CN109251398A - Semi-conductive shielding material for insulation and preparation method thereof - Google Patents
Semi-conductive shielding material for insulation and preparation method thereof Download PDFInfo
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- CN109251398A CN109251398A CN201810735514.XA CN201810735514A CN109251398A CN 109251398 A CN109251398 A CN 109251398A CN 201810735514 A CN201810735514 A CN 201810735514A CN 109251398 A CN109251398 A CN 109251398A
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention provides a semiconductive shielding material for insulation and a preparation method thereof. The semi-conductive shielding material for insulation comprises the following components: ethylene-vinyl acetate copolymer: 46 to 55 parts by weight, preferably 46 to 54 parts by weight, more preferably 47 to 53 parts by weight; conductive carbon black: 25 to 45 parts by weight, preferably 30 to 42 parts by weight, more preferably 32 to 40 parts by weight; white oil: 2 to 10 parts by weight, preferably 3 to 9 parts by weight, more preferably 4 to 8 parts by weight; antioxidant: 0.1 to 0.4 part by weight, preferably 0.2 to 0.4 part by weight; lubricant: 1 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 1.5 to 7 parts by weight; c5 resin: 2 to 8 parts by weight, preferably 3 to 7 parts by weight; more preferably 3.5 to 6.5 parts by weight; a crosslinking agent: 1.0 to 3.2 parts by weight, preferably 1.2 to 2.8 parts by weight, and more preferably 1.2 to 2.5 parts by weight. The semiconductive shielding material for insulation has good mechanical property and electrical property. The semiconductive insulating shielding material disclosed by the invention can reduce the compatibility with polyethylene, so that the peel strength of the semiconductive insulating shielding material is reduced.
Description
Technical field
The present invention relates to a kind of insulation semiconductive shieldin materials and preparation method thereof, belong to cable material field.
Background technique
Conductor thread core, insulating layer and the sheath three parts group that the essential structure of power cable is twisted by copper or aluminium single line
At.In the structure of middle high-pressure electric power cable, is concentrated to mitigate the electric field stress inside cable, it is twisted to eliminate conductor wire core
Influence, the stress distribution of homogeneous insulation layers surface field, improve cable internal electric field through improving the electricity of cable to distribution
Gas intensity, it is desirable that between conductor wire core and insulating layer, respectively added with one layer of semiconductive shielding layer between insulating layer and restrictive coating,
It is properly termed as conductor shield and insulation screen, respectively so as to improve the electric property and safety of the longtime running ability of cable
Reliability.
In the prior art, it should be adhesion type that the construction of cable and technique, which require conductor shield, and insulation screen is then
Rippability is needed to have, and uses and extrudes technique.And the common insulation semiconductive shieldin material of insulation screen is prepared, it shells
All cable can be caused to construct and using upper in the presence of very big in many external screen residues of insulation screen remained on surface from after
Risk.
Summary of the invention
Problems to be solved by the invention
In view of above-mentioned defect existing in the prior art, the present invention provides a kind of insulation semiconductive shieldin material and its preparation
Method.Insulation of the invention can reduce the compatibility with polyethylene with semiconductive shieldin material, to reduce insulation semiconductive
Shield the peel strength of material.Conductive black particle in insulation semiconductive shieldin material of the invention can be opened, conductive charcoal
It is black to be uniformly dispersed, to further decrease peel strength, and can reduce after removing in insulation shielding layer surface
Residue.
The solution to the problem
The present invention provides a kind of insulation semiconductive shieldin material, including following components:
Ethylene-vinyl acetate copolymer: 46~55 parts by weight, preferably 46~54 parts by weight, more preferable 47~53 weight
Part；
Conductive black: 25~45 parts by weight, preferably 30~42 parts by weight, more preferable 32~40 parts by weight；
White oil: 2~10 parts by weight, preferably 3~9 parts by weight, more preferable 4~8 parts by weight；
Antioxidant: 0.1~0.4 parts by weight, preferably 0.2~0.4 parts by weight；
Lubricant: 1~10 parts by weight, preferably 1~8 parts by weight, more preferable 1.5~7 parts by weight；
C5 resin: 2~8 parts by weight, preferably 3~7 parts by weight；More preferable 3.5~6.5 parts by weight；
Crosslinking agent: 1.0~3.2 parts by weight, preferably 1.2~2.8 parts by weight, more preferable 1.2~2.5 parts by weight.
Insulation semiconductive shieldin material according to the present invention, wherein acetic acid second in the ethylene-vinyl acetate copolymer
The content of allyl ester monomer unit is 17~30 mass %.
Insulation semiconductive shieldin material according to the present invention, wherein the ethylene-vinyl acetate copolymer is according to ASTM
The melt flow index that D1238-2004 is measured under 190 DEG C and 2.16kg load is 4~7g/10min.
Insulation semiconductive shieldin material according to the present invention, wherein the white oil includes 1# white oil, 10# white oil and 15#
The combination of one or more of white oil.
Insulation semiconductive shieldin material according to the present invention, wherein the antioxidant includes antioxidant 300, antioxidant AT-
10, the combination of one or more of antioxidant 264 and antioxidant 2246.
Insulation semiconductive shieldin material according to the present invention, wherein the lubricant includes silicone, zinc stearate, oleic acid
The combination of one or more of amide, polyester wax and polyethylene wax.
It is according to the present invention insulation use semiconductive shieldin material, wherein the average molecular weight of the C5 resin 2500Da with
Under, preferably between 1000~2500Da；The softening point temperature of the C5 resin be 100~140 DEG C, preferably 110~130
℃。
Insulation semiconductive shieldin material according to the present invention, wherein the crosslinking agent includes peroxide type initiators, excellent
Choosing includes cumyl peroxide.
The present invention also provides a kind of preparation methods of insulation semiconductive shieldin material according to the present invention comprising will be described
The step of each component of insulation semiconductive shieldin material mixes.
The insulation according to the present invention preparation method of semiconductive shieldin material, specifically includes the following steps:
1) ethylene-vinyl acetate copolymer, conductive black, white oil, antioxidant, lubricant and C5 resin are kneaded
Uniformly, it enters back into single-screw machine to be granulated, obtains particulate material；
2) it after the particulate material being put into container, is placed in 50~70 DEG C of heater and particulate material is heated to 50~70
℃；Then placing 8~16 hours after particulate material being uniformly mixed with crosslinking agent in 50~70 DEG C of heaters makes particulate material
Crosslinking agent is absorbed, insulation semiconductive shieldin material is obtained.
The effect of invention
Insulation of the invention has preferable mechanical performance, preferable electrical property with semiconductive shieldin material.Of the invention is exhausted
Edge can reduce the compatibility with polyethylene with semiconductive shieldin material, so that the removing for reducing insulation semiconductive shieldin material is strong
Degree.
In addition, the conductive black particle in insulation semiconductive shieldin material of the invention can be opened, conductive black energy
It is enough uniformly dispersed, to further decrease peel strength, and the residual after removing in insulation shielding layer surface can be reduced
Object.
Specific embodiment
It will be detailed below various exemplary embodiments, feature and aspect of the invention.Dedicated word " example herein
Property " mean " being used as example, embodiment or illustrative ".Here as any embodiment illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiments.
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 other example,
Method well known to those skilled in the art, means, equipment and step are not described in detail, in order to highlight master of the invention
Purport.
The present invention provides a kind of insulation semiconductive shieldin material, including following components:
Ethylene-vinyl acetate copolymer: 46~55 parts by weight, preferably 46~54 parts by weight, more preferable 47~53 weight
Part；
Conductive black: 25~45 parts by weight, preferably 30~42 parts by weight, more preferable 32~40 parts by weight；
White oil: 2~10 parts by weight, preferably 3~9 parts by weight, more preferable 4~8 parts by weight；
Antioxidant: 0.1~0.4 parts by weight, preferably 0.2~0.4 parts by weight；
Lubricant: 1~10 parts by weight, preferably 1~8 parts by weight, more preferable 1.5~7 parts by weight；
C5 resin: 2~8 parts by weight, preferably 3~7 parts by weight；More preferable 3.5~6.5 parts by weight；
Crosslinking agent: 1.0~3.2 parts by weight, preferably 1.2~2.8 parts by weight, more preferable 1.2~2.5 parts by weight.
Ethylene-vinyl acetate copolymer of the invention has good flexibility and elasticity, still is able to have at -50 DEG C
There are preferable pliability, the transparency and lustrous surface.The chemical stability of ethylene-vinyl acetate copolymer is good, anti-ageing
Change and resistance to ozone intensity is good, non-toxic, the present invention is using ethylene-vinyl acetate copolymer as substrate, to be prepared
The insulation semiconductive shieldin material haveing excellent performance.
In the case where the melt index of ethylene-vinyl acetate copolymer is constant, with mentioning for vinyl acetate content
Height, elasticity, flexibility and the compatibility of ethylene-vinyl acetate copolymer, transparency etc. can be with improves；With acetic acid second
The reduction of enester content, then rigidity, wearability and insulating properties can be with improves.In the vinegar of ethylene-vinyl acetate copolymer
In the case that the content of vinyl acetate is constant, with the increase of melt index, softening point and intensity can be with declines, but processability
It can be improved with lustrous surface；With the reduction of melt index, molecular weight increase, impact property and environment resistant stress and cracking
Property can be improved.Ethylene-vinyl acetate copolymer of the invention is according to ASTM D1238-2004 in 190 DEG C and 2.16kg
The melt flow index measured under load is 4~7g/10min.So as to further obtain the insulation haveing excellent performance with partly leading
Electrical shielding material.
According to the present invention insulate uses semiconductive shieldin material, Vinyl Acetate Monomer in ethylene-vinyl acetate copolymer
The content of unit is 17~30 mass %.
In the present invention, the additional amount of ethylene-vinyl acetate copolymer be 46~55 parts by weight, preferably 46~54
Parts by weight, more preferably 47~53 parts by weight.When the additional amount of ethylene-vinyl acetate copolymer is lower than 46 parts by weight, no
It can play the role of corresponding, the rigidity of the insulation semiconductive shieldin material being prepared, wearability and insulating properties performance are poor；
When the additional amount of ethylene-vinyl acetate copolymer is higher than 55 parts by weight, the content of other ingredients can be reduced accordingly, be influenced absolutely
The overall performance of edge semiconductive shieldin material.
In general, conductive black of the invention can be east YD-250C, Yong Dongte 260, forever east YD-280C, brother forever
Rival Asia 7090, Cabot carbon black VXC200, Cabot carbon black VXC68 etc..In the present invention, the additional amount of conductive black is 25
~45 parts by weight, preferably 30~42 parts by weight, more preferable 32~40 parts by weight.Conductive black additional amount in 25~45 weights
When measuring between part, electric conductivity suitably insulation semiconductive shieldin material can be obtained.
White oil of the invention is the mixture of the refining liquid hydrocarbon obtained by petroleum, the cycloalkane and alkane being predominantly saturated
Mixture, crude oil through normal pressure and vacuum fractionation, solvent extraction and dewaxing, hydrofinishing and obtain.White oil of the invention is a kind of high
Degree refining product, colourless, tasteless, nontoxic, unstressed configuration can improve the plasticity of insulation semiconductive shieldin material of the invention
And lubricity.
White oil of the invention may include the group of one or more of 1# white oil, 10# white oil and 15# white oil etc.
It closes.In the present invention, the additional amount of white oil is 2~10 parts by weight, preferably 3~9 parts by weight, more preferable 4~8 parts by weight.When white
When the additional amount of oil is between 2~10 parts by weight, the plasticity and lubricity of insulation semiconductive shieldin material of the invention are more
It is excellent.
Antioxidant of the invention includes antioxidant 300 (4,4 '-thiobis (6- tert-butyl-m-cresol)), antioxidant AT-10
(four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters), antioxidant 264 (2,6- di-t-butyl -4- first
Phenol) and one or more of antioxidant 2246 (2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol)) combination.
Preferably, in the present invention, two or more different antioxidant can be used, to further increase insulation with partly leading
The inoxidizability of electrical shielding material.In the present invention, the additional amount of antioxidant is 0.1~0.4 parts by weight, preferably 0.2~0.4 weight
Part.
C5 resin of the invention is the low molecule calorimetric that the alkene that generates or cyclenes hydrocarbon-fraction are polymerized after petroleum cracking
Plastic resin.Such as: TaiWan, China member good YL-120, YL-120H, YL-140, YL-130, YL-90 etc..The C5 resin is put down
Average molecular weight is in 2500Da hereinafter, it is preferred that between 1000~2500Da；The softening point temperature of the C5 resin can for 100~
140 DEG C, preferably 110~130 DEG C.By be added C5 resin, do not influence the heat ageing of insulation semiconductive shieldin material, heat is prolonged
On the basis of the performances such as stretching, the peel strength of product can be also further decreased.
In the present invention, the additional amount of C5 resin is 2~8 parts by weight, preferably 3~7 parts by weight；More preferably 3.5~6.5
Parts by weight.When the additional amount of C5 resin is between 2~8 parts by weight, the stripping of insulation semiconductive shieldin material can be effectively improved
From intensity, and it will not influence the performances such as the heat ageing of insulation semiconductive shieldin material, heat extension.
Crosslinking agent of the invention includes peroxide type initiators, preferably includes cumyl peroxide.Peroxidating two is different
The molecular formula C of propyl benzene18H22O2, relative molecular mass 270.37 is white crystals thing, and fusing point is 41~42 DEG C, and relative density is
1.082g/cm3, decomposition temperature is 120~125 DEG C.Cumyl peroxide is stable at room temperature, light-exposed to gradually become micro- Huang
Color.It is not soluble in water, it is dissolved in ethyl alcohol, ether, acetic acid, benzene and petroleum ether.The active o content 5.92% of cumyl peroxide is (pure
It spends 100%), 5.62% (purity 95%).Cumyl peroxide be dissolved in the half-life period in benzene be 171 DEG C: 1min；117℃:
10h；101℃:100h.In the present invention, the additional amount of crosslinking agent be 1.0~3.2 parts by weight, preferably 1.2~2.8 parts by weight,
More preferable 1.2~2.5 parts by weight.
Lubricant of the invention can be one of silicone, zinc stearate, oleamide, polyester wax, polyethylene wax etc.
Or two or more combination.In the present invention, the additional amount of lubricant be 1~10 parts by weight, preferably 1~8 parts by weight, more preferably
1.5~7 parts by weight.
In addition, insulation of the invention does not preferably contain nitrile rubber and trisiloxanes imidazol ion liquid with semiconductive shieldin material
At least one of body surfactant.
The present invention also provides a kind of preparation methods of insulation semiconductive shieldin material according to the present invention, including will be described exhausted
The step of each component mixing of edge semiconductive shieldin material.
Specifically, the preparation method comprises the following steps:
1) ethylene-vinyl acetate copolymer, conductive black, white oil, antioxidant, lubricant and C5 resin are kneaded
Uniformly, it enters back into single-screw machine to be granulated, obtains particulate material；
2) it after the particulate material after granulation being put into container, is placed in 50~70 DEG C of heater and particulate material is heated to 50
~70 DEG C；Then placing 8~16 hours after particulate material being uniformly mixed with crosslinking agent in 50~70 DEG C of heaters makes
Pellet absorbs to get insulation semiconductive shieldin material crosslinking agent.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1-9
The exhausted of embodiment 1-9 is prepared according to the mass fraction of each component in the following table 1, table 2, and by following preparation methods
Edge semiconductive shieldin material.
Embodiment 1-9 insulation with semiconductive shieldin material the preparation method comprises the following steps:
Ethylene-vinyl acetate copolymer, conductive black, white oil, antioxidant, lubricant and C5 resin are kneaded equal
It is even, it enters back into single-screw machine and is granulated, obtain particulate material.
After particulate material is put into container, it is placed in 60 DEG C of baking oven and particulate material is heated to 60 DEG C；Then by particulate material with
Crosslinking agent be uniformly mixed after in 60 DEG C of heaters place 16 hours make particulate material to crosslinking agent fully absorbed to get
Semiconductive shieldin material is used in insulation.
1 embodiment 1-4 of table
2 embodiment 5-9 of table
Comparative example 1-4
It is prepared pair according to the mass fraction of each component in the following table 3, and according to preparation method identical with embodiment 1-9
The insulation semiconductive shieldin material of ratio 1-4.
3 comparative example 1-4 of table
Performance test
The preparation method of test piece is prepared according to standard JB/T10738-2007.Then according to the experiment item in the following table 4
Mesh is tested for the property the test piece being prepared, as a result as illustrated in tables 5-7.
4 testing standard of table and requirement
The test result of 5 embodiment 1-4 of table
The test result of 6 embodiment 5-9 of table
The test result of 7 comparative example 1-4 of table
The all data index of the embodiment of the present invention 1-9 insulation semiconductive shieldin material it can be seen from table 5 and table 6
Technical standard requirement is had reached, and there is good ageing-resistant performance, long service life, and it is strong to all have lower removing
Degree.In addition, insulation semiconductive shieldin material obtained by embodiment 8,9 has lower peel strength with respect to other embodiments, and
Residual after removing in insulating surface is considerably less.
As can be seen from Table 7, in comparative example 1-3 the content of ethylene-vinyl acetate copolymer not within the scope of the application,
And C5 resin is not contained, the insulation being prepared is unable to satisfy heat aging performance standard requirements with semiconductive shieldin material.In addition,
Inventors have found that ageing properties reduce after nitrile rubber is added in insulation semiconductive shieldin material.Due to comparative example 1-3's
Ageing properties are too low, therefore, even if peel strength can meet the requirements after its air heat ageing, the insulation semiconductive shieldin material
Also it can not be used for a long time.
Comparative example 4 does not use C5 resin, and peel strength is high, it is difficult to the requirement being up to state standards；And the application is implemented
1-9 is not on the basis of influencing other performances of insulation semiconductive shieldin material for example, can reduce product by using C5 resin
Peel strength.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of insulation semiconductive shieldin material, which is characterized in that including following components:
Ethylene-vinyl acetate copolymer: 46~55 parts by weight, preferably 46~54 parts by weight, more preferable 47~53 parts by weight；
Conductive black: 25~45 parts by weight, preferably 30~42 parts by weight, more preferable 32~40 parts by weight；
White oil: 2~10 parts by weight, preferably 3~9 parts by weight, more preferable 4~8 parts by weight；
Antioxidant: 0.1~0.4 parts by weight, preferably 0.2~0.4 parts by weight；
Lubricant: 1~10 parts by weight, preferably 1~8 parts by weight, more preferable 1.5~7 parts by weight；
C5 resin: 2~8 parts by weight, preferably 3~7 parts by weight；More preferable 3.5~6.5 parts by weight；
Crosslinking agent: 1.0~3.2 parts by weight, preferably 1.2~2.8 parts by weight, more preferable 1.2~2.5 parts by weight.
2. insulation semiconductive shieldin material according to claim 1, which is characterized in that the ethylene-vinyl acetate is total
The content of Vinyl Acetate Monomer unit is 17~30 mass % in polymers.
3. insulation semiconductive shieldin material according to claim 1 or 2, which is characterized in that the ethylene-vinyl acetate
Copolymer is 4~7g/ according to the melt flow index that ASTM D1238-2004 is measured under 190 DEG C and 2.16kg load
10min。
4. insulation semiconductive shieldin material according to claim 1-3, which is characterized in that the white oil includes 1#
The combination of one or more of white oil, 10# white oil and 15# white oil.
5. insulation semiconductive shieldin material according to claim 1-4, which is characterized in that the antioxidant includes
The combination of one or more of antioxidant 300, antioxidant AT-10, antioxidant 264 and antioxidant 2246.
6. insulation semiconductive shieldin material according to claim 1-5, which is characterized in that the lubricant includes
The combination of one or more of silicone, zinc stearate, oleamide, polyester wax and polyethylene wax.
7. insulation semiconductive shieldin material according to claim 1-6, which is characterized in that the C5 resin is put down
Average molecular weight is in 2500Da hereinafter, it is preferred that between 1000~2500Da；The softening point temperature of the C5 resin is 100~140
DEG C, preferably 110~130 DEG C.
8. insulation semiconductive shieldin material according to claim 1-7, which is characterized in that the crosslinking agent includes
Peroxide type initiators preferably include cumyl peroxide.
9. the preparation method that semiconductive shieldin material is used in a kind of insulation according to claim 1-8, which is characterized in that
Include the steps that mixing each component of the insulation semiconductive shieldin material.
10. the preparation method that semiconductive shieldin material is used in insulation according to claim 9, which is characterized in that including following step
It is rapid:
1) ethylene-vinyl acetate copolymer, conductive black, white oil, antioxidant, lubricant and C5 resin are kneaded uniformly,
It enters back into single-screw machine to be granulated, obtains particulate material；
2) it after the particulate material being put into container, is placed in 50~70 DEG C of heater and the particulate material is heated to 50~70
℃；Then placing 8~16 hours after the particulate material being uniformly mixed with crosslinking agent in 50~70 DEG C of heaters makes institute
It states particulate material to absorb the crosslinking agent, obtains insulation semiconductive shieldin material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154172A (en) * | 2020-01-08 | 2020-05-15 | 江苏科麦特科技发展有限公司 | Shielding type plastic film and composite belt prepared from same |
| CN114316421A (en) * | 2021-12-28 | 2022-04-12 | 高邮市金国电缆材料厂有限公司 | Strippable semiconductive shielding material for crosslinked polyethylene insulated cable and preparation method thereof |
| CN115627025A (en) * | 2022-11-10 | 2023-01-20 | 南京中超新材料股份有限公司 | Strippable semi-conductive shielding material and preparation method thereof |
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