CN112538204A - Wear-resistant and tensile-resistant halogen-free wire and cable and manufacturing method thereof - Google Patents
Wear-resistant and tensile-resistant halogen-free wire and cable and manufacturing method thereof Download PDFInfo
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- CN112538204A CN112538204A CN202011395466.8A CN202011395466A CN112538204A CN 112538204 A CN112538204 A CN 112538204A CN 202011395466 A CN202011395466 A CN 202011395466A CN 112538204 A CN112538204 A CN 112538204A
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- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000005299 abrasion Methods 0.000 claims abstract description 32
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 19
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 19
- -1 polyethylene Polymers 0.000 claims abstract description 18
- 239000004698 Polyethylene Substances 0.000 claims abstract description 15
- 229920000573 polyethylene Polymers 0.000 claims abstract description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
- 239000012974 tin catalyst Substances 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 7
- 239000000347 magnesium hydroxide Substances 0.000 claims description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 7
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims description 4
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 22
- 239000000779 smoke Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08L23/06—Polyethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/14—Insulating conductors or cables by extrusion
- H01B13/148—Selection of the insulating material therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an abrasion-resistant tension-resistant halogen-free wire and cable and a manufacturing method thereof, and aims to provide an abrasion-resistant tension-resistant halogen-free wire and cable with high elongation at break, high tensile strength and high heat and aging resistance, which comprises a conductive wire core, wherein the conductive wire core is sleeved in an insulating layer, and the insulating layer comprises the following components in parts by weight: 10-30 parts of polyethylene, 10-30 parts of ethylene-vinyl acetate copolymer, 0.5-1.2 parts of high-efficiency antioxidant, 0.05-0.08 part of organic tin catalyst, 0.8-2 parts of flame retardant and 0.3-0.5 part of stearic acid, and belongs to the technical field of wires and cables.
Description
Technical Field
The invention belongs to the field of wires and cables, and particularly relates to an abrasion-resistant and tension-resistant halogen-free wire and cable and a manufacturing method thereof.
Background
The basic structure of the wire cable consists of four parts, namely a wire core, an insulating layer, a shielding layer and a protective layer; the core wire is a conductive part of the power cable, is used for transmitting electric energy and is a main part of the power cable; the insulation layer electrically isolates the wire cores from the ground and the wire cores of different phases, ensures electric energy transmission, protects the power cable from the invasion of external impurities and moisture, and prevents external force from directly damaging the wire cable.
With the improvement of environmental awareness of people and the acceleration of the pace of social and economic construction in China, the low-smoke halogen-free cable does not emit toxic smoke during combustion because the low-smoke halogen-free cable does not contain halogen (F, Cl, Br, I and At) and does not contain substances with large environmental pollution, and the low-smoke halogen-free flame-retardant cable is widely applied to important departments and public places such as high-rise buildings, subways, power plants, nuclear power plants, rail transit and the like.
According to the aging requirements of national halogen-free low-smoke flame-retardant cable materials for electric wires and cables, GB/T32129-2015 polyolefin insulation materials and sheaths, the aging resistance standard of WDZ-YJ-H150/WDZ-YJ-J150 is 150 ℃ for 168 hours, the maximum change rate of tensile strength is +/-25%, and the maximum change rate of elongation at break is +/-25%.
The international standard electrical appliance wiring electric wire and cable and the test method thereof are UL-758/2010(ISBN-7629-1166-2) and UL-1581 with the aging resistance standard of 150 ℃, the tensile strength is more than or equal to 80 percent, and the elongation at break is more than or equal to 80 percent in 7 days.
At the moment, the elongation at break and the tensile strength of polyolefin insulating materials and coatings on the current market can only reach about 70 percent, and the polyolefin insulating materials and the coatings are easy to age and wear, so that the service life of the products is seriously influenced, and great troubles are brought to market use.
Disclosure of Invention
The invention aims to provide an abrasion-resistant and tension-resistant halogen-free wire and cable with high elongation at break, high tensile strength and high thermal aging resistance.
The second purpose of the invention is to provide a manufacturing method of the abrasion-resistant and tension-resistant halogen-free wire and cable.
The wear-resistant and tension-resistant halogen-free wire cable comprises a conductive wire core, wherein the conductive wire core is sleeved in an insulating layer, and the insulating layer comprises the following components in parts by weight: 10-30 parts of polyethylene, 10-30 parts of ethylene-vinyl acetate copolymer, 0.5-1.2 parts of high-efficiency antioxidant, 0.05-0.08 part of organic tin catalyst, 0.8-2 parts of flame retardant and 0.3-0.5 part of stearic acid.
Further, in the anti-wear and tensile halogen-free electric wire and cable, the organic tin catalyst is dibutyltin dilaurate, dimethyltin, dioctyltin, tetraphenyltin, tin oxide or stannous octoate.
Further, in the abrasion-resistant and tension-resistant halogen-free wire and cable, the flame retardant is magnesium hydroxide or aluminum hydroxide.
Further, the polyethylene is low-density polyethylene with the density of 0.915-0.940 g/cc; the mole fraction of vinyl acetate of the ethylene-vinyl acetate copolymer is 15-25%.
Further, the high-efficiency antioxidant of the abrasion-resistant tensile halogen-free wire and cable is prepared from the following components in parts by weight: 24-36 parts of 2, 6-di-tert-butylphenol, 12-18 parts of methyl acrylate, 76-115 parts of isopropanol, 0.25-0.45 part of inorganic base, 52-79 parts of 3, 5-methyl ester, 17-27 parts of propylene glycol methyl ether acetate, 38-58 parts of gamma-methacryloxypropyl trimethoxy silane, 1-1.5 parts of acetic acid, 1.5-2.6 parts of n-butyl titanate and 16-24.5 parts of pentaerythritol.
Further, in the above abrasion-resistant and tension-resistant halogen-free wire and cable, the inorganic base is one or any combination of potassium hydroxide and sodium hydroxide
Further, the high-efficiency antioxidant of the abrasion-resistant tension-resistant halogen-free wire and cable is mainly prepared by the following method:
1) weighing each component;
2) adding the isopropanol, 2, 6-di-tert-butylphenol and inorganic base weighed in the claim 8 into a reaction kettle under the protection of nitrogen, heating to 35-50 ℃ while stirring, heating to 90-100 ℃ after uniformly stirring the materials, vacuumizing to 0.08-1.0Mpa, dropwise adding acrylic ester, heating to 120-125 ℃, carrying out heat preservation reaction for 2-3 hours, and cooling to 45-55 ℃ after the reaction is finished to obtain a 3, 5-methyl ester mixture;
3) introducing nitrogen for protection, dissolving pentaerythritol by using an organic solvent, then adding the pentaerythritol into the 3, 5-methyl ester mixture prepared in the step 1), uniformly stirring at 45-55 ℃, adding acetic acid to regulate the pH value, then adding n-butyl titanate, heating to 170-190 ℃, and reacting at constant temperature for 7-9 hours; cooling to 80-90 ℃ after the reaction is finished, dripping gamma-methacryloxypropyltrimethoxysilane, reacting for 1.5-2.5 hours at the constant temperature of 80-90 ℃, reducing the pressure to 0.08-0.12Mpa after the reaction is finished, and vacuumizing to remove the solvent to obtain a semi-finished product;
4) the mass ratio of the semi-finished product prepared in the step 3) to tris [2, 4-di-tert-butylphenyl ] phosphite is 7: 3, uniformly mixing at 18-22 ℃.
The second technical scheme provided by the invention is that the preparation method of the abrasion-resistant tension-resistant halogen-free wire and cable sequentially comprises the following steps:
1) stranding a plurality of strands of copper wires;
2) processing the insulating layer material, coating the molten colloidal particles outside the copper wire bundles to form an insulating layer, and naturally cooling and forming to obtain a semi-finished wire cable;
3) and conveying the semi-finished wire and cable into water, cooling by water cooling, and rolling.
Further, in the preparation method of the abrasion-resistant and tension-resistant halogen-free wire and cable, the insulating layer material is prepared by the following steps:
1) weighing the components in parts by weight according to the claim 1;
2) putting the polyethylene and the ethylene-vinyl acetate copolymer weighed in the step 1) into a mixer, and starting a vacuum machine to dry for 10-15min under the conditions of absolute pressure of 0.01-0.02Mpa and temperature of 30-40 ℃;
3) adding high-efficiency antioxidant, organic tin catalyst, flame retardant and stearic acid, heating to 90-130 deg.C, stirring at high speed, mixing and crosslinking for 1-3 h;
4) then putting the mixture into a double-screw machine for extrusion molding and drying.
Further, in the preparation method of the abrasion-resistant tensile halogen-free wire and cable, the rotation speed of the extruder in the step 4) is 500-.
Compared with the prior art, the technical scheme provided by the invention has the following technical advantages:
1. the electric wire and cable prepared by the technical scheme provided by the invention meet the low-smoke halogen-free and electric performance indexes of GB/T32129-2015, and are environment-friendly.
2. The electric wire and cable manufactured by the technical scheme provided by the invention can effectively avoid the problems of oxidation and aging of rubber on the surface of the cable in long-time use, has high elongation at break and high tensile strength, and prolongs the service life of the cable.
3. The technical scheme provided by the invention breaks through the traditional frame of an antioxidant product, takes hindered phenol and other compounds and derivatives thereof as main raw materials, introduces the organic silicon chain forging to change the structure of the original product, provides the heat resistance of the original product and prolongs the service life of the product.
4. The invention improves the high-temperature stability of the antioxidant, improves the heat-resistant aging performance of the polyethylene cable, delays the attenuation of the tensile strength of the system, improves the compatibility of the antioxidant and the polyethylene cable system, reduces the precipitation phenomenon and improves the extraction resistance.
5. The application provides a technical scheme in introduce the methacryloxy, can have the cross-linking effect with the polyolefin system under the high temperature condition, add the phosphite substance simultaneously and have synergistic effect, compromise the characteristic of eliminating the free radical and decomposing hydroperoxide, improve the antioxidant capacity of system greatly to product life has been prolonged.
Detailed Description
The following detailed description of the embodiments of the present invention refers to the accompanying drawings, which are incorporated in and constitute a part of this specification.
Example 1
The invention discloses an abrasion-resistant and tension-resistant halogen-free cable which comprises a conductive wire core, wherein the conductive wire core is sleeved in an insulating layer, and the insulating layer comprises the following components in parts by weight: 18 parts of polyethylene (with the density of 0.915 g/cubic centimeter), 30 parts of ethylene-vinyl acetate copolymer (the mole fraction of vinyl acetate in the ethylene-vinyl acetate copolymer is 25%), 0.9 part of high-efficiency antioxidant, 0.06 part of dibutyltin dilaurate, 1.2 parts of magnesium hydroxide and 0.3 part of stearic acid.
The high-efficiency antioxidant is prepared from the following components in parts by weight: 36 parts of 2, 6-di-tert-butylphenol, 15 parts of methyl acrylate, 100 parts of isopropanol, 0.45 part of potassium hydroxide, 60 parts of 3, 5-methyl ester, 20 parts of propylene glycol methyl ether acetate, 48 parts of gamma-methacryloxypropyl trimethoxy silane, 1 part of acetic acid, 2 parts of n-butyl titanate and 20 parts of pentaerythritol.
Example 2
The invention discloses an abrasion-resistant and tension-resistant halogen-free cable which comprises a conductive wire core, wherein the conductive wire core is sleeved in an insulating layer, and the insulating layer comprises the following components in parts by weight: 10 parts of polyethylene (with the density of 0.925 g/cubic centimeter), 15 parts of ethylene-vinyl acetate copolymer (the mole fraction of vinyl acetate in the ethylene-vinyl acetate copolymer is 24%), 0.7 part of high-efficiency antioxidant, 0.07 part of dimethyl tin, 1.0 part of magnesium hydroxide or aluminum hydroxide and 0.5 part of stearic acid.
The high-efficiency antioxidant is prepared from the following components in parts by weight: 30 parts of 2, 6-di-tert-butylphenol, 12 parts of methyl acrylate, 100 parts of isopropanol, 0.30 part of potassium hydroxide, 79 parts of 3, 5-methyl ester, 27 parts of propylene glycol methyl ether acetate, 38 parts of gamma-methacryloxypropyl trimethoxy silane, 1.2 parts of acetic acid, 1.5 parts of n-butyl titanate and 16 parts of pentaerythritol.
Example 3
The invention discloses an abrasion-resistant and tension-resistant halogen-free cable which comprises a conductive wire core, wherein the conductive wire core is sleeved in an insulating layer, and the insulating layer comprises the following components in parts by weight: 28 parts of polyethylene (with the density of 0.940 g/cubic centimeter), 15 parts of ethylene-vinyl acetate copolymer (the mole fraction of vinyl acetate in the ethylene-vinyl acetate copolymer is 20%), 1.2 parts of high-efficiency antioxidant, 0.08 part of stannous octoate, 2 parts of magnesium hydroxide or aluminum hydroxide and 0.4 part of stearic acid.
The high-efficiency antioxidant is prepared from the following components in parts by weight: 24 parts of 2, 6-di-tert-butylphenol, 18 parts of methyl acrylate, 76 parts of isopropanol, 0.25 part of sodium hydroxide, 52 parts of 3, 5-methyl ester, 25 parts of propylene glycol methyl ether acetate, 38 parts of gamma-methacryloxypropyl trimethoxy silane, 1.5 parts of acetic acid, 1.5 parts of n-butyl titanate and 24.5 parts of pentaerythritol.
Example 4
The invention discloses an abrasion-resistant and tension-resistant halogen-free wire cable which comprises a conductive wire core, wherein the conductive wire core is sleeved in an insulating layer, and the insulating layer comprises the following components in parts by weight: 30 parts of polyethylene (with the density of 0.935 g/cubic centimeter), 20 parts of ethylene-vinyl acetate copolymer (the mole fraction of vinyl acetate in the ethylene-vinyl acetate copolymer is 20 percent), 0.5 part of high-efficiency antioxidant, 0.1 part of tetraphenyltin, 0.8 part of aluminum hydroxide and 0.3 part of stearic acid.
The high-efficiency antioxidant is prepared from the following components in parts by weight: 28 parts of 2, 6-di-tert-butylphenol, 18 parts of methyl acrylate, 100 parts of isopropanol, 0.40 part of potassium hydroxide, 52 parts of 3, 5-methyl ester, 17 parts of propylene glycol methyl ether acetate, 58 parts of gamma-methacryloxypropyl trimethoxy silane, 1.0 part of acetic acid, 2.6 parts of n-butyl titanate and 20 parts of pentaerythritol.
Example 5
The invention discloses an abrasion-resistant and tension-resistant halogen-free cable which comprises a conductive wire core, wherein the conductive wire core is sleeved in an insulating layer, and the insulating layer comprises the following components in parts by weight: 25 parts of polyethylene (with the density of 0.940 g/cubic centimeter), 10 parts of ethylene-vinyl acetate copolymer (the mole fraction of vinyl acetate in the ethylene-vinyl acetate copolymer is 25%), 1 part of high-efficiency antioxidant, 0.07 part of dioctyltin, 2 parts of magnesium hydroxide and 0.3-0.5 part of stearic acid.
The high-efficiency antioxidant is prepared from the following components in parts by weight: 30 parts of 2, 6-di-tert-butylphenol, 13 parts of methyl acrylate, 80 parts of isopropanol, 0.30 part of potassium hydroxide, 60 parts of 3, 5-methyl ester, 20 parts of propylene glycol methyl ether acetate, 40 parts of gamma-methacryloxypropyl trimethoxy silane, 1 part of acetic acid, 2 parts of n-butyl titanate and 20 parts of pentaerythritol.
The high-efficiency antioxidant described in examples 1 to 5 is mainly prepared by the following method:
1) weighing the components according to the weight numbers in the embodiments 1 to 5;
2) adding weighed isopropanol, 2, 6-di-tert-butylphenol and inorganic base (sodium hydroxide or potassium hydroxide) into a reaction kettle under the protection of nitrogen, heating to 35-50 ℃ (preferably 40 ℃) while stirring, uniformly stirring, heating to 90-100 ℃ (preferably 90 ℃), vacuumizing to 0.08-1.0Mpa (preferably 0.09Mpa), dropwise adding acrylate, heating to 120-125 ℃ (preferably 122 ℃), keeping the temperature for reaction for 2-3 hours (preferably 2.5 hours), cooling to 45-55 ℃ (preferably 50 ℃) after the reaction is finished to obtain a 3, 5-methyl ester mixture;
3) introducing nitrogen for protection, dissolving pentaerythritol by using an organic solvent, then adding the pentaerythritol into the 3, 5-methyl ester mixture prepared in the step 1), uniformly stirring at 45-55 ℃ (preferably 50 ℃), adding acetic acid to adjust the pH value, then adding n-butyl titanate, heating to 170-190 ℃ (preferably 180 ℃), and reacting for 7-9 hours at constant temperature; cooling to 80-90 deg.C (preferably 90 deg.C) after reaction, adding gamma-methacryloxypropyltrimethoxysilane dropwise, reacting at 80-90 deg.C (preferably 85 deg.C) for 1.5-2.5 hr, reducing pressure to 0.08-0.12Mpa (preferably 90 deg.C) after reaction, and vacuum-pumping to remove solvent to obtain semi-finished product;
4) the mass ratio of the semi-finished product prepared in the step 3) to tris [2, 4-di-tert-butylphenyl ] phosphite is 7: 3, uniformly mixing at 18-22 ℃ (preferably 20 ℃).
The preparation method of the insulating layer material of the embodiment 1 to the embodiment 5 comprises the following steps:
1) weighing the components in any weight part in examples 1 to 5;
2) putting the polyethylene (with the density of 0.915-0.940 g/cubic centimeter) and the ethylene-vinyl acetate copolymer (the vinyl acetate mole fraction in the ethylene-vinyl acetate copolymer is 15-25%) weighed in the step 1) into a mixer, and drying for 10-15min (12min) by starting a vacuum machine under the conditions of the absolute pressure of 0.01-0.02Mpa (preferably 0.015Mpa) and the temperature of 30-40 ℃ (preferably 35 ℃);
3) adding high-efficiency antioxidant, catalyst (dibutyltin dilaurate or dimethyltin or dioctyltin or tetraphenyltin or tin oxide or stannous octoate), flame retardant (magnesium hydroxide or aluminum hydroxide) and stearic acid, heating to 90-130 deg.C (preferably 120 deg.C), stirring at high speed, mixing, and crosslinking for 1-3h (preferably 2 hr);
4) then the mixture is put into a double-screw machine and extruded and dried for 2 hours at the rotation speed of 500-700rpm (preferably 600rpm) and at the temperature of 100-120 ℃ (preferably 110 ℃).
The preparation method of the abrasion-resistant and tension-resistant halogen-free electric wire and cable described in the embodiment 1 to the embodiment 5 sequentially comprises the following steps:
1) stranding a plurality of strands of copper wires (treated according to actual needs);
2) processing the insulating layer material, coating the molten colloidal particles outside the copper wire bundles to form an insulating layer, and naturally cooling and forming to obtain a semi-finished wire cable;
3) and conveying the semi-finished wire and cable into water, cooling by water cooling, and rolling.
The flame retardant grades of the abrasion-resistant and tension-resistant halogen-free electric wires and cables provided in the examples 1 to 5 of the application are classified into B grades according to the test conditions specified in GB/T18380.3-2002.
Under the test conditions specified in GB/T17651-1998, the smoke concentration light transmittance generated by the cables provided in examples 1-5 when burning is 68-78%, which is better than the standard specified by the national standard.
The halogen acid gas generated during the combustion of the cables provided in examples 1 to 5 is less than 0.2mg/g, which is lower than the standard specified in the national standard, under the test conditions specified in GB/T17650-1998. The PH value is 4.3-5.5, the conductivity is less than 10 mu s/mm, and the national standard requirement is met.
According to the provisions of GB/T12706.1, examples 1 to 5 provide cables with insulation resistance constants ki greater than 3.96M Ω. km, which are superior to the standards prescribed by the national standards.
The application provides an insulating layer material detection test as follows:
remarking: the wear rate test method comprises the following steps: the cables prepared in examples 1 to 5 were fixed on an abrasion resistance tester under the same conditions and subjected to abrasion grinding 100 times, and then the abrasion rate was calculated as (mass before abrasion-mass after abrasion)/mass before abrasion.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. The wear-resistant and tension-resistant halogen-free wire and cable is characterized by comprising a conductive wire core, wherein the conductive wire core is sleeved in an insulating layer, and the insulating layer comprises the following components in parts by weight: 10-30 parts of polyethylene, 10-30 parts of ethylene-vinyl acetate copolymer, 0.5-1.2 parts of high-efficiency antioxidant, 0.05-0.08 part of organic tin catalyst, 0.8-2 parts of flame retardant and 0.3-0.5 part of stearic acid.
2. The abrasion-resistant, pull-resistant, halogen-free wire cable of claim 1 wherein the organotin catalyst is dibutyltin dilaurate, dimethyltin, dioctyltin, tetraphenyltin, tin oxide, stannous octoate.
3. The abrasion-resistant, tension-resistant and halogen-free wire and cable according to claim 1 wherein the flame retardant is magnesium hydroxide or aluminum hydroxide.
4. The abrasion-resistant, pull-resistant and halogen-free electrical wire and cable of claim 1 wherein the polyethylene is a low density polyethylene having a density of 0.915-0.940 g/cc; the mole fraction of vinyl acetate of the ethylene-vinyl acetate copolymer is 15-25%.
5. The abrasion-resistant and tension-resistant halogen-free electric wire and cable as claimed in claim 1, wherein the high-efficiency antioxidant is prepared from the following components in parts by weight: 24-36 parts of 2, 6-di-tert-butylphenol, 12-18 parts of methyl acrylate, 76-115 parts of isopropanol, 0.25-0.45 part of inorganic base, 52-79 parts of 3, 5-methyl ester, 17-27 parts of propylene glycol methyl ether acetate, 38-58 parts of gamma-methacryloxypropyl trimethoxy silane, 1-1.5 parts of acetic acid, 1.5-2.6 parts of n-butyl titanate and 16-24.5 parts of pentaerythritol.
6. The abrasion-resistant, pull-resistant and halogen-free electrical wire and cable of claim 5 wherein the inorganic base is one or any combination of potassium hydroxide and sodium hydroxide.
7. The abrasion-resistant, tension-resistant and halogen-free electric wire and cable according to claim 5, wherein the high-efficiency antioxidant is prepared by the following method:
1) weighing the components according to the weight of claim 1;
2) adding the isopropanol, 2, 6-di-tert-butylphenol and inorganic base weighed in the claim 8 into a reaction kettle under the protection of nitrogen, heating to 35-50 ℃ while stirring, heating to 90-100 ℃ after uniformly stirring the materials, vacuumizing to 0.08-1.0Mpa, dropwise adding acrylic ester, heating to 120-125 ℃, carrying out heat preservation reaction for 2-3 hours, and cooling to 45-55 ℃ after the reaction is finished to obtain a 3, 5-methyl ester mixture;
3) introducing nitrogen for protection, dissolving pentaerythritol by using an organic solvent, then adding the pentaerythritol into the 3, 5-methyl ester mixture prepared in the step 1), uniformly stirring at 45-55 ℃, adding acetic acid to regulate the pH value, then adding n-butyl titanate, heating to 170-190 ℃, and reacting at constant temperature for 7-9 hours; cooling to 80-90 ℃ after the reaction is finished, dripping gamma-methacryloxypropyltrimethoxysilane, reacting for 1.5-2.5 hours at the constant temperature of 80-90 ℃, reducing the pressure to 0.08-0.12Mpa after the reaction is finished, and vacuumizing to remove the solvent to obtain a semi-finished product;
4) the mass ratio of the semi-finished product prepared in the step 3) to tris [2, 4-di-tert-butylphenyl ] phosphite is 7: 3, uniformly mixing at 18-22 ℃.
8. The preparation method of the abrasion-resistant and tension-resistant halogen-free wire and cable of claim 1, which comprises the following steps in sequence:
1) stranding a plurality of strands of copper wires;
2) processing the insulating layer material, coating the molten colloidal particles outside the copper wire bundles to form an insulating layer, and naturally cooling and forming to obtain a semi-finished wire cable;
3) and conveying the semi-finished wire and cable into water, cooling by water cooling, and rolling.
9. The method for preparing abrasion-resistant and tension-resistant halogen-free wire and cable according to claim 8, wherein the insulation layer material is prepared by the following steps:
1) weighing the components in parts by weight according to the claim 1;
2) putting the polyethylene and the ethylene-vinyl acetate copolymer weighed in the step 1) into a mixer, and starting a vacuum machine to dry for 10-15min under the conditions of absolute pressure of 0.01-0.02Mpa and temperature of 30-40 ℃;
3) adding high-efficiency antioxidant, organic tin catalyst, flame retardant and stearic acid, heating to 90-130 deg.C, stirring at high speed, mixing and crosslinking for 1-3 h;
4) then putting the mixture into a double-screw machine for extrusion molding and drying.
10. The method as claimed in claim 9, wherein the rotation speed of the extruder in step 4) is 500-700rpm, and the drying temperature is 100-120 ℃.
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