CN110760140B - Flame-retardant cable insulating material and preparation method thereof - Google Patents
Flame-retardant cable insulating material and preparation method thereof Download PDFInfo
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- CN110760140B CN110760140B CN201911010754.4A CN201911010754A CN110760140B CN 110760140 B CN110760140 B CN 110760140B CN 201911010754 A CN201911010754 A CN 201911010754A CN 110760140 B CN110760140 B CN 110760140B
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- 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 70
- 239000003063 flame retardant Substances 0.000 title claims abstract description 70
- 239000011810 insulating material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 51
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 21
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 17
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 15
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 15
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 13
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims abstract description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004633 polyglycolic acid Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000012774 insulation material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 34
- 238000005303 weighing Methods 0.000 claims description 32
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 31
- 239000000347 magnesium hydroxide Substances 0.000 claims description 31
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 3
- 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 group 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 claims description 2
- 230000032683 aging Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
-
- 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
- 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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
Abstract
The invention discloses a flame-retardant cable insulating material and a preparation method thereof, and belongs to the technical field of cable materials. The flame-retardant cable insulating material is prepared from the following components in parts by weight: 80-100 parts of polyvinyl chloride, 40-50 parts of epoxy resin, 10-20 parts of butyl acrylate, 8-15 parts of pentaerythritol, 1-5 parts of sodium lignosulfonate-maleic anhydride graft copolymer, 3-8 parts of methacryloxy silane, 1-5 parts of barium stearate, 30-50 parts of flame retardant, 10-15 parts of antioxidant and 2-3 parts of polyglycolic acid. The material is based on polyvinyl chloride and epoxy resin, and is added with other various raw materials to act together, so that the cable insulation material with good mechanical property, high temperature resistance, aging resistance and excellent flame retardant property is prepared.
Description
Technical Field
The invention relates to an insulated cable material, in particular to a flame-retardant insulated cable material, and belongs to the technical field of cable materials.
Background
With the development of society, the information technology is rapidly advanced, the comprehensive wiring is the basis of information transmission in buildings, the power cables are various in selection, and the demand is increased continuously. The power cable as an information transmission channel is mainly laid in indoor places such as commercial districts, residential districts and industrial districts, once the indoor fire occurs, flame can rapidly spread and expand along with the cable line, so that not only is information transmission obstructed, but also life and property safety is seriously threatened. Once a fire occurs in a building, heat and toxic gas released by the cables become important safety hazards, and people become more and more important topics in the industry for flame retardance and fire prevention of power cables.
The cable material must be resistant to sun exposure, UV radiation, ozone aging, chemical attack, while still ensuring or temporarily ensuring its normal operation in the event of an unexpected disaster. With the frequent occurrence of electrical fire accidents, the flame retardant problem of the electric wire and the cable gradually draws attention from all countries in the world; the cable releases a large amount of smoke and toxic and corrosive gas during burning, which are dangerous factors in fire, prevents people from safely evacuating and extinguishing fire in the fire, and seriously loses lives and properties. . The cable material is generally made of polyvinyl chloride, has a series of advantages of good mechanical property, excellent electrical property, chemical resistance, cold resistance, oil resistance and the like, and is an ideal industrial wire and cable material. However, the conventional polyvinyl chloride materials have poor aging resistance and flame retardant property and reduced safety, which limits the application thereof.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a flame-retardant cable insulating material, which is prepared by taking polyvinyl chloride and epoxy resin as the basis and adding other various raw materials for combined action, and has good mechanical property, aging resistance and excellent flame retardance.
The invention also provides a preparation method of the flame-retardant insulated cable material.
The invention adopts the following technical scheme:
a flame-retardant cable insulating material is prepared from the following raw materials in parts by weight: 80-100 parts of polyvinyl chloride, 40-50 parts of epoxy resin, 10-20 parts of butyl acrylate, 8-15 parts of pentaerythritol, 1-5 parts of sodium lignosulfonate-maleic anhydride graft copolymer, 3-8 parts of methacryloxy silane, 1-5 parts of barium stearate, 30-50 parts of flame retardant, 10-15 parts of antioxidant and 2-3 parts of polyglycolic acid;
the flame retardant is prepared by adopting the following method: respectively weighing dodecamolybdophosphate and magnesium hydroxide, putting the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.3-0.8: 1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature for 1 hour at a high speed, cooling to room temperature, and drying to obtain the dodecamolybdophosphate and magnesium hydroxide.
Preferably, the antioxidant is antioxidant 1010.
Preferably, the flame-retardant cable insulating material is prepared from the following raw materials in parts by weight: 90 parts of polyvinyl chloride, 45 parts of epoxy resin, 15 parts of butyl acrylate, 12 parts of pentaerythritol, 3 parts of a sodium lignosulfonate-maleic anhydride graft copolymer, 5 parts of methacryloxy silane, 3 parts of barium stearate, 40 parts of a flame retardant, 12 parts of an antioxidant and 2.5 parts of polyglycolic acid.
The sodium lignosulfonate-maleic anhydride graft copolymer is prepared by the following method: weighing 10g of sodium lignosulphonate, dissolving in 100ml of distilled water, pouring into a reaction bottle, adding 0.25g of sodium bisulfite and 0.5g of ammonium persulfate, and uniformly stirring at room temperature to obtain a mixed solution A; weighing 10g of maleic anhydride and ammonia water with equal mass, stirring and mixing at room temperature for reaction for 30-40 minutes to obtain a mixed solution B, then uniformly mixing the mixed solution A and the mixed solution B, controlling the reaction temperature to be 45 ℃, reacting for 2 hours, then precipitating, filtering, washing and drying a reaction product at 45 ℃ to constant weight.
A preparation method of a flame-retardant cable insulating material comprises the following steps:
(1) weighing 10g of sodium lignosulphonate, dissolving in 100ml of distilled water, pouring into a reaction bottle, adding 0.25g of sodium bisulfite and 0.5g of ammonium persulfate, and uniformly stirring at room temperature to obtain a mixed solution A; weighing 10g of maleic anhydride and ammonia water with equal mass, stirring and mixing at room temperature for reaction for 30-40 minutes to obtain a mixed solution B, then uniformly mixing the mixed solution A and the mixed solution B, controlling the reaction temperature to be 45 ℃, reacting for 2 hours, then precipitating, filtering, washing and drying a reaction product at 45 ℃ to constant weight to obtain a sodium lignosulfonate-maleic anhydride graft copolymer for later use;
(2) respectively weighing dodecamolybdophosphate and magnesium hydroxide, putting the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.3-0.8: 1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for reaction for 1 hour, cooling to room temperature, and drying to obtain a flame retardant for later use;
(3) weighing polyvinyl chloride, epoxy resin and butyl acrylate according to parts by weight, placing the weighed materials into an internal mixer, internally mixing the materials for 15 minutes at 140 ℃, adding a flame retardant and a sodium lignosulfonate-maleic anhydride graft copolymer after complete melting, continuously internally mixing the materials for 15 minutes, uniformly mixing the materials, then adding pentaerythritol, methacryloxy silane, barium stearate, an antioxidant and polyglycolic acid, continuously internally mixing the materials for 5 minutes, transferring the mixed materials into an extruder, extruding the mixed materials and granulating the mixed materials.
The invention has the beneficial effects that: according to the invention, a proper amount of silane coupling agent is adopted to modify polyoxometallate dodecamolybdyl phosphate and magnesium hydroxide in a specific ratio to obtain a new flame retardant, the flame retardant property of the cable can be greatly improved after the novel flame retardant is added and used, and meanwhile, the cable is good in mechanical property and aging resistance, high in safety and long in service life. Compared with the conventional flame retardant magnesium hydroxide, the flame retardant prepared by the method has greatly improved flame retardant property. In addition, the added sodium lignosulfonate-maleic anhydride graft copolymer and other raw materials act together to obviously improve the thermal stability of the cable insulation material, and the cable insulation material is suitable for being used in a high-temperature environment of not higher than 200 ℃.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A flame-retardant cable insulating material is prepared from the following raw materials in parts by weight: 80 parts of polyvinyl chloride, 40 parts of epoxy resin, 10 parts of butyl acrylate, 8 parts of pentaerythritol, 1 part of sodium lignosulfonate-maleic anhydride graft copolymer, 3 parts of methacryloxy silane, 1 part of barium stearate, 30 parts of flame retardant, 101010 parts of antioxidant and 2 parts of polyglycolic acid.
The preparation method of the flame-retardant cable insulating material comprises the following steps:
(1) weighing 10g of sodium lignosulphonate, dissolving in 100ml of distilled water, pouring into a reaction bottle, adding 0.25g of sodium bisulfite and 0.5g of ammonium persulfate, and uniformly stirring at room temperature to obtain a mixed solution A; weighing 10g of maleic anhydride and ammonia water with equal mass, stirring and mixing at room temperature for reaction for 30-40 minutes to obtain a mixed solution B, then uniformly mixing the mixed solution A and the mixed solution B, controlling the reaction temperature to be 45 ℃, reacting for 2 hours, then precipitating, filtering, washing and drying a reaction product at 45 ℃ to constant weight to obtain a sodium lignosulfonate-maleic anhydride graft copolymer for later use;
(2) respectively weighing dodecamolybdophosphate and magnesium hydroxide, putting the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.3-0.8: 1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for reaction for 1 hour, cooling to room temperature, and drying to obtain a flame retardant for later use;
(3) weighing polyvinyl chloride, epoxy resin and butyl acrylate according to parts by weight, placing the weighed materials into an internal mixer, internally mixing the materials for 15 minutes at 140 ℃, adding a flame retardant and a sodium lignosulfonate-maleic anhydride graft copolymer after complete melting, continuously internally mixing the materials for 15 minutes, uniformly mixing the materials, then adding pentaerythritol, methacryloxy silane, barium stearate, an antioxidant and polyglycolic acid, continuously internally mixing the materials for 5 minutes, transferring the mixed materials into an extruder, extruding the mixed materials and granulating the mixed materials.
Example 2
A flame-retardant cable insulating material is prepared from the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 50 parts of epoxy resin, 20 parts of butyl acrylate, 15 parts of pentaerythritol, 5 parts of sodium lignosulfonate-maleic anhydride graft copolymer, 8 parts of methacryloxy silane, 5 parts of barium stearate, 50 parts of flame retardant, 101015 parts of antioxidant and 3 parts of polyglycolic acid.
The preparation method of the flame-retardant cable insulating material comprises the following steps:
(1) weighing 10g of sodium lignosulphonate, dissolving in 100ml of distilled water, pouring into a reaction bottle, adding 0.25g of sodium bisulfite and 0.5g of ammonium persulfate, and uniformly stirring at room temperature to obtain a mixed solution A; weighing 10g of maleic anhydride and ammonia water with equal mass, stirring and mixing at room temperature for reaction for 30-40 minutes to obtain a mixed solution B, then uniformly mixing the mixed solution A and the mixed solution B, controlling the reaction temperature to be 45 ℃, reacting for 2 hours, then precipitating, filtering, washing and drying a reaction product at 45 ℃ to constant weight to obtain a sodium lignosulfonate-maleic anhydride graft copolymer for later use;
(2) respectively weighing dodecamolybdophosphate and magnesium hydroxide, putting the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.3-0.8: 1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for reaction for 1 hour, cooling to room temperature, and drying to obtain a flame retardant for later use;
(3) weighing polyvinyl chloride, epoxy resin and butyl acrylate according to parts by weight, placing the weighed materials into an internal mixer, internally mixing the materials for 15 minutes at 140 ℃, adding a flame retardant and a sodium lignosulfonate-maleic anhydride graft copolymer after complete melting, continuously internally mixing the materials for 15 minutes, uniformly mixing the materials, then adding pentaerythritol, methacryloxy silane, barium stearate, an antioxidant and polyglycolic acid, continuously internally mixing the materials for 5 minutes, transferring the mixed materials into an extruder, extruding the mixed materials and granulating the mixed materials.
Example 3
A flame-retardant cable insulating material is prepared from the following raw materials in parts by weight: 90 parts of polyvinyl chloride, 45 parts of epoxy resin, 15 parts of butyl acrylate, 12 parts of pentaerythritol, 3 parts of a sodium lignosulfonate-maleic anhydride graft copolymer, 5 parts of methacryloxy silane, 3 parts of barium stearate, 40 parts of a flame retardant, 12 parts of an antioxidant and 2.5 parts of polyglycolic acid.
The preparation method of the flame-retardant cable insulating material comprises the following steps:
(1) weighing 10g of sodium lignosulphonate, dissolving in 100ml of distilled water, pouring into a reaction bottle, adding 0.25g of sodium bisulfite and 0.5g of ammonium persulfate, and uniformly stirring at room temperature to obtain a mixed solution A; weighing 10g of maleic anhydride and ammonia water with equal mass, stirring and mixing at room temperature for reaction for 30-40 minutes to obtain a mixed solution B, then uniformly mixing the mixed solution A and the mixed solution B, controlling the reaction temperature to be 45 ℃, reacting for 2 hours, then precipitating, filtering, washing and drying a reaction product at 45 ℃ to constant weight to obtain a sodium lignosulfonate-maleic anhydride graft copolymer for later use;
(2) respectively weighing dodecamolybdophosphate and magnesium hydroxide, putting the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.3-0.8: 1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for reaction for 1 hour, cooling to room temperature, and drying to obtain a flame retardant for later use;
(3) weighing polyvinyl chloride, epoxy resin and butyl acrylate according to parts by weight, placing the weighed materials into an internal mixer, internally mixing the materials for 15 minutes at 140 ℃, adding a flame retardant and a sodium lignosulfonate-maleic anhydride graft copolymer after complete melting, continuously internally mixing the materials for 15 minutes, uniformly mixing the materials, then adding pentaerythritol, methacryloxy silane, barium stearate, an antioxidant and polyglycolic acid, continuously internally mixing the materials for 5 minutes, transferring the mixed materials into an extruder, extruding the mixed materials and granulating the mixed materials.
Comparative example 1
The formula and the preparation method of the flame-retardant cable insulating material are the same as those of example 3, and the only difference is that: the flame retardant is magnesium hydroxide.
Comparative example 2
The formula and the preparation method of the flame-retardant cable insulating material are the same as those of example 3, and the only difference is that: the preparation method of the flame retardant comprises the following steps: weighing magnesium hydroxide, placing the magnesium hydroxide into a high-speed mixer, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for reaction for 1 hour, cooling to room temperature, and drying to obtain the flame retardant.
Comparative example 3
The formula and the preparation method of the flame-retardant cable insulating material are the same as those of example 3, and the only difference is that: the preparation method of the flame retardant comprises the following steps: weighing the dodecamolybdic phosphate, putting the dodecamolybdic phosphate into a high-speed mixer, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture into the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for reaction for 1 hour, cooling to room temperature, and drying to obtain the flame retardant.
Comparative example 4
The formula and the preparation method of the flame-retardant cable insulating material are the same as those of example 3, and the only difference is that: the preparation method of the flame retardant comprises the following steps: the preparation method comprises the steps of weighing dodecamolybdophosphate and magnesium hydroxide respectively, placing the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.1:1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for 1 hour, cooling to room temperature, and drying to obtain the flame retardant.
Comparative example 5
The formula and the preparation method of the flame-retardant cable insulating material are the same as those of example 3, and the only difference is that: the preparation method of the flame retardant comprises the following steps: the preparation method comprises the steps of weighing dodecamolybdophosphate and magnesium hydroxide respectively, placing the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.2:1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for 1 hour, cooling to room temperature, and drying to obtain the flame retardant.
Comparative example 6
The formula and the preparation method of the flame-retardant cable insulating material are the same as those of example 3, and the only difference is that: the preparation method of the flame retardant comprises the following steps: the preparation method comprises the steps of weighing dodecamolybdophosphate and magnesium hydroxide respectively, placing the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 1:1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for reaction for 1 hour, cooling to room temperature, and drying to obtain the flame retardant.
Comparative example 7
The formula and the preparation method of the flame-retardant cable insulating material are the same as those of example 3, and the only difference is that: the preparation method of the flame retardant comprises the following steps: the preparation method comprises the steps of weighing dodecamolybdophosphate and magnesium hydroxide respectively, placing the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 1.2:1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for 1 hour, cooling to room temperature, and drying to obtain the flame retardant.
The cable materials of examples 1-3 and comparative examples 1-7 were subjected to performance tests, and the specific test results are shown in table 1. The specific test method of the invention comprises the following steps:
tensile property: the tensile strength and elongation at break were measured according to JIS K6251.
Flame retardancy: the oxygen index was determined according to the GB/T2406 standard.
And (3) testing the vertical burning grade: flammability UL94 rating.
Volume resistivity: the resistivity at 20 ℃ was determined according to GB/T15662-1995 standard.
Hot air aging resistance: the treatment was carried out at 140 ℃ for 200 hours, and then the strength retention was measured.
Table 1 results of performance testing
From the above data, it can be seen that the cable insulation material prepared by the present invention has better mechanical properties, flame retardancy, insulation properties, high temperature resistance and aging resistance than the product prepared by using conventional magnesium hydroxide, modified polyoxometallate and other ranges of magnesium hydroxide and dodecamolybdophosphate mixed modification.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make many changes or modifications to the equivalent embodiments without departing from the scope of the present invention.
Claims (5)
1. The flame-retardant cable insulating material is characterized by being prepared from the following raw materials in parts by weight: 80-100 parts of polyvinyl chloride, 40-50 parts of epoxy resin, 10-20 parts of butyl acrylate, 8-15 parts of pentaerythritol, 1-5 parts of sodium lignosulfonate-maleic anhydride graft copolymer, 3-8 parts of methacryloxy silane, 1-5 parts of barium stearate, 30-50 parts of flame retardant, 10-15 parts of antioxidant and 2-3 parts of polyglycolic acid;
the flame retardant is prepared by adopting the following method: respectively weighing dodecamolybdophosphate and magnesium hydroxide, putting the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.3-0.8: 1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature for 1 hour at a high speed, cooling to room temperature, and drying to obtain the dodecamolybdophosphate and magnesium hydroxide.
2. The flame retardant cable insulation of claim 1, wherein said antioxidant is antioxidant 1010.
3. The flame-retardant cable insulation material according to claim 1, characterized in that it is prepared from the following raw materials in parts by weight: 90 parts of polyvinyl chloride, 45 parts of epoxy resin, 15 parts of butyl acrylate, 12 parts of pentaerythritol, 3 parts of a sodium lignosulfonate-maleic anhydride graft copolymer, 5 parts of methacryloxy silane, 3 parts of barium stearate, 40 parts of a flame retardant, 12 parts of an antioxidant and 2.5 parts of polyglycolic acid.
4. The flame retardant cable insulation of claim 1 or 3 wherein said sodium lignosulfonate-maleic anhydride graft copolymer is prepared by the following method: weighing 10g of sodium lignosulphonate, dissolving in 100ml of distilled water, pouring into a reaction bottle, adding 0.25g of sodium bisulfite and 0.5g of ammonium persulfate, and uniformly stirring at room temperature to obtain a mixed solution A; weighing 10g of maleic anhydride and ammonia water with equal mass, stirring and mixing at room temperature for reaction for 30-40 minutes to obtain a mixed solution B, then uniformly mixing the mixed solution A and the mixed solution B, controlling the reaction temperature to be 45 ℃, reacting for 2 hours, then precipitating, filtering, washing and drying a reaction product at 45 ℃ to constant weight.
5. A method for preparing the flame retardant cable insulation material of claim 1, comprising the steps of:
(1) weighing 10g of sodium lignosulphonate, dissolving in 100ml of distilled water, pouring into a reaction bottle, adding 0.25g of sodium bisulfite and 0.5g of ammonium persulfate, and uniformly stirring at room temperature to obtain a mixed solution A; weighing 10g of maleic anhydride and ammonia water with equal mass, stirring and mixing at room temperature for reaction for 30-40 minutes to obtain a mixed solution B, then uniformly mixing the mixed solution A and the mixed solution B, controlling the reaction temperature to be 45 ℃, reacting for 2 hours, then precipitating, filtering, washing and drying a reaction product at 45 ℃ to constant weight to obtain a sodium lignosulfonate-maleic anhydride graft copolymer for later use;
(2) respectively weighing dodecamolybdophosphate and magnesium hydroxide, putting the dodecamolybdophosphate and the magnesium hydroxide into a high-speed mixer according to the weight ratio of 0.3-0.8: 1, stirring at a high speed for 10-15 minutes at 100 ℃, then adding a silane coupling agent KH550 accounting for 2% of the total weight of the mixture, controlling the temperature to be 120-130 ℃, stirring at a constant temperature at a high speed for reaction for 1 hour, cooling to room temperature, and drying to obtain a flame retardant for later use;
(3) weighing polyvinyl chloride, epoxy resin and butyl acrylate according to parts by weight, placing the weighed materials into an internal mixer, internally mixing the materials for 15 minutes at 140 ℃, adding a flame retardant and a sodium lignosulfonate-maleic anhydride graft copolymer after complete melting, continuously internally mixing the materials for 15 minutes, uniformly mixing the materials, then adding pentaerythritol, methacryloxy silane, barium stearate, an antioxidant and polyglycolic acid, continuously internally mixing the materials for 5 minutes, transferring the mixed materials into an extruder, extruding the mixed materials and granulating the mixed materials.
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