研究", 《2015年全国高分子学术论文报告会论文摘要集—主题J高性能高分子》 * |
| 杨曦等: "高导热聚酰亚胺/氮化硼复合材料的制备与表征", 《胶体与聚合物》 * |
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