CN109762277A - It is a kind of with isolation-it is bis- exceed seep structure high PTC intensity conducing composite material, with and the preparation method and application thereof - Google Patents
It is a kind of with isolation-it is bis- exceed seep structure high PTC intensity conducing composite material, with and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109762277A CN109762277A CN201910008138.9A CN201910008138A CN109762277A CN 109762277 A CN109762277 A CN 109762277A CN 201910008138 A CN201910008138 A CN 201910008138A CN 109762277 A CN109762277 A CN 109762277A
- Authority
- CN
- China
- Prior art keywords
- kynoar
- composite material
- density polyethylene
- linear low
- conducing composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 100
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 100
- 230000008595 infiltration Effects 0.000 claims abstract description 34
- 238000001764 infiltration Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 239000011231 conductive filler Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 23
- -1 Kynoar Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 17
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 238000005253 cladding Methods 0.000 claims abstract description 12
- 239000012467 final product Substances 0.000 claims abstract description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 40
- 229920001684 low density polyethylene Polymers 0.000 claims description 12
- 239000004702 low-density polyethylene Substances 0.000 claims description 12
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229920000131 polyvinylidene Polymers 0.000 claims 1
- 239000002033 PVDF binder Substances 0.000 abstract description 25
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 25
- 239000000155 melt Substances 0.000 abstract description 7
- 239000011540 sensing material Substances 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 description 16
- 229920000573 polyethylene Polymers 0.000 description 16
- 238000005325 percolation Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010117 shenhua Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Thermistors And Varistors (AREA)
Abstract
The present embodiments relate to it is a kind of with isolation-it is bis- exceed seep structure high PTC intensity conducing composite material, with and the preparation method and application thereof.The conducing composite material is by including that the raw material of following components is made: linear low density polyethylene, Kynoar, conductive filler and antioxidant；Preparation method includes the following steps: linear low density polyethylene, conductive filler and antioxidant the melt blending in mixer, and the temperature that mixer is arranged is 130-160 DEG C, and cladding masterbatch is made；Then Kynoar is added into mixer, the temperature that mixer is arranged is 130-150 DEG C, will be taken out after cladding masterbatch and Kynoar melt blending；Hot pressing to obtain the final product.CB/LLDPE/PVDF conducing composite material obtained has isolation-is bis- to exceed infiltration structure, and conductive content is low, PTC intensity is high, stability is high, can be used as temperature sensing material.
Description
Technical field
The present invention relates to conductive polymer composite fields, and in particular to a kind of with the bis- height for exceeding infiltration structure of isolation-
The conducing composite material of PTC intensity, with and the preparation method and application thereof.
Background technique
Conductive polymeric composite (CPCs) is that one or more of conductive fillers and one or more are polymer-based
Bluk recombination is prepared.The minimum critical content that conducting particles constitutes conductive network is defined as percolation threshold.However the prior art
Prepared CPCs, it usually needs add a large amount of conductive filler, percolation threshold is larger.
Reduce the emphasis and hot spot that percolation threshold is always CPCs research.The method for reducing percolation threshold has very much, conductive
Filler and use, isolation structure, it is double exceed seep structure and can reduce percolation threshold.(the Journal of Materials such as Bao
Science, 2013,48,4892-4898) first pass through solution mixing method by carbon black dispersion at low density polyethylene (LDPE) (LDPE)
Xiang Zhong makes carbon black/LDPE selectively be dispersed in single ultra-high molecular weight polyethylene then by mixing with UHMWPE mechanical lapping
(UHMWPE) between particle, formation isolation-is bis- to exceed infiltration structure, but the shortcomings that this preparation method is to need in organic solvent
It carries out, and scattered nano material may reunite or settle again, also to remove solvent, technics comparing is complicated, the time
Period is long, and production efficiency is low.Melt blending is the most frequently used simple blending technology, but melt blending is due to shearing force
In the presence of, composite material " isolation-is bis- to exceed infiltration " structure can be destroyed, makes filler distribution in intrinsic silicon, therefore, melt blending preparation
" isolation-is bis- to exceed infiltration " report research of structure is considerably less, this is also the difficult point studied at present.
CPCs to environmental stimuli (temperature, liquid, gas, strain) have responsiveness, an important feature of CPCs be with
The raising of temperature its resistivity be gradually increased, and increase sharply near macromolecule fusing point, show ptc characteristics (positive temperature
Coefficient effect).One important performance of this polymer composite type temperature sensitive sensor is exactly high PTC intensity, PTC
Intensity is normally defined the logarithm of maximum resistivity and room temperature resistivity ratio on temperature resistance curve.Based on its high PTC intensity,
CPCs has been widely used in electric-heating belt, self limiting temperature heating, microswitch sensors, electric current and temperature overload protective device
Equal fields, are reduced or turned off electric current at relatively high temperatures, play a protective role.
Therefore, it is necessary to develop it is a kind of by be adapted to industrial applications simplest melt-blending process prepare have it is low
Conductive content, and the conducing composite material with high PTC strength and stability.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
To solve in polymer/conductive filler composite conducting system in the prior art, conductive filler amount is high, PTC is strong
Disadvantage low, that stability is poor is spent, the purpose of the present invention is to provide a kind of with the bis- high PTC intensity for exceeding infiltration structure of isolation-
Conducing composite material, with and the preparation method and application thereof.Preparation method provided by the invention, with linear low density polyethylene
(LLDPE) and Kynoar (PVDF) blend is matrix, with conductive black (CB) for conductive filler, using suitable for industrialization
The melt-blending process of application, using the difference of linear low density polyethylene and Kynoar two kinds of polymer fusing point, cooperation is super
Strong shear power, CB/LLDPE/PVDF conducing composite material obtained, with low conductive content, high PTC intensity and high stability
Advantage, and can be used as temperature sensing material.
Solution
Purpose to realize the present invention, the embodiment of the invention provides a kind of with the bis- high PTC intensity for exceeding infiltration structure of isolation-
Conducing composite material, the conducing composite material by include following components raw material be made: linear low density polyethylene gathers inclined fluorine
Ethylene, conductive filler and antioxidant.
In one possible implementation, Kynoar is powdered ultra-fine polyvinylidene fluoride to above-mentioned conducing composite material
Alkene；Optionally, the Average Particle Diameters of Kynoar are 300-800nm.
Above-mentioned conducing composite material in one possible implementation, linear low density polyethylene and Kynoar
Mass ratio is 1:2-10；It is optionally 1:4-9；It is still optionally further 1:9.
In one possible implementation, the quality of conductive filler is linear low density polyethylene to above-mentioned conducing composite material
The 2%-15% of alkene and Kynoar gross mass；Optionally, the quality of conductive filler is linear low density polyethylene and gathers inclined
The 2%-6% of vinyl fluoride gross mass, 3%-10%, 5%-12%, 4%-14%；Still optionally further, the quality of conductive filler
For the 2%-6% of linear low density polyethylene and Kynoar gross mass.
In one possible implementation, conductive filler includes conductive black to above-mentioned conducing composite material.
Above-mentioned conducing composite material in one possible implementation, antioxidant include antioxidant 1010 (four [β-(3,
5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), antioxidant 300 (4,4 '-thiobis-(first between 6- tertiary butyl
At least one of phenol)) or antioxidant 2246 (2,2'- methylene bis (4- methyl-6-tert-butylphenol))；It is optionally antioxidant
1010。
In one possible implementation, the quality of antioxidant is linear low density polyethylene to above-mentioned conducing composite material
The 0.02%-5% of quality；It is optionally 0.05%-2%；It is still optionally further 0.08%-1.2%；Further optionally
It is 1%.
The embodiment of the invention also provides a kind of conducing composite materials with the bis- high PTC intensity for exceeding infiltration structure of isolation-
Preparation method, include the following steps:
By linear low density polyethylene, conductive filler and antioxidant in mixer melt blending, the temperature of mixer is set
Degree is 130-160 DEG C, is optionally 140-160 DEG C, and cladding masterbatch is made；Then Kynoar is added into mixer, if
The temperature for setting mixer is 130-150 DEG C, 130-140 DEG C is optionally, after cladding masterbatch and Kynoar melt blending
It takes out；Hot pressing to obtain the final product.
In one possible implementation, Kynoar is powdered ultra-fine Kynoar to above-mentioned preparation method；
Optionally, the Average Particle Diameters of Kynoar are 300-800nm.
Above-mentioned preparation method in one possible implementation, the quality of linear low density polyethylene and Kynoar
Than for 1:2-10；It is optionally 1:4-9；It is still optionally further 1:9.
Above-mentioned preparation method in one possible implementation, the quality of conductive filler be linear low density polyethylene and
The 2%-15% of Kynoar gross mass；Optionally, the quality of conductive filler is linear low density polyethylene and polyvinylidene fluoride
The 2%-6% of alkene gross mass, 3%-10%, 5%-12%, 4%-14%；Still optionally further, the quality of conductive filler is line
The 2%-6% of property low density polyethylene (LDPE) and Kynoar gross mass.
Above-mentioned preparation method in one possible implementation, by linear low density polyethylene, conductive filler and antioxygen
Agent melt blending 1-15min in mixer is optionally 2-10min, is still optionally further 3-5min.
Above-mentioned preparation method in one possible implementation, by cladding masterbatch and when Kynoar melt blending,
The revolving speed of mixer is 60-100rpm.
Above-mentioned preparation method in one possible implementation, by cladding masterbatch and when Kynoar melt blending,
Incorporation time is 2-15min, is optionally 3-10min, is still optionally further 5-6min.
In one possible implementation, hot pressing temperature is 165-180 DEG C to above-mentioned preparation method.
In one possible implementation, hot pressing pressure 9-11MPa is optionally 10MPa to above-mentioned preparation method.
In one possible implementation, hot pressing time 2-15min is optionally 3-10min to above-mentioned preparation method,
It is still optionally further 4-5min.
In one possible implementation, conductive filler includes conductive black to above-mentioned preparation method.
In one possible implementation, antioxidant includes antioxidant 1010 (four [β-(3,5- bis- to above-mentioned preparation method
Tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), antioxidant 300 (4,4 '-thiobis-(6- tertiary butyl metacresol)) or
At least one of antioxidant 2246 (2,2'- methylene bis (4- methyl-6-tert-butylphenol))；It is optionally antioxidant 1010.
In one possible implementation, the quality of antioxidant is linear low density polyethylene quality to above-mentioned preparation method
0.02%-5%；It is optionally 0.05%-2%；It is still optionally further 0.08%-1.2%.
The embodiment of the invention also provides the above-mentioned conducing composite materials with the bis- high PTC intensity for exceeding infiltration structure of isolation-
Application in temperature overload protection field.
Beneficial effect
(1) what is provided in the embodiment of the present invention has isolation-is bis- to exceed the conducing composite material for seeping the high PTC intensity of structure,
With high conductivity and high PTC intensity, in the case where conductive filler content is very low, so that it may significantly improve the conduction of composite material
Property, and conductive filler content, in percolation threshold, conducing composite material can reach high PTC intensity and high stability.
(2) what is provided in the embodiment of the present invention has the conducing composite materials of the bis- high PTC intensity for exceeding infiltration structure of isolation-
Preparation method will coat masterbatch and the PVDF melt blending at 130-150 DEG C, this temperature by controlling the temperature of mixer
Lower than PVDF fusing point, being higher than LLDPE fusing point, (for the LLDPE and PVDF used in the embodiment, which is 120
DEG C, PVDF fusing point is 160 DEG C), it melts at this temperature, powdered PVDF does not melt, and can keep the spherical shape of graininess PVDF
Form does not change, and has repulsive interaction to conductive filler, so that conductive filler not can enter in PVDF phase, but selectivity
It is distributed in LLDPE phase, continuous phase is collectively formed with LLDPE, the continuous phase that conductive filler and LLDPE are formed is wrapped in PVDF
Grain, formation isolation-is bis- to exceed infiltration structure, to reduce conductive filler excess effusion value, can be made strong with low conductive content, high PTC
The CB/LLDPE/PVDF conducing composite material of degree and stability.
(3) what is provided in the embodiment of the present invention has the conducing composite materials of the bis- high PTC intensity for exceeding infiltration structure of isolation-
The superpower shearing force (effect that two rotors in mixer generate shearing force in the rotation) of preparation method, mixer can
So that cladding masterbatch with PVDF is full and uniform mixes.And the temperature melt blending because selecting to be lower than PVDF fusing point, powdered PVDF
Do not melt, spherical morphology can be kept not change, thus the superpower shearing force of mixer will not damage containment-it is bis- exceed infiltration knot
Structure, so as to using most simple common blending technology --- melt-blending process has the bis- CB/ for exceeding infiltration structure of isolation-to prepare
LLDPE/PVDF conducing composite material is suitable for industrial applications.
(4) what is provided in the embodiment of the present invention has the conducing composite materials of the bis- high PTC intensity for exceeding infiltration structure of isolation-
In preparation method, other Kynoar is equally applicable in the micron-scale for conventional partial size, but uses ultra-fine Kynoar powder
End, performance is more excellent, and effect is more preferable.Meanwhile using ultra-fine Kynoar, also can avoid using the poly- inclined of conventional micron rank
The step of when vinyl fluoride to the pretreatment of raw material (grinding, screening).
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 be conducing composite material made from the embodiment of the present invention 1 as temperature sensing resistor device during heating
Application test, the figure left side are at 31 DEG C of room temperature, and light bulb shines；Figure the right is at 114 DEG C, and light bulb is dimmed.
Fig. 2 is in effect example 2 of the present invention, and CB/LLDPE/PVDF conductive composite material resistance rate produced by the present invention is with CB
The relational graph of changes of contents, built-in figure are to be exceeded to seep theoretical obtained matched curve according to classics.
Fig. 3 is the conduction that the embodiment of the present invention 2, embodiment 3, embodiment 4, embodiment 5 obtain in effect example 3 of the present invention
The temperature-resistance behavior curve of composite material；Built-in figure is that the embodiment of the present invention 2, embodiment 3, embodiment 4, embodiment 5 obtain
Conducing composite material PTC intensity.
Specific embodiment
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, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Linear low density polyethylene used is purchased from Chinese Shenhua, trade mark DFDA7042 in following embodiment, and density is
0.918g/cm3, 120 DEG C of fusing point；
Kynoar is ultra-fine Kynoar powder, is purchased from Su Wei Solvay, and the trade mark is Solef 461, and density is
1.76g/cm3, fusing point is 160 DEG C, melt flow index 10g/10min (230 DEG C/21.6kg), partial size 300nm；
Conductive black is purchased from U.S. Cabot Cabot, marque VXC-72, partial size 30nm, and specific surface area is
254m2/g；
Antioxidant 1010 is purchased from Double Bond Chemical Ind.,Co.,Ltd..
Embodiment 1
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 45g, conductive black 1g and antioxidant 1010
0.05g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 2% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
Preparation method includes the following steps:
Linear low density polyethylene and Kynoar is vacuum dried；At 150 DEG C, by linear low density polyethylene
It is added in mixer, melts 2min；Then conductive black is added according to the above ratio and antioxidant 1010, melt blending 4min is obtained
Coat masterbatch；Ultra-fine Kynoar powder is added, at 135 DEG C, 5min is blended under the conditions of being 60rpm in revolving speed, is then discharged；It will
The sample that mixing obtains hot pressing 5min under the conditions of 180 DEG C, 10MPa, be pressed into conductive black filling sample to get have every
From-it is bis- exceed seep structure high PTC intensity conducing composite material.
130-140 DEG C of this melt temperature scope is higher than the fusing point of linear low density polyethylene, lower than Kynoar
Fusing point.
Embodiment 2
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 45g, conductive black 1.3g and antioxidant 1010
0.05g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 2.6% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is linear low density polyethylene quality
1%.
The preparation method is the same as that of Example 1.
Embodiment 3
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 45g, conductive black 1.4g and antioxidant 1010
0.05g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 2.8% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is linear low density polyethylene quality
1%.
The preparation method is the same as that of Example 1.
Embodiment 4
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 45g, conductive black 1.5g and antioxidant 1010
0.05g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 3% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 5
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 45g, conductive black 2g and antioxidant 1010
0.05g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 4% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 6
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 45g, conductive black 2.5g and antioxidant 1010
0.05g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 5% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 7
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 45g, conductive black 3g and antioxidant 1010
0.05g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 6% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 8
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 6g, Kynoar 54g, conductive black 1.2g and antioxidant 1010
0.06g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 2% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 9
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 6g, Kynoar 54g, conductive black 1.5g and antioxidant 1010
0.06g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 2.5% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is linear low density polyethylene quality
1%.
The preparation method is the same as that of Example 1.
Embodiment 10
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 6g, Kynoar 54g, conductive black 1.6g and antioxidant 1010
0.06g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 2.7% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is linear low density polyethylene quality
1%.
The preparation method is the same as that of Example 1.
Embodiment 11
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 6g, Kynoar 54g, conductive black 1.8g and antioxidant 1010
0.06g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 3% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 12
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 6g, Kynoar 54g, conductive black 2.4g and antioxidant 1010
0.06g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 4% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 13
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 6g, Kynoar 54g, conductive black 3g and antioxidant 1010
0.06g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 5% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 14
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 6g, Kynoar 54g, conductive black 3.6g and antioxidant 1010
0.06g；
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:9；The quality of conductive black is linear low close
Spend the 6% of polyethylene and Kynoar gross mass；The quality of antioxidant 1010 is the 1% of linear low density polyethylene quality.
The preparation method is the same as that of Example 1.
Embodiment 1-14 raw material weight (g) summary is shown in Table 1: where CB content refers in the present invention: CB mass and linear
The ratio of low density polyethylene (LDPE) and Kynoar gross mass.
Table 1
Embodiment 15
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 20g, antioxidant 1010 0.1g；Conductive black
Additional amount be respectively 0.75g, 1g, 1.25g, 1.5g, 1.75g, 2g, 2.25g, 2.5g.
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:4；The quality of antioxidant 1010 is linear low
The 2% of density polyethylene quality；The quality of conductive black is the 3% of linear low density polyethylene and Kynoar gross mass,
4%, 5%, 6%, 7%, 8%, 9%, 10%.
Preparation method includes the following steps:
Linear low density polyethylene and Kynoar is vacuum dried；At 150 DEG C, by linear low density polyethylene
It is added in mixer, melts 10min；Then conductive black is added according to the above ratio and antioxidant 1010, melt blending 2min is obtained
Coat masterbatch；Ultra-fine Kynoar powder is added, at 130 DEG C, 10min is blended under the conditions of being 80rpm in revolving speed, is then discharged；
The sample that mixing is obtained hot pressing 3min under the conditions of 170 DEG C, 10MPa is pressed into the sample of conductive black filling to get having
Isolation-is bis- to exceed the conducing composite material for seeping the high PTC intensity of structure.The percolation threshold of the CB/LLDPE/PVDF composite material is
5-6wt%.
Embodiment 16
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 12.5g, antioxidant 300 0.06g；Conductive charcoal
Black additional amount is respectively 0.875g, 1.05g, 1.225g, 1.4g, 1.575g, 1.75g, 1.925g, 2.1g.
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:2.5；The quality of antioxidant 300 is linear low
The 1.2% of density polyethylene quality；The quality of conductive black is respectively linear low density polyethylene and Kynoar gross mass
5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%.
Preparation method includes the following steps:
Linear low density polyethylene and Kynoar is vacuum dried；At 150 DEG C, by linear low density polyethylene
It is added in mixer, melts 1min；Then conductive black is added according to the above ratio and antioxidant 300, melt blending 10min is obtained
Coat masterbatch；Ultra-fine Kynoar powder is added, at 140 DEG C, 3min is blended under the conditions of being 100rpm in revolving speed, is then discharged；
The sample that mixing is obtained hot pressing 10min under the conditions of 175 DEG C, 10MPa is pressed into the sample of conductive black filling to get tool
There are isolation-is bis- to exceed the conducing composite material for seeping the high PTC intensity of structure.The percolation threshold of the CB/LLDPE/PVDF composite material
For 7-8wt%.
Embodiment 17
A kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, the conducing composite material is by including
The raw material of following components is made: linear low density polyethylene 5g, Kynoar 7.5g, antioxidant 2246 0.04g；Conductive charcoal
Black additional amount is respectively 0.5g, 0.875g, 1.125g, 1.25g, 1.375g, 1.5g, 1.625g, 1.75g.
I.e. the mass ratio of linear low density polyethylene and Kynoar is 1:1.5；The quality of antioxidant 2246 is linear
The 0.8% of low density polyethylene (LDPE) quality；The quality of conductive black is linear low density polyethylene and Kynoar gross mass
4%, 7%, 9%, 10%, 11%, 12%, 13%, 14%.
Preparation method includes the following steps:
Linear low density polyethylene and Kynoar is vacuum dried；At 150 DEG C, by linear low density polyethylene
It is added in mixer, melts 3min；Then conductive black and antioxidant 300, melt blending 3min are added according to the above ratio to be wrapped
Cover masterbatch；Ultra-fine Kynoar powder is added, at 140 DEG C, 6min is blended under the conditions of being 100rpm in revolving speed, is then discharged；It will
The sample that mixing obtains hot pressing 10min under the conditions of 180 DEG C, 10MPa is pressed into the sample of conductive black filling to get having
Isolation-is bis- to exceed the conducing composite material for seeping the high PTC intensity of structure.The percolation threshold of the CB/LLDPE/PVDF composite material is
9-10wt%.
Effect example
1, have the bis- conducing composite materials for exceeding the high PTC intensity for seeping structure of isolation-as temperature for what embodiment 1 obtained
Sense resistor tests its application during heating, as shown in Figure 1, as a result, it has been found that, when room temperature (31 DEG C), lampet
Bubble can shine (the figure left side)；During heating, when close to LLDPE fusing point (114 DEG C), small bulbs are dark, and (figure is right
Side).This is because resistance increases during heating, the electric current in access reduces, and is not enough to be formed conductive path, cuts off
Electric current.Illustrate that conducing composite material made from embodiment 1 has protective effect to circuit, can apply to protect in temperature overload and lead
Domain.
2, Fig. 2 be CB/LLDPE/PVDF conducing composite material made from the embodiment of the present invention (linear low density polyethylene and
The mass ratio of Kynoar is 1:9, and the quality of antioxidant 1010 is the 1% of linear low density polyethylene quality) resistivity with
The relational graph of CB changes of contents, built-in figure are to be exceeded to seep theoretical obtained matched curve (P is the quality point of conductive filler according to classics
Number, Pc is percolation threshold).By the Fitting Calculation, the percolation threshold of the CB/LLDPE/PVDF composite material is 2.5-3wt%.When
When CB content increases to 3wt% from 2wt%, the resistivity of composite material reduces about ten orders of magnitude.Addition PVDF causes
Volume excluding effect reduce percolation threshold.
3, Fig. 3 is that (CB content is respectively the obtained conducing composite material of embodiment 2, embodiment 3, embodiment 4, embodiment 5
2.6%, 2.8%, 3%, 4%) temperature-resistance behavior.Testing procedure is as follows: the sample that molding obtains is cut into strip by 1.,
It is stained with copper mesh at the both ends of strip, material is contacted with copper mesh well, reduces the contact resistance in test process.2. using
KEITHLEY 2636B carries out electric performance test, while the temperature-resistance row to composite material in program-controlled heating and cooling to sample
To be studied, wherein the rate of program-controlled heating and cooling is 2 DEG C/min, obtains embodiment 2, embodiment 3, embodiment 4, embodiment 5
The temperature resistance curve of obtained conducing composite material.3. the temperature resistance curve obtained according to step 2, calculating embodiment 2,
The PTC intensity for the conducing composite material that embodiment 3, embodiment 4, embodiment 5 obtain, is as a result shown in built-in figure.
It can see from built-in figure, it is conductive when CB content is lower than 2.5wt% (conducing composite material of embodiment 2)
Composite material PTC intensity is 3；When CB content is at 2.5-3wt% (conducing composite material of embodiment 3), conducing composite material
PTC intensity reaches maximum value 6；CB content is continued growing, when CB content is more than 3wt% (conducing composite material of embodiment 4),
Conducing composite material PTC intensity is 3, PTC strength reduction.
4, the PTC strength stability of conducing composite material made from embodiment 3 (CB content is 2.8%) is studied.
As a result, it has been found that conducing composite material PTC intensity made from embodiment 3 is high, by multiple heating and cooling, room temperature resistance is kept substantially
It is constant, and there is high PTC intensity and high stability simultaneously.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, under the conducing composite material is by including
The raw material for stating component is made: linear low density polyethylene, Kynoar, conductive filler and antioxidant.
2. a kind of preparation method of the conducing composite material with the bis- high PTC intensity for exceeding infiltration structure of isolation-, including following steps
Rapid: by linear low density polyethylene, conductive filler and antioxidant, melt blending, the temperature that mixer is arranged are in mixer
130-160 DEG C, cladding masterbatch is made；Then Kynoar is added into mixer, the temperature that mixer is arranged is 130-150
DEG C, it will be taken out after cladding masterbatch and Kynoar melt blending；Hot pressing to obtain the final product.
3. conducing composite material according to claim 1 or preparation method as claimed in claim 2, it is characterised in that: poly-
Vinylidene is powdered ultra-fine Kynoar；Optionally, the Average Particle Diameters of Kynoar are 300-800nm.
4. conducing composite material according to claim 1 or preparation method as claimed in claim 2, it is characterised in that: line
Property low density polyethylene (LDPE) and Kynoar mass ratio be 1:2-10；It is optionally 1:4-9；It is still optionally further 1:9.
5. conducing composite material according to claim 1 or preparation method as claimed in claim 2, it is characterised in that: lead
Electric filler includes conductive black；
And/or the quality of conductive filler is the 2%-15% of linear low density polyethylene and Kynoar gross mass；Optionally
For 2%-6%, 3%-10%, 5%-12%, 4%-14%；It is still optionally further 2%-6%.
6. conducing composite material according to claim 1 or preparation method as claimed in claim 2, it is characterised in that: anti-
Oxygen agent includes at least one of antioxidant 1010, antioxidant 300 or antioxidant 2246；It is optionally antioxidant 1010；
And/or the quality of antioxidant is the 0.02%-5% of linear low density polyethylene quality；It is optionally 0.05%-2%；
It is still optionally further 0.08%-1.2%；Further it is optionally 1%.
7. preparation method according to claim 2, it is characterised in that: by linear low density polyethylene, conductive filler and resist
Oxygen agent melt blending in mixer, the temperature that mixer is arranged is 140-160 DEG C；
And/or at a temperature of 130-140 DEG C, it will be taken out after cladding masterbatch and Kynoar melt blending；
And/or by linear low density polyethylene, conductive filler and antioxidant in mixer melt blending 1-15min, optionally
It is still optionally further 3-5min for 2-10min.
8. preparation method according to claim 2, it is characterised in that: by cladding masterbatch and Kynoar melt blending
When, the revolving speed of mixer is 60-100rpm；
And/or when by cladding masterbatch and Kynoar melt blending, incorporation time 2-15min is optionally 3-10min,
It is still optionally further 5-6min.
9. preparation method according to claim 2, it is characterised in that: hot pressing temperature is 165-180 DEG C；
And/or hot pressing pressure 9-11MPa, it is optionally 10MPa；
And/or hot pressing time 2-15min, it is optionally 3-10min, is still optionally further 4-5min.
10. conducing composite material made from conducing composite material described in claim 1 or preparation method as claimed in claim 2
Application in temperature overload protection field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910008138.9A CN109762277B (en) | 2019-01-04 | 2019-01-04 | high-PTC-strength conductive composite material with isolation-double percolation structure, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910008138.9A CN109762277B (en) | 2019-01-04 | 2019-01-04 | high-PTC-strength conductive composite material with isolation-double percolation structure, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109762277A true CN109762277A (en) | 2019-05-17 |
| CN109762277B CN109762277B (en) | 2020-12-29 |
Family
ID=66453424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910008138.9A Active CN109762277B (en) | 2019-01-04 | 2019-01-04 | high-PTC-strength conductive composite material with isolation-double percolation structure, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109762277B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554588A (en) * | 2013-09-27 | 2014-02-05 | 安徽华印机电股份有限公司 | Macromolecular PTC composite material with crystalline polymer as matrix |
| CN104725749A (en) * | 2015-03-31 | 2015-06-24 | 四川大学 | Ternary-blend-based composite material with ultralow conductive percolation value and preparation method of composite material |
| CN105837950A (en) * | 2016-06-22 | 2016-08-10 | 四川大学 | Polyolefin-based conductive and dielectric composite material and preparation method thereof |
-
2019
- 2019-01-04 CN CN201910008138.9A patent/CN109762277B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554588A (en) * | 2013-09-27 | 2014-02-05 | 安徽华印机电股份有限公司 | Macromolecular PTC composite material with crystalline polymer as matrix |
| CN104725749A (en) * | 2015-03-31 | 2015-06-24 | 四川大学 | Ternary-blend-based composite material with ultralow conductive percolation value and preparation method of composite material |
| CN105837950A (en) * | 2016-06-22 | 2016-08-10 | 四川大学 | Polyolefin-based conductive and dielectric composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LI CHUAN JIA, ETC.: ""A Unique Double Percolated Polymer Composite for Highly Efficient Electromagnetic Interference Shielding"", 《MACROMOLECULAR MATERIALS AND ENGINEERING》 * |
| YU BAO. ETC.: ""Preparation and properties of carbon black/polymer composites with segregated and double-percolated network structures"", 《JOURNAL OF MATERIALS SCIENCE》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109762277B (en) | 2020-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Carbon‐black‐filled polyolefine as a positive temperature coefficient material: Effect of composition, processing, and filler treatment | |
| Xi et al. | Positive temperature coefficient effect of LMWPE–UHMWPE blends filled with short carbon fibers | |
| US4265789A (en) | Conductive polymer processable as a thermoplastic | |
| US5106540A (en) | Conductive polymer composition | |
| US3591526A (en) | Method of manufacturing a temperature sensitive,electrical resistor material | |
| EP0197781B1 (en) | Melt-shapeable fluoropolymer compositions | |
| KR102044107B1 (en) | Conductive Polymer Compositions, Conductive Polymer Sheets, Electrical Components, and Methods for Making the Same | |
| Yang et al. | Electrical properties and morphology of carbon black‐filled HDPE/EVA composites | |
| CN103113732B (en) | A kind of conductive polymer composite and preparation method thereof | |
| CN106188815A (en) | The cross-linked ethylene TFE copolymer material of heat resistant | |
| Segal et al. | Thermoplastic polyurethane–carbon black compounds: structure, electrical conductivity and sensing of liquids | |
| CN103588983A (en) | Preparation method for flexible high-molecular PTC material | |
| CN107446336A (en) | A kind of low smell exempts to spray PC/ABS materials and preparation method thereof | |
| CN101456988B (en) | Conductive polymer with positive temperature coefficient effect | |
| CN109517367A (en) | A kind of conductive thermoplastic dynamic vulcanization silicon rubber and preparation method thereof | |
| CN104861273A (en) | Composite material for thermistor and preparation method and application of composite material | |
| CN109762277A (en) | It is a kind of with isolation-it is bis- exceed seep structure high PTC intensity conducing composite material, with and the preparation method and application thereof | |
| EP0371059A1 (en) | Conductive polymer composition | |
| EP0074281B1 (en) | Heating diesel fuel | |
| CN107230511B (en) | Conductive polymer compositions, electric device and preparation method thereof | |
| CN106883505B (en) | Flexible semiconducting shielding material of one kind and preparation method thereof | |
| CN109294050A (en) | Silane-crosslinkable semiconductive inner shield material and preparation method thereof | |
| US3409584A (en) | Tetrafluoroethylene products and methods | |
| CN102604281A (en) | Preparation method of crosslinking-free polymer-based high-temperature PTC (positive temperature coefficient) material | |
| CN105482462A (en) | High-temperature-resistant and low-smoke-zero-halogen cable material and preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |