CN109294050A - Silane-crosslinkable semiconductive inner shield material and preparation method thereof - Google Patents
Silane-crosslinkable semiconductive inner shield material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of silane-crosslinkable semiconductive inner shield material and preparation method thereof, is expected by the grafting A that mass ratio is 5~9:1 and catalysis B expects to form after mixing through warm water crosslinking；Wherein: the grafting A material composition, by weight are as follows: 50~100 parts of ethylene-vinyl acetate copolymer, 10~50 parts of polyethylene, 1~4 part of silane, 0.2~1 part of initiator, 0.1~1 part of antioxidant, 5~10 parts of lubricant；The catalysis B material composition, by weight are as follows: 100 parts of ethylene-vinyl acetate copolymer, 80~95 parts of conductive filler, 10~20 parts of lubricant, 1~5 part of dispersing agent, 0.5~3 part of catalyst, 0.5~2 part of antioxidant；The ethylene-vinyl acetate copolymer, VA content are 15~20, and melt flow rate (MFR) is 2.3~7.5g/10min (test condition: 190 DEG C, 2.16kg, similarly hereinafter)；The melt flow rate (MFR) of the polyethylene is 2~20g/10min.Silane-crosslinkable semiconductive inner shield material of the invention has good conductive property, and can especially guarantee that product is effectively crosslinked.
Description
Technical field
The present invention relates in a kind of wire and cable semiconductive modified material more particularly to a kind of silane-crosslinkable semiconductive
Shielding material and preparation method thereof.
Background technique
As society and expanding economy, power consumption are continuously increased, high pressure, super-pressure power supply are more and more.High pressure,
In super-pressure service cable, when semiconductive shieldin material essential material, it is radial that main function improves cable internal electric field
Distribution, homogenizing electric field directly or indirectly improve the service life of cable to improve the electrical strength of cable.In shielding material mark
In standard, there are many shielding material of type, but still account for absolute majority both at home and abroad with the shielding material of peroxide crosslinking.In medium voltage electricity
In cable, 10kV chemical crosslinking power cable dosage is very big, and cross-linking type semiconductive inner shield material used is almost all peroxide
Cross-linking type.With the progress of raw material technology of preparing, it is originally used for the organosilane crosslinked polyethylene of low tension wire cable product, is existed
It is applied in 10kV power cable.If inner shield partly can be led using organosilane crosslinked polyethylene and silane-crosslinkable simultaneously
Material produces medium-pressure power cable by the way of steam or warm water crosslinking, with use processes for chemically crosslinked polyethylene, peroxide crosslinking
The mode that shielding material, connection curing tube are crosslinked is compared, and efficiency and cost will be greatly reduced.Therefore, exploitation silane-crosslinkable half
Conductive inner shield material will become the research and development hot spot in industry.Document report about silane-crosslinkable inner shield material at present
Road or related patents are actually rare, and patent CN107868328A is prepared for silane-crosslinkable semi-conductive screen in such a way that A, B expect
Material.But in the mixed proportion of its A, B material, B expects that proportion is larger, while the content of carbon black in A material is higher, and causing can in material
Crosslink part is less, it is difficult to form the product being effectively crosslinked, it is difficult to guarantee the molten reality of leaching that product is effectively crosslinked by verifying product
It tests.
Summary of the invention
The object of the present invention is to provide a kind of preparations different from silane-crosslinkable semiconductive shieldin material reported at present
Technology, provides a kind of silane-crosslinkable semiconductive inner shield material and preparation method thereof that can be effectively crosslinked, which has good
Electric conductivity, can especially guarantee that product is effectively crosslinked, can be used as the inner shield material of midium voltage cable cable.
The technical solution for realizing the object of the invention is silane-crosslinkable semiconductive inner shield material, and the silane-crosslinkable is partly led
The raw material composition of electric inner shield material forms after expecting mixing for the grafting A material and catalysis B for being 5~9:1 by mass ratio through warm water crosslinking；
Wherein:
The grafting A material composition, by weight are as follows: 50~100 parts of ethylene-vinyl acetate copolymer, polyethylene 10~50
Part, 1~4 part of silane, 0.2~1 part of initiator, 0.1~1 part of antioxidant, 5~10 parts of lubricant；
The catalysis B material composition, by weight are as follows: 100 parts of ethylene-vinyl acetate copolymer, 80~95 parts of conductive filler,
10~20 parts of lubricant, 1~5 part of dispersing agent, 0.5~3 part of catalyst, 0.5~2 part of antioxidant；
The ethylene-vinyl acetate copolymer, VA content are 15~20, and melt flow rate (MFR) is 2.3~7.5g/
10min；The melt flow rate (MFR) of the polyethylene is 2~20g/10min.
Preferably, the mass ratio of the grafting A material and catalysis B material is preferably 6~9:1, it is cross-linking in material to improve
The content of component, guarantees crosslink material validity, and the mass ratio that grafting A material and catalysis B expect is more preferably 8~9:1；The temperature
Water crosslinking is carried out in progress or steam in about 90 DEG C of water.
The conductive filler is one of highly conductive carbon black, carbon nanotube, graphene or a variety of combinations, and synthesis is examined
Consider cost, additive amount, electric conductivity, the mixture of preferably highly conductive carbon black and carbon nanotube.
The polyethylene is low density polyethylene (LDPE) or linear low density polyethylene.
The silane is selected from vinyltrimethoxysilane, vinyl-three (2- methoxy ethoxy) silane, vinyl
Triethoxysilane, three tert-butoxy silane of vinyl, vinyl silane tri-butyl peroxy, vinyltriacetoxy silane
One of or a variety of combinations guarantee within the defined warm water crosslinking time real to make material that there is faster crosslinking rate
It is existing full cross-linked, preferably vinyltrimethoxysilane.
The antioxidant is selected from antioxidant 1010, antioxidant 1024, antioxidant 1076, irgasfos 168, antioxidant
One of 300 or a variety of combinations, it is to guarantee that material has good resistant to thermal aging and resistance to metal-catalyzed ageing properties, preferably
For the antioxidant 300 with radical terminator and hydrogen peroxide decomposition agent dual function and there is metallic ion passivation effect
Antioxidant 1024 be used in mixed way.
The initiator is selected from di-tert-butyl peroxide, dibenzoyl peroxide, cumyl peroxide, peroxide
Change the neodecanoic acid tert-butyl ester, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, 1,1- di-tert-butyl peroxide -3,3,5 three
One of hexahydrotoluene, 4,4- bis- (tert-butyl hydroperoxide) n-butyl pentanoate, methyl ethyl ketone peroxide, cyclohexane peroxide or
A variety of combination, it is contemplated that technical maturity, preferably cumyl peroxide.
The lubricant be selected from one of polyethylene wax, EVA wax, stearate and white oil or a variety of combinations,
In view of the compatibility, lubrication and plasticization effect of processing performance, lubricant and substrate, preferably zinc stearate and white oil.
The dispersing agent is selected from for one of TAS-2A, EBS, nanometer calcium carbonate or a variety of combinations, preferably
EBS。
The catalyst is selected from dibutyl tin dilaurate, Bis(lauroyloxy)dioctyltin, stannous octoate, two acetic acid
One of dibutyl tin, two (dodecyl sulphur) dibutyl tins, two mercaptan tin alkyls, dialkyl tin dimaleate are a variety of
Combination, it is contemplated that technical maturity, preferably dibutyl tin dilaurate.
Meanwhile the present invention also provides a kind of preparation method of silane-crosslinkable semiconductive inner shield material, specific steps are as follows:
By weight, by 50~100 parts of ethylene-vinyl acetate copolymer, 10~50 parts of polyethylene, 1~4 part of silane,
0.2~1 part of initiator, 0.1~1 part of antioxidant, 5~10 parts of lubricant are mixed with grafting A material；Successively by ethyl vinyl acetate second
Alkene copolymer, polyethylene, silane, initiator, antioxidant and lubricant are granulated after mixing by setting ratio through double screw extruder,
Extruder temperature of each section is successively are as follows: 120~145 DEG C of an area, two 155~175 DEG C of areas, and three 180~190 DEG C of areas, four areas 190~
200 DEG C, five 190~200 DEG C of areas, six 185~195 DEG C of areas, seven 180~185 DEG C of areas, eight 170~180 DEG C of areas, nine areas 165~
175 DEG C, 140~150 DEG C of head temperature；
By weight, by 100 parts of ethylene-vinyl acetate copolymer, 80~95 parts of conductive filler, lubricant 10~20
Part, it 1~5 part of dispersing agent, 0.5~3 part of catalyst, is squeezed out after 0.5~2 part of antioxidant mixing through reciprocating single-bolt extruder,
It is granulated, preparation catalysis B material；
A material and the respective packaging of catalysis B material are grafted to get finished product.
After above-mentioned technical proposal, the present invention has the effect of below positive:
Semiconductive inner shield material of the invention is realized by using the better conductive black of electric conductivity or conductive powder body
The reduction of the conductive powder body additive amount of common low electric conductivity energy in shielding material；On the basis of the reduction of conductive powder body additive amount,
The further conductive powder body by script addition in A material, addition is in B material；Being used in combination through the above technical solution, greatly improves
The ratio of crosslinkable component in material makes material be easy to get higher crosslinking degree, realizes effectively crosslinking, guarantees by micro-
The decahydronaphthalenes of boiling soaks molten test in 5 hours.
Specific embodiment
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And it can be implemented in accordance with the contents of the specification, and in order to allow above and other objects of the present invention, feature and advantage can
It is clearer and more comprehensible, the followings are specific embodiments of the present invention.
(embodiment 1)
The present embodiment provides the silane-crosslinkable semiconductive inner shield material that one kind can be effectively crosslinked, raw material includes:
A material, 60 parts of ethylene-vinyl acetate copolymers, 40 parts of polyethylene, 1.5 parts of vinyltrimethoxysilanes, 0.3 part
Cumyl peroxide, 0.8 part of antioxidant 300,0.2 part of antioxidant, 1024,9 parts of white oils.
B material, 100 parts of ethylene-vinyl acetate copolymers, 90 parts of conductive fillers (graphene), 10 parts of white oils, 2 parts of EBS, 0.6
Part zinc stearate, 1 part of dibutyl tin dilaurate, 0.8 part of antioxidant 300.
The silane-crosslinkable semiconductive inner shield material that can be effectively crosslinked the preparation method is as follows:
(1) by above-mentioned A material by self-measuring device, automatic blanking, which enters in twin-screw, to be kneaded, grafting, extruding pelletization,
It is dry, grafting A material is made；Extruder temperature of each section is successively are as follows: 125 DEG C of an area, two 160 DEG C of areas, three 180 DEG C of areas, four areas 190
DEG C, five 190 DEG C of areas, six 185 DEG C of areas, seven 180 DEG C of areas, eight 170 DEG C of areas, nine 165 DEG C of areas, 145 DEG C of head temperature.
(2) by above-mentioned B material by automatic gauge scale device, automatic blanking enters extruding pelletization in reciprocating single screw rod, system
B material must be catalyzed；
(3) grafting A material and catalysis B material are mixed with mass ratio 6:1, after extrusion molding, in about 90 DEG C of water
Middle crosslinking is to get the silane-crosslinkable semiconductive inner shield material cable product that can be effectively crosslinked.
The performance test results are shown in Table 1.
(embodiment 2)
A material, 75 parts of ethylene-vinyl acetate copolymers, 25 parts of polyethylene, 2.5 parts of vinyltrimethoxysilanes, 0.6 part
Cumyl peroxide, 0.6 part of antioxidant 300,0.2 part of antioxidant, 1024,8 parts of white oils.
B material, 100 parts of ethylene-vinyl acetate copolymers, 89 parts of conductive fillers (conductive black and carbon nanotube mixture),
15 parts of white oils, 3 parts of EBS, 0.8 part of zinc stearate, 1.5 parts of dibutyl tin dilaurates, 1.3 parts of antioxidant 300s.
The silane-crosslinkable semiconductive inner shield material that can be effectively crosslinked the preparation method is as follows:
(1) by above-mentioned A material by self-measuring device, automatic blanking, which enters in twin-screw, to be kneaded, grafting, extruding pelletization,
It is dry, grafting A material is made；Extruder temperature of each section is successively are as follows: 125 DEG C of an area, two 160 DEG C of areas, three 180 DEG C of areas, four areas 190
DEG C, five 190 DEG C of areas, six 185 DEG C of areas, seven 180 DEG C of areas, eight 170 DEG C of areas, nine 165 DEG C of areas, 145 DEG C of head temperature.
(2) by above-mentioned B material by automatic gauge scale device, automatic blanking enters extruding pelletization in reciprocating single screw rod, system
B material must be catalyzed；
(3) grafting A material and catalysis B material are mixed with mass ratio 8:1, after extrusion molding, in about 90 DEG C of water
Middle crosslinking is to get the silane-crosslinkable semiconductive inner shield material cable product that can be effectively crosslinked.
The performance test results are shown in Table 1.
(embodiment 3)
The present embodiment provides the silane-crosslinkable semiconductive inner shield material that one kind can be effectively crosslinked, raw material includes:
A material, 90 parts of ethylene-vinyl acetate copolymers, 10 parts of polyethylene, 3.5 parts of vinyltrimethoxysilanes, 0.8 part
Cumyl peroxide, 0.4 part of antioxidant 300,0.2 part of antioxidant, 1024,6 parts of white oils.
B material, 100 parts of ethylene-vinyl acetate copolymers, 95 parts of conductive fillers (highly conductive carbon black), 18 parts of white oils, 4 parts
EBS, 1 part of zinc stearate, 2.5 parts of dibutyl tin dilaurates, 1.8 parts of antioxidant 300s.
The silane-crosslinkable semiconductive inner shield material that can be effectively crosslinked the preparation method is as follows:
(1) by above-mentioned A material by self-measuring device, automatic blanking, which enters in twin-screw, to be kneaded, grafting, extruding pelletization,
It is dry, grafting A material is made；
(2) by above-mentioned B material by automatic gauge scale device, automatic blanking enters extruding pelletization in reciprocating single screw rod, system
B material must be catalyzed；
(3) grafting A material and catalysis B material are mixed with mass ratio 9:1, after extrusion molding, in about 90 DEG C of water
Middle crosslinking is to get the silane-crosslinkable semiconductive inner shield material cable product that can be effectively crosslinked.
The performance test results are shown in Table 1.
Table 1
In the present invention, by using the better conductive black of some electric conductivities or similar components, carbon black can be reduced
Content improves resin, that is, crosslinkable moiety ratio, while the component that conductive black or similar components are expected as B, is made into simultaneous
Have catalysis and semiconductive masterbatch, then mixed with A material, forms final products, thus crosslinkable component ratio is few in solution material,
It cannot be guaranteed that the problem of product is effectively crosslinked, develops the silane-crosslinkable semiconductive inner shield material that can be effectively crosslinked.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. silane-crosslinkable semiconductive inner shield material, it is characterised in that: the raw material of the silane-crosslinkable semiconductive inner shield material
Composition forms after expecting mixing for the grafting A material and catalysis B for being 5~9:1 by mass ratio through warm water crosslinking；Wherein:
The grafting A material composition, by weight are as follows: 50~100 parts of ethylene-vinyl acetate copolymer, 10~50 parts of polyethylene, silicon
1~4 part of alkane, 0.2~1 part of initiator, 0.1~1 part of antioxidant, 5~10 parts of lubricant；
The catalysis B material composition, by weight are as follows: 100 parts of ethylene-vinyl acetate copolymer, 80~95 parts of conductive filler, lubrication
10~20 parts of agent, 1~5 part of dispersing agent, 0.5~3 part of catalyst, 0.5~2 part of antioxidant；
The ethylene-vinyl acetate copolymer, VA content are 15~20, and melt flow rate (MFR) is 2.3~7.5g/10min；Institute
The melt flow rate (MFR) for stating polyethylene is 2~20g/10min.
2. silane-crosslinkable semiconductive inner shield material according to claim 1, it is characterised in that: the conductive filler is
One of highly conductive carbon black, carbon nanotube, graphene or a variety of combinations.
3. silane-crosslinkable semiconductive inner shield material according to claim 1, it is characterised in that: the polyethylene is low
Density polyethylene or linear low density polyethylene.
4. silane-crosslinkable semiconductive inner shield material according to claim 1, it is characterised in that: the silane is selected from second
Alkenyl trimethoxy silane, vinyl-three (2- methoxy ethoxy) silane, vinyltriethoxysilane, three uncle of vinyl
One of butoxy silane, vinyl silane tri-butyl peroxy, vinyltriacetoxy silane or a variety of combinations.
5. silane-crosslinkable semiconductive inner shield material according to claim 1, it is characterised in that: the antioxidant is choosing
From one of antioxidant 1010, antioxidant 1024, antioxidant 1076, irgasfos 168, antioxidant 300 or a variety of combinations.
6. silane-crosslinkable semiconductive inner shield material according to claim 1, it is characterised in that: the initiator is choosing
From di-tert-butyl peroxide, dibenzoyl peroxide, cumyl peroxide, new peroxide tert-butyl caprate, peroxidating second
Tert-butyl acrylate, peroxidized t-butyl perbenzoate, -3,3,5 trimethyl-cyclohexane of 1,1- di-tert-butyl peroxide, (the tertiary fourth of 4,4- bis-
Base peroxidating) n-butyl pentanoate, methyl ethyl ketone peroxide, one of cyclohexane peroxide or a variety of combinations.
7. silane-crosslinkable semiconductive inner shield material according to claim 1, it is characterised in that: the lubricant is choosing
From one of polyethylene wax, EVA wax, stearate and white oil or a variety of combinations.
8. silane-crosslinkable semiconductive inner shield material according to claim 1, it is characterised in that: the dispersing agent is choosing
From for one of TAS-2A, EBS, nanometer calcium carbonate or a variety of combinations.
9. silane-crosslinkable semiconductive inner shield material according to claim 1, it is characterised in that: the catalyst is choosing
From dibutyl tin dilaurate, Bis(lauroyloxy)dioctyltin, stannous octoate, dibutyltin diacetate, two (dodecyl sulphur)
One of dibutyl tin, two mercaptan tin alkyls, dialkyl tin dimaleate or a variety of combinations.
10. the preparation method of silane-crosslinkable semiconductive inner shield material, it is characterised in that: specific steps are as follows:
By weight, by 50~100 parts of ethylene-vinyl acetate copolymer, 10~50 parts of polyethylene, 1~4 part of silane, cause
0.2~1 part of agent, 0.1~1 part of antioxidant, 5~10 parts of lubricant are mixed with grafting A material；
By weight, by 100 parts of ethylene-vinyl acetate copolymer, 80~95 parts of conductive filler, 10~20 parts of lubricant, point
1~5 part of powder, 0.5~3 part of catalyst, 0.5~2 part of antioxidant is mixed with catalysis B material；
A material and the respective packaging of catalysis B material are grafted to get finished product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112094454A (en) * | 2020-08-13 | 2020-12-18 | 江阴市海江高分子材料有限公司 | Silane self-crosslinking double-component internal shielding material for overhead cable |
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| CN114196100A (en) * | 2021-12-09 | 2022-03-18 | 江苏东方电缆材料有限公司 | Built-up silane self-crosslinking double-component internal shielding material and preparation method thereof |
| CN114196100B (en) * | 2021-12-09 | 2023-03-28 | 江苏东方电缆材料有限公司 | Built-up silane self-crosslinking double-component internal shielding material and preparation method thereof |
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