CN111253679B - Composite material and preparation method and application thereof - Google Patents
Composite material and preparation method and application thereof Download PDFInfo
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- CN111253679B CN111253679B CN202010199051.7A CN202010199051A CN111253679B CN 111253679 B CN111253679 B CN 111253679B CN 202010199051 A CN202010199051 A CN 202010199051A CN 111253679 B CN111253679 B CN 111253679B
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000004743 Polypropylene Substances 0.000 claims abstract description 43
- 229920001155 polypropylene Polymers 0.000 claims abstract description 39
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 32
- -1 polypropylene Polymers 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000155 melt Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000005540 biological transmission Effects 0.000 claims description 9
- 238000004146 energy storage Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 8
- 238000007731 hot pressing Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L27/20—Homopolymers or copolymers of hexafluoropropene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
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Abstract
A composite material and a preparation method and application thereof are disclosed, wherein the composite material is composed of polyvinylidene fluoride-hexafluoropropylene and polypropylene. The polyvinylidene fluoride-hexafluoropropylene is used as a raw material, the polyvinylidene fluoride-hexafluoropropylene/polypropylene composite material is prepared by a melt blending method, the polyvinylidene fluoride-hexafluoropropylene and polypropylene matrix in the composite material is good in compatibility and dispersibility, and a 5-30 micron film prepared by further hot pressing or co-extrusion has the advantages of high dielectric constant and good processing performance, and has wide application prospects in the fields of film capacitors and the like.
Description
Technical Field
The present invention relates to organic film dielectric capacitor technology, and is especially one kind of composite material and its preparation process and application.
Background
Polypropylene materials are widely used in many fields, and among them, they are important in dielectric materials for capacitors because polypropylene films have low dielectric loss and high breakdown strength. The film capacitor prepared by the biaxially oriented polypropylene is an important electric and electronic component, is widely applied in various fields, can play the roles of filtering, smoothing and rectifying, and can also be used as a direct current support, but the low dielectric constant (2.2) limits the capacitance per unit volume and the energy storage characteristic, and the overlarge volume of the film capacitor becomes an obstacle for further development of an electronic and electric system, so that the capacitor is imperatively promoted to be miniaturized.
At present, one main research direction for improving the dielectric constant of the dielectric material is to add inorganic nanoparticles, but the easy agglomeration property of the inorganic nanoparticles and the poor compatibility with a polymer matrix cause the processing performance of an inorganic nanoparticle/polypropylene system to be extremely poor, and engineering application is difficult to obtain in practice. The defects of inorganic nano-particle fillers can be overcome by blending the high-dielectric polymer and the polypropylene to improve the dielectric property of the material, but the compatibility of the common high-dielectric polymer and the nonpolar polypropylene has certain problems due to high polarity, for example, the blending effect of the polypropylene and the polyvinylidene fluoride is poor, uniform mixing cannot be realized, and the compatibility can be improved by adding a large amount of compatilizers.
Disclosure of Invention
The application provides a composite material and a preparation method and application thereof, in particular to a method for improving the dielectric property of polypropylene by using polyvinylidene fluoride-hexafluoropropylene, which adopts a copolymer of polyvinylidene fluoride: the polyvinylidene fluoride-hexafluoropropylene and the polypropylene are blended, so that the good compatibility of the polyvinylidene fluoride-hexafluoropropylene and the polypropylene can be realized, and the dispersibility of the copolymer is obviously improved, thereby effectively improving the dielectric property of the composite material. Can make up for the defects of the prior art. The product of the invention has the following characteristics: easy popularization, strong practicability and easy preparation method, and can greatly improve the capacitance per unit volume and the energy storage characteristic of the dielectric medium of the film capacitor.
The invention provides a composite material which is composed of polyvinylidene fluoride-hexafluoropropylene and polypropylene.
In the composite material provided by the invention, the volume fraction of polyvinylidene fluoride-hexafluoropropylene in the composite material is 1-70%;
in the composite material provided by the invention, the volume fraction of polyvinylidene fluoride-hexafluoropropylene in the composite material is 5-70%.
In another aspect, the present invention provides a method for preparing the above composite material, comprising the steps of: the polyvinylidene fluoride-hexafluoropropylene and the polypropylene are prepared into the composite material by adopting a melt blending method.
In the preparation method of the composite material provided by the invention, the melt blending temperature is 190-280 ℃.
In the preparation method of the composite material provided by the invention, the melt blending time is 10-60 min.
In another aspect, the present invention provides the use of the above composite material in power transmission and electrical energy storage.
In the application of the composite material in power transmission and electric energy storage, the composite material is applied to a high dielectric film or an insulating pipe.
In the application of the composite material in power transmission and electric energy storage, the thickness of the high dielectric film is 5-30 μm; optionally, the high dielectric film has a dielectric constant of 2.4 to 5.
On the other hand, the invention provides application of polyvinylidene fluoride-hexafluoropropylene in improving the dielectric property of polypropylene.
Compared with the prior art, the invention has the following beneficial effects:
compared with the polyvinylidene fluoride/polypropylene composite material, the polyvinylidene fluoride-hexafluoropropylene/polypropylene composite material prepared by the invention is obviously improved, the uniformity and the practicability of the composite material are increased due to the improvement of the compatibility and the dispersibility, and the dielectric constant is effectively improved.
The composite material prepared by the method can be used for preparing high dielectric films and insulating pipes, and has wide potential application in the fields of power transmission and electric energy storage.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Other advantages of the invention may be realized and attained by the instrumentalities and combinations particularly pointed out in the specification.
Drawings
The accompanying drawings are included to provide an understanding of the present invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the examples serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a graph comparing polyvinylidene fluoride/polypropylene (PVDF/PP) (left film) in comparative example 1 and polyvinylidene fluoride-hexafluoropropylene/polypropylene (PVDF-HFP/PP) (right film) composite film in example 1, both having a filler content of 30 vol.%.
Fig. 2 is a graph showing the dielectric constant with frequency for polyvinylidene fluoride-hexafluoropropylene/polypropylene (PVDF-HFP/PP) in example 1 (30 vol.% content of polyvinylidene fluoride-hexafluoropropylene) and polypropylene (PP for short) in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below. It should be noted that the embodiments and features of the embodiments of the present invention may be arbitrarily combined with each other without conflict.
The embodiment of the application provides a composite material, and the composite material is composed of polyvinylidene fluoride-hexafluoropropylene and polypropylene.
In the embodiment of the application, the volume fraction of polyvinylidene fluoride-hexafluoropropylene in the composite material is 1-70%;
in the examples of the present application, the volume fraction of polyvinylidene fluoride-hexafluoropropylene in the composite material is 5-70%.
On the other hand, the embodiment of the invention provides a preparation method of the composite material, and the preparation method comprises the following steps: the polyvinylidene fluoride-hexafluoropropylene and the polypropylene are prepared into the composite material by adopting a melt blending method.
In the examples of the present application, the melt blending temperature is 190-280 ℃.
In the examples of the present application, the melt blending time is 10 to 60 min.
In another aspect, embodiments of the present disclosure provide applications of the above composite material in power transmission and electric energy storage.
In the embodiment of the application, the composite material is applied to a high dielectric film or an insulating pipe.
In the embodiment of the application, the thickness of the high dielectric film is 5-30 μm; optionally, the high dielectric film has a dielectric constant of 2.4 to 5.
On the other hand, the embodiment of the invention provides application of polyvinylidene fluoride-hexafluoropropylene in improving the dielectric property of polypropylene.
The present invention will be described in detail below with reference to specific examples.
Polyvinylidene fluoride-hexafluoropropylene powder was purchased from akoma, brand 2801, polypropylene pellets were purchased from northern european chemicals, brand HC300, polyvinylidene fluoride pellets were purchased from suwei, usa, brand 6020.
Example 1
1) Uniformly stirring 2.4 g of polyvinylidene fluoride-hexafluoropropylene (30 vol.%) and 2.6 g of polypropylene (70 vol.%), adding into a container, blending at 190 ℃ and 70rpm for 30 minutes, and extruding and granulating to obtain the polyvinylidene fluoride-hexafluoropropylene/polypropylene composite material.
2) Placing a certain amount of polyvinylidene fluoride-hexafluoropropylene/polypropylene granules on a polyimide film with a template with a fixed thickness (20 microns), then covering a layer of polyimide film, clamping the polyimide film between two steel plates with smooth surfaces, preheating for 10 minutes at 190 ℃, then hot-pressing for 10 minutes under the pressure of 10MPa, and taking out the pressed polyvinylidene fluoride-hexafluoropropylene/polypropylene film with the thickness of about 20 microns after cooling.
The film for polyvinylidene fluoride-hexafluoropropylene/polypropylene capacitor prepared by the formula and the process has the filler shown in figure 1, good compatibility and dispersibility, ensures the uniformity of the film, and has the dielectric constant of 3.3 and the performance improved by 50 percent compared with pure polypropylene as shown in figure 2. The invention has the advantages of simple preparation process and stable performance, and has a prospect of practical application.
Comparative example 1
1) Uniformly stirring 2.4 g of polyvinylidene fluoride (30 vol.%) and 2.6 g of polypropylene (70 vol.%), adding into a container, blending at 190 ℃ and 70rpm for 30 minutes, and extruding and granulating to obtain the polyvinylidene fluoride/polypropylene composite material.
2) Placing a certain amount of polyvinylidene fluoride/polypropylene granules on a polyimide film provided with a template with a fixed thickness (20 microns), then covering a layer of polyimide film, clamping the polyimide film between two steel plates with smooth surfaces, preheating for 10 minutes at 190 ℃, then hot-pressing for 10 minutes under the pressure of 10MPa, and taking out the pressed polyvinylidene fluoride/polypropylene film with the thickness of 20 microns after cooling.
Comparative example 2
Placing a certain amount of polypropylene granules on a polyimide film with a template with a fixed thickness (20 microns), then covering a layer of polyimide film, clamping the polyimide film between two steel plates with smooth surfaces, preheating for 10 minutes at 190 ℃, then hot-pressing for 10 minutes under the pressure of 10MPa, and taking out the pressed 20-micron polypropylene film after cooling.
Test example
The dielectric performance test method in structural design and preparation of dielectric composite material with high energy storage density [ D ] (Zhengming Sheng, Beijing university of science and technology, 2018.) is as follows:
and (3) dielectric property test: the method comprises the steps of respectively evaporating copper electrodes on two surfaces of a film by using a high-vacuum resistance evaporation coating machine, then placing the film coated with the copper electrodes into a precision impedance analyzer (Agilent 4294A), clamping the copper electrodes by using a clamp, and testing 100Hz-10 at room temperature7Dielectric properties in the Hz range.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The composite material is characterized by being prepared by melting and blending polyvinylidene fluoride-hexafluoropropylene and polypropylene; the volume fraction of polyvinylidene fluoride-hexafluoropropylene in the composite material is 1-70%;
the melt blending temperature is 190-280 ℃;
the melt blending time is 10-60 min.
2. A method of making the composite material of claim 1, comprising the steps of: the polyvinylidene fluoride-hexafluoropropylene and the polypropylene are prepared into the composite material by adopting a melt blending method.
3. The method for preparing a composite material according to claim 2, wherein the melt blending temperature is 190-280 ℃.
4. A method of producing a composite material according to claim 2 or 3, wherein the melt blending time is 10-60 min.
5. Use of the composite material of claim 1 in electrical transmission and storage of electrical energy.
6. Use of the composite material according to claim 5 in power transmission and electrical energy storage, wherein the composite material is used in high dielectric films or insulating pipes.
7. Use of the composite material according to claim 6 for power transmission and storage of electrical energy, wherein the high dielectric film has a thickness of 5-30 μm.
8. Use of a composite according to claim 6 or 7 for power transmission and storage of electrical energy, wherein the high dielectric film has a dielectric constant of 2.4 to 5.
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