CN116023744A - Halogen-free flame-retardant polyolefin composition and preparation method thereof - Google Patents
Halogen-free flame-retardant polyolefin composition and preparation method thereof Download PDFInfo
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- CN116023744A CN116023744A CN202211716829.2A CN202211716829A CN116023744A CN 116023744 A CN116023744 A CN 116023744A CN 202211716829 A CN202211716829 A CN 202211716829A CN 116023744 A CN116023744 A CN 116023744A
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- halogen
- flame retardant
- free flame
- polyolefin composition
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 164
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 95
- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 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 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 91
- 239000000779 smoke Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 48
- 230000001629 suppression Effects 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 72
- -1 fatty acid radical Chemical class 0.000 claims description 69
- 238000002156 mixing Methods 0.000 claims description 51
- 230000003078 antioxidant effect Effects 0.000 claims description 50
- 239000004743 Polypropylene Substances 0.000 claims description 45
- 229920001155 polypropylene Polymers 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 19
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 11
- 239000012964 benzotriazole Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 150000003751 zinc Chemical class 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 10
- 239000005078 molybdenum compound Substances 0.000 claims description 9
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000004611 light stabiliser Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 7
- 229920005672 polyolefin resin Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 230000004580 weight loss Effects 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- LRGQZEKJTHEMOJ-UHFFFAOYSA-N propane-1,2,3-triol;zinc Chemical compound [Zn].OCC(O)CO LRGQZEKJTHEMOJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 33
- 241000519995 Stachys sylvatica Species 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 description 25
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 25
- 229920001903 high density polyethylene Polymers 0.000 description 25
- 239000004700 high-density polyethylene Substances 0.000 description 25
- 229920005604 random copolymer Polymers 0.000 description 21
- 229920002545 silicone oil Polymers 0.000 description 18
- 238000001125 extrusion Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 229920001400 block copolymer Polymers 0.000 description 12
- 238000004898 kneading Methods 0.000 description 11
- 239000012752 auxiliary agent Substances 0.000 description 9
- 238000013329 compounding Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 239000000314 lubricant Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- ZLJVDFMPHYWVJP-UHFFFAOYSA-N 3,5-ditert-butyl-n'-(3,5-ditert-butyl-4-hydroxybenzoyl)-4-hydroxybenzohydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(=O)NNC(=O)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZLJVDFMPHYWVJP-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- 229960001954 piperazine phosphate Drugs 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a halogen-free flame-retardant polyolefin composition and a preparation method thereof. The invention effectively solves the problem of smoke generated in the processing and forming process of the halogen-free flame retardant by applying the carrier-free smoke-suppressing master batch to the halogen-free flame retardant material, and particularly for the high-viscosity halogen-free flame retardant polyolefin material, the smoke generated in the processing and forming process is obviously reduced; when the halogen-free flame retardant polyolefin composition is burnt, the smoke quantity is obviously reduced; in addition, the carrier-free smoke suppression master batch increases the heat stability and flame retardant efficiency of the halogen-free flame retardant polyolefin composition; the surface of the product piece formed by extruding the halogen-free flame-retardant polyolefin composition into a plate and sucking plastic has less pits, white spots and pits and smooth surface.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a halogen-free flame-retardant polyolefin composition and a preparation method thereof.
Background
Flame retardant technologies are mainly classified into halogen-containing flame retardant and halogen-free flame retardant. In the prior art, the halogen flame retardant is generally prepared by blending a halogen-containing flame retardant with other materials, and the halogen-containing flame retardant material can generate and accumulate high-toxicity dioxin organic halogen chemical substances which cannot be degraded or are difficult to degrade when being heated and decomposed or combusted, so that the environment is polluted and the health of human beings is influenced, the production and circulation of a plurality of halogen-containing flame retardants are forbidden in each country at present, and particularly, the application of decabromodiphenyl ethane in certain occasions is limited in Canada in 2019. The halogen-free flame retardant traditional multipurpose red phosphorus, ammonium polyphosphate, phosphate organic phosphorus flame retardant and metal hydroxide have the problems of low flame retardant efficiency, poor water resistance, easy precipitation, poor compatibility with polymers, poor processability or high increment and the like.
Multi-purpose expansion halogen-free in the market at presentA flame retardant. The intumescent halogen-free flame retardant comprises three elements of an acid source, an air source and a carbon source, and can form a compact foaming expansion carbon layer on the surface of a high polymer material at high temperature so as to isolate oxygen and heat. Wherein, phosphorus and nitrogen are main active components, and the intumescent halogen-free flame retardant generally has partial flame retardant decomposition at the temperature of more than 200 ℃ to contain NH 3 、CO、P 2 O 5 And CN - And toxic smoke is emitted, so that the environment and the physical health of related personnel are affected.
The existing intumescent halogen-free flame retardant has the defects of poor compatibility with polyolefin resin, difficult effective dispersion in the resin, poor dispersibility, poor water resistance and the like, so that the flame retardant property and mechanical property of the flame retardant material are reduced, especially the pits on the surfaces of extruded plates and profiles are more, the flame retardant on the surfaces of products is easy to separate out under the conditions of high temperature and high humidity, and the separation phenomenon is gradually increased along with the rise of temperature and humidity.
The halogen-free flame retardant material, especially under the condition that the viscosity of matrix resin is particularly high, is difficult to disperse in the extrusion processing process of a double-screw extruder, the screw torque is increased in the extrusion process, the shearing heat is higher, the host current is larger, and the flame retardant is easier to be partially decomposed, so that a large amount of smoke is generated in the extrusion modification, extrusion plate molding, plastic suction and blow molding processes.
The flame retardant compositions and flame retardant resin compositions containing the same disclosed by Japanese Kokai Co Ltd Ai Dike in the series of patents CN 110582553A, CN 111433326B, CN 105209576A, CN 109563410B, CN107075378A, CN 111278950A and CN 110869447B, which represent advanced home and abroad intumescent halogen-free flame retardant synthesis and application, have high flame retardance and good product stability, but have poor compatibility with polyolefin resin when being directly added and applied, poor dispersibility in the processing process and easy decomposition in the production and processing of high-viscosity matrix materials.
Patent CN104672492a discloses that organic silicone oil can inhibit scorching materials in the processing of piperazine phosphate compound flame retardant, patent CN 110483898A discloses that lubricant and silicone oil substance coat flame retardant to improve water resistance and moisture absorption migration in polypropylene material, patent CN107075378A discloses that silicone oil and silane coupling agent can prevent the flame retardant from agglomerating, improve dispersibility and endow water resistance and heat resistance, such directly spraying or dripping silicone oil, coupling agent and lubricant on halogen-free flame retardant, and can not completely solve the problem of high dispersion of flame retardant in material, secondary agglomeration phenomenon still occurs in the processing process, especially the problem of how many small pits are exposed on surface white spots when extruding plate or extruded section bar, and large smoke and fume can be generated in the high temperature processing process.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant polyolefin composition and a preparation method thereof, so as to realize the purposes that the halogen-free flame-retardant polyolefin composition generates less smoke in the processing and forming process and the smoke quantity is obviously reduced in the combustion process.
In order to solve the technical problems, the invention adopts the basic conception of the technical scheme that:
a halogen-free flame-retardant polyolefin composition comprises polyolefin resin, a halogen-free flame retardant and carrier-free smoke suppression master batch.
The polyolefin resin includes one or more of polyethylene, low density polyethylene, ultra-high molecular weight polyethylene, high density polyethylene, polypropylene, homo-polypropylene, random copolymer polypropylene, block copolymer polypropylene impact copolymer polypropylene, high impact copolymer polypropylene, isotactic polypropylene, syndiotactic polypropylene, semi-isotactic polypropylene, maleic anhydride modified polypropylene, polybutene, cyclic olefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene and other alpha-olefin polymers, ethylene/propylene block or random copolymer, ethylene/octene block or random copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer and other alpha-olefin copolymers.
The halogen-free flame retardant comprises a phosphorus-nitrogen expansion halogen-free flame retardant, and is flame-retardant through a porous carbon layer condensed phase. The halogen-free flame retardant comprises one or more of Chinese pusefur 100C, 100D and 110DN, chinese Koafo 70FR1420, FR-1420E, chinese Xuesen FR-8301, FR-8330, FR-8332, FR-8320, FR-8310, FR-8300, chinese European Prime MB-2200 and NP-2200, chinese Jieshi PNA260, PNA220, MB32B, MB32C, MB C, chinese Su Tebao FR158, HF-800AM70, chinese Kang Nuode HF-802B, chinese Li Saide LFR-6002, japanese Ai Dike FP-2100JC, FP-2000, FP-2500S, german Kolaen AP766 and AP420 flame retardants.
The carrier-free smoke suppression master batch is applied to the halogen-free flame retardant material, so that the problem of smoke generated in the processing and forming process of the halogen-free flame retardant is effectively solved, and particularly for the high-viscosity halogen-free flame retardant polyolefin material, the smoke generated in the processing and forming process is obviously reduced; when the halogen-free flame retardant polyolefin composition is burnt, the smoke quantity is obviously reduced; in addition, the carrier-free smoke suppression master batch increases the heat stability and flame retardant efficiency of the halogen-free flame retardant polyolefin composition; the surface of the product piece formed by extruding the halogen-free flame-retardant polyolefin composition into a plate and sucking plastic has less pits, white spots and pits and smooth surface.
Further, the carrier-free smoke suppression master batch comprises: porous adsorption material, high heat-resistant antioxidant, zinc salt, molybdenum compound and coating agent TAS-2.
Further, the carrier-free smoke suppression master batch comprises the following components in percentage by mass:
preferably, the method comprises the steps of,
further, the porous adsorption material is prepared by dry pressing and high-temperature sintering on nano porous aluminosilicate coated micro-particle-level soda lime borosilicate hollow microspheres and grinding; preferably, the particle size is 10-80 μm;
the porous adsorption material can eliminate part of low molecular gas matters generated by decomposing the halogen-free flame retardant in the production process through physical adsorption and chemical chelation.
Preferably, the high heat-resistant antioxidant comprises a hindered phenol antioxidant and phosphite antioxidant compound;
the high heat-resistant antioxidants include: one or more mixtures of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, n-stearyl 3- (3, 4-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 3, 9-bis [1, 1-dimethyl-2- [ (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ] -2,4,8, 10-tetraoxaspiro [5.5] undecane, 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-benzoyl) hydrazine, phenyl tris (2, 4-di-tert-butyl) phosphite, bisoctadecylpentaerythritol bisphosphite.
Preferably, the zinc salt comprises one or more of zinc stannate, zinc stannate hydrate, zinc borate, zinc glycerolate and zinc molybdate; preferably, zinc stannate; preferably, the zinc salt has an average particle diameter of 1-10 μm and a specific surface area of not less than 2m 2 Per gram, the free water content is less than 1%; the zinc salt is used as an inorganic flame-retardant smoke suppressant to achieve the aim of smoke suppression.
Preferably, the molybdenum compound comprises one or more of molybdenum trioxide, ammonium octamolybdate and calcium molybdate; preferably ammonium octamolybdate; preferably, the theoretical molybdenum content is 45.39%; molybdenum compound is used as a compound organic flame-retardant smoke suppressant.
Preferably, the coating agent TAS-2A has a main structure of RCONXCH 2 -CH 2 NXCOR, wherein X is higher fatty acid radical, R is higher alkane, and main chain molecule is solvated chain segment lipophilic group, preferably, melting point is 65 ℃, thermal weight loss is less than or equal to 1.8% at 250 ℃, and flash point is more than or equal to 275 ℃.
The main structure of the coating agent TAS-2A is RCONXCH 2 -CH 2 NXCOR, wherein X is higher fatty acid radical, R is higher alkane, main chain molecule is solvated chain segment lipophilic group, and ester base group is introduced, so that compatibility and dispersibility of the halogen-free flame retardant composition and matrix resin can be improved, the melting point is 65 ℃, the thermal weight loss is less than or equal to 1.8% at 250 ℃, and the flash point is more than or equal to 275% At the temperature of the preparation, the preparation is used as a coating material of the compound smoke suppressant.
Further, the halogen-free flame retardant polyolefin composition also comprises a compatilizer and a coupling agent;
preferably, the halogen-free flame retardant polyolefin composition comprises the following components in percentage by mass:
preferably, the coupling agent comprises one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and mixtures thereof;
preferably, the compatilizer comprises one or two of polyolefin-based grafted maleic anhydride and polyolefin-based grafted glycidyl methacrylate;
preferably, the polyolefin-based grafted maleic anhydride and/or the polyolefin-based grafted glycidyl methacrylate has a grafting ratio of 0.9-1.2% and a melt index of not more than 2g/10min.
The compatilizer is polyolefin-based grafted maleic anhydride or polyolefin-based grafted glycidyl methacrylate, and the addition of the compatilizer can improve the dispersibility and compatibility of the flame retardant in the resin.
Further, the halogen-free flame retardant polyolefin composition also comprises a processing aid, wherein the mass percentage of the processing aid is 0.3-1%;
preferably, the processing aid comprises one or more of hindered phenol antioxidants, phosphite antioxidants, thioester antioxidants, benzotriazole antioxidants, benzophenone antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, white oil, silicone master batch, erucamide, polypropylene wax and polyethylene wax and mixtures thereof;
A method for preparing the halogen-free flame retardant polyolefin composition according to the technical scheme,
1) Pre-mixing polyolefin resin, halogen-free flame retardant and carrier-free smoke suppression master batch uniformly;
2) And mixing, and then carrying out melt blending by a double-screw extruder to obtain the halogen-free flame retardant polyolefin composition.
Further, in the step 1), the preparation method of the carrier-free smoke suppression master batch comprises the following steps: mixing porous adsorption material, high heat-resistant antioxidant, zinc salt and molybdenum compound to form a mixture, melting coating agent TAS-2 at high temperature, continuously spraying into the mixture, mixing, cooling, pulverizing, and sieving.
Further, in the step 1), the porous adsorption material, the high heat-resistant antioxidant, the zinc salt and the molybdenum compound are sequentially added into a high-mixing pot, and are mixed at the normal temperature at the speed of 200-300r/min and then are mixed at the speed of 600-1400r/min to form a mixture.
Further, in the step 2), the vacuum extraction pressure value of the metering section of the double-screw extruder is between-0.8 MPa and-1.0 MPa; preferably, -0.9MPa;
preferably, in step 2), the screw combination of the twin screw extruder comprises 90 degree and 45 degree screw elements;
preferably, the temperature of each section of the screw is 150-210 ℃.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects.
The invention effectively solves the problem of smoke generated in the processing and forming process of the halogen-free flame retardant by applying the carrier-free smoke-suppressing master batch to the halogen-free flame retardant material, and particularly for the high-viscosity halogen-free flame retardant polyolefin material, the smoke generated in the processing and forming process is obviously reduced; when the halogen-free flame retardant polyolefin composition is burnt, the smoke quantity is obviously reduced; in addition, the carrier-free smoke suppression master batch increases the heat stability and flame retardant efficiency of the halogen-free flame retardant polyolefin composition; the surface of the product piece formed by extruding the halogen-free flame-retardant polyolefin composition into a plate and sucking plastic has less pits, white spots and pits and smooth surface.
The carrier-free smoke-suppressing master batch is compounded by a plurality of substances, the base material and the flame retardant are protected at high temperature by adding the high-heat-resistant antioxidant to prevent the base material and the flame retardant from being heated and decomposed in the processing process, and then the smoke generated by shearing the hot halogen-free flame retardant material in the screw cylinder is partially absorbed by the porous adsorption material through physical adsorption and chemical chelation, so that the smoke in the production and processing process is effectively reduced, and the smoke in the combustion process of the halogen-free flame retardant material is greatly reduced by compounding and adding the zinc salt and the molybdenum compound. The problems of large smoke quantity of the expansion type halogen-free flame retardant material in the production and processing process and large smoke quantity of the flame retardant material in the combustion process are solved through the synergistic effect of the substances.
The halogen-free flame-retardant polyolefin composition has the advantages that the viscosity of the matrix material is high, the screw torque is high, the host current is high, the shearing heat is high, the material is more likely to decompose to generate larger smoke, the addition of smoke suppression master batches is required to be reasonably designed, the production and processing technology is required to be reasonably designed, the optimal smoke suppression effect can be achieved through reasonably adjusting the threaded element and the production technology, the production and processing environment is effectively improved, and the physical and mental health of field personnel is ensured.
The invention solves the problem that the flame retardant is difficult to disperse under a high-viscosity base material by adding the compatilizer and the coupling agent and reasonably combining and producing the screw thread elements, and does not generate pits, white spots, pits and the like on the surface of a product piece during the processes of extruding, sucking plastic and blow molding.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions will be clearly and completely described below, and the following examples are provided for illustrating the present invention but are not intended to limit the scope of the present invention.
In the following examples, halogen-free flame retardants used are commercially available in a large scale, preferably the main stream of the norfloxacin flame retardants at home and abroad, namely FP-2000, 110DN, MB32B and 70FR1420.
The ingredients and the method for preparing the carrier-free smoke suppression master batch are as follows:
the mass percentage of the nano porous aluminosilicate coated micro-particle-grade soda lime borosilicate hollow microsphere porous material is 30%;
40% of compound high heat-resistant antioxidant;
10 mass percent of zinc glycerolate;
the mass percentage of the molybdenum trioxide is 15%;
the mass percentage of the TAS-2A is 5%; the main structure of the coating agent TAS-2 is RCONXCH 2 -CH 2 NXCOR, wherein X is higher fatty acid radical, R is higher alkane, the melting point is 65 ℃, the thermal weight loss is less than or equal to 1.8% at 250 ℃, and the flash point is more than or equal to 275 ℃.
The compound high heat-resistant antioxidant is prepared by compounding 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine and phenyl tris (2, 4-di-tert-butyl) phosphite, and further comprises 20% by mass and 60% by mass, and effectively protects the decomposition of a base material and a flame retardant in the production and processing process.
The preparation method of the carrier-free smoke suppression master batch comprises the following steps: in a high-temperature spray gun-equipped high-mixing pot, sequentially adding porous material, compound high-heat-resistance antioxidant, zinc glycerate and molybdenum trioxide, and mixing at low speed of 200r/min for 1min and then at high speed of 600r/min for 3min at normal temperature. The temperature of the high-temperature spray gun is set at 55 ℃, TAS-2A is continuously sprayed through 5 percent of the mass percent of the spray gun, the high-temperature mixing pot is kept at 110 ℃, and the high-speed mixing is carried out for 3min at 600 r/min. Discharging, cooling, pulverizing, and sieving to obtain powder with particle diameter of 10-80 μm.
As another formulation and method for preparing a carrier-free smoke suppressing masterbatch, the following is adopted:
the mass percentage of the nano porous aluminosilicate coated micro-particle-grade soda lime borosilicate hollow microsphere porous material is 20%;
20% of compound high heat-resistant antioxidant;
25% of zinc borate by mass;
the mass percentage of the calcium molybdate is 25 percent;
the mass percentage of the TAS-2A is 10%; the main structure of the coating agent TAS-2 is RCONXCH 2 -CH 2 NXCOR, wherein X is higher fatty acid radical, R is higher alkane, the melting point is 65 ℃, the thermal weight loss is less than or equal to 1.8% at 250 ℃, and the flash point is more than or equal to 275 ℃.
The compound high heat-resistant antioxidant is prepared by compounding 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine and phenyl tris (2, 4-di-tert-butyl) phosphite, and further comprises 20% by mass and 60% by mass, and effectively protects the decomposition of a base material and a flame retardant in the production and processing process.
The preparation method of the carrier-free smoke suppression master batch comprises the following steps: sequentially adding a self-made nanoscale porous material, a compound high-heat-resistance antioxidant, zinc borate and calcium molybdate into a high-temperature spray gun-equipped high-mixing pot, and mixing at a low speed of 300r/min for 1min and at a high speed of 1400r/min for 3min at normal temperature. The temperature of the high-temperature spray gun is set at 55 ℃, TAS-2A is continuously sprayed through 5% of the mass percent of the spray gun, the high-temperature mixing pot is kept at 110 ℃, and the high-speed mixing is carried out for 3min at 1400 r/min. Discharging, cooling, pulverizing, and sieving to obtain powder with particle diameter of 10-80 μm.
In the following examples, the preferred material proportions and preparation methods of the carrier-free smoke suppression master batch used are as follows:
the mass percentage of the nano porous aluminosilicate coated micro-particle-grade soda lime borosilicate hollow microsphere porous material is 22%;
30% of compound high heat-resistant antioxidant;
18% of zinc stannate;
the mass percentage of the ammonium octamolybdate is 20%;
the mass percentage of the TAS-2A is 10%; the main structure of the coating agent TAS-2 is RCONXCH 2 -CH 2 NXCOR, wherein X is higher fatty acid radical, R is higher alkane, the melting point is 65 ℃, the thermal weight loss is less than or equal to 1.8% at 250 ℃, and the flash point is more than or equal to 275 ℃.
The compound high heat-resistant antioxidant is prepared by compounding 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, 1, 2-bis (3, 5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine and phenyl tris (2, 4-di-tert-butyl) phosphite, and further comprises 20% by mass and 60% by mass, and effectively protects the decomposition of a base material and a flame retardant in the production and processing process.
The preparation method of the carrier-free smoke suppression master batch comprises the following steps: sequentially adding a self-made nano porous material, a compound high heat-resistant antioxidant, zinc stannate and ammonium octamolybdate in a high-temperature spray gun-equipped high-mixing pot, and mixing at a low speed of 220r/min for 1min and at a high speed of 800r/min for 3min at normal temperature. The temperature of the high-temperature spray gun is set at 55 ℃, TAS-2A is continuously sprayed through 10 percent of the mass percent of the spray gun, the high-temperature mixing pot is kept at 110 ℃, and the high-speed mixing is carried out for 3min at 800 r/min. Discharging, cooling, pulverizing, and sieving to obtain powder with particle diameter of 10-80 μm.
Example 1
A FP-2000 flame-retardant low-smoke high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
46% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 29% of halogen-free flame retardant FP-2000, 5% of carrier-free smoke suppression master batch, 3% of polyolefin-based grafted maleic anhydride, 0.5% of silane coupling agent KH-550, and 0.5% of auxiliary agent compounding materials such as hindered phenol antioxidant, phosphite antioxidant, silicone oil, polypropylene wax and the like.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is-0.9 MPa, and the length-diameter ratio of the twin-screw extruder is 48:1.
The preparation method comprises the steps of pre-mixing random copolymer polypropylene, ethylene/octene segmented copolymer, high-density polyethylene, halogen-free flame retardant FP-2000, carrier-free smoke suppression master batch, polyolefin-based grafted maleic anhydride and other processing aids hindered phenol antioxidant, phosphite antioxidant, silicone oil and polypropylene wax according to mass proportion at a high speed mixer of 750r/min for 1min, uniformly spraying silane coupling agent KH-550, mixing for 3min at a high speed, and feeding at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Example 2
A110 DN flame-retardant low-smoke high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
47% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 110DN of halogen-free flame retardant, 28% of carrier-free smoke-suppressing master batch, 5% of polyolefin-based grafted glycidyl methacrylate, 3% of titanate coupling agent NXH-201, 0.5% of phosphite antioxidant, hindered amine light stabilizer, ultraviolet absorbent, silicone master batch, erucamide and other auxiliary agent compound materials, and 0.5%.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The preparation method comprises the steps of pre-mixing auxiliary compounds such as random copolymer polypropylene, ethylene/octene segmented copolymer, high-density polyethylene, halogen-free flame retardant 110DN, carrier-free smoke suppression master batch, polyolefin-based grafted glycidyl methacrylate, phosphite antioxidants serving as other processing aids, hindered amine light stabilizer, ultraviolet absorbent, silicone master batch, erucamide and the like according to mass proportion at a high speed mixer of 750r/min for 1min, uniformly spraying titanate coupling agent NXH-201, mixing at a high speed for 3min, and feeding at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Example 3
A MB32B flame-retardant low-smoke high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
36% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 39% of halogen-free flame retardant MB32B, 5% of carrier-free smoke-suppressing master batch, 3% of polyolefin-based grafted glycidyl methacrylate, 0.5% of aluminate coupling agent LS-822, 0.5% of hindered phenol antioxidant, benzophenone antioxidant, hindered amine light stabilizer, silicone master batch, polyethylene wax and other auxiliary agent compound materials.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The preparation method comprises the steps of pre-mixing auxiliary compound materials such as random copolymer polypropylene, ethylene/octene segmented copolymer, high-density polyethylene, halogen-free flame retardant MB32B, carrier-free smoke suppression master batch, polyolefin-based grafted glycidyl methacrylate, hindered phenol antioxidants of other processing aids, benzophenone antioxidants, hindered amine light stabilizer, silicone master batch, polyethylene wax and the like according to mass proportion at a high speed mixer of 750r/min for 1min, uniformly spraying aluminate coupling agent LS-822, mixing at a high speed for 3min, and feeding at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Example 4
A70 FR1420 flame-retardant low-smoke high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
34% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 40% of halogen-free flame retardant 70FR1420, 5% of carrier-free smoke suppression master batch, 4% of polyolefin-based grafted maleic anhydride, 0.5% of silane coupling agent KH-570, and 0.5% of auxiliary agent compounding materials such as hindered phenol antioxidant, benzotriazole antioxidant, ultraviolet absorber, silicone oil, polypropylene wax and the like.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The preparation method comprises the steps of pre-mixing auxiliary compounds such as random copolymerized polypropylene, ethylene/octene segmented copolymer, high-density polyethylene, halogen-free flame retardant 70FR1420, carrier-free smoke suppression master batch, polyolefin-based grafted maleic anhydride and other processing aids hindered phenol antioxidants, benzotriazole antioxidants, ultraviolet absorbers, silicone oil, polypropylene wax and the like according to mass proportion at a high speed mixer of 750r/min for 1min, uniformly spraying silane coupling agent KH-570, mixing for 3min at a high speed, and feeding at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Example 5
A70 FR1420 flame-retardant low-smoke high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
the block copolymer polypropylene impact copolymer comprises 49% by weight of polypropylene, 9% by weight of ethylene/octene block copolymer, 10% by weight of high-density polyethylene, 25% by weight of halogen-free flame retardant 70FR1420, 3% by weight of carrier-free smoke-suppressing master batch, 2% by weight of polyolefin-based grafted maleic anhydride, 1% by weight of silane coupling agent KH-570, 1% by weight of hindered phenol antioxidant, benzotriazole antioxidant, ultraviolet absorber, silicone oil, polypropylene wax and other auxiliary compound.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The block copolymer polypropylene impact copolymer polypropylene, ethylene/octene block copolymer, high-density polyethylene, halogen-free flame retardant 70FR1420, carrier-free smoke suppression master batch, polyolefin-based grafted maleic anhydride, other processing aid hindered phenol antioxidants, benzotriazole antioxidants, ultraviolet absorber, silicone oil, polypropylene wax and other auxiliary compound are mixed in advance for 1min according to the mass ratio at a high speed mixer of 750r/min, then silane coupling agent KH-570 is uniformly sprayed and mixed for 3min at high speed, and the mixture is fed at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Example 6
A70 FR1420 flame-retardant low-smoke high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
the block copolymer polypropylene impact copolymer polypropylene comprises 39% by mass, 9% by mass of ethylene/octene block copolymer, 10% by mass of high-density polyethylene, 25.4% by mass of halogen-free flame retardant 70FR1420, 10% by mass of carrier-free smoke-suppressing master batch, 6% by mass of polyolefin-based grafted maleic anhydride, 0.3% by mass of silane coupling agent KH-570, and 0.3% by mass of auxiliary agent compounding materials such as hindered phenol antioxidant, benzotriazole antioxidant, ultraviolet absorber, silicone oil, polypropylene wax and the like.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The block copolymer polypropylene impact copolymer polypropylene, ethylene/octene block copolymer, high-density polyethylene, halogen-free flame retardant 70FR1420, carrier-free smoke suppression master batch, polyolefin-based grafted maleic anhydride, other processing aid hindered phenol antioxidants, benzotriazole antioxidants, ultraviolet absorber, silicone oil, polypropylene wax and other auxiliary compound are mixed in advance for 1min according to the mass ratio at a high speed mixer of 750r/min, then silane coupling agent KH-570 is uniformly sprayed and mixed for 3min at high speed, and the mixture is fed at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 1
An FP-2000 flame-retardant high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
51% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 29% of halogen-free flame retardant FP-2000, 3% of polyolefin-based grafted maleic anhydride, 0.5% of silane coupling agent KH-550 and 3% of auxiliary compound containing agent such as hindered phenol antioxidant, thioester antioxidant, silicone oil, erucamide, polypropylene wax and the like.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The random copolymer polypropylene, the ethylene/octene segmented copolymer, the high-density polyethylene, the halogen-free flame retardant FP-2000, the compatilizer and other processing aids are pre-mixed for 1min according to the mass ratio at a high-speed mixer of 750r/min, and then the coupling agent is uniformly sprayed and mixed for 3min at a high speed, and the mixture is fed at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 2
A110 DN flame-retardant high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
52% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 110DN of halogen-free flame retardant, 28% of polyolefin-based grafted glycidyl methacrylate, 3% of aluminate coupling agent LS-822, 0.5% of benzophenone antioxidant, hindered amine light stabilizer, ultraviolet absorber, white oil, polyethylene wax and other auxiliary compound materials, and 0.5%.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The preparation method comprises the steps of pre-mixing random copolymer polypropylene, ethylene/octene segmented copolymer, high-density polyethylene, halogen-free flame retardant 110DN, compatilizer and other processing aids according to mass proportion at a high-speed mixer of 750r/min for 1min, uniformly spraying a coupling agent, mixing for 3min at a high speed, and feeding at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 3
An MB32B flame-retardant high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
41% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 39% of halogen-free flame retardant MB32B, 3% of polyolefin-based grafted glycidyl methacrylate, 0.5% of silane coupling agent KH-560, and 0.5% of auxiliary agent compounding materials such as benzophenone antioxidant, hindered phenol antioxidant, ultraviolet absorber, silicone oil, erucamide, polyethylene wax and the like.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The random copolymer polypropylene, the ethylene/octene segmented copolymer, the high-density polyethylene, the halogen-free flame retardant MB32B, the compatilizer and other processing aids are pre-mixed for 1min according to the mass proportion at a high-speed mixer of 750r/min, and then the coupling agent is uniformly sprayed and mixed for 3min at a high speed, and the mixture is fed at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 4
A70 FR1420 flame-retardant high-viscosity halogen-free flame-retardant polyolefin composition comprises the following components in percentage by mass:
38% of random copolymer polypropylene, 8% of ethylene/octene block copolymer, 8% of high-density polyethylene, 70FR1420 of halogen-free flame retardant, 42% of polyolefin-based grafted maleic anhydride, 3% of silane coupling agent KH-550, 0.5% of phosphite antioxidant, hindered amine light stabilizer, silicone oil, silicone master batch, polyethylene wax and other auxiliary compound, and 3%.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The preparation method comprises the steps of pre-mixing auxiliary compounds such as random copolymerized polypropylene, ethylene/octene segmented copolymer, high-density polyethylene, halogen-free flame retardant 70FR1420, polyolefin-based grafted maleic anhydride, other processing aids hindered phenol antioxidants, benzotriazole antioxidants, ultraviolet absorbers, silicone oil, polypropylene wax and the like according to mass proportion at a high speed mixer of 750r/min for 1min, uniformly spraying silane coupling agent KH-570, mixing for 3min at a high speed, and feeding at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 5
The FP-2000 flame-retardant low-smoke high-viscosity halogen-free flame-retardant polyolefin composition without the compatilizer and the coupling agent comprises the following components in percentage by mass:
49.5% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 29% of halogen-free flame retardant FP-2000, 5% of carrier-free smoke suppression master batch, and 0.5% of auxiliary agent compounding materials such as hindered phenol antioxidant, phosphite antioxidant, silicone oil, polypropylene wax and the like.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The auxiliary agent compound of random copolymer polypropylene, ethylene/octene segmented copolymer, high-density polyethylene, halogen-free flame retardant FP-2000, carrier-free smoke suppression master batch and other processing aids such as hindered phenol antioxidant, phosphite antioxidant, silicone oil, polypropylene wax and the like is pre-mixed for 4min according to mass proportion at a high-speed mixer of 750r/min, and fed at a main feeding port of a double-screw extruder. Except for a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section, kneading blocks are added in other sections as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, a polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 6
The FP-2000 flame-retardant low-smoke-amount high-viscosity halogen-free flame-retardant polyolefin composition with common screw thread element combination comprises the following components in percentage by mass:
46% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 8% of high-density polyethylene, 29% of halogen-free flame retardant FP-2000, 5% of carrier-free smoke-suppressing master batch, 3% of polyolefin-based grafted maleic anhydride, 0.5% of silane coupling agent KH-570, and 3% of auxiliary agent compound such as hindered phenol antioxidant, benzotriazole antioxidant, phosphite antioxidant, white oil, silicone master batch, polypropylene wax and the like.
The preparation method comprises the following steps:
the processing temperature of the melt extrusion of the extruder is as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-220 ℃, the current of the main machine is 350-430A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, and the length-diameter ratio of the double-screw extruder is 48:1.
The preparation method comprises the steps of pre-mixing auxiliary compound materials such as random copolymer polypropylene, ethylene/octene segmented copolymer, high-density polyethylene, halogen-free flame retardant FP-2000, carrier-free smoke suppression master batch, polyolefin-based grafted maleic anhydride and other processing aids hindered phenol antioxidant, benzotriazole antioxidant, phosphite antioxidant, white oil, silicone master batch, polypropylene wax and the like according to mass proportion at a high speed mixer of 750r/min for 1min, uniformly spraying a coupling agent, mixing at a high speed for 3min, and feeding at a main feeding port of a double-screw extruder. The combination of the thread elements of the screw is used for producing a common polyolefin material combination for automobiles, the polyolefin composition of the halogen-free flame retardant composition is prepared by melt blending of a double screw extruder, and particles are prepared by granulating after traction cooling.
Experimental example 1
The present experimental example was a test for the properties of the particles obtained in examples 1 to 4 and comparative examples 1 to 6, specifically:
the particles prepared in examples 1 to 4 and comparative examples 1 to 6 were injection molded to prepare a spline, in which:
(1) Tensile strength and strain at break: the speed was 50mm/min as tested according to ISO 527;
(2) Notched Izod impact Strength: tested according to ISO 179, 23 ℃, pendulum 5.5J;
(3) Density: tested according to ISO 1183;
(4) Melt index: 2.16kg at 230℃according to ISO 1133-1;
(5) Vertical combustion: 1.6mm according to UL94 test;
(6) Water cutting particle surface: after the modified water-cooled bracing wires are granulated, the surface condition of the particles is observed, and the dispersibility and the decomposition condition are judged;
(7) The appearance surface of the plate is as follows: extruding the materials of the examples and the comparative examples through a three-roller plate extruding machine, and observing whether pits and pits exist on the surfaces;
(8) Smoke amount: according to the specific optical density test method GB/T10671-2008 of solid material smoke production, the specific optical density in the flaming mode and the flameless mode is observed, and the radiation illuminance is 50KW/m 2 And meanwhile, the smoke quantity of a die orifice of the extruder is observed when the bracing piece is extruded normally.
The test results are shown in table 1 below:
table 1:
as can be seen from the test results of the examples and comparative examples in Table 1, the halogen-free flame retardant compositions of examples 1 to 4 of the present invention were excellent in tensile strength and notched impact strength, excellent in breaking strain, and high in flame retarding efficiency as demonstrated by the breaking strain data, notched impact strength, water-cut particle surface and plate appearance surface, and excellent in dispersibility in polyolefin materials.
Examples 1,2,3,4 were compared with comparative examples 1,2,3,4, respectively, and by adding the unsupported smoke suppressing master batch, the flame smoke density and the flameless smoke density were both greatly reduced from the comparative data analysis of 4 groups of different flame retardants, and in addition, the smoke amount of the extruder die opening is obvious.
Comparative example 5 and comparative example 6 have a very large influence on dispersibility and compatibility of materials, and are liable to generate white spots and pocks, but have a small influence on smoke density of materials, compared with example 1.
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the invention, and it is intended to cover the invention as defined by the appended claims.
Claims (10)
1. A halogen-free flame retardant polyolefin composition, comprising a polyolefin resin, a halogen-free flame retardant, characterized in that: the smoke suppression master batch is free of carriers; the carrier-free smoke suppression master batch comprises the following components in percentage by mass:
2. The halogen-free flame retardant polyolefin composition of claim 1, wherein: the porous adsorption material is prepared by coating fine-grade soda lime borosilicate hollow microspheres with nano-grade porous aluminosilicate, performing dry pressing and high-temperature sintering on the hollow microspheres, and grinding the hollow microspheres; preferably, the particle size is 10-80. Mu.m.
3. A halogen-free flame retardant polyolefin composition according to claim 1 or 2, characterized in that: the high heat-resistant antioxidant comprises a hindered phenol antioxidant and phosphite antioxidant compound.
4. A halogen-free flame retardant polyolefin composition according to any of claims 1-3, characterized in that: the zinc salt comprises one or more of zinc stannate, zinc stannate hydrate, zinc borate, zinc glycerolate and zinc molybdate; preferably, zinc stannate; preferably, the zinc salt has an average particle diameter of 1-10 μm and a specific surface area of 2m or more 2 Per gram, the free water content is less than 1%;
preferably, the molybdenum compound comprises one or more of molybdenum trioxide, ammonium octamolybdate and calcium molybdate; preferably ammonium octamolybdate; preferably, the theoretical molybdenum content is 45.39%;
preferably, the coating agent TAS-2 has a main structure of RCONXCH 2 -CH 2 NXCOR, wherein X is higher fatty acid radical, R is higher alkane, preferably, the melting point is 65 ℃, the thermal weight loss is less than or equal to 1.8% at 250 ℃, and the flash point is more than or equal to 275 ℃.
5. A halogen-free flame retardant polyolefin composition according to any of claims 1-4, characterized in that: the halogen-free flame retardant polyolefin composition also comprises a compatilizer and a coupling agent;
the halogen-free flame retardant polyolefin composition comprises the following components in percentage by mass:
preferably, the coupling agent comprises one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and mixtures thereof;
preferably, the compatilizer comprises one or two of polyolefin-based grafted maleic anhydride and polyolefin-based grafted glycidyl methacrylate;
preferably, the polyolefin-based grafted maleic anhydride and/or the polyolefin-based grafted glycidyl methacrylate has a grafting ratio of 0.9-1.2% and a melt index of not more than 2g/10min.
6. A halogen-free flame retardant polyolefin composition according to any of claims 1-5, characterized in that: the halogen-free flame-retardant polyolefin composition also comprises a processing aid, wherein the mass percentage of the processing aid is 0.3-1%;
preferably, the processing aid comprises one or more of hindered phenol antioxidants, phosphite antioxidants, thio-ester antioxidants, benzotriazole antioxidants, benzophenone antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, white oil, silicone master batch, erucamide, polypropylene wax and polyethylene wax and mixtures thereof.
7. A process for preparing a halogen-free flame retardant polyolefin composition according to any of claims 1 to 6, characterized in that:
1) Pre-mixing polyolefin resin, halogen-free flame retardant and carrier-free smoke suppression master batch uniformly;
2) And mixing, and then carrying out melt blending by a double-screw extruder to obtain the halogen-free flame retardant polyolefin composition.
8. The method for preparing a halogen-free flame retardant polyolefin composition according to claim 7, wherein: in the step 1), the preparation method of the carrier-free smoke suppression master batch comprises the following steps: mixing porous adsorption material, high heat-resistant antioxidant, zinc salt and molybdenum compound to form a mixture, melting coating agent TAS-2 at high temperature, continuously spraying into the mixture, mixing, cooling, pulverizing, and sieving.
9. The method for preparing a halogen-free flame retardant polyolefin composition according to claim 7 or 8, characterized in that: in the step 1), the porous adsorption material, the high heat-resistant antioxidant, the zinc salt and the molybdenum compound are sequentially added into a high-mixing pot, and are mixed at the normal temperature at the speed of 200-300r/min and then are mixed at the speed of 600-1400r/min to form a mixture.
10. A process for the preparation of a halogen-free flame retardant polyolefin composition according to any of claims 7-9, characterized in that: in the step 2), the vacuum extraction pressure value of the metering section of the double-screw extruder is between-0.8 MPa and-1.0 MPa; preferably, -0.9MPa;
Preferably, in step 2), the screw combination of the twin screw extruder comprises 90 degree and 45 degree screw elements;
preferably, the temperature of each section of the screw is 150-210 ℃.
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