CN115785591B - Anti-aging insulating flame-retardant power cable - Google Patents
Anti-aging insulating flame-retardant power cable Download PDFInfo
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- CN115785591B CN115785591B CN202211614545.2A CN202211614545A CN115785591B CN 115785591 B CN115785591 B CN 115785591B CN 202211614545 A CN202211614545 A CN 202211614545A CN 115785591 B CN115785591 B CN 115785591B
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- flame retardant
- power cable
- aging
- flame
- cable
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 88
- 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 55
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 33
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229920002627 poly(phosphazenes) Polymers 0.000 claims abstract description 25
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims abstract description 23
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 63
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 10
- 239000006084 composite stabilizer Substances 0.000 claims description 10
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 10
- 229920002379 silicone rubber Polymers 0.000 claims description 10
- 239000004945 silicone rubber Substances 0.000 claims description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 8
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 claims description 8
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 8
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 8
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 9
- 238000007112 amidation reaction Methods 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 35
- 229920000915 polyvinyl chloride Polymers 0.000 description 35
- 239000000243 solution Substances 0.000 description 24
- 238000002485 combustion reaction Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000009413 insulation Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 6
- 235000013539 calcium stearate Nutrition 0.000 description 6
- 239000008116 calcium stearate Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- GGHVZKXIPULPLP-UHFFFAOYSA-N 6-(2,5-dioxopyrrol-1-yl)hexanoyl chloride Chemical compound ClC(=O)CCCCCN1C(=O)C=CC1=O GGHVZKXIPULPLP-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect 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
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an anti-aging insulating flame-retardant power cable, which comprises a cable core, a metal sheath and a nonmetal outer sheath, wherein the metal sheath and the nonmetal outer sheath are sequentially coated on the cable core from inside to outside. The nonmetal outer sheath is a PVC sheath, and the halogen-free flame retardant is generated by amidation reaction of phosphorothioate, polyphosphazene rich in triazine and 6-maleimide caproyl chloride, so that the dispersibility of the phosphorothioate and polyphosphazene rich in triazine as flame retardants in a matrix material is improved, the flame retardant performance of the material is synergistically improved, and the anti-aging insulated flame-retardant power cable prepared by the method has line integrity and good flame resistance under the condition that the temperature is 950-1000 ℃ and the loading voltage is 0.6 kV.
Description
Technical Field
The invention relates to the technical field of cable materials, in particular to an anti-aging insulating flame-retardant power cable.
Background
With the vigorous development of the modern industry, the supply demand of power cables is rapidly increased, the power cables are called arteries and nerves of national economy, and the degree of urban cabling becomes an important sign for measuring the urban modernization progress and living environment. In order to meet the power demand and the stability and economy of power transmission, the power grid is continuously developed towards high capacity and high voltage, which will put higher demands on the transmission and reliability of the power cable, and further accelerate the aging of the power cable, such as thermal, electrical and mechanical aging.
The cable is typically a rope-like cable stranded from several wires or groups of wires (at least two in each group), each group being insulated from each other and often twisted around a center, with a highly insulating coating over the entire outer surface. The cable has the characteristics of inner electrifying and outer insulation, and the insulation performance of the aged insulation material is deteriorated to a certain extent, such as hardening, embrittlement, insulation resistance reduction and even cracking. After the insulation material ages, the insulation capability is rapidly reduced, the resistance of the conductor (copper core) is increased, and according to Joule's law Q=i2Rt, under the condition that the current and time are unchanged, the resistance is increased, so that the heating amount is increased, the temperature is increased, and the aging of the insulation material is accelerated. And finally, the insulating material loses the insulating property, insulation impact occurs, and the broken cable metal wire core is conducted through direct contact or electric arc to generate short circuit. The resulting localized high temperature or heat build-up in a short period of time ignites the cable insulation assembly, thereby igniting the entire cable and adjacent combustibles causing a fire to occur.
In order to reduce the occurrence of fire and the death rate of the fire, it is very important to improve the flame retardant performance of the cable, and a large amount of flame retardant is usually added into the covering layer of the cable to overcome the inflammable defect of the cable, including inorganic flame retardant, organic halogen flame retardant, organic phosphorus flame retardant, intumescent flame retardant and the like. The organic halogen flame retardant can generate toxic and corrosive gas when burning, and can cause harm to human health and ecological environment, and along with the improvement of environmental awareness, more and more flame retardants are developed towards high efficiency, low smoke, no halogen and environmental protection.
CN103214767a discloses an anti-aging flame-retardant polyvinyl chloride power cable material and a preparation method thereof, wherein the main components and contents of the power cable material are as follows: the following components are calculated by weight portion, polyvinyl chloride 50-90 portions, aluminum hydroxide 30-40 portions, zinc borate 2-8 portions, antimonous oxide 2-6 portions and the balance of calcium-zinc complex. The anti-aging flame-retardant polyvinyl chloride power cable material is prepared by extruding and granulating in a double screw after being uniformly mixed in a mixer. The flame retardant is a complex of aluminum hydroxide, zinc borate, antimony trioxide and calcium zinc, and the flame-retardant polyvinyl chloride power cable provided by the invention has excellent ageing resistance and fire resistance, so that the flame-retardant quality performance and ageing resistance of the polyvinyl chloride cable are effectively improved. The flame retardant used in the invention is an inorganic flame retardant material such as aluminum hydroxide, zinc borate, antimonous oxide and the like, and has the problems of large addition amount, poor fire resistance and the like.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the technical problem to be solved by the present invention is to provide an environment-friendly, flame-retardant, long-service-life, fire-resistant and anti-aging insulated flame-retardant power cable.
In order to achieve the above purpose, the invention provides an anti-aging insulation resistance power cable which has good flame retardant property and fire resistance and still has line integrity under the condition of a loading voltage of 0.6kV at a temperature of 950-1000 ℃.
In order to achieve the above object, the present invention adopts the following technical scheme:
an anti-aging insulating flame-retardant power cable comprises a cable core, a metal sheath and a nonmetal outer sheath, wherein the metal sheath and the nonmetal outer sheath are sequentially coated on the cable core from inside to outside.
The invention relates to a preparation process of an anti-aging insulating flame-retardant power cable, which comprises the following steps: and twisting N conductors into a bundle, sequentially wrapping PTFE wrapping layers and insulating layers on the outer sides of the N conductors to obtain wire cores, arranging 5 groups of wire cores into bundles to form cable cores, filling flame-retardant filler in gaps between the cable cores, and sequentially wrapping an aluminum sheath, a steel tape armor layer and a nonmetallic outer sheath on the outer sides of the cable cores to obtain the anti-aging insulating flame-retardant power cable.
Preferably, the conductor is one of copper wires and aluminum alloy, and N is more than or equal to 3.
Preferably, the flame retardant filler is one of glass fiber and carbon fiber.
Preferably, the nonmetallic outer sheath is a PVC sheath, and comprises the following components in parts by weight: 80-100 parts of PVC resin, 10-30 parts of polyvinylidene chloride, 10-20 parts of silicone rubber, 10-20 parts of superfine calcium carbonate, 5-10 parts of calcium-zinc composite stabilizer, 0.5-0.9 part of anti-aging agent, 0.5-0.9 part of antioxidant, 40-60 parts of plasticizer, 10-15 parts of halogen-free flame retardant and 0.1-0.3 part of lubricant.
Preferably, the anti-aging agent is one of 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline and 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine.
Preferably, the antioxidant is one or more than two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, tri [2, 4-di-tert-butylphenyl ] phosphite, dilauryl thiodipropionate and 2, 8-di-tert-butyl-4-methylphenol.
Preferably, the plasticizer is one of dioctyl phthalate, dioctyl adipate and dioctyl sebacate.
Preferably, the preparation method of the halogen-free flame retardant comprises the following steps:
1) 2-mercaptobenzimidazole, acetonitrile and triethylamine are mixed and then are subjected to coupling reaction with diphenyl phosphoryl chloride to generate phosphorothioate;
2) Carrying out precipitation polymerization reaction on melamine and hexachlorocyclotriphosphazene to generate triazine-rich polyphosphazene;
3) Amidation reaction of thiophosphate, triazine-rich polyphosphazene and 6-maleimide caproyl chloride to produce the halogen-free flame retardant.
Further preferably, the preparation method of the halogen-free flame retardant comprises the following steps:
1) Mixing 5-8g of 2-mercaptobenzimidazole, 150-200mL of acetonitrile and 5-10mL of triethylamine at room temperature, and uniformly stirring to obtain a mixed system 1; dissolving 8-12g of diphenyl phosphoryl chloride in 100-150mL of acetonitrile to obtain an acetonitrile solution of diphenyl phosphoryl chloride; then dripping acetonitrile solution of diphenyl phosphoryl chloride into the mixed system 1 at the speed of 1-2 drops/second, reacting for 2-4 hours at room temperature, heating to 70-100 ℃ and reacting for 10-12 hours; cooling to room temperature, filtering, washing the filter cake with saturated sodium bicarbonate and water for 2-3 times, and drying at 60-80deg.C for 10-12 hr to obtain phosphorothioate;
2) Dissolving 0.3-0.5g melamine in 20-30mL pyridine to obtain solution A; dissolving 0.5-1g of hexachlorocyclotriphosphazene in 10-20mL of pyridine to obtain a solution B; then adding the solution B into the solution A; heating to 100-120 ℃ and reacting for 20-24h; cooling to room temperature after the reaction is finished; filtering, washing the filter cake with water and absolute ethyl alcohol for 2-3 times respectively, and drying at 50-80 ℃ for 10-12 hours to obtain triazine-rich polyphosphazene;
3) 3-5g of 6-maleimide caproic acid is dissolved in 10-15mL of thionyl chloride, and stirred and reacted for 8-9 hours at the temperature of 60-100 ℃; after the reaction is finished, cooling to room temperature, and decompressing and evaporating the solvent to obtain 6-maleimide caproyl chloride; dispersing 1-3g of phosphorothioate and 2-4g of polyphosphazene rich in triazine in 200-300mL of pyridine, and performing ultrasonic treatment at 30-50 ℃ under the conditions of 80-120W and 40-60kHz for 20-30min to obtain a mixed system 2; dropwise adding 10-20mL of 6-maleimide caproyl chloride into the mixed system 2 at a speed of 2-3 drops/sec; reacting at 100-140 ℃ for 20-24h, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with absolute ethyl alcohol and water for 2-3 times respectively, and drying at 60-80 ℃ for 10-12h to obtain the halogen-free flame retardant.
In the prior art, melamine and diphenyl phosphoryl chloride are nitrogen flame retardants and phosphorus flame retardants respectively, but the flame retardant performance is not high. The inventor generates phosphorothioate through the reaction of diphenyl phosphoryl chloride and mercaptobenzimidazole with a rigid structure, the compound is rich in N, S and other flame-retardant elements, and can decompose acidic substances in the combustion process to promote the formation of a carbon layer on the surface of a matrix; the melamine is used as a nucleophilic reagent to react with hexachlorocyclotriphosphazene to prepare triazine-rich polyphosphazene, and the polyphosphazene has good thermal stability; finally, the halogen-free flame retardant obtained by amidation reaction with 6-maleimide caproyl chloride can obviously improve the compatibility of phosphorothioate and polyphosphazene rich in triazine in a matrix. When the material burns, the thiophosphate can produce acid compound to promote the formation of carbon layer on the surface of the matrix and cover the surface of the material to isolate oxygen, while the polyphosphazene rich in triazine can be pyrolyzed at high temperature to produce P-containing fragments, benzimidazole with rigid structure and other matters, and the P-containing fragments can produce P, PO and PO 2 Free radicals, by capturing H and OH free radicals, act to quench the free radical chain reaction during combustion, and benzimidazole and thiophenol can be further decomposed to produce sulfur/nitrogenThe synergistic effect of the nonflammable gas, acting as a diluent for oxygen and fuel, the phosphorothioate and the triazine-rich polyphosphazene improves the flame retardant properties of the material.
Preferably, the lubricant is one of talcum powder, calcium stearate and polyethylene wax.
Further preferably, the preparation method of the PVC sheath comprises the following steps:
weighing raw materials according to a formula, uniformly mixing PVC resin, polyvinylidene chloride and silicone rubber to obtain a main material, and then blending and granulating to obtain a base resin; banburying for 1-3min, and heating to 80-90deg.C for 4-5min; adding superfine calcium carbonate, calcium zinc composite stabilizer, antioxidant, plasticizer, halogen-free flame retardant and lubricant, mixing for 1-2min, feeding into an open mill, passing through for 6-7 times, and finally extruding in an extruder at 185-190 ℃ and steam pressure of 0.8-1.5MPa to obtain the PVC sheath.
Compared with the prior art, the invention has the beneficial effects that: the cable prepared by the invention has the advantages of good ageing resistance, high flame retardant efficiency, long service life, low production cost and the like; the halogen-free flame retardant is prepared by amidation reaction of phosphorothioate, polyphosphazene rich in triazine and 6-maleimide caproyl chloride, has good compatibility with a cable material matrix, can be well dispersed in the matrix material, contains rich flame retardant elements such as N, S, and can decompose acidic substances in the combustion process to promote the formation of a carbon layer on the surface of the matrix; the triazine-rich polyphosphazene plays a role in quenching free radical chain reaction in the combustion process by capturing H and OH free radicals, benzimidazole and benzene mercaptan can be further decomposed to generate sulfur/nitrogen nonflammable gas, the sulfur/nitrogen nonflammable gas serves as a diluent for oxygen and fuel, flame propagation is prevented, the purpose of flame retardance is achieved, and the cooperation of phosphorothioate and triazine-rich polyphosphazene improves the flame retardance of the material.
Detailed Description
For the sake of brevity, the articles used in the examples below are commercially available products unless otherwise specified, and the methods used are conventional methods unless otherwise specified.
The sources of part of raw materials used in the invention are as follows:
the copper wire has a wire diameter of 0.1-0.68mmm and a minimum insulation resistance of 25Ω, which is a strengthening company of Jiaying mechanical equipments, inc.
Kaolin, the granularity is less than or equal to 76 mu m, and the mineral products are processed in the Qiangdong of Ming county.
PVC resin with average polymerization degree of 750-850, K value of 60-62, adhesion degree of 87-95, brand SG-7, and Qilu petrochemical property.
Polyvinylidene chloride with density of 1.31g/cm 3 The viscosity is 10 mPa.s, the trade name is A050, suzhou crystal plastic rice new material Co.
Silicone rubber, viscosity (25 ℃) 25-35cs, volatiles (150 ℃ C..times.3 h): less than or equal to 2 percent, the surface curing time less than or equal to 2 hours, and Shandong national chemical Co., ltd.
Superfine calcium carbonate, the content of the calcium carbonate is 96-99%, the mesh number is 800 mesh, and the mineral products are processed in Lingshu county.
The melting range of the calcium-zinc composite stabilizer is 72 ℃, the content of metal oxide is 28%, the moisture content is less than or equal to 1.0%, the Congo red time is 44min at 200 ℃, the volatile content is less than or equal to 1.0%, and Henan Qing ai Co., ltd.
4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine with a content of 99%, jiangsu Runfeng synthetic technology Co., ltd.
Dilauryl thiodipropionate with a content of 99% and a density of 0.915g/cm 3 Melting point is 39-40deg.C, west AnMusen bioengineering Co., ltd.
Dioctyl phthalate with a content of 99% and a density of 0.985g/cm 3 Boiling point is 416.36 ℃, shandong Qianxiang chemical industry Co., ltd.
2-mercaptobenzimidazole having a density of 1.42g/cm 3 The melting point is 304 ℃, the drying weight loss is less than or equal to 0.2 percent, the moisture content is less than or equal to 0.2 percent, and the Jinan Baite New material Co., ltd.
Melamine with 99% content, boiling point 557.54 deg.C and density 1.661g/cm 3 Industrial and chemical industry for sunny day in Jinan provinceTechnology Co., ltd.
Hexachlorocyclotriphosphazene with 99% content and density of 1.98g/cm 3 Jiangsu Runfeng synthetic technology Co., ltd.
Diphenyl phosphoryl chloride with purity of 99% and density of 1.24g/cm 3 Hubei huge science and technology limited company.
Example 1
A preparation process of an anti-aging insulating flame-retardant power cable comprises the following steps: and 6 conductors are twisted into bundles and sequentially wrapped with PTFE wrapping layers and insulating layers on the outer sides to obtain wire cores, then 5 groups of wire cores are arranged into bundles to form cable cores, glass fibers are filled among the holes among the cable cores, and finally an aluminum sheath, a steel tape armor layer and a PVC sheath are sequentially wrapped on the outer sides of the cable cores to obtain the anti-aging insulating flame-retardant power cable.
The preparation method of the PVC sheath comprises the following steps: uniformly mixing 100g of PVC resin, 30g of polyvinylidene chloride and 20g of silicone rubber to obtain a main material, and then placing the main material in a double-screw extruder for blending and granulating to obtain a base resin; opening an internal mixer, preheating to 50 ℃, adding the base resin into the internal mixer, banburying for 2min, and then heating to 85 ℃ for continuous banburying for 5min; adding 20g of superfine calcium carbonate, 10g of calcium-zinc composite stabilizer, 0.9g of 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, 0.9g of dilauryl thiodipropionate, 60g of dioctyl phthalate, 15g of halogen-free flame retardant and 0.3g of calcium stearate, mixing for 2min, conveying to an open mill, carrying out thin passing for 7 times, and finally extruding in a double-screw extruder at the temperature of 185 ℃ and the steam pressure of 1.2MPa to obtain the PVC sheath.
The preparation method of the halogen-free flame retardant comprises the following steps:
1) Mixing 6.2g of 2-mercaptobenzimidazole, 150mL of acetonitrile and 8mL of triethylamine at room temperature, and uniformly stirring to obtain a mixed system 1; 10.3g of diphenylphosphoryl chloride was dissolved in 100mL of acetonitrile to obtain an acetonitrile solution of diphenylphosphoryl chloride; then dripping acetonitrile solution of diphenyl phosphoryl chloride into the mixed system 1 at the speed of 1 drop/second, reacting for 3 hours at room temperature, heating to 85 ℃ and reacting for 12 hours; cooling to room temperature, filtering, washing the filter cake with saturated sodium bicarbonate and water for 3 times respectively, and drying at 80 ℃ for 12 hours to obtain phosphorothioate;
2) 0.5g melamine was dissolved in 30mL pyridine to give solution A; 0.8g of hexachlorocyclotriphosphazene is dissolved in 15mL of pyridine to obtain a solution B; then adding the solution B into the solution A; heating to 110 ℃, and reacting for 24 hours; cooling to room temperature after the reaction is finished; filtering, washing the filter cake with water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 hours to obtain triazine-rich polyphosphazene;
3) 4.5g of 6-maleimide caproic acid is dissolved in 12mL of thionyl chloride and stirred for reaction for 8 hours at 80 ℃; after the reaction is finished, cooling to room temperature, and decompressing and evaporating the solvent to obtain 6-maleimide caproyl chloride; dispersing 2g of phosphorothioate and 3.5g of polyphosphazene rich in triazine in 250mL of pyridine, and then carrying out ultrasonic treatment at 40 ℃ and 100W and 50kHz for 30min to obtain a mixed system 2; 15mL of 6-maleimidocaproyl chloride was added dropwise to mixing system 2 at a rate of 2 drops/sec; and (3) reacting at 120 ℃ for 24 hours, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with absolute ethyl alcohol and water for 3 times respectively, and drying at 80 ℃ for 12 hours to obtain the halogen-free flame retardant.
Comparative example 1
A preparation process of an anti-aging insulating flame-retardant power cable comprises the following steps: and 6 conductors are twisted into bundles and sequentially wrapped with PTFE wrapping layers and insulating layers on the outer sides to obtain wire cores, then 5 groups of wire cores are arranged into bundles to form cable cores, glass fibers are filled among the holes among the cable cores, and finally an aluminum sheath, a steel tape armor layer and a PVC sheath are sequentially wrapped on the outer sides of the cable cores to obtain the anti-aging insulating flame-retardant power cable.
The preparation method of the PVC sheath comprises the following steps: uniformly mixing 100g of PVC resin, 30g of polyvinylidene chloride and 20g of silicone rubber to obtain a main material, and then placing the main material in a double-screw extruder for blending and granulating to obtain a base resin; opening an internal mixer, preheating to 50 ℃, adding the base resin into the internal mixer, banburying for 2min, and then heating to 85 ℃ for continuous banburying for 5min; adding 20g of superfine calcium carbonate, 10g of calcium-zinc composite stabilizer, 0.9g of 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, 0.9g of dilauryl thiodipropionate, 60g of dioctyl phthalate, 15g of halogen-free flame retardant and 0.3g of calcium stearate, mixing for 2min, conveying to an open mill, carrying out thin passing for 7 times, and finally extruding in a double-screw extruder at the temperature of 185 ℃ and the steam pressure of 1.2MPa to obtain the PVC sheath.
The preparation method of the halogen-free flame retardant comprises the following steps:
1) Mixing 6.2g of 2-mercaptobenzimidazole, 150mL of acetonitrile and 8mL of triethylamine at room temperature, and uniformly stirring to obtain a mixed system 1; 10.3g of diphenylphosphoryl chloride was dissolved in 100mL of acetonitrile to obtain an acetonitrile solution of diphenylphosphoryl chloride; then dripping acetonitrile solution of diphenyl phosphoryl chloride into the mixed system 1 at the speed of 1 drop/second, reacting for 3 hours at room temperature, heating to 85 ℃ and reacting for 12 hours; cooling to room temperature, filtering, washing the filter cake with saturated sodium bicarbonate and water for 3 times respectively, and drying at 80 ℃ for 12 hours to obtain phosphorothioate;
2) 4.5g of 6-maleimide caproic acid is dissolved in 12mL of thionyl chloride and stirred for reaction for 8 hours at 80 ℃; after the reaction is finished, cooling to room temperature, and decompressing and evaporating the solvent to obtain 6-maleimide caproyl chloride; dispersing 2g of phosphorothioate in 250mL of pyridine, and performing ultrasonic treatment at 40 ℃ and 100W and 50kHz for 30min to obtain a mixed solution; 15mL of 6-maleimide caproyl chloride was added dropwise to the mixture at a rate of 2 drops/sec; and (3) reacting at 120 ℃ for 24 hours, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with absolute ethyl alcohol and water for 3 times respectively, and drying at 80 ℃ for 12 hours to obtain the halogen-free flame retardant.
Comparative example 2
A preparation process of an anti-aging insulating flame-retardant power cable comprises the following steps: and 6 conductors are twisted into bundles and sequentially wrapped with PTFE wrapping layers and insulating layers on the outer sides to obtain wire cores, then 5 groups of wire cores are arranged into bundles to form cable cores, glass fibers are filled among the holes among the cable cores, and finally an aluminum sheath, a steel tape armor layer and a PVC sheath are sequentially wrapped on the outer sides of the cable cores to obtain the anti-aging insulating flame-retardant power cable.
The preparation method of the PVC sheath comprises the following steps: uniformly mixing 100g of PVC resin, 30g of polyvinylidene chloride and 20g of silicone rubber to obtain a main material, and then placing the main material in a double-screw extruder for blending and granulating to obtain a base resin; opening an internal mixer, preheating to 50 ℃, adding the base resin into the internal mixer, banburying for 2min, and then heating to 85 ℃ for continuous banburying for 5min; adding 20g of superfine calcium carbonate, 10g of calcium-zinc composite stabilizer, 0.9g of 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, 0.9g of dilauryl thiodipropionate, 60g of dioctyl phthalate, 15g of halogen-free flame retardant and 0.3g of calcium stearate, mixing for 2min, conveying to an open mill, carrying out thin passing for 7 times, and finally extruding in a double-screw extruder at the temperature of 185 ℃ and the steam pressure of 1.2MPa to obtain the PVC sheath.
The preparation method of the halogen-free flame retardant comprises the following steps:
1) Mixing 6.2g of 2-mercaptobenzimidazole, 150mL of acetonitrile and 8mL of triethylamine at room temperature, and uniformly stirring to obtain a mixed system 1; 10.3g of diphenylphosphoryl chloride was dissolved in 100mL of acetonitrile to obtain an acetonitrile solution of diphenylphosphoryl chloride; then dripping acetonitrile solution of diphenyl phosphoryl chloride into the mixed system 1 at the speed of 1 drop/second, reacting for 3 hours at room temperature, heating to 85 ℃ and reacting for 12 hours; cooling to room temperature, filtering, washing the filter cake with saturated sodium bicarbonate and water for 3 times respectively, and drying at 80 ℃ for 12 hours to obtain phosphorothioate;
2) 0.5g melamine was dissolved in 30mL pyridine to give solution A; 0.8g of hexachlorocyclotriphosphazene is dissolved in 15mL of pyridine to obtain a solution B; then adding the solution B into the solution A; heating to 110 ℃, and reacting for 24 hours; cooling to room temperature after the reaction is finished; filtering, washing the filter cake with water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 hours to obtain triazine-rich polyphosphazene;
3) And uniformly mixing 2g of phosphorothioate and 3.5g of polyphosphazene rich in triazine to obtain the halogen-free flame retardant.
Comparative example 3
A preparation process of an anti-aging insulating flame-retardant power cable comprises the following steps: and 6 conductors are twisted into bundles and sequentially wrapped with PTFE wrapping layers and insulating layers on the outer sides to obtain wire cores, then 5 groups of wire cores are arranged into bundles to form cable cores, glass fibers are filled among the holes among the cable cores, and finally an aluminum sheath, a steel tape armor layer and a PVC sheath are sequentially wrapped on the outer sides of the cable cores to obtain the anti-aging insulating flame-retardant power cable.
The preparation method of the PVC sheath comprises the following steps: uniformly mixing 100g of PVC resin, 30g of polyvinylidene chloride and 20g of silicone rubber to obtain a main material, and then placing the main material in a double-screw extruder for blending and granulating to obtain a base resin; opening an internal mixer, preheating to 50 ℃, adding the base resin into the internal mixer, banburying for 2min, and then heating to 85 ℃ for continuous banburying for 5min; adding 20g of superfine calcium carbonate, 10g of calcium-zinc composite stabilizer, 0.9g of 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, 0.9g of dilauryl thiodipropionate, 60g of dioctyl phthalate, 15g of halogen-free flame retardant and 0.3g of calcium stearate, mixing for 2min, conveying to an open mill, carrying out thin passing for 7 times, and finally extruding in a double-screw extruder at the temperature of 185 ℃ and the steam pressure of 1.2MPa to obtain the PVC sheath.
The preparation method of the halogen-free flame retardant comprises the following steps:
1) 0.5g melamine was dissolved in 30mL pyridine to give solution A; 0.8g of hexachlorocyclotriphosphazene is dissolved in 15mL of pyridine to obtain a solution B; then adding the solution B into the solution A; heating to 110 ℃, and reacting for 24 hours; cooling to room temperature after the reaction is finished; filtering, washing the filter cake with water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 12 hours to obtain triazine-rich polyphosphazene;
2) 4.5g of 6-maleimide caproic acid is dissolved in 12mL of thionyl chloride and stirred for reaction for 8 hours at 80 ℃; after the reaction is finished, cooling to room temperature, and decompressing and evaporating the solvent to obtain 6-maleimide caproyl chloride; 3.5g of polyphosphazene rich in triazine is dispersed in 250mL of pyridine and then is subjected to ultrasonic treatment for 30min at 40 ℃ under the conditions of 100W and 50kHz to obtain a mixed solution; 15mL of 6-maleimidocaproyl chloride was added dropwise to the mixture at a rate of 2 drops/sec; and (3) reacting at 120 ℃ for 24 hours, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with absolute ethyl alcohol and water for 3 times respectively, and drying at 80 ℃ for 12 hours to obtain the halogen-free flame retardant.
Comparative example 4
A preparation process of an anti-aging insulating flame-retardant power cable comprises the following steps: and 6 conductors are twisted into bundles and sequentially wrapped with PTFE wrapping layers and insulating layers on the outer sides to obtain wire cores, then 5 groups of wire cores are arranged into bundles to form cable cores, glass fibers are filled among the holes among the cable cores, and finally an aluminum sheath, a steel tape armor layer and a PVC sheath are sequentially wrapped on the outer sides of the cable cores to obtain the anti-aging insulating flame-retardant power cable.
The preparation method of the PVC sheath comprises the following steps: uniformly mixing 100g of PVC resin, 30g of polyvinylidene chloride and 20g of silicone rubber to obtain a main material, and then placing the main material in a double-screw extruder for blending and granulating to obtain a base resin; opening an internal mixer, preheating to 50 ℃, adding the base resin into the internal mixer, banburying for 2min, and then heating to 85 ℃ for continuous banburying for 5min; adding 20g of superfine calcium carbonate, 10g of calcium-zinc composite stabilizer, 0.9g of 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine, 0.9g of dilauryl thiodipropionate, 60g of dioctyl phthalate, 15g of halogen-free flame retardant and 0.3g of calcium stearate, mixing for 2min, conveying to an open mill, carrying out thin passing for 7 times, and finally placing in an extruder, and extruding at the temperature of 185 ℃ and the steam pressure of 1.2MPa to obtain the PVC sheath.
The halogen-free flame retardant is resorcinol bis (diphenyl phosphate).
Test example 1
Determination of flame retardant properties:
vertical combustion test: the PVC sheaths prepared in example 1 and comparative examples 1-4 were cut into strips with dimensions of 130mm x 13mm x 3mm, 5 samples were tested for each group of bars using GB/T2408-2021 "horizontal and vertical methods for measuring Plastic Combustion Performance", the flame was moved to the lower end of the sample to be tested for 10s, the flame was removed, if the sample was extinguished within 30s, the sample was re-ignited, the combustion conditions of the sample were observed and the time for which the sample was continuously combusted was recorded, and the vertical combustion rating was determined from the recorded test results. The vertical burn test mainly observes whether the sample self-extinguishes or drops occur during the combustion process within 10s or 30 s. Stopping burning the vertical sample within 10 seconds; no dripping is generated, namely UL94-V0 grade is achieved; the sample strip is extinguished within 30 seconds after ignition, and no polymer molten drop is generated in the combustion process, so that the sample strip is UL94-V1 grade; the sample strip is extinguished within 30 seconds after ignition and molten drops are generated in the combustion process, so that the sample strip belongs to the UL94-V2 grade.
Limiting oxygen index test: cutting the PVC sheaths prepared in the examples 1 and comparative examples 1-4 into strips with the dimensions of 120mm multiplied by 6.5mm multiplied by 3mm, testing the limiting oxygen index of the composite material by a limiting oxygen index tester, marking the 50mm position of the sample strip, putting the sample strip into a combustion cylinder, igniting one end of the sample strip, recording the combustion time and position of the sample strip, repeating the operation until the sample strip is just burnt to the 50mm position when the combustion time is 3min, recording the LOI value at the moment, and testing the result as shown in the table 1:
table 1: flame retardant property test result of PVC sheath
From the experimental data in table 1, it can be seen that the PVC jacket prepared in example 1 has the best flame retardant performance, while the difference between example 1 and other comparative examples is that phosphorothioate, polyphosphazene rich in triazine, 6-maleimide caproyl chloride are added to generate the halogen-free flame retardant through amidation reaction, and the possible reason is that the flame retardant can be better dispersed in a matrix material, phosphorothioate is rich in N, S and other flame retardant elements, and the compound can decompose acidic substances during combustion to promote formation of carbon layer on the surface of the matrix; the triazine-rich polyphosphazene plays a role in quenching free radical chain reaction in the combustion process by capturing H and OH free radicals, benzimidazole and benzene mercaptan can be further decomposed to generate sulfur/nitrogen nonflammable gas, the sulfur/nitrogen nonflammable gas serves as a diluent for oxygen and fuel, flame propagation is prevented, the purpose of flame retardance is achieved, and the cooperation of phosphorothioate and triazine-rich polyphosphazene improves the flame retardance of the material.
Test example 2
Line integrity test: line integrity test for Electrical or optical cables under flame conditions section 21 according to GB/T19216.21-2003: test procedure and Cable with rated Voltage of 0.6/1.0kV and below were tested for line integrity on the anti-aging insulated flame retardant power cable prepared in example 1, and whether continuous power supply was possible was judged based on the indication of the terminal indicator light. The test results are: and under the condition of 950-1000 ℃ and 0.6kV loading, the indicator lamp is not extinguished within 90 minutes, and the test result is qualified.
Claims (6)
1. The utility model provides an ageing resistance insulating fire-retardant power cable, includes cable core and from interior metal sheath and the nonmetal oversheath of cladding cable core in proper order outward, its characterized in that, concretely preparation technology is as follows: twisting N conductors into a bundle, sequentially wrapping PTFE wrapping layers and insulating layers on the outer sides of the N conductors to obtain wire cores, bundling 5 groups of wire cores to form cable cores, filling flame-retardant filler in gaps between the cable cores, and sequentially wrapping an aluminum sheath, a steel tape armor layer and a nonmetallic outer sheath on the outer sides of the cable cores to obtain the anti-aging insulating flame-retardant power cable;
the nonmetallic outer sheath is a PVC sheath and comprises the following components in parts by weight: 80-100 parts of PVC resin, 10-30 parts of polyvinylidene chloride, 10-20 parts of silicone rubber, 10-20 parts of superfine calcium carbonate, 5-10 parts of calcium-zinc composite stabilizer, 0.5-0.9 part of anti-aging agent, 0.5-0.9 part of antioxidant, 40-60 parts of plasticizer, 10-15 parts of halogen-free flame retardant and 0.1-0.3 part of lubricant;
the preparation method of the halogen-free flame retardant comprises the following steps:
1) Mixing 5-8g of 2-mercaptobenzimidazole, 150-200mL of acetonitrile and 5-10mL of triethylamine at room temperature, and uniformly stirring to obtain a mixed system 1; dissolving 8-12g of diphenyl phosphoryl chloride in 100-150mL of acetonitrile to obtain an acetonitrile solution of diphenyl phosphoryl chloride; then dripping acetonitrile solution of diphenyl phosphoryl chloride into the mixed system 1 at the speed of 1-2 drops/second, reacting for 2-4 hours at room temperature, heating to 70-100 ℃ and reacting for 10-12 hours; cooling to room temperature, filtering, washing the filter cake with saturated sodium bicarbonate and water for 2-3 times, and drying at 60-80deg.C for 10-12 hr to obtain phosphorothioate;
2) Dissolving 0.3-0.5g melamine in 20-30mL pyridine to obtain solution A; dissolving 0.5-1g of hexachlorocyclotriphosphazene in 10-20mL of pyridine to obtain a solution B; then adding the solution B into the solution A; heating to 100-120 ℃ and reacting for 20-24h; cooling to room temperature after the reaction is finished; filtering, washing the filter cake with water and absolute ethyl alcohol for 2-3 times respectively, and drying at 50-80 ℃ for 10-12 hours to obtain triazine-rich polyphosphazene;
3) 3-5g of 6-maleimide caproic acid is dissolved in 10-15mL of thionyl chloride, and stirred and reacted for 8-9 hours at the temperature of 60-100 ℃; after the reaction is finished, cooling to room temperature, and decompressing and evaporating the solvent to obtain 6-maleimide caproyl chloride; dispersing 1-3g of phosphorothioate and 2-4g of polyphosphazene rich in triazine in 200-300mL of pyridine, and performing ultrasonic treatment at 30-50 ℃ under the conditions of 80-120W and 40-60kHz for 20-30min to obtain a mixed system 2; dropwise adding 10-20mL of 6-maleimide caproyl chloride into the mixed system 2 at a speed of 2-3 drops/sec; reacting at 100-140 ℃ for 20-24h, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with absolute ethyl alcohol and water for 2-3 times respectively, and drying at 60-80 ℃ for 10-12h to obtain the halogen-free flame retardant.
2. The anti-aging insulated flame retardant power cable of claim 1, wherein: the conductor is one of copper wires and aluminum alloy, and N is more than or equal to 3.
3. The anti-aging insulated flame retardant power cable of claim 1, wherein: the flame-retardant filler is one of glass fiber and carbon fiber.
4. The anti-aging insulated flame retardant power cable of claim 1, wherein: the anti-aging agent is one of 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline and 4,4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine.
5. The anti-aging insulated flame retardant power cable of claim 1, wherein: the antioxidant is one or more than two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, tri [2, 4-di-tert-butylphenyl ] phosphite, dilauryl thiodipropionate and 2, 8-di-tert-butyl-4-methylphenol.
6. The anti-aging insulated flame-retardant power cable according to claim 1, wherein the PVC jacket is prepared by the following method: uniformly mixing PVC resin, polyvinylidene chloride and silicone rubber to obtain a main material, and then blending and granulating to obtain a base resin; banburying for 1-3min, and heating to 80-90deg.C for 4-5min; adding superfine calcium carbonate, calcium zinc composite stabilizer, antioxidant, plasticizer, halogen-free flame retardant and lubricant, mixing for 1-2min, feeding into an open mill, passing through for 6-7 times, and finally extruding in an extruder at 185-190 ℃ and steam pressure of 0.8-1.5MPa to obtain the PVC sheath.
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| CN (1) | CN115785591B (en) |
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| CN115785591A (en) | 2023-03-14 |
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Denomination of invention: An anti-aging insulated flame retardant power cable Granted publication date: 20231013 Pledgee: China Life Property insurance Co.,Ltd. Qingdao Branch Pledgor: Qingdao Jiaozhou Bay Cable Co.,Ltd. Registration number: Y2024370010047 |