CN114163716A - High-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material and preparation method thereof - Google Patents
High-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material and preparation method thereof Download PDFInfo
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- CN114163716A CN114163716A CN202111609244.6A CN202111609244A CN114163716A CN 114163716 A CN114163716 A CN 114163716A CN 202111609244 A CN202111609244 A CN 202111609244A CN 114163716 A CN114163716 A CN 114163716A
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- carbon black
- crosslinked polyethylene
- silane crosslinked
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- resistant silane
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- 239000006229 carbon black Substances 0.000 title claims abstract description 77
- 239000004718 silane crosslinked polyethylene Substances 0.000 title claims abstract description 21
- 239000011810 insulating material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 11
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000004611 light stabiliser Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920001684 low density polyethylene Polymers 0.000 claims description 5
- 239000004702 low-density polyethylene Substances 0.000 claims description 5
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 239000004811 fluoropolymer Substances 0.000 claims 1
- 229920002313 fluoropolymer Polymers 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 6
- 238000001125 extrusion Methods 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 3
- 235000019241 carbon black Nutrition 0.000 description 49
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- 230000006353 environmental stress Effects 0.000 description 3
- 238000002715 modification method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 241000272165 Charadriidae Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 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
- 229920001400 block copolymer Polymers 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- 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
- C08L2312/08—Crosslinking by silane
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Abstract
The invention relates to a high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulating material and a preparation method thereof. The high-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material and the preparation method adopt the organic-inorganic composite modifier and the surfactant to modify the carbon black, and form multi-level stable chemical bond connection under the action of the compatilizer, so that the high-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material can be uniformly dispersed in matrix resin and well compatible, the stable structure of the material ensures that the photo-oxidative-aging-resistant performance meets the requirement, meanwhile, the cracking resistance is excellent, the extrusion surface of the overhead cable produced by using the material is smooth and fine, the tracking resistance meets the requirement, and the long-term safe and stable operation of the overhead cable is ensured.
Description
The technical field is as follows:
the invention relates to the technical field of cable materials, in particular to a high-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material and a preparation method thereof.
Background art:
to outdoor built on stilts insulated cable, service environment is various, and takes place light oxygen ageing easily under weather conditions such as air, rainwater, light irradiation for a long time, causes the destruction of insulating layer structure, can seriously influence the safety in utilization and the life-span of cable, insulating cracking phenomenon appears even, causes the occurence of failure. In addition, when the cable transmits high voltage, the temperature of the conductor is raised by large current, the temperature is raised and then is conducted to the insulating layer, the electrical insulation property of the material is affected, the creepage and scratch phenomena of the cable insulation are caused, and the electric trace needs to be extinguished at the initial stage. Aiming at the problems, the industry uses an ultraviolet resistant agent and carbon black to modify crosslinked polyethylene to meet the requirements of light-oxygen aging resistance, but in an actual material system, the carbon black is added into a high polymer matrix and exists in a particle state, the carbon black is difficult to disperse well under the condition of more than 2 percent of addition amount, and the problem that the carbon black is not organic compatible with the matrix exists, at the moment, the carbon black is similar to impurities, the mechanical strength and the electrical strength of an insulating layer can be influenced, and the risks of mechanical cracking, breakdown and the like are brought to cables.
Further, enterprises improve the compatibility problem with matrix resin by using a coupling agent to perform surface treatment on carbon black, but the coupling agent is only in a physical coating state and lacks chemical bond connection due to common addition process even if the carbon black is fully treated, so that the carbon black subjected to surface treatment cannot be well dispersed and organically compatible, and the problems of inconsistent performance and non-uniform actual weather resistance can be caused. In addition, the extrusion performance is influenced by adding more carbon black, so that the extruded surface of the cable is not smooth, and the normal use is influenced by the serious bulge.
The invention content is as follows:
common modification methods for powders include inorganic modification using acids and salts, and organic modification using organic salts and coupling agents. The carbon black is pretreated by adopting a special modification method, and the carbon black is comprehensively modified by using an organic-inorganic composite modifier and a compatible modifier, so that the problem of dispersion after more carbon black is added can be effectively solved, the carbon black and a matrix can form stable chemical bond connection, the material structure is stable, a very good photo-oxidative aging resistance effect is achieved, and the requirement of tracking resistance is met.
The organic-inorganic composite modifier is compounded by organic quaternary ammonium salt, inorganic zinc salt, calcium salt and the like, and the compatilizer is maleic anhydride grafted polyethylene, maleic anhydride grafted metallocene polyethylene or maleic anhydride grafted block copolymer. In the process of modifying and pretreating carbon black, the organic-inorganic composite modifier can be attached to the surface of the carbon black to form various bonds, and further can establish stable chemical bonds with matrix resin under the action of the compatilizer, so that carbon black particles and the matrix resin are well compatible, and the carbon black is uniformly dispersed, the influence on the structure of a material after more carbon black is added is solved, the material is free from cracking risk in the using process, and the surface is more delicate.
The invention provides a high-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material, which is a weather-resistant insulating material product developed based on a one-step silane crosslinked polyethylene insulating material process and is prepared from the following raw materials in parts by weight:
wherein the linear low density polyethylene resin A has a melt flow rate (190 ℃, 2.16kg) of 1.8 to 3.5g/10 min; the melt flow rate (190 ℃, 2.16kg) of the linear low-density polyethylene resin B is 18-21g/10 min; the melt flow rate (190 ℃, 2.16kg) of the high-pressure low-density polyethylene is 1.7-2.6g/10 min;
the silane coupling agent is vinyl trimethoxy silane coupling agent;
the initiator is dicumyl peroxide;
the light stabilizer is a hindered amine light stabilizer;
the antioxidant is one or a combination of more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 4 '-thiobis (6-tert-butyl-3-methylphenol) and N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine;
the organic-inorganic composite modifier is composed of one of octadecyl quaternary ammonium salt, dioctadecyl benzyl quaternary ammonium salt and hexadecyl trimethyl ammonium bromide and one of zinc stearate, barium stearate, nano calcium carbonate and magnesium hydroxide;
the surfactant is one of vinyl triethoxysilane, vinyl tri (beta-methoxyethoxy) silane and titanate coupling agent;
the compatilizer is one of maleic anhydride grafted polyethylene and maleic anhydride grafted metallocene polyethylene;
the catalyst is dibutyltin dilaurate;
the rheological modifier is one of fluorine-containing polymer, polyethylene wax and siloxane master batch.
The preparation method of the high-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material comprises the following steps:
(1) carrying out modification treatment on carbon black to prepare carbon black modified master batches;
adding carbon black, a light stabilizer and an organic-inorganic composite modifier into a high-speed mixer in proportion, adding a surfactant after starting mixing, mixing at a high speed for 2-5 minutes, adding high-pressure low-density polyethylene, a rheological agent, a compatilizer and a catalyst, mixing for 1-2 minutes, adding a mixed material into a 65 double-screw extruder, pulling the mixed and plasticized material through a die orifice, cooling by water, drying by blowing, granulating, and then feeding into a fluidized bed for drying by blowing to obtain carbon black modified master batches, wherein the 65 double-screw extruder comprises the following processing processes: the first area is 135 +/-5 ℃; the second zone is 145 +/-5 ℃; a third area is 155 +/-5 ℃; the fourth zone is 165 +/-5 ℃; 170 +/-5 ℃ from the fifth area to the ninth area; ten regions 165 +/-5 ℃; an eleventh zone is 160 +/-5 ℃; the head is 160 +/-5 ℃;
(2) weighing and proportioning linear low-density polyethylene resin A, linear low-density polyethylene resin B, an antioxidant and the carbon black modified master batch by a weightlessness type weigher, adding the weighed and proportioned materials into a reciprocating extruder, mixing, extruding and granulating the mixed and plasticized material mass by a single screw, dehydrating by a centrifugal dehydrator and subsequently drying to obtain carbon black pre-dispersed resin particles; the processing temperatures of the reciprocating extruder units are shown in the following table
(3) Heating and drying the prepared carbon black pre-dispersed resin particles, and using a shaking tank, wherein the heating temperature is 60-70 ℃, and the drying time is 1-2 hours;
(4) adding the dried carbon black pre-dispersion resin particles into a shaking tank, preheating and drying for 30-60 minutes at the preheating temperature of 60-70 ℃, adding the compound silane coupling agent, and fully mixing for 1-2 hours in the shaking tank to obtain a finished product.
The invention has the beneficial effects that: the high-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material and the preparation method adopt the organic-inorganic composite modifier and the surfactant to modify the carbon black, and are connected with a chemical bond forming multi-level stability under the action of the compatilizer, so that the carbon black can be uniformly dispersed in matrix resin and well compatible, the stable structure of the material ensures that the photo-oxidative-aging-resistant performance meets the requirement, meanwhile, the cracking-resistant performance is excellent, the extruded surface of the overhead cable produced by using the material is smooth and fine, the tracking-resistant performance meets the requirement, and the long-term safe and stable operation of the overhead cable is ensured.
The specific implementation mode is as follows:
the following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly define the scope of the invention.
As shown in figure 1, the invention provides a preparation method of a high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulating material, which comprises the following steps:
(1) carrying out modification treatment on carbon black to prepare carbon black modified master batches;
adding carbon black, a light stabilizer and an organic-inorganic composite modifier into a high-speed mixer in proportion, adding a surfactant after starting mixing, mixing at a high speed for 2-5 minutes, adding high-pressure low-density polyethylene, a rheological agent, a compatilizer and a catalyst, mixing for 1-2 minutes, adding a mixed material into a 65 double-screw extruder, pulling the mixed and plasticized material through a die orifice, cooling by water, drying by blowing, granulating, and then feeding into a fluidized bed for drying by blowing to obtain carbon black modified master batches, wherein the 65 double-screw extruder comprises the following processing processes: the first area is 135 +/-5 ℃; the second zone is 145 +/-5 ℃; a third area is 155 +/-5 ℃; the fourth zone is 165 +/-5 ℃; 170 +/-5 ℃ from the fifth area to the ninth area; ten regions 165 +/-5 ℃; an eleventh zone is 160 +/-5 ℃; the head is 160 +/-5 ℃;
(2) weighing and proportioning linear low-density polyethylene resin A, linear low-density polyethylene resin B, an antioxidant and the carbon black modified master batch by a weightlessness type weigher, adding the weighed and proportioned materials into a reciprocating extruder, mixing, extruding and granulating the mixed and plasticized material mass by a single screw, dehydrating by a centrifugal dehydrator and subsequently drying to obtain carbon black pre-dispersed resin particles; the processing temperatures of the reciprocating extruder units are shown in the following table
(3) Heating and drying the prepared carbon black pre-dispersed resin particles, and using a shaking tank, wherein the heating temperature is 60-70 ℃, and the drying time is 1-2 hours;
(4) adding the dried carbon black pre-dispersion resin particles into a shaking tank, preheating and drying for 30-60 minutes at the preheating temperature of 60-70 ℃, adding the compound silane coupling agent, and fully mixing for 1-2 hours in the shaking tank to obtain a finished product.
Examples 1 and 2 of the present invention are shown in the following tables:
| name of Material | Example 1 | Example 2 |
| Sea-land petrochemical LLDPE7042 | 70 | 70 |
| Sea-land petrochemical LLDPEM2320 | 15 | 15 |
| Shanghai lithiation DJ200A | 5 | 5 |
| Silane A171 | 1.4 | 1.4 |
| Peroxidation ofDiisopropylbenzene | 0.08 | 0.08 |
| Antioxidant 1010 | 0.15 | 0.15 |
| Antioxidant 1024 | 0.15 | 0.15 |
| Light stabilizer 770DF | 0.2 | 0.2 |
| Carbon Black N550 | 2.5 | 4 |
| Octadecyl Quaternary ammonium salt | 0.4 | 0.6 |
| Zinc stearate | 0.4 | 0.6 |
| Silane coupling agent A151 | 0.02 | 0.04 |
| Compatilizer MC226 | 1 | 1.5 |
| Dibutyl tin dilaurate | 0.05 | 0.05 |
| PPA5924 | 3 | 3 |
Comparative examples are shown in the following table:
the test data for the inventive and comparative examples are shown in the following table:
according to experimental test performance data and extrusion test observation, the extrusion surfaces of the samples in the examples 1 and 2 are smooth and fine, the data stability is good, particularly, the artificial weathering performance test data is ideal, the photo-oxidation aging resistance is excellent, and the test piece prepared subsequently passes the method I of GB/T6553-2014 standard 5.2: constant electrographic voltage method 1A4.5 grade (4.5kv/6h) experimental test.
Comparative examples 1-1 and 2-1, in which carbon black was organically modified using only ammonium salt and surfactant, the artificial weathering data was poor from the comparative data, and when the amount of carbon black added was 4%, the extruded surface was longer and the environmental stress cracking resistance test failed; comparative examples 1-2 and 2-2, in which carbon blacks were modified with inorganic modifiers and surfactants, the weathering data were worse from the comparative data, and at 4% carbon black addition, significantly smaller particles were extruded and the environmental stress cracking resistance test failed. The results show that the carbon black modified by the two modification modes does not establish stable chemical bond connection with matrix resin, has obvious performance deterioration under the simulated photo-oxidation aging effect, and is unqualified.
Comparative examples 1-3 and 2-3 compare the example with the example and subtract the addition of the surfactant, the organic-inorganic composite modifier modifies the carbon black, and under the action of the compatilizer, under the condition, various bonds are established between the carbon black and the organic-inorganic composite modifier, the experimental data shows that the artificial weathering is qualified, but the comparative data of 42 days and 21 days of ageing shows that the phenomenon of approaching the standard line occurs, and the surface structure stability is damaged to a certain extent under the action of long-time ageing. Further, the extrusion surface was observed at a carbon black content of 4%, and comparative examples 2 to 3 exhibited roughness. Comparative examples 1-4 and 2-4 did not use a compatibilizer, the weathering data was biased, and comparative examples 2-4, with 4% carbon black added, did not pass the environmental stress crack resistance test.
It can be seen from the comprehensive data that the embodiment of the invention adopts the organic-inorganic composite modifier and the surfactant to modify the carbon black, and is connected with the formed multi-layer stable chemical bonds under the action of the compatilizer, so that the carbon black can be uniformly dispersed in the matrix resin and well compatible, and the stable structure of the material ensures that the photo-oxidative aging resistance meets the requirements and the cracking resistance is excellent. The extrusion surface of the overhead cable produced by using the material is smooth and fine, the tracking resistance meets the requirements, and the long-term safe and stable operation of the overhead cable is ensured.
Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. The high-carbon-black photo-oxidative-aging-resistant silane crosslinked polyethylene insulating material is characterized by being prepared from the following raw materials in parts by weight:
2. the high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation of claim 1, wherein the linear low density polyethylene resin a has a melt flow rate (190 ℃, 2.16kg) of 1.8-3.5g/10 min; the melt flow rate (190 ℃, 2.16kg) of the linear low-density polyethylene resin B is 18-21g/10 min; the melt flow rate (190 ℃, 2.16kg) of the high-pressure low-density polyethylene is 1.7-2.6g/10 min.
3. The high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation of claim 1, wherein the silane coupling agent is a vinyltrimethoxysilane coupling agent; the initiator is dicumyl peroxide; the light stabilizer is a hindered amine light stabilizer.
4. The high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation as claimed in claim 1, wherein the antioxidant is one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 4 '-thiobis (6-tert-butyl-3-methylphenol), N' -bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine.
5. The high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation material of claim 1, wherein the organic-inorganic composite modifier is one of octadecyl quaternary ammonium salt, dioctadecyl benzyl quaternary ammonium salt and hexadecyl trimethyl ammonium bromide and one of zinc stearate, barium stearate, nano calcium carbonate and magnesium hydroxide.
6. The high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation as claimed in claim 1, wherein the surfactant is one of vinyltriethoxysilane, vinyltris (β -methoxyethoxy) silane, titanate coupling agent.
7. The high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation as claimed in claim 1, wherein the compatibilizer is one of maleic anhydride grafted polyethylene and maleic anhydride grafted metallocene polyethylene.
8. The high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation of claim 1, wherein the catalyst is dibutyltin dilaurate.
9. The high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation material of claim 1, wherein the rheology modifier is one of fluoropolymer, polyethylene wax, and silicone masterbatch.
10. A method for preparing the high carbon black photo-oxidative aging resistant silane crosslinked polyethylene insulation material according to any one of claims 1 to 9, comprising the steps of:
(1) carrying out modification treatment on carbon black to prepare carbon black modified master batches;
adding carbon black, a light stabilizer and an organic-inorganic composite modifier into a high-speed mixer in proportion, adding a surfactant after starting mixing, mixing at a high speed for 2-5 minutes, adding high-pressure low-density polyethylene, a rheological agent, a compatilizer and a catalyst, mixing for 1-2 minutes, adding a mixed material into a 65 double-screw extruder, pulling the mixed and plasticized material through a die orifice, cooling by water, drying by blowing, granulating, and then feeding into a fluidized bed for drying by blowing to obtain carbon black modified master batches, wherein the 65 double-screw extruder comprises the following processing processes: the first area is 135 +/-5 ℃; the second zone is 145 +/-5 ℃; a third area is 155 +/-5 ℃; the fourth zone is 165 +/-5 ℃; 170 +/-5 ℃ from the fifth area to the ninth area; ten regions 165 +/-5 ℃; an eleventh zone is 160 +/-5 ℃; the head is 160 +/-5 ℃;
(2) weighing and proportioning linear low-density polyethylene resin A, linear low-density polyethylene resin B, an antioxidant and the carbon black modified master batch by a weightlessness type weigher, adding the weighed and proportioned materials into a reciprocating extruder, mixing, extruding and granulating the mixed and plasticized material mass by a single screw, dehydrating by a centrifugal dehydrator and subsequently drying to obtain carbon black pre-dispersed resin particles; the processing temperature of the reciprocating type extruding unit is
A high-order machine: the first zone is 140 +/-5 ℃; the second zone is 160 +/-5 ℃; a third region 165 +/-5 ℃; the fourth zone is 170 +/-5 ℃; the fifth zone is 165 +/-5 ℃;
a lower-stage machine: the first zone is 140 +/-5 ℃; the second zone is 155 +/-5 ℃; a third area is 155 +/-5 ℃; the head is 150 +/-5 ℃;
(3) heating and drying the prepared carbon black pre-dispersion resin particles at the temperature of 60-70 ℃ for 1-2 hours;
(4) adding the dried carbon black pre-dispersion resin particles into a shaking tank, preheating and drying for 30-60 minutes at the preheating temperature of 60-70 ℃, adding the compound silane coupling agent, and fully mixing for 1-2 hours in the shaking tank to obtain a finished product.
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| CN116262845A (en) * | 2022-11-15 | 2023-06-16 | 浙江万马高分子材料集团有限公司 | Weather-proof and tracking-resistant silane crosslinked polyethylene insulating material and preparation method thereof |
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Denomination of invention: High carbon black, photo oxidative aging resistant, silane crosslinked polyethylene insulation material and preparation method Granted publication date: 20230623 Pledgee: China Postal Savings Bank Co.,Ltd. Nanjing Gaochun Branch Pledgor: NANJING ZHONGCHAO NEW MATERIALS Corp. Registration number: Y2024980002363 |