CN110862620A - Halogen-free flame-retardant filling material for nuclear power station cable and preparation method thereof - Google Patents
Halogen-free flame-retardant filling material for nuclear power station cable and preparation method thereof Download PDFInfo
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- CN110862620A CN110862620A CN201911223253.4A CN201911223253A CN110862620A CN 110862620 A CN110862620 A CN 110862620A CN 201911223253 A CN201911223253 A CN 201911223253A CN 110862620 A CN110862620 A CN 110862620A
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- Prior art keywords
- retardant
- flame retardant
- flame
- halogen
- parts
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 162
- 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 154
- 238000011049 filling Methods 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920002627 poly(phosphazenes) Polymers 0.000 claims abstract description 74
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 229920000098 polyolefin Polymers 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 9
- 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 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 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 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 6
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 6
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 6
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 6
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 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 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 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 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 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 3
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 claims description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- ZJDGKLAPAYNDQU-UHFFFAOYSA-J [Zr+4].[O-]P([O-])=O.[O-]P([O-])=O Chemical compound [Zr+4].[O-]P([O-])=O.[O-]P([O-])=O ZJDGKLAPAYNDQU-UHFFFAOYSA-J 0.000 claims description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- ZJKCITHLCNCAHA-UHFFFAOYSA-K aluminum dioxidophosphanium Chemical compound [Al+3].[O-][PH2]=O.[O-][PH2]=O.[O-][PH2]=O ZJKCITHLCNCAHA-UHFFFAOYSA-K 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-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
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- GHKADIDUAMVZKK-UHFFFAOYSA-N OCOC(=O)C=C.OCOC(=O)C=C.OCOC(=O)C=C Chemical compound OCOC(=O)C=C.OCOC(=O)C=C.OCOC(=O)C=C GHKADIDUAMVZKK-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000003094 microcapsule Substances 0.000 abstract 2
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- -1 0.5 part of graphene Chemical compound 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- FOYWCEUVVIHJKD-UHFFFAOYSA-N 2-methyl-5-(1h-pyrazol-5-yl)pyridine Chemical group C1=NC(C)=CC=C1C1=CC=NN1 FOYWCEUVVIHJKD-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009941 weaving Methods 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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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- 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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- H—ELECTRICITY
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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
- H01B3/30—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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention relates to a halogen-free flame-retardant filling material for a nuclear power station cable and a preparation method thereof, wherein the filling material comprises the following components in parts by weight: 15-20 parts of polyolefin, 1-3 parts of maleic anhydride and silane coupling agent copolymer compatilizer, 75-80 parts of polyphosphazene microencapsulated flame retardant, 0.5-2 parts of flame retardant synergist, 0.5-3 parts of polyfunctional group crosslinking agent and 0.5-2 parts of lubricant; the polyphosphazene microencapsulated flame retardant and the flame retardant synergist can play a role in multi-component synergistic flame retardance, greatly improve the flame retardant property of the filling material and reduce the combustion heat release amount; the microcapsule flame retardant shell and the maleic anhydride and silane coupling agent copolymer compatilizer can improve the dispersibility and compatibility of the microcapsule core flame retardant substance in the filling material, thereby improving the processing performance and the comprehensive physical properties of the halogen-free flame retardant filling material.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a halogen-free flame-retardant filling material for a nuclear power station cable and a preparation method thereof.
Background
At present, high-safety cables for high-temperature gas cooled reactors and CAP1400 nuclear power and core key materials thereof which are advanced in the world comprise series cables such as power, control, instruments, high temperature, network communication, coaxial cables and the like and series key materials such as insulation, sheaths, filling and the like. The high safety performance of the nuclear power cable is reflected in long service life (more than or equal to 60 years), high irradiation dose resistance (more than or equal to 2500kGy), functional integrity under design accident conditions, and simultaneously, the high safety performance of the nuclear power cable needs to meet the performances of mechanical performance, electrical performance, flame retardant performance, acid and alkali medium resistance and the like.
The cable material used in the nuclear power station environment has a strict requirement, and the filling material is extruded and filled in the sheath to provide the flame retardant property for the whole cable in the cable weaving and extrusion processing process.
In order to obtain better flame retardant performance, a higher content of flame retardant needs to be added into the filling material. Halogen-containing flame retardant is not suitable for the current trend of halogen-free environmental protection, and the halogen-free flame retardant is increasingly used in cable materials. Whether the flame retardant is a metal hydroxide flame retardant or a nitrogen-phosphorus type halogen-free flame retardant, the high filling amount of the flame retardant inevitably deteriorates the comprehensive physical properties of the polyolefin material.
Disclosure of Invention
In order to solve the technical problems of poor flame retardant property, mechanical property and processability of the cable filling material, the halogen-free flame retardant filling material for the nuclear power station cable and the preparation method thereof are provided. The invention adopts the compatilizer with high maleic anhydride content and the flame retardant coated by the polyphosphazene to solve the problems of poor flame retardant property, mechanical property and processability of the existing filling material for the nuclear power station cable.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the halogen-free flame-retardant filling material for the nuclear power station cable comprises the following components in parts by weight: 15-20 parts of polyolefin, 1-3 parts of maleic anhydride and silane coupling agent copolymer compatilizer, 75-80 parts of polyphosphazene microencapsulated flame retardant, 0.5-2 parts of flame retardant synergist, 0.5-3 parts of polyfunctional group crosslinking agent and 0.5-2 parts of lubricant;
the structural formula of the maleic anhydride and silane coupling agent copolymer compatilizer is as follows:
in the formula, the value ranges of x and y are both 15-100, R1Is selected from-Si (OCH)3)3、-Si(OC2H5)3、-Si(OC2H4OCH3)3、-Si(OCH(CH3)2)3、-Si(OCHO)3、-Si(CH3)(OCH3)2、-Si(CH3)(OC2H5)2、-COOC3H6Si(CH3)(OCH3)2、-COOC3H6Si(CH3)(OC2H5)2、-COOC3H6Si(OSi(CH3)3)3、-COOC3H6Si(OC2H5)3One of (1), R2Is selected from-H or-CH3The mass percentage of the maleic anhydride in the compatilizer is 10-70%.
Further, the preparation method of the maleic anhydride and silane coupling agent copolymer compatilizer comprises the following steps: maleic anhydride and a silane coupling agent are taken as raw materials, a free radical initiator and an organic solvent are added, and the temperature is raised to 60-80 ℃ in a nitrogen atmosphere for carrying out polymerization reaction for 8-12 h; cooling to room temperature after the reaction is finished, recovering the solvent by rotary evaporation, and drying the obtained product in a vacuum oven at 50 ℃ to constant weight to obtain viscous liquid, namely the maleic anhydride and silane coupling agent copolymer compatilizer;
the silane coupling agent is selected from one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, triacetoxyvinylsilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltris (trimethylsiloxy) silane and methacryloxypropyltriethoxysilane, preferably from one or more of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltriisopropoxysilane;
the free radical initiator is azobisisobutyronitrile or dibenzoyl peroxide;
the organic solvent is one of butanone, trichloromethane and tetrahydrofuran;
the mass ratio of the maleic anhydride to the silane coupling agent is 1: 10-10: 1, and the preferable mass ratio is 1: 4-4: 1; the amount of the free radical initiator is 0.5-4 wt% of the total mass of the maleic anhydride and the silane coupling agent, and the preferable amount is 1-2 wt%.
Further, the polyolefin is selected from one or more of linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-octene copolymer and ethylene propylene diene monomer rubber which are mixed according to any proportion.
Further, the polyphosphazene microencapsulated flame retardant is in a capsule structure consisting of a shell layer polyphosphazene and a core flame retardant substance; the core flame-retardant substance is selected from one or more of aluminum hydroxide, magnesium aluminum double hydroxide, zinc aluminum double hydroxide, magnesium iron double hydroxide, zinc iron double hydroxide, nickel iron double hydroxide, zinc borate, ammonium polyphosphate, inorganic aluminum hypophosphite, organic aluminum phosphinate, zinc borate, triazine charring agent, melamine cyanurate and melamine polyphosphate which are mixed according to any proportion; the mass ratio of the shell layer polyphosphazene to the core flame-retardant substance is (3-6) to 20.
Furthermore, the preparation method of the polyphosphazene microencapsulated flame retardant comprises the following steps: uniformly stirring a part of pyridine, melamine, 4' -diaminodiphenyl ether and a flame retardant substance in an ice-water bath under the protection of nitrogen to form a mixed solution A; dissolving hexachlorocyclotriphosphazene in the rest pyridine to form a mixed solution B; and adding the mixed solution B into the mixed solution A, heating to 80 ℃ for reaction for 12 hours, and filtering, washing and drying after the reaction is finished to obtain the polyphosphazene microencapsulated flame retardant.
Furthermore, the mass ratio of the pyridine to the melamine to the 4,4' -diaminodiphenyl ether to the flame retardant to the hexachlorocyclotriphosphazene is 50 (1-2) to 20 (1-2), and the hexachlorocyclotriphosphazene accounts for 40% of the mass fraction of the mixed solution B.
Further, the flame retardant synergist is one or more selected from carbon nano tubes, graphene oxide, molybdenum disulfide, boron nitride, montmorillonite, boron nitride, zirconium phosphonate and microencapsulated red phosphorus which are mixed according to any proportion.
Further, the multifunctional crosslinking agent is one or more selected from triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate or pentaerythritol tetraacrylate, which are mixed in any proportion.
Further, the lubricant is one or more selected from silicone powder, zinc stearate, paraffin wax or PE wax which are mixed according to any proportion.
The invention also provides a preparation method of the halogen-free flame-retardant filling material for the nuclear power station cable, which comprises the following steps: weighing polyolefin and a flame-retardant synergist according to a formula, mixing the polyolefin and the flame-retardant synergist in an internal mixer at 140-200 ℃ to be uniform, adding a maleic anhydride and silane coupling agent copolymer compatilizer, a polyphosphazene microencapsulated flame retardant, a polyfunctional group cross-linking agent and a lubricant, mixing uniformly, and extruding and granulating at 140-200 ℃ to prepare halogen-free flame-retardant filling granules;
the prepared halogen-free flame-retardant filling granular material is used for a filling layer of a conductive wire core of a cable of a nuclear power station, when the halogen-free flame-retardant filling granular material is used as a coating material of the filling layer of the conductive wire core of the cable of the nuclear power station, irradiation crosslinking treatment needs to be carried out on the halogen-free flame-retardant filling granular material, and the irradiation crosslinking treatment is carried out under 10KW and 10MeV electron beams with the irradiation dose of 80 KGy-240 KGy.
The beneficial technical effects are as follows:
the polyphosphazene microencapsulated flame retardant is used as a main flame retardant, and the polyphosphazene of the shell layer is rich in phosphorus-nitrogen flame retardant elements and can play a role in synergistic flame retardance with the flame retardant of the core, so that the flame retardance can be improved; the flame retardant synergist and the polyphosphazene microencapsulated flame retardant further play a role in multi-component synergistic flame retardance; the copolymer compatilizer with the maleic anhydride content of 10-70 wt% can obviously improve the interfacial compatibility of the filler and the polyolefin base material, further improve the flame retardant property and the shell forming property of the halogen-free flame-retardant filling material and reduce the heat release of the material.
The polyphosphazene microencapsulated flame retardant is used as a main flame retardant, and because the polarity of the polyphosphazene of the macromolecular shell layer is more similar to that of a halogen-free flame retardant and a polymer, the polyphosphazene microencapsulated flame retardant has better interface compatibility in a polymer material; in addition, the selected compatilizer is a maleic anhydride and silane coupling agent copolymer compatilizer, the content of the maleic anhydride is 10-70 wt%, and under the condition of the same addition amount of the compatilizer, the content of the maleic anhydride is greatly increased, so that the interfacial compatibility of the filler and the base material can be obviously improved, and the dispersibility and the processing performance of the halogen-free flame retardant in the filling material are improved; thereby further improving the mechanical property, the processing property and the comprehensive physical property of the filling material.
Detailed Description
The invention is further described below with reference to specific examples, but without limiting the scope of the invention.
Example 1
Preparation of polyphosphazene microencapsulated flame retardant:
under the condition of ice-water bath, adding 450 parts by mass of pyridine, 10 parts by mass of melamine, 20 parts by mass of 4,4' -diaminodiphenyl ether and 200 parts by mass of a flame retardant into a reactor which is provided with a stirrer, a reflux condenser tube and dry nitrogen gas: uniformly stirring aluminum hydroxide to obtain a mixed solution A; dissolving 20 parts by mass of hexachlorocyclotriphosphazene in 50 parts by mass of pyridine to form a mixed solution B; dropwise adding the mixed solution B into the mixed solution A at the speed of 1mL/min, heating from the temperature of ice water bath to 80 ℃ after dropwise adding, reacting for 12 hours, and sequentially filtering, washing and drying the obtained product after the reaction is finished to obtain the polyphosphazene microencapsulated aluminum hydroxide flame retardant, wherein the mass ratio of the shell polyphosphazene to the core aluminum hydroxide is 5: 20.
Example 2
The preparation method of the polyphosphazene microencapsulated flame retardant is the same as that in example 1, except that the mass ratio of the pyridine to the melamine to the 4,4' -diaminodiphenyl ether to the flame retardant to the hexachlorocyclotriphosphazene is 50:2:2:20:1, and the flame retardant is zinc borate, so as to prepare the polyphosphazene microencapsulated zinc borate flame retardant.
Example 3
The preparation method of the polyphosphazene microencapsulated flame retardant is the same as that in example 1, except that the mass ratio of the pyridine to the melamine to the 4,4' -diaminodiphenyl ether to the flame retardant to the hexachlorocyclotriphosphazene is 50:2:1:20:2, and the flame retardant is ammonium polyphosphate to prepare the polyphosphazene microencapsulated ammonium polyphosphate flame retardant.
Example 4
The preparation method of the polyphosphazene microencapsulated flame retardant of the embodiment is the same as that of the embodiment 1, except that the flame retardant is magnesium hydroxide to prepare the polyphosphazene microencapsulated magnesium hydroxide flame retardant.
Example 5
The preparation method of the polyphosphazene microencapsulated flame retardant of the embodiment is the same as that of the embodiment 1, except that the flame retardant is melamine cyanurate to prepare the polyphosphazene microencapsulated melamine cyanurate flame retardant.
Example 6
The preparation method of the polyphosphazene microencapsulated flame retardant of the embodiment is the same as that of the embodiment 1, except that the flame retardant is triazine charring agent to prepare the polyphosphazene microencapsulated triazine charring agent flame retardant.
Example 7
The preparation method of the polyphosphazene microencapsulated flame retardant of the embodiment is the same as that of the embodiment 1, except that the flame retardant is zinc-aluminum double hydroxide to prepare the polyphosphazene microencapsulated zinc-aluminum double hydroxide flame retardant.
Example 8
The preparation method of the polyphosphazene microencapsulated flame retardant of the embodiment is the same as that of the embodiment 1, except that the flame retardant is inorganic aluminum hypophosphite to prepare the polyphosphazene microencapsulated inorganic aluminum hypophosphite flame retardant.
Example 9
The preparation method of the polyphosphazene microencapsulated flame retardant of the embodiment is the same as that of the embodiment 1, except that the flame retardant is nickel iron double hydroxide to prepare the polyphosphazene microencapsulated nickel iron double hydroxide flame retardant.
Example 10
The halogen-free flame-retardant filling material for the nuclear power station cable comprises the following components in parts by weight:
polyolefin: 15 parts of ethylene-propylene-diene monomer rubber,
3 parts of maleic anhydride and silane coupling agent copolymer compatilizer: the structural formula of the compatibilizer in this example is as follows,
wherein R is1Is selected from-Si (OCH)3)3、R2Selected from-H, the content of maleic anhydride is 10 wt%, and the preparation method comprises the following steps:
using 9 parts by mass of maleic anhydride and 1 part by mass of vinyltrimethoxysilane as raw materials, and adding 0.1 part of azobisisobutyronitrile and 100 parts by mass of trichloromethane; heating to 60 ℃ in a nitrogen atmosphere for polymerization for 12 hours; after the reaction is finished, cooling to room temperature, carrying out rotary evaporation to recover the solvent, drying the obtained product in a vacuum oven at 50 ℃ to constant weight to obtain a viscous liquid product, namely the compatilizer in the embodiment, wherein the content of the maleic anhydride is 10 wt%;
polyphosphazene microencapsulated flame retardant: 60 parts of polyphosphazene microencapsulated aluminum hydroxide flame retardant, 10 parts of polyphosphazene microencapsulated zinc borate flame retardant and 5 parts of polyphosphazene microencapsulated ammonium polyphosphate,
flame retardant synergist: 0.5 part of graphene, namely 0.5 part of graphene,
a polyfunctional group crosslinking agent: 0.5 part of pentaerythritol tetraacrylate,
lubricant: 0.5 part of silicone powder;
the preparation method of the halogen-free flame-retardant filling material for the nuclear power station cable comprises the following steps:
weighing polyolefin and the flame-retardant synergist according to the formula, mixing the polyolefin and the flame-retardant synergist in an internal mixer at 140 ℃ until the mixture is uniform, then adding the maleic anhydride and silane coupling agent copolymer compatilizer, the polyphosphazene microencapsulated flame retardant, the polyfunctional group cross-linking agent and the lubricant, mixing the mixture uniformly, and extruding and granulating the mixture at 140 ℃ to prepare the halogen-free flame-retardant filling granules;
the prepared halogen-free flame-retardant filling aggregate is used for a filling layer of a conductive wire core of a cable of a nuclear power station, and is subjected to irradiation crosslinking treatment under the conditions that the power and the energy are respectively 10KW and 10MeV electron beams, and the irradiation dose is 110 KGy.
Example 11
The halogen-free flame-retardant filling material for the nuclear power station cable comprises the following components in parts by weight:
polyolefin: 20 parts of ethylene-vinyl acetate copolymer (vinyl acetate content: 80 wt%),
3 parts of maleic anhydride and silane coupling agent copolymer compatilizer: the structural formula of the compatibilizer in this example is as follows,
wherein R is1Selected from the group consisting of-Si (OC)2H5)3、R2The content of the maleic anhydride selected from-H is 70 wt%, and the preparation method comprises the following steps: taking 3 parts by mass of maleic anhydride and 7 parts by mass of vinyltriethoxysilane as raw materials, and adding 0.4 part of dibenzoyl peroxide and 100 parts by mass of tetrahydrofuran; heating to 80 ℃ in nitrogen atmosphere for polymerization for 8 hours; after the reaction is finished, cooling to room temperature, carrying out rotary evaporation to recover the solvent, drying the obtained product in a vacuum oven at 50 ℃ to constant weight to obtain a viscous liquid product, namely the compatilizer of the embodiment, wherein the content of maleic anhydride is 70 wt%;
polyphosphazene microencapsulated flame retardant: 70 parts of polyphosphazene microencapsulated magnesium hydroxide, 5 parts of polyphosphazene microencapsulated melamine cyanurate, 5 parts of polyphosphazene microencapsulated triazine charring agent,
flame retardant synergist: 2 parts of montmorillonite, namely 2 parts of montmorillonite,
a polyfunctional group crosslinking agent: 3 parts of trimeric isocyanuric acid triallyl ester,
lubricant: 0.5 part of paraffin and 1.5 parts of silicone powder;
the preparation method of the halogen-free flame-retardant filling material for the nuclear power station cable comprises the following steps:
weighing polyolefin and the flame-retardant synergist according to the formula, mixing the polyolefin and the flame-retardant synergist in an internal mixer at 140 ℃ until the mixture is uniform, then adding the maleic anhydride and silane coupling agent copolymer compatilizer, the polyphosphazene microencapsulated flame retardant, the polyfunctional group cross-linking agent and the lubricant, mixing the mixture uniformly, and extruding and granulating the mixture at 140 ℃ to prepare the halogen-free flame-retardant filling granules;
the prepared halogen-free flame-retardant filling aggregate is used for a filling layer of a conductive wire core of a cable of a nuclear power station, and is subjected to irradiation crosslinking treatment under the conditions that the power and the energy are respectively 10KW and 10MeV electron beams, and the irradiation dose is 240 KGy.
Example 12
The halogen-free flame-retardant filling material for the nuclear power station cable comprises the following components in parts by weight:
polyolefin: 18 parts of ethylene-octene copolymer,
2 parts of maleic anhydride and silane coupling agent copolymer compatilizer: the structural formula of the compatibilizer in this example is as follows,
wherein R is1Is selected from-Si (CH)3)(OC2H5)2、R2Is selected from-CH3The maleic anhydride content is 50 wt%, and the preparation method comprises the following steps: taking 5 parts by mass of maleic anhydride and 5 parts by mass of vinyl methyl diethoxy silane as raw materials, and adding 0.05 part of azobisisobutyronitrile and 100 parts by mass of trichloromethane; heating to 80 ℃ in nitrogen atmosphere for polymerization for 12 hours; after the reaction is finished, cooling to room temperature, carrying out rotary evaporation to recover the solvent, drying the obtained product in a vacuum oven at 50 ℃ to constant weight to obtain a viscous liquid product, namely the compatilizer in the embodiment, wherein the content of maleic anhydride is 50 wt%;
polyphosphazene microencapsulated flame retardant: 45 parts of polyphosphazene microencapsulated zinc-aluminum double hydroxide, 15 parts of polyphosphazene microencapsulated zinc borate and 15 parts of polyphosphazene microencapsulated inorganic aluminum hypophosphite,
flame retardant synergist: 1 part of boron nitride, namely boron nitride,
a polyfunctional group crosslinking agent: 1 part of trimethylolpropane trimethacrylate,
lubricant: 1.5 parts of silicone powder and 0.5 part of PE wax;
the preparation method of the halogen-free flame-retardant filling material for the nuclear power station cable comprises the following steps:
weighing polyolefin and a flame-retardant synergist according to the formula, mixing the polyolefin and the flame-retardant synergist in an internal mixer at 200 ℃ until the mixture is uniform, then adding a maleic anhydride and silane coupling agent copolymer compatilizer, a polyphosphazene microencapsulated flame retardant, a polyfunctional group cross-linking agent and a lubricant, mixing uniformly, and extruding and granulating at 200 ℃ to prepare halogen-free flame-retardant filling granules;
the prepared halogen-free flame-retardant filling aggregate is used for a filling layer of a conductive wire core of a cable of a nuclear power station, and is subjected to irradiation crosslinking treatment under the conditions that the power and the energy are respectively 10KW and 10MeV electron beams, and the irradiation dose is 200 KGy.
Example 13
The halogen-free flame-retardant filling material for the nuclear power station cable comprises the following components in parts by weight:
polyolefin: 10 parts of linear low-density polyethylene, 8 parts of ethylene-octene copolymer,
1 part of maleic anhydride and silane coupling agent copolymer compatilizer: the structural formula of the compatibilizer in this example is as follows,
wherein R is1Is selected from-COOC3H6Si(OC2H5)3、R2Selected from-H, maleic anhydride content of 30% by weight, the vapour phase is determined by: taking 7 parts by mass of maleic anhydride and 3 parts by mass of vinyl triisopropoxysilane as raw materials, and adding 0.2 part of dibenzoyl peroxide and 100 parts by mass of tetrahydrofuran; heating to 80 ℃ in nitrogen atmosphere for polymerization for 10 hours; after the reaction is finished, cooling to room temperature, carrying out rotary evaporation to recover the solvent, drying the obtained product in a vacuum oven at 50 ℃ to constant weight to obtain a viscous liquid product, namely the compatilizer in the embodiment, wherein the content of maleic anhydride is 30 wt%;
polyphosphazene microencapsulated flame retardant: 50 parts of polyphosphazene microencapsulated nickel-iron double hydroxide, 10 parts of polyphosphazene microencapsulated triazine charring agent and 20 parts of polyphosphazene microencapsulated melamine cyanurate,
flame retardant synergist: 2 parts of triallyl cyanurate, namely adding 2 parts of triallyl cyanurate,
a polyfunctional group crosslinking agent: 3 parts of trimeric isocyanuric acid triallyl ester,
lubricant: 1.5 parts of silicone powder;
the preparation method of the halogen-free flame-retardant filling material for the nuclear power station cable comprises the following steps:
weighing polyolefin and the flame-retardant synergist according to the formula, mixing the polyolefin and the flame-retardant synergist in an internal mixer at 160 ℃ until the mixture is uniform, then adding the maleic anhydride and silane coupling agent copolymer compatilizer, the polyphosphazene microencapsulated flame retardant, the polyfunctional group cross-linking agent and the lubricant, mixing the mixture uniformly, and extruding and granulating the mixture at 160 ℃ to prepare the halogen-free flame-retardant filling granules;
the prepared halogen-free flame-retardant filling aggregate is used for a filling layer of a conductive wire core of a cable of a nuclear power station, and is subjected to irradiation crosslinking treatment under the conditions that the power and the energy are respectively 10KW and 10MeV electron beams, and the irradiation dose is 200 KGy.
Comparative example 1
The filler material of this comparative example was the same as that of example 10 except that the preparation of the polyphosphazene microencapsulated flame retardant was not carried out, and the polyphosphazene microencapsulated flame retardant was replaced with a mixture of polyphosphazene, aluminum hydroxide, zinc borate, and ammonium polyphosphate in equal proportion.
Comparative example 2
The filling material of this comparative example was the same as that of example 11 except that the preparation of the polyphosphazene microencapsulated flame retardant was not carried out, and the polyphosphazene microencapsulated flame retardant was replaced in equal proportion by a mixture of polyphosphazene, magnesium hydroxide, melamine cyanurate, and triazine-based char-forming agent.
Comparative example 3
The filler material of this comparative example was the same as that of example 12 except that the polyphosphazene microencapsulated flame retardant was not prepared, but the polyphosphazene microencapsulated flame retardant was replaced in equal proportion by a mixture of polyphosphazene, zinc aluminum double hydroxide, zinc borate, inorganic aluminum hypophosphite.
Comparative example 4
The filling material of this comparative example was the same as that of example 13, except that the preparation of the polyphosphazene microencapsulated flame retardant was not carried out, and the polyphosphazene microencapsulated flame retardant was replaced with polyphosphazene, nickel iron double hydroxide, triazine-based char-forming agent, melamine cyanurate in equal proportion.
The filling materials of examples 10 to 13 and comparative examples 1 to 4 were made into sheets according to the irradiation crosslinking treatment conditions in the corresponding examples 10 to 13, and the performance of the filling materials was tested, and the test results are shown in table 1 below.
TABLE 1 Properties of Filler materials of examples 10 to 13 and comparative examples 1 to 4
Claims (10)
1. The halogen-free flame-retardant filling material for the cable of the nuclear power station is characterized by comprising the following components in parts by weight: 15-20 parts of polyolefin, 1-3 parts of maleic anhydride and silane coupling agent copolymer compatilizer, 75-80 parts of polyphosphazene microencapsulated flame retardant, 0.5-2 parts of flame retardant synergist, 0.5-3 parts of polyfunctional group crosslinking agent and 0.5-2 parts of lubricant;
the structural formula of the maleic anhydride and silane coupling agent copolymer compatilizer is as follows:
in the formula, the value ranges of x and y are both 15-100, R1Is selected from-Si (OCH)3)3、-Si(OC2H5)3、-Si(OC2H4OCH3)3、-Si(OCH(CH3)2)3、-Si(OCHO)3、-Si(CH3)(OCH3)2、-Si(CH3)(OC2H5)2、-COOC3H6Si(CH3)(OCH3)2、-COOC3H6Si(CH3)(OC2H5)2、-COOC3H6Si(OSi(CH3)3)3、-COOC3H6Si(OC2H5)3One of (1), R2Is selected from-H or-CH3The mass percentage of the maleic anhydride in the compatilizer is 10-70%.
2. The halogen-free flame-retardant filling material for the cable of the nuclear power station as claimed in claim 1, wherein the preparation method of the copolymer compatilizer of maleic anhydride and silane coupling agent comprises the following steps:
maleic anhydride and a silane coupling agent are taken as raw materials, a free radical initiator and an organic solvent are added, and the temperature is raised to 60-80 ℃ in a nitrogen atmosphere for carrying out polymerization reaction for 8-12 h; and after the reaction is finished, cooling to room temperature, carrying out rotary evaporation to recover the solvent, and drying the obtained product in a vacuum oven at 50 ℃ to constant weight to obtain viscous liquid, namely the maleic anhydride and silane coupling agent copolymer compatilizer.
3. The halogen-free flame retardant filling material for the cable of the nuclear power station as claimed in claim 2, wherein the silane coupling agent is selected from one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, triacetoxyvinylsilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltris (trimethylsiloxy) silane, and methacryloxypropyltriethoxysilane;
the free radical initiator is azobisisobutyronitrile or dibenzoyl peroxide;
the organic solvent is one of butanone, trichloromethane and tetrahydrofuran;
the mass ratio of the maleic anhydride to the silane coupling agent is 1: 10-10: 1; the amount of the free radical initiator is 0.5-4 wt% of the total mass of the maleic anhydride and the silane coupling agent.
4. The halogen-free flame-retardant filling material for the cable of the nuclear power station as claimed in claim 1, wherein the polyolefin is one or more selected from linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-octene copolymer and ethylene propylene diene monomer rubber which are mixed according to any proportion.
5. The halogen-free flame-retardant filling material for the cable of the nuclear power station as claimed in claim 1, wherein the polyphosphazene microencapsulated flame retardant consists of a shell layer polyphosphazene and a core flame-retardant substance; the core flame-retardant substance is selected from one or more of aluminum hydroxide, magnesium aluminum double hydroxide, zinc aluminum double hydroxide, magnesium iron double hydroxide, zinc iron double hydroxide, nickel iron double hydroxide, zinc borate, ammonium polyphosphate, inorganic aluminum hypophosphite, organic aluminum phosphinate, zinc borate, triazine charring agent, melamine cyanurate and melamine polyphosphate which are mixed according to any proportion; the mass ratio of the shell layer polyphosphazene to the core flame-retardant substance is (3-6) to 20.
6. The halogen-free flame-retardant filling material for the cable of the nuclear power station as claimed in claim 5, wherein the preparation method of the polyphosphazene microencapsulated flame retardant comprises the following steps: uniformly stirring a part of pyridine, melamine, 4' -diaminodiphenyl ether and a flame retardant substance in an ice-water bath under the protection of nitrogen to form a mixed solution A; dissolving hexachlorocyclotriphosphazene in the rest pyridine to form a mixed solution B; and adding the mixed solution B into the mixed solution A, heating to 80 ℃ for reaction for 12 hours, and filtering, washing and drying after the reaction is finished to obtain the polyphosphazene microencapsulated flame retardant.
7. The halogen-free flame-retardant filling material for the nuclear power station cable as claimed in claim 6, wherein the mass ratio of the pyridine to the melamine to the 4,4' -diaminodiphenyl ether to the flame retardant to the hexachlorocyclotriphosphazene is 50 (1-2) to 20 (1-2), and the hexachlorocyclotriphosphazene accounts for 40% of the mixed solution B.
8. The halogen-free flame retardant filling material for the cable of the nuclear power station as claimed in claim 1, wherein the flame retardant synergist is one or more selected from carbon nanotubes, graphene oxide, molybdenum disulfide, boron nitride, montmorillonite, boron nitride, zirconium phosphonate and microencapsulated red phosphorus, and is mixed in any proportion.
9. The halogen-free flame-retardant filling material for the nuclear power station cable as claimed in claim 1, wherein the multifunctional crosslinking agent is one or more selected from triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, trimethylol triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate, and is mixed in any proportion; the lubricant is one or more selected from silicone powder, zinc stearate, paraffin or PE wax mixed according to any proportion.
10. The preparation method of the halogen-free flame-retardant filling material for the cable of the nuclear power station as claimed in any one of claims 1 to 9, characterized by comprising the following steps: weighing polyolefin and a flame-retardant synergist according to a formula, mixing the polyolefin and the flame-retardant synergist in an internal mixer at 140-200 ℃ to be uniform, adding a maleic anhydride and silane coupling agent copolymer compatilizer, a polyphosphazene microencapsulated flame retardant, a polyfunctional group cross-linking agent and a lubricant, mixing uniformly, and extruding and granulating at 140-200 ℃ to prepare halogen-free flame-retardant filling granules;
the prepared halogen-free flame-retardant filling granular material is used for a filling layer of a conductive wire core of a cable of a nuclear power station, when the halogen-free flame-retardant filling granular material is used as a coating material of the filling layer of the conductive wire core of the cable of the nuclear power station, irradiation crosslinking treatment needs to be carried out on the halogen-free flame-retardant filling granular material, and the irradiation crosslinking treatment is carried out under 10KW and 10MeV electron beams with the irradiation dose of 80 KGy-240 KGy.
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