CN117165000A - Low-smoke flame-retardant polyolefin composition and preparation method thereof - Google Patents
Low-smoke flame-retardant polyolefin composition and preparation method thereof Download PDFInfo
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- CN117165000A CN117165000A CN202311142650.5A CN202311142650A CN117165000A CN 117165000 A CN117165000 A CN 117165000A CN 202311142650 A CN202311142650 A CN 202311142650A CN 117165000 A CN117165000 A CN 117165000A
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- flame retardant
- polypropylene
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 119
- 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 100
- 239000000779 smoke Substances 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 31
- 230000001629 suppression Effects 0.000 claims abstract description 28
- 238000012545 processing Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 12
- -1 (3, 5-di-tert-butyl-4-hydroxy-phenylpropionyl) phosphite Chemical compound 0.000 claims description 43
- 239000004743 Polypropylene Substances 0.000 claims description 32
- 229920001155 polypropylene Polymers 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 27
- 239000007822 coupling agent Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 229920005604 random copolymer Polymers 0.000 claims description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 229920001684 low density polyethylene Polymers 0.000 claims description 8
- 239000004702 low-density polyethylene Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 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 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- 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 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- LRGQZEKJTHEMOJ-UHFFFAOYSA-N propane-1,2,3-triol;zinc Chemical compound [Zn].OCC(O)CO LRGQZEKJTHEMOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 2
- 230000004580 weight loss Effects 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
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000011833 salt mixture Substances 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 abstract description 14
- 150000002367 halogens Chemical class 0.000 abstract description 14
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 239000011342 resin composition Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000519995 Stachys sylvatica Species 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 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
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UQJKREIYJZRSFC-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)C(OC(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC)C(CO)(CO)CO Chemical compound C(CCCCCCCCCCCCCCCCC)C(OC(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC)C(CO)(CO)CO UQJKREIYJZRSFC-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 238000004458 analytical method Methods 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material 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
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 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
- 239000003094 microcapsule Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 229920000642 polymer Polymers 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a preparation of a carrier-free smoke suppression master batch and a high-viscosity flame retardant polyolefin composition, in particular to a halogen flame retardant polyolefin resin composition with excellent low smoke generation, better dispersibility, flame retardance and smooth surface of a finished product. The flame-retardant polyolefin resin composition has extremely low smoke amount in the processing process, particularly in the material combustion process, is more environment-friendly, and effectively reduces the smoke amount of the product material in the ignition combustion process and the smoke density of the material in the processing process by adding the self-made carrier-free smoke suppression master batch.
Description
Technical Field
The invention relates to a preparation of a carrier-free smoke suppression master batch and a high-viscosity flame retardant polyolefin composition, in particular to a halogen flame retardant polyolefin resin composition with excellent low smoke generation, better dispersibility, flame retardance and smooth surface of a finished product. The flame-retardant polyolefin resin composition has extremely low smoke amount in the material combustion process, and the self-made carrier-free smoke suppression master batch is added, so that the problem that a great amount of smoke is released in the combustion process by the halogen flame-retardant material is effectively solved, and the influence of the smoke on the physical health of field personnel in a fire scene is avoided. The product has high melt strength, is more suitable for plates and profiles with higher requirements on appearance surfaces such as extrusion grade, plastic sucking products and blow molding products, and is applied to the fields of automobiles, buildings, household appliances and the like with flame retardance and appearance requirements.
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 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, and the production and circulation of a plurality of halogen-containing flame retardants are forbidden in various countries at present, and the application of halogen-containing flame retardants is more and more limited. 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.
At present, the multi-purpose intumescent halogen-free flame retardant is on the market. 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 halogen flame retardant material has obviously lower smoke quantity than the expansion halogen-free flame retardant material in the modification processing and product forming processes, but generates a large amount of smoke in the combustion process, has higher toxicity and has great influence on human health and environment.
The halogen flame-retardant material is mainly compounded of decabromodiphenyl ethane and antimonous oxide, and more magnesium silicate salt substances are added to assist flame retardance and reduce cost, so that the flame retardant and the filler added by the halogen flame-retardant material cannot be melted in the modification processing process, and particularly under the condition of high temperature, the flame retardant and the filler are difficult to disperse in the extrusion processing process of a double-screw extruder, and have agglomeration phenomenon, so that a large number of white spots, pits and pits are formed on the surface of the product. In addition, when the high-viscosity resin is used as a matrix, the screw torque is increased in the extrusion process, the shearing heat is higher, the host current is larger, and the material is easy to be partially decomposed, so that more carbonization phenomena can be generated in the extrusion modification, extrusion plate molding, plastic suction and blow molding processes.
The flame retardant compositions and the flame retardant resin compositions containing the same disclosed by Japanese patent No. Ai Dike, such as patent No. 110582553A, patent No. CN 111433326B, patent No. CN 105209576A, patent No. CN 109563410B, patent No. CN107075378A, patent No. CN 111278950A, patent No. CN 110869447B and the like, represent advanced synthesis and application of intumescent halogen-free flame retardants at home and abroad, have high flame retardance and good product stability, but have the problems of poor compatibility with polyolefin resin when being directly added and applied, poor dispersibility in the processing process, easy decomposition during the production and processing of high-viscosity matrix materials, low cost performance compared with similar flame retardants at home and abroad and the like. Domestic 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 the water resistance and moisture absorption migration property of the flame retardant in polypropylene material, patent CN107075378A discloses that silicone oil and silane coupling agent can prevent the flame retardant from agglomerating, improve the dispersibility and endow water resistance and heat resistance, the silicone oil, coupling agent and lubricant are directly sprayed or dripped on halogen-free flame retardant, the problem that the flame retardant is highly dispersed in the material, secondary agglomeration phenomenon still occurs in the processing process, particularly the problem that the surface white spots are more or less pits are exposed when a plate or an extruded profile is extruded, and large smoke and gas are generated in the high-temperature processing process.
At present, the research on the smoke generation amount of the high-viscosity halogen flame-retardant polyolefin material in combustion at home and abroad has almost no relevant report.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of a carrier-free smoke suppression master batch and a high-viscosity flame-retardant polyolefin composition, and the problem that the smoke amount of a product is very large during combustion is effectively solved by preparing the carrier-free smoke suppression master batch and applying the carrier-free smoke suppression master batch to a flame-retardant material. In addition, the unsupported smoke suppressing master batch increases the flame retardant efficiency of the flame retardant polyolefin composition. The addition of the compatilizer and the reasonable improvement of the processing technology effectively improve the dispersibility of the flame retardant polyolefin composition and obviously improve the problems of pockmarks, white spots, pits and the like on the surfaces of extruded plates, plastic uptake or blow molding products.
The carrier-free smoke suppression master batch consists of five organic and inorganic substances, wherein the mass percentage of the substance a is 20-30%, the mass percentage of the substance b is 20-40%, the mass percentage of the substance c is 10-25%, the mass percentage of the substance d is 15-25%, and the mass percentage of the substance e is 5-15%.
The substance a is a porous adsorption material, the porous adsorption material is prepared by drying, pressing and sintering fine-grade soda lime borosilicate hollow microspheres on nanoscale porous aluminosilicate, grinding the microspheres into powder for self-control, and the particle size is 10-80 mu m, and patent CN113462074B is described. 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.
The material is a high heat-resistant antioxidant which is a compound of hindered phenol antioxidants and phosphite antioxidants and is one or a mixture of more of pentaerythritol tetra (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) isocyanuric acid, 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, tris (2, 4-di-tert-butyl) phosphite and dioctadecyl dipentaerythritol.
The substance c of the invention is one or a mixture of zinc salts of zinc stannate, zinc stannate hydrate, zinc borate, zinc glycerolate and zinc molybdate, more preferably zinc stannate, and has an average particle diameter (D50) of 1.7 μm and a specific surface area of 4.5m 2 And/g, the free water content is less than 1%, and the inorganic flame-retardant smoke suppressant is used as an inorganic flame-retardant smoke suppressant.
The substance d is one or a mixture of molybdenum compounds of molybdenum trioxide, ammonium octamolybdate and calcium molybdate, and further preferably the ammonium octamolybdate, and the theoretical molybdenum content is 45.39 percent, so that the compound organic flame-retardant smoke suppressant is prepared.
The material e of the invention is a coating agent TAS-2A, and is characterized in that the structure of the coating agent is mainly adjusted on the basis of ethylene bis fatty acid amide, main chain molecules are solvated chain segment lipophilic groups, polar groups are introduced, the 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 ℃ as a coating material of the compound smoke suppressant.
The preparation method of the carrier-free smoke suppression master batch comprises the following steps:
step one: adding the component a, the component b, the component c and the component d in sequence in a high-temperature spray gun-equipped high-mixing pot, mixing at a low speed for a certain time at a normal temperature of 200-300r/min, and then mixing at a high speed of 600-1400r/min for 1-4min.
Step two: the temperature of the high-temperature spray gun is set to be 50-60 ℃, TAS-2A is continuously sprayed into the high-temperature spray gun according to a certain amount by the spray gun, the high-temperature mixing pot is kept at 100-120 ℃, and the high-speed mixing is carried out for 3-5min at 600-1400 r/min.
Step three: discharging, cooling, pulverizing, and sieving to obtain powder with particle diameter of 10-80 μm.
The flame retardant polyolefin composition of the invention is a final shaped product. The combination formula of the composition comprises the following components:
40-56% of polyolefin resin by mass;
30-50% of flame retardant;
3-10% of carrier-free smoke suppression master batch;
2-6% of compatilizer;
0.3 to 1 percent of coupling agent by mass percent;
the processing auxiliary agent accounts for 0.3 to 1 percent.
The polyolefin resin of the flame-retardant polyolefin composition is one or more of the following 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, cycloolefin 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 flame retardant of the flame retardant polyolefin composition is commercially available, and is characterized in that the compound flame retardant composition is a mixture of a plurality of flame retardants and fillers, namely decabromodiphenyl ethane, antimonous oxide, anti-dripping agent and talcum powder.
The average grain diameter of decabromodiphenyl ethane of the flame retardant is smaller than 5 mu m, the total bromine content is smaller than 20ppm, and the whiteness is not required.
The anti-dripping agent is AS or MS coated with polytetrafluoroethylene in a microcapsule mode, and the effective content of the polytetrafluoroethylene is 52%.
The talcum powder has the silicon content of more than 55 percent, the average grain diameter of less than 8 mu m and the diameter-thickness ratio of more than 20:1.
the compatilizer of the flame retardant polyolefin composition is polyolefin-based grafted maleic anhydride or polyolefin-based grafted glycidyl methacrylate, the addition of the compatilizer can improve the dispersibility and compatibility of the flame retardant in resin, the grafting rate of the maleic anhydride or the glycidyl methacrylate is 0.9-1.2%, the melt index is not higher than 2g/10min, and the invention further preferably selects the polyolefin-based grafted maleic anhydride.
The coupling agent of the flame retardant polyolefin composition is one or a mixture of more of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent, and the titanate coupling agent is further preferred.
The processing aid of the flame retardant polyolefin composition comprises one or a mixture of more of hindered phenol antioxidants, phosphite antioxidants, thioester antioxidants, benzotriazole antioxidants, benzophenone antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, white oil, silicone master batches, erucamide, polypropylene wax and polyethylene wax.
The preparation method of the flame retardant polyolefin composition comprises the following steps:
step one: the polyolefin resin, the flame retardant, the carrier-free smoke suppression master batch, the compatilizer and the processing aid are mixed uniformly in advance in a high-speed mixer according to the mass proportion requirement, and fed at a main feeding port of a double-screw extruder;
step two: the vacuum extraction pressure value of the metering section of the double-screw extruder is about-0.9 MPa, kneading blocks are added in other sections except a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, the temperature of each section of the screw is set in a range of 150-210 ℃, and the reasonable host rotation speed is set. The flame retardant polyolefin composition is prepared by melt blending through a twin screw extruder.
Compared with the prior art, the invention has the following beneficial effects:
at present, few researches on comprehensive smoke reduction of high-viscosity flame-retardant polyolefin materials at home and abroad exist, the carrier-free smoke suppression master batch is compounded by various substances, firstly, a matrix material and a flame retardant are protected at high temperature by adding a high-heat-resistant antioxidant, the thermal decomposition is prevented in the processing process, then the smoke generated by shearing the flame-retardant material in the screw cylinder is partially absorbed by a porous adsorption material through physical adsorption and chemical chelation, so that the smoke in the production and processing process is effectively reduced, and zinc salt and molybdenum compounds are compounded and added, so that the smoke in the combustion process of the flame-retardant material is further reduced. The problem of large smoke amount in the combustion process of the flame retardant material and the smoke of the flame retardant material in the production and processing process is solved through the synergistic effect of the substances.
The base material for the flame-retardant polyolefin composition has high viscosity, high screw torque, high host current and high shearing heat in the processing process, is more likely to cause material decomposition to generate larger smoke, and needs to reasonably design the production and processing technology to achieve the optimal smoke suppression effect by reasonably adjusting the threaded element and the production technology, effectively improve the production and processing environment and ensure the physical and mental health of field personnel.
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 the problems of no 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
The present invention will be further illustrated by the following examples and comparative examples, without departing from the spirit of the invention, which should not be limited to what is specifically illustrated by the following examples.
In the following examples, all of the flame retardants used are commercially available in bulk, and the preferred formulation of the formulated flame retardant composition is as follows:
48.4 percent of decabromodiphenyl ethane;
11.8 percent of antimony trioxide;
39.2 percent of talcum powder;
the mass percentage of the anti-dripping agent is 0.6 percent.
In the following examples, the preferred materials for the no-carrier smoke suppression master batch are as follows;
22 mass percent of self-made nanoscale porous material;
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%.
In the following experimental examples, the compound high heat-resistant antioxidant is further preferably compounded by 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 the compound high heat-resistant antioxidant is further compounded according to the mass percentage of 20 to 60, so that the decomposition of the base material and the flame retardant in the production and processing process is effectively protected.
In the following experimental examples, the preparation method of the carrier-free smoke suppression master batch is preferably as follows: 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.
In the following experimental examples, the polyolefin resin used has a melt index of less than 3.0g/10min according to the international standard ISO1133-1 method.
Example 1
A low-smoke high-viscosity flame-retardant toughening polypropylene composition comprises the following components in percentage by mass:
44% of random copolymer polypropylene, 10% of ethylene/octene segmented copolymer, 39% of compound flame retardant, 3% of carrier-free smoke suppression master batch, 3% of compatilizer, 0.5% of coupling agent and 0.5% of other processing aids.
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 170-210 ℃, 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 compound flame retardant composition, the carrier-free smoke suppression master batch, the compatilizer and other processing aids are pre-mixed for 1min at a high-speed mixer of 750r/min according to mass proportion, 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 flame-retardant polyolefin composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Example 2
A low-smoke high-viscosity flame-retardant toughening polypropylene composition comprises the following components in percentage by mass:
40% of random copolymer polypropylene, 8% of ethylene/octene segmented copolymer, 39% of compound flame retardant, 9% of carrier-free smoke suppression master batch, 3% of compatilizer, 0.5% of coupling agent and 0.5% of other processing aids.
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 170-210 ℃, 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 compound flame retardant composition, the carrier-free smoke suppression master batch, the compatilizer and other processing aids are pre-mixed for 1min at a high-speed mixer of 750r/min according to mass proportion, 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 flame-retardant polyolefin composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Example 3
A low-smoke high-viscosity flame-retardant polyethylene composition comprises the following components in percentage by mass:
40% of high-density polyethylene, 10% of metallocene low-density polyethylene, 40% of compound flame retardant, 6% of carrier-free smoke suppression master batch, 3% of compatilizer, 0.5% of coupling agent and 0.5% of other processing aids.
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 120-140 ℃, the temperature of the second area to the machine head is 150-200 ℃, the current of the main machine is 360-450A, 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 high-density polyethylene, the metallocene low-density polyethylene, the compound flame retardant composition, the carrier-free smoke suppression master batch, the compatilizer and other processing aids are pre-mixed for 1min at a high-speed mixer of 750r/min according to mass proportion, 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 flame-retardant polyolefin composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 1
A high-viscosity flame-retardant toughened polypropylene composition comprises the following components in percentage by mass:
47% of random copolymer polypropylene, 10% of ethylene/octene segmented copolymer, 39% of compound flame retardant, 3% of compatilizer, 0.5% of coupling agent and 0.5% of other processing aids.
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 170-210 ℃, 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 composite flame retardant composition compatilizer and other processing aids are mixed in advance for 1min at a high speed mixer of 750r/min according to mass proportion, and then the coupling agent is sprayed uniformly and mixed for 3min at high speed, and the materials are 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 flame-retardant polyolefin composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 2
A low-smoke high-viscosity flame-retardant polyethylene composition comprises the following components in percentage by mass:
46% of high-density polyethylene, 10% of metallocene low-density polyethylene, 40% of compound flame retardant, 3% of compatilizer, 0.5% of coupling agent and 0.5% of other processing aids.
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 120-140 ℃, the temperature of the second area to the machine head is 150-200 ℃, the current of the main machine is 360-450A, 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 high-density polyethylene, the metallocene low-density polyethylene, the compound flame retardant composition, the compatilizer and other processing aids are mixed in advance for 1min at the speed of 750r/min of a high-speed mixer according to mass proportion, and then the coupling agent 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 flame-retardant polyolefin composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Comparative example 3
A low-smoke high-viscosity flame-retardant polyethylene composition produced by a common screw rod comprises the following components in percentage by mass:
40% of high-density polyethylene, 10% of metallocene low-density polyethylene, 40% of compound flame retardant, 6% of carrier-free smoke suppression master batch, 3% of compatilizer, 0.5% of coupling agent and 0.5% of other processing aids.
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 120-140 ℃, the temperature of the second area to the machine head is 150-200 ℃, the current of the main machine is 360-450A, 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 high-density polyethylene, the metallocene low-density polyethylene, the compound flame retardant composition, the carrier-free smoke suppression master batch, the compatilizer and other processing aids are pre-mixed for 1min at a high-speed mixer of 750r/min according to mass proportion, 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. The combination of the thread elements of the screw is used for producing a common polyolefin material combination for automobiles, the flame-retardant polyolefin composition is prepared by melt blending through a double-screw extruder, and particles are prepared by granulating after traction cooling.
Performance testing
The materials prepared in the above examples and comparative examples 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.
Table 1 results of performance testing of flame retardant polyolefin compositions of examples and comparative examples
As is clear from the test results of the examples and comparative examples in Table 1, the flame retardant polyolefin-based compositions prepared in examples 1 to 3 of the present invention have excellent tensile strength and notched impact strength, excellent strain at break, and high flame retarding efficiency and excellent dispersibility in polyolefin compositions, as demonstrated by the strain at break data, notched impact strength, the surface of water-cut particles and the surface of plate appearance.
From the analysis of examples 1 and 2, the reduction of smoke in flame and flameless state of the flame retardant polyolefin composition is further aided by the increase of the content of the unsupported smoke suppressing masterbatch.
Examples 1 and 2 were compared with comparative examples 1 and 2, respectively, and by adding the unsupported smoke suppressing master batch, the flame smoke density and the flameless smoke density were both greatly reduced as well as the amount of fuming from the extruder die opening were also evident from the comparative data analysis of 2 groups of different flame retardants.
Comparative example 3 the particular screw combination process also has a very important effect on the dispersion of the flame retardant in the material compared to example 3.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (10)
1. A low-smoke flame-retardant polyolefin composition and a preparation method thereof are characterized in that the preparation method comprises the preparation of a carrier-free smoke-suppressing master batch and the preparation of a flame-retardant polyolefin-based composition.
2. The carrier-free smoke suppression master batch according to claim 1, wherein the carrier-free smoke suppression master batch comprises the following components: 20-30% of a substance by mass, 20-40% of b substance by mass, 10-25% of c substance by mass, 15-25% of d substance by mass and 5-15% of e substance by mass.
The specific composition substances are as follows:
the substance a is a porous adsorption material, which is characterized in that the porous adsorption material is prepared by dry pressing and high-temperature sintering fine-particle-grade soda lime borosilicate hollow microspheres coated by nano-scale porous aluminosilicate, and then grinding the hollow microspheres into powder with the particle size of 10-80 mu m, wherein patent CN113462074B is described;
the substance b is a high heat-resistant antioxidant, and is characterized in that the high heat-resistant antioxidant is a compound of hindered phenol antioxidants and phosphite antioxidants, and is a compound of pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, n-stearyl 3- (3, 4-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, 1,3, 5-trimethyl-2, 4, 6-tri (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-phenylpropionyl) phosphite, or bis-octadecyl pentaerythritol bis-hydrazine;
the substance c is one or more zinc salt mixtures of zinc stannate, zinc stannate hydrate, zinc borate, zinc glycerolate and zinc molybdate;
the substance d is one or a mixture of more of molybdenum trioxide, ammonium octamolybdate and calcium molybdate;
the e substance is a coating agent TAS-2A, and is characterized in that the coating agent is mainly structurally regulated on the basis of ethylene bis fatty acid amide, main chain molecules are solvated chain segment lipophilic groups, and polar groups are introduced, so that the 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 ℃.
3. The method for preparing the carrier-free smoke suppression master batch according to claim 1 comprises the following steps:
sequentially adding the component a, the component b, the component c and the component d in a high-temperature spray gun in a high-mixing pot, mixing at a low speed of 200-300r/min for a certain time at normal temperature, mixing at a high speed of 600-1400r/min for 1-4min, continuously spraying the melted component e under a certain pressure by the high-temperature spray gun, continuously mixing at a high speed for 3-5min, discharging, cooling, crushing and screening for standby.
4. The flame retardant and the flame retardant synergistic filler according to claim 1 are commercially available, wherein the flame retardant is a mixture of a plurality of flame retardants selected from decabromodiphenylethane, antimony trioxide, talc and anti-drip agents.
5. The flame retardant polyolefin composition of claim 1, wherein the polyolefin resin is one or more of the following 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.
6. The preparation of a low smoke flame retardant polyolefin composition according to claim 1, in combination with the formulation:
40-56% of polyolefin resin by mass;
30-50% of flame retardant;
3-10% of carrier-free smoke suppression master batch;
2-6% of compatilizer;
0.3 to 1 percent of coupling agent by mass percent;
the processing auxiliary agent accounts for 0.3 to 1 percent.
7. The compatibilizer of claim 6 wherein the compatibilizer is a polyolefin-based grafted maleic anhydride or a polyolefin-based grafted glycidyl methacrylate and the addition thereof improves the dispersibility and compatibility of the flame retardant in the resin, the grafting ratio of the maleic anhydride or the glycidyl methacrylate is 0.9-1.2%, and the melt index is not higher than 2g/10min.
8. The coupling agent of claim 6, wherein the coupling agent is one or more of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
9. The halogen-free flame retardant polyolefin composition of claim 6, wherein the processing aid comprises one or a mixture of more of hindered phenolic antioxidants, phosphite antioxidants, thioester antioxidants, benzotriazole antioxidants, benzophenone antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, white oil, silicone master batches, erucamide, polypropylene wax and polyethylene wax.
10. The flame retardant polyolefin composition according to claims 6-8, which is prepared by a process comprising:
(1) The polyolefin resin, the flame retardant composition, the carrier-free smoke suppression master batch, the compatilizer and the processing aid are mixed uniformly in advance in a high-speed mixer according to the mass proportion requirement, and fed at a main feeding port of a double-screw extruder.
(2) The vacuum extraction pressure value of the metering section of the double-screw extruder is about-0.9 MPa, kneading blocks are added in other sections except a feeding port, a natural exhaust port, a vacuum exhaust port and a conveying section as much as possible, the application of 90-degree and 45-degree screw elements in a screw combination is increased, the temperature of each section of the screw is set in a range of 150-210 ℃, and the reasonable host rotation speed is set. The flame retardant polyolefin composition is prepared by melt blending through a twin screw extruder.
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