CN114516985B - Insulating coating material and application thereof - Google Patents
Insulating coating material and application thereof Download PDFInfo
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- CN114516985B CN114516985B CN202210190950.XA CN202210190950A CN114516985B CN 114516985 B CN114516985 B CN 114516985B CN 202210190950 A CN202210190950 A CN 202210190950A CN 114516985 B CN114516985 B CN 114516985B
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- flame retardant
- insulating coating
- coating material
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- ultraviolet crosslinking
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- 239000000463 material Substances 0.000 title claims abstract description 101
- 239000011248 coating agent Substances 0.000 title claims abstract description 71
- 238000000576 coating method Methods 0.000 title claims abstract description 71
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003063 flame retardant Substances 0.000 claims abstract description 60
- 238000004132 cross linking Methods 0.000 claims abstract description 40
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 230000002195 synergetic effect Effects 0.000 claims abstract description 26
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 8
- 239000004698 Polyethylene Substances 0.000 claims abstract description 6
- -1 polyethylene Polymers 0.000 claims abstract description 6
- 229920000573 polyethylene Polymers 0.000 claims abstract description 6
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 4
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 3
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 32
- 229920002379 silicone rubber Polymers 0.000 claims description 32
- 239000004945 silicone rubber Substances 0.000 claims description 32
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 31
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 31
- 239000000347 magnesium hydroxide Substances 0.000 claims description 31
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 25
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012965 benzophenone Substances 0.000 claims description 9
- 239000004640 Melamine resin Substances 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 3
- LGRQUXHYJBFGTM-UHFFFAOYSA-N 4H-imidazole Chemical compound C1C=NC=N1 LGRQUXHYJBFGTM-UHFFFAOYSA-N 0.000 claims description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 230000032683 aging Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 238000011056 performance test Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003878 thermal aging Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 101100389815 Caenorhabditis elegans eva-1 gene Proteins 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012815 thermoplastic material 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
-
- 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
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- 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
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Conductors (AREA)
Abstract
The invention provides an insulating coating material and application thereof, and relates to the technical field of power cable sheath materials. The insulating coating material provided by the invention comprises the following components in parts by weight: 35-45 parts of linear low-density polyethylene, 35-45 parts of ethylene-octene copolymer, 10-35 parts of ethylene-vinyl acetate copolymer, 5-10 parts of polyethylene grafted maleic anhydride, 150 parts of flame retardant, 7-12 parts of synergistic flame retardant and the like. According to the invention, the specific flame retardant, the synergistic flame retardant and the ultraviolet crosslinking agent are introduced on the basis of the existing cable sheath material base resin, and the synergistic effect among the components is achieved, so that the prepared insulating coating material has excellent flame retardant property, can meet the GB 32147B1 level flame retardant requirement, can realize ultraviolet crosslinking, and can meet the material temperature-resistant 105 ℃ level requirement after crosslinking.
Description
Technical Field
The invention relates to the technical field of power cable sheath materials, in particular to an insulating coating material and application thereof.
Background
The low-smoke halogen-free flame-retardant sheath cable material is generally a thermoplastic material, and the temperature resistance grade is about 90 ℃ and cannot meet the requirements of some high-temperature scenes. In order to improve the high temperature resistance of the cable material, the material can be subjected to crosslinking modification treatment. However, compared with GB/T19666 and GB/T17651, the GB/T31247 B1 level flame retardant has higher requirements on heat release and smoke release performance of the sheath material, and the traditional sheath material is difficult to meet. In addition, the low-smoke halogen-free sheath cable material can seriously influence the ultraviolet crosslinking efficiency due to the fact that the addition amount of the flame retardant is large, so that the crosslinking degree is unqualified.
Disclosure of Invention
In order to solve the above-mentioned problems in the prior art, a main object of the present invention is to provide an insulating coating material and application thereof.
In order to achieve the above purpose, in a first aspect, the invention provides an insulating coating material, which comprises the following components in parts by weight:
wherein the flame retardant is a compound of aluminum hydroxide and magnesium hydroxide, the aluminum hydroxide is silane coated aluminum hydroxide, and the magnesium hydroxide is silane coated magnesium hydroxide;
the synergistic flame retardant is a compound of red phosphorus master batch and methyl vinyl silicone rubber, and the red phosphorus master batch is a coated red phosphorus master batch coated by amine resin;
the ultraviolet crosslinking agent is at least one of imidazole ultraviolet crosslinking agents and benzophenone ultraviolet crosslinking agents.
In the technical scheme of the invention, the flame retardant adopts magnesium hydroxide and aluminum hydroxide which are subjected to surface coating treatment by silane to be used together. The inventor finds through a large number of experiments that the heat release value of the prepared insulating coating material is too high due to the fact that aluminum hydroxide is used as a flame retardant singly; however, the magnesium hydroxide alone used as a flame retardant can affect the crosslinking degree of the insulating coating material and further affect the high temperature resistance of the insulating coating material, although the magnesium hydroxide has a good effect of reducing the heat release of the material. The two can play a role in mutual synergy when being used in a compounding way.
In the technical scheme of the invention, the synergistic flame retardant is compounded by adopting special coated red phosphorus master batch and methyl vinyl silicone rubber. On one hand, the silicon-phosphorus synergistic flame retardance is favorable for the material to form a flame retardant material with low heat release and high char formation, and the cable structure can be effectively protected in the B1 bunching combustion process; on the other hand, the methyl vinyl silicone rubber contains unsaturated groups, which is favorable for crosslinking the material under the ultraviolet initiation condition, thereby promoting the ultraviolet crosslinking agent to exert stable crosslinking effect in the system.
In the technical scheme of the invention, at least one of imidazole ultraviolet crosslinking agents and benzophenone ultraviolet crosslinking agents is selected as the ultraviolet crosslinking agent, and compared with other types of ultraviolet crosslinking agents, the ultraviolet crosslinking agent has high activity, can play a better crosslinking role in flame-retardant cable materials containing a large amount of fillers, and is easier to crosslink under the condition of a large amount of fillers.
According to the technical scheme, the specific flame retardant, the synergistic flame retardant and the ultraviolet crosslinking agent are introduced on the basis of the existing cable sheath material base resin, and the components are synergistic, so that the prepared insulating coating material is excellent in flame retardant property, can meet the GB 32147B1 level flame retardant requirement, can realize ultraviolet crosslinking, and can meet the 105 ℃ level requirement of material temperature resistance after crosslinking.
The specific preparation method of the red phosphorus master batch used in the invention is a conventional synthesis method in the field, and specifically comprises the following steps: preparing melamine and formaldehyde into transparent melamine-formaldehyde prepolymer for standby under alkaline condition; mixing superfine red phosphorus with melamine-formaldehyde prepolymer according to the following proportion of (3-5): 1, uniformly mixing and stirring to obtain a uniformly dispersed red phosphorus/melamine-formaldehyde mixture; adding a certain amount of emulsifying agent into the grease, and uniformly stirring and dispersing for later use; adding red phosphorus/melamine-formaldehyde mixture into oil containing an emulsifier, and stirring to obtain stable suspension; adding acid into the suspension while stirring at constant temperature until the reaction is completed, filtering, washing the obtained solid substance with ethyl acetate, and drying at constant temperature of 60-100 ℃ in a vacuum drying oven to obtain melamine resin microencapsulated red phosphorus; microencapsulating red phosphorus by melamine resin: eva= (70-90): (10-20) adding melamine resin microencapsulated red phosphorus and EVA into an internal mixer for banburying to a material temperature of 110-130 ℃, discharging, and granulating by a single screw at a granulating temperature of 90-110 ℃ to obtain the red phosphorus master batch.
As a preferred embodiment of the insulating coating material of the present invention, the weight ratio of aluminum hydroxide to magnesium hydroxide in the flame retardant is aluminum hydroxide: magnesium hydroxide= (1.5-4): 1.
The heat release amount of the insulating coating material can be further reduced by optimizing the weight ratio of aluminum hydroxide and magnesium hydroxide in the flame retardant. The inventor finds out through a plurality of experiments that when the weight ratio of the aluminum hydroxide to the magnesium hydroxide in the flame retardant is (1.5-4): 1, the heat release peak value and the total heat release amount of the prepared insulating coating material are lower.
As a preferred embodiment of the insulating coating material of the present invention, the weight ratio of aluminum hydroxide to magnesium hydroxide in the flame retardant is aluminum hydroxide: magnesium hydroxide= (2-3): 1.
The inventors have found through a large number of experiments that when the weight ratio of aluminum hydroxide to magnesium hydroxide in the flame retardant is (2-3): 1, the peak heat release and the total heat release amount of the prepared insulating coating material can be further reduced.
As a preferred embodiment of the insulating coating material, the weight ratio of the red phosphorus master batch to the methyl vinyl silicone rubber in the synergistic flame retardant is that: methyl vinyl silicone rubber= (1-3): 1.
The weight ratio of the red phosphorus master batch to the methyl vinyl silicone rubber in the synergistic flame retardant has a great influence on the heat release amount of the insulating coating material. When the weight ratio of the red phosphorus master batch to the methyl vinyl silicone rubber in the synergistic flame retardant is (1-3): 1, the prepared insulating coating material shows lower heat release peak value and total heat release amount.
As a preferred embodiment of the insulating coating material of the present invention, the weight ratio of the methyl vinyl silicone rubber to the ultraviolet crosslinking agent in the synergistic flame retardant is that of methyl vinyl silicone rubber: ultraviolet crosslinking agent= (1.5-2): 1.
The inventor finds that the weight ratio of the methyl vinyl silicone rubber to the ultraviolet crosslinking agent has larger influence on the tensile strength change rate and the elongation at break change rate before and after heat aging after crosslinking of the insulating coating material through a large number of experiments. When the weight ratio of the methyl vinyl silicone rubber to the ultraviolet crosslinking agent is (1.5-2): 1, the absolute value of the tensile strength change rate and the elongation at break change rate before and after heat aging after crosslinking of the corresponding insulating coating material is lower, and the thermal aging resistance of the material is better.
As a preferred embodiment of the insulating coating material of the present invention, the imidazole-based uv-crosslinking agent is at least one of 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl 1, 2-diimidazole, 1, 3-diazacyclopentadiene, 2-methyl-1, 3-azole; the benzophenone ultraviolet crosslinking agent is at least one of benzophenone and 4-phenylbenzophenone.
As a preferred embodiment of the insulating coating material of the present invention, the methyl vinyl silicone rubber has a vinyl group content of 0.10 to 0.15% as measured according to GB/T36691-2018.
The vinyl content of the methyl vinyl silicone rubber affects the tensile strength change rate and the elongation at break change rate before and after heat aging after crosslinking of the insulating coating material. The inventor finds that the insulating coating material prepared by methyl vinyl silicone rubber with the vinyl content of 0.10-0.15 percent can show more excellent heat aging resistance after being crosslinked through a large number of experiments.
As a preferred embodiment of the insulating coating material according to the present invention, the processing aid is at least one of an antioxidant and a lubricant.
As a preferred embodiment of the insulating coating material, the antioxidant is at least one of antioxidant 1010 and antioxidant 168; the lubricant is at least one of calcium stearate, polyethylene wax, silicone oil and silicone master batch.
In a second aspect, the invention also provides an application of the insulating coating material in preparing a power cable sheath material.
Compared with the prior art, the invention has the beneficial effects that:
according to the technical scheme, the specific flame retardant, the synergistic flame retardant and the ultraviolet crosslinking agent are introduced on the basis of the existing cable sheath material base resin, and the components are synergistic, so that the prepared insulating coating material is excellent in flame retardant property, can meet the GB 32147B1 level flame retardant requirement, can realize ultraviolet crosslinking, and can meet the 105 ℃ level requirement of material temperature resistance after crosslinking.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described by means of specific examples.
The raw material sources of the examples and comparative examples of the present invention are as follows:
1. linear Low Density Polyethylene (LLDPE)
LLDPE-1: melt mass flow rate was 3g/min, brand LLDPE 3518PA, available from Exxon;
LLDPE-2: melt mass flow rate was 4.5g/min, brand LLDPE 4536PA, available from Exxon;
2. ethylene-octene copolymer (POE)
POE-1: the melt mass flow rate was 1g/min, brand POE 8100, available from Dow chemical;
POE-2: melt mass flow rate 5g/min, brand POE 8200, available from Dow chemical;
3. ethylene-vinyl acetate copolymer (EVA)
EVA-1: melt mass flow rate was 3g/min, grade EVA UL00328, available from Exxon;
EVA-2: melt mass flow rate 7g/min, grade EVA UL00728, available from Exxon;
4. polyethylene grafted maleic anhydride (PE-g-MAH)
PE-g-MAH-1: the trade name MC218, light available from energy;
PE-g-MAH-2: the trade name is MC226, light available from energy sources;
5. flame retardant
1. Aluminum hydroxide
Aluminum hydroxide a: the D50 particle size is 2 mu m without modification treatment, and the brand is AH-01DG, and the modified aluminum is purchased from the Zhonger aluminum industry;
aluminum hydroxide B: the aluminum hydroxide is subjected to surface coating treatment by adopting silane, the D50 particle size of the coated magnesium hydroxide is about 2 mu m, and the brand is AH-01DGM, and the magnesium hydroxide is purchased from the Zhonger aluminum industry;
2. magnesium hydroxide
Magnesium hydroxide a: without modification, the D50 particle size was 2 μm, and the brand was Aitemag 14, purchased from Jiangsu Ai Teke;
magnesium hydroxide B: the magnesium hydroxide is subjected to surface coating treatment by adopting silane, and the D50 particle size of the magnesium hydroxide after the coating treatment is about 2 mu m, and the magnesium hydroxide is sold under the trademark Aitemag 14FD and is purchased from Ai Teke company;
3. other inorganic flame retardants in general
Zinc borate: the brand Estone ZB-03 is purchased from Anhui Yishitong;
6. synergistic flame retardant
1. Red phosphorus master batch: homemade, red phosphorus content is 75%;
2. methyl vinyl silicone rubber
Methyl vinyl silicone rubber a: vinyl content 0.07%, brand 110-1A, available from Dongjue silicone;
methyl vinyl silicone rubber B: vinyl content of 0.10%, brand 110-1B, available from Dongjue silicone;
methyl vinyl silicone rubber C: vinyl content of 0.15%, brand 110-2A, available from Dongjue silicone;
methyl vinyl silicone rubber D: vinyl content 0.18%, brand 110-2B, available from Dongjue silicone;
7. ultraviolet crosslinking agent
1. Imidazole ultraviolet crosslinking agent
2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl 1, 2-diimidazole: the brand B-CIM is purchased from Shanghai Ala Latin;
1, 3-diazacyclopentadiene, purchased from Shanghai Ala-dine;
2-methyl-1, 3-azole, trade name 2MZ-CN, available from brillouin, japan;
2. benzophenone ultraviolet crosslinking agent
Benzophenone: the brand is BP, purchased from Jiangyin Yuxing;
4-phenylbenzophenone: purchased from Shanghai Ala;
3. other types of uv crosslinking agents
4, 6-trimethylbenzoyl) -phenylphosphine oxide, available under the trade designation Irgacure 819 from Beijing Yili Fine chemical Co., ltd;
8. processing aid
1. An antioxidant: the antioxidant 1010 and the antioxidant 168 are mixed according to the weight ratio of 1:1, and the antioxidant 1010 and the antioxidant 168 are all commercial products;
2. lubricant
Calcium stearate: are commercially available;
polyethylene wax: are commercially available.
In the following examples and comparative examples, antioxidants and lubricants were obtained commercially, and the same were used in parallel experiments unless otherwise specified.
The specific preparation method of the red phosphorus master batch used in the embodiment and the comparative example comprises the following steps: preparing melamine and formaldehyde into transparent melamine-formaldehyde prepolymer for standby under alkaline condition; mixing superfine red phosphorus with melamine-formaldehyde prepolymer according to a proportion of 4:1, uniformly mixing and stirring to obtain a uniformly dispersed red phosphorus/melamine-formaldehyde mixture; adding a certain amount of emulsifying agent into the grease, and uniformly stirring and dispersing for later use; adding red phosphorus/melamine-formaldehyde mixture into oil containing an emulsifier, and stirring to obtain stable suspension; adding acid into the suspension while stirring at constant temperature until the reaction is completed, filtering, washing the obtained solid substance with ethyl acetate, and drying at constant temperature of 70 ℃ in a vacuum drying oven to obtain melamine resin microencapsulated red phosphorus; microencapsulating red phosphorus by melamine resin: eva=85: 15, the melamine resin microencapsulated red phosphorus and EVA are put into an internal mixer for banburying to a material temperature of 120 ℃, and then are discharged, and the red phosphorus master batch is prepared through single screw granulation, wherein the granulation temperature is 90-110 ℃.
The relevant performance test criteria or methods in the examples and comparative examples of the present invention are shown in table 1. The samples were prepared as follows: the insulating coating materials prepared in each example and comparative example are pressed into tablets at 180 ℃ for 10min on a flat vulcanizing machine, the pressure is 15Mpa, the thickness of the sample tablet is 1mm, the ultraviolet irradiation crosslinking is prepared,
(1) The ultraviolet crosslinking method comprises the following steps: the UV lamp with the total power of 18KW irradiates for 5 seconds to realize crosslinking, the crosslinking is cooled to normal temperature, and the heat release peak value and the total heat release amount of the test material are carried out after the test material is placed for 16 hours;
(2) Thermal extension test method: according to the steps specified in GB/T2951.21-2008;
(3) The thermal aging test method comprises the following steps: the test was carried out after aging at 136℃for 168 hours according to the test method in GB/T32129-2015.
TABLE 1 Performance test Standard
Note that: (1) The heat release peak value and the total heat release amount in the application reflect the flame retardant property of the material, and when the heat release peak value and the total heat release amount are qualified, the material passes the B1-level flame retardant requirement;
(2) After crosslinking, the thermal elongation reaches the standard, the corresponding material can realize good ultraviolet crosslinking, and the lower the thermal elongation is, the higher the crosslinking degree is;
(3) The change rate of the tensile strength and the change rate of the elongation at break before and after heat aging reach the standard, so that the heat aging resistance of the material is good, and the grade requirement of the heat resistance of 105 ℃ is met; the lower the absolute values of the tensile strength change rate and the elongation at break change rate are, the better.
The preparation method of the insulating coating material in the embodiment and the comparative example comprises the following steps: mixing the raw materials in an internal mixer according to a proportion, discharging after mixing until the temperature of the raw materials is 145-160 ℃ and mixing for more than 10 minutes, and then adding the raw materials into a single-screw granulator, wherein the rotating speed of the screw of the single-screw granulator is controlled to be 50rpm, and the length-diameter ratio is controlled to be 20:1, granulating by adopting an air-cooled die face granulating mode at the temperature of 120 ℃ to obtain the insulating coating material.
The components of examples 1-5 and comparative examples 1-5 are shown in Table 2 below, and the amounts of the respective components are in parts by weight; the corresponding performance test results are shown in table 3.
TABLE 2 composition of examples 1-5, comparative examples 1-5
TABLE 3 Performance test results for examples 1-5, comparative examples 1-5
As can be seen from tables 2 and 3, the insulating coating materials prepared in examples 1 to 5 satisfy the requirements of B1 flame retardance, the thermal elongation before and after ultraviolet crosslinking is less than or equal to 100%, and the tensile strength change rate and the elongation at break change rate of the insulating coating materials before and after thermal aging reach the standards, thereby satisfying the class requirement of temperature resistance of 105 ℃.
Compared with the example 1, the comparative example 1 adopts zinc borate to replace aluminum hydroxide B, and the correspondingly prepared insulating coating material does not meet the B1-grade flame retardant requirement;
compared with the embodiment 1, the flame retardant in the comparative example 2 adopts aluminum hydroxide and magnesium hydroxide which are not coated, the flame retardance of the insulating coating material prepared correspondingly is obviously reduced, the B1-level flame retardance requirement is not met, and meanwhile, the heat aging resistance of the material is reduced, and the heat aging resistance requirement is not met;
compared with the embodiment 1, the red phosphorus master batch is not added in the synergistic flame retardant in the comparative example 3, and the correspondingly prepared insulating coating material does not meet the B1-level flame retardant requirement;
compared with the embodiment 1, the methyl vinyl silicone rubber is not added in the synergistic flame retardant in the comparative example 4, the correspondingly prepared insulating coating material does not meet the B1-level flame retardant requirement, the crosslinking degree is reduced, and the ultraviolet crosslinking requirement is not met;
compared with example 1, the type of the ultraviolet crosslinking agent in comparative example 5 is different, the heat release peak value of the insulating coating material prepared in comparative example 5 does not reach the standard, the crosslinking degree is reduced, the ultraviolet crosslinking requirement is not met, and in addition, the heat aging resistance of the insulating coating material prepared in comparative example 5 is low, and the heat aging resistance requirement is not met.
The influence of the weight ratio of aluminum hydroxide and magnesium hydroxide in the flame retardant on the performance of the insulating coating material was examined with example 1 as a reference object. The conditions of the related components are shown in the following table 4, and the amounts of the components are calculated according to parts by weight; the corresponding performance test results are shown in table 5.
TABLE 4 composition of examples 1, 6-11
TABLE 5 Performance test results for examples 1, 6-11
As is clear from tables 4 and 5, the peak heat release and the total heat release amounts of the insulating coating materials corresponding to examples 8 and 9 were the lowest in the above examples; next, the peak heat release and total heat release amounts of the insulating coating materials corresponding to examples 1, 7, and 10 were also lower, but higher than those of the insulating coating materials corresponding to examples 8 and 9; the peak heat release and the total amount of heat release of the insulating coating material corresponding to examples 6 and 11 are highest in the above examples. Thus, it was revealed that when the weight ratio of aluminum hydroxide to magnesium hydroxide in the flame retardant was (2-3): 1, the peak heat release and the total amount of heat release of the prepared insulating coating material exhibited the lowest value under the same conditions, i.e., the flame retardant property of the insulating coating material was more excellent.
Taking example 2 as a reference object, the influence of the weight ratio of the red phosphorus master batch and the methyl vinyl silicone rubber in the synergistic flame retardant on the performance of the insulating coating material is examined. The conditions of the related components are shown in the following table 6, and the weight parts of the components are used; the corresponding performance test results are shown in table 7.
TABLE 6 composition of examples 2, 12-15
TABLE 7 Performance test results for examples 2, 12-15
As is clear from tables 6 and 7, the peak heat release and the total heat release amounts of the insulating coating materials according to examples 2 and 13 to 14 were lower than those of the insulating coating materials according to examples 12 and 15. Therefore, the weight ratio of the two components composing the synergistic flame retardant in the invention has larger influence on the heat release amount of the insulating coating material. When the weight ratio of the red phosphorus master batch to the methyl vinyl silicone rubber in the synergistic flame retardant is (1-3): 1, the prepared insulating coating material can show lower heat release peak value and total heat release amount.
Taking the example 2 as a reference object, the influence of the weight ratio of the methyl vinyl silicone rubber and the ultraviolet crosslinking agent in the synergistic flame retardant on the performance of the insulating coating material is examined. The conditions of the related components are shown in the following table 8, and the weight parts of the components are used; the corresponding performance test results are shown in table 9.
TABLE 8 composition of examples 2, 16-19
TABLE 9 Performance test results for examples 2, 16-19
As is clear from tables 8 and 9, the absolute values of the tensile strength change rate and the elongation at break change rate before and after heat aging after crosslinking of the insulating coating material according to examples 2 and 17 to 18 are smaller than the absolute values of the tensile strength change rate and the elongation at break change rate before and after heat aging after crosslinking of the insulating coating material according to examples 16 and 19. In the technical scheme, when the weight ratio of the methyl vinyl silicone rubber to the ultraviolet crosslinking agent is (1.5-2): 1, the tensile strength change rate and the elongation at break change rate of the prepared insulating coating material before and after heat aging after crosslinking can be further reduced, so that the new heat aging resistance performance of the material is improved.
The effect of vinyl content in methyl vinyl silicone rubber on the performance of the insulating coating material was examined with reference to example 5. The conditions of the related components are shown in the following table 10, and the amounts of the components are calculated according to parts by weight; the corresponding performance test results are shown in table 11.
TABLE 10 composition of examples 5, 20-22
TABLE 11 Performance test results for examples 5, 20-22
As is clear from tables 10 and 11, the absolute values of the tensile strength change rate and the elongation at break change rate before and after heat aging after crosslinking of the insulating clad materials prepared in examples 5 and 21 were significantly lower than the absolute values of the tensile strength change rate and the elongation at break change rate before and after heat aging after crosslinking of the insulating clad materials prepared in examples 20 and 22. The vinyl content of the methyl vinyl silicone rubber in the synergistic flame retardant has great influence on the tensile strength change rate and the elongation at break change rate before and after heat aging after crosslinking of the insulating coating material, and the too low or too high vinyl content of the methyl vinyl silicone rubber is unfavorable for improving the heat aging resistance of the material.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The ultraviolet crosslinking type insulating coating material is characterized by comprising the following components in parts by weight:
35-45 parts of linear low density polyethylene
35-45 parts of ethylene-octene copolymer
10-35 parts of ethylene-vinyl acetate copolymer
5-10 parts of polyethylene grafted maleic anhydride
150 parts of flame retardant
7-12 parts of synergistic flame retardant
1-4 parts of ultraviolet crosslinking agent
2-4 parts of processing aid;
wherein the flame retardant is a compound of aluminum hydroxide and magnesium hydroxide, the aluminum hydroxide is silane coated aluminum hydroxide, and the magnesium hydroxide is silane coated magnesium hydroxide;
the synergistic flame retardant is a compound of red phosphorus master batch and methyl vinyl silicone rubber, and the red phosphorus master batch is a coated red phosphorus master batch coated by melamine resin;
the ultraviolet crosslinking agent is at least one of imidazole ultraviolet crosslinking agents and benzophenone ultraviolet crosslinking agents;
the synergistic flame retardant comprises the following red phosphorus master batches in percentage by weight: methyl vinyl silicone rubber= (1-3): 1;
the methyl vinyl silicone rubber has vinyl molar content of 0.10-0.15% measured according to GB/T36691-2018;
the weight ratio of the aluminum hydroxide to the magnesium hydroxide in the flame retardant is that: magnesium hydroxide= (1.5-4): 1.
2. The ultraviolet crosslinking type insulating coating material according to claim 1, wherein the weight ratio of aluminum hydroxide to magnesium hydroxide in the flame retardant is: magnesium hydroxide= (2-3): 1.
3. The ultraviolet crosslinking type insulating coating material according to claim 1, wherein the weight ratio of the methyl vinyl silicone rubber in the synergistic flame retardant to the ultraviolet crosslinking agent is that of the methyl vinyl silicone rubber: ultraviolet crosslinking agent= (1.5-2): 1.
4. The ultraviolet crosslinking type insulating coating material according to claim 1, wherein the imidazole type ultraviolet crosslinking agent is at least one of 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl 1, 2-diimidazole, 1, 3-diazacyclopentadiene and 2-methyl-1, 3-azole; the benzophenone ultraviolet crosslinking agent is at least one of benzophenone and 4-phenylbenzophenone.
5. The ultraviolet crosslinking type insulating coating material according to claim 1, wherein the processing aid is at least one of an antioxidant and a lubricant.
6. The ultraviolet-crosslinking insulating coating material according to claim 5, wherein the antioxidant is at least one of antioxidant 1010 and antioxidant 168; the lubricant is at least one of calcium stearate, polyethylene wax, silicone oil and silicone master batch.
7. Use of the uv-crosslinked insulating coating material according to any one of claims 1 to 6 for the preparation of a power cable sheathing compound.
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