CN117402438A - Preparation method and application of self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material - Google Patents
Preparation method and application of self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material Download PDFInfo
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- CN117402438A CN117402438A CN202311547049.4A CN202311547049A CN117402438A CN 117402438 A CN117402438 A CN 117402438A CN 202311547049 A CN202311547049 A CN 202311547049A CN 117402438 A CN117402438 A CN 117402438A
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- Prior art keywords
- free flame
- retardant
- cable material
- self
- smoke halogen
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 181
- 239000000463 material Substances 0.000 title claims abstract description 146
- 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 142
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 125
- 238000004132 cross linking Methods 0.000 title claims abstract description 88
- 239000000779 smoke Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012767 functional filler Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 24
- 239000004020 conductor Substances 0.000 claims abstract description 4
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 70
- 239000003431 cross linking reagent Substances 0.000 claims description 58
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 47
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 34
- 239000003963 antioxidant agent Substances 0.000 claims description 32
- 230000003078 antioxidant effect Effects 0.000 claims description 32
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 29
- 229910000077 silane Inorganic materials 0.000 claims description 29
- 239000012752 auxiliary agent Substances 0.000 claims description 24
- 229920005672 polyolefin resin Polymers 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 22
- 238000007906 compression Methods 0.000 claims description 20
- 230000006835 compression Effects 0.000 claims description 20
- -1 polysiloxane Polymers 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 17
- 239000000347 magnesium hydroxide Substances 0.000 claims description 16
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 16
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000011229 interlayer Substances 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 12
- 229920002943 EPDM rubber Polymers 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 11
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 10
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 9
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012796 inorganic flame retardant Substances 0.000 claims description 9
- 235000002949 phytic acid Nutrition 0.000 claims description 9
- 229940068041 phytic acid Drugs 0.000 claims description 9
- 239000000467 phytic acid Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- 229910019015 Mg-Ag Inorganic materials 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound 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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010690 paraffinic oil Substances 0.000 claims description 2
- 229920003257 polycarbosilane Polymers 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
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- 230000008901 benefit Effects 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
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- 230000002195 synergetic effect Effects 0.000 description 4
- 229910003023 Mg-Al Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- 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
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
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Abstract
A preparation method and application of a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material belong to the field of cable manufacturing. The method comprises the following steps: 1. preparing functional filler; 2. preparing polyolefin grafted functional filler; 3. preparing a catalytic flame-retardant master batch; 4. preparing a soft low-smoke halogen-free flame-retardant polyolefin cable material; 5. the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material is prepared. The self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material can be extruded and coated on a conductor or a single-core wire, can be used as an insulated or sheathed cable, can meet the requirements of the application field of medium-low voltage cables, can reduce the energy consumption in the crosslinking of the cable, can meet the requirements of the cable on performances such as softness, environmental friendliness, fire safety, temperature resistance and the like, and is suitable for the development targets of environmental protection and low carbon. The invention can obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material.
Description
Technical Field
The invention belongs to the field of cable manufacture, and particularly relates to a self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material, and a preparation method and application thereof.
Background
Polyolefin materials are widely used as insulation and sheathing materials for cables due to their excellent properties. Because polyolefin materials have limited heat resistance, crosslinking techniques are often used to improve their heat resistance and to increase operating temperatures. The crosslinking technology commonly used at present comprises methods such as chemical crosslinking, irradiation crosslinking, ultraviolet crosslinking and the like, and in practical application, the application fields of the method are different in consideration of advantages and disadvantages of different methods. In recent years, a polyolefin crosslinking method featuring a self-crosslinking technology has gained general attention in the cable industry, and the method has low requirements on equipment of cable enterprises and meets the environmental protection requirements. The self-crosslinking technology is mainly used for crosslinking the polyethylene cable material, and the method has limited crosslinking degree and higher requirements on material formula and processing technology, so that the technology of the self-crosslinking halogen-free flame-retardant polyolefin cable material meeting the requirements on flexibility and flame retardant property still has great difficulty.
CN113969009a provides a high temperature resistant self-crosslinking halogen-free flame retardant cable material, its preparation method and application, its component uses polyethylene and ethylene-vinyl acetate copolymer as resin, adopts tributyl phosphate fire retardant 2-5 parts and calcium silicate filler 1-3 parts, the cable material does not need to undergo physical irradiation procedures such as electron accelerator, etc., can self-crosslink under natural conditions in summer, used for manufacturing the high voltage special cable for new energy electric automobile. The patent does not provide flame retardant performance data.
CN113185796a provides a room temperature self-crosslinking 125 ℃ halogen-free flame-retardant cable material and a preparation method thereof, wherein maleic anhydride of a side chain of a maleic anhydride grafting material is used as a reactive point, a second component polyamine compound is introduced, and a coupling agent is added to treat modified magnesium hydroxide, aluminum hydroxide and a char forming auxiliary agent as a flame-retardant system, so that the flame-retardant cable material is prepared through A, B components. Wherein the resin matrix comprises maleic anhydride grafted polyethylene, metallocene polyethylene, ethylene-vinyl acetate copolymer and ethylene-butyl acrylate copolymer, and the polyamine compound is one or a mixture of several of polyethylene polyamine, ethylenediamine, diethylenetriamine, triethyltetramine and tetraethylpentamine. The patent does not provide data on the flexibility of the cable material.
As a key raw material of the halogen-free flame-retardant polyolefin cable material, the resin matrix commonly used at present is an ethylene-vinyl acetate copolymer, the halogen-free flame retardant is an inorganic flame retardant such as magnesium hydroxide or aluminum hydroxide, and the composition and the formula of the resin matrix are relatively mature in the preparation of the halogen-free flame-retardant cable material, however, a self-crosslinking system based on silane crosslinking is difficult to break through a technical barrier of processing and crosslinking due to the higher consumption of the inorganic flame retardant. Meanwhile, the polyethylene-based formulation technology often results in higher hardness of cable materials, and is difficult to use for production and manufacture of cables with higher flexibility requirements. Therefore, developing a low smoke halogen-free flame retardant polyolefin cable material which is soft, heat-resistant, flame retardant, environment-friendly and self-crosslinking is a material requirement with wide practical value in the cable field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material, and a preparation method and application thereof. The invention takes ethylene propylene diene monomer rubber and polyolefin elastomer representing flexible polyolefin materials as resin matrixes, and is compounded with an ethylene-vinyl acetate copolymer and an inorganic synergistic flame-retardant system, and a self-crosslinking flexible low-smoke halogen-free flame-retardant polyolefin cable material is developed by introducing functional fillers with flame-retardant elements and polyhydroxy groups, combining the plasticizing function of a flexible auxiliary agent and utilizing the surface modification and crosslinking functions of a silane coupling agent, and through the process steps of preparing the functional fillers, preparing polyolefin grafted functional fillers, preparing catalytic flame-retardant master batches and the like.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material is specifically completed by the following steps:
1. preparing functional filler:
(1) performing heat treatment on the layered double hydroxide in a muffle furnace at 400-600 ℃ for 2-10 h to obtain a layered double oxide;
(2) Preparing solution according to the mass ratio of deionized water, lamellar bimetal oxide and interlayer modifier of 100 (5-50) (0.5-5), processing the prepared solution for 0.5-2 h under the ultrasonic with the power of 200-500W, then putting the solution into a hydrothermal reaction kettle, reacting for 1-10 h at the temperature of 110-150 ℃, filtering the solution after the reaction kettle is cooled to the room temperature, washing a filter cake with deionized water for 3-5 times, and finally drying the filter cake in an oven at the temperature of 80-120 ℃ for 2-8 h to obtain functional filler;
2. preparing polyolefin grafted functional filler:
(1) preparing a vinyl silane solution according to the mass ratio of (0.05-0.5) to (0.5-5) of absolute ethyl alcohol, deionized water and a vinyl silane coupling agent of 1;
(2) adding functional filler into a high-speed mixer, mixing for 1-5 min at the rotating speed of 500-1500 rpm, adding a vinyl silane solution into the high-speed mixer according to the mass ratio of the functional filler to the vinyl silane coupling agent of 1 (0.01-0.1), mixing for 1-5 min at the rotating speed of 500-1500 rpm, and drying the mixture in an oven at 80-120 ℃ for 2-8 h to obtain the vinyl silane modified functional filler;
(3) according to the mass ratio of the vinyl silane coupling agent to the cross-linking agent of 1 (0.1-1), dissolving the cross-linking agent in the vinyl silane coupling agent to obtain a silane solution of the cross-linking agent, according to the mass ratio of the polyolefin resin to the vinyl silane modified functional filler to the silane solution of the cross-linking agent of 1 (0.5-1), adding the silane solution of the cross-linking agent into a high-speed mixer (0.005-0.1), mixing the silane modified functional filler with the high-speed mixer at 500-1500 rpm for 1-5 min, adding the mixed material into a double-screw extruder, extruding and granulating to obtain the polyolefin grafted functional filler;
3. Preparing a catalytic flame-retardant master batch:
(1) the halogen-free flame retardant, the flexible auxiliary agent, the vinyl silane coupling agent and the catalyst are added into a high-speed mixer according to the mass ratio of 100 (2-20) (0.5-5) (0.05-0.5), and mixed for 1-5 min at the rotating speed of 500-1500 rpm to obtain the functional composite flame retardant;
(2) adding polyolefin into an internal mixer, adding the functional composite flame retardant into the internal mixer according to the mass ratio of the polyolefin to the functional composite flame retardant of 1 (1-5), mixing until the temperature of the internal mixer reaches 120-150 ℃, turning the material out of the internal mixer, and continuously granulating to obtain the catalytic flame-retardant master batch;
4. preparing a soft low-smoke halogen-free flame-retardant polyolefin cable material:
according to the mass ratio of 1 (0.2-2): (2-10): (5-20): (0.1-1.0): (0.02-0.2) of polyolefin resin, halogen-free flame retardant, polyolefin grafted functional filler, catalytic flame retardant master batch, processing aid, antioxidant and cross-linking agent, adding into a high-speed mixer, adopting the high-speed mixer to mix for 1-5 min at the rotating speed of 500-1500 rpm, adding the mixed material into a double-screw extruder, granulating, and obtaining the soft low-smoke halogen-free flame retardant polyolefin cable material;
5. preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material:
Extruding the soft low-smoke halogen-free flame-retardant polyolefin cable material by adopting a single screw extruder to obtain a required shape, and placing the cable material in a natural environment to obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material.
A self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material can be extruded and coated on a conductor or a single-core wire, and can be used as an insulating or sheath cable, thereby meeting the requirements of the application field of medium-voltage cables.
The principle of the invention is as follows:
the principle of the invention is that the following three points are: firstly, by means of interlayer chemical characteristics of layered double metal hydroxide, polyhydroxy phytic acid is introduced between layers to form structural functional filler with flame retardant property and dehydration capability, so that the flame retardant property of the material can be improved, the consumption of flame retardant can be reduced, the self-crosslinking capability can be improved, and the crosslinking degree of the material can be ensured; secondly, silane grafting reaction is utilized, a silane coupling agent is used for modifying the surfaces of the flame retardant and the filler to introduce silicon hydroxyl and double bond functional groups, and the silane coupling agent and the polyolefin undergo grafting reaction under the action of a crosslinking agent, so that the grafting efficiency is improved, and the crosslinking reaction process is enhanced; thirdly, the dispersibility of the functional filler with flame retardant elements and polyhydroxy groups is guaranteed by preparing the polyolefin grafted functional filler, the method is one of key processes for obtaining the cable material with high crosslinking degree, the plasticizing function of the flexible auxiliary agent, the modified crosslinking function of the flame retardant and the dispersing catalytic function of the catalyst are organically combined by preparing the catalytic flame retardant master batch, and the two key processes for obtaining the cable material with high crosslinking degree are combined to prepare the soft low-smoke halogen-free flame retardant polyolefin cable material with self-crosslinking capacity by a one-step method.
Compared with the prior art, the invention has the following advantages:
(1) The invention takes polyolefin as a matrix, combines with inorganic environment-friendly flame retardant, utilizes the structure and performance advantages of two-dimensional functional filler, realizes the promotion of flame retardant property and self-crosslinking capability, well balances the mechanical property, insulating property, aging property and processing property, obtains self-crosslinking soft low-smoke halogen-free flame retardant polyolefin cable material, meets the development requirements of environment, low-carbon and fire safety cables and materials thereof, and is suitable for manufacturing and application of cables required in the fields of automobiles, new energy, electric and electronic, rail transit and the like.
(2) The invention takes the one-step preparation process as the main process, combines the grafting modification of the functional filler and the structuring treatment of the catalytic flame-retardant master batch, and realizes the self-crosslinking process of the soft low-smoke halogen-free flame-retardant polyolefin cable material at normal temperature by means of the high-temperature grafting crosslinking process. The method provided by the invention does not need special equipment, has controllable process parameters and high preparation efficiency, uses conventional instruments and equipment in the cable field, and is suitable for manufacturing and application in the industrial field.
(3) The invention fully utilizes the interlayer structure characteristics of the layered double hydroxide and the synergistic flame retardant effect thereof, and is compounded with the phosphorus-containing phytic acid with a polyhydroxy structure, and the double reinforcement of flame retardant and self-crosslinking functions is realized while the dispersibility is improved through intercalation modification and grafting modification methods. The phytic acid with the polyhydroxy phosphorus structure is introduced between layers, so that the problem of controllable dehydration is solved, the flame-retardant synergistic effect of the phytic acid is brought into play, and the problem of pre-crosslinking caused by polyhydroxy dehydration is avoided through polyolefin grafting, so that the stability of a composite system is improved.
(4) The self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material provided by the invention accords with the development trend of the cable material under the low-carbon environment-friendly background, can meet the requirements of the electric wires and cables on performances such as softness, environment friendliness, fire safety, temperature resistance and the like, and has the characteristics of low carbon, energy conservation and environment friendliness.
(5) The self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material prepared by the invention has better comprehensive performance, and is characterized in that: the flame retardant property is excellent, and the oxygen index is higher than 32%; excellent softening performance, shore A can be as low as 82A; the mechanical property is excellent, the tensile strength is more than 11MPa, and the elongation at break is more than 200%; the heat aging performance is excellent, and the retention rate of the tensile strength and the elongation at break is more than 80 percent through a heat aging test at 168 hours@135 ℃.
The invention can obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material.
Detailed Description
The first embodiment is as follows: the preparation method of the self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material is specifically completed by the following steps:
1. preparing functional filler:
(1) performing heat treatment on the layered double hydroxide in a muffle furnace at 400-600 ℃ for 2-10 h to obtain a layered double oxide;
(2) Preparing solution according to the mass ratio of deionized water, lamellar bimetal oxide and interlayer modifier of 100 (5-50) (0.5-5), processing the prepared solution for 0.5-2 h under the ultrasonic with the power of 200-500W, then putting the solution into a hydrothermal reaction kettle, reacting for 1-10 h at the temperature of 110-150 ℃, filtering the solution after the reaction kettle is cooled to the room temperature, washing a filter cake with deionized water for 3-5 times, and finally drying the filter cake in an oven at the temperature of 80-120 ℃ for 2-8 h to obtain functional filler;
2. preparing polyolefin grafted functional filler:
(1) preparing a vinyl silane solution according to the mass ratio of (0.05-0.5) to (0.5-5) of absolute ethyl alcohol, deionized water and a vinyl silane coupling agent of 1;
(2) adding functional filler into a high-speed mixer, mixing for 1-5 min at the rotating speed of 500-1500 rpm, adding a vinyl silane solution into the high-speed mixer according to the mass ratio of the functional filler to the vinyl silane coupling agent of 1 (0.01-0.1), mixing for 1-5 min at the rotating speed of 500-1500 rpm, and drying the mixture in an oven at 80-120 ℃ for 2-8 h to obtain the vinyl silane modified functional filler;
(3) according to the mass ratio of the vinyl silane coupling agent to the cross-linking agent of 1 (0.1-1), dissolving the cross-linking agent in the vinyl silane coupling agent to obtain a silane solution of the cross-linking agent, according to the mass ratio of the polyolefin resin to the vinyl silane modified functional filler to the silane solution of the cross-linking agent of 1 (0.5-1), adding the silane solution of the cross-linking agent into a high-speed mixer (0.005-0.1), mixing the silane modified functional filler with the high-speed mixer at 500-1500 rpm for 1-5 min, adding the mixed material into a double-screw extruder, extruding and granulating to obtain the polyolefin grafted functional filler;
3. Preparing a catalytic flame-retardant master batch:
(1) the halogen-free flame retardant, the flexible auxiliary agent, the vinyl silane coupling agent and the catalyst are added into a high-speed mixer according to the mass ratio of 100 (2-20) (0.5-5) (0.05-0.5), and mixed for 1-5 min at the rotating speed of 500-1500 rpm to obtain the functional composite flame retardant;
(2) adding polyolefin into an internal mixer, adding the functional composite flame retardant into the internal mixer according to the mass ratio of the polyolefin to the functional composite flame retardant of 1 (1-5), mixing until the temperature of the internal mixer reaches 120-150 ℃, turning the material out of the internal mixer, and continuously granulating to obtain the catalytic flame-retardant master batch;
4. preparing a soft low-smoke halogen-free flame-retardant polyolefin cable material:
according to the mass ratio of 1 (0.2-2): (2-10): (5-20): (0.1-1.0): (0.02-0.2) of polyolefin resin, halogen-free flame retardant, polyolefin grafted functional filler, catalytic flame retardant master batch, processing aid, antioxidant and cross-linking agent, adding into a high-speed mixer, adopting the high-speed mixer to mix for 1-5 min at the rotating speed of 500-1500 rpm, adding the mixed material into a double-screw extruder, granulating, and obtaining the soft low-smoke halogen-free flame retardant polyolefin cable material;
5. preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material:
Extruding the soft low-smoke halogen-free flame-retardant polyolefin cable material by adopting a single screw extruder to obtain a required shape, and placing the cable material in a natural environment to obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the layered double hydroxide in the step one (1) is Mg-Ag layered double hydroxide or Zn-Al layered double hydroxide; the interlayer modifier in the step one (2) is phytic acid. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the vinyl silane coupling agent in the step II (1), the step II (3) and the step III (1) is one or a combination of more of vinyl trimethoxy silane, vinyl triethoxy silane and vinyl tri (beta-methoxyethoxy) silane; the cross-linking agent in the second step (3) and the fourth step comprises organic peroxide and auxiliary cross-linking agent, wherein the mass ratio of the organic peroxide to the auxiliary cross-linking agent is 1 (0.2-2); the organic peroxide is one of dicumyl peroxide and 2, 4-di-tert-butyl cumyl peroxide; the auxiliary cross-linking agent is one of triallyl isocyanurate, triallyl cyanurate and trimethylolpropane trimethacrylate. The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the polyolefin resin in the second step (3) and the fourth step is one or a combination of more than one of ethylene propylene diene monomer, polyolefin elastomer and ethylene-vinyl acetate copolymer; the density of the ethylene propylene diene monomer is 0.86g/cm 3 ～0.90g/cm 3 The Shore A hardness is lower than 80; the polyolefin elastomer has a density of 0.86g/cm 3 ～0.90g/cm 3 Ethylene-octene copolymer having a Shore A hardness of less than 85; the ethylene-vinyl acetate copolymer contains 17% -40% of vinyl acetate, and the Shore A hardness is lower than 85. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: the halogen-free flame retardant in the step three (1) and the step four comprises an inorganic flame retardant and a flame retardant synergist; the mass ratio of the inorganic flame retardant to the flame retardant synergist is 1 (0.01-0.1); the inorganic flame retardant is one or a combination of more of magnesium hydroxide, aluminum hydroxide and zinc borate; the flame retardant synergist is one or a combination of more of polycarbosilane, polysiloxane and silicone resin; the flexible auxiliary agent in the step three (1) is one or the combination of a plurality of paraffinic oil, naphthenic oil and white oil; the catalyst in the step three (1) is one of dibutyl tin dilaurate and stannous octoate. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the processing aid in the fourth step is one or a combination of more of polyethylene wax, stearic acid, zinc stearate, silicone and zinc oxide; the antioxidant comprises a primary antioxidant and an auxiliary antioxidant, wherein the mass ratio of the primary antioxidant to the auxiliary antioxidant is 1 (0.2-2); the main antioxidant is one or a combination of more of an antioxidant 1010, an antioxidant 1076 and an antioxidant 1098; the auxiliary antioxidant is one or the combination of more of antioxidant 168, antioxidant DLTP, antioxidant DSTP and antioxidant 1024. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the temperature of the twin-screw extruder in the second step (3) is set as follows: the conveying section is at 80-120 ℃, the compression section is at 140-180 ℃, the metering section is at 160-200 ℃, and the machine head is at 180-200 ℃. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the temperature of the twin-screw extruder in the fourth step is set as follows: the conveying section is at 60-100 ℃, the compression section is at 100-140 ℃, the metering section is at 100-140 ℃, and the machine head is at 110-140 ℃. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the temperature of the single screw extruder in the fifth step is set as follows: the conveying section is at 80-120 ℃, the compression section is at 140-180 ℃, the metering section is at 160-200 ℃, and the machine head is at 180-200 ℃. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the self-crosslinking soft low-smoke zero-halogen flame-retardant polyolefin cable material can be extruded and coated on a conductor or a single-core wire, and can be used as an insulating or sheath cable to meet the requirements of the application field of medium-voltage cables.
The following examples are used to verify the benefits of the present invention:
example 1: the preparation method of the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material is specifically completed by the following steps:
1. preparing functional filler:
(1) performing heat treatment on the layered double hydroxide in a muffle furnace at 500 ℃ for 6 hours to obtain a layered double oxide;
(2) preparing a solution according to the mass ratio of deionized water to layered double metal oxide to interlayer modifier of 100:10:4, treating the prepared solution for 1h under the ultrasonic with the power of 300W, then putting the solution into a hydrothermal reaction kettle, reacting for 8h at 120 ℃, filtering the solution after the reaction kettle is cooled to room temperature, washing a filter cake with deionized water for 5 times, and finally drying the filter cake in a baking oven at 100 ℃ for 6h to obtain the functional filler;
2. Preparing polyolefin grafted functional filler:
(1) preparing a vinyl silane solution according to the mass ratio of absolute ethyl alcohol, deionized water and a vinyl silane coupling agent of 1:0.1:0.5;
(2) adding the functional filler into a high-speed mixer, mixing for 3min at the rotating speed of 1000rpm, adding a vinyl silane solution into the high-speed mixer according to the mass ratio of the functional filler to the vinyl silane coupling agent of 1:0.02, mixing for 3min at the rotating speed of 1000rpm, and drying the mixture in a baking oven at 120 ℃ for 6h to obtain the vinyl silane modified functional filler;
(3) according to the mass ratio of the vinyl silane coupling agent to the cross-linking agent of 1:0.5, dissolving the cross-linking agent in the vinyl silane coupling agent to obtain a silane solution of the cross-linking agent, adding the silane solution of the cross-linking agent into a high-speed mixer according to the mass ratio of the polyolefin resin to the vinyl silane modified functional filler to the silane solution of the cross-linking agent of 1:0.85:0.04, mixing the materials for 3min at the rotating speed of 1000rpm by adopting the high-speed mixer, adding the mixed materials into a double-screw extruder, extruding and granulating to obtain the polyolefin grafted functional filler;
3. preparing a catalytic flame-retardant master batch:
(1) adding the halogen-free flame retardant, the flexible auxiliary agent, the vinyl silane coupling agent and the catalyst into a high-speed mixer according to the mass ratio of 100:7.5:3.5:0.25, and mixing for 4min at the rotating speed of 1200rpm to obtain the functional composite flame retardant;
(2) Adding polyolefin into an internal mixer, adding the functional composite flame retardant into the internal mixer according to the mass ratio of the polyolefin to the functional composite flame retardant of 1:2.2, mixing until the temperature of the internal mixer reaches 140 ℃, turning the material out of the internal mixer, and continuously granulating to obtain a catalytic flame-retardant master batch;
4. preparing a soft low-smoke halogen-free flame-retardant polyolefin cable material:
according to the mass ratio of polyolefin resin, halogen-free flame retardant, polyolefin grafted functional filler, catalytic flame retardant master batch, processing aid, antioxidant and cross-linking agent being 1:1.25:7.67:16.13:0.50:0.25:0.20, adding the materials into a high-speed mixer, adopting the high-speed mixer to mix for 2min at the rotating speed of 1200rpm, adding the mixed materials into a double-screw extruder, and granulating to obtain the soft low-smoke halogen-free flame retardant polyolefin cable material;
5. preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material:
extruding the soft low-smoke halogen-free flame-retardant polyolefin cable material by adopting a single screw extruder to obtain a required shape, and placing the cable material in a natural environment to obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material;
the layered double hydroxide in the step one (1) is Mg-Al layered double hydroxide;
The interlayer modifier in the step one (2) is phytic acid;
the vinyl silane coupling agent in the step two (1), the step two (3) and the step three (1) is vinyl triethoxysilane;
the cross-linking agent in the step two (3) and the step four is a mixture of 2, 4-di-tert-butyl cumyl peroxide and triallyl isocyanurate, wherein the mass ratio of the 2, 4-di-tert-butyl cumyl peroxide to the triallyl isocyanurate is 0.4:0.6;
the polyolefin resin in the second step (3) and the fourth step is a mixture of EVA, POE and EPDM, wherein the mass ratio of the EVA to the POE to the EPDM is 20:10:6;
the halogen-free flame retardant in the step three (1) and the step four is a mixture of magnesium hydroxide and polysiloxane, wherein the mass ratio of the magnesium hydroxide to the polysiloxane is 42:3;
the flexible auxiliary agent in the step three (1) is naphthenic oil;
the catalyst in the step three (1) is dibutyl tin dilaurate;
the processing aid in the fourth step is a mixture of polyethylene wax and zinc stearate, wherein the mass ratio of the polyethylene wax to the zinc stearate is 1.5:0.5;
the antioxidant in the fourth step is a mixture of an antioxidant 1010 and an antioxidant 168, wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 is 0.6:0.4;
The temperature of the twin-screw extruder in the second step (3) is set as follows: the conveying section is 90 ℃, the compression section is 150 ℃, the metering section is 180 ℃, and the machine head is 180 ℃;
the temperature of the twin-screw extruder in the fourth step is set as follows: the conveying section is 70 ℃, the compression section is 120 ℃, the metering section is 120 ℃, and the machine head is 130 ℃;
the temperature of the single screw extruder in the fifth step is set as follows: the conveying section is 100 ℃, the compression section is 160 ℃, the metering section is 190 ℃, and the machine head is 190 ℃.
Example 2: the preparation method of the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material is specifically completed by the following steps:
1. preparing functional filler:
(1) performing heat treatment on the layered double hydroxide in a muffle furnace at 500 ℃ for 6 hours to obtain a layered double oxide;
(2) preparing a solution according to the mass ratio of deionized water to layered double metal oxide to interlayer modifier of 100:10:5, treating the prepared solution for 1h under the ultrasonic with the power of 300W, then putting the solution into a hydrothermal reaction kettle, reacting for 8h at 120 ℃, filtering the solution after the reaction kettle is cooled to room temperature, washing a filter cake with deionized water for 5 times, and finally drying the filter cake in a baking oven at 100 ℃ for 6h to obtain the functional filler;
2. Preparing polyolefin grafted functional filler:
(1) preparing a vinyl silane solution according to the mass ratio of absolute ethyl alcohol, deionized water and a vinyl silane coupling agent of 1:0.1:0.5;
(2) adding the functional filler into a high-speed mixer, mixing for 3min at the rotating speed of 1000rpm, adding a vinyl silane solution into the high-speed mixer according to the mass ratio of the functional filler to the vinyl silane coupling agent of 1:0.02, mixing for 3min at the rotating speed of 1000rpm, and drying the mixture in a baking oven at 120 ℃ for 6h to obtain the vinyl silane modified functional filler;
(3) according to the mass ratio of the vinyl silane coupling agent to the cross-linking agent of 1:0.5, dissolving the cross-linking agent in the vinyl silane coupling agent to obtain a silane solution of the cross-linking agent, adding the silane solution of the cross-linking agent into a high-speed mixer according to the mass ratio of the polyolefin resin to the vinyl silane modified functional filler to the silane solution of the cross-linking agent of 1:0.85:0.05, mixing the materials for 3min at the rotating speed of 1000rpm by adopting the high-speed mixer, adding the mixed materials into a double-screw extruder, extruding and granulating to obtain the polyolefin grafted functional filler;
3. preparing a catalytic flame-retardant master batch:
(1) adding the halogen-free flame retardant, the flexible auxiliary agent, the vinyl silane coupling agent and the catalyst into a high-speed mixer according to the mass ratio of 100:10.5:3.7:0.26, and mixing for 4min at the rotating speed of 1200rpm to obtain the functional composite flame retardant;
(2) Adding polyolefin into an internal mixer, adding the functional composite flame retardant into the internal mixer according to the mass ratio of the polyolefin to the functional composite flame retardant of 1:2.0, mixing until the temperature of the internal mixer reaches 140 ℃, turning the material out of the internal mixer, and continuously granulating to obtain a catalytic flame-retardant master batch;
4. preparing a soft low-smoke halogen-free flame-retardant polyolefin cable material:
according to the mass ratio of polyolefin resin to halogen-free flame retardant to polyolefin grafted functional filler to catalytic flame retardant master batch to processing aid to antioxidant to cross-linking agent of 1:0.33:3.80:10.90:0.33:0.16:0.12, adding the materials into a high-speed mixer, adopting the high-speed mixer to mix for 2min at the rotating speed of 1200rpm, adding the mixed materials into a double-screw extruder, and granulating to obtain the soft low-smoke halogen-free flame retardant polyolefin cable material;
5. preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material:
extruding the soft low-smoke halogen-free flame-retardant polyolefin cable material by adopting a single screw extruder to obtain a required shape, and placing the cable material in a natural environment to obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material;
the layered double hydroxide in the step one (1) is Mg-Al layered double hydroxide;
The interlayer modifier in the step one (2) is phytic acid;
the vinyl silane coupling agent in the step two (1), the step two (3) and the step three (1) is vinyl triethoxysilane;
the cross-linking agent in the step two (3) and the step four is a mixture of 2, 4-di-tert-butyl cumyl peroxide and triallyl isocyanurate, wherein the mass ratio of the 2, 4-di-tert-butyl cumyl peroxide to the triallyl isocyanurate is 0.3:0.6;
the polyolefin resin in the second step (3) and the fourth step is a mixture of POE and EPDM, wherein the mass ratio of the POE to the EPDM is 25:15;
the halogen-free flame retardant in the step three (1) and the step four is a mixture of magnesium hydroxide and polysiloxane, wherein the mass ratio of the magnesium hydroxide to the polysiloxane is 38:2;
the flexible auxiliary agent in the step three (1) is naphthenic oil;
the catalyst in the step three (1) is dibutyl tin dilaurate;
the processing aid in the fourth step is a mixture of silicone and zinc oxide, wherein the mass ratio of the silicone to the zinc oxide is 1.5:0.5;
the antioxidant in the fourth step is a mixture of an antioxidant 1010 and an antioxidant 168, wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 is 0.6:0.4;
The temperature of the twin-screw extruder in the second step (3) is set as follows: the conveying section is 90 ℃, the compression section is 150 ℃, the metering section is 180 ℃, and the machine head is 180 ℃;
the temperature of the twin-screw extruder in the fourth step is set as follows: the conveying section is 70 ℃, the compression section is 120 ℃, the metering section is 120 ℃, and the machine head is 130 ℃;
the temperature of the single screw extruder in the fifth step is set as follows: the conveying section is 100 ℃, the compression section is 160 ℃, the metering section is 190 ℃, and the machine head is 190 ℃.
Example 3: the preparation method of the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material is specifically completed by the following steps:
1. preparing functional filler:
(1) performing heat treatment on the layered double hydroxide in a muffle furnace at 500 ℃ for 6 hours to obtain a layered double oxide;
(2) preparing a solution according to the mass ratio of deionized water to layered double metal oxide to interlayer modifier of 100:10:3, treating the prepared solution for 1h under the ultrasonic with the power of 300W, then putting the solution into a hydrothermal reaction kettle, reacting for 8h at 120 ℃, filtering the solution after the reaction kettle is cooled to room temperature, washing a filter cake with deionized water for 5 times, and finally drying the filter cake in a baking oven at 100 ℃ for 6h to obtain the functional filler;
2. Preparing polyolefin grafted functional filler:
(1) preparing a vinyl silane solution according to the mass ratio of absolute ethyl alcohol, deionized water and a vinyl silane coupling agent of 1:0.1:0.5;
(2) adding the functional filler into a high-speed mixer, mixing for 3min at the rotating speed of 1000rpm, adding the vinyl silane solution into the high-speed mixer according to the mass ratio of the functional filler to the vinyl silane coupling agent of 1:0.025, mixing for 3min at the rotating speed of 1000rpm, and drying the mixture in a baking oven at 120 ℃ for 6h to obtain the vinyl silane modified functional filler;
(3) according to the mass ratio of the vinyl silane coupling agent to the cross-linking agent of 1:0.75, dissolving the cross-linking agent in the vinyl silane coupling agent to obtain a silane solution of the cross-linking agent, adding the silane solution of the cross-linking agent into a high-speed mixer according to the mass ratio of the polyolefin resin to the vinyl silane modified functional filler to the silane solution of the cross-linking agent of 1:1.025:0.0875, adopting the high-speed mixer to mix for 3min at the rotating speed of 1000rpm, adding the mixed material into a double-screw extruder, extruding and granulating to obtain the polyolefin grafted functional filler;
3. preparing a catalytic flame-retardant master batch:
(1) adding the halogen-free flame retardant, the flexible auxiliary agent, the vinyl silane coupling agent and the catalyst into a high-speed mixer according to the mass ratio of 100:5:3.5:0.25, and mixing for 4min at the rotating speed of 1200rpm to obtain the functional composite flame retardant;
(2) Adding polyolefin into an internal mixer, adding the functional composite flame retardant into the internal mixer according to the mass ratio of the polyolefin to the functional composite flame retardant of 1:2.1, mixing until the temperature of the internal mixer reaches 140 ℃, turning the material out of the internal mixer, and continuously granulating to obtain a catalytic flame-retardant master batch;
4. preparing a soft low-smoke halogen-free flame-retardant polyolefin cable material:
according to the mass ratio of polyolefin resin, halogen-free flame retardant, polyolefin grafted functional filler, catalytic flame retardant master batch, processing aid, antioxidant and cross-linking agent being 1:2.00:3.38:12.90:0.40:0.20:0.12, adding the materials into a high-speed mixer, adopting the high-speed mixer to mix for 2min at the rotating speed of 1200rpm, adding the mixed materials into a double-screw extruder, and granulating to obtain the soft low-smoke halogen-free flame retardant polyolefin cable material;
5. preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material:
extruding the soft low-smoke halogen-free flame-retardant polyolefin cable material by adopting a single screw extruder to obtain a required shape, and placing the cable material in a natural environment to obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material;
the layered double hydroxide in the step one (1) is Mg-Al layered double hydroxide;
The interlayer modifier in the step one (2) is phytic acid;
the vinyl silane coupling agent in the step two (1), the step two (3) and the step three (1) is vinyl triethoxysilane;
the cross-linking agent in the step two (3) and the step four is a mixture of 2, 4-di-tert-butyl cumyl peroxide and triallyl isocyanurate, wherein the mass ratio of the 2, 4-di-tert-butyl cumyl peroxide to the triallyl isocyanurate is 0.4:0.5;
the polyolefin resin in the second step (3) and the fourth step is a mixture of EVA and POE, wherein the mass ratio of EVA to POE is 20:14;
the halogen-free flame retardant in the step three (1) and the step four is a mixture of magnesium hydroxide and polysiloxane, wherein the mass ratio of the magnesium hydroxide to the polysiloxane is 48:2;
the flexible auxiliary agent in the step three (1) is naphthenic oil;
the catalyst in the step three (1) is dibutyl tin dilaurate;
the processing aid in the fourth step is a mixture of silicone and zinc stearate, wherein the mass ratio of the silicone to the zinc stearate is 1.5:0.5;
the antioxidant in the fourth step is a mixture of an antioxidant 1010 and an antioxidant 168, wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 is 0.6:0.4;
The temperature of the twin-screw extruder in the second step (3) is set as follows: the conveying section is 90 ℃, the compression section is 150 ℃, the metering section is 180 ℃, and the machine head is 180 ℃;
the temperature of the twin-screw extruder in the fourth step is set as follows: the conveying section is 70 ℃, the compression section is 120 ℃, the metering section is 120 ℃, and the machine head is 130 ℃;
the temperature of the single screw extruder in the fifth step is set as follows: the conveying section is 100 ℃, the compression section is 160 ℃, the metering section is 190 ℃, and the machine head is 190 ℃.
Comparative example 1: the functional filler, the vinyl silane coupling agent, the cross-linking agent, the polyolefin resin, the halogen-free flame retardant, the flexible auxiliary agent, the catalyst, the processing aid and the antioxidant are prepared according to the method in the step one of the embodiment 1, and the used functional filler, the vinyl silane coupling agent, the cross-linking agent, the polyolefin resin, the halogen-free flame retardant, the flexible auxiliary agent, the catalyst, the processing aid and the antioxidant are identical to those in the embodiment 1, except that the self-crosslinking flexible low-smoke halogen-free flame retardant polyolefin cable material is prepared in the comparative embodiment 1 by adopting a conventional processing method, and the process is as follows: uniformly mixing the flame retardant and the functional filler by adopting a high-speed mixer at the rotating speed of 1000 rpm; adding a vinyl silane coupling agent, and uniformly mixing by adopting a high-speed mixer at the rotating speed of 1000rpm to obtain silane modified mixed filler; adding polyolefin resin, a flexible auxiliary agent, silane modified mixed filler, a processing auxiliary agent, an antioxidant and a catalyst, and uniformly mixing by adopting a high-speed mixer at the rotating speed of 1000rpm to obtain a mixed material; putting the mixed materials into an internal mixer, uniformly mixing to 110 ℃, adding a cross-linking agent, and continuously mixing to 120 ℃; transferring into double-stage granulation to obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material;
The temperature of the double-screw extruder for the double-stage granulation is set as follows: the conveying section is 120 ℃, the compression section is 130 ℃, the metering section is 140 ℃, and the machine head is 140 ℃; the temperature of the single screw extruder for the double-stage granulation is set as follows: the conveying section is 150 ℃, the compression section is 160 ℃, the metering section is 190 ℃, and the machine head is 190 ℃.
Comparative example 2: the differences between this embodiment and embodiment 2 are: the magnesium hydroxide was chosen to replace the functional filler prepared in example 2, specifically by the following steps:
1. preparing polyolefin grafted functional filler:
(1) preparing a vinyl silane solution according to the mass ratio of absolute ethyl alcohol, deionized water and a vinyl silane coupling agent of 1:0.1:0.5;
(2) adding magnesium hydroxide into a high-speed mixer, mixing for 3min at the rotating speed of 1000rpm, adding a vinyl silane solution into the high-speed mixer according to the mass ratio of the magnesium hydroxide to the vinyl silane coupling agent of 1:0.02, mixing for 3min at the rotating speed of 1000rpm, and drying the mixture in a baking oven at 120 ℃ for 6h to obtain vinyl silane modified magnesium hydroxide;
(3) according to the mass ratio of the vinyl silane coupling agent to the cross-linking agent of 1:0.5, dissolving the cross-linking agent in the vinyl silane coupling agent to obtain a silane solution of the cross-linking agent, adding the silane solution of the cross-linking agent into a high-speed mixer according to the mass ratio of the polyolefin resin to the vinyl silane modified magnesium hydroxide to the silane solution of the cross-linking agent of 1:0.85:0.05, mixing the materials for 3min at the rotating speed of 1000rpm by adopting the high-speed mixer, adding the mixed materials into a double-screw extruder, extruding and granulating to obtain the polyolefin grafted magnesium hydroxide;
2. Preparing a catalytic flame-retardant master batch:
(1) adding the halogen-free flame retardant, the flexible auxiliary agent, the vinyl silane coupling agent and the catalyst into a high-speed mixer according to the mass ratio of 100:10.5:3.7:0.26, and mixing for 4min at the rotating speed of 1200rpm to obtain the functional composite flame retardant;
(2) adding polyolefin into an internal mixer, adding the functional composite flame retardant into the internal mixer according to the mass ratio of the polyolefin to the functional composite flame retardant of 1:2.0, mixing until the temperature of the internal mixer reaches 140 ℃, turning the material out of the internal mixer, and continuously granulating to obtain a catalytic flame-retardant master batch;
3. preparing a soft low-smoke halogen-free flame-retardant polyolefin cable material:
according to the mass ratio of polyolefin resin to halogen-free flame retardant to polyolefin grafted functional filler to catalytic flame retardant master batch to processing aid to antioxidant to cross-linking agent of 1:0.33:3.80:10.90:0.33:0.16:0.12, adding the materials into a high-speed mixer, adopting the high-speed mixer to mix for 2min at the rotating speed of 1200rpm, adding the mixed materials into a double-screw extruder, and granulating to obtain the soft low-smoke halogen-free flame retardant polyolefin cable material;
4. preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material:
extruding the soft low-smoke halogen-free flame-retardant polyolefin cable material by adopting a single screw extruder to obtain a required shape, and placing the cable material in a natural environment to obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material;
The vinyl silane coupling agent in the first step (1), the first step (3) and the second step (1) is vinyl triethoxysilane;
the cross-linking agent in the step one (3) and the step three is a mixture of 2, 4-di-tert-butyl cumyl peroxide and triallyl isocyanurate, wherein the mass ratio of the 2, 4-di-tert-butyl cumyl peroxide to the triallyl isocyanurate is 0.3:0.6;
the polyolefin resin in the step one (3) and the step three is a mixture of POE and EPDM, wherein the mass ratio of the POE to the EPDM is 25:15;
the halogen-free flame retardant in the second step (1) and the third step is a mixture of magnesium hydroxide and polysiloxane, wherein the mass ratio of the magnesium hydroxide to the polysiloxane is 38:2;
the flexible auxiliary agent in the second step (1) is naphthenic oil;
the catalyst in the step two (1) is dibutyl tin dilaurate;
the processing aid in the third step is a mixture of silicone and zinc oxide, wherein the mass ratio of the silicone to the zinc oxide is 1.5:0.5;
the antioxidant in the third step is a mixture of an antioxidant 1010 and an antioxidant 168, wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 is 0.6:0.4;
the temperature of the twin-screw extruder in the step one (3) is set as follows: the conveying section is 90 ℃, the compression section is 150 ℃, the metering section is 180 ℃, and the machine head is 180 ℃;
The temperature of the twin-screw extruder described in step three was set as follows: the conveying section is 70 ℃, the compression section is 120 ℃, the metering section is 120 ℃, and the machine head is 130 ℃;
the temperature of the single screw extruder in the fourth step is set as follows: the conveying section is 100 ℃, the compression section is 160 ℃, the metering section is 190 ℃, and the machine head is 190 ℃.
Comparative example 3: the difference between this embodiment and embodiment 3 is that: the use of flexible aids is omitted. Other steps and parameters were the same as in example 3.
The properties of the self-crosslinking type soft low-smoke halogen-free flame retardant polyolefin cable materials prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1;
TABLE 1
From the performance results in table 1, it can be seen that:
example 1 and comparative example 1 when the same material composition is used, the self-crosslinking soft low smoke halogen-free flame retardant polyolefin cable material prepared by the process steps of the invention in example 1 is superior to the material prepared by the traditional method in comparative example 1 in performance, and the heat aging test result reveals that example 1 has better network structure and heat resistance due to better self-crosslinking performance;
the example 2 and the comparative example 2 have the same process steps, the example 2 adopts the functional filler prepared by the design of the invention, the comparative example 2 does not contain the functional filler, the magnesium hydroxide with the same dosage is used for replacing the functional filler to keep the composition of the filler, and the test result shows that the prepared functional filler has obvious flame retardant synergistic effect and the effect of enhancing self-crosslinking performance, and the prepared self-crosslinking soft low-smoke halogen-free flame retardant polyolefin cable material is superior to the system of the comparative example 2 without the functional filler in flame retardant performance, mechanical performance and heat aging resistance;
The material composition of example 3 and comparative example 3 was adjusted when the same process steps were used, the flexible auxiliary agent was used in example 3, but the flexible auxiliary agent was not added in comparative example 3, and the test results revealed that the introduction of the flexible auxiliary agent was favorable for reducing the hardness of the material, and favorable for the improvement of the elongation at break, and at the same time, the heat aging test results revealed that example 3 had lower tensile strength and elongation at break change rate than comparative example 3, and also demonstrated that the introduction of the flexible auxiliary agent was favorable for improving the self-crosslinking property due to the increased movement ability of the molecular chain, so that the material formed a better network structure, and the heat resistance was improved.
Based on the comparison of the results of the above examples and the comparative examples, the self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material provided by the invention has obvious characteristics and advantages in the aspects of preparation of functional fillers, composition of raw materials and design of process steps, a more effective crosslinking network is established in the cable material by utilizing a polyhydroxy modified layered structure and a polyolefin grafting method, the tensile property, flame retardant property and thermal aging property of the cable material are obviously improved, the hardness of the cable material is reduced, the flexibility of the cable material is improved, the technical barrier that a self-crosslinking system based on silane crosslinking is difficult to process and crosslink due to higher consumption of inorganic flame retardants is broken through, and the low-smoke halogen-free flame-retardant polyolefin cable material with softness, heat resistance, flame retardance, environmental friendliness and self crosslinking is obtained.
Claims (10)
1. The preparation method of the self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material is characterized by comprising the following steps of:
1. preparing functional filler:
(1) performing heat treatment on the layered double hydroxide in a muffle furnace at 400-600 ℃ for 2-10 h to obtain a layered double oxide;
(2) preparing solution according to the mass ratio of deionized water, lamellar bimetal oxide and interlayer modifier of 100 (5-50) (0.5-5), processing the prepared solution for 0.5-2 h under the ultrasonic with the power of 200-500W, then putting the solution into a hydrothermal reaction kettle, reacting for 1-10 h at the temperature of 110-150 ℃, filtering the solution after the reaction kettle is cooled to the room temperature, washing a filter cake with deionized water for 3-5 times, and finally drying the filter cake in an oven at the temperature of 80-120 ℃ for 2-8 h to obtain functional filler;
2. preparing polyolefin grafted functional filler:
(1) preparing a vinyl silane solution according to the mass ratio of (0.05-0.5) to (0.5-5) of absolute ethyl alcohol, deionized water and a vinyl silane coupling agent of 1;
(2) adding functional filler into a high-speed mixer, mixing for 1-5 min at the rotating speed of 500-1500 rpm, adding a vinyl silane solution into the high-speed mixer according to the mass ratio of the functional filler to the vinyl silane coupling agent of 1 (0.01-0.1), mixing for 1-5 min at the rotating speed of 500-1500 rpm, and drying the mixture in an oven at 80-120 ℃ for 2-8 h to obtain the vinyl silane modified functional filler;
(3) According to the mass ratio of the vinyl silane coupling agent to the cross-linking agent of 1 (0.1-1), dissolving the cross-linking agent in the vinyl silane coupling agent to obtain a silane solution of the cross-linking agent, according to the mass ratio of the polyolefin resin to the vinyl silane modified functional filler to the silane solution of the cross-linking agent of 1 (0.5-1), adding the silane solution of the cross-linking agent into a high-speed mixer (0.005-0.1), mixing the silane modified functional filler with the high-speed mixer at 500-1500 rpm for 1-5 min, adding the mixed material into a double-screw extruder, extruding and granulating to obtain the polyolefin grafted functional filler;
3. preparing a catalytic flame-retardant master batch:
(1) the halogen-free flame retardant, the flexible auxiliary agent, the vinyl silane coupling agent and the catalyst are added into a high-speed mixer according to the mass ratio of 100 (2-20) (0.5-5) (0.05-0.5), and mixed for 1-5 min at the rotating speed of 500-1500 rpm to obtain the functional composite flame retardant;
(2) adding polyolefin into an internal mixer, adding the functional composite flame retardant into the internal mixer according to the mass ratio of the polyolefin to the functional composite flame retardant of 1 (1-5), mixing until the temperature of the internal mixer reaches 120-150 ℃, turning the material out of the internal mixer, and continuously granulating to obtain the catalytic flame-retardant master batch;
4. preparing a soft low-smoke halogen-free flame-retardant polyolefin cable material:
According to the mass ratio of 1 (0.2-2): (2-10): (5-20): (0.1-1.0): (0.02-0.2) of polyolefin resin, halogen-free flame retardant, polyolefin grafted functional filler, catalytic flame retardant master batch, processing aid, antioxidant and cross-linking agent, adding into a high-speed mixer, adopting the high-speed mixer to mix for 1-5 min at the rotating speed of 500-1500 rpm, adding the mixed material into a double-screw extruder, granulating, and obtaining the soft low-smoke halogen-free flame retardant polyolefin cable material;
5. preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material:
extruding the soft low-smoke halogen-free flame-retardant polyolefin cable material by adopting a single screw extruder to obtain a required shape, and placing the cable material in a natural environment to obtain the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material.
2. The method for preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material according to claim 1, wherein the layered double hydroxide in the step one (1) is Mg-Ag layered double hydroxide or Zn-Al layered double hydroxide; the interlayer modifier in the step one (2) is phytic acid.
3. The preparation method of the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material is characterized in that the vinyl silane coupling agent in the second step (1), the second step (3) and the third step (1) is one or a combination of more of vinyl trimethoxy silane, vinyl triethoxy silane and vinyl tri (beta-methoxyethoxy) silane; the cross-linking agent in the second step (3) and the fourth step comprises organic peroxide and auxiliary cross-linking agent, wherein the mass ratio of the organic peroxide to the auxiliary cross-linking agent is 1 (0.2-2); the organic peroxide is one of dicumyl peroxide and 2, 4-di-tert-butyl cumyl peroxide; the auxiliary cross-linking agent is one of triallyl isocyanurate, triallyl cyanurate and trimethylolpropane trimethacrylate.
4. The preparation method of the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material according to claim 1, which is characterized in that the polyolefin resin in the second step (3) and the fourth step is one or a combination of more than one of ethylene propylene diene monomer rubber, polyolefin elastomer and ethylene-vinyl acetate copolymer; the density of the ethylene propylene diene monomer is 0.86g/cm 3 ～0.90g/cm 3 The Shore A hardness is lower than 80; the polyolefin elastomer has a density of 0.86g/cm 3 ～0.90g/cm 3 Ethylene-octene copolymer having a Shore A hardness of less than 85; the ethylene-vinyl acetate copolymer contains 17% -40% of vinyl acetate, and the Shore A hardness is lower than 85.
5. The preparation method of the self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material is characterized in that the halogen-free flame retardant in the step III (1) and the step IV comprises an inorganic flame retardant and a flame retardant synergist; the mass ratio of the inorganic flame retardant to the flame retardant synergist is 1 (0.01-0.1); the inorganic flame retardant is one or a combination of more of magnesium hydroxide, aluminum hydroxide and zinc borate; the flame retardant synergist is one or a combination of more of polycarbosilane, polysiloxane and silicone resin; the flexible auxiliary agent in the step three (1) is one or the combination of a plurality of paraffinic oil, naphthenic oil and white oil; the catalyst in the step three (1) is one of dibutyl tin dilaurate and stannous octoate.
6. The method for preparing the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material according to claim 1, wherein the processing aid in the fourth step is one or a combination of more of polyethylene wax, stearic acid, zinc stearate, silicone and zinc oxide; the antioxidant comprises a primary antioxidant and an auxiliary antioxidant, wherein the mass ratio of the primary antioxidant to the auxiliary antioxidant is 1 (0.2-2); the main antioxidant is one or a combination of more of an antioxidant 1010, an antioxidant 1076 and an antioxidant 1098; the auxiliary antioxidant is one or the combination of more of antioxidant 168, antioxidant DLTP, antioxidant DSTP and antioxidant 1024.
7. The method for preparing a self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material according to claim 1, wherein the temperature of the twin-screw extruder in the step two (3) is set as follows: the conveying section is at 80-120 ℃, the compression section is at 140-180 ℃, the metering section is at 160-200 ℃, and the machine head is at 180-200 ℃.
8. The method for preparing the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material according to claim 1, wherein the temperature of the twin-screw extruder in the fourth step is set as follows: the conveying section is at 60-100 ℃, the compression section is at 100-140 ℃, the metering section is at 100-140 ℃, and the machine head is at 110-140 ℃.
9. The method for preparing the self-crosslinking soft low-smoke halogen-free flame-retardant polyolefin cable material according to claim 1, wherein the temperature of the single screw extruder in the fifth step is set as follows: the conveying section is at 80-120 ℃, the compression section is at 140-180 ℃, the metering section is at 160-200 ℃, and the machine head is at 180-200 ℃.
10. The application of the self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material prepared by the preparation method of claim 1 is characterized in that the self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material can be extruded and coated on a conductor or a single-core wire, and can be used as an insulated or sheathed cable to meet the requirements of the application field of medium-voltage cables.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311547049.4A CN117402438A (en) | 2023-11-20 | 2023-11-20 | Preparation method and application of self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311547049.4A CN117402438A (en) | 2023-11-20 | 2023-11-20 | Preparation method and application of self-crosslinking type soft low-smoke halogen-free flame-retardant polyolefin cable material |
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| CN117402438A true CN117402438A (en) | 2024-01-16 |
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