CN108997754A - A kind of polyimides high-temperature dielectric composite membrane and preparation method thereof - Google Patents
A kind of polyimides high-temperature dielectric composite membrane and preparation method thereof Download PDFInfo
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The purpose of the present invention is to provide a kind of polyimides high-temperature dielectric composite film materials and preparation method thereof, the composite membrane is blended by least one of hexagonal boron nitride nanosheet, molybdenum disulfide nano sheet with polyimides, wherein the mass fraction of hexagonal boron nitride nanosheet is 6%-12%, and the mass fraction of molybdenum disulfide nano sheet is 1%-2%.The introducing of nanometer sheet filler not only increases the hot property of polyimide film, while further improving the high temperature dielectric properties that traditional PI film is never related to.The composite membrane has lower dielectric loss, higher breakdown strength, energy storage density and energy storage efficiency at normal temperature, and lower conductance loss and higher disruptive field intensity and energy storage density are still maintained under 150 DEG C of high temperature.
Description
Technical field
The present invention relates to composite film material technical fields, and in particular to a kind of polyimides high-temperature dielectric composite membrane and its
Preparation method.
Background technique
The concern of power energy storage increasingly increases, and has also greatly caused scientist to the emerging of flexible dielectric material research
Interest.In order to meet application of emerging high-energy density (UE)-capacitor in terms of hybrid vehicle, electronic weaponry,
It include the various aspects such as high-energy, high power density, excellent machinability, environmental protection, flexible energy stores to improved dielectric material
More stringent requirements are proposed for performance, and bigger challenge is especially proposed in terms of high temperature resistant.
Polyimides (PI) refers to the quasi polymer for containing imide ring (- CO-NH-CO-) on main chain, wherein to contain
The polymer of phthalimide structure is mostly important.Polyimides has been widely used as a kind of special engineered material in aviation, boat
It, the fields such as microelectronics, nanometer, liquid crystal, seperation film, laser.Polyimides is the optimal high-molecular organic material of comprehensive performance
One of, high temperature resistant has high insulation up to 400 DEG C or more, -200~300 DEG C of long-term use temperature range, and without sharp melting point
Performance.
Molybdenum disulfide is (MoS2) it is a kind of black solid powder with silver gray metallic luster, have preferable hydrophobic
Property, concentrated acid is dissolved in, excellent rub resistance wearing character is shown.By MoS2Powder removes manufactured MoS2Nanometer sheet has only
The catalytic performance of spy, optical property, piezoelectric property, thus by extensive concern.Unlike graphene, MoS2Nanometer sheet with
The number of plies is reduced, and when being especially reduced to monoatomic layer, band gap is changed into direct band gap from indirect bandgap 1.2eV
1.9eV, stronger fluorescent effect are attributable to the electronic structure that band gap transformation generates and change.In addition, MoS2Nanometer sheet is unique
Structure feature and physicochemical characteristics become the important source material in flexible electronic device.Molybdenum disulfide or semiconductor material
Material, dielectric properties can be improved by being introduced into composite material.
Hexagonal boron nitride (h-BN) is similar to graphite-structure, and the two possesses many denominators, as along perpendicular to basal plane
Anisotropy, high mechanical strength, good thermal conductivity and lubricity.Hexagonal boron nitride is removed as flaky nanometer structure, filling
Interfacial polarization effect can be increased into composite material, what high temperature dielectric properties of the breakdown strength of matrix helped to improve.
The comprehensive performance of pure polyimide film material is simultaneously imperfect, it usually needs composite wood is made together with other fillers
Material, filler used include boron nitride or aluminium nitride powder (CN106380844B, CN106084219B, CN104892968B),
Barium titanate (CN108059725A), molybdenum disulfide (CN105037765A), metal oxide (CN106832361A) etc..These
Polyimide film material more pays close attention to hot property (resistance to high/low temperature or thermal conductivity), and there are techniques and complicated component, inorganic filler
The deficiencies of loading is big, filler and basal body interface effect are weaker, and seldom it is related to the dielectricity of polyimide composite film material
It can research, especially high temperature (150 DEG C) Dielectric Properties.
Summary of the invention
It is an object of the invention to solve the problems, such as that high temperature dielectric properties existing for existing polyimide film material are imperfect,
There is provided a kind of molybdenum disulfide nano sheet, hexagonal boron nitride nanosheet filling-modified polyimide composite film material, the membrane material
Good, high temperature dielectric properties and thermal stability with excellent flexibility.To achieve the above object, the technology used in the present invention side
Case is as follows:
A kind of polyimides high-temperature dielectric composite membrane, by hexagonal boron nitride nanosheet, molybdenum disulfide nano sheet at least
One kind is blended with polyimides, and wherein the mass fraction of hexagonal boron nitride nanosheet is 6%-12%, molybdenum disulfide nano
The mass fraction of piece is 1%-2%.
Another object of the present invention is to provide the preparation method of above-mentioned polyimides high-temperature dielectric composite membrane, including it is following
Step:
(a) polyamic acid is prepared；
(b) hexagonal boron nitride nanosheet (BNNS) and molybdenum disulfide nano sheet are prepared；
(c) dispersion of at least one of hexagonal boron nitride nanosheet, molybdenum disulfide nano sheet is obtained in organic solvent
Dispersion liquid, by dispersion liquid and polyamic acid casting film-forming after mixing, then heating carries out hot imidization reaction, finally obtains
Polyimides high-temperature dielectric composite membrane.
Further, the preparation method of polyamic acid is specific as follows: octadecylamine (ODA) being dissolved in N- under protective atmosphere
In N dimethyl pyrrolidones (NMP), then pyromellitic acid anhydride (PMDA) is added portionwise, ice-water bath be stirred to react after 1-2h from
Heart separation.Wherein the molar ratio of pyromellitic acid anhydride and octadecylamine is (1.00-1.04): 1.
Further, the preparation method of hexagonal boron nitride nanosheet is specific as follows: by hexagonal boron nitride mineral dust and urine
Element is added to the water, and the used membrane filtration of supernatant is taken after ultrasonic disperse is uniform, obtained solid is dispersed again in water, repeats to divide
Hexagonal boron nitride nanosheet, drying for standby are obtained after dissipating-filtering repeatedly (more than three times, being dispersed with water).Wherein six side
The mass ratio of boron nitride mineral dust and urea is 1:(100-110).
Further, the preparation method of molybdenum disulfide nano sheet specifically: by molybdenum disulfide powder ultrasonic disperse in three second
The used membrane filtration of supernatant is taken in hydramine, after centrifugation, obtained solid is dispersed again in water, and it is multiple to repeat dispersion-filtering
Molybdenum disulfide nano sheet, drying for standby are obtained after (more than three times, being dispersed with water).Wherein molybdenum disulfide and triethanolamine
Mass ratio be 1:(100-110).
Further, ultrasonic disperse time first time is 6- when preparing hexagonal boron nitride nanosheet and molybdenum disulfide nano sheet
10h, ultrasound are centrifuged 10-30min after the completion with the revolving speed of 2000-4000rpm, supernatant 200-230nm are taken after the completion of centrifugation
Membrane filtration, dispersion-filtering whole process number of repetition be 3 times or more.
Further, in step (c) by hexagonal boron nitride nanosheet ultrasonic disperse in N-N dimethyl pyrrolidone, then
Be added polyamic acid and ultrasonic mixing it is uniform, gained mixed liquor casting film-forming on substrate, then respectively 100 DEG C, 200 DEG C,
1-1.2h is placed at 300 DEG C and carries out hot imidization reaction, and it is multiple to obtain polyimides/hexagonal boron nitride nanosheet binary high-temperature dielectric
Film is closed, the mass fraction of hexagonal boron nitride nanosheet is 6%-12% in the composite membrane.
Further, in step (c) by hexagonal boron nitride nanosheet and molybdenum disulfide nano sheet ultrasonic disperse in N-N diformazan
In base pyrrolidones, adds polyamic acid and ultrasonic mixing is uniform, then gained mixed liquor casting film-forming on substrate is distinguished
1-1.2h is placed at 100 DEG C, 200 DEG C, 300 DEG C and carries out hot imidization reaction, obtains polyimides/hexagonal nanometer boron nitride
Piece/molybdenum disulfide nano sheet ternary high-temperature dielectric composite membrane, the mass fraction of hexagonal boron nitride nanosheet is in the composite membrane
6%-12%, the mass fraction of molybdenum disulfide nano sheet are 1%-2%.
Urea and triethanolamine removing boron nitride is respectively adopted in the present invention and molybdenum disulfide obtains corresponding nanometer sheet, by
The energy of ultrasonic wave promotes the urea being dissolved in water and triethanolamine hydrolysis, hydrolyzes the amino and few layer boron nitride and less of generation
Layer molybdenum disulfide generates bonding by chemical bond, is as a result exactly the defect and edge that amino can be made to be connected to h-BN and molybdenum disulfide
Place, so that the interlayer of molybdenum disulfide and boron nitride is easily opened, and amino can also prevent boron nitride nanosheet and molybdenum disulfide
The reunion of nanometer sheet.On the other hand, compared with in-situ polymerization prepares the mode of composite membrane, present invention use gathers before first preparing PAA
The mode that body is mixed with molybdenum disulfide nano sheet or hexagonal boron nitride nanosheet again can be effectively prevented during in-situ polymerization
Influence of the impurity that common molybdenum disulfide nano sheet and hexagonal boron nitride nanosheet introduce to polymerization reaction, is also possible to prevent to draw
The moisture entered influences subsequent hot imidization degree.
Compared with prior art, beneficial effects of the present invention specific manifestation are as follows:
(1) limitation that traditional polyimide film is absorbed in hot property is breached, the filler by introducing nanometer chip architecture obtains
Obtained while having the composite film material of preferable hot property and dielectric properties.The polyimide composite film being prepared is at normal temperature
Dielectric constant with higher, lower dielectric loss and higher breakdown strength, energy storage density and energy storage efficiency, and it is thin
Film flexibility is good, still has excellent mechanical property at high temperature.
(2) first polyimides is modified with the filler with special construction and material, has been obtained functional compound
Membrane material.Compared with powder, molybdenum disulfide nano sheet has big surface area, can form enough interfaces with polyimide matrix
Polarization；Furthermore molybdenum disulfide is semiconductor material, and dielectric constant with higher can largely improve composite membrane
Dielectric constant.Hexagonal boron nitride nanosheet equally possesses big surface area, can generate bigger interface with polyimide matrix
Polarization improves dielectric constant simultaneously.In addition, hexagonal boron nitride nanosheet has good insulation performance, can effectively improve
The disruptive field intensity of composite membrane.Most important, hexagonal boron nitride nanosheet has good heating conduction, can effectively reduce poly-
The high-temperature electrical conductivity of acid imide membrane material is lost, and effectively improves the energy storage density of composite material at high temperature.
(3) polyimides belongs to hexagonal boron nitride nanosheet, the mixed process of molybdenum disulfide nano sheet in recombination process
Physical process does not chemically react, and technique is simpler, operates more convenient, no pollution to the environment, and loading is more flexible
Controllably.
Detailed description of the invention
Fig. 1 is the TEM figure of hexagonal boron nitride nanosheet made from the embodiment of the present invention 1.
Fig. 2 is polyimides/hexagonal boron nitride nanosheet composite membrane SEM cross-section diagram made from the embodiment of the present invention 1.
Fig. 3 is polyimides/hexagonal boron nitride nanosheet composite membrane made from the embodiment of the present invention 1 and pure PI at 150 DEG C
The energy storage density comparison diagram of film.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Comparative example 1
Prepare pure polyimide film
1) in view of the easy moisture absorption of PMDA leads to performance depreciation, to obtain the sufficiently large polyamic acid of molecular weight, according to PMDA:
The molar ratio of ODA is that 1.002:1 feeds intake, and concrete operations are as follows: 10mmol ODA being dissolved in nmp solvent first, is stirred
The weighing 10.02mmol PMDA after ODA is completely dissolved is mixed, it is added in batches in 30min and fills ODA-NMP mixing
In the four-hole boiling flask of solution, then four-hole boiling flask is placed in ice water bath apparatus and guarantees low temperature environment, prevents point of polyamic acid
Solution.By lasting stirring in 24 hours, the polyamic acid with certain viscosity, weak yellow liquid shape is obtained.It is collected in centrifugation
Guan Zhong is installed with packaging bag and is carefully deposited in refrigerator.Entire experimental provision is stringent moisture-proof anti-oxidation, arranges in pairs or groups in experimental rig
Before starting operation after good, it need to be passed through nitrogen checking experiment device air-tightness, while draining the air of experimental provision.
2) after polyamic acid solution obtained being taken out magnetic agitation 12h, using ultrasonic cleaning machine ultrasonic disperse 1h, then will
It is placed in casting film-forming on glass plate, then carries out hot imidization reaction, the specific method is as follows: the film being cast is placed in vacuum
In drying box, it is heat-treated 1h under the conditions of 100 DEG C, 200 DEG C, 300 DEG C respectively, obtains pure PI film.The purpose of hot imidization is
Keep intramolecular dehydration cyclic, obtains the pure Kapton of high molecular weight.
Embodiment 1
Prepare hexagonal boron nitride nanosheet/polyimides binary composite membrane
1) h-BN and urea are weighed by the mass ratio of 1:100, be dispersed in 100mL water and stirred evenly.By gained
Mixture, which is placed in sonicator, to be ultrasonically treated 8 hours, is then centrifuged 20min with 3000rpm revolving speed.Supernatant is used
The membrane filtration of 220nm, obtained solid matter are uniformly dispersed with deionized water, are filtered again.By dispersing (moisture three times
Dissipate) and filtering (same filter membrane) after, collect filter paper on few layer of BNNS, place it in 70 DEG C of vacuum dry 8h.
2) it is that 1.002:1 feeds intake according to the molar ratio of PMDA:ODA, 10mmol ODA is dissolved in nmp solvent,
Stirring weighs 10.02mmol PMDA after ODA is completely dissolved, it is added in batches in 30min and fills ODA-NMP and mixes
In the four-hole boiling flask for closing solution, then four-hole boiling flask is placed in ice water bath apparatus and guarantees low temperature environment, prevents polyamic acid
It decomposes.By lasting stirring in 24 hours, the polyamic acid with certain viscosity, weak yellow liquid shape is obtained.Be collected in from
In heart pipe, is installed with packaging bag and carefully deposited in refrigerator.Entire experimental provision is passed through nitrogen in advance.
3) it is that BNNS is enable to be uniformly dispersed in Kapton, a certain amount of BNNS is needed to be added in nmp solvent, and
Ultrasonic disperse 0.5h, then dispersion liquid is added in polyamic acid, ultrasonic disperse 1h after magnetic agitation 12h, then by above-mentioned solution
It is placed in casting film-forming on glass plate, is then reacted according to the identical method of comparative example 1 progress hot imidization, finally obtains difference
The BNNS nanometer sheet of loading/PI binary composite membrane.Prepare respectively BNNS loading be 8wt%, 12wt% BNNS nanometer sheet/
PI binary composite membrane.
The SEM photograph point of few layer BNNS and 12wt%BNNS nanometer sheet/PI binary composite membrane section made from the present embodiment
Not not as depicted in figs. 1 and 2.It, can be with it will be seen from figure 1 that apparent lattice fringe is presented in the region, and from electron diffraction diagram
Find out that nanometer sheet is hexagonal crystal system, it is good that these all demonstrate prepared nanometer sheet crystallinity.In addition can be observed containing 4 layers
The thickness of BNNS is about 2nm, and the thickness 0.333nm of this and the individual layer nanometer sheet reported in document is consistent.Fig. 2 shows
For BNNS in polyimide matrix, whole well dispersed, the exposed BNNS on surface is less, most of to be all embedded in polyimides
In matrix, illustrate that BNNS and polyimides compatibility are preferable, uniform dispersed filler is in matrix.
Embodiment 2
Prepare molybdenum disulfide nano sheet/hexagonal boron nitride nanosheet/polyimides tri compound film
1) molybdenum disulfide black powder and triethanolamine are weighed by the mass ratio of 1:100, be mixed evenly.Gained is mixed
Conjunction object, which is placed in sonicator, to be ultrasonically treated 8 hours, is then centrifuged 20min with the revolving speed of 3000rpm, supernatant is used
The membrane filtration of 220nm, obtained solid matter are uniformly dispersed with deionized water, are filtered again.By dispersing (moisture three times
Dissipate) and filtering (same filter membrane) after, collect filter paper on few layer of molybdenum disulfide nano sheet, place it in 70 DEG C of vacuum dry
8h。
2) hexagonal boron nitride nanosheet (BNNS) and polyamic acid are prepared respectively according to the method for embodiment 1.
3) a certain amount of BNNS and molybdenum disulfide nano sheet are added in nmp solvent, ultrasonic disperse 0.5h, then by dispersion liquid
It is added in polyamic acid, above-mentioned solution is then placed on glass plate and is cast by re-ultrasonic dispersion 1h after magnetic agitation 12h
Then film carries out the sub- amidation process of heat according to method identical with comparative example 1, finally obtains the molybdenum disulfide of different loadings
Nanometer sheet/BNNS nanometer sheet/PI tri compound film.Prepare respectively molybdenum disulfide and BNNS loading be 1wt% and 8wt%,
The molybdenum disulfide nano sheet of 1wt% and 12wt%/BNNS nanometer sheet/PI tri compound film.
HIOKI3532-50LCR type dielectric and magnetic instrument and ferroelectricity instrument are utilized respectively to comparative example 1 of the present invention and embodiment 1-2
Polyimide film obtained has carried out the performances such as dielectric and ferroelectricity and has been tested, as a result as shown in the table:
The performance test results of 1 comparative example of table and embodiment 1-2 polyimide film
As known from Table 1, the addition of (1) boron nitride can effectively inhibit the disruptive field intensity of Kapton under high temperature to reduce
Trend, this breakdown form for being primarily due to polyimides is thermal breakdown, and boron nitride has high thermal conductivity；(2) boron nitride
The energy storage density that can also be improved under Kapton room temperature is added, and slows down the downward trend of energy storage density under high temperature；(3)
The addition of molybdenum disulfide and boron nitride increases the dielectric constant of Kapton.
Claims (10)
1. a kind of polyimides high-temperature dielectric composite membrane, it is characterised in that: the ingredient of the composite membrane includes polyimides and filler,
The filler is selected from least one of hexagonal boron nitride nanosheet, molybdenum disulfide nano sheet.
2. polyimides high-temperature dielectric composite membrane as described in claim 1, it is characterised in that: the ingredient of the composite membrane includes six
Square boron nitride nanosheet, polyimides, wherein the mass fraction of hexagonal boron nitride nanosheet is 6%-12%.
3. polyimides high-temperature dielectric composite membrane as described in claim 1, it is characterised in that: the ingredient of the composite membrane includes six
Square boron nitride nanosheet, molybdenum disulfide nano sheet and polyimides, wherein the mass fraction of hexagonal boron nitride nanosheet be
6%-12%, the mass fraction of molybdenum disulfide nano sheet are 1%-2%.
4. a kind of preparation method of polyimides high-temperature dielectric composite membrane, which comprises the following steps:
(a) polyamic acid is prepared；
(b) hexagonal boron nitride nanosheet and molybdenum disulfide nano sheet are prepared；
(c) dispersion of at least one of hexagonal boron nitride nanosheet, molybdenum disulfide nano sheet is dispersed in organic solvent
Liquid, by dispersion liquid and polyamic acid casting film-forming after mixing, then heating carries out hot imidization reaction, finally obtains polyamides
Imines high-temperature dielectric composite membrane.
5. preparation method as claimed in claim 4, which is characterized in that the preparation method of polyamic acid is specific as follows: protection gas
Octadecylamine is dissolved in N-N dimethyl pyrrolidone under atmosphere, then pyromellitic acid anhydride is added portionwise, ice-water bath stirring is anti-
It is centrifugated after answering 1-2h, wherein the molar ratio of pyromellitic acid anhydride and octadecylamine is (1.00-1.04): 1.
6. preparation method as claimed in claim 4, which is characterized in that the preparation method of hexagonal boron nitride nanosheet is specifically such as
Under: hexagonal boron nitride mineral dust and urea are added to the water, the used membrane filtration of supernatant is taken after ultrasonic disperse is uniform, by institute
It obtains solid to be dispersed again in water, repeats to obtain hexagonal boron nitride nanosheet, drying for standby, wherein six after dispersion-filtering is multiple
The mass ratio of square boron nitride mineral dust and urea is 1:(100-110).
7. preparation method as claimed in claim 4, which is characterized in that the preparation method of molybdenum disulfide nano sheet specifically: will
Molybdenum disulfide powder ultrasonic disperse takes the used membrane filtration of supernatant in triethanolamine, after centrifugation, and obtained solid is divided again
It dissipates in water, repeats to obtain molybdenum disulfide nano sheet after dispersion-filtering is multiple, drying for standby, wherein molybdenum disulfide and three ethyl alcohol
The mass ratio of amine is 1:(100-110).
8. preparation method as claimed in claims 6 or 7, it is characterised in that: preparation hexagonal boron nitride nanosheet or molybdenum disulfide
Ultrasonic disperse time first time is 6-10h when nanometer sheet, and ultrasound is centrifuged 10-30min after the completion with the revolving speed of 2000-4000rpm,
The membrane filtration of supernatant 200-230nm is taken after the completion of centrifugation, dispersion-filtering number of repetition is 3 times or more.
9. preparation method as claimed in claim 4, it is characterised in that: by hexagonal boron nitride nanosheet ultrasound point in step (c)
It is dispersed in N-N dimethyl pyrrolidone, adds polyamic acid and ultrasonic mixing is uniform, gained mixed liquor is cast on substrate
Then film places 1-1.2h respectively at 100 DEG C, 200 DEG C, 300 DEG C and carries out hot imidization reaction, obtains polyimides/six sides
Boron nitride nanosheet binary high-temperature dielectric composite membrane, wherein the mass fraction of hexagonal boron nitride nanosheet is 6%-12%.
10. preparation method as claimed in claim 4, it is characterised in that: by hexagonal boron nitride nanosheet and two sulphur in step (c)
Change molybdenum nanometer sheet ultrasonic disperse in N-N dimethyl pyrrolidone, adds polyamic acid and ultrasonic mixing is uniform, gained mixing
Then liquid casting film-forming on substrate places 1-1.2h respectively at 100 DEG C, 200 DEG C, 300 DEG C and carries out hot imidization reaction, obtains
To polyimides/hexagonal boron nitride nanosheet/molybdenum disulfide nano sheet ternary high-temperature dielectric composite membrane, wherein hexagonal boron nitride is received
The mass fraction of rice piece is 6%-12%, and the mass fraction of molybdenum disulfide nano sheet is 1%-2%.
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