CN108047447A - A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability - Google Patents

A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability Download PDF

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CN108047447A
CN108047447A CN201711290939.6A CN201711290939A CN108047447A CN 108047447 A CN108047447 A CN 108047447A CN 201711290939 A CN201711290939 A CN 201711290939A CN 108047447 A CN108047447 A CN 108047447A
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temperature
heating rate
kept
warming
laminated film
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刘晓旭
赵文君
李彦鹏
朱波
岳东
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Shaanxi University of Science and Technology
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Heilongjiang University of Science and Technology
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    • 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
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    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • 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
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract

A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability, it is related to a kind of preparation method of polyimide material laminated film.The invention aims to solve the problems, such as that the thermal conductivity of existing polyimides, Inverter fed motor life-span and tensile strength are low.Method：First, boron nitride nanometer pipe powder is prepared；2nd, in-situ polymerization obtains the polyimide material laminated film of high thermoelectricity capability.The thermal conductivity of the polyimide material laminated film of high thermoelectricity capability prepared by the present invention is 0.29Wm‑1K‑1~0.45Wm‑1K‑1, Inverter fed motor life-span is 2.9h~6.7h, and tensile property is 101MPa~126MPa.The present invention can obtain a kind of polyimide material laminated film of high thermoelectricity capability.

Description

A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability
Technical field
The present invention relates to a kind of preparation methods of polyimide material laminated film.
Background technology
Polyimides is a kind of higher high molecular material of industrialized heat resistance rating at present, because it has simultaneously Superior power, heat with insulation etc. comprehensive performances, therefore its can be used as film, coating, plastics, adhesive, foamed plastics, fiber, point It is widely used from film, aligning agent for liquid crystal, photoresist etc. in various high-technology fields, composite material is also electrical exhausted The fields such as edge, aerospace microelectronics have obtained large-scale application.But at present prepared by high-end polyimide-based composite material During technology is still researched and developed in by international coverage, the thermal conductivity and insulation performance of the composite material of polyimides are especially improved simultaneously It is still industry technology bottleneck.
The thermal conductivity of current pure domestic polyimides is 0.2Wm-1K-1Left and right, Inverter fed motor life-span are generally 2h~3h.With There are still larger gaps in comprehensive performance again for the external high-end Kapton of import.
The content of the invention
The invention aims to solve, the thermal conductivity of existing polyimides, Inverter fed motor life-span and tensile strength are low to ask Topic, and a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability is provided.
A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability, is specifically realized by the following steps 's：
First, boron nitride nanometer pipe powder is prepared：
1., by multi-walled carbon nanotube, B2O3Powder and the mixing of Mo powder, then 10min~30min is ground in mortar, obtain powder The mixture of shape；
Step 1 1. described in the mass ratio of multi-walled carbon nanotube and Mo powder be (0.3~0.8):1；
Step 1 1. described in B2O3The mass ratio of powder and Mo powder is (2~3):1；
2., powdered mixture is put into porcelain boat, then porcelain boat is put into pipe examination stove, then is filled with into tube furnace lazy Property gas, then under inert gas atmosphere with the heating rate of 3 DEG C/min~6 DEG C/min by tube furnace from room temperature to 1200 DEG C~1400 DEG C, then keep the temperature 2h~4h, then the temperature by tube furnace in the case where inert gas atmosphere and temperature is 1200 DEG C~1400 DEG C Degree is down to room temperature, obtains white crude；
3., white crude is added in the nitric acid that mass fraction is 68%, then low whipping speed for 100r/min~ 20min~40min is stirred to react under conditions of 200r/min, then is warming up to 50 DEG C, then the 1h~3h that flows back at 50 DEG C, then carry out Vacuum filtration, the nitric acid that removal mass fraction is 68%, obtains solid matter；Solid matter is cleaned 5 times using deionized water ~7 times, then 5h~8h is dried in the case where temperature is 50 DEG C~70 DEG C, then be ground, obtain boron nitride nanometer pipe powder；
Step 1 3. described in white crude quality and mass fraction be 68% the volume ratio of nitric acid be (0.5g ~2g):50mL；
2nd, in-situ polymerization：
1., by step 1 3. in obtained boron nitride nanometer pipe powder be added in dimethyl acetamide, then in stirring speed It spends to be stirred to react 2h~5h under 100r/min~300r/min, then 12h is ultrasonically treated in the case where ultrasonic power is 100W~500W ~for 24 hours, obtain boron nitride nano-tube dispersion liquid；
Step 2 1. described in boron nitride nano-tube dispersion liquid in boron nitride nano-tube mass fraction for 0.5%~ 5%；
2., add in diamines into boron nitride nano-tube dispersion liquid, then be ultrasonically treated in the case where ultrasonic power is 100W~300W 2h~6h, then low whipping speed add in dianhydrides 5 times~8 times for lower point of 100r/min~300r/min, then low whipping speed is 12h~for 24 hours is stirred under 100r/min~300r/min, obtains the solution containing polyamic acid and boron nitride nano-tube；
Step 2 2. described in the volume ratio of quality and boron nitride nano-tube dispersion liquid of diamines be 3g:(50mL~ 60mL)；
Step 2 2. described in diamines and dianhydride molar ratio be 1:1；
3., 2h~8h will be stood in the vacuum tank at room temperature of the solution containing polyamic acid and boron nitride nano-tube, then Curtain coating, spin coating or plastic film mulch on clean plate, then with the heating rate of 3 DEG C/min~6 DEG C/min from room temperature to 75 DEG C~ 85 DEG C, and 0.5h~1.5h is kept the temperature at 75 DEG C~85 DEG C；
115 DEG C~125 DEG C are warming up to from 75 DEG C~85 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min again, then 115 DEG C~125 DEG C at keep the temperature 0.5h~1.5h；
Again 145 DEG C~155 DEG C are warming up to from 115 DEG C~125 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 145 DEG C~155 DEG C；
Again 205 DEG C~215 DEG C are warming up to from 145 DEG C~155 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 205 DEG C~215 DEG C；
Again 235 DEG C~245 DEG C are warming up to from 205 DEG C~215 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 235 DEG C~245 DEG C；
Again 295 DEG C~305 DEG C are warming up to from 235 DEG C~245 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 295 DEG C~305 DEG C；
Again 345 DEG C~355 DEG C are warming up to from 295 DEG C~305 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 345 DEG C~355 DEG C；
Room temperature is naturally cooling to again, is demoulded, is obtained the polyimide material laminated film of high thermoelectricity capability；
Step 2 3. described in high thermoelectricity capability acid imide Material cladding film thickness be 40 μm~50 μm.
The principle of the present invention and advantage：
First, for the present invention by the use of boron nitride nanometer pipe powder as filler, the process to be flowed back by concentrated nitric acid not only removes gold Metal catalyst, while realize and the hydroxylated surface of boron nitride nano-tube is handled, it improves it and disperses in polyimide matrix, Its interaction with matrix is improved simultaneously, the polyimide material laminated film of high thermoelectricity capability can be obtained；
2nd, preparation process of the present invention is simple, is easy to industrialized production, the polyimide material THIN COMPOSITE of the high thermoelectricity capability Film can be widely used for the fields such as electric insulation and aerospace；
3rd, the thermal conductivity of the polyimide material laminated film of high thermoelectricity capability prepared by the present invention is 0.29Wm-1K-1~ 0.45Wm-1K-1, Inverter fed motor life-span is 2.9h~6.7h, and tensile property is 101MPa~126MPa.
The present invention can obtain a kind of polyimide material laminated film of high thermoelectricity capability.
Description of the drawings
Fig. 1 is that the polyimide material laminated film of high thermoelectricity capability prepared by embodiment one amplifies 20000 times of SEM Figure；
Fig. 2 is that the polyimide material laminated film of high thermoelectricity capability prepared by embodiment two amplifies 50000 times of SEM Figure；
Fig. 3 is the thermal conductivity figure of the polyimide material laminated film of high thermoelectricity capability, and A is comparative example system in Fig. 3 The thermal conductivity of standby polyimide material, B are the thermal conductivity of polyimide material laminated film prepared by embodiment one, and C is real The thermal conductivity of the polyimide material laminated film of the preparation of example two is applied, D is polyimide material THIN COMPOSITE prepared by embodiment three The thermal conductivity of film, E are the thermal conductivity of polyimide material laminated film prepared by example IV；
Fig. 4 is the Inverter fed motor life-span figure of the polyimide material laminated film of high thermoelectricity capability, and A is comparative example in 4 The Inverter fed motor life-span of the polyimide material of preparation, B are the Inverter fed motor of polyimide material laminated film prepared by embodiment one Service life, C are the Inverter fed motor life-span of polyimide material laminated film prepared by embodiment two, and D is polyamides prepared by embodiment three The Inverter fed motor life-span of imines material laminated film, E are the Inverter fed motor longevity of polyimide material laminated film prepared by example IV Life；
Fig. 5 is the tensile strength figure of the polyimide material laminated film of high thermoelectricity capability, and A is comparative example in Fig. 5 The tensile strength of the polyimide material of preparation, B are the tensile strength of polyimide material laminated film prepared by embodiment one, C is the tensile strength of polyimide material laminated film prepared by embodiment two, and D is polyimide material prepared by embodiment three The tensile strength of laminated film, E are the tensile strength of polyimide material laminated film prepared by example IV.
Specific embodiment
Specific embodiment one：Present embodiment is a kind of preparation of the polyimide material laminated film of high thermoelectricity capability Method is specifically realized by the following steps：
First, boron nitride nanometer pipe powder is prepared：
1., by multi-walled carbon nanotube, B2O3Powder and the mixing of Mo powder, then 10min~30min is ground in mortar, obtain powder The mixture of shape；
Step 1 1. described in the mass ratio of multi-walled carbon nanotube and Mo powder be (0.3~0.8):1；
Step 1 1. described in B2O3The mass ratio of powder and Mo powder is (2~3):1；
2., powdered mixture is put into porcelain boat, then porcelain boat is put into pipe examination stove, then is filled with into tube furnace lazy Property gas, then under inert gas atmosphere with the heating rate of 3 DEG C/min~6 DEG C/min by tube furnace from room temperature to 1200 DEG C~1400 DEG C, then keep the temperature 2h~4h, then the temperature by tube furnace in the case where inert gas atmosphere and temperature is 1200 DEG C~1400 DEG C Degree is down to room temperature, obtains white crude；
3., white crude is added in the nitric acid that mass fraction is 68%, then low whipping speed for 100r/min~ 20min~40min is stirred to react under conditions of 200r/min, then is warming up to 50 DEG C, then the 1h~3h that flows back at 50 DEG C, then carry out Vacuum filtration, the nitric acid that removal mass fraction is 68%, obtains solid matter；Solid matter is cleaned 5 times using deionized water ~7 times, then 5h~8h is dried in the case where temperature is 50 DEG C~70 DEG C, then be ground, obtain boron nitride nanometer pipe powder；
Step 1 3. described in white crude quality and mass fraction be 68% the volume ratio of nitric acid be (0.5g ~2g):50mL；
2nd, in-situ polymerization：
1., by step 1 3. in obtained boron nitride nanometer pipe powder be added in dimethyl acetamide, then in stirring speed It spends to be stirred to react 2h~5h under 100r/min~300r/min, then 12h is ultrasonically treated in the case where ultrasonic power is 100W~500W ~for 24 hours, obtain boron nitride nano-tube dispersion liquid；
Step 2 1. described in boron nitride nano-tube dispersion liquid in boron nitride nano-tube mass fraction for 0.5%~ 5%；
2., add in diamines into boron nitride nano-tube dispersion liquid, then be ultrasonically treated in the case where ultrasonic power is 100W~300W 2h~6h, then low whipping speed add in dianhydrides 5 times~8 times for lower point of 100r/min~300r/min, then low whipping speed is 12h~for 24 hours is stirred under 100r/min~300r/min, obtains the solution containing polyamic acid and boron nitride nano-tube；
Step 2 2. described in the volume ratio of quality and boron nitride nano-tube dispersion liquid of diamines be 3g:(50mL~ 60mL)；
Step 2 2. described in diamines and dianhydride molar ratio be 1:1；
3., 2h~8h will be stood in the vacuum tank at room temperature of the solution containing polyamic acid and boron nitride nano-tube, then Curtain coating, spin coating or plastic film mulch on clean plate, then with the heating rate of 3 DEG C/min~6 DEG C/min from room temperature to 75 DEG C~ 85 DEG C, and 0.5h~1.5h is kept the temperature at 75 DEG C~85 DEG C；
115 DEG C~125 DEG C are warming up to from 75 DEG C~85 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min again, then 115 DEG C~125 DEG C at keep the temperature 0.5h~1.5h；
Again 145 DEG C~155 DEG C are warming up to from 115 DEG C~125 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 145 DEG C~155 DEG C；
Again 205 DEG C~215 DEG C are warming up to from 145 DEG C~155 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 205 DEG C~215 DEG C；
Again 235 DEG C~245 DEG C are warming up to from 205 DEG C~215 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 235 DEG C~245 DEG C；
Again 295 DEG C~305 DEG C are warming up to from 235 DEG C~245 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 295 DEG C~305 DEG C；
Again 345 DEG C~355 DEG C are warming up to from 295 DEG C~305 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min, then 0.5h~1.5h is kept the temperature at 345 DEG C~355 DEG C；
Room temperature is naturally cooling to again, is demoulded, is obtained the polyimide material laminated film of high thermoelectricity capability；
Step 2 3. described in high thermoelectricity capability acid imide Material cladding film thickness be 40 μm~50 μm.
The principle and advantage of present embodiment：
First, present embodiment by the use of boron nitride nanometer pipe powder as filler, not only go by the process to be flowed back by concentrated nitric acid It except metallic catalyst, while realizes and the hydroxylated surface of boron nitride nano-tube is handled, improve it in polyimide matrix It is scattered, while its interaction with matrix is improved, the polyimide material laminated film of high thermoelectricity capability can be obtained；
2nd, present embodiment preparation process is simple, is easy to industrialized production, and the polyimide material of the high thermoelectricity capability is answered It closes film and can be widely used for the fields such as electric insulation and aerospace；
3rd, the thermal conductivity of the polyimide material laminated film of high thermoelectricity capability prepared by present embodiment is 0.29Wm- 1K-1~0.45Wm-1K-1, Inverter fed motor life-span is 2.9h~6.7h, and tensile property is 101MPa~126MPa.
Present embodiment can obtain a kind of polyimide material laminated film of high thermoelectricity capability.
Specific embodiment two：Present embodiment is with one difference of specific embodiment：Step 1 1. described in it is more The mass ratio of wall carbon nano tube and Mo powder is (0.3~0.5):1.Other steps are same as the specific embodiment one.
Specific embodiment three：Present embodiment is with one of specific embodiment one or two difference：Step 1 1. in The B2O3The mass ratio of powder and Mo powder is (2~2.5):1.Other steps are the same as one or two specific embodiments.
Specific embodiment four：Present embodiment is with one of specific embodiment one to three difference：Step 1 2. in Powdered mixture is put into porcelain boat, then porcelain boat is put into pipe examination stove, then inert gas is filled with into tube furnace, then Under inert gas atmosphere with the heating rate of 3 DEG C/min~5 DEG C/min by tube furnace from room temperature to 1200 DEG C~1300 DEG C, 2h~3h is kept the temperature in the case where inert gas atmosphere and temperature is 1200 DEG C~1300 DEG C again, then the temperature of tube furnace is down to room temperature, Obtain white crude.Other steps are identical with specific embodiment one to three.
Specific embodiment five：Present embodiment is with one of specific embodiment one to four difference：Step 1 3. in The volume ratio for the nitric acid that the quality of the white crude is 68% with mass fraction is (0.5g~1g):50mL.Other steps Suddenly it is identical with specific embodiment one to four.
Specific embodiment six：Present embodiment is with one of specific embodiment one to five difference：Step 2 1. in The mass fraction of boron nitride nano-tube is 1%~3% in the boron nitride nano-tube dispersion liquid.Other steps and specific implementation Mode one to five is identical.
Specific embodiment seven：Present embodiment is with one of specific embodiment one to six difference：Step 2 2. in The diamines is 4,4 '-diaminodiphenyl ether.Other steps are identical with specific embodiment one to six.
Specific embodiment eight：Present embodiment is with one of specific embodiment one to seven difference：Step 2 2. in The dianhydride is biphenyl type dianhydride or equal benzene-type dianhydride；The biphenyl type dianhydride be 3,3', 4,4'- biphenyltetracarboxyacid acids two Acid anhydride；The equal benzene-type dianhydride is pyromellitic acid anhydride.Other steps are identical with specific embodiment one to seven.
Specific embodiment nine：Present embodiment is with one of specific embodiment one to eight difference：Step 2 3. in Will in the vacuum tank of the solution containing polyamic acid and boron nitride nano-tube at room temperature stand 2h~6h, then be cast, spin coating or Plastic film mulch is on clean plate, then with the heating rate of 3 DEG C/min~5 DEG C/min from room temperature to 75 DEG C~80 DEG C, and 75 DEG C~80 DEG C at keep the temperature 0.5h~1h；
115 DEG C~120 DEG C are warming up to from 75 DEG C~80 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min again, then 115 DEG C~120 DEG C at keep the temperature 0.5h~1h；
Again 145 DEG C~150 DEG C are warming up to from 115 DEG C~120 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min, then 0.5h~1h is kept the temperature at 145 DEG C~150 DEG C；
Again 205 DEG C~210 DEG C are warming up to from 145 DEG C~150 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min, then 0.5h~1h is kept the temperature at 205 DEG C~210 DEG C；
Again 235 DEG C~240 DEG C are warming up to from 205 DEG C~210 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min, then 0.5h~1h is kept the temperature at 235 DEG C~240 DEG C；
Again 295 DEG C~300 DEG C are warming up to from 235 DEG C~240 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min, then 0.5h~1h is kept the temperature at 295 DEG C~300 DEG C；
Again 345 DEG C~350 DEG C are warming up to from 295 DEG C~300 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min, then 0.5h~1h is kept the temperature at 345 DEG C~350 DEG C；
Room temperature is naturally cooling to again, is demoulded, is obtained the polyimide material laminated film of high thermoelectricity capability.Other steps with Specific embodiment one to eight is identical.
Specific embodiment ten：Present embodiment is with one of specific embodiment one to nine difference：Step 2 3. in Will in the vacuum tank of the solution containing polyamic acid and boron nitride nano-tube at room temperature stand 6h~8h, then be cast, spin coating or Plastic film mulch is on clean plate, then with the heating rate of 5 DEG C/min~6 DEG C/min from room temperature to 80 DEG C~85 DEG C, and 80 DEG C~85 DEG C at keep the temperature 1h~1.5h；
120 DEG C~125 DEG C are warming up to from 80 DEG C~85 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min again, then 120 DEG C~125 DEG C at keep the temperature 1h~1.5h；
Again 150 DEG C~155 DEG C are warming up to from 120 DEG C~125 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min, then 1h~1.5h is kept the temperature at 150 DEG C~155 DEG C；
Again 210 DEG C~215 DEG C are warming up to from 150 DEG C~155 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min, then 1h~1.5h is kept the temperature at 210 DEG C~215 DEG C；
Again 240 DEG C~245 DEG C are warming up to from 210 DEG C~215 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min, then 1h~1.5h is kept the temperature at 240 DEG C~245 DEG C；
Again 300 DEG C~305 DEG C are warming up to from 240 DEG C~245 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min, then 1h~1.5h is kept the temperature at 300 DEG C~305 DEG C；
Again 350 DEG C~355 DEG C are warming up to from 300 DEG C~305 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min, then 1h~1.5h is kept the temperature at 350 DEG C~355 DEG C；
Room temperature is naturally cooling to again, is demoulded, is obtained the polyimide material laminated film of high thermoelectricity capability.Other steps with Specific embodiment one to nine is identical.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment one：A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability, specifically by following What step was completed：
First, boron nitride nanometer pipe powder is prepared：
1., by 0.5g multi-walled carbon nanotubes, 2.5g B2O3Powder and the mixing of 1g Mo powder, then 20min is ground in mortar, it obtains To powdered mixture；
2., powdered mixture is put into porcelain boat, then porcelain boat is put into pipe examination stove, then is filled with into tube furnace lazy Property gas, then under inert gas atmosphere with the heating rate of 5 DEG C/min by tube furnace from room temperature to 1300 DEG C, then lazy Property gas atmosphere and temperature to keep the temperature 3h at 1300 DEG C, then the temperature of tube furnace is down to room temperature, obtains white crude；
3., 1g white crudes are added in the nitric acid that 50mL mass fractions are 68%, then low whipping speed is 100r/ 30min is stirred to react under conditions of min, then is warming up to 50 DEG C, then the 2h that flows back at 50 DEG C, then be filtered by vacuum, remove matter The nitric acid that fraction is 68% is measured, obtains solid matter；Using deionized water to solid matter clean 5 times, then temperature be 60 DEG C Lower drying 6h, then be ground, obtain boron nitride nanometer pipe powder；
2nd, in-situ polymerization：
1., by step 1 3. in obtained boron nitride nanometer pipe powder be added in dimethyl acetamide, then in stirring speed It spends to be stirred to react 3h under 100r/min, then 16h is ultrasonically treated in the case where ultrasonic power is 300W, obtain boron nitride nano-tube and disperse Liquid；
Step 2 1. described in boron nitride nano-tube dispersion liquid in boron nitride nano-tube mass fraction be 0.5%；
2., add in diamines into boron nitride nano-tube dispersion liquid, then 4h is ultrasonically treated in the case where ultrasonic power is 300W, then Mixing speed is obtained to stir 16h under 200r/min containing poly- for lower point of 6 addition dianhydrides of 100r/min, then low whipping speed The solution of amic acid and boron nitride nano-tube；
Step 2 2. described in diamines be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride be pyromellitic acid anhydride；
Step 2 2. described in the volume ratio of quality and boron nitride nano-tube dispersion liquid of diamines be 3g:55mL；
Step 2 2. described in diamines and dianhydride molar ratio be 1:1；
3., 4h, then spin coating will be stood in the vacuum tank at room temperature of the solution containing polyamic acid and boron nitride nano-tube In on clean plate, then with the heating rate of 5 DEG C/min from room temperature to 80 DEG C, and 1h is kept the temperature at 80 DEG C；
120 DEG C are warming up to from 80 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 120 DEG C；
150 DEG C are warming up to from 120 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 150 DEG C；
210 DEG C are warming up to from 150 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 210 DEG C；
240 DEG C are warming up to from 210 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 240 DEG C；
300 DEG C are warming up to from 240 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 300 DEG C；
350 DEG C are warming up to from 300 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 350 DEG C；
Room temperature is naturally cooling to again, is demoulded, is obtained the polyimide material laminated film of high thermoelectricity capability；
Step 2 3. described in high thermoelectricity capability acid imide Material cladding film thickness be 50 μm.
Embodiment two：The present embodiment and the difference of embodiment one are：Step 2 1. described in boron nitride nano-tube point The mass fraction of boron nitride nano-tube is 1% in dispersion liquid.Other steps and parameter and one all same of embodiment.
Embodiment three：The present embodiment and the difference of embodiment one are：Step 2 1. described in boron nitride nano-tube point The mass fraction of boron nitride nano-tube is 3% in dispersion liquid.Other steps and parameter and one all same of embodiment.
Example IV：The present embodiment and the difference of embodiment one are：Step 2 1. described in boron nitride nano-tube point The mass fraction of boron nitride nano-tube is 5% in dispersion liquid.Other steps and parameter and one all same of embodiment.
Comparative example：Polyimide material is prepared according to the following steps：A kind of polyimides material of high thermoelectricity capability Expect the preparation method of laminated film, be specifically realized by the following steps：
First, diamines is added in dimethyl acetamide, then 4h is ultrasonically treated in the case where ultrasonic power is 300W, then stirred Speed is obtained to stir 16h under 200r/min containing polyamide for lower point of 6 addition dianhydrides of 100r/min, then low whipping speed The solution of acid；
The quality of diamines described in step 1 and the volume ratio of dimethyl acetamide are 3g:55mL；
The molar ratio of diamines and dianhydride described in step 1 is 1:1；
Diamines described in step 1 is 4,4 '-diaminodiphenyl ether；
Dianhydride described in step 1 is pyromellitic acid anhydride；
2nd, 4h will be stood in the vacuum tank at room temperature of the solution containing polyamic acid, then be spun on clean plate, then With the heating rate of 5 DEG C/min from room temperature to 80 DEG C, and 1h is kept the temperature at 80 DEG C；
120 DEG C are warming up to from 80 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 120 DEG C；
150 DEG C are warming up to from 120 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 150 DEG C；
210 DEG C are warming up to from 150 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 210 DEG C；
240 DEG C are warming up to from 210 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 240 DEG C；
300 DEG C are warming up to from 240 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 300 DEG C；
350 DEG C are warming up to from 300 DEG C with the heating rate of 5 DEG C/min again, then 1h is kept the temperature at 350 DEG C；
Room temperature is naturally cooling to again, is demoulded, is obtained polyimide material；
The thickness of polyimide material described in step 2 is 50 μm.
Fig. 1 is that the polyimide material laminated film of high thermoelectricity capability prepared by embodiment one amplifies 20000 times of SEM Figure；
From fig. 1, it can be seen that when the mass fraction of boron nitride nano-tube in boron nitride nano-tube dispersion liquid is 0.5%, nitridation Boron nanotube is wrapped to form extremely uniform aggregated structure by polyimide molecule chain, and boron nitride nano-tube is in the composite And its be uniformly uniformly dispersed, boron nitride nano-tube and polyimides two-phase compatibility are good.
Fig. 2 is that the polyimide material laminated film of high thermoelectricity capability prepared by embodiment two amplifies 50000 times of SEM Figure；
As can be seen from Figure 2, when the mass fraction of boron nitride nano-tube in boron nitride nano-tube dispersion liquid doubles, reach When 1%, the dispersiveness in polyimide matrix is not substantially change, it is seen that boron nitride nano-tube is polyimide-based There are good dispersivenesses in body.
The polyimide material laminated film of high thermoelectricity capability is made into thickness as 1mm, the disk of a diameter of 10mm, in room The thermal conductivity of the polyimide material laminated film of the high thermoelectricity capability of the lower test of temperature, as shown in Figure 3；
Fig. 3 is the thermal conductivity figure of the polyimide material laminated film of high thermoelectricity capability, and A is comparative example system in Fig. 3 The thermal conductivity of standby polyimide material, B are the thermal conductivity of polyimide material laminated film prepared by embodiment one, and C is real The thermal conductivity of the polyimide material laminated film of the preparation of example two is applied, D is polyimide material THIN COMPOSITE prepared by embodiment three The thermal conductivity of film, E are the thermal conductivity of polyimide material laminated film prepared by example IV；
As can be seen from Figure 3, the addition of boron nitride nano-tube effectively improves the heat conductivility of composite material, in micro addition nitrogen Change boron nanotube, when component is 0.5%, thermal conductivity factor is obviously improved, and is when component reaches 5%, and thermal conductivity factor is promoted near 80%.
According to International Electrotechnical Commission thin-film material Inverter fed motor aging life-span testing standard IEC-60343, test field strength is 80Kv/mm, the Inverter fed motor aging life-span of polyimide material laminated film and polyimide material to high thermoelectricity capability carry out Test, as shown in Figure 4；
Fig. 4 is the Inverter fed motor life-span figure of the polyimide material laminated film of high thermoelectricity capability, and A is comparative example in 4 The Inverter fed motor life-span of the polyimide material of preparation, B are the Inverter fed motor of polyimide material laminated film prepared by embodiment one Service life, C are the Inverter fed motor life-span of polyimide material laminated film prepared by embodiment two, and D is polyamides prepared by embodiment three The Inverter fed motor life-span of imines material laminated film, E are the Inverter fed motor longevity of polyimide material laminated film prepared by example IV Life；
As can be seen from Figure 4, the addition of boron nitride nano-tube not only promotes the heat conductivility of composite material, also greatly improves In the corona aging service life of composite material, when component reaches 5%, the corona aging service life almost improves about 2 times.
Fig. 5 is the tensile strength figure of the polyimide material laminated film of high thermoelectricity capability, and A is comparative example in Fig. 5 The tensile strength of the polyimide material of preparation, B are the tensile strength of polyimide material laminated film prepared by embodiment one, C is the tensile strength of polyimide material laminated film prepared by embodiment two, and D is polyimide material prepared by embodiment three The tensile strength of laminated film, E are the tensile strength of polyimide material laminated film prepared by example IV；
As can be seen from Figure 5, it is compound when the mass fraction of boron nitride nano-tube in boron nitride nano-tube dispersion liquid is less than 3% The tensile strength of material is obviously improved, when the mass fraction of boron nitride nano-tube in boron nitride nano-tube dispersion liquid is When 1%, the tensile strength of composite material about improves 25%, even if component further increases, the tensile strength of composite material Significant deterioration does not occur yet.

Claims (10)

  1. A kind of a kind of 1. preparation method of the polyimide material laminated film of high thermoelectricity capability, it is characterised in that high thermoelectricity capability The preparation method of polyimide material laminated film be specifically realized by the following steps：
    First, boron nitride nanometer pipe powder is prepared：
    1., by multi-walled carbon nanotube, B2O3Powder and the mixing of Mo powder, then 10min~30min is ground in mortar, it obtains powdered Mixture；
    Step 1 1. described in the mass ratio of multi-walled carbon nanotube and Mo powder be (0.3~0.8):1；
    Step 1 1. described in B2O3The mass ratio of powder and Mo powder is (2~3):1；
    2., powdered mixture is put into porcelain boat, then porcelain boat is put into pipe examination stove, then indifferent gas is filled with into tube furnace Body, then under inert gas atmosphere with the heating rate of 3 DEG C/min~6 DEG C/min by tube furnace from room temperature to 1200 DEG C~ 1400 DEG C, then 2h~4h is kept the temperature in the case where inert gas atmosphere and temperature is 1200 DEG C~1400 DEG C, then the temperature of tube furnace is dropped To room temperature, white crude is obtained；
    3., white crude is added in the nitric acid that mass fraction is 68%, then low whipping speed is 100r/min~200r/ 20min~40min is stirred to react under conditions of min, then is warming up to 50 DEG C, then the 1h~3h that flows back at 50 DEG C, then carry out vacuum It filters, the nitric acid that removal mass fraction is 68% obtains solid matter；Using deionized water to solid matter cleaning 5 times~7 It is secondary, then 5h~8h is dried in the case where temperature is 50 DEG C~70 DEG C, then be ground, obtain boron nitride nanometer pipe powder；
    Step 1 3. described in white crude quality and mass fraction be 68% nitric acid volume ratio for (0.5g~ 2g):50mL；
    2nd, in-situ polymerization：
    1., by step 1 3. in obtained boron nitride nanometer pipe powder be added in dimethyl acetamide, then low whipping speed is Be stirred to react 2h~5h under 100r/min~300r/min, then be ultrasonically treated in the case where ultrasonic power is 100W~500W 12h~ For 24 hours, boron nitride nano-tube dispersion liquid is obtained；
    Step 2 1. described in boron nitride nano-tube dispersion liquid in boron nitride nano-tube mass fraction be 0.5%~5%；
    2., add in diamines into boron nitride nano-tube dispersion liquid, then be ultrasonically treated in the case where ultrasonic power is 100W~300W 2h~ 6h, then low whipping speed are lower point of 5 times~8 times addition dianhydrides of 100r/min~300r/min, then low whipping speed is 100r/ 12h~for 24 hours is stirred under min~300r/min, obtains the solution containing polyamic acid and boron nitride nano-tube；
    Step 2 2. described in the volume ratio of quality and boron nitride nano-tube dispersion liquid of diamines be 3g:(50mL~60mL)；
    Step 2 2. described in diamines and dianhydride molar ratio be 1:1；
    3., 2h~8h will be stood in the vacuum tank at room temperature of the solution containing polyamic acid and boron nitride nano-tube, then be cast, Spin coating or plastic film mulch are on clean plate, then with the heating rate of 3 DEG C/min~6 DEG C/min from room temperature to 75 DEG C~85 DEG C, And 0.5h~1.5h is kept the temperature at 75 DEG C~85 DEG C；
    Be warming up to 115 DEG C~125 DEG C from 75 DEG C~85 DEG C again with the heating rate of 3 DEG C/min~6 DEG C/min, then 115 DEG C~ 0.5h~1.5h is kept the temperature at 125 DEG C；
    145 DEG C~155 DEG C are warming up to from 115 DEG C~125 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min again, then at 145 DEG C 0.5h~1.5h is kept the temperature at~155 DEG C；
    205 DEG C~215 DEG C are warming up to from 145 DEG C~155 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min again, then at 205 DEG C 0.5h~1.5h is kept the temperature at~215 DEG C；
    235 DEG C~245 DEG C are warming up to from 205 DEG C~215 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min again, then at 235 DEG C 0.5h~1.5h is kept the temperature at~245 DEG C；
    295 DEG C~305 DEG C are warming up to from 235 DEG C~245 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min again, then at 295 DEG C 0.5h~1.5h is kept the temperature at~305 DEG C；
    345 DEG C~355 DEG C are warming up to from 295 DEG C~305 DEG C with the heating rate of 3 DEG C/min~6 DEG C/min again, then at 345 DEG C 0.5h~1.5h is kept the temperature at~355 DEG C；
    Room temperature is naturally cooling to again, is demoulded, is obtained the polyimide material laminated film of high thermoelectricity capability；
    Step 2 3. described in high thermoelectricity capability acid imide Material cladding film thickness be 40 μm~50 μm.
  2. 2. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special The mass ratio for levying the multi-walled carbon nanotube described in being step 1 1. and Mo powder is (0.3~0.5):1.
  3. 3. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special Levy the B described in being step 1 1.2O3The mass ratio of powder and Mo powder is (2~2.5):1.
  4. 4. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special Sign in step 1 2. in powdered mixture is put into porcelain boat, then porcelain boat is put into pipe examination stove, then into tube furnace Be filled with inert gas, then under inert gas atmosphere with the heating rate of 3 DEG C/min~5 DEG C/min by tube furnace from room temperature To 1200 DEG C~1300 DEG C, then 2h~3h is kept the temperature in the case where inert gas atmosphere and temperature is 1200 DEG C~1300 DEG C, then by tubular type The temperature of stove is down to room temperature, obtains white crude.
  5. 5. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special Sign be step 1 3. described in white crude quality and mass fraction be 68% nitric acid volume ratio for (0.5g~ 1g):50mL。
  6. 6. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special Levy in step 2 1. described in boron nitride nano-tube dispersion liquid in boron nitride nano-tube mass fraction be 1%~3%.
  7. 7. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special It is 4,4 '-diaminodiphenyl ether to levy the diamines described in being step 2 2..
  8. 8. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special It is biphenyl type dianhydride or equal benzene-type dianhydride to levy the dianhydride described in being step 2 2.；The biphenyl type dianhydride be 3,3', 4, 4'- biphenyl tetracarboxylic dianhydrides；The equal benzene-type dianhydride is pyromellitic acid anhydride.
  9. 9. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special Levy in step 2 3. in will be stood in the vacuum tank at room temperature of the solution containing polyamic acid and boron nitride nano-tube 2h~ 6h, then be cast, spin coating or plastic film mulch are on clean plate, then with the heating rate of 3 DEG C/min~5 DEG C/min from room temperature to 75 DEG C~80 DEG C, and 0.5h~1h is kept the temperature at 75 DEG C~80 DEG C；
    Be warming up to 115 DEG C~120 DEG C from 75 DEG C~80 DEG C again with the heating rate of 3 DEG C/min~5 DEG C/min, then 115 DEG C~ 0.5h~1h is kept the temperature at 120 DEG C；
    145 DEG C~150 DEG C are warming up to from 115 DEG C~120 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min again, then at 145 DEG C 0.5h~1h is kept the temperature at~150 DEG C；
    205 DEG C~210 DEG C are warming up to from 145 DEG C~150 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min again, then at 205 DEG C 0.5h~1h is kept the temperature at~210 DEG C；
    235 DEG C~240 DEG C are warming up to from 205 DEG C~210 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min again, then at 235 DEG C 0.5h~1h is kept the temperature at~240 DEG C；
    295 DEG C~300 DEG C are warming up to from 235 DEG C~240 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min again, then at 295 DEG C 0.5h~1h is kept the temperature at~300 DEG C；
    345 DEG C~350 DEG C are warming up to from 295 DEG C~300 DEG C with the heating rate of 3 DEG C/min~5 DEG C/min again, then at 345 DEG C 0.5h~1h is kept the temperature at~350 DEG C；
    Room temperature is naturally cooling to again, is demoulded, is obtained the polyimide material laminated film of high thermoelectricity capability.
  10. 10. a kind of preparation method of the polyimide material laminated film of high thermoelectricity capability according to claim 1, special Levy in step 2 3. in will be stood in the vacuum tank at room temperature of the solution containing polyamic acid and boron nitride nano-tube 6h~ 8h, then be cast, spin coating or plastic film mulch are on clean plate, then with the heating rate of 5 DEG C/min~6 DEG C/min from room temperature to 80 DEG C~85 DEG C, and 1h~1.5h is kept the temperature at 80 DEG C~85 DEG C；
    Be warming up to 120 DEG C~125 DEG C from 80 DEG C~85 DEG C again with the heating rate of 5 DEG C/min~6 DEG C/min, then 120 DEG C~ 1h~1.5h is kept the temperature at 125 DEG C；
    150 DEG C~155 DEG C are warming up to from 120 DEG C~125 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min again, then at 150 DEG C 1h~1.5h is kept the temperature at~155 DEG C；
    210 DEG C~215 DEG C are warming up to from 150 DEG C~155 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min again, then at 210 DEG C 1h~1.5h is kept the temperature at~215 DEG C；
    240 DEG C~245 DEG C are warming up to from 210 DEG C~215 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min again, then at 240 DEG C 1h~1.5h is kept the temperature at~245 DEG C；
    300 DEG C~305 DEG C are warming up to from 240 DEG C~245 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min again, then at 300 DEG C 1h~1.5h is kept the temperature at~305 DEG C；
    350 DEG C~355 DEG C are warming up to from 300 DEG C~305 DEG C with the heating rate of 5 DEG C/min~6 DEG C/min again, then at 350 DEG C 1h~1.5h is kept the temperature at~355 DEG C；
    Room temperature is naturally cooling to again, is demoulded, is obtained the polyimide material laminated film of high thermoelectricity capability.
CN201711290939.6A 2017-12-07 2017-12-07 A kind of preparation method of the polyimide material laminated film of high thermoelectricity capability Pending CN108047447A (en)

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