CN108794813A - Compounded mix of a kind of polyimides and barium titanate and preparation method thereof, composite dielectric material and preparation method thereof - Google Patents
Compounded mix of a kind of polyimides and barium titanate and preparation method thereof, composite dielectric material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
Compounded mix of a kind of polyimides and barium titanate and preparation method thereof, composite dielectric material and preparation method thereof.The method for preparing the compounded mix of polyimides and barium titanate, including：Barium titanate is subjected to ultrasonic disperse in n,N-dimethylacetamide solution, under the protection of inert gas, by the barium titanate suspension and 4 after dispersion, then Pyromellitic Acid anhydride reactant is added in the mixing of 4 '-diaminodiphenyl ethers.Polyimides can preferably wrap up nucleocapsid of the barium titanate surface formation using barium titanate as core, polyimides for shell in compounded mix made from this method, which can be improved the conductivity of compounded mix.
Description
Technical field
The present invention relates to dielectric material technical fields, and the compounded mix of more particularly to a kind of polyimides and barium titanate and
Preparation method, composite dielectric material and preparation method thereof.
Background technology
Polarized a kind of material can be generated under DC Electric Field is referred to as dielectric material.Polymer is in external electric field
Also polarization phenomena be will produce under effect, this phenomenon can further cause storage and loss of the polymer to charge, this performance
Just it is called the dielectric properties of polymer.
But the dielectric constant of polymer material is generally all relatively low, it is difficult to meet advanced electronic component and electrical
The growing requirement of technology, the dielectric material of one-component are difficult to take into account excellent machine while obtaining preferable dielectric properties
Tool performance.With the development of high molecular material, people for the polymer composite with excellent dielectric performance research by
Gradually deeply, preparing the polymer-based dielectric composite material with good dielectric properties, mechanical performance has important science to grind
Study carefully value and commercial Application meaning.
Invention content
The first object of the present invention is to provide a kind of method for the compounded mix preparing polyimides and barium titanate, the party
Polyimides can preferably wrap up barium titanate surface in compounded mix made from method.
The second object of the present invention is to provide a kind of compounded mix, which is made by above-mentioned preparation method.
The third object of the present invention is to provide a kind of composite dielectric material, with higher conductivity.
The fourth object of the present invention is to provide a kind of preparation method of composite dielectric material, and this method is simple, easy to operate.
The present invention solves its technical problem using following technical scheme to realize.
The present invention proposes a kind of method for the compounded mix preparing polyimides and barium titanate, including：
Barium titanate is subjected to ultrasonic disperse in n,N-dimethylacetamide solution, under the protection of inert gas, will be divided
Barium titanate suspension and 4 after dissipating, 4 '-diaminodiphenyl ethers mixing, is then added Pyromellitic Acid anhydride reactant.
A kind of compounded mix is made by the method for the above-mentioned compounded mix for preparing polyimides and barium titanate, compound
It is the nucleocapsid of shell that filler, which is by core, polyimides of barium titanate,.
A kind of composite dielectric material, composite dielectric material are made by above-mentioned compounded mix with polytetrafluoroethylene (PTFE).
A method of composite dielectric material is prepared, including：Above-mentioned compounded mix and polytetrafluoroethylene (PTFE) are blended in 50-
It is melted under 60 DEG C of water bath condition.
The advantageous effect of the embodiment of the present invention is：Barium titanate is subjected to ultrasonic disperse in n,N-dimethylacetamide solution,
Certifiable barium titanate is well dispersed in n,N-dimethylacetamide solution.Under the protection of inert gas, by the titanium after dispersion
Sour barium suspension and 4, the mixing of 4 '-diaminodiphenyl ethers may make 4,4 '-diaminodiphenyl ethers to be substantially dissolved in barium titanate suspension
In liquid, after pyromellitic dianhydride is added, pyromellitic dianhydride and 4, the 4 '-diaminodiphenyl ethers fully dissolved react, reaction life
At polyimides.Since during the reaction, 4,4 '-diaminodiphenyl ethers and barium titanate are well dispersed in N, N- dimethyl second
In amide solution, be then conducive to polyimides being preferably coated on the formation of barium titanate surface using barium titanate as core, polyimides
For the nucleocapsid of shell, which can be improved the conductivity of compounded mix.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the thermogravimetric analysis collection of illustrative plates of the compounded mix of the embodiment of the present invention 1；
Fig. 2 is the infrared spectrum test chart of the compounded mix of the embodiment of the present invention 1；
Fig. 3 is the compounded mix SEM spectrum of the embodiment of the present invention 2 and comparative example 2；
Fig. 4 is the compounded mix SEM spectrum of the embodiment of the present invention 1 and comparative example 1；
Fig. 5 is the test chart of the conductivity of the composite dielectric material of 1-3 of the embodiment of the present invention and comparative example 1-3；
Fig. 6 is the survey of the dielectric constant and dielectric loss of the composite dielectric material of 1-3 of the embodiment of the present invention and comparative example 1-3
Attempt；
Fig. 7 is dielectric constant and dielectric of the composite dielectric material of the embodiment of the present invention 1 and comparative example 1 under 1KHz frequencies
The test chart of loss；
Fig. 8 is the test chart of the breakdown strength of the composite dielectric material of 1-3 of the embodiment of the present invention.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to compounded mix of a kind of polyimides of the embodiment of the present invention and barium titanate and preparation method thereof, compound Jie
Electric material and preparation method thereof is specifically described.
The dielectric properties of composite material are related with the structure of filler, in the compounded mix for preparing polyimides and barium titanate
When, during carrying out directly coating polyimides to barium titanate surface, cover polyimides it is easy reunite in a solvent it is blocking,
It is not easy to disperse so that the degree that polyimides is coated on barium titanate surface is relatively low, and effect is not so good.And due to polyimides point
Subchain is longer, is not easy to be adhered to barium titanate surface, poor so as to cause the electrical property of composite material.
Based on this, the application proposes a kind of method for the compounded mix preparing polyimides and barium titanate, including：
Barium titanate is subjected to ultrasonic disperse in n,N-dimethylacetamide solution, under the protection of inert gas, will be divided
Barium titanate suspension and 4 after dissipating, 4 '-diaminodiphenyl ethers mixing, is then added Pyromellitic Acid anhydride reactant.Wherein, equal benzene
The weight ratio of tetracarboxylic acid anhydride and 4,4 '-diaminodiphenyl ethers is 1-1.1:1.
Barium titanate (BT) is subjected to ultrasonic disperse in n,N-dimethylacetamide (DMAc) solution, it is ensured that barium titanate is abundant
It is dispersed in n,N-dimethylacetamide solution (ODA).Under the protection of inert gas, by after dispersion barium titanate suspension with
4,4 '-diaminodiphenyl ethers (PMDA) mix, and 4,4 '-diaminodiphenyl ethers may make to be substantially dissolved in barium titanate suspension,
After pyromellitic dianhydride (PMDA) is added, pyromellitic dianhydride and 4, the 4 '-diaminodiphenyl ethers fully dissolved react, reaction
Generate polyimides (PI).Since during the reaction, 4,4 '-diaminodiphenyl ethers and barium titanate are well dispersed in N, N- bis-
In methyl vinyl amine aqueous solution, then be conducive to preferably for polyimides to be coated on barium titanate surface.Wherein, inert gas includes nitrogen
Gas or argon gas.
In order to enable 4,4 '-diaminodiphenyl ethers are substantially dissolved in barium titanate suspension, in the present embodiment, are being added
After entering 4,4 '-diaminodiphenyl ethers, 1-2h is so that 4 for stirring, and 4 '-diaminodiphenyl ethers are completely dissolved.
In addition, in order to enable pyromellitic dianhydride and 4,4 '-diaminodiphenyl ethers fully react, pyromellitic dianhydride point is more
Minor tick is added.Wherein, the time interval that benzene tetracarboxylic acid acid anhydride is added every time is 1-1.2h, in some embodiments,
4 additions of benzene tetracarboxylic acid acid anhydride point, the amount being added every time are the 1/4 of pyromellitic dianhydride total amount.A small amount of pyromellitic dianhydride exists
1-1.2h can be with 4, and 4 '-diaminodiphenyl ethers come into full contact with reaction, add pyromellitic dianhydride continuation after complete reaction
Reaction, is conducive to that the reaction was complete, and the polyimides generated can preferably be coated on barium titanate surface.
A kind of compounded mix is made by the method for the above-mentioned compounded mix for preparing polyimides and barium titanate, compound
It is the nucleocapsid of shell that filler, which is by core, polyimides of barium titanate,.
This structure can effectively prevent secondary agglomeration of barium titanate during further processing, prevent between barium titanate
Mutually overlap joint forms leakage path.Tests prove that the structure can effectively improve the conductivity of compounded mix, compound Jie is improved
The electrical property of electric material.
A kind of composite dielectric material, composite dielectric material are made by above-mentioned compounded mix with polytetrafluoroethylene (PTFE).
The preparation method of the composite dielectric material includes：Above-mentioned compounded mix and polytetrafluoroethylene (PTFE) are blended in 50-60
DEG C water bath condition under melt.
After compounded mix and polytetrafluoroethylene (PTFE) fully melt under 50-60 DEG C of water bath condition, the melt cast that will obtain
It is molded on clean sheet glass, material molding to be composite carries out annealing 30min under conditions of being placed on 180-220 DEG C and obtains
Composite dielectric material.
It should be noted that in order to enable compounded mix is sufficiently mixed with polytetrafluoroethylene (PTFE), by compounded mix and polytetrafluoro
The water bath condition of 50-60 DEG C of ethylene is stirred 1-2h.
Compounded mix in the composite dielectric material has obtained fully dispersed, forms using barium titanate as core, polyimides
For the nucleocapsid of shell, polyimides can improve dispersibility of the barium titanate in poly tetrafluoro ethylene matrix, compounded mix and poly- four
The interface formed between vinyl fluoride is more, and interfacial polarization effect enhancing, dielectric constant has obtained effective promotion.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
The barium titanate of 1.3636g is taken to be placed in progress ultrasonic disperse 1h in the n,N-dimethylacetamide solution of 17.5mL, it will
Barium titanate suspension after dispersion is transferred in three-neck flask, and the 4 of 0.0701g, 4 '-diaminodiphenyl ethers, in nitrogen protection are added
Under, 1h is stirred at room temperature, until 4,4 '-diaminodiphenyl ethers are completely dissolved.Divide 4 addition Pyromellitic Acids under nitrogen protection
Acid anhydride, the amount being added every time are 0.0197g, and the time interval that pyromellitic dianhydride is added every time is 1h.Add whole equal benzene four
After formic anhydride, continues stirring 4h under nitrogen protection and obtain compounded mix.
According to weight ratio it is 7 by compounded mix and polytetrafluoroethylene (PTFE):3 mixing, continue to stir under 55 DEG C of water bath condition
1h.After the completion of stirring, the composite material of gained is cast on clean sheet glass, moulding by casting.After material molding to be composite,
The 30min that anneals under conditions of being placed in 200 DEG C obtains composite dielectric material.
Embodiment 2
It takes the barium titanate of 1.8182g to be placed in progress ultrasonic disperse 1h in the n,N-dimethylacetamide solution of 15mL, will divide
Barium titanate suspension after dissipating is transferred in three-neck flask, and the 4 of 0.9011g, 4 '-diaminodiphenyl ethers, in nitrogen protection are added
Under, 1h is stirred at room temperature, until 4,4 '-diaminodiphenyl ethers are completely dissolved.Divide 4 addition Pyromellitic Acids under nitrogen protection
Acid anhydride, the amount being added every time are 0.0245g, and the time interval that pyromellitic dianhydride is added every time is 1h.Add whole equal benzene four
After formic anhydride, continues stirring 4h under nitrogen protection and obtain compounded mix.
According to weight ratio it is 6 by compounded mix and polytetrafluoroethylene (PTFE):4 mixing, continue to stir under 55 DEG C of water bath condition
1h.After the completion of stirring, the composite material of gained is cast on clean sheet glass, moulding by casting.After material molding to be composite,
The 30min that anneals under conditions of being placed in 200 DEG C obtains composite dielectric material.
Embodiment 3
The barium titanate of 2.2727g is taken to be placed in progress ultrasonic disperse 1h in the n,N-dimethylacetamide solution of 12.5mL, it will
Barium titanate suspension after dispersion is transferred in three-neck flask, and the 4 of 0.1101g, 4 '-diaminodiphenyl ethers, in nitrogen protection are added
Under, 1h is stirred at room temperature, until 4,4 '-diaminodiphenyl ethers are completely dissolved.Divide 4 addition Pyromellitic Acids under nitrogen protection
Acid anhydride, the amount being added every time are 0.030g, and the time interval that pyromellitic dianhydride is added every time is 1h.Add whole equal benzene four
After formic anhydride, continues stirring 4h under nitrogen protection and obtain compounded mix.
According to weight ratio it is 5 by compounded mix and polytetrafluoroethylene (PTFE):5 mixing, continue to stir under 55 DEG C of water bath condition
1h.After the completion of stirring, the composite material of gained is cast on clean sheet glass, moulding by casting.After material molding to be composite,
The 30min that anneals under conditions of being placed in 200 DEG C obtains composite dielectric material.
Embodiment 4
The barium titanate of 1.3636g is taken to be placed in progress ultrasonic disperse 1h in the n,N-dimethylacetamide solution of 17.5mL, it will
Barium titanate suspension after dispersion is transferred in three-neck flask, and the 4 of 0.0701g, 4 '-diaminodiphenyl ethers, in nitrogen protection are added
Under, 1h is stirred at room temperature, until 4,4 '-diaminodiphenyl ethers are completely dissolved.Divide 4 addition Pyromellitic Acids under nitrogen protection
Acid anhydride, the amount being added every time are 0.0187g, and the time interval that pyromellitic dianhydride is added every time is 1h.Add whole equal benzene four
After formic anhydride, continues stirring 4h under nitrogen protection and obtain compounded mix.
According to weight ratio it is 7 by compounded mix and polytetrafluoroethylene (PTFE):3 mixing, continue to stir under 55 DEG C of water bath condition
1h.After the completion of stirring, the composite material of gained is cast on clean sheet glass, moulding by casting.After material molding to be composite,
The 30min that anneals under conditions of being placed in 180 DEG C obtains composite dielectric material.
Comparative example 1
Polyimides and barium titanate are dispersed in n,N-dimethylacetamide solution using solution blended process, so that poly-
The barium titanate surface that acid imide is directly coated on obtains compounded mix.
According to weight ratio it is 7 by compounded mix and polytetrafluoroethylene (PTFE):3 mixing, continue to stir under 55 DEG C of water bath condition
1h.After the completion of stirring, the composite material of gained is cast on clean sheet glass, moulding by casting.After material molding to be composite,
The 30min that anneals under conditions of being placed in 200 DEG C obtains composite dielectric material.
Comparative example 2
Polyimides and barium titanate are dispersed in n,N-dimethylacetamide solution using solution blended process, so that poly-
The barium titanate surface that acid imide is directly coated on obtains compounded mix.
According to weight ratio it is 6 by compounded mix and polytetrafluoroethylene (PTFE):4 mixing, continue to stir under 55 DEG C of water bath condition
1h.After the completion of stirring, the composite material of gained is cast on clean sheet glass, moulding by casting.After material molding to be composite,
The 30min that anneals under conditions of being placed in 200 DEG C obtains composite dielectric material.
Comparative example 3
Polyimides and barium titanate are dispersed in n,N-dimethylacetamide solution using solution blended process, so that poly-
The barium titanate surface that acid imide is directly coated on obtains compounded mix.
According to weight ratio it is 5 by compounded mix and polytetrafluoroethylene (PTFE):5 mixing, continue to stir under 55 DEG C of water bath condition
1h.After the completion of stirring, the composite material of gained is cast on clean sheet glass, moulding by casting.After material molding to be composite,
The 30min that anneals under conditions of being placed in 200 DEG C obtains composite dielectric material.
Test example 1
Thermogravimetric analysis is carried out to the compounded mix of embodiment 1, knot is as shown in Figure 1.
The heat decomposition temperature that can be seen that the polyimides obtained by in-situ polymerization from the result of Fig. 1 is about 497 DEG C.
When temperature reaches 800 DEG C, the quality of barium titanate only has micro variation, this mass loss is mainly derived from barium titanate and produced
The oxygen-containing functional group that the combination water carried in journey and barium titanate surface carry.And compounded mix matter when temperature reaches 800 DEG C
Amount drops to original 91% or so, i.e., mass loss is than about 9%.Since at 800 DEG C, barium titanate itself will not decompose,
So mass loss of the compounded mix at 800 DEG C largely derives from falling for polyimides.This phenomenon illustrates, in metatitanic acid
When wrapping up polyimides on barium, the mass ratio of polyimides and barium titanate is about 1:10.
Test example 2
Fourier is carried out to the compounded mix of embodiment 1 and converts infrared spectrum analysis, test results are shown in figure 2.
It can be obtained from the result of Fig. 2,1775cm-1There is the asymmetric stretching vibration peak of C=O, 1725cm at place-1
There is the symmetrical stretching vibration peak of C=O, 1369cm at place-1There is the symmetrical stretching vibration peaks and 721cm of C-N at place-1Place
The presence at existing imide ring deformation vibration peak, these characteristic peaks confirms that polyimides is successfully realized on barium titanate surface
Fabricated in situ.
Test example 3
The compounded mix of embodiment 2 and comparative example 2 is observed under a scanning electron microscope with barium titanate, is obtained
The results are shown in Figure 3.Wherein, Fig. 3 (a) is that the SEM of barium titanate schemes；Fig. 3 (b) is the SEM figures of the compounded mix of comparative example 2；Figure
3 (c) is the SEM figures of the compounded mix of embodiment 2.
It can be seen that, the agglomeration of barium titanate particles is then extremely serious, and part barium titanate is agglomerated into directly from Fig. 3 (a)
Diameter is more than 10 μm of spheric granules.This is because the specific surface area of barium titanate is bigger, there is higher surface energy, it is easier to send out
It is raw to reunite.
It can be seen that, in contrast to pure barium titanate, the barium titanate after polyimides package is directly utilized from Fig. 3 (b)
Grain surface becomes to stick together, this illustrates that polyimides can mix package by simple solution really and arrive barium titanate surface.But
After package reunites acid imide, since the strand of polyimides is very long, polyimides is by single metatitanic acid after ultrasonic disperse
Titanate particle is rolled into the aggregate that size is 50 μm again.Therefore, directly coating polyimides does not improve the group of barium titanate
Poly- situation, only so that aggregate surface becomes coarse so that the shape of aggregate becomes irregular.
And in Fig. 3 (c), it will be seen that after barium titanate in situ Polymerization polyimides, it can be seen that size
About the barium titanate of 87nm is still single dispersion to be presented, and each barium titanate surface is all shrouded outside one layer of polymeric
Shell forms one kind using barium titanate as core, using polyimides as " nucleocapsid " structure of shell, among this structure filling to PVDF matrixes
Can be effectively increased interface, and the formation of this structure can effectively prevent barium titanate among further processing process two
Secondary reunion, mutually overlap joint forms leakage path between preventing barium titanate.
Test example 4
The compounded mix liquid of the compounded mix liquid of embodiment 2 and comparative example 2 is added to N, N- dimethyl second
In the centrifuge tube of amide solution, its rate settled is verified.
Experiment finds that the compounded mix of comparative example 2 just settles down completely in 30min or so, and the compound of embodiment 2 is filled out
Expect the placement even across 45 days, also only a little sedimentation.It illustrates to coat on barium titanate surface by in-situ polymerization
After polyimides, its dispersion stabilization can be promoted.
Test example 5
The composite dielectric material of embodiment 1 and comparative example 1 is observed under a scanning electron microscope, obtained result
As shown in Figure 4.Wherein, Fig. 4 (a) and (b) scheme for the SEM of the composite dielectric material of comparative example 1；Fig. 4 (c) and (d) are embodiment
The SEM of 2 composite dielectric material schemes.
Interpretation of result：It is compound in the composite dielectric material prepared by the method for comparative example 1 as shown in Fig. 4 (a) and (b)
The particle of material forms larger irregular reunion in PVDF matrixes, and the diameter of aggregate has been even more than 50 μm.This is
When due to directly coating PI, the strand of PI is very long, and a large amount of BT cages near strand are entered, a densification is re-formed
New PI be wrapped in the reunion of BT, this reunion by the fabulous PI of mechanical performance due to being wrapped in, it is difficult to further pass through machine
The effect of tool power is broken up again, and the addition of this filler can not be obviously improved the dielectric properties of composite material.And in Fig. 4 (c)
(d) in, the composite dielectric material system that through this embodiment prepared by 2 situ aggregation method then embodies different filler point
Bulk condition, it can be seen that compounded mix is in almost single dispersion in PVDF matrixes, and particle size is in Nano grade.This be because
For PI is generated in BT in situ Polymerizations so that the surfaces BT have effectively coated PI, and the presence of PI effectively improves BT and exists
Dispersibility in PVDF matrixes.
Test example 6
The conductivity of the composite dielectric material of embodiment 1-3 and comparative example 1-3, dielectric constant and dielectric loss are surveyed
Examination, result are as shown in Figure 5 and Figure 6, wherein Fig. 6 (a) is the test result of dielectric constant, and Fig. 6 (b) is the survey of dielectric loss
Test result.
Interpretation of result：From fig. 5, it is seen that after BT in situ Polymerizations PI, the conductivity of obtained composite material
Composite dielectric material system compared to comparative example 1-3 is significantly improved, and material is integrally still within state of insulation.Electrically
Can dispersion situation of the Discrepancy Description compounded mix in PVDF matrixes it is different, the in-situ polymerization of embodiment 1-3 prepares compound
Filler has better dispersibility, and compounded mix forms more multiple solutions among polymeric matrix, and due to the electricity of PI
Conductance is far above the conductivity of BT, and compounded mix particle is under the action of external electric field, due to the difference of interface material electric conductivity,
Bilayer model is spread in PVDF matrixes, the charge for foring a gradient bigger between PI, BT, thus passes through in-situ polymerization
The conductivity higher of obtained composite dielectric material system.
Can be seen that the composite dielectric material that in-situ polymerization through this embodiment obtains from Fig. 6 (a) has more
Big dielectric constant, when the content of compounded mix is 50wt%, under 100 Hz frequencies, dielectric constant has reached 109.This is
Because in-situ polymerizations of the PI on the surfaces BT makes the surfaces BT effectively coat PI, the presence of PI effectively improves BT and exists
Dispersibility in PVDF matrixes, the interface formed between compounded mix and PVDF matrixes is more, interfacial polarization effect enhancing, so
Dielectric constant has obtained effective promotion.
From Fig. 6 (b) as can be seen that corresponding 102-103Hz frequencies are lost in conductance in the dielectric loss of two kinds of composite materials
All there are one obvious promotions within section, and conductance loss corresponds to the interfacial polarization of material, this result means
Either directly long-chain PI is utilized to wrap up BT, forms coarse wrapping agglomeration body, still in-situ polymerization PI through this embodiment
It wraps up BT and forms nucleocapsid, can relatively effectively promote the interfacial polarization between filler and polymeric matrix.Also,
Since compounded mix prepared by in-situ polymerization is dispersed more preferable between polymer, thus the corresponding dielectric damage of its composite material
Consumption is also relatively smaller.In addition, the dielectric of the composite dielectric material for the compounded mix that situ aggregation method through this embodiment obtains
Loss is reduced with the increase of filler loading.
Test example 7
Dielectric constant under 1KHz frequencies of the composite dielectric material of embodiment 1 and comparative example 1 and dielectric loss are carried out
Test, test results are shown in figure 7.Wherein, wherein Fig. 7 (a) is the test result of dielectric constant, and Fig. 7 (b) damages for dielectric
The test result of consumption.
Interpretation of result：By Fig. 7 (a) it is found that for composite dielectric material prepared by comparative example 1, the change of filer content
Change on dielectric constant substantially without influence.This is because when directly coating PI, the strand of PI is very long, near strand
A large amount of BT cages enter, and re-form the reunion that a fine and close new PI is wrapped in BT, this reunion is due to fabulous by mechanical performance
PI be wrapped in, it is difficult to further broken up again by the effect of mechanical force, the addition of this filler can not be obviously improved multiple
The dielectric properties of condensation material.And for the situ aggregation method of the present embodiment prepare composite dielectric material for, dielectric constant with
It the increase of filer content and increases.This is because in-situ polymerizations of the PI on the surfaces BT makes the surfaces BT effectively coat
The presence of PI, PI effectively improve dispersibilities of the BT in PVDF matrixes, the boundary formed between compounded mix and PVDF matrixes
Face is more, and interfacial polarization effect enhancing, so dielectric constant has obtained effective promotion, and compounded mix content is higher, dielectric
Constant is bigger.
It can see by Fig. 7 (b), the dielectric loss for the compounded mix that through this embodiment prepared by 1 in-situ polymerization
Dielectric loss than the composite material of the preparation of comparative example 1 is small.This is because compounded mix prepared by in-situ polymerization is in polymer
Between dispersibility it is more preferable, thus the corresponding dielectric loss of its composite material is also relatively smaller.
Test example 8
The breakdown strength of the composite dielectric material of embodiment 1-3 is tested, test results are shown in figure 8.
Interpretation of result：From Fig. 8 it will be seen that as compounded mix content increases, the breakdown of composite dielectric material
Intensity first subtracts and increases afterwards.When the content of compounded mix increases to 30 wt% from 0, breakdown strength is reduced to from 102.5MV/m
38.47MV/m.And when the content of compounded mix rises to 40wt%, breakdown strength is increased to 123.07MV/m；When compound
When the content of filler is 50wt%, breakdown strength is increased to 133.29MV/m.Breakdown strength is preceding with the increase of filler loading
The result subtracted after increasing.
In conclusion a kind of polyimides of the embodiment of the present invention and the compounded mix and preparation method thereof, multiple of barium titanate
Dielectric material and preparation method thereof is closed, the compounded mix being prepared forms the nucleocapsid using barium titanate as core, polyimides for shell
The conductivity of compounded mix can be improved in structure, the structure.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of method for the compounded mix preparing polyimides and barium titanate, which is characterized in that including：
Barium titanate is subjected to ultrasonic disperse in n,N-dimethylacetamide solution, under the protection of inert gas, after dispersion
Barium titanate suspension and 4,4 '-diaminodiphenyl ethers mixing, then be added Pyromellitic Acid anhydride reactant.
2. the method for the compounded mix according to claim 1 for preparing polyimides and barium titanate, which is characterized in that described
The molal weight ratio of pyromellitic dianhydride and the 4,4 '-diaminodiphenyl ether is 1-1.1：1.
3. the method for the compounded mix according to claim 1 or 2 for preparing polyimides and barium titanate, which is characterized in that
When the Pyromellitic Acid anhydride reactant is added, the pyromellitic dianhydride is spaced is added several times.
4. the method for the compounded mix according to claim 3 for preparing polyimides and barium titanate, which is characterized in that described
4 additions of pyromellitic dianhydride point, the amount being added every time are the 1/4 of pyromellitic dianhydride total amount.
5. the method for the compounded mix according to claim 1 for preparing polyimides and barium titanate, which is characterized in that described
Inert gas includes nitrogen and argon gas.
6. a kind of compounded mix, which is characterized in that it prepares polyimides and barium titanate by claim 1-5 any one of them
The method of compounded mix be made, the compounded mix be by core, the polyimides of the barium titanate be the nucleocapsid knot of shell
Structure.
7. a kind of composite dielectric material, which is characterized in that the composite dielectric material by described in claim 6 compounded mix with
Polytetrafluoroethylene (PTFE) is made.
8. a kind of method preparing composite dielectric material, which is characterized in that including：By described in claim 6 compounded mix with
Polytetrafluoroethylene (PTFE) is blended under 50-60 DEG C of water bath condition and melts.
9. the method according to claim 8 for preparing composite dielectric material, which is characterized in that further include：Institute after reacting
State compounded mix and polytetrafluoroethylene (PTFE) system moulding by casting, annealing.
10. the method according to claim 9 for preparing composite dielectric material, which is characterized in that the annealing temperature is
180-220℃。
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| CN110746649A (en) * | 2019-09-24 | 2020-02-04 | 惠州市志海新威科技有限公司 | High-performance flame-retardant synergist and preparation method thereof |
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