CN103342027A - Preparation method of contrivable polymer-based multi-layer dielectric composite material - Google Patents
Preparation method of contrivable polymer-based multi-layer dielectric composite material Download PDFInfo
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- CN103342027A CN103342027A CN2013102957592A CN201310295759A CN103342027A CN 103342027 A CN103342027 A CN 103342027A CN 2013102957592 A CN2013102957592 A CN 2013102957592A CN 201310295759 A CN201310295759 A CN 201310295759A CN 103342027 A CN103342027 A CN 103342027A
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Abstract
The invention discloses a preparation method of a contrivable polymer base multi-layer dielectric composite material. The method comprises the following steps of: extruding a polymer-based electric conduction compound system and a polymer dielectric system through fusion so as to prepare the polymer base multi-layer dielectric composite material conducting layers and dielectric layers which are alternately distributed. The material has the anisotropic electrical properties, the material is high conductivity on a parallel layer direction and is high dielectric property on a vertical layer direction; the dielectric property is carried out design and regulate and control through number of layers, the layer thickness ratio of the conducting layers and the dielectric layers, single layer thickness, temperature, frequency and application stress. The preparation method provided by the invention has the advantages that the equipment is simple, the efficiency is high, the operation is easy, the method is suitable for continuous and mass production, and the producing multi-layer dielectric composite material is a flake shape, a film shape, a strip shape, a fiber shape and a grain shape.
Description
Technical field
The invention belongs to polymer base functional composite material preparation technology field, be specifically related to the preparation method of a kind of programmable polymer Quito layer dielectric composite material.
Background technology
Polymer base dielectric composite material (Polymer/conducting filler dielectric composite with the conducting particles filling, PCD) just very high dielectric constant can be obtained by adding small amount of filler, mechanical performance and processing characteristics preferably can also be kept simultaneously.But, when particle addition during near the conduction excess effusion value of system, dielectric constant will improve rapidly, and dielectric properties are all responsive unusually to filer content, test condition etc., thereby cause performance problem of unstable in processing and the use.Therefore, how when obtaining high-k, retention is stable is emphasis and the difficult point problem in PCD investigation of materials field always.
Studies show that in a large number the key that addresses this problem is to utilize the dispersion of conducting particles in matrix to promote the polymer molecule polarization, avoid it to be overlapped on direction of an electric field mutually again and form conductive path and cause that electricity leads loss.For example form the structure of similar capacitor by the orientation form of process for modifying surface or regulation and control filler, reached and improved the purpose [Chinese invention patent ZL 03104776.9] that molecular polarization reduces the particle overlap joint.These methods are still wayward to the dispersion of conducting particles, are difficult to avoid cause the instability of performance because of the influence of particle content variation to dielectric properties.Adjusting than conducting particles is disperseed directly coats it with high dielectric material, thoroughly stops the adjacent particles overlap joint to form conductive path, to the improvement of dielectric properties seem more effective [Chinese invention patent CN101007892A].But this method technology is comparatively complicated, coating thickness is wayward, but for design and the preparation of PCD material provides a new thinking: utilize the dispersion of conducting particles in polymer to form the polarization that numerous small electric containers promote polymer molecule on the one hand, on the other hand by constructing the distribution space of conducting particles in matrix, cut off it and form the possibility of conductive path at direction of an electric field, thereby realize that dielectricity improves and stable dual purpose.
Summary of the invention
The objective of the invention is the preparation present situation at the polymer base dielectric composite material of conducting particles filling, and the preparation method of a kind of programmable polymer Quito layer dielectric composite material is provided, to solve problems such as existing PCD dielectric material unstable properties, difficult regulation and control.
Technical scheme of the present invention is: polymer-matrix electric conduction compound system and polymer dielectric system are prepared polymer Quito layer dielectric composite material that conductive layer and dielectric layer are alternately arranged through the fusion coextrusion.
In technique scheme, described polymer-matrix electric conduction compound system is the polymer composite body system that conducting particles is filled, and the volume fraction of conducting particles is 0.01-40%.
In technique scheme, the polymeric matrix of described polymer-matrix electric conduction compound system is to be selected from a kind of in polyethylene, polypropylene, polyvinyl chloride, Kynoar, polytetrafluoroethylene (PTFE), polytetrafluoroethyl-ne alkene copolymer and the polyvinylidene fluoride alkene copolymer, and conductive filler is one or more in metal, carbon black, CNT, Graphene, the carbon fiber.
In technique scheme, described polymer dielectric substance is a kind of straight polymer dielectric system, or is the co-mixing system of two kinds of polymer or the polymer matrix composite system of filling for dielectric particle.
In technique scheme, the polymeric matrix of described polymer dielectric system is to be selected from a kind of in polyethylene, polypropylene, polyvinyl chloride, Kynoar, polytetrafluoroethylene (PTFE), polytetrafluoroethyl-ne alkene copolymer and the polyvinylidene fluoride alkene copolymer or two kinds.
In technique scheme, the multilayer dielectric composite that described conductive layer and dielectric layer are alternately arranged can utilize many extruder coextrusion, also can export the mould place in co-extrusion some layers of multiplier are installed, the number of plies of material can be regulated and control between the 2-4000 layer, the bed thickness ratio of conductive layer and dielectric layer can be regulated and control arbitrarily between 1:0-0:1, and thickness in monolayer is minimum can be to 50 nanometers.
In technique scheme, the dielectric properties of the multilayer dielectric composite that described conductive layer and dielectric layer are alternately arranged can be by the number of plies, conductive layer and dielectric layer bed thickness ratio, thickness in monolayer, temperature, frequency, stress application designs and regulate and control, and makes dielectric constant adjustable between 10-100000.
In technique scheme, the multilayer dielectric composite that makes can be sheet, membranaceous, strip, fibrous, granular.
The present invention has following advantage: equipment 1, involved in the present invention is simple, and Mould Machining is easy, is easy to assembling, low cost of manufacture, and cleaning and safeguard all very conveniently, and the process energy consumption is low, efficient is high, easy operating, can be continuously, large-scale production.
2, the polymer Quito layer dielectric composite material by the present invention's preparation has anisotropic electrical property, is high conductivity in the parallel layers direction, is high dielectric property in the perpendicular layers direction.
3, conductive layer and the dielectric layer of the polymer Quito layer dielectric composite material by the present invention preparation are alternately arranged, thereby compare with conventional P CD material, and its dielectric properties are easy to regulation and control.
The present invention also has more otherwise advantages.
Description of drawings
Fig. 1 is co-extrusion device structural representation involved in the present invention.In the drawings, A, B: extruder, C: connector, D: convergence device, E: layer multiplier, F: outlet mould.
The structural representation of polymer Quito layer dielectric composite material that Fig. 2 alternately arranges for conductive layer and the dielectric layer of the present invention preparation.In the drawings, h
d: the thickness in monolayer of dielectric layer, h
e: the thickness in monolayer of conductive layer.
The specific embodiment
By the following examples the present invention is further described specifically.In following each embodiment, the consumption of each component is weight consumption.Be necessary to be pointed out that at this following examples are only for the present invention is described further; can not be interpreted as limiting the scope of the invention; this art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
The good effect that the present invention produces can describe with embodiment.
Embodiment 1
The Kynoar and the pure Kynoar that have added 15 wt% carbon blacks are carried out coextrusion at 200 ℃, prepared 2,64 and 256 layers of alternately laminar composite (conductive layer is 1:1 with the bed thickness ratio of dielectric layer).The electric performance test result shows that three kinds of materials are about 10 in the resistivity of parallel layers direction
3Ohm.cm, and at the dielectric constant (10 of perpendicular layers direction
4Hz) then significantly improve along with the increase of the number of plies, be respectively 15,31 and 55, dielectric loss then only is increased to 0.23 from 0.15.
Embodiment 2
The polyethylene and the virgin pp that have added 12 wt% carbon blacks and the composite conducting particles of CNT are carried out coextrusion at 200 ℃, prepared 2,128,512 and 2048 layers of alternately laminar composite (conductive layer is 1:1 with the bed thickness ratio of dielectric layer).The electric performance test result shows that four kinds of materials are about 300 Ohm.cm in the resistivity of parallel layers direction, and at the dielectric constant (10 of perpendicular layers direction
4Hz) then significantly improve along with the increase of the number of plies, be respectively 12,87,230 and 460, dielectric loss then only is increased to 0.55 from 0.17.
Embodiment 3
The Kynoar that has added 15 wt% carbon blacks is carried out coextrusion with the Kynoar that has added 20 wt% barium titanates at 200 ℃, prepared 2,64 and 256 layers of alternately laminar composite (conductive layer is 1:1 with the bed thickness ratio of dielectric layer).The electric performance test result shows that four kinds of materials are about 10 in the resistivity of parallel layers direction
3Ohm.cm, and at the dielectric constant (10 of perpendicular layers direction
4Hz) then significantly improve along with the increase of the number of plies, be respectively 16,43 and 67, dielectric loss then only is increased to 0.29 from 0.15.
Embodiment 4
The Kynoar and the pure Kynoar that have added 15 wt% carbon blacks are carried out coextrusion at 200 ℃, prepared 64 layers of alternately laminar composite.Test result shows, along with the increase of conductive layer/dielectric layer bed thickness ratio (under the constant situation of total bed thickness and total number of plies, conductive layer thickness in monolayer (h
e) increase dielectric layer thickness in monolayer (h
d) will reduce), the dielectric constant (10 of material
4Hz) improve gradually.Work as h
e/ h
d=1/3 o'clock is 19, works as h
e/ h
d=1/1 o'clock is 31, works as h
e/ h
d=, 3/1 o'clock is 87.
Embodiment 5
The polypropylene and the virgin pp that have added 18 wt% carbon blacks are carried out coextrusion at 200 ℃, prepared 128 layers of alternately laminar composite (conductive layer is 1:1 with the bed thickness ratio of dielectric layer).The electric performance test result shows that material is about 10 in the resistivity of parallel layers direction
3Ohm.cm, at the dielectric constant of perpendicular layers direction then along with the increase of frequency reduces gradually, 10
2Be 96,10 during Hz
3Be 76,10 during Hz
4Be 42 during Hz.
Claims (10)
1. the preparation method of programmable polymer Quito layer dielectric composite material is characterized in that polymer-matrix electric conduction compound system and polymer dielectric system are prepared polymer Quito layer dielectric composite material that conductive layer and dielectric layer are alternately arranged through the fusion coextrusion.
2. according to the preparation method of the described a kind of programmable polymer of claim 1 Quito layer dielectric composite material, it is characterized in that the polymer-matrix electric conduction compound system is the polymer composite body system that conducting particles is filled, the volume fraction of conducting particles is 0.01-40%.
3. according to the described polymer-matrix electric conduction compound system of claim 2, it is characterized in that polymeric matrix is to be selected from a kind of in polyethylene, polypropylene, polyvinyl chloride, Kynoar, polytetrafluoroethylene (PTFE), polytetrafluoroethyl-ne alkene copolymer and the polyvinylidene fluoride alkene copolymer, conductive filler is one or more in metal, carbon black, CNT, Graphene, the carbon fiber.
4. according to the preparation method of the described a kind of programmable polymer of claim 1 Quito layer dielectric composite material, it is characterized in that the polymer dielectric substance is a kind of straight polymer dielectric system or is the co-mixing system of two kinds of polymer or the polymer matrix composite system of filling for dielectric particle.
5. according to the described polymer dielectric of claim 4 system, it is characterized in that polymeric matrix is to be selected from a kind of in polyethylene, polypropylene, polyvinyl chloride, Kynoar, polytetrafluoroethylene (PTFE), polytetrafluoroethyl-ne alkene copolymer and the polyvinylidene fluoride alkene copolymer or two kinds.
6. according to the preparation method of the described a kind of programmable polymer of claim 1 Quito layer dielectric composite material, it is characterized in that the multilayer dielectric composite that conductive layer and dielectric layer are alternately arranged can utilize many extruder coextrusion, also can export the mould place in co-extrusion some layers of multiplier are installed, the number of plies of material can be regulated and control between the 2-4000 layer, the bed thickness ratio of conductive layer and dielectric layer can be regulated and control arbitrarily between 1:0-0:1, and thickness in monolayer is minimum can be to 50 nanometers.
According to described layer of multiplier of claim 6 the layer multiplication, it is characterized in that the polymer laminar melt will be divided into m thigh (m is adjustable between 2-10) after entering each layer multiplier, m thigh melt is superimposed along thickness direction in the exit then, the number of plies that makes whole material with enter layer multiplier before compare and improve m doubly, and just will improve m through its number of plies behind n (n is adjustable between the 1-20) layer multiplier
nDoubly.
8. according to the preparation method of claim 1,6 and 7 described a kind of programmable polymer Quito layer dielectric composite material, it is characterized in that the multilayer dielectric material that makes has anisotropic electrical property, show as high conductivity in the parallel layers direction, show as high dielectric property in the perpendicular layers direction.
9. according to the preparation method of claim 1,6,7 and 8 described a kind of programmable polymer Quito layer dielectric composite material, it is characterized in that bed thickness ratio, thickness in monolayer, temperature, frequency that the dielectric properties of multilayer dielectric composite can be by the number of plies, conductive layer and dielectric layer, stress application designs and regulate and control, and makes dielectric constant adjustable between 10-100000.
10. according to the preparation method of the described a kind of programmable polymer of claim 1 Quito layer dielectric composite material, it is characterized in that the multilayer dielectric composite that makes can be sheet, membranaceous, strip, fibrous, granular.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103753726A (en) * | 2014-01-06 | 2014-04-30 | 四川大学 | Method for preparing heat-conductive composite material |
| CN105219021A (en) * | 2015-08-19 | 2016-01-06 | 中南大学 | A kind of dielectric composite material |
| CN106218188A (en) * | 2016-07-27 | 2016-12-14 | 中国海洋大学 | There is the high dielectric of laminated construction, the preparation method of low-loss composite |
| CN106413367A (en) * | 2016-09-05 | 2017-02-15 | 四川大学 | Novel multifunctional macromolecule based multilayer electromagnetic shielding material and preparation method thereof |
| CN108748942A (en) * | 2018-06-01 | 2018-11-06 | 芜湖市亿仑电子有限公司 | A kind of preparation method of polymer-based dielectric material |
| CN109167530A (en) * | 2018-09-20 | 2019-01-08 | 北京中石伟业科技股份有限公司 | It is a kind of can low voltage drive dielectric elastomer driver and preparation method thereof, energy converter |
| CN109181311A (en) * | 2018-08-30 | 2019-01-11 | 贵州省建材产品质量监督检验院 | A kind of asymmetric graphene silicon rubber dielectric composite material of multilayer and preparation method thereof |
| CN112876789A (en) * | 2021-01-18 | 2021-06-01 | 江苏集萃先进高分子材料研究所有限公司 | Conductive particle filled polymer layered composite dielectric material and preparation method thereof |
| CN112918031A (en) * | 2021-01-26 | 2021-06-08 | 清华大学 | High-dielectric-elasticity composite material and preparation method and application thereof |
| CN114249921A (en) * | 2021-11-22 | 2022-03-29 | 四川大学 | Nanofiber filler for capacitor film, capacitor film comprising same, and preparation method of capacitor film |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103753726A (en) * | 2014-01-06 | 2014-04-30 | 四川大学 | Method for preparing heat-conductive composite material |
| CN103753726B (en) * | 2014-01-06 | 2016-11-23 | 四川大学 | A kind of method preparing heat-conductive composite material |
| CN105219021A (en) * | 2015-08-19 | 2016-01-06 | 中南大学 | A kind of dielectric composite material |
| CN106218188A (en) * | 2016-07-27 | 2016-12-14 | 中国海洋大学 | There is the high dielectric of laminated construction, the preparation method of low-loss composite |
| CN106218188B (en) * | 2016-07-27 | 2018-09-28 | 中国海洋大学 | The preparation method of high dielectric, low-loss composite material with laminated construction |
| CN106413367A (en) * | 2016-09-05 | 2017-02-15 | 四川大学 | Novel multifunctional macromolecule based multilayer electromagnetic shielding material and preparation method thereof |
| CN106413367B (en) * | 2016-09-05 | 2019-07-26 | 四川大学 | A kind of multifunctional macromolecule Quito layer electromagnetic shielding material and preparation method thereof |
| CN108748942A (en) * | 2018-06-01 | 2018-11-06 | 芜湖市亿仑电子有限公司 | A kind of preparation method of polymer-based dielectric material |
| CN109181311A (en) * | 2018-08-30 | 2019-01-11 | 贵州省建材产品质量监督检验院 | A kind of asymmetric graphene silicon rubber dielectric composite material of multilayer and preparation method thereof |
| CN109167530A (en) * | 2018-09-20 | 2019-01-08 | 北京中石伟业科技股份有限公司 | It is a kind of can low voltage drive dielectric elastomer driver and preparation method thereof, energy converter |
| CN109167530B (en) * | 2018-09-20 | 2020-06-05 | 北京中石伟业科技股份有限公司 | Dielectric elastomer driver capable of being driven at low voltage, preparation method thereof and transducer |
| CN112876789A (en) * | 2021-01-18 | 2021-06-01 | 江苏集萃先进高分子材料研究所有限公司 | Conductive particle filled polymer layered composite dielectric material and preparation method thereof |
| CN112918031A (en) * | 2021-01-26 | 2021-06-08 | 清华大学 | High-dielectric-elasticity composite material and preparation method and application thereof |
| CN112918031B (en) * | 2021-01-26 | 2022-04-29 | 清华大学 | High-dielectric-elasticity composite material, preparation method thereof and application thereof in flexible sensing |
| CN114249921A (en) * | 2021-11-22 | 2022-03-29 | 四川大学 | Nanofiber filler for capacitor film, capacitor film comprising same, and preparation method of capacitor film |
| CN114249921B (en) * | 2021-11-22 | 2023-03-10 | 四川大学 | Nanofiber filler for capacitor film, capacitor film comprising same, and method for producing capacitor film |
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