CN109438857A - EP rubbers semiconductive external shield material that can be effectively crosslinked and preparation method thereof - Google Patents
EP rubbers semiconductive external shield material that can be effectively crosslinked and preparation method thereof Download PDFInfo
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- CN109438857A CN109438857A CN201811159324.4A CN201811159324A CN109438857A CN 109438857 A CN109438857 A CN 109438857A CN 201811159324 A CN201811159324 A CN 201811159324A CN 109438857 A CN109438857 A CN 109438857A
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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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08K2201/011—Nanostructured additives
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2312/00—Crosslinking
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Abstract
The invention discloses the EP rubbers semiconductive external shield material and preparation method thereof that one kind can be effectively crosslinked, and form after expecting and being catalyzed B material mixing by mass ratio for the grafting A of 5~9:1 through warm water crosslinking；Wherein: the grafting A material composition, by weight are as follows: 100 parts of granular pattern EP rubbers, 1~4 part of silane, 0.2~1 part of initiator, 1~4 part of anti-aging agent, 2~5 parts of promotor, 5~15 parts of softening agent；1~5 part of lubricant；The catalysis B material composition, by weight are as follows: 100 parts of ethylene-vinyl acetate copolymer, 80~130 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 EP rubbers semiconductive external shield material that can be effectively crosslinked of the invention has good conductive property, and can especially guarantee that product is effectively crosslinked.
Description
Technical field
The present invention relates to a kind of wire and cable semiconductive modified materials, more particularly to a kind of the third rubber of second that can be effectively crosslinked
Glue semiconductive external shield 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 can be effectively crosslinked
EP rubbers semiconductive external shield material will become the research and development hot spot in industry.At present about silane-crosslinkable inner shield
The document report or related patents of material are actually rare, and patent CN107868328A is prepared for silane-crosslinkable in such a way that A, B expect
Semiconductive shieldin 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, leads
Cause crosslinkable moiety in material less, it is difficult to form the product being effectively crosslinked, it is difficult to guarantee that product is effectively handed over by verifying product
The molten experiment of the leaching of connection.
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 EP rubbers semiconductive external shield material that can be effectively crosslinked and preparation method thereof that can be effectively crosslinked, the material
Material has good conductive property, and can especially guarantee that product is effectively crosslinked, and can be used as the inner shield material of midium voltage cable cable.
The technical solution for realizing the object of the invention is the EP rubbers semiconductive external shield material that can be effectively crosslinked, described to have
The raw material composition for imitating the EP rubbers semiconductive external shield material of crosslinking is expected for the grafting A for being 5~9:1 by mass ratio and catalysis B material
It is formed after mixing through warm water crosslinking；Wherein:
The grafting A material composition, by weight are as follows: 100 parts of granular pattern EP rubbers, 1~4 part of silane, initiator 0.2~
1 part, 1~4 part of anti-aging agent, 2~5 parts of promotor, 5~15 parts of softening agent；1~5 part of lubricant；
The catalysis B material composition, by weight are as follows: 100 parts of ethylene-vinyl acetate copolymer, conductive filler 80~130
Part, 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 being grafted in A material, VA content are 15%~20%, the ethylene-in catalysis B material
Acetate ethylene copolymer, VA content are 25%~30%, the melt flow rate (MFR) under 190 DEG C, the test condition of 2.16kg
For 2.3~7.5g/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 preferred Tao Shi 4725P of granular pattern EP rubbers.
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 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, for make inner shield, insulation, external shield crosslinking rate have better concertedness, protect simultaneously
Card realizes full cross-linked, preferably vinyltriethoxysilane within the defined warm water crosslinking time.
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.
The initiator is peroxide initiator, is selected from di-tert-butyl peroxide, dibenzoyl peroxide, peroxide
Change diisopropylbenzene (DIPB), new peroxide tert-butyl caprate, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, the tertiary fourth of 1,1- bis-
- 3,3,5 trimethyl-cyclohexane of base peroxidating, 4,4- bis- (tert-butyl hydroperoxide) n-butyl pentanoate, methyl ethyl ketone peroxide, peroxidating
One of hexamethylene or a variety of combinations, it is contemplated that technical maturity, preferably cumyl peroxide.
The anti-aging agent is RD.
The promotor is zinc oxide.
The softening agent is white oil.
The lubricant is stearic acid.
The dispersing agent is selected from for one of TAS-2A, EBS, nanometer calcium carbonate or a variety of combinations, preferably
TAS-2A。
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 preparation method for the EP rubbers semiconductive external shield material that can be effectively crosslinked the present invention also provides one kind, tool
Body step are as follows:
By weight, successively by 100 parts of granular pattern EP rubbers, 1~4 part of silane, 0.2~1 part of initiator, anti-aging agent
1~4 part, 2~5 parts of promotor, 5~15 parts of softening agent, 1~5 part of lubricant is added in mixer by setting ratio, immediately after
Start to be kneaded, taper feeding hopper is sent into discharging when mixing to material temperature is 110 DEG C~120 DEG C, is granulated through twin-screw, cold cut, obtained
It is grafted A material.Wherein, preferably extruder temperature of each section is successively are as follows: extruder temperature of each section is successively are as follows: 120~145 DEG C of an area, two
155~175 DEG C of area, three 180~190 DEG C of areas, four 190~200 DEG C of areas, five 190~200 DEG C of areas, six 185~195 DEG C of areas, 7th area
180~185 DEG C, eight 170~180 DEG C of areas, nine 165~175 DEG C of areas, 140~150 DEG C of head temperature.
By weight, by 100 parts of ethylene-vinyl acetate copolymer, 80~130 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-
How the decahydronaphthalene 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 EP rubbers semiconductive external shield material that can be effectively crosslinked that one kind can be effectively crosslinked, raw materials
Include:
A material, 100 parts of granular pattern EP rubbers, 1.5 parts of vinyltriethoxysilane, 0.3 part of cumyl peroxide, 3
Part anti-aging agent RD, 4.5 parts of promotor zinc oxide, 14 parts of softening agent white oils；After 4 parts of stearic acid are by setting ratio mixing, through double spiral shells
A material is made in bar granulation, cold cut.Wherein, preferably extruder temperature of each section is successively are as follows: extruder temperature of each section is successively are as follows: an area
125 DEG C, two 160 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, 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.
B material, by 100 parts of ethylene-vinyl acetate copolymers, 90 parts of conductive fillers (highly conductive carbon black and carbon nanotube it is mixed
Close object), 10 parts of white oils, 2 parts of TAS-2A, 0.6 part of zinc stearate, 1 part of dibutyl tin dilaurate, 0.8 part of antioxidant 300, lead to
Automatic gauge scale device is crossed, automatic blanking enters extruding pelletization in reciprocating single screw rod, and catalyst B material is made.
Grafting A material and catalysis B material are mixed with mass ratio 6:1, after extrusion molding, handed in about 90 DEG C of water
Connection is to get the silane-crosslinkable EP rubbers semiconductive external shield material that can be effectively crosslinked.
The performance test results are shown in Table 1.
(embodiment 2)
A material, successively by 100 parts of granular pattern EP rubbers, 2.5 parts of vinyltriethoxysilane, 0.6 part of peroxidating two is different
Propyl benzene, 2 parts of anti-aging agent RDs, 3.5 parts of promotor zinc oxide, 10 parts of softening agent white oils；After 3 parts of stearic acid are by setting ratio mixing,
It is granulated through twin-screw, cold cut, A material is made.Wherein, preferably extruder temperature of each section is successively are as follows: extruder temperature of each section is successively are as follows:
One 125 DEG C of area, two 160 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, five 190 DEG C of areas, six 185 DEG C of areas, seven 180 DEG C of areas, eight areas 170
DEG C, nine 165 DEG C of areas, 145 DEG C of head temperature.
B material, by 100 parts of ethylene-vinyl acetate copolymers, 110 parts of conductive fillers (highly conductive carbon black), 10 parts of white oils, 3 parts
EBS, 0.8 part of zinc stearate, 1.5 parts of dibutyl tin dilaurates, 1.3 parts of antioxidant 300s, by automatic gauge scale device, certainly
Dynamic blanking enters extruding pelletization in reciprocating single screw rod, and catalyst B material is made.
Grafting A material and catalysis B material are mixed with mass ratio 8:1, after extrusion molding, handed in about 90 DEG C of water
Connection is to get the silane-crosslinkable EP rubbers semiconductive external shield material that can be effectively crosslinked.
The performance test results are shown in Table 1.
(embodiment 3)
The present embodiment provides the EP rubbers semiconductive external shield material that can be effectively crosslinked that one kind can be effectively crosslinked, raw materials
Include:
The preparation of A material: successively by 100 parts of granular pattern EP rubbers, 3.5 parts of vinyltrimethoxysilanes, 0.8 part of peroxide
Change diisopropylbenzene (DIPB), 1.5 parts of anti-aging agent RDs, 2.5 parts of promotor zinc oxide, 6 parts of softening agent white oils；2 parts of stearic acid press setting ratio
It after mixing, is granulated through twin-screw, cold cut, A material is made.Wherein, preferably extruder temperature of each section is successively are as follows: extruder temperature of each section
Successively are as follows: 125 DEG C of an area, two 160 DEG C of areas, three 180 DEG C of areas, four 190 DEG C of areas, 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.
The preparation of B material: by 100 parts of ethylene-vinyl acetate copolymers, 125 parts of conductive fillers (graphene), 10 parts of white oils, 4
Part EBS, 1 part of zinc stearate, 2.5 parts of dibutyl tin dilaurates, 1.8 parts of antioxidant 300s, by automatic gauge scale device, certainly
Dynamic blanking enters extruding pelletization in reciprocating single screw rod, and catalyst B material is made.
Grafting A material and catalysis B material are mixed with mass ratio 9:1, after extrusion molding, handed in about 90 DEG C of water
Connection is to get the silane-crosslinkable EP rubbers semiconductive external shield material 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 EP rubbers semiconductive external shield that can be effectively crosslinked that can be effectively crosslinked
Material.
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. the EP rubbers semiconductive external shield material that can be effectively crosslinked, it is characterised in that: the EP rubbers that can be effectively crosslinked
It is that the grafting A for being 5~9:1 by mass ratio expects and catalysis B expects after mixing through warm water crosslinking that the raw material of semiconductive external shield material, which forms,
It forms；Wherein:
The grafting A material composition, by weight are as follows: 100 parts of granular pattern EP rubbers, 1~4 part of silane, 0.2~1 part of initiator,
1~4 part of anti-aging agent, 2~5 parts of promotor, 5~15 parts of softening agent；1~5 part of lubricant；
The catalysis B material composition, by weight are as follows: 100 parts of ethylene-vinyl acetate copolymer, 80~130 parts of conductive filler, profit
10~20 parts of lubrication prescription, 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 is 25%~30%, under 190 DEG C, the test condition of 2.16kg
Melt flow rate (MFR) is 2.3~7.5g/10min.
2. the EP rubbers semiconductive external shield material according to claim 1 that can be effectively crosslinked, it is characterised in that: described
Conductive filler is one of highly conductive carbon black, carbon nanotube, graphene or a variety of combinations.
3. the EP rubbers semiconductive external shield material according to claim 1 that can be effectively crosslinked, it is characterised in that: described anti-
Old agent is RD, and the promotor is zinc oxide, and the softening agent is white oil.
4. the EP rubbers semiconductive external shield material according to claim 1 that can be effectively crosslinked, it is characterised in that: described
Silane is vinyl silanes, is selected from vinyltrimethoxysilane, vinyl-three (2- methoxy ethoxy), three second of vinyl
Oxysilane, three tert-butoxy silane of vinyl, vinyl silane tri-butyl peroxy, in vinyltriacetoxy silane
One or more combinations.
5. the EP rubbers semiconductive external shield material according to claim 1 that can be effectively crosslinked, it is characterised in that: described
Antioxidant is selected from one of antioxidant 1010, antioxidant 1024, antioxidant 1076, irgasfos 168, antioxidant 300 or more
The combination of kind.
6. the EP rubbers semiconductive external shield material according to claim 1 that can be effectively crosslinked, it is characterised in that: described to draw
Hair agent is peroxide type initiators, is selected from di-tert-butyl peroxide, dibenzoyl peroxide, cumyl peroxide, mistake
Aoxidize the neodecanoic acid tert-butyl ester, peroxide acetic acid butyl ester, peroxidized t-butyl perbenzoate, 1,1- di-tert-butyl peroxide -3,3,5
One of trimethyl-cyclohexane, 4,4- bis- (tert-butyl hydroperoxide) n-butyl pentanoate, methyl ethyl ketone peroxide, cyclohexane peroxide
Or a variety of combination.
7. the EP rubbers semiconductive external shield material according to claim 1 that can be effectively crosslinked, it is characterised in that: described
Lubricant is stearic acid.
8. the EP rubbers semiconductive external shield material according to claim 1 that can be effectively crosslinked, it is characterised in that: described
Dispersing agent is selected from for one of TAS-2A, EBS, nanometer calcium carbonate or a variety of combinations.
9. the EP rubbers semiconductive external shield material according to claim 1 that can be effectively crosslinked, it is characterised in that: described
Catalyst is selected from dibutyl tin dilaurate, Bis(lauroyloxy)dioctyltin, stannous octoate, dibutyltin diacetate, two (ten
Dialkyl group sulphur) dibutyl tin, two mercaptan tin alkyls, one of dialkyl tin dimaleate or a variety of combinations.
10. the preparation method for the EP rubbers semiconductive external shield material that can be effectively crosslinked, it is characterised in that: specific steps are as follows:
By weight, by 50~100 parts of ethylene-vinyl acetate copolymer, 0~50 part of polyethylene, 1~4 part of silane, initiator
0.2~1 part, 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, 80~130 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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Cited By (1)
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| CN110564042A (en) * | 2019-09-20 | 2019-12-13 | 深圳市宏商材料科技股份有限公司 | composition for preparing conductive heat-shrinkable composite material, conductive heat-shrinkable composite material and preparation method thereof |
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