CN109627563A - A kind of easily peelable EVA/POP semiconductive external shield material - Google Patents
A kind of easily peelable EVA/POP semiconductive external shield material Download PDFInfo
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- CN109627563A CN109627563A CN201811588449.9A CN201811588449A CN109627563A CN 109627563 A CN109627563 A CN 109627563A CN 201811588449 A CN201811588449 A CN 201811588449A CN 109627563 A CN109627563 A CN 109627563A
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- pop
- eva
- external shield
- easily peelable
- shield material
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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
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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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
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of easily peelable EVA/POP semiconductive external shield materials, including vinyl-vinyl acetate copolymer, propylene-based elastomeric POP, conductive black, dispersing agent, crosslinking agent, assistant crosslinking agent, remover, lubricant, antioxidant, sequentially add mixer, in 100~130 DEG C of 10~20min of melting mixing, pass through single screw extrusion machine again, pelletizing is squeezed out, product is obtained.Substrate of the present invention is EVA/POP mixture, replace the EVA of part by adding a certain amount of POP, reduce the molecular structure similarity of it and insulating layer XLPE, it is removing auxiliary agent that addition simultaneously, which has the octavinyl-POSS of cage structure, the peel strength with insulating layer is not only effectively reduced, while improving processing fluidity.
Description
Technical field
The present invention relates to a kind of preparation methods of easily peelable EVA/POP semiconductive external shield material, more particularly to one kind
The preparation method of the easily peelable EVA/POP semiconductive external shield material of high-tension cable.
Background technique
It is insulating materials that high-tension cable, which generallys use crosslinked polyethylene (XLPE), uses carbon black filled EVA for external shield
Material, since the molecular structure of EVA and XLPE are closely similar, the peel strength of the two is often relatively high, gives subsequent construction band
To bother.Method by adding the removing auxiliary agent of certain small organic molecules, can a degree of stripping for reducing EVA and XLPE
From intensity, but some small organic molecules are since heatproof is poor or contains trace impurity, can occur in the subsequent vulcanization of cable point
Solution, be easy to cause external shield surface bulge phenomenon occur.
Summary of the invention
That the purpose of the present invention is to provide a kind of processing fluidities is good, mechanical property is good, conductive good easily peelable EVA/
POP semiconductive external shield material.
The technical solution of the invention is as follows:
A kind of easily peelable EVA/POP semiconductive external shield material of the invention, it is characterised in that preparation method is as follows, below
Substance indicated with parts by weight:
By 100 parts of EVA, 0~100 part of POP, 0~100 part of conductive black, 0~10 part of dispersing agent, 0~2 part of crosslinking agent,
0~4 part of assistant crosslinking agent, 0~8 part of remover, 0~5 part of lubricant, 0~2 part of antioxidant, sequentially add mixer, 100~
130 DEG C of 10~20min of melting mixing, then by single screw extrusion machine, pelletizing is squeezed out, a kind of easily peelable EVA/POP half is made
Conductive external shield material.
EVA of the present invention is the EVA resin of VA content 15%~35%, melt index≤15.0g/10min
(190 DEG C/2.16KG), tensile strength >=7.5MPa, elongation at break >=300%, melting temperature≤100 DEG C.Preferred EVA
For VA content 28%, 5.0~8.0g/10min of melt index (190 DEG C/2.16KG), tensile strength >=10MPa, elongation at break
>=500%.
POP of the present invention is granular propylene-based elastomeric, and tensile strength >=10MPa, shore hardness is
70A~90A, melt index are 3.0~15.0g/10min (190 DEG C/2.16KG).Preferred POP, tensile strength >=
16MPa, shore hardness are 80A~88A, and melt index is 6.0~10.0g/10min (190 DEG C/2.16KG).
Conductive black of the present invention be the superconductive carbon black with high structure, bigger serface, resistivity≤
1.5 Ω .cm, iodine absorption value >=600g/kg, DBP oil factor >=200ml/100g, specific surface area >=1200m2/ g, ash content≤
2.0%.Preferred superconductive carbon black, resistivity are 0.8~1.0 Ω .cm, iodine absorption value 800~1000g/kg, DBP oil factor
>=300ml/100g, ash content≤1.5%, particle size≤20nm, appearance are soft sheet-like particle.
Dispersing agent of the present invention is the good Polymeric dispersants of temperature tolerance.Such as acrylic block copolymers
EFKA4585, macromolecule dispersing agent Hydropalat3275, polycarboxylic acid salt Texaphor963 etc..Preferred dispersing agent is third
Olefin(e) acid block copolymer EFKA4585, appearance are transparent liquid.
Crosslinking agent of the present invention is organic peroxide, such as cumyl peroxide (DCP), 2,5- dimethyl-
2,5 di-t-butyl hexane peroxides (double 25), benzoyl peroxide (BPO) etc..Preferred crosslinking agent is DCP, fusing point 41~
42 DEG C, relative density (20 DEG C) 1.082,120~125 DEG C of decomposition temperature.
Assistant crosslinking agent of the present invention is triallyl compound, such as trimethylolpropane trimethacrylate
(TMPTA), triallyl cyanurate (TAC), iso-cyanuric acid triallyl ester (TAIC) etc..Preferably assistant crosslinking agent is
TAIC, purity >=99%.
Remover of the present invention is polysilsesquioxane (POSS), such as vinyl POSS, amino POSS and benzene
Base POSS.Preferred POSS is the octavinyl-POSS with cage structure, purity >=98%, molecular weight 633.
Lubricant of the present invention is the compound system of white oil and stearate.White oil is the paraffin of cosmetics-stage
Oil, stearate can be zinc stearate, calcium stearate, magnesium stearate etc..Preferred white oil is the 50# white oil of cosmetics-stage,
Its kinematic viscosity (40 DEG C) >=48cSt, flash-point >=235 DEG C.Preferred stearate is zinc stearate, and appearance is white powder
End.
Antioxidant of the present invention is antioxidant 300,1010,264 or DLTP.Preferred antioxidant is 1010,
Fusing point is 110~125 DEG C, density 1.15g/cm3, purity >=98%.
Easily peelable EVA/POP semiconductive external shield material of the invention a kind of, formula for raw stock used by preparing and
Processing technology has the following characteristics that
Substrate of the present invention is EVA/POP mixture, and the EVA of part, drop are replaced by adding a certain amount of POP
The low molecular structure similarity of it and insulating layer XLPE, while adding that have the octavinyl-POSS of cage structure be that removing helps
Agent not only effectively reduces the peel strength with insulating layer, while improving processing fluidity.
The removing auxiliary agent POSS that the present invention uses has good temperature tolerance, and cable is after high temperature vulcanized, external shield table
Face is smooth, and no bulge phenomenon occurs.
For the mixer temperature used in the present invention for 105~115 DEG C, mixing time is 10~20min, after mixing feeding into
Enter single screw rod, be earnestly granulated, a kind of easily peelable EVA/POP semiconductive external shield material is made.
Below with reference to embodiment, the invention will be further described.
Specific embodiment
Following embodiment and comparative example raw materials trade mark transitivity are listed in table 1 in the present invention:
Table 1
The easily peelable EVA/POP semiconductive external shield material of the one kind obtained in the following examples and comparative examples, removing
Intensity is carried out by JB/T10738-2007, test condition: at temperature (20 ± 5) DEG C, application makes 10mm belt strip from insulated separation
Pulling force, pull open at least distance of 100mm long, in the case where peel angle is 180 ° approximate, speed (250 ± 50) mm/min measures its drawing
Power, unit N/cm.Its mechanical property carries out on electronic tensile machine according to GB/T2951.11-2008 standard, stretches speed
Degree is 250mm/min.Its resistivity is carried out according to the standard of GB/T12706-2002 using resistivity tester.
Embodiment described below and comparative example, the 35KV power cable that the cable sample used insulate for XLPE, vulcanization are put
After setting 48 hours, dependence test is carried out.
The formula of the embodiment of the present invention 1~3 and comparative example 4~6, and its composition are shown in Table 2:
Table 2
The above embodiment of the present invention 1~3 and the test result of comparative example 4~6 are listed in Table 3 with performance indicator:
Table 3
Examples 1 to 3: using EVA and POP for substrate, is remover by addition polysilsesquioxane (POSS), other
See Table 2 for details for each component.It is can be found that by the test result of Examples 1 to 3 in table 3: the easily peelable EVA/POP of prepared one kind
Semiconductive external shield material, peel strength is moderate (10.9~15.6N/cm), and remove after insulating layer without stain；Its processing stream
Dynamic property is good, 3.8~5.1g/10min of melt index (190 DEG C/2.16kg)；Its mechanical property is good, tensile strength >=12.5MPa,
Elongation at break >=280%；Its resistivity is moderate (15~20 Ω .cm)；And after cable vulcanization, external shield smooth surface, no drum
Packet phenomenon.
Comparative example 4~6: comparative example 1~3, the insulating layer after comparative example 4~6 is removed have different degrees of stain.
Wherein, the stain quantity of comparative example 5 is most, and peel strength is also maximum (36.8N/cm)；And it is added to remover II (PE wax)
Comparative example 6, there is bulge phenomenon, cannot reach requirement as defined in cable in the external shield surface after vulcanization.
Above embodiments show semiconductive external shield material prepared by the present invention, and not only peel strength is moderate, after removing
For insulating layer without stain, and with external shield smooth surface after vulcanization without bulge, processing fluidity is good, mechanical property is good and conductive
Good feature.
Disclosed above is several specific embodiments of the invention, but the application is not only limited to this, any basic herein
On, the part of wherein formula and technique is changed, it all should be within the scope of protection of this application.
Claims (10)
1. a kind of easily peelable EVA/POP semiconductive external shield material, it is characterized in that: preparation method is as follows, following substance adds
Dosage is all indicated with parts by weight:
By 100 parts of vinyl-vinyl acetate copolymer, 0.1~100 part of propylene-based elastomeric POP, 0.1~100 part of conduction
Carbon black, 0.1~10 part of dispersing agent, 0.1~2 part of crosslinking agent, 0.1~4 part of assistant crosslinking agent, 0.1~8 part of remover, 0.1~5 part
Lubricant, 0.1~2 part of antioxidant, sequentially add mixer, in 100~130 DEG C of 10~20min of melting mixing, then pass through single spiral shell
Bar extruder squeezes out pelletizing, obtains product.
2. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
EVA be VA content 15%~35% vinyl-vinyl acetate copolymer, melt index under the conditions of 190 DEG C/2.16KG≤
15.0g/10min, tensile strength >=7.5MPa, elongation at break >=300%, melting temperature≤100 DEG C.
3. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
POP be granular propylene-based elastomeric, tensile strength >=10MPa, shore hardness be 70A~90A, melt index is 190
DEG C/2.16KG under the conditions of be 3.0~15.0g/10min.
4. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
Conductive black be the superconductive carbon black with high structure, bigger serface, resistivity≤1.5 Ω .cm, iodine absorption value >=
600g/kg, DBP oil factor >=200ml/100g, specific surface area >=1000m2/ g, ash content≤2.0%.
5. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
Dispersing agent be acrylic block copolymers EFKA4585, macromolecule dispersing agent Hydropalat3275 or polycarboxylic acid salt
Texaphor963。
6. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
Crosslinking agent be cumyl peroxide (DCP), 2,5- dimethyl -2,5 di-t-butyl hexane peroxide (double 25) or peroxidating
Benzoyl (BPO).
7. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
Assistant crosslinking agent be trimethylolpropane trimethacrylate, triallyl cyanurate or iso-cyanuric acid triallyl ester.
8. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
Remover be vinyl POSS, amino POSS or phenyl POSS.
9. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
Lubricant be white oil and stearate compound system；White oil be cosmetics-stage paraffin oil, stearate be zinc stearate,
Calcium stearate or magnesium stearate.
10. the easily peelable EVA/POP semiconductive external shield material of one kind according to claim 1, it is characterized in that: being used
Antioxidant be antioxidant 300,1010,264 or DLTP.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811588449.9A CN109627563A (en) | 2018-12-25 | 2018-12-25 | A kind of easily peelable EVA/POP semiconductive external shield material |
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| CN201811588449.9A CN109627563A (en) | 2018-12-25 | 2018-12-25 | A kind of easily peelable EVA/POP semiconductive external shield material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206412A (en) * | 2011-05-04 | 2011-10-05 | 郭清海 | Functional master batch for antisticking BOPA film and production process thereof |
| CN102304329A (en) * | 2011-07-25 | 2012-01-04 | 俞明高 | Self-adhesive protective film and initial adhesion regulating method of self-adhesive protective film |
| CN103554802A (en) * | 2013-10-24 | 2014-02-05 | 苏州市双鑫新材料科技有限公司 | Formula of strippable semiconductive outer shielding material for cable |
| CN105348631A (en) * | 2015-12-08 | 2016-02-24 | 江苏德威新材料股份有限公司 | Easy-to-peel semiconductive insulation shielding material for power cable and preparation method of easy-to-peel semiconductive insulation shielding material |
-
2018
- 2018-12-25 CN CN201811588449.9A patent/CN109627563A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206412A (en) * | 2011-05-04 | 2011-10-05 | 郭清海 | Functional master batch for antisticking BOPA film and production process thereof |
| CN102304329A (en) * | 2011-07-25 | 2012-01-04 | 俞明高 | Self-adhesive protective film and initial adhesion regulating method of self-adhesive protective film |
| CN103554802A (en) * | 2013-10-24 | 2014-02-05 | 苏州市双鑫新材料科技有限公司 | Formula of strippable semiconductive outer shielding material for cable |
| CN105348631A (en) * | 2015-12-08 | 2016-02-24 | 江苏德威新材料股份有限公司 | Easy-to-peel semiconductive insulation shielding material for power cable and preparation method of easy-to-peel semiconductive insulation shielding material |
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Application publication date: 20190416 |