CN106084219B - A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film - Google Patents
A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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Abstract
A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film, it is related to a kind of method for preparing laminated film.The invention aims to further reduce pure polymide dielectric constant, its electrical insulation capability and mechanical property are improved, solves the problems, such as that it is restricted in special dimension application.Method：First, ultrathin boron nitride powder is prepared；2nd, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film, obtains high-performance polyimide/ultrathin boron nitride laminated film.High-performance polyimide prepared by the present invention/ultrathin boron nitride laminated film has promotion, and simple for process on power, heat, electrical property, is easy to amplify industrialized production.The present invention can obtain a kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film.
Description
Technical field
The present invention relates to a kind of methods for preparing laminated film.
Background technology
As electric insulation and power electronics, a member in the speciality polymer material of aerospace, polyimides is with it
It the features such as excellent thermal stability, mechanical performance and high temperature insulation characteristic, is studied extensively by scholars and industrial quarters.It is but traditional
There is also some shortcomings for pure polyimides, limit its application in some special dimensions, if it is used in microelectronic circuits plate,
Dielectric constant is relatively high, this will bring a large amount of energy loss；Its electrical insulation capability can't fully meet variable-frequency motor
The insulation in the fields of grade needs, and product demand of the China in the field also relies primarily on imported from America；To improve it in various applications
The service life in field, mechanical property still need further to be improved.Therefore, polyimides excellent properties itself are being utilized
Under the premise of, further improve the comprehensive performances such as polyimides power, heat, electricity and still widely closed in academia and engineer application field
Note and research.
Invention content
The invention aims to further reduce pure polymide dielectric constant, its electrical insulation capability and mechanical property are improved
Can, solve the problems, such as that it is restricted in special dimension application, and it is compound to provide a kind of high-performance polyimide/ultrathin boron nitride
The preparation method of film.
A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film, is completed according to the following steps：
First, ultrathin boron nitride powder is prepared：
1., boron nitride powder and oxide be added in concentrated acid, then ice-water bath and mixing speed 100r/min~
60min~120min is stirred to react under 300r/min, obtains mixture A；Mixture A is heated to 50 DEG C, then in temperature is 50
DEG C and mixing speed to be stirred to react 60min~180min under 100r/min~300r/min, be cooled to room temperature, then to mixing
Mass fraction is instilled as 85% hydrogen peroxide solution using the rate of addition of 1mL/min in object A, obtains mixture B；In ice-water bath
Under, deionized water is added in into mixture B, obtains mixture C；Again by mixture C centrifugal speed for 6000r/min~
5min~15min is centrifuged under 8000r/min, centrifugate is removed, obtains the presoma of thin layer boron nitride；It uses first
The presoma of the hydrochloric acid cleaning thin layer boron nitride of 0.5mol/L 3 times reuses the presoma 5 of deionized water cleaning thin layer boron nitride
It is secondary~8 times, the presoma of the thin layer boron nitride after being cleaned；
Step 1 1. described in boron nitride powder quality and concentrated acid volume ratio be (4g~8g):400mL；
Step 1 1. described in oxide quality and concentrated acid volume ratio be (20g~40g):400mL；
Step 1 1. described in concentrated acid and mass fraction be 85% the volume ratio of hydrogen peroxide solution be 400：(5~
10)；
Step 1 1. described in concentrated acid and deionized water volume ratio be 400:(300~400)；
2., by the presoma of the thin layer boron nitride after cleaning in temperature be vacuum drying 12h at 80 DEG C~100 DEG C~for 24 hours,
Obtain the presoma of dried thin layer boron nitride；The presoma of dried thin layer boron nitride is added in organic solvent,
It is again ultrasound 12h under 100W~500W~for 24 hours in ultrasonic power, obtains the precursor solution of thin layer boron nitride；In centrifugal speed
To centrifuge 5min~10min to the precursor solution of thin layer boron nitride, then take upper strata centrifugate under 3000r/min, obtain
Superthin layer nitrogenizes B solution；Superthin layer nitridation B solution is filtered by vacuum, then by the solid matter obtained after suction filtration in temperature
It is that 12h~for 24 hours is dried in vacuo at 80 DEG C~100 DEG C to spend, and obtains superthin layer boron nitride powder；
Step 1 2. described in dried thin layer boron nitride the quality of presoma and the volume ratio of organic solvent be
(1g~3g):100mL；
2nd, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film：
1., by step 1 2. in obtained superthin layer boron nitride powder be dissolved into organic solvent, obtaining mass fraction is
0.25%~5% ultrathin boron nitride solution；
2., diamines be added to the superthin layer that mass fraction is 0.25%~5% nitrogenize in B solution, then low whipping speed
It is ultrasound 12h under 100W~500W to be stirred to react 60min~120min under 100r/min~300r/min, then in ultrasonic power
~for 24 hours, obtain diamine solution；Again by dianhydride powder under conditions of ice-water bath and mixing speed is 100r/min~300r/min
Divide 5 times and be added in diamine solution, obtain the thick solution containing polyamic acid and superthin layer boron nitride；
Step 2 2. described in diamines quality and mass fraction be 0.25%~3% superthin layer nitrogenize B solution
Volume ratio is 3g:(40mL~60mL)；
Step 2 2. described in dianhydride and diamines molar ratio be 1:1；
3., 2h will be stood in the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature
~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
350 DEG C, then 1h~2h is kept the temperature at 350 DEG C, then cooled to room temperature finally demoulds, and obtains high-performance polyimide/ultra-thin
Boron nitride laminated film；
Step 2 3. described in high-performance polyimide/ultrathin boron nitride laminated film thickness be 30 μm~50 μm.
The principle of the present invention and advantage：
First, the present invention is presoma using a kind of high heat conduction hexagonal boron nitride particles, is then prepared using chemical method ultra-thin
Layer boron nitride piece improves the dispersibility in hexagonal boron nitride and organic solvent, so solve hexagonal boron nitride with it is polyimide-based
The problems such as compatability is poor, and interface resistance is big, last in-situ polymerization synthesized high-performance polyimides/ultrathin boron nitride THIN COMPOSITE
Film this to expand polyimide-based composite material new application prospect be of great significance；
2nd, high-performance polyimide/ultrathin boron nitride laminated film prepared by the present invention has on power, heat, electrical property
It is promoted, and simple for process, is easy to amplify industrialized production；
3rd, the tensile strength of high-performance polyimide/ultrathin boron nitride laminated film prepared by the present invention is more than 150MPa；
4th, the dielectric constant of high-performance polyimide/ultrathin boron nitride laminated film prepared by the present invention is minimum
3.2, the dielectric constant than pure Kapton reduces 6%；
5th, the Inverter fed motor life-span of high-performance polyimide/ultrathin boron nitride laminated film for preparing of the present invention for 4.9h~
5.9h, the resistivity than Kapton improve 1.3 times~1.8 times；
The present invention can obtain a kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film.
Description of the drawings
Fig. 1 is the TEM figures of superthin layer boron nitride powder prepared by one step 1 of embodiment；
Fig. 2 is the SEM figures of high-performance polyimide/ultrathin boron nitride laminated film prepared by one step 2 of embodiment；
Fig. 3 is the B element scanning of high-performance polyimide/ultrathin boron nitride laminated film prepared by one step 2 of embodiment
Figure；
Fig. 4 is the N element scanning of high-performance polyimide/ultrathin boron nitride laminated film prepared by one step 2 of embodiment
Figure；
Fig. 5 be high-performance polyimide/ultrathin boron nitride laminated film elongation at break with tensile strength variation diagram,
The elongation at break of the 1 high-performance polyimide/ultrathin boron nitride laminated film prepared for one step 2 of embodiment is with drawing in Fig. 5
The change curve of intensity is stretched, 2 be the disconnected of high-performance polyimide/ultrathin boron nitride laminated film of two step 2 of embodiment preparation
Split change curve of the elongation with tensile strength, the 3 high-performance polyimide/ultrathin boron nitrides prepared for three step 2 of embodiment
For the elongation at break of laminated film with the change curve of tensile strength, 4 be that high-performance ultrathins prepared by example IV step 2 gather
The elongation at break of acid imide/boron nitride laminated film is with the change curve of tensile strength, the 5 pure polyamides prepared for contrast test
The elongation at break of imines with tensile strength change curve；
Fig. 6 is the dielectric properties figure of high-performance polyimide/ultrathin boron nitride laminated film, and 1 is one step of embodiment in Fig. 6
The dielectric properties curve of the rapid two high-performance polyimide/ultrathin boron nitride laminated films prepared, 2 be two step 2 system of embodiment
The dielectric properties curve of standby high-performance polyimide/ultrathin boron nitride laminated film, 3 height prepared for three step 2 of embodiment
The dielectric properties curve of performance polyimides/ultrathin boron nitride laminated film, 4 high-performance prepared for example IV step 2 are gathered
The dielectric properties curve of acid imide/ultrathin boron nitride laminated film.
Specific embodiment
Specific embodiment one：Present embodiment is a kind of system of high-performance polyimide/ultrathin boron nitride laminated film
Preparation Method is completed according to the following steps：
First, ultrathin boron nitride powder is prepared：
1., boron nitride powder and oxide be added in concentrated acid, then ice-water bath and mixing speed for 100r/min~
60min~120min is stirred to react under 300r/min, obtains mixture A；Mixture A is heated to 50 DEG C, then in temperature is 50
DEG C and mixing speed to be stirred to react 60min~180min under 100r/min~300r/min, be cooled to room temperature, then to mixing
Mass fraction is instilled as 85% hydrogen peroxide solution using the rate of addition of 1mL/min in object A, obtains mixture B；In ice-water bath
Under, deionized water is added in into mixture B, obtains mixture C；Again by mixture C centrifugal speed for 6000r/min~
5min~15min is centrifuged under 8000r/min, centrifugate is removed, obtains the presoma of thin layer boron nitride；It uses first
The presoma of the hydrochloric acid cleaning thin layer boron nitride of 0.5mol/L 3 times reuses the presoma 5 of deionized water cleaning thin layer boron nitride
It is secondary~8 times, the presoma of the thin layer boron nitride after being cleaned；
Step 1 1. described in boron nitride powder quality and concentrated acid volume ratio be (4g~8g):400mL；
Step 1 1. described in oxide quality and concentrated acid volume ratio be (20g~40g):400mL；
Step 1 1. described in concentrated acid and mass fraction be 85% the volume ratio of hydrogen peroxide solution be 400:(5~
10)；
Step 1 1. described in concentrated acid and deionized water volume ratio be 400:(300~400)；
2., by the presoma of the thin layer boron nitride after cleaning in temperature be vacuum drying 12h at 80 DEG C~100 DEG C~for 24 hours,
Obtain the presoma of dried thin layer boron nitride；The presoma of dried thin layer boron nitride is added in organic solvent,
It is again ultrasound 12h under 100W~500W~for 24 hours in ultrasonic power, obtains the precursor solution of thin layer boron nitride；In centrifugal speed
To centrifuge 5min~10min to the precursor solution of thin layer boron nitride, then take upper strata centrifugate under 3000r/min, obtain
Superthin layer nitrogenizes B solution；Superthin layer nitridation B solution is filtered by vacuum, then by the solid matter obtained after suction filtration in temperature
It is that 12h~for 24 hours is dried in vacuo at 80 DEG C~100 DEG C to spend, and obtains superthin layer boron nitride powder；
Step 1 2. described in dried thin layer boron nitride the quality of presoma and the volume ratio of organic solvent be
(1g~3g):100mL；
2nd, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film：
1., by step 1 2. in obtained superthin layer boron nitride powder be dissolved into organic solvent, obtaining mass fraction is
0.25%~5% ultrathin boron nitride solution；
2., diamines be added to the superthin layer that mass fraction is 0.25%~5% nitrogenize in B solution, then low whipping speed
It is ultrasound 12h under 100W~500W to be stirred to react 60min~120min under 100r/min~300r/min, then in ultrasonic power
~for 24 hours, obtain diamine solution；Again by dianhydride powder under conditions of ice-water bath and mixing speed is 100r/min~300r/min
Divide 5 times and be added in diamine solution, obtain the thick solution containing polyamic acid and superthin layer boron nitride；
Step 2 2. described in diamines quality and mass fraction be 0.25%~3% superthin layer nitrogenize B solution
Volume ratio is 3g:(40mL~60mL)；
Step 2 2. described in dianhydride and diamines molar ratio be 1:1；
3., 2h will be stood in the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature
~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
350 DEG C, then 1h~2h is kept the temperature at 350 DEG C, then cooled to room temperature finally demoulds, and obtains high-performance polyimide/ultra-thin
Boron nitride laminated film；
Step 2 3. described in high-performance polyimide/ultrathin boron nitride laminated film thickness be 30 μm~50 μm.
The principle and advantage of present embodiment：
First, present embodiment is presoma using a kind of high heat conduction hexagonal boron nitride particles, is then prepared using chemical method
Superthin layer boron nitride piece improves hexagonal boron nitride and the dispersibility in organic solvent, and then it is sub- with polyamides to solve hexagonal boron nitride
The problems such as amido compatability is poor, and interface resistance is big, last in-situ polymerization synthesized high-performance polyimides/ultrathin boron nitride are multiple
Closing film, this is of great significance to the new application prospect for expanding polyimide-based composite material；
2nd, high-performance polyimide/ultrathin boron nitride laminated film prepared by present embodiment is on power, heat, electrical property
There is promotion, and simple for process, be easy to amplify industrialized production；
3rd, the tensile strength of high-performance polyimide/ultrathin boron nitride laminated film prepared by present embodiment is more than
150MPa；
4th, the dielectric constant of high-performance polyimide/ultrathin boron nitride laminated film prepared by present embodiment is minimum
It is 3.2, the dielectric constant than pure Kapton reduces 6%；
5th, the Inverter fed motor life-span of high-performance polyimide/ultrathin boron nitride laminated film prepared by present embodiment is
4.9h~5.9h, the resistivity than Kapton improve 1.3 times~1.8 times；
Present embodiment can obtain a kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film.
1. the boron nitride powder is conventional multilayer bulk boron nitride powder to present embodiment step 1.
Specific embodiment two：Present embodiment is with one difference of specific embodiment：Step 1 1. described in it is dense
Acid is the concentrated sulfuric acid or mixed acid that mass fraction is 98%；The mixed acid be mass fraction be 98% the concentrated sulfuric acid, quality
The mixed liquor of nitric acid that the phosphoric acid and mass fraction that score is 85% are 98%；Mass fraction is 98% in the mixed acid
The volume ratio of nitric acid that the phosphoric acid and mass fraction that the concentrated sulfuric acid, mass fraction are 85% are 98% is 1:1:5.Other steps and tool
Body embodiment one is identical.
Specific embodiment three：One of present embodiment and specific embodiment one or two difference are：Step 1 1. in
The oxide is potassium permanganate or potassium ferrate.Other steps are the same as one or two specific embodiments.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference are：Step 1 2. in
The organic solvent is N-Methyl pyrrolidone, dimethylformamide or dimethylacetylamide.Other steps and specific implementation
Mode one to three is identical.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference are：Step 2 1. in
The organic solvent is N-Methyl pyrrolidone, dimethylformamide or dimethylacetylamide.Other steps and specific implementation
Mode one to four is identical.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference are：Step 2 2. in
The diamines is 4,4 '-diaminodiphenyl ether.Other steps are identical with specific embodiment one to five.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference are：Step 2 2. in
The dianhydride powder is biphenyl type dianhydride or equal benzene-type dianhydride；The biphenyl type dianhydride be 3,3', 4,4'- biphenyltetracarboxyacid acids
Dianhydride；The equal benzene-type dianhydride is pyromellitic acid anhydride.Other steps are identical with specific embodiment one to six.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference are：Step 2 2. in
Each time for adding in dianhydride powder is 10min.Other steps are identical with specific embodiment one to seven.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference are：Step 2 3. in
The plate is glass plate or steel plate.Other steps are identical with specific embodiment one to eight.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference are：Step 1 1. in
The quality of the boron nitride powder and the volume ratio of concentrated acid are 6g:400mL.Other steps and one to nine phase of specific embodiment
Together.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment one：A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film, is according to the following steps
It completes：
First, ultrathin boron nitride powder is prepared：
1., 6g boron nitride powders and 20g oxides be added in 400mL concentrated acids, then be in ice-water bath and mixing speed
60min is stirred to react under 100r/min, obtains mixture A；Mixture A is heated to 50 DEG C, then for 50 DEG C and stir in temperature
Speed is to be stirred to react 60min under 100r/min, is cooled to room temperature, then dripped with the rate of addition of 1mL/min into mixture A
Enter the hydrogen peroxide solution that 10mL mass fractions are 85%, obtain mixture B；Under ice-water bath, 350mL is added in into mixture B
Deionized water obtains mixture C；Mixture C is centrifuged into 5min, removal centrifugation in the case where centrifugal speed is 6000r/min again
Liquid obtains the presoma of thin layer boron nitride；First using the presoma 3 times of the hydrochloric acid of 0.5mol/L cleaning thin layer boron nitride, then
Use the presoma 5 times of deionized water cleaning thin layer boron nitride, the presoma of the thin layer boron nitride after being cleaned；
Step 1 1. described in concentrated acid be the concentrated sulfuric acid that mass fraction is 98%；
Step 1 1. described in oxide be potassium permanganate；
2., by the presoma of the thin layer boron nitride after cleaning in temperature to be dried in vacuo 12h at 80 DEG C, obtain dried
The presoma of thin layer boron nitride；The presoma of dried thin layer boron nitride is added in organic solvent, then in ultrasonic power
For ultrasound 12h under 300W, the precursor solution of thin layer boron nitride is obtained；Thin layer is nitrogenized in the case where centrifugal speed is 3000r/min
The precursor solution of boron centrifuges 5min, then takes upper strata centrifugate, obtains superthin layer nitridation B solution；By superthin layer boron nitride
Solution is filtered by vacuum, then by the solid matter obtained after suction filtration in temperature to be dried in vacuo 12h at 80 DEG C, obtain superthin layer
Boron nitride powder；
Step 1 2. described in dried thin layer boron nitride the quality of presoma and the volume ratio of organic solvent be
1g:100mL；
Step 1 2. described in organic solvent be dimethylacetylamide；
2nd, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film：
1., by step 1 2. in obtained superthin layer boron nitride powder be dissolved into dimethylacetylamide, obtain quality point
Number is 0.25% ultrathin boron nitride solution；
2., diamines be added to the superthin layer that mass fraction is 0.25% nitrogenize in B solution, then low whipping speed is
60min, then the ultrasound 12h in the case where ultrasonic power is 300W are stirred to react under 100r/min, obtains diamine solution；Again in ice-water bath and
Mixing speed, which divides dianhydride powder 5 times under conditions of being 100r/min, to be added in diamine solution, is obtained thick containing polyamides
The solution of amino acid and superthin layer boron nitride；
Step 2 2. described in quality and the mass fraction of diamines be that 0.25% superthin layer nitrogenizes the volume of B solution
Than for 3g:40mL；
Step 2 2. described in dianhydride and diamines molar ratio be 1:1；
Step 2 2. described in diamines be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；The equal benzene-type dianhydride is Pyromellitic Acid two
Acid anhydride；
Step 2 2. described in each time for adding in dianhydride powder be 10min；
3., will be stood in the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature
2h, then be spun on clean glass plate, then with the heating rate of 3 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
2h, then cooled to room temperature are kept the temperature, finally demoulds, obtains high-performance polyimide/ultrathin boron nitride laminated film；
Step 2 3. described in high-performance polyimide/ultrathin boron nitride laminated film thickness be 40 μm.
1. the boron nitride powder is conventional multilayer bulk boron nitride powder to one step 1 of embodiment.
Embodiment two：A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film, is according to the following steps
It completes：
First, ultrathin boron nitride powder is prepared：
1., 6g boron nitride powders and 20g oxides be added in 400mL concentrated acids, then be in ice-water bath and mixing speed
60min is stirred to react under 100r/min, obtains mixture A；Mixture A is heated to 50 DEG C, then for 50 DEG C and stir in temperature
Speed is to be stirred to react 60min under 100r/min, is cooled to room temperature, then dripped with the rate of addition of 1mL/min into mixture A
Enter the hydrogen peroxide solution that 10mL mass fractions are 85%, obtain mixture B；Under ice-water bath, 350mL is added in into mixture B
Deionized water obtains mixture C；Mixture C is centrifuged into 10min, removal centrifugation in the case where centrifugal speed is 6000r/min again
Liquid obtains the presoma of thin layer boron nitride；First using the presoma 3 times of the hydrochloric acid of 0.5mol/L cleaning thin layer boron nitride, then
Use the presoma 5 times of deionized water cleaning thin layer boron nitride, the presoma of the thin layer boron nitride after being cleaned；
Step 1 1. described in concentrated acid be the concentrated sulfuric acid that mass fraction is 98%；
Step 1 1. described in oxide be potassium permanganate；
2., by the presoma of the thin layer boron nitride after cleaning in temperature to be dried in vacuo 12h at 80 DEG C, obtain dried
The presoma of thin layer boron nitride；The presoma of dried thin layer boron nitride is added in organic solvent, then in ultrasonic power
For ultrasound 12h under 300W, the precursor solution of thin layer boron nitride is obtained；Thin layer is nitrogenized in the case where centrifugal speed is 3000r/min
The precursor solution of boron centrifuges 5min, then takes upper strata centrifugate, obtains superthin layer nitridation B solution；By superthin layer boron nitride
Solution is filtered by vacuum, then by the solid matter obtained after suction filtration in temperature to be dried in vacuo 12h at 80 DEG C, obtain superthin layer
Boron nitride powder；
Step 1 2. described in dried thin layer boron nitride the quality of presoma and the volume ratio of organic solvent be
1g:100mL；
Step 1 2. described in organic solvent be N-Methyl pyrrolidone；
2nd, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film：
1., by step 1 2. in obtained superthin layer boron nitride powder be dissolved into dimethylacetylamide, obtain quality point
Number is 0.5% ultrathin boron nitride solution；
2., diamines be added to the superthin layer that mass fraction is 0.5% nitrogenize in B solution, then low whipping speed is
60min, then the ultrasound 12h in the case where ultrasonic power is 300W are stirred to react under 100r/min, obtains diamine solution；Again in ice-water bath and
Mixing speed, which divides dianhydride powder 5 times under conditions of being 100r/min, to be added in diamine solution, is obtained thick containing polyamides
The solution of amino acid and superthin layer boron nitride；
Step 2 2. described in quality and the mass fraction of diamines be that 0.5% superthin layer nitrogenizes the volume ratio of B solution
For 3g:60mL；
Step 2 2. described in dianhydride and diamines molar ratio be 1:1；
Step 2 2. described in diamines be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；The equal benzene-type dianhydride is Pyromellitic Acid two
Acid anhydride；
Step 2 2. described in each time for adding in dianhydride powder be 10min；
3., will be stood in the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature
2h, then be spun on clean glass plate, then with the heating rate of 5 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
1h, then cooled to room temperature are kept the temperature, finally demoulds, obtains high-performance polyimide/ultrathin boron nitride laminated film；
Step 2 3. described in high-performance polyimide/ultrathin boron nitride laminated film thickness be 40 μm.
1. the boron nitride powder is conventional multilayer bulk boron nitride powder to two step 1 of embodiment.
Embodiment three：A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film, is according to the following steps
It completes：
First, ultrathin boron nitride powder is prepared：
1., 6g boron nitride powders and 20g oxides be added in 400mL concentrated acids, then be in ice-water bath and mixing speed
60min is stirred to react under 100r/min, obtains mixture A；Mixture A is heated to 50 DEG C, then for 50 DEG C and stir in temperature
Speed is to be stirred to react 60min under 100r/min, is cooled to room temperature, then dripped with the rate of addition of 1mL/min into mixture A
Enter the hydrogen peroxide solution that 10mL mass fractions are 85%, obtain mixture B；Under ice-water bath, 350mL is added in into mixture B
Deionized water obtains mixture C；Mixture C is centrifuged into 5min, removal centrifugation in the case where centrifugal speed is 6000r/min again
Liquid obtains the presoma of thin layer boron nitride；First using the presoma 3 times of the hydrochloric acid of 0.5mol/L cleaning thin layer boron nitride, then
Use the presoma 5 times of deionized water cleaning thin layer boron nitride, the presoma of the thin layer boron nitride after being cleaned；
Step 1 1. described in concentrated acid be the concentrated sulfuric acid that mass fraction is 98%；
Step 1 1. described in oxide be potassium permanganate；
2., by the presoma of the thin layer boron nitride after cleaning in temperature to be dried in vacuo 12h at 80 DEG C, obtain dried
The presoma of thin layer boron nitride；The presoma of dried thin layer boron nitride is added in organic solvent, then in ultrasonic power
For ultrasound 12h under 300W, the precursor solution of thin layer boron nitride is obtained；Thin layer is nitrogenized in the case where centrifugal speed is 3000r/min
The precursor solution of boron centrifuges 5min, then takes upper strata centrifugate, obtains superthin layer nitridation B solution；By superthin layer boron nitride
Solution is filtered by vacuum, then by the solid matter obtained after suction filtration in temperature to be dried in vacuo 12h at 80 DEG C, obtain superthin layer
Boron nitride powder；
Step 1 2. described in dried thin layer boron nitride the quality of presoma and the volume ratio of organic solvent be
1g:100mL；
Step 1 2. described in organic solvent be dimethylformamide；
2nd, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film：
1., by step 1 2. in obtained superthin layer boron nitride powder be dissolved into dimethylacetylamide, obtain quality point
Number is 1% ultrathin boron nitride solution；
2., diamines be added to the superthin layer that mass fraction is 1% nitrogenize in B solution, then low whipping speed is 100r/
60min, then the ultrasound 12h in the case where ultrasonic power is 300W are stirred to react under min, obtains diamine solution；Again in ice-water bath and stirring
Speed, which divides dianhydride powder 5 times under conditions of being 100r/min, to be added in diamine solution, is obtained thick containing polyamic acid
With the solution of superthin layer boron nitride；
Step 2 2. described in diamines quality and mass fraction be 1% the volume ratio of superthin layer nitridation B solution be
3g:60mL；
Step 2 2. described in dianhydride and diamines molar ratio be 1:1；
Step 2 2. described in diamines be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；The equal benzene-type dianhydride is Pyromellitic Acid two
Acid anhydride；
Step 2 2. described in each time for adding in dianhydride powder be 10min；
3., will be stood in the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature
2h, then be spun on clean glass plate, then with the heating rate of 5 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
1h, then cooled to room temperature are kept the temperature, finally demoulds, obtains high-performance polyimide/ultrathin boron nitride laminated film；
Step 2 3. described in high-performance polyimide/ultrathin boron nitride laminated film thickness be 40 μm.
1. the boron nitride powder is conventional multilayer bulk boron nitride powder to three step 1 of embodiment.
Example IV：A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film, is according to the following steps
It completes：
First, ultrathin boron nitride powder is prepared：
1., 6g boron nitride powders and 20g oxides be added in 400mL concentrated acids, then be in ice-water bath and mixing speed
60min is stirred to react under 100r/min, obtains mixture A；Mixture A is heated to 50 DEG C, then for 50 DEG C and stir in temperature
Speed is to be stirred to react 60min under 100r/min, is cooled to room temperature, then dripped with the rate of addition of 1mL/min into mixture A
Enter the hydrogen peroxide solution that 10mL mass fractions are 85%, obtain mixture B；Under ice-water bath, 350mL is added in into mixture B
Deionized water obtains mixture C；Mixture C is centrifuged into 5min, removal centrifugation in the case where centrifugal speed is 6000r/min again
Liquid obtains the presoma of thin layer boron nitride；First using the presoma 3 times of the hydrochloric acid of 0.5mol/L cleaning thin layer boron nitride, then
Use the presoma 5 times of deionized water cleaning thin layer boron nitride, the presoma of the thin layer boron nitride after being cleaned；
Step 1 1. described in concentrated acid be the concentrated sulfuric acid that mass fraction is 98%；
Step 1 1. described in oxide be potassium permanganate；
2., by the presoma of the thin layer boron nitride after cleaning in temperature to be dried in vacuo 12h at 80 DEG C, obtain dried
The presoma of thin layer boron nitride；The presoma of dried thin layer boron nitride is added in organic solvent, then in ultrasonic power
For ultrasound 12h under 300W, the precursor solution of thin layer boron nitride is obtained；Thin layer is nitrogenized in the case where centrifugal speed is 3000r/min
The precursor solution of boron centrifuges 5min, then takes upper strata centrifugate, obtains superthin layer nitridation B solution；By superthin layer boron nitride
Solution is filtered by vacuum, then by the solid matter obtained after suction filtration in temperature to be dried in vacuo 12h at 80 DEG C, obtain superthin layer
Boron nitride powder；
Step 1 2. described in dried thin layer boron nitride the quality of presoma and the volume ratio of organic solvent be
1g:100mL；
Step 1 2. described in organic solvent be N-Methyl pyrrolidone；
2nd, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film：
1., by step 1 2. in obtained superthin layer boron nitride powder be dissolved into dimethylacetylamide, obtain quality point
Number is 3% ultrathin boron nitride solution；
2., diamines be added to the superthin layer that mass fraction is 3% nitrogenize in B solution, then low whipping speed is 100r/
60min, then the ultrasound 12h in the case where ultrasonic power is 300W are stirred to react under min, obtains diamine solution；Again in ice-water bath and stirring
Speed, which divides dianhydride powder 5 times under conditions of being 100r/min, to be added in diamine solution, is obtained thick containing polyamic acid
With the solution of superthin layer boron nitride；
Step 2 2. described in diamines quality and mass fraction be 3% the volume ratio of superthin layer nitridation B solution be
3g:60mL；
Step 2 2. described in dianhydride and diamines molar ratio be 1:1；
Step 2 2. described in diamines be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；The equal benzene-type dianhydride is Pyromellitic Acid two
Acid anhydride；
Step 2 2. described in each time for adding in dianhydride powder be 10min；
3., will be stood in the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature
2h, then be spun on clean glass plate, then with the heating rate of 5 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
1h, then cooled to room temperature are kept the temperature, finally demoulds, obtains high-performance polyimide/ultrathin boron nitride laminated film；
Step 2 3. described in high-performance polyimide/ultrathin boron nitride laminated film thickness be 40 μm.
1. the boron nitride powder is conventional multilayer bulk boron nitride powder to example IV step 1.
Fig. 1 is the TEM figures of superthin layer boron nitride powder prepared by one step 1 of embodiment；
From fig. 1, it can be seen that block-like boron nitride has been stripped into the boron nitride of thin slice, transmission electron microscope shows many thin slices
It is packed together, super rich boron nitride piece is high-visible in edge.
Fig. 2 is the SEM figures of high-performance polyimide/ultrathin boron nitride laminated film prepared by one step 2 of embodiment；
As can be seen from Figure 2, thin layer boron nitride lamella is wrapped up by polyimides, is uniformly dispersed in polyimide matrix, piece
Layer structure is apparent, and most lamellas are parallel with film surface direction, and such structure is conducive to promote its electrical insulation properties.
High-performance polyimide/the ultrathin boron nitride prepared using scanning electron microscopy Electronic Speculum to one step 2 of embodiment is multiple
The B element for closing film is scanned, as shown in Figure 3；
Fig. 3 is the B element scanning of high-performance polyimide/ultrathin boron nitride laminated film prepared by one step 2 of embodiment
Figure；
As can be seen from Figure 3, boron element is evenly distributed in composite material, because polyimide matrix does not contain B element, this
Characterize the presence of provable boron nitride in the composite.
High-performance ultrathin polyimides/the boron nitride prepared using scanning electron microscopy Electronic Speculum to one step 2 of embodiment is multiple
The N element for closing film is scanned, as shown in Figure 4；
Fig. 4 is the N element scanning of high-performance polyimide/ultrathin boron nitride laminated film prepared by one step 2 of embodiment
Figure；
As can be seen from Figure 4, N element is evenly distributed in composite material, this characterization can further prove boron nitride compound
Presence in material.
High-performance ultrathin polyimides/the boron nitride prepared using micro-control electronic universal tester to one step 2 of embodiment
Laminated film, high-performance ultrathin polyimides/boron nitride laminated film of two step 2 of embodiment preparation, three step 2 of embodiment
High-performance ultrathin polyamides prepared by the high-performance ultrathin polyimides/boron nitride laminated film and example IV step 2 of preparation is sub-
The tensile strength of amine/boron nitride laminated film is characterized, as shown in Figure 5；
Fig. 5 be high-performance polyimide/ultrathin boron nitride laminated film elongation at break with tensile strength variation diagram,
The elongation at break of the 1 high-performance polyimide/ultrathin boron nitride laminated film prepared for one step 2 of embodiment is with drawing in Fig. 5
The change curve of intensity is stretched, 2 be the disconnected of high-performance polyimide/ultrathin boron nitride laminated film of two step 2 of embodiment preparation
Split change curve of the elongation with tensile strength, the 3 high-performance polyimide/ultrathin boron nitrides prepared for three step 2 of embodiment
For the elongation at break of laminated film with the change curve of tensile strength, 4 be that high-performance ultrathins prepared by example IV step 2 gather
The elongation at break of acid imide/boron nitride laminated film is with the change curve of tensile strength, the 5 pure polyamides prepared for contrast test
The elongation at break of imines with tensile strength change curve；
The significant tensile strength and elongation at break for improving composite material of the addition of a small amount of boron nitride as can be seen from Figure 5, this
Be conducive to expand the service life of composite polyimide material in practical applications.
High-performance polyimide/the ultrathin boron nitride prepared using precise impedance analyzer to one step 2 of embodiment is compound
It is prepared by film, high-performance ultrathin polyimides/boron nitride laminated film of two step 2 of embodiment preparation, three step 2 of embodiment
High-performance polyimide/ultrathin boron nitride laminated film and example IV step 2 prepare high-performance ultrathin polyimides/
The dielectric properties of boron nitride laminated film are characterized, and figure is as indicated with 6；
Fig. 6 is the dielectric properties figure of high-performance polyimide/ultrathin boron nitride laminated film, and 1 is one step of embodiment in Fig. 6
The dielectric properties curve of the rapid two high-performance polyimide/ultrathin boron nitride laminated films prepared, 2 be two step 2 system of embodiment
The dielectric properties curve of standby high-performance polyimide/ultrathin boron nitride laminated film, 3 height prepared for three step 2 of embodiment
The dielectric properties curve of performance polyimides/ultrathin boron nitride laminated film, 4 high-performance prepared for example IV step 2 are gathered
The dielectric properties curve of acid imide/ultrathin boron nitride laminated film.
Contrast test：The preparation method of pure polyimides is completed according to the following steps：
First, diamines is added in N-Methyl pyrrolidone, then low whipping speed is is stirred to react under 100r/min
60min, then the ultrasound 12h in the case where ultrasonic power is 300W, obtain diamine solution；It is again 100r/min in ice-water bath and mixing speed
Under conditions of dianhydride powder point is added in diamine solution for 5 times, obtain thick containing polyamic acid solution；
The quality of diamines described in step 1 and the volume ratio of N-Methyl pyrrolidone are 3g:60mL；
The molar ratio of dianhydride and diamines described in step 1 is 1:1；Diamines described in step 1 is 4,4 '-diamino hexichol
Ether；
Dianhydride powder described in step 1 is equal benzene-type dianhydride；The equal benzene-type dianhydride is pyromellitic acid anhydride；
Each time for adding in dianhydride powder described in step 1 is 10min；
2nd, it will be stood in the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature
2h, then be spun on clean glass plate, then with the heating rate of 5 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
2h, then cooled to room temperature are kept the temperature, finally demoulds, obtains high-performance polyimide/ultrathin boron nitride laminated film；
The thickness of high-performance polyimide/ultrathin boron nitride laminated film described in step 2 is 40 μm.
High-performance polyimide/ultra-thin nitridation prepared by the pure polyimides of contrast test preparation, one step 2 of embodiment
Boron laminated film, high-performance polyimide/ultrathin boron nitride laminated film of two step 2 of embodiment preparation, three step of embodiment
High-performance polyamides prepared by the two high-performance polyimide/ultrathin boron nitride laminated films prepared and example IV step 2 is sub-
The thermal conductivity factor and Inverter fed motor life-span of amine/ultrathin boron nitride laminated film are tested, and data are shown in Table 1；
Table 1
As known from Table 1, the addition of a small amount of thin layer boron nitride, greatly improved polyimide composite film heat conductivility and
Inverter fed motor life-span.
Claims (4)
1. the preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film, it is characterised in that a kind of high-performance is gathered
The preparation method of acid imide/ultrathin boron nitride laminated film is completed according to the following steps：
First, ultrathin boron nitride powder is prepared：
1., boron nitride powder and oxide be added in concentrated acid, then in ice-water bath and mixing speed be 100r/min~300r/
60min~120min is stirred to react under min, obtains mixture A；Mixture A is heated to 50 DEG C, then for 50 DEG C and stir in temperature
Speed is mixed to be stirred to react 60min~180min under 100r/min~300r/min, is cooled to room temperature, then into mixture A
Mass fraction is instilled as 85% hydrogen peroxide solution using the rate of addition of 1mL/min, obtains mixture B；Under ice-water bath, to mixed
It closes in object B and adds in deionized water, obtain mixture C；Again by mixture C under centrifugal speed 6000r/min~8000r/min from
The heart detaches 5min~15min, removes centrifugate, obtains the presoma of thin layer boron nitride；It is clear using the hydrochloric acid of 0.5mol/L first
The presoma 3 times of thin layer boron nitride is washed, the presoma 5 times~8 times of deionized water cleaning thin layer boron nitride is reused, is cleaned
The presoma of thin layer boron nitride afterwards；
Step 1 1. described in oxide be potassium permanganate or potassium ferrate；
Step 1 1. described in concentrated acid be mixed acid；The mixed acid be mass fraction be 98% the concentrated sulfuric acid, quality point
Number is the mixed liquor of nitric acid that 85% phosphoric acid and mass fraction are 98%；In the mixed acid mass fraction be 98% it is dense
The volume ratio of nitric acid that the phosphoric acid and mass fraction that sulfuric acid, mass fraction are 85% are 98% is 1:1:5；
Step 1 1. described in boron nitride powder quality and concentrated acid volume ratio be (4g~8g):400mL；
Step 1 1. described in oxide quality and concentrated acid volume ratio be (20g~40g):400mL；
Step 1 1. described in concentrated acid and mass fraction be 85% the volume ratio of hydrogen peroxide solution be 400:(5~10)；
Step 1 1. described in concentrated acid and deionized water volume ratio be 400:(300~400)；
2., by the presoma of the thin layer boron nitride after cleaning in temperature be vacuum drying 12h at 80 DEG C~100 DEG C~for 24 hours, obtain
The presoma of dried thin layer boron nitride；The presoma of dried thin layer boron nitride is added in organic solvent, then
Ultrasonic power is ultrasound 12h~for 24 hours under 100W~500W, obtains the precursor solution of thin layer boron nitride；It is in centrifugal speed
5min~10min is centrifuged to the precursor solution of thin layer boron nitride under 3000r/min, then takes upper strata centrifugate, is surpassed
Thin layer nitrogenizes B solution；Superthin layer nitridation B solution is filtered by vacuum, then by the solid matter obtained after suction filtration in temperature
It is that 12h~for 24 hours is dried in vacuo at 80 DEG C~100 DEG C, obtains superthin layer boron nitride powder；
Step 1 2. described in organic solvent be N-Methyl pyrrolidone, dimethylformamide or dimethylacetylamide；
Step 1 2. described in dried thin layer boron nitride presoma quality and organic solvent volume ratio for (1g~
3g):100mL；
2nd, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film：
1., by step 1 2. in obtained superthin layer boron nitride powder be dissolved into organic solvent, obtaining mass fraction is
0.25%~5% ultrathin boron nitride solution；
Step 2 1. described in organic solvent be N-Methyl pyrrolidone, dimethylformamide or dimethylacetylamide；
2., diamines be added to the superthin layer that mass fraction is 0.25%~5% nitrogenize in B solution, then low whipping speed is
Be stirred to react 60min~120min under 100r/min~300r/min, then ultrasonic power for ultrasound 12h under 100W~500W~
For 24 hours, diamine solution is obtained；Again by dianhydride powder point under conditions of ice-water bath and mixing speed is 100r/min~300r/min
It is added in diamine solution for 5 times, obtains the thick solution containing polyamic acid and superthin layer boron nitride；
Step 2 2. described in diamines be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；The equal benzene-type dianhydride is pyromellitic acid anhydride；
Step 2 2. described in quality and the mass fraction of diamines be that 0.25%~3% superthin layer nitrogenizes the volume of B solution
Than for 3g:(40mL~60mL)；
Step 2 2. described in dianhydride and diamines molar ratio be 1:1；
3., will be stood in the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature 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
350 DEG C, then 1h~2h is kept the temperature at 350 DEG C, then cooled to room temperature finally demoulds, and obtains high-performance polyimide/ultra-thin
Boron nitride laminated film；
Step 2 3. described in high-performance polyimide/ultrathin boron nitride laminated film thickness be 30 μm~50 μm.
2. a kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film according to claim 1, special
The each time for adding in dianhydride powder levied described in being step 2 2. is 10min.
3. a kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film according to claim 1, special
It is glass plate or steel plate to levy the plate described in being step 2 3..
4. a kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film according to claim 1, special
It is 6g to levy the quality of the boron nitride powder described in being step 1 1. and the volume ratio of concentrated acid:400mL.
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