CN106084219A - 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
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Abstract
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film, it relates to a kind of method preparing laminated film.The invention aims to reduce pure polymide dielectric constant further, improve its electrical insulation capability and mechanical property, solve it and apply the problem being restricted at special dimension.Method: one, prepare ultrathin boron nitride powder；Two, 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 lifting on power, heat, electrical property, and technique is simple, it is easy to amplify industrialized production.The present invention can obtain the preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film.
Description
Technical field
The present invention relates to a kind of method preparing laminated film.
Background technology
As electric insulation and power electronics, a member in aerospace speciality polymer material, polyimides is with it
The features such as excellent heat stability, mechanical performance and high temperature insulation characteristic, widely studied by scholars and industrial quarters.But it is traditional
Pure polyimides there is also some shortcomings, limits its application at some special dimensions, as it is in microelectronic circuits plate, its
Dielectric constant is of a relatively high, and this will bring substantial amounts of energy loss；Its electrical insulation capability can't fully meet frequency conversion motor
Deng the insulation needs in field, China's product demand in this field also relies primarily on imported from America；For improving it in various application
In the service life in field, its mechanical property still needs further to be improved.Therefore, the excellent properties of polyimides own is being utilized
Under premise, improve the combination properties such as polyimides power, heat, electricity further and still closed widely at academia and engineer applied field
Note and research.
Summary of the invention
The invention aims to reduce pure polymide dielectric constant further, improve its electrical insulation capability and mechanical property
Can, solve it and apply the problem being restricted at special dimension, and provide a kind of high-performance polyimide/ultrathin boron nitride to be combined
The preparation method of thin film.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film, completes according to the following steps:
One, ultrathin boron nitride powder is prepared:
1., boron nitride powder and oxide are joined in concentrated acid, then in ice-water bath and mixing speed 100r/min～
Under 300r/min, stirring reaction 60min～120min, obtains mixture A；Mixture A is heated to 50 DEG C, then is 50 in temperature
DEG C and mixing speed be stirring reaction 60min～180min under 100r/min～300r/min, be cooled to room temperature, then to mixing
Instilling mass fraction with the rate of addition of 1mL/min in thing A is the hydrogen peroxide solution of 85%, obtains mixture B；At ice-water bath
Under, in mixture B, add deionized water, obtain mixture C；Again by mixture C centrifugal speed be 6000r/min～
Centrifugation 5min～15min under 8000r/min, removes centrifugal liquid, obtains the presoma of thin layer boron nitride；First by
The presoma of the hydrochloric acid cleaning thin layer boron nitride of 0.5mol/L 3 times, re-uses deionized water and cleans the presoma 5 of thin layer boron nitride
Secondary～8 times, the presoma of the thin layer boron nitride after being cleaned；
Step one 1. described in the quality of boron nitride powder and the volume ratio of concentrated acid be (4g～8g): 400mL；
Step one 1. described in the quality of oxide and the volume ratio of concentrated acid be (20g～40g): 400mL；
Step one 1. described in the volume ratio of the hydrogen peroxide solution that concentrated acid and mass fraction are 85% be 400:(5～
10)；
Step one 1. described in the volume ratio of concentrated acid and deionized water be 400:(300～400)；
2., will clean after the presoma of thin layer boron nitride at temperature is 80 DEG C～100 DEG C, be vacuum dried 12h～24h,
Obtain the presoma of dried thin layer boron nitride；The presoma of dried thin layer boron nitride is joined in organic solvent,
Ultrasonic 12h～24h under ultrasonic power is 100W～500W, obtains the precursor solution of thin layer boron nitride again；In centrifugal speed
For precursor solution centrifugation 5min～10min to thin layer boron nitride under 3000r/min, then take upper strata centrifugal liquid, obtain
Superthin layer boron nitride solution；Superthin layer boron nitride solution is carried out vacuum filtration, then by the solid matter that obtains after sucking filtration in temperature
Degree is vacuum drying 12h～24h at 80 DEG C～100 DEG C, obtains superthin layer boron nitride powder；
Step one 2. described in the quality of presoma of dried thin layer boron nitride with the volume ratio of organic solvent be
(1g～3g): 100mL；
Two, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film:
1., by step one 2. in the superthin layer boron nitride powder that obtains be dissolved in organic solvent, obtaining mass fraction is
The ultrathin boron nitride solution of 0.25%～5%；
2., by diamidogen join in the superthin layer boron nitride solution that mass fraction is 0.25%～5%, then low whipping speed
60min～120min, more ultrasonic 12h under ultrasonic power is 100W～500W is reacted for stirring under 100r/min～300r/min
～24h, obtain two amine aqueous solutions；Again by dianhydride powder under conditions of ice-water bath and mixing speed are 100r/min～300r/min
Point join in two amine aqueous solutions for 5 times, obtain thick containing polyamic acid with the solution of superthin layer boron nitride；
Step 2 2. described in the superthin layer boron nitride solution that quality and mass fraction are 0.25%～3% of diamidogen
Volume ratio is 3g:(40mL～60mL)；
Step 2 2. described in the mol ratio of dianhydride and diamidogen be 1:1；
3., the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature will stand 2h
～6h, then be cast, spin coating or plastic film mulch 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 at 350 DEG C, be incubated 1h～2h, then naturally cool to room temperature, the last demoulding, obtain high-performance polyimide/ultra-thin
Boron nitride laminated film；
Step 2 3. described in the thickness of high-performance polyimide/ultrathin boron nitride laminated film be 30 μm～50 μm.
The principle of the present invention and advantage:
One, the present invention utilizes a kind of high heat conduction hexagonal boron nitride particles to be presoma, then utilizes chemical method to prepare ultra-thin
Layer boron nitride sheet, improves hexagonal boron nitride and the dispersibility in organic solvent, and then solves hexagonal boron nitride with 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
This is significant to the new application prospect expanding polyimide-based composite material for film；
Two, high-performance polyimide prepared by the present invention/ultrathin boron nitride laminated film has on power, heat, electrical property
Promote, and technique is simple, it is easy to amplify industrialized production；
Three, the hot strength of high-performance polyimide prepared by the present invention/ultrathin boron nitride laminated film is more than 150MPa；
Four, the dielectric constant of high-performance polyimide prepared by the present invention/ultrathin boron nitride laminated film is minimum
3.2, reduce 6% than the dielectric constant of pure Kapton；
Five, the Inverter fed motor life-span of high-performance polyimide prepared by the present invention/ultrathin boron nitride laminated film be 4.9h～
5.9h, improves 1.3 times～1.8 times than the resistivity of Kapton；
The present invention can obtain the preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the superthin layer boron nitride powder of embodiment one step one preparation；
Fig. 2 is the SEM figure of high-performance polyimide/ultrathin boron nitride laminated film prepared by embodiment one step 2；
Fig. 3 is the B element scanning of high-performance polyimide/ultrathin boron nitride laminated film prepared by embodiment one step 2
Figure；
Fig. 4 is the N element scanning of high-performance polyimide/ultrathin boron nitride laminated film prepared by embodiment one step 2
Figure；
Fig. 5 is the elongation at break variation diagram with hot strength of high-performance polyimide/ultrathin boron nitride laminated film,
In Fig. 5,1 is that the elongation at break of high-performance polyimide/ultrathin boron nitride laminated film prepared by embodiment one step 2 is with drawing
Stretching the change curve of intensity, 2 is the disconnected of high-performance polyimide/ultrathin boron nitride laminated film of preparing of embodiment two step 2
Splitting the percentage elongation change curve with hot strength, 3 is high-performance polyimide/ultrathin boron nitride prepared by embodiment three step 2
The elongation at break of laminated film is with the change curve of hot strength, and 4 is that high-performance ultrathin prepared by embodiment four step 2 gathers
The elongation at break of acid imide/boron nitride laminated film is with the change curve of hot strength, the 5 pure polyamides prepared for contrast test
The elongation at break of imines is with the change curve of hot strength；
Fig. 6 is the dielectric properties figure of high-performance polyimide/ultrathin boron nitride laminated film, and in Fig. 6,1 is embodiment one step
The dielectric properties curve of the high-performance polyimide/ultrathin boron nitride laminated film of rapid two preparations, 2 is embodiment two step 2 system
The dielectric properties curve of standby high-performance polyimide/ultrathin boron nitride laminated film, 3 is height prepared by embodiment three step 2
The dielectric properties curve of performance polyimides/ultrathin boron nitride laminated film, 4 is high-performance poly prepared by embodiment four step 2
The dielectric properties curve of acid imide/ultrathin boron nitride laminated film.
Detailed description of the invention
Detailed description of the invention one: present embodiment is the system of a kind of high-performance polyimide/ultrathin boron nitride laminated film
Preparation Method completes according to the following steps:
One, ultrathin boron nitride powder is prepared:
1., boron nitride powder and oxide are joined in concentrated acid, then ice-water bath and mixing speed be 100r/min～
Under 300r/min, stirring reaction 60min～120min, obtains mixture A；Mixture A is heated to 50 DEG C, then is 50 in temperature
DEG C and mixing speed be stirring reaction 60min～180min under 100r/min～300r/min, be cooled to room temperature, then to mixing
Instilling mass fraction with the rate of addition of 1mL/min in thing A is the hydrogen peroxide solution of 85%, obtains mixture B；At ice-water bath
Under, in mixture B, add deionized water, obtain mixture C；Again by mixture C centrifugal speed be 6000r/min～
Centrifugation 5min～15min under 8000r/min, removes centrifugal liquid, obtains the presoma of thin layer boron nitride；First by
The presoma of the hydrochloric acid cleaning thin layer boron nitride of 0.5mol/L 3 times, re-uses deionized water and cleans the presoma 5 of thin layer boron nitride
Secondary～8 times, the presoma of the thin layer boron nitride after being cleaned；
Step one 1. described in the quality of boron nitride powder and the volume ratio of concentrated acid be (4g～8g): 400mL；
Step one 1. described in the quality of oxide and the volume ratio of concentrated acid be (20g～40g): 400mL；
Step one 1. described in the volume ratio of the hydrogen peroxide solution that concentrated acid and mass fraction are 85% be 400:(5～
10)；
Step one 1. described in the volume ratio of concentrated acid and deionized water be 400:(300～400)；
2., will clean after the presoma of thin layer boron nitride at temperature is 80 DEG C～100 DEG C, be vacuum dried 12h～24h,
Obtain the presoma of dried thin layer boron nitride；The presoma of dried thin layer boron nitride is joined in organic solvent,
Ultrasonic 12h～24h under ultrasonic power is 100W～500W, obtains the precursor solution of thin layer boron nitride again；In centrifugal speed
For precursor solution centrifugation 5min～10min to thin layer boron nitride under 3000r/min, then take upper strata centrifugal liquid, obtain
Superthin layer boron nitride solution；Superthin layer boron nitride solution is carried out vacuum filtration, then by the solid matter that obtains after sucking filtration in temperature
Degree is vacuum drying 12h～24h at 80 DEG C～100 DEG C, obtains superthin layer boron nitride powder；
Step one 2. described in the quality of presoma of dried thin layer boron nitride with the volume ratio of organic solvent be
(1g～3g): 100mL；
Two, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film:
1., by step one 2. in the superthin layer boron nitride powder that obtains be dissolved in organic solvent, obtaining mass fraction is
The ultrathin boron nitride solution of 0.25%～5%；
2., by diamidogen join in the superthin layer boron nitride solution that mass fraction is 0.25%～5%, then low whipping speed
60min～120min, more ultrasonic 12h under ultrasonic power is 100W～500W is reacted for stirring under 100r/min～300r/min
～24h, obtain two amine aqueous solutions；Again by dianhydride powder under conditions of ice-water bath and mixing speed are 100r/min～300r/min
Point join in two amine aqueous solutions for 5 times, obtain thick containing polyamic acid with the solution of superthin layer boron nitride；
Step 2 2. described in the superthin layer boron nitride solution that quality and mass fraction are 0.25%～3% of diamidogen
Volume ratio is 3g:(40mL～60mL)；
Step 2 2. described in the mol ratio of dianhydride and diamidogen be 1:1；
3., the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature will stand 2h
～6h, then be cast, spin coating or plastic film mulch 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 at 350 DEG C, be incubated 1h～2h, then naturally cool to room temperature, the last demoulding, obtain high-performance polyimide/ultra-thin
Boron nitride laminated film；
Step 2 3. described in the thickness of high-performance polyimide/ultrathin boron nitride laminated film be 30 μm～50 μm.
The principle of present embodiment and advantage:
One, present embodiment utilizes a kind of high heat conduction hexagonal boron nitride particles to be presoma, then utilizes chemical method to prepare
Superthin layer boron nitride sheet, 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 is multiple
This is significant to the new application prospect expanding polyimide-based composite material to close thin film；
Two, high-performance polyimide prepared by present embodiment/ultrathin boron nitride laminated film is on power, heat, electrical property
There is lifting, and technique is simple, it is easy to amplify industrialized production；
Three, the hot strength of high-performance polyimide prepared by present embodiment/ultrathin boron nitride laminated film is more than
150MPa；
Four, the dielectric constant of high-performance polyimide prepared by present embodiment/ultrathin boron nitride laminated film is minimum
It is 3.2, reduces 6% than the dielectric constant of pure Kapton；
Five, the Inverter fed motor life-span of high-performance polyimide prepared by present embodiment/ultrathin boron nitride laminated film is
4.9h～5.9h, improves 1.3 times～1.8 times than the resistivity of Kapton；
Present embodiment can obtain the preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film.
The 1. described boron nitride powder of present embodiment step one is conventional multilayer bulk boron nitride powder.
Detailed description of the invention two: present embodiment with detailed description of the invention one difference is: step one 1. described in dense
Acid is concentrated sulphuric acid that mass fraction is 98% or mixed acid；Described mixed acid be mass fraction be concentrated sulphuric acid, the quality of 98%
Mark is phosphoric acid and the mixed liquor of nitric acid that mass fraction is 98% of 85%；In described mixed acid, mass fraction is 98%
Concentrated sulphuric acid, mass fraction are the phosphoric acid of 85% and the volume ratio of nitric acid that mass fraction is 98% is 1:1:5.Other steps and tool
Body embodiment one is identical.
Detailed description of the invention three: present embodiment with one of detailed description of the invention one or two difference is: step one 1. in
Described oxide is potassium permanganate or potassium ferrate.Other steps are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment with one of detailed description of the invention one to three difference is: step one 2. in
Described organic solvent is N-Methyl pyrrolidone, dimethylformamide or dimethyl acetylamide.Other steps be embodied as
Mode one to three is identical.
Detailed description of the invention five: present embodiment with one of detailed description of the invention one to four difference is: step 2 1. in
Described organic solvent is N-Methyl pyrrolidone, dimethylformamide or dimethyl acetylamide.Other steps be embodied as
Mode one to four is identical.
Detailed description of the invention six: present embodiment with one of detailed description of the invention one to five difference is: step 2 2. in
Described diamidogen is 4,4 '-diaminodiphenyl ether.Other steps are identical with detailed description of the invention one to five.
Detailed description of the invention seven: present embodiment with one of detailed description of the invention one to six difference is: step 2 2. in
Described dianhydride powder is biphenyl type dianhydride or equal benzene-type dianhydride；Described biphenyl type dianhydride is 3,3', 4,4'-biphenyltetracarboxyacid acid
Dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride.Other steps are identical with detailed description of the invention one to six.
Detailed description of the invention eight: present embodiment with one of detailed description of the invention one to seven difference is: step 2 2. in
The described time every time adding dianhydride powder is 10min.Other steps are identical with detailed description of the invention one to seven.
Detailed description of the invention nine: present embodiment with one of detailed description of the invention one to eight difference is: step 2 3. in
Described plate is glass plate or steel plate.Other steps are identical with detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment with one of detailed description of the invention one to nine difference is: step one 1. in
The quality of described boron nitride powder and the volume ratio of concentrated acid are 6g:400mL.Other steps and detailed description of the invention one to nine phase
With.
Employing following example checking beneficial effects of the present invention:
Embodiment one: the preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film, is according to the following steps
Complete:
One, ultrathin boron nitride powder is prepared:
1., 6g boron nitride powder and 20g oxide are joined in 400mL concentrated acid, then at ice-water bath and mixing speed be
Under 100r/min, stirring reaction 60min, obtains mixture A；Mixture A is heated to 50 DEG C, then is 50 DEG C and stirring in temperature
Speed is stirring reaction 60min under 100r/min, is cooled to room temperature, then rate of addition with 1mL/min drips in mixture A
Enter the hydrogen peroxide solution that 10mL mass fraction is 85%, obtain mixture B；Under ice-water bath, in mixture B, add 350mL
Deionized water, obtains mixture C；Again by mixture C centrifugation 5min under centrifugal speed is 6000r/min, remove centrifugal
Liquid, obtains the presoma of thin layer boron nitride；Hydrochloric acid first by 0.5mol/L cleans the presoma 3 times of thin layer boron nitride, then
The presoma of use deionized water cleaning thin layer boron nitride 5 times, the presoma of the thin layer boron nitride after being cleaned；
Step one 1. described in concentrated acid be mass fraction be the concentrated sulphuric acid of 98%；
Step one 1. described in oxide be potassium permanganate；
2., will clean after the presoma of thin layer boron nitride at temperature is 80 DEG C, be vacuum dried 12h, obtain dried
The presoma of thin layer boron nitride；The presoma of dried thin layer boron nitride is joined in organic solvent, then at ultrasonic power
For 12h ultrasonic under 300W, obtain the precursor solution of thin layer boron nitride；Under centrifugal speed is 3000r/min, thin layer is nitrogenized
The precursor solution centrifugation 5min of boron, then take upper strata centrifugal liquid, obtain superthin layer boron nitride solution；By superthin layer boron nitride
Solution carries out vacuum filtration, then the solid matter obtained after sucking filtration is vacuum dried at temperature is 80 DEG C 12h, obtains superthin layer
Boron nitride powder；
Step one 2. described in the quality of presoma of dried thin layer boron nitride with the volume ratio of organic solvent be
1g:100mL；
Step one 2. described in organic solvent be dimethyl acetylamide；
Two, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film:
1., by step one 2. in the superthin layer boron nitride powder that obtains be dissolved in dimethyl acetylamide, obtain quality and divide
Number is the ultrathin boron nitride solution of 0.25%；
2., by diamidogen join in the superthin layer boron nitride solution that mass fraction is 0.25%, then low whipping speed is
Stirring reaction 60min under 100r/min, more ultrasonic 12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Again at ice-water bath and
Mixing speed is to divide dianhydride powder 5 times under conditions of 100r/min to join in two amine aqueous solutions, obtains thick containing polyamides
Amino acid and the solution of superthin layer boron nitride；
Step 2 2. described in the volume of the superthin layer boron nitride solution that quality and mass fraction are 0.25% of diamidogen
Ratio is 3g:40mL；
Step 2 2. described in the mol ratio of dianhydride and diamidogen be 1:1；
Step 2 2. described in diamidogen be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；Described equal benzene-type dianhydride is Pyromellitic Acid two
Acid anhydride；
Step 2 2. described in the time every time adding dianhydride powder be 10min；
3., will the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature stand
2h, then be spun on the glass plate of cleaning, then with the heating rate of 3 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
Insulation 2h, then naturally cool to room temperature, the last demoulding, obtain high-performance polyimide/ultrathin boron nitride laminated film；
Step 2 3. described in the thickness of high-performance polyimide/ultrathin boron nitride laminated film be 40 μm.
The 1. described boron nitride powder of embodiment one step one is conventional multilayer bulk boron nitride powder.
Embodiment two: the preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film, is according to the following steps
Complete:
One, ultrathin boron nitride powder is prepared:
1., 6g boron nitride powder and 20g oxide are joined in 400mL concentrated acid, then at ice-water bath and mixing speed be
Under 100r/min, stirring reaction 60min, obtains mixture A；Mixture A is heated to 50 DEG C, then is 50 DEG C and stirring in temperature
Speed is stirring reaction 60min under 100r/min, is cooled to room temperature, then rate of addition with 1mL/min drips in mixture A
Enter the hydrogen peroxide solution that 10mL mass fraction is 85%, obtain mixture B；Under ice-water bath, in mixture B, add 350mL
Deionized water, obtains mixture C；Again by mixture C centrifugation 10min under centrifugal speed is 6000r/min, remove centrifugal
Liquid, obtains the presoma of thin layer boron nitride；Hydrochloric acid first by 0.5mol/L cleans the presoma 3 times of thin layer boron nitride, then
The presoma of use deionized water cleaning thin layer boron nitride 5 times, the presoma of the thin layer boron nitride after being cleaned；
Step one 1. described in concentrated acid be mass fraction be the concentrated sulphuric acid of 98%；
Step one 1. described in oxide be potassium permanganate；
2., will clean after the presoma of thin layer boron nitride at temperature is 80 DEG C, be vacuum dried 12h, obtain dried
The presoma of thin layer boron nitride；The presoma of dried thin layer boron nitride is joined in organic solvent, then at ultrasonic power
For 12h ultrasonic under 300W, obtain the precursor solution of thin layer boron nitride；Under centrifugal speed is 3000r/min, thin layer is nitrogenized
The precursor solution centrifugation 5min of boron, then take upper strata centrifugal liquid, obtain superthin layer boron nitride solution；By superthin layer boron nitride
Solution carries out vacuum filtration, then the solid matter obtained after sucking filtration is vacuum dried at temperature is 80 DEG C 12h, obtains superthin layer
Boron nitride powder；
Step one 2. described in the quality of presoma of dried thin layer boron nitride with the volume ratio of organic solvent be
1g:100mL；
Step one 2. described in organic solvent be N-Methyl pyrrolidone；
Two, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film:
1., by step one 2. in the superthin layer boron nitride powder that obtains be dissolved in dimethyl acetylamide, obtain quality and divide
Number is the ultrathin boron nitride solution of 0.5%；
2., by diamidogen join in the superthin layer boron nitride solution that mass fraction is 0.5%, then low whipping speed is
Stirring reaction 60min under 100r/min, more ultrasonic 12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Again at ice-water bath and
Mixing speed is to divide dianhydride powder 5 times under conditions of 100r/min to join in two amine aqueous solutions, obtains thick containing polyamides
Amino acid and the solution of superthin layer boron nitride；
Step 2 2. described in the volume ratio of the superthin layer boron nitride solution that quality and mass fraction are 0.5% of diamidogen
For 3g:60mL；
Step 2 2. described in the mol ratio of dianhydride and diamidogen be 1:1；
Step 2 2. described in diamidogen be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；Described equal benzene-type dianhydride is Pyromellitic Acid two
Acid anhydride；
Step 2 2. described in the time every time adding dianhydride powder be 10min；
3., will the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature stand
2h, then be spun on the glass plate of cleaning, then with the heating rate of 5 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
Insulation 1h, then naturally cool to room temperature, the last demoulding, obtain high-performance polyimide/ultrathin boron nitride laminated film；
Step 2 3. described in the thickness of high-performance polyimide/ultrathin boron nitride laminated film be 40 μm.
The 1. described boron nitride powder of embodiment two step one is conventional multilayer bulk boron nitride powder.
Embodiment three: the preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film, is according to the following steps
Complete:
One, ultrathin boron nitride powder is prepared:
1., 6g boron nitride powder and 20g oxide are joined in 400mL concentrated acid, then at ice-water bath and mixing speed be
Under 100r/min, stirring reaction 60min, obtains mixture A；Mixture A is heated to 50 DEG C, then is 50 DEG C and stirring in temperature
Speed is stirring reaction 60min under 100r/min, is cooled to room temperature, then rate of addition with 1mL/min drips in mixture A
Enter the hydrogen peroxide solution that 10mL mass fraction is 85%, obtain mixture B；Under ice-water bath, in mixture B, add 350mL
Deionized water, obtains mixture C；Again by mixture C centrifugation 5min under centrifugal speed is 6000r/min, remove centrifugal
Liquid, obtains the presoma of thin layer boron nitride；Hydrochloric acid first by 0.5mol/L cleans the presoma 3 times of thin layer boron nitride, then
The presoma of use deionized water cleaning thin layer boron nitride 5 times, the presoma of the thin layer boron nitride after being cleaned；
Step one 1. described in concentrated acid be mass fraction be the concentrated sulphuric acid of 98%；
Step one 1. described in oxide be potassium permanganate；
2., will clean after the presoma of thin layer boron nitride at temperature is 80 DEG C, be vacuum dried 12h, obtain dried
The presoma of thin layer boron nitride；The presoma of dried thin layer boron nitride is joined in organic solvent, then at ultrasonic power
For 12h ultrasonic under 300W, obtain the precursor solution of thin layer boron nitride；Under centrifugal speed is 3000r/min, thin layer is nitrogenized
The precursor solution centrifugation 5min of boron, then take upper strata centrifugal liquid, obtain superthin layer boron nitride solution；By superthin layer boron nitride
Solution carries out vacuum filtration, then the solid matter obtained after sucking filtration is vacuum dried at temperature is 80 DEG C 12h, obtains superthin layer
Boron nitride powder；
Step one 2. described in the quality of presoma of dried thin layer boron nitride with the volume ratio of organic solvent be
1g:100mL；
Step one 2. described in organic solvent be dimethylformamide；
Two, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film:
1., by step one 2. in the superthin layer boron nitride powder that obtains be dissolved in dimethyl acetylamide, obtain quality and divide
Number is the ultrathin boron nitride solution of 1%；
2., by diamidogen join in the superthin layer boron nitride solution that mass fraction is 1%, then low whipping speed is 100r/
Stirring reaction 60min under min, more ultrasonic 12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Again in ice-water bath and stirring
Speed is to divide dianhydride powder 5 times under conditions of 100r/min to join in two amine aqueous solutions, obtains thick containing polyamic acid
Solution with superthin layer boron nitride；
Step 2 2. described in the quality of diamidogen with the volume ratio of the superthin layer boron nitride solution that mass fraction is 1% be
3g:60mL；
Step 2 2. described in the mol ratio of dianhydride and diamidogen be 1:1；
Step 2 2. described in diamidogen be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；Described equal benzene-type dianhydride is Pyromellitic Acid two
Acid anhydride；
Step 2 2. described in the time every time adding dianhydride powder be 10min；
3., will the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature stand
2h, then be spun on the glass plate of cleaning, then with the heating rate of 5 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
Insulation 1h, then naturally cool to room temperature, the last demoulding, obtain high-performance polyimide/ultrathin boron nitride laminated film；
Step 2 3. described in the thickness of high-performance polyimide/ultrathin boron nitride laminated film be 40 μm.
The 1. described boron nitride powder of embodiment three step one is conventional multilayer bulk boron nitride powder.
Embodiment four: the preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film, is according to the following steps
Complete:
One, ultrathin boron nitride powder is prepared:
1., 6g boron nitride powder and 20g oxide are joined in 400mL concentrated acid, then at ice-water bath and mixing speed be
Under 100r/min, stirring reaction 60min, obtains mixture A；Mixture A is heated to 50 DEG C, then is 50 DEG C and stirring in temperature
Speed is stirring reaction 60min under 100r/min, is cooled to room temperature, then rate of addition with 1mL/min drips in mixture A
Enter the hydrogen peroxide solution that 10mL mass fraction is 85%, obtain mixture B；Under ice-water bath, in mixture B, add 350mL
Deionized water, obtains mixture C；Again by mixture C centrifugation 5min under centrifugal speed is 6000r/min, remove centrifugal
Liquid, obtains the presoma of thin layer boron nitride；Hydrochloric acid first by 0.5mol/L cleans the presoma 3 times of thin layer boron nitride, then
The presoma of use deionized water cleaning thin layer boron nitride 5 times, the presoma of the thin layer boron nitride after being cleaned；
Step one 1. described in concentrated acid be mass fraction be the concentrated sulphuric acid of 98%；
Step one 1. described in oxide be potassium permanganate；
2., will clean after the presoma of thin layer boron nitride at temperature is 80 DEG C, be vacuum dried 12h, obtain dried
The presoma of thin layer boron nitride；The presoma of dried thin layer boron nitride is joined in organic solvent, then at ultrasonic power
For 12h ultrasonic under 300W, obtain the precursor solution of thin layer boron nitride；Under centrifugal speed is 3000r/min, thin layer is nitrogenized
The precursor solution centrifugation 5min of boron, then take upper strata centrifugal liquid, obtain superthin layer boron nitride solution；By superthin layer boron nitride
Solution carries out vacuum filtration, then the solid matter obtained after sucking filtration is vacuum dried at temperature is 80 DEG C 12h, obtains superthin layer
Boron nitride powder；
Step one 2. described in the quality of presoma of dried thin layer boron nitride with the volume ratio of organic solvent be
1g:100mL；
Step one 2. described in organic solvent be N-Methyl pyrrolidone；
Two, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film:
1., by step one 2. in the superthin layer boron nitride powder that obtains be dissolved in dimethyl acetylamide, obtain quality and divide
Number is the ultrathin boron nitride solution of 3%；
2., by diamidogen join in the superthin layer boron nitride solution that mass fraction is 3%, then low whipping speed is 100r/
Stirring reaction 60min under min, more ultrasonic 12h under ultrasonic power is 300W, obtain two amine aqueous solutions；Again in ice-water bath and stirring
Speed is to divide dianhydride powder 5 times under conditions of 100r/min to join in two amine aqueous solutions, obtains thick containing polyamic acid
Solution with superthin layer boron nitride；
Step 2 2. described in the quality of diamidogen with the volume ratio of the superthin layer boron nitride solution that mass fraction is 3% be
3g:60mL；
Step 2 2. described in the mol ratio of dianhydride and diamidogen be 1:1；
Step 2 2. described in diamidogen be 4,4 '-diaminodiphenyl ether；
Step 2 2. described in dianhydride powder be equal benzene-type dianhydride；Described equal benzene-type dianhydride is Pyromellitic Acid two
Acid anhydride；
Step 2 2. described in the time every time adding dianhydride powder be 10min；
3., will the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature stand
2h, then be spun on the glass plate of cleaning, then with the heating rate of 5 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
Insulation 1h, then naturally cool to room temperature, the last demoulding, obtain high-performance polyimide/ultrathin boron nitride laminated film；
Step 2 3. described in the thickness of high-performance polyimide/ultrathin boron nitride laminated film be 40 μm.
The 1. described boron nitride powder of embodiment four step one is conventional multilayer bulk boron nitride powder.
Fig. 1 is the TEM figure of the superthin layer boron nitride powder of embodiment one step one preparation；
From fig. 1, it can be seen that the boron nitride of bulk has been stripped sheet boron nitride, transmission electron microscope shows a lot of thin slice
Being packed together, super rich boron nitride sheet is high-visible in edge.
Fig. 2 is the SEM figure of high-performance polyimide/ultrathin boron nitride laminated film prepared by embodiment one step 2；
As can be seen from Figure 2, thin layer boron nitride lamella is wrapped up by polyimides, is uniformly dispersed in polyimide matrix, sheet
Rotating fields is obvious, and most lamella is parallel with film surface direction, and this kind of structure is conducive to promoting its electrical insulation properties.
High-performance polyimide/the ultrathin boron nitride using scanning electron microscopy Electronic Speculum to prepare embodiment one step 2 is multiple
The B element closing thin 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 embodiment one step 2
Figure；
As can be seen from Figure 3, boron element is evenly distributed in composite, because polyimide matrix does not contains B element, this
Characterize the existence in the composite of provable boron nitride.
High-performance ultrathin polyimides/the boron nitride using scanning electron microscopy Electronic Speculum to prepare embodiment one step 2 is multiple
The N element closing thin 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 embodiment one step 2
Figure；
As can be seen from Figure 4, N element is evenly distributed in composite, and this characterizes can prove that boron nitride is compound further
Existence in material.
Use high-performance ultrathin polyimides/boron nitride that embodiment one step 2 is prepared by micro-control electronic universal tester
High-performance ultrathin polyimides/boron nitride laminated film prepared by laminated film, embodiment two step 2, embodiment three step 2
High-performance ultrathin polyamides prepared by the high-performance ultrathin polyimides/boron nitride laminated film of preparation and embodiment four step 2 is sub-
The hot strength of amine/boron nitride laminated film characterizes, as shown in Figure 5；
Fig. 5 is the elongation at break variation diagram with hot strength of high-performance polyimide/ultrathin boron nitride laminated film,
In Fig. 5,1 is that the elongation at break of high-performance polyimide/ultrathin boron nitride laminated film prepared by embodiment one step 2 is with drawing
Stretching the change curve of intensity, 2 is the disconnected of high-performance polyimide/ultrathin boron nitride laminated film of preparing of embodiment two step 2
Splitting the percentage elongation change curve with hot strength, 3 is high-performance polyimide/ultrathin boron nitride prepared by embodiment three step 2
The elongation at break of laminated film is with the change curve of hot strength, and 4 is that high-performance ultrathin prepared by embodiment four step 2 gathers
The elongation at break of acid imide/boron nitride laminated film is with the change curve of hot strength, the 5 pure polyamides prepared for contrast test
The elongation at break of imines is with the change curve of hot strength；
The interpolation of a small amount of boron nitride significantly improves hot strength and the elongation at break of composite as can be seen from Figure 5, this
Be conducive to expanding composite polyimide material service life in actual applications.
High-performance polyimide/the ultrathin boron nitride using precise impedance analyser to prepare embodiment one step 2 is combined
Prepared by high-performance ultrathin polyimides/boron nitride laminated film, embodiment three step 2 prepared by thin film, embodiment two step 2
High-performance polyimide/ultrathin boron nitride laminated film and embodiment four step 2 prepare high-performance ultrathin polyimides/
The dielectric properties of boron nitride laminated film characterize, and figure is as indicated with 6；
Fig. 6 is the dielectric properties figure of high-performance polyimide/ultrathin boron nitride laminated film, and in Fig. 6,1 is embodiment one step
The dielectric properties curve of the high-performance polyimide/ultrathin boron nitride laminated film of rapid two preparations, 2 is embodiment two step 2 system
The dielectric properties curve of standby high-performance polyimide/ultrathin boron nitride laminated film, 3 is height prepared by embodiment three step 2
The dielectric properties curve of performance polyimides/ultrathin boron nitride laminated film, 4 is high-performance poly prepared by embodiment four step 2
The dielectric properties curve of acid imide/ultrathin boron nitride laminated film.
Contrast test: the preparation method of pure polyimides completes according to the following steps:
One, diamidogen is joined in N-Methyl pyrrolidone, then low whipping speed is stirring reaction under 100r/min
60min, more ultrasonic 12h under ultrasonic power is 300W, obtain two amine aqueous solutions；It is 100r/min at ice-water bath and mixing speed again
Under conditions of dianhydride powder divided 5 times join in two amine aqueous solutions, obtain thick containing polyamic acid solution；
The quality of the diamidogen described in step one and the volume ratio of N-Methyl pyrrolidone are 3g:60mL；
Dianhydride described in step one is 1:1 with the mol ratio of diamidogen；Diamidogen described in step one is 4,4 '-diaminourea hexichol
Ether；
Dianhydride powder described in step one is equal benzene-type dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride；
The time every time adding dianhydride powder described in step one is 10min；
Two, will the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature stand
2h, then be spun on the glass plate of cleaning, then with the heating rate of 5 DEG C/min from room temperature to 350 DEG C, then at 350 DEG C
Insulation 2h, then naturally cool to room temperature, the last demoulding, obtain high-performance polyimide/ultrathin boron nitride laminated film；
The thickness of the high-performance polyimide described in step 2/ultrathin boron nitride laminated film is 40 μm.
High-performance polyimide/ultra-thin nitridation prepared by pure polyimides prepared by contrast test, embodiment one step 2
High-performance polyimide/ultrathin boron nitride laminated film prepared by boron laminated film, embodiment two step 2, embodiment three step
High-performance polyamides prepared by the high-performance polyimide/ultrathin boron nitride laminated film of two preparations and embodiment four step 2 is sub-
Heat conductivity and the Inverter fed motor life-span of amine/ultrathin boron nitride laminated film test, and data are shown in Table 1；
Table 1
As known from Table 1, the interpolation of a small amount of thin layer boron nitride, be greatly improved polyimide composite film heat conductivility and
The Inverter fed motor life-span.
Claims (10)
1. the preparation method of high-performance polyimide/ultrathin boron nitride laminated film, it is characterised in that a kind of high-performance poly
The preparation method of acid imide/ultrathin boron nitride laminated film completes according to the following steps:
One, ultrathin boron nitride powder is prepared:
1., boron nitride powder and oxide are joined in concentrated acid, then be 100r/min～300r/ at ice-water bath and mixing speed
Under min, stirring reaction 60min～120min, obtains mixture A；Mixture A is heated to 50 DEG C, then is 50 DEG C and stir in temperature
Mixing speed is stirring reaction 60min～180min under 100r/min～300r/min, is cooled to room temperature, then in mixture A
Instilling mass fraction with the rate of addition of 1mL/min is the hydrogen peroxide solution of 85%, obtains mixture B；Under ice-water bath, to mixed
Compound B adds deionized water, obtains mixture C；Again by mixture C under centrifugal speed 6000r/min～8000r/min from
The heart separates 5min～15min, removes centrifugal liquid, obtains the presoma of thin layer boron nitride；Hydrochloric acid first by 0.5mol/L is clear
Wash the presoma 3 times of thin layer boron nitride, re-use deionized water and clean the presoma 5 times～8 times of thin layer boron nitride, cleaned
After the presoma of thin layer boron nitride；
Step one 1. described in the quality of boron nitride powder and the volume ratio of concentrated acid be (4g～8g): 400mL；
Step one 1. described in the quality of oxide and the volume ratio of concentrated acid be (20g～40g): 400mL；
Step one 1. described in the volume ratio of the hydrogen peroxide solution that concentrated acid and mass fraction are 85% be 400:(5～10)；
Step one 1. described in the volume ratio of concentrated acid and deionized water be 400:(300～400)；
2., will clean after the presoma of thin layer boron nitride at temperature is 80 DEG C～100 DEG C, be vacuum dried 12h～24h, obtain
The presoma of dried thin layer boron nitride；The presoma of dried thin layer boron nitride is joined in organic solvent, then
Ultrasonic power is ultrasonic 12h～24h under 100W～500W, obtains the precursor solution of thin layer boron nitride；In centrifugal speed it is
Precursor solution centrifugation 5min～10min to thin layer boron nitride under 3000r/min, then take upper strata centrifugal liquid, surpassed
Thin layer boron nitride solution；Superthin layer boron nitride solution is carried out vacuum filtration, then by the solid matter that obtains after sucking filtration in temperature
It is vacuum drying 12h～24h at 80 DEG C～100 DEG C, obtains superthin layer boron nitride powder；
Step one 2. described in the quality of presoma and the volume ratio of organic solvent of dried thin layer boron nitride be (1g～
3g):100mL；
Two, the ultra-thin polyimides of in-situ polymerization synthesized high-performance/boron nitride laminated film:
1., by step one 2. in the superthin layer boron nitride powder that obtains be dissolved in organic solvent, obtaining mass fraction is
The ultrathin boron nitride solution of 0.25%～5%；
2., by diamidogen join in the superthin layer boron nitride solution that mass fraction is 0.25%～5%, then low whipping speed is
Under 100r/min～300r/min stirring reaction 60min～120min, then under ultrasonic power is 100W～500W ultrasonic 12h～
24h, obtains two amine aqueous solutions；Under conditions of ice-water bath and mixing speed are 100r/min～300r/min, dianhydride powder is divided again
Join in two amine aqueous solutions for 5 times, obtain thick containing polyamic acid with the solution of superthin layer boron nitride；
Step 2 2. described in the volume of the superthin layer boron nitride solution that quality and mass fraction are 0.25%～3% of diamidogen
Ratio is 3g:(40mL～60mL)；
Step 2 2. described in the mol ratio of dianhydride and diamidogen be 1:1；
3., by the thick solution containing polyamic acid and superthin layer boron nitride vacuum tank at room temperature stands 2h～
6h, then be cast, spin coating or plastic film mulch 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 at 350 DEG C, be incubated 1h～2h, then naturally cool to room temperature, the last demoulding, obtain high-performance polyimide/ultra-thin
Boron nitride laminated film；
Step 2 3. described in the thickness of high-performance polyimide/ultrathin boron nitride laminated film be 30 μm～50 μm.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, it is special
Levy be the concentrated acid described in step one is 1. be mass fraction be concentrated sulphuric acid or the mixed acid of 98%；Described mixed acid is quality
Phosphoric acid and the mixed liquor of nitric acid that mass fraction is 98% that concentrated sulphuric acid that mark is 98%, mass fraction are 85%；Described
In mixed acid mass fraction be 98% concentrated sulphuric acid, mass fraction be 85% phosphoric acid and the body of nitric acid that mass fraction is 98%
Long-pending ratio is 1:1:5.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, it is special
Levy and be that the oxide described in step one is 1. is potassium permanganate or potassium ferrate.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, it is special
Levy and be that the organic solvent described in step one is 2. is N-Methyl pyrrolidone, dimethylformamide or dimethyl acetylamide.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, it is special
Levy and be that the organic solvent described in step 2 is 1. is N-Methyl pyrrolidone, dimethylformamide or dimethyl acetylamide.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, it is special
Levy and be that the diamidogen described in step 2 is 2. is 4,4 '-diaminodiphenyl ether.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, it is special
Levy and be that the dianhydride powder described in step 2 is 2. is biphenyl type dianhydride or equal benzene-type dianhydrides；Described biphenyl type dianhydride is 3,
3', 4,4'-biphenyl tetracarboxylic dianhydride；Described equal benzene-type dianhydride is pyromellitic acid anhydride.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, it is special
Levy and be that the time every time adding dianhydride powder described in step 2 is 2. is 10min.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, it is special
Levy and be that the plate described in step 2 is 3. is glass plate or steel plate.
The preparation method of a kind of high-performance polyimide/ultrathin boron nitride laminated film the most according to claim 1, its
It is characterised by that the quality of the boron nitride powder described in step one is 1. and the volume ratio of concentrated acid are 6g:400mL.
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