CN116285081A - Halogen-free flame-retardant irradiation crosslinked polyolefin cable material and preparation method thereof - Google Patents
Halogen-free flame-retardant irradiation crosslinked polyolefin cable material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 58
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 49
- 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 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004132 cross linking Methods 0.000 claims abstract description 87
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 43
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 41
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 18
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 15
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 14
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 14
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 14
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 description 10
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 10
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000012796 inorganic flame retardant Substances 0.000 description 7
- 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 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
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- 239000006185 dispersion Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- 238000007789 sealing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- 230000015556 catabolic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
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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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
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- Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a halogen-free flame-retardant irradiation crosslinked polyolefin cable material and a preparation method thereof. The halogen-free flame-retardant irradiation crosslinked polyolefin cable material in the technical scheme of the invention comprises the following components in parts by mass: 80 to 90 parts of polyolefin resin, 5 to 20 parts of crosslinking auxiliary agent, 60 to 100 parts of composite halogen-free flame retardant, 10 to 20 parts of compatilizer, 0.5 to 2.0 parts of antioxidant and 0.5 to 2.0 parts of dispersing agent. The crosslinking auxiliary agent is prepared by mixing and reacting raw materials comprising cage-type polyhedral polysilsesquioxane and DOPO, and comprises the following steps: s1, weighing dried polyhedral oligomeric silsesquioxane and DOPO, respectively adding an organic solvent, and stirring and dissolving to obtain a first solvent and a second solvent; s2, stirring the first solvent at 60-80 ℃, slowly dripping the second solvent, adding an acid binding agent, and reacting for 10-14 h at 70-80 ℃; s3, purifying by adopting water and acetonitrile, and grinding the product at room temperature to obtain the crosslinking auxiliary agent.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a halogen-free flame-retardant irradiation crosslinked polyolefin cable material and a preparation method thereof.
Background
The current cable is widely applied, and the requirements of domestic cable materials are continuously promoted in large-scale power grid construction projects such as national networking, boosting capacity expansion construction of a skeleton power grid, western electric east delivery project and the like and infrastructure construction of communication industry. With the continuous increase of the application of the electric wires and cables, the fire disaster caused by the cables is increased, and the requirements of the physical and mechanical properties, the temperature resistance, the fireproof and flame-retardant properties and the like of the cables are continuously improved. The impossibility of strictly introducing and using non-environment-friendly electric wires and cables has been made in many developed countries, so that there are more stringent requirements on the types of flame retardants and auxiliaries used for flame-retardant cables. Therefore, research on manufacturing of halogen-free, nontoxic and heat-resistant composite cables has more important significance.
The irradiation crosslinking is a method for physically crosslinking the polyolefin cable material by using high-energy rays, and is an effective mode capable of improving the temperature resistance, mechanical performance and ageing resistance of the material on the premise of not introducing a large amount of chemical substances. The radiation dose absorbed by irradiation crosslinking is only partially used for chemical and molecular structural transformation, most of the radiation energy is converted into excitation and heat of molecules, and as the polymer is inefficient for heat transfer, the absorbed energy can lead to the temperature of the material to be increased, the molecular chains to be broken, and the mechanical property to be reduced. Therefore, the irradiation dose cannot be too high during irradiation crosslinking, and the requirements of obtaining high crosslinking density and excellent mechanical properties are often met with lower energy consumption by adding a crosslinking auxiliary agent. At present, the domestic halogen-free flame-retardant irradiation crosslinking polyolefin cable material mainly adopts an inorganic metal hydroxide system, has the defect of low flame retardant efficiency, and needs to add a large amount of flame retardant to meet the flame retardant requirement, so that the mechanical property and the processing property of the material are poor, and the toughness after irradiation crosslinking is poor. Chinese patent application (publication No. CN 112708186A) discloses an irradiation crosslinking super-flexible, bending-resistant, abrasion-resistant and low-smoke halogen-free composition and application thereof, wherein aluminum hydroxide treated by surface silane is used as a flame retardant, TAIC is used as a crosslinking auxiliary agent, and the heat resistance and the flexibility are excellent. However, the TAIC crosslinking agent has single function, and a large amount of aluminum hydroxide flame retardant is required to be added to obtain high crosslinking density and excellent flame retardant property at the same time, so that the mechanical property of the material is affected. Chinese patent application (publication No. CN 111269266B) discloses a preparation method of a cyano-containing aryl ether phosphazene type halogen-free flame retardant, which effectively solves the problems of poor mechanical property, easy aging and the like of materials caused by excessive addition of inorganic fillers in the traditional flame retardant cable, but the flame retardant still needs to use high irradiation dose or add a crosslinking auxiliary agent again to obtain high crosslinking density, and has single function.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a halogen-free flame-retardant irradiation crosslinked polyolefin cable material and a preparation method thereof, wherein the polyolefin cable material with uniform crosslinking degree and good flame-retardant effect is obtained at a lower irradiation dose, and the problems of heat effect, nonuniform crosslinking degree and the like in irradiation crosslinking are overcome. The halogen-free flame-retardant irradiation crosslinked polyolefin cable material in the technical scheme of the invention comprises the following components in parts by mass: 80 to 90 parts of polyolefin resin, 5 to 20 parts of crosslinking auxiliary agent, 60 to 100 parts of composite halogen-free flame retardant, 10 to 20 parts of compatilizer, 0.5 to 2.0 parts of antioxidant and 0.5 to 2.0 parts of dispersing agent.
The polyolefin-based resin of the present invention is not limited, and may be one or more of polyethylene resin, polypropylene resin, ethylene copolymer, and propylene copolymer, and preferably a mixture of polyethylene resin, ethylene-octene copolymer, and ethylene-vinyl acetate copolymer in a mass ratio of 1:0.3 to 0.4:0.3 to 0.4.
Further, the crosslinking assistant is prepared by mixing and reacting raw materials comprising cage polyhedral Polysilsesquioxane (POSS) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO).
The POSS-DOPO system crosslinking auxiliary agent has a large number of double bonds, has higher reactivity, can be used as a crosslinking point in the irradiation crosslinking process, improves the crosslinking density, can reduce the total irradiation dose, effectively reduces the cracking of materials under large irradiation dose and the performance degradation caused by the cracking, avoids the problems of heat effect and uneven crosslinking degree caused by irradiation, reduces energy consumption and improves the production efficiency; the POSS-DOPO system crosslinking auxiliary agent has good flame retardant property, and flame retardant elements such as phosphorus, silicon and the like are designed on the same molecule, so that migration of an organic phosphorus flame retardant is reduced, the formed-Si-O-Si-ceramic layer barrier and-Si-O-P-coacervate can effectively prevent molten drops, and the flame retardant is compounded with a halogen-free flame retardant, so that the flame retardant has coacervate and gas-phase flame retardant effects, the addition amount of the inorganic flame retardant is effectively reduced, and high-efficiency flame retardance is realized.
Further, the mass ratio of cage polyhedral polysilsesquioxane to DOPO was 1.0:1.2 to 1.5.
Further, the cage type polyhedral oligomeric silsesquioxane is octavinyl-POSS and has a structural formula shown in a formula I:
further, DOPO has a structural formula as shown in formula II:
the preparation method of the cross-linking auxiliary agent comprises the following steps:
s1, weighing dried polyhedral oligomeric silsesquioxane and DOPO, respectively adding an organic solvent, and stirring and dissolving to obtain a first solvent and a second solvent;
s2, stirring the first solvent at 60-80 ℃, slowly dripping the second solvent, adding an acid binding agent, and reacting for 10-14 h at 70-80 ℃;
s3, purifying by adopting water and acetonitrile, and grinding the product at room temperature to obtain the crosslinking auxiliary agent.
Further, the organic solvent is one or more of ethanol, acetone, dimethyl sulfoxide and chloroform.
Further, the volume-mass ratio of the organic solvent to the polyhedral oligomeric silsesquioxane or DOPO is 10-30 ml/g.
Further, the chemical reaction formula occurring in step S2 is shown in formula iii:
further, the acid binding agent is one or more of triethylamine, ethylenediamine and isopropylamine.
Further, adding an acid binding agent to regulate the pH value to 7-8.
Further, the composite halogen-free flame retardant comprises the following components in percentage by mass: 30-60% of aluminum hydroxide, 20-40% of ammonium polyphosphate (APP) and 10-25% of Melamine Cyanurate (MCA).
The components of the composite halogen-free flame retardant are respectively subjected to surface modification by a silane coupling agent, and the specific process of the surface modification is as follows: pouring any component of the composite halogen-free flame retardant into a high-speed stirrer, uniformly spraying silane coupling agent with the mass of 1.0-2.2% into the stirrer by using an atomization device under the high-speed stirring at 500-600 rpm, heating to 95-100 ℃, stirring for 3-5 min, drying and cooling.
The surface modified flame retardant can be well fused with the matrix polyolefin resin, promote the uniform dispersion of the matrix polyolefin resin in the system, and can not adversely affect the mechanical properties while improving the flame retardant property of the polyolefin cable material.
Further, the silane coupling agent selected for the halogen-free flame retardant is KH-560.
Further, the compatilizer is one or more of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, polyethylene grafted acrylonitrile and polypropylene grafted acrylonitrile.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 164, antioxidant DNP and antioxidant TNP, and the preferred mass ratio is 1:0.4 to 0.6 of antioxidant 1010 and antioxidant 168.
Further, the dispersing agent is a low molecular wax-type dispersing agent, and is one or more of polyethylene wax, oxidized polyethylene wax and polyethylene glycol.
The invention also provides a preparation method of the halogen-free flame-retardant irradiation crosslinked polyolefin cable material, which comprises the following steps:
(1) Kneading and banburying a crosslinking auxiliary agent and part of the polyolefin resin, and extruding and granulating to obtain a polyolefin resin master batch I containing the crosslinking auxiliary agent;
(2) Mixing the composite halogen-free flame retardant, the compatilizer, the antioxidant, the dispersing agent and the rest of the polyolefin resin, and extruding and granulating to obtain polyolefin resin master batch II;
(3) Mixing the polyolefin resin master batch I containing the crosslinking auxiliary agent with the polyolefin resin master batch II, extruding, water-cooling, granulating, injection molding, and finally performing irradiation crosslinking to obtain the halogen-free flame-retardant irradiation crosslinked polyolefin cable material.
According to the invention, the kneading is carried out, the banburying granulation is carried out, and the polyolefin resin is added for mixing twice, so that the difficult problem of difficult blanking of the crosslinking auxiliary agent powder can be effectively solved, the feeding is more uniform during extrusion granulation, and the uniform dispersion of various auxiliary agents such as flame retardants is facilitated.
Further, the mass of the portion of the polyolefin-based resin previously added in the step (1) is 40 to 50% of the total mass of the polyolefin-based resin.
Further, the banburying temperature in the step (1) and the step (2) is 120-180 ℃ and the time is 5-10 min.
Further, the irradiation crosslinking process in the step (3) adopts Co 60 The gamma rays are used as high-energy rays and are radiated in a nitrogen atmosphere, and the radiation dosage is 6-18Mrad.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) According to the invention, a POSS-DOPO system crosslinking auxiliary agent is adopted, and a composite halogen-free flame retardant is combined, so that the polyolefin cable material with good mechanical property, flame retardant property and heat resistance is obtained through irradiation crosslinking with lower radiation dose;
(2) The POSS-DOPO system crosslinking auxiliary agent contains a large number of double bonds, brings higher reactivity, can serve as crosslinking points in the irradiation process, and effectively improves the crosslinking density;
(3) The POSS-DOPO system crosslinking auxiliary agent designs flame retardant elements such as phosphorus, silicon and the like on the same molecule, reduces migration of an organic phosphorus flame retardant, and the formed-Si-O-Si-ceramic layer barrier and-Si-O-P-coacervate can effectively prevent molten drops, has coacervate phase and gas phase synergistic flame retardant effect, and is compounded with a composite halogen-free flame retardant to realize high-efficiency flame retardance;
(4) The POSS-DOPO system crosslinking auxiliary agent can effectively reduce the total irradiation dose, prevent the cracking of materials and the performance degradation caused by the cracking under the large irradiation dose, avoid the problems of uneven crosslinking degree and the thermal effect caused by irradiation, reduce the energy consumption and improve the production efficiency;
(5) The invention is kneaded and then mixed with the polyolefin resin in two steps, which can effectively solve the difficult problem of difficult discharging of the crosslinking auxiliary agent powder, so that the feeding is more uniform during extrusion and granulation, and the invention is beneficial to the uniform dispersion of various auxiliary agents such as flame retardant and the like.
Detailed Description
The technical scheme of the present invention will be further described by the following specific examples, and it should be understood that the specific examples described herein are only for aiding in understanding the present invention, and are not intended to be limiting. Unless otherwise indicated, all materials used in the examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
The ethylene-vinyl acetate copolymer used in the following examples had a vinyl acetate content of 26% and a melt index of 2.0g/10min.
Example 1
The preparation method of the crosslinking assistant comprises the following steps:
s1, weighing 2.2 parts of dried polyhedral oligomeric silsesquioxane and 2.8 parts of DOPO, respectively adding chloroform according to the volume-mass ratio of 20ml/g, and stirring and dissolving to obtain a first solvent and a second solvent;
s2, stirring the first solvent at 80 ℃, slowly dropwise adding the second solvent within 1h, simultaneously adding an acid binding agent to adjust the pH value to 7.5, and maintaining the reaction for 12h at 80 ℃;
s3, purifying by using distilled water and acetonitrile, and grinding the product at room temperature to obtain the crosslinking auxiliary agent.
The aluminum hydroxide, ammonium polyphosphate and melamine cyanurate in the composite halogen-free flame retardant are subjected to surface modification respectively, the specific modification method is that the aluminum hydroxide or the ammonium polyphosphate or the melamine cyanurate is poured into a high-speed stirrer, and a silane coupling agent KH-560 with the mass of 2.0% of that of the inorganic flame retardant is uniformly sprayed into the stirrer under high-speed stirring at 500rpm by an atomization device, and the temperature is raised to 100 ℃ for continuous stirring for 5min, so that the aluminum hydroxide or the ammonium polyphosphate or the melamine cyanurate is uniformly dispersed on the surface of the inorganic flame retardant powder, and the inorganic flame retardant powder is dried and cooled.
The preparation method of the halogen-free flame-retardant irradiation crosslinked polyolefin cable material comprises the following steps:
(1) Compounding 50 parts of Linear Low Density Polyethylene (LLDPE), 25 parts of ethylene-vinyl acetate copolymer (EVA) and 15 parts of ethylene-octene copolymer (POE) into polyolefin resin, kneading 5 parts of crosslinking auxiliary agent and 40% of polyolefin resin, putting into an internal mixer, banburying for 5min at 140 ℃, and carrying out single-screw extrusion granulation to obtain a polyolefin resin master batch I containing the crosslinking auxiliary agent;
(2) Adding a surface-modified flame retardant (45 parts of aluminum hydroxide, 25 parts of ammonium polyphosphate and 15 parts of melamine cyanurate), 10 parts of maleic anhydride grafted polyethylene, 1.0 part of antioxidant 1010, 0.5 part of antioxidant 168, 1.5 parts of polyethylene wax and the rest of polyolefin resin into an internal mixer, banburying for 5min at 140 ℃, and carrying out single-screw extrusion granulation to obtain a polyolefin resin master batch II;
(3) Mixing polyolefin resin master batch I and polyolefin resin master batch II containing crosslinking auxiliary agent, extruding by a double screw extruder, water-cooling, granulating, injection molding, placing the sample in a glass bottle, filling nitrogen, sealing, and Co-extruding to obtain the final product 60 Performing irradiation crosslinking by gamma rays, wherein the irradiation dose is 14Mrad, and obtaining a halogen-free flame-retardant irradiation crosslinking polyolefin cable material; the temperature 1 to 10 zones of the twin-screw extruder were set as follows: 170 ℃, 175 ℃, 185 ℃, 190 ℃, 200 ℃, 195 ℃, 190 ℃, 185 ℃.
Example 2
This example differs from example 1 only in that 2.0 parts of dried polyhedral oligomeric silsesquioxane and 3.0 parts of DOPO were weighed in the preparation method of the crosslinking assistant, and chloroform was added respectively in a volume-mass ratio of 20 ml/g.
Example 3
The difference between this example and example 1 is only that the additive amount of the crosslinking assistant in the preparation method of the halogen-free flame retardant irradiation crosslinked polyolefin cable material is 10 parts and the irradiation dose is 10Mrad.
Example 4
The difference between this example and example 1 is only that the additive amount of the crosslinking assistant in the preparation method of the halogen-free flame retardant irradiation crosslinked polyolefin cable material is 15 parts and the irradiation dose is 10Mrad.
Example 5
The difference between the embodiment and the embodiment 1 is that the aluminum hydroxide, the ammonium polyphosphate and the melamine cyanurate in the composite halogen-free flame retardant are subjected to surface modification respectively, the specific modification method is that the aluminum hydroxide or the ammonium polyphosphate or the melamine cyanurate is poured into a high-speed stirrer, the silane coupling agent with the mass of 1.5 percent of the inorganic flame retardant is evenly sprayed into the stirrer under high-speed stirring at 500rpm by an atomization device, the temperature is raised to 100 ℃ and the stirring is continued for 5 minutes, so that the aluminum hydroxide or the ammonium polyphosphate or the melamine cyanurate is evenly dispersed on the surface of the inorganic flame retardant powder, and the inorganic flame retardant is dried and cooled.
Example 6
This example differs from example 1 only in that the composite halogen-free flame retardant is 30 parts aluminum hydroxide, 20 parts ammonium polyphosphate and 15 parts melamine cyanurate.
Comparative example 1
The comparative example differs from example 1 only in the preparation method of halogen-free flame retardant irradiation crosslinked polyolefin cable material, comprising the steps of:
(1) 50 parts of Linear Low Density Polyethylene (LLDPE), 25 parts of ethylene-vinyl acetate copolymer (EVA), 15 parts of ethylene-octene copolymer (POE) are compounded into polyolefin resin, and a surface modified flame retardant (45 parts of aluminum hydroxide, 25 parts of ammonium polyphosphate and 15 parts of melamine cyanurate), 10 parts of maleic anhydride grafted polyethylene, 1.0 part of antioxidant 1010, 0.5 part of antioxidant 168, 1.5 parts of polyethylene wax and the polyolefin resin are put into an internal mixer to be banburying for 5 minutes at 140 ℃, and single screw extrusion granulation is carried out to obtain polyolefin resin master batches;
(2) Extruding polyolefin resin master batch by a double screw extruder, water-cooling, granulating, injection molding, placing a sample in a glass bottle, filling nitrogen, sealing, and Co-extruding to obtain a product 60 Performing irradiation crosslinking by gamma rays, wherein the irradiation dose is 14Mrad, and obtaining a halogen-free flame-retardant irradiation crosslinking polyolefin cable material; the temperature 1 to 10 zones of the twin-screw extruder were set as follows: 170 ℃, 175 ℃, 185 ℃, 190 ℃, 200 ℃, 195 ℃, 190 ℃, 185 ℃.
Comparative example 2
The comparative example differs from example 1 only in that the amount of crosslinking aid added in the preparation method of the halogen-free flame retardant irradiation crosslinked polyolefin cable material was 20 parts.
Comparative example 3
The comparative example differs from example 1 only in that 2.5 parts of dried polyhedral oligomeric silsesquioxane and 2.5 parts of DOPO were weighed in the preparation method of the crosslinking assistant, and chloroform was added respectively in a volume-mass ratio of 20 ml/g.
Comparative example 4
The comparative example differs from example 1 only in that 1.5 parts of dried polyhedral oligomeric silsesquioxane and 3.5 parts of DOPO were weighed in the preparation method of the crosslinking assistant, and chloroform was added respectively in a volume-mass ratio of 20 ml/g.
Comparative example 5
The comparative example differs from example 1 only in that the preparation method of the halogen-free flame retardant irradiation crosslinked polyolefin cable material uses aluminum hydroxide, ammonium polyphosphate and melamine cyanurate which have not been modified by a silane coupling agent.
Comparative example 6
The comparative example differs from example 1 only in the preparation method of halogen-free flame retardant irradiation crosslinked polyolefin cable material, comprising the steps of:
(1) Compounding 50 parts of Linear Low Density Polyethylene (LLDPE), 25 parts of ethylene-vinyl acetate copolymer (EVA) and 15 parts of ethylene-octene copolymer (POE) into polyolefin resin, kneading 5 parts of crosslinking auxiliary agent and 50% of polyolefin resin, putting into an internal mixer, banburying for 5min at 140 ℃, and carrying out single-screw extrusion granulation to obtain a polyolefin resin master batch I containing the crosslinking auxiliary agent;
(2) 10 parts of maleic anhydride grafted polyethylene, 1.0 part of antioxidant 1010, 0.5 part of antioxidant 168, 1.5 parts of polyethylene wax and the rest of polyolefin resin are put into an internal mixer to be banburying for 5min at 140 ℃, and single-screw extrusion granulation is carried out to obtain polyolefin resin master batch II;
(3) Mixing polyolefin resin master batch I and polyolefin resin master batch II containing crosslinking auxiliary agent, extruding by a double screw extruder, water-cooling, granulating, injection molding, placing the sample in a glass bottle, filling nitrogen, sealing, and Co-extruding to obtain the final product 60 Performing irradiation crosslinking by gamma rays, wherein the irradiation dose is 14Mrad, and obtaining a halogen-free flame-retardant irradiation crosslinking polyolefin cable material; the temperature 1 to 10 zones of the twin-screw extruder were set as follows: 170 ℃, 175 ℃, 185 ℃, 190 ℃, 200 ℃, 195 ℃, 190 ℃, 185 ℃.
Comparative example 7
The comparative example differs from example 1 only in the preparation method of halogen-free flame retardant irradiation crosslinked polyolefin cable material, comprising the steps of:
(1) 50 parts of Linear Low Density Polyethylene (LLDPE), 25 parts of ethylene-vinyl acetate copolymer (EVA), 15 parts of ethylene-octene copolymer (POE), a surface modified flame retardant (45 parts of aluminum hydroxide, 25 parts of ammonium polyphosphate and 15 parts of melamine cyanurate), 10 parts of maleic anhydride grafted polyethylene, 1.0 part of antioxidant 1010, 0.5 part of antioxidant 168, 1.5 parts of polyethylene wax and 5 parts of crosslinking auxiliary agent are put into an internal mixer to be banburying at 140 ℃ for 10min, and single screw extrusion granulation is carried out to obtain polyolefin resin master batches;
(2) Extruding polyolefin resin master batch by a double screw extruder, water-cooling, granulating, injection molding, placing a sample in a glass bottle, filling nitrogen, sealing, and Co-extruding to obtain a product 60 Performing irradiation crosslinking by gamma rays, wherein the irradiation dose is 14Mrad, and obtaining a halogen-free flame-retardant irradiation crosslinking polyolefin cable material; the temperature 1 to 10 zones of the twin-screw extruder were set as follows: 170 ℃, 175 ℃, 185 ℃, 190 ℃, 200 ℃, 195 ℃, 190 ℃, 185 ℃.
The halogen-free flame-retardant irradiation crosslinked polyolefin cable materials obtained in the above examples and comparative examples were subjected to performance test, the degree of crosslinking was characterized by gel content, the samples were immersed in toluene at 100℃for 24 hours, dried and constant weight, the mass of the undissolved samples was measured, and the gel content, i.e., the degree of crosslinking and the data of mechanical properties were shown in Table 1 below, as percentages of mass of the undissolved samples/total mass of the samples.
TABLE 1 halogen-free flame retardant irradiation crosslinked polyolefin cable material performance data sheet
The polyolefin cable material obtained in examples 1-6 has good mechanical properties and heat resistance, the crosslinking auxiliary agent is not added in comparative example 1, the crosslinking degree is obviously reduced, the tensile strength of the obtained polyolefin cable material is reduced, and meanwhile, the synergistic flame retardance of the crosslinking agent is absent, so that the flame retardance of the obtained polyolefin cable material cannot reach V-0, the heat aging resistance is reduced, the consumption of the crosslinking auxiliary agent in comparative example 2 is high, the crosslinking degree can be improved to a limited extent, the hardness of the obtained polyolefin cable material is relatively high, the elongation at break is reduced, the cage-type polyhedral polysilsesquioxane in the crosslinking auxiliary agent in comparative example 3 is relatively high, the crosslinking degree of the obtained polyolefin cable material is relatively high, the elongation at break is reduced, DOPO in the crosslinking auxiliary agent in comparative example 4 is relatively high, part of active double bonds in the crosslinking agent are completely reacted, the effect of enhancing irradiation crosslinking can be achieved, the crosslinking degree is obviously reduced, the mechanical properties of the obtained polyolefin cable material are reduced, the flame retardant in comparative example 5 is not modified, the dispersion uniformity of the components such as polyolefin resin is reduced, the heat resistance and the flame retardance of the obtained polyolefin cable material are both the heat resistance and the flame resistance of the obtained polyolefin cable material are relatively low, the heat resistance of the polyolefin cable material is remarkably reduced, and the heat resistance of the polyolefin cable material is not even subjected to the test of the heat resistance is substantially reduced, and the heat resistance of the test performance of the polyolefin material is not even lower than the heat resistance and the heat resistance is substantially lower than the test performance and the test performance is 7.
Finally, it should be noted that the specific embodiments described herein are merely illustrative of the spirit of the invention and are not limiting of the invention's embodiments. Those skilled in the art to which the invention pertains may make various modifications or additions to the described embodiments or may be substituted in a similar manner, without and without all of the embodiments herein being fully understood. While these obvious variations and modifications, which come within the spirit of the invention, are within the scope of the invention, they are to be construed as being without departing from the spirit of the invention.
Claims (9)
1. The halogen-free flame-retardant irradiation crosslinked polyolefin cable material is characterized by comprising the following components in parts by weight: 80 to 90 parts of polyolefin resin, 5 to 20 parts of crosslinking auxiliary agent, 60 to 100 parts of composite halogen-free flame retardant, 10 to 20 parts of compatilizer, 0.5 to 2.0 parts of antioxidant and 0.5 to 2.0 parts of dispersing agent.
2. The halogen-free flame-retardant irradiation crosslinked polyolefin cable material according to claim 1, wherein the crosslinking auxiliary agent is prepared by mixing and reacting raw materials comprising cage-type polyhedral polysilsesquioxane and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
3. The halogen-free flame retardant irradiation crosslinked polyolefin cable material according to claim 2, wherein the mass ratio of cage polyhedral polysilsesquioxane to 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1.0:1.2 to 1.5.
4. A halogen-free flame retardant irradiation crosslinked polyolefin cable material according to claim 2 or 3, wherein the cage type polyhedral oligomeric silsesquioxane is octavinyl-POSS having a structural formula as shown in formula i:
5. the halogen-free flame retardant irradiation crosslinked polyolefin cable material according to claim 2, wherein the preparation method of the crosslinking auxiliary agent comprises the following steps:
s1, weighing dried polyhedral oligomeric silsesquioxane and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, respectively adding an organic solvent, and stirring and dissolving to obtain a first solvent and a second solvent;
s2, stirring the first solvent at 60-80 ℃, slowly dripping the second solvent, adding an acid binding agent, and reacting for 10-14 h at 70-80 ℃;
s3, purifying by adopting water and acetonitrile, and grinding the product at room temperature to obtain the crosslinking auxiliary agent.
6. The halogen-free flame-retardant irradiation crosslinked polyolefin cable material according to claim 1, wherein the composite halogen-free flame retardant comprises the following components in percentage by mass: 30-60% of aluminum hydroxide, 20-40% of ammonium polyphosphate and 10-25% of melamine cyanurate.
7. The halogen-free flame retardant irradiation crosslinked polyolefin cable material according to claim 6, wherein the components of the composite halogen-free flame retardant are respectively subjected to surface modification by a silane coupling agent, and the surface modification comprises the following steps: pouring any component of the composite halogen-free flame retardant into a high-speed stirrer, uniformly spraying silane coupling agent with the mass of 1.0-2.2% into the stirrer by using an atomization device under the high-speed stirring at 500-600 rpm, heating to 95-100 ℃, stirring for 3-5 min, drying and cooling.
8. A method for preparing the halogen-free flame retardant irradiation crosslinked polyolefin cable material as claimed in claim 1, comprising the steps of:
(1) Kneading and banburying a crosslinking auxiliary agent and part of the polyolefin resin, and extruding and granulating to obtain a polyolefin resin master batch I containing the crosslinking auxiliary agent;
(2) Mixing the composite halogen-free flame retardant, the compatilizer, the antioxidant, the dispersing agent and the rest of the polyolefin resin, and extruding and granulating to obtain polyolefin resin master batch II;
(3) Mixing the polyolefin resin master batch I containing the crosslinking auxiliary agent with the polyolefin resin master batch II, extruding, water-cooling, granulating, injection molding, and finally performing irradiation crosslinking to obtain the halogen-free flame-retardant irradiation crosslinked polyolefin cable material.
9. The method for preparing halogen-free flame retardant irradiation crosslinked polyolefin cable material according to claim 8, wherein the irradiation crosslinking process in the step (3) is to adopt Co 60 The gamma rays are used as high-energy rays and are radiated in a nitrogen atmosphere, and the radiation dosage is 6-18Mrad.
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