CN117229587A - Flame-retardant polyolefin composition and preparation method thereof - Google Patents
Flame-retardant polyolefin composition and preparation method thereof Download PDFInfo
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- CN117229587A CN117229587A CN202311142560.6A CN202311142560A CN117229587A CN 117229587 A CN117229587 A CN 117229587A CN 202311142560 A CN202311142560 A CN 202311142560A CN 117229587 A CN117229587 A CN 117229587A
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- flame retardant
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- polypropylene
- screw extruder
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 147
- 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 135
- 239000000203 mixture Substances 0.000 title claims abstract description 128
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001125 extrusion Methods 0.000 claims abstract description 20
- 238000004381 surface treatment Methods 0.000 claims abstract description 16
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 71
- 239000004743 Polypropylene Substances 0.000 claims description 59
- 229920001155 polypropylene Polymers 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 36
- 238000004132 cross linking Methods 0.000 claims description 27
- 229920005604 random copolymer Polymers 0.000 claims description 23
- 150000003254 radicals Chemical class 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 12
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 11
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- JKBYAWVSVVSRIX-UHFFFAOYSA-N octadecyl 2-(1-octadecoxy-1-oxopropan-2-yl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)SC(C)C(=O)OCCCCCCCCCCCCCCCCCC JKBYAWVSVVSRIX-UHFFFAOYSA-N 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 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
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- 229940114926 stearate Drugs 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 238000001035 drying Methods 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
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-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
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-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
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 229920002313 fluoropolymer Polymers 0.000 claims 1
- 238000009472 formulation Methods 0.000 claims 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical class [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 12
- 239000004033 plastic Substances 0.000 abstract description 12
- 238000000071 blow moulding Methods 0.000 abstract description 10
- 239000011342 resin composition Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 16
- 230000003078 antioxidant effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 3
- 241000519995 Stachys sylvatica Species 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- LJDGJCNHVGGOFW-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2-bromophenoxy)benzene Chemical compound BrC1=CC=CC=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br LJDGJCNHVGGOFW-UHFFFAOYSA-N 0.000 description 2
- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- NLBLNZDNOSSGPW-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3-dibromophenoxy)benzene Chemical compound BrC1=CC=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2Br)Br)=C1Br NLBLNZDNOSSGPW-UHFFFAOYSA-N 0.000 description 1
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 1
- VIHUMJGEWQPWOT-UHFFFAOYSA-N 1,2,3-tribromo-4-(3-bromophenoxy)benzene Chemical compound BrC1=CC=CC(OC=2C(=C(Br)C(Br)=CC=2)Br)=C1 VIHUMJGEWQPWOT-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 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
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229960001954 piperazine phosphate Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a preparation of a compound flame retardant, a surface treatment thereof, and a preparation of a flame retardant polyolefin composition, and more particularly, to a flame retardant polyolefin resin composition having excellent melt strength, dispersibility, flame retardancy, smoothness of the surface of a product, and excellent precipitation resistance. The flame-retardant polyolefin resin composition has high melt strength and high product stability, 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.
Description
Technical Field
The present invention relates to a preparation of a compound flame retardant, a surface treatment thereof, and a preparation of a flame retardant polyolefin composition, and more particularly, to a flame retardant polyolefin resin composition having excellent melt strength, and particularly excellent dispersibility, flame retardancy, and smooth surface of a product. The flame-retardant polyolefin resin composition has low melting point and high product stability, 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 use of partial halogen-containing flame retardants is restricted in various countries due to environmental protection factors. The Style's convention was passed in Switzerland in 2001, primarily for protecting humans and the natural environment from persistent organic pollutants. The 2009 convention lists pentabromodiphenyl ether and octabromodiphenyl ether to the convention controlled list, the 2013 hexabromocyclododecane was added to the list, and the 2017 convention amendment list decabromodiphenyl ether was added to the list. China signed the convention in 2001 and partially fulfilled the convention for polybrominated diphenyl ethers in 2014. Mainly inhibit production and circulation of hexabromodiphenyl ether, tetrabromodiphenyl ether, pentabromodiphenyl ether, hexabromodiphenyl ether and heptabromodiphenyl ether. Aiming at decabromodiphenyl ether, china completes basic work of fulfilling the convention, but the related amendment is not yet effective in China. Aiming at hexabromocyclododecane, 5-year exemption period is applied in China, and the production and use of hexabromocyclododecane are completely eliminated in 2021 and 12. Decabromodiphenyl ethane is used as a novel flame retardant, and at present, the halogen flame retardant at home and abroad is used for replacing decabromodiphenyl ether, which accords with requirements of the Sjog's convention, european RoHS directive, european Union REACH regulation and China's harmful substance restriction and use management method of electric and electronic products '. The halogen-free flame retardant traditional multipurpose red phosphorus, ammonium polyphosphate, phosphate organic phosphorus flame retardant and metal hydroxide are low in flame retardant efficiency, poor in water resistance, easy to precipitate, poor in compatibility with polymers, poor in processability or high in increment and the like, and the novel piperazine pyrophosphate and melamine pyrophosphate compound flame retardant is poor in long-term aging precipitation and dispersibility, and still has great difficulty in normal production although the water resistance and precipitation resistance are greatly improved.
The halogen flame retardant resin material in the domestic market is mainly used for injection molding products, is very few in products for plastic suction and blow molding, mainly has large addition amount of halogen flame retardant in a material formula, has poor compatibility with polyolefin resin, and particularly has large screw torque and high host current in the extrusion processing process of a double screw extruder under the condition of extremely high viscosity of matrix resin, so that the halogen flame retardant is very difficult to disperse. When the halogen flame retardant material is processed by a plastic sucking or blow molding process, undispersed flame retardant or filler can present a large number of white spots, pits and pits on the surface of a product piece in the high-temperature softening and stretching process, so that the product piece is poor.
The flame-retardant polyolefin material of the plastic sucking grade or the blow molding grade is required to have higher melt strength, and particularly is used for products with large longitudinal deep drawing size or large thin-wall product pieces, and the problem that the product pieces are difficult to mold or nonuniform in wall thickness in the plastic sucking or blow molding process is caused by low melt strength.
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 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 too small and too many pits are exposed when a plate or an extruded profile is extruded, and partial precipitation phenomenon exists under the condition of high temperature and high humidity. The application of halogen-containing flame retardant polyolefin materials to plastic uptake and blow molded products is very small.
Disclosure of Invention
In order to overcome the defects of white spots, pits and the like on the surface of the molded product and the problems in terms of plastic sucking and blow molding processing, the invention provides a flame retardant composition and a preparation method of a polyolefin-based composition thereof.
The flame retardant composition consists of four flame retardant substances, wherein the mass percentage of the decabromodiphenyl ethane of the flame retardant is 35-50%, the mass percentage of the antimony trioxide of the flame retardant synergist is 6-18%, the mass percentage of the polytetrafluoroethylene of the anti-dripping agent is 0.4-2%, and the mass percentage of the magnesium silicate salt of the flame retardant synergist is 10-50%.
The flame retardant decabromodiphenyl ethane of the invention has a 1% thermal weight loss temperature of not less than 330 ℃, and particle size (D) 50 ) Not more than 3 μm, whiteness not less than 89, and pH 7-9.
The flame-retardant synergistic filler of the invention is magnesium silicate, the PH value is 9-9.5, the mass percentage of silicon dioxide is more than 61%, and the average grain diameter (D 50 ) The weight percentage of the silicon dioxide is 3-8 mu m, the rigidity of the material is increased, the material cost is reduced, the invention further preferably selects 5 mu m magnesium silicate salt, the weight percentage of the silicon dioxide is 62 percent, and the PH value is 9.3.
The preparation method of the flame retardant composition comprises the steps of placing four flame retardant substances in a high-speed mixer according to a certain mass ratio, uniformly mixing for 5min at 100-120 ℃, and cooling to room temperature for standby.
The surface treatment of the flame retardant composition achieves good compatibility and dispersibility of the flame retardant and a matrix resin material through chemical coupling and physical lubrication pre-dispersion. The surface-treated flame retardant composition is easy to store, can be directly added into polyolefin resin, and has no pits or pits on the surface of a product piece after plastic suction or blow molding.
The preparation method for the surface treatment of the flame retardant composition mainly comprises the following steps:
step one: adding the component A in proportion in a high-temperature spray gun-equipped high-pressure mixing pot, and mixing at a low speed of 200-300r/min for 1-2 min at the high temperature of 100-120 ℃.
Step two: the temperature of the high-temperature spray gun is set to be 50-60 ℃, the component B is continuously sprayed into the high-temperature spray gun according to a certain amount, the high-temperature mixing pot is kept at 100-120 ℃, and the high-speed mixing is carried out for 3-5 min at 600-1400 r/min.
Step three: adding the component C and the component D into a feeding port of a high-pressure mixing pot, mixing at a high speed of 600-1400r/min for 3-5 min, discharging and cooling for standby.
The component A of the surface pretreatment material of the flame retardant composition is a standby flame retardant composition, and the addition amount of the flame retardant composition is 91-96% by mass.
The component B of the surface pretreatment material of the flame retardant composition is a coupling agent, the coupling agent is one or a mixture of more of a silane coupling agent, a maleic anhydride graft, a titanate coupling agent and an aluminate coupling agent, and is bonded with the surface of the flame retardant at high temperature, and the invention further preferably comprises the silane coupling agent, wherein the addition amount of the silane coupling agent is 0.5-2% by mass.
The component C of the surface pretreatment material of the flame retardant composition is a hyperdispersant, and the hyperdispersant is one or a mixture of a polyester hyperdispersant, a polyether hyperdispersant and a polyolefin hyperdispersant. One part of the hyper-dispersant is an anchoring group, and the anchoring group can be tightly combined on the surface of the particle through the actions of ion pairs, hydrogen bonds, van der Waals force and the like to prevent the hyper-dispersant from being desorbed; the other part is a solvated chain, which is a polymer chain solvated by a medium, and the solvated chain can play a role in dispersing and stabilizing particles through a steric effect. The invention further preferably discloses an acrylic polyester hyperdispersant, wherein the polyester hyperdispersant is a polymer obtained by free radical random polymerization of m-pentadecyl phenyl acrylate, phosphonic acid and (methyl) alkyl acrylate, and the addition amount of the polyester hyperdispersant is 3-5% by mass.
The component D of the surface pretreatment material of the flame retardant composition is stearate, the stearate is one or a mixture of more of magnesium stearate, calcium stearate, potassium stearate and zinc stearate, and the mixture neutralizes part of the acidity of the halogen-free flame retardant, promotes the dispersion of the flame retardant, changes the crystallinity of matrix resin and has the addition amount of 0.5-2% by mass.
The flame retardant composition of the present invention the polyolefin-based composition is the final shaped product. The combination formula of the composition comprises the following components:
53-58% of polyolefin resin by mass;
40-45% of the surface treatment flame retardant composition by mass percent;
0.2-2% of cross-linking auxiliary agent by mass percent;
0.02 to 0.1 percent of free radical initiator;
the processing auxiliary agent accounts for 0.5 to 2 percent.
The polyolefin resin of the flame retardant composition of the present invention 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 cross-linking auxiliary agent of the flame retardant composition disclosed by the invention is one of trimethylolpropane trimethacrylate (TMPTMA), divinylbenzene (DVB), triallyl cyanurate (TAIC) and polyethylene glycol dimethacrylate (MPL). Under the action of shearing heat, the high-viscosity polyolefin resin causes the breakage of a resin molecular chain, a part of macromolecular free radicals with tertiary carbon atoms are generated, after a crosslinking auxiliary agent is added, macromolecular free radical degradation and crosslinking are simultaneously carried out in the actual extrusion melt blending process, and under the action of high-temperature shearing, polyolefin and a toughening agent material are partially micro-crosslinked, so that the high-temperature flame retardant material is helpful for later-stage plastic suction, the adhesion state of the halogen-free flame retardant material at high temperature is increased, the anti-dripping agent can be removed, the influence of the anti-dripping agent on the pockmark on the surface of a product part is reduced, and in addition, the flame retardant effect of the halogen-free flame retardant material can be improved. The invention further preferably uses TMPTMA as a crosslinking aid, wherein the double bonds in the TMPTMA molecule can participate in the crosslinking reaction.
The free radical initiator of the polyolefin-based composition of the flame retardant composition is one or a mixture of a plurality of dicumyl peroxide (DCP), benzoyl Peroxide (BPO), di-tert-butyl peroxide (DBP) and Azobisisobutyronitrile (AIBN). The present invention further prefers DBP as a free radical initiator to initiate the reaction of polypropylene and crosslinking aid at a temperature and shear rate in the extruder.
The processing aid of the polyolefin-based composition of the flame retardant composition comprises one or a mixture of more of hindered phenol antioxidants, phosphite antioxidants, dioctadecyl thiodipropionate, white oil, silicone oil, zinc stearate, calcium stearate, silicone master batches, erucamide and polyethylene wax.
The preparation method of the polyolefin-based composition of the flame retardant composition comprises the following steps:
step one: firstly, uniformly mixing polyolefin resin, a crosslinking auxiliary agent and a free radical initiator in a high-speed mixer according to a certain mass ratio, adding the mixture into a single screw extruder with an aspect ratio of 56:1 for melt mixing extrusion, and granulating and drying to obtain a high-melt-strength matrix standby material;
step two: then the high-melt-strength matrix standby material, the surface treatment flame retardant composition and the processing aid are mixed uniformly in advance in a high-speed mixer according to the mass proportion requirement, and are melted, mixed and extruded in a double-screw extruder with the length-diameter ratio of more than 40:1, and the invention further prefers a 44:1 double-screw extruder;
step three: 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 degrees 0, 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:
the invention carries out surface treatment on the flame retardant composition, carries out surface treatment on the flame retardant composition through the combined action of the coupling agent, the hyper-dispersant and the stearate, and adopts a solid-liquid-solid coating modification mode to synergistically improve the dispersibility and compatibility of the halogen-free flame retardant composition through chemical reaction and physical dispersion pretreatment, thereby further effectively solving the problems of pockmarks, protrusions and pits of the appearance of the product.
The cross-linking auxiliary agent and the free radical initiator are added in the preparation process of the polyolefin-based composition of the flame retardant composition, and the polyolefin resin is slightly cross-linked in the extrusion processing process, so that the plastic sucking or blow molding formability is improved, larger deep stretching and more complex product parts can be formed, and the thickness uniformity of the thin-wall product parts is ensured.
The processing technology for preparing the polyolefin-based composition of the flame retardant composition is different from that of conventional modified polyolefin, and the problems of plastic sucking or blow molding formability and wall thickness of product parts are effectively solved by micro-crosslinking of the polyolefin. Meanwhile, the special arrangement method of the double screws can further promote the dispersion of the flame retardant.
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 flame retardant materials are commercially available in bulk, and the preferred flame retardant compositions are formulated and processed as follows:
the flame retardant composition comprising 45 percent, 14 percent, 1 percent and 40 percent of decabromodiphenyl ethane, antimonous oxide, polytetrafluoroethylene and magnesium silicate salt in percentage by mass is placed in a high-speed mixer, evenly mixed for 5 minutes at 105 ℃, and cooled to room temperature for standby.
In the following examples, the surface pretreatment materials of the flame retardant composition used in the present invention are self-made in a batch, and the preferable material ratios are as follows:
94% by mass of the flame retardant composition;
1.5 percent of titanate coupling agent by mass;
4% of acrylic polyester hyperdispersant by mass;
the mass percent of the magnesium stearate is 0.5 percent.
In the following examples, the surface pretreatment materials of the flame retardant compositions used were self-prepared in batches according to the invention, preferably by the following processing techniques:
in a high-temperature spray gun equipped high-pressure mixing pot, 94% halogen-free flame retardant composition is put into the high-pressure mixing pot, and the high-pressure mixing pot is mixed for 1min at a low speed of 300r/min at a high temperature of 105 ℃. The high temperature spray gun temperature was set to 55 ℃, the titanate coupling agent mixture was continuously sprayed through the spray gun at 1.5%, the high mixing kettle was kept at 105 ℃, and high speed 750r/min was mixed for 4min. Adding the acrylic polyester hyperdispersant and the zinc stearate into a feeding port of a high-speed mixing pot, mixing at a high speed of 750r/min for 3min, discharging and cooling for standby.
In the following comparative examples, the flame retardant used was a commercially available same-brand flame retardant from the same manufacturer.
Example 1
A flame retardant composition polypropylene base masterbatch comprises the following components in percentage by mass:
58.2% of random copolymer polypropylene, 39.5% of surface pretreatment flame retardant composition, 0.77% of cross-linking auxiliary TMPTMA, 0.03% of free radical initiator DBP, 0.2% of processing auxiliary hindered phenol antioxidant, 0.2% of phosphite antioxidant, 0.1% of thiodipropionic acid dioctadecyl alcohol ester and 1% of silicone master batch.
The preparation method comprises the following steps:
the technological parameters of melt extrusion by a single screw extruder are as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-190 ℃, the current of the main machine is 350-400A, the rotating speed of the main machine is 250rpm, the vacuum extraction pressure value of the metering section is about-0.5 MPa, the materials are premixed for 2min at 350r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 56:1.
Feeding random copolymer polypropylene, a crosslinking auxiliary agent and a free radical initiator in a main feeding port of a single screw extruder according to a specified mass ratio, plugging a natural exhaust port, carrying out melt blending by the single screw extruder to obtain pre-crosslinked polypropylene, and granulating after traction cooling to obtain particles.
The technological parameters of melt extrusion by a twin-screw extruder are 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, the materials are premixed for 3min at 750r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 48:1.
The pre-crosslinked random copolymer polypropylene, the processing aid and the surface pretreatment flame retardant composition are mixed uniformly in advance in a high-speed mixer according to a specified mass ratio, 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 polypropylene-based composition of the flame retardant composition is prepared by melt blending of a double-screw extruder, and particles are prepared by granulating after traction cooling.
Example 2
A flame retardant composition polyethylene-based composition comprises the following components in percentage by mass:
58% of high-density polyethylene, 40.8% of surface pretreatment flame retardant composition, 0.19% of crosslinking auxiliary TMPTMA, 0.01% of free radical initiator DBP, 0.2% of processing auxiliary hindered phenol antioxidant, 0.2% of phosphite antioxidant, 0.1% of dioctadecyl thiodipropionate and 0.5% of silicone oil.
The preparation method comprises the following steps:
the technological parameters of melt extrusion by a single screw extruder are as follows: the temperature of the first area is 120-150 ℃, the temperature of the second area to the machine head is 150-180 ℃, the current of the main machine is 350-400A, the rotating speed of the main machine is 200rpm, the vacuum extraction pressure value of the metering section is about-0.5 MPa, the materials are premixed for 2min at 350r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 56:1.
Feeding high-density polyethylene, a crosslinking auxiliary agent and a free radical initiator in a main feeding port of a single screw extruder according to a specified mass ratio, plugging a natural exhaust port, carrying out melt blending by the single screw extruder to obtain pre-crosslinked polypropylene, and granulating after traction cooling to obtain particles.
The technological parameters of melt extrusion by a twin-screw extruder are as follows: the temperature of the first area is 120-150 ℃, the temperature of the second area to the machine head is 160-170 ℃, the current of the main machine is 390-460A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, the materials are premixed for 3min at 750r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 48:1.
The pre-crosslinked high-density polyethylene, the processing aid and the surface pre-treatment flame retardant composition are mixed uniformly in advance in a high-speed mixer according to a specified mass ratio, 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 polyethylene-based composition of the flame retardant composition is prepared through melt blending of a double-screw extruder, and particles are prepared through granulating after traction cooling.
Example 3
A halogen-free flame retardant composition metallocene linear low density polyethylene (mLLDPE) toughened polypropylene-based composition comprises the following components in percentage by mass:
40% of random copolymer polypropylene, 10.8% of metallocene linear low density polyethylene (mLLDPE), 39.8% of surface pretreatment flame retardant composition, 0.38% of cross-linking auxiliary TMPTMA, 0.02% of free radical initiator DBP, 0.2% of processing auxiliary hindered phenol antioxidant, 0.2% of phosphite antioxidant, 0.1% of thiodipropionate dioctadecyl ester and 0.5% of silicone oil.
The preparation method comprises the following steps:
the technological parameters of melt extrusion by a single screw extruder are as follows: the temperature of the first area is 120-150 ℃, the temperature of the second area to the machine head is 170-200 ℃, the current of the main machine is 340-360A, the rotating speed of the main machine is 220rpm, the vacuum extraction pressure value of the metering section is about-0.5 MPa, the materials are premixed for 2min at 350r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 56:1.
Feeding random copolymer polypropylene, metallocene linear low density polyethylene (mLLDPE), a crosslinking auxiliary agent and a free radical initiator in a main feeding port of a single screw extruder according to a specified mass ratio, plugging a natural exhaust port, carrying out melt blending by the single screw extruder to obtain pre-crosslinked polypropylene, and granulating after traction cooling to obtain particles.
The technological parameters of melt extrusion by a twin-screw extruder are as follows: the temperature of the first area is 120-150 ℃, the temperature of the second area to the machine head is 160-200 ℃, the current of the main machine is 350-420A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, the materials are premixed for 3min at 750r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 48:1.
The pre-crosslinked random copolymer polypropylene, the metallocene linear low density polyethylene, the processing aid and the surface pretreatment flame retardant composition are mixed uniformly in advance in a high-speed mixer according to a specified mass ratio, 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 polyethylene-based composition of the flame retardant composition is prepared through melt blending of a double-screw extruder, and particles are prepared through granulating after traction cooling.
Comparative example 1
The flame retardant composition is polypropylene-based master batch, is not subjected to surface treatment, and comprises the following components in percentage by mass:
58.2% of random copolymer polypropylene, 39.5% of flame retardant composition without surface pretreatment, 0.77% of cross-linking auxiliary TMPTMA, 0.03% of free radical initiator DBP, 0.2% of processing auxiliary hindered phenol antioxidant, 0.2% of phosphite antioxidant, 0.1% of dioctadecyl thiodipropionate and 1% of silicone master batch.
The preparation method comprises the following steps:
the technological parameters of melt extrusion by a single screw extruder are as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-190 ℃, the current of the main machine is 350-400A, the rotating speed of the main machine is 250rpm, the vacuum extraction pressure value of the metering section is about-0.5 MPa, the materials are premixed for 2min at 350r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 56:1.
Feeding random copolymer polypropylene, a crosslinking auxiliary agent and a free radical initiator in a main feeding port of a single screw extruder according to a specified mass ratio, plugging a natural exhaust port, carrying out melt blending by the single screw extruder to obtain pre-crosslinked polypropylene, and granulating after traction cooling to obtain particles.
The technological parameters of melt extrusion by a twin-screw extruder are 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 370-450A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, the materials are premixed for 3min at 750r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 48:1.
The pre-crosslinked random copolymer polypropylene, the processing aid and the surface pretreatment flame retardant composition are mixed uniformly in advance in a high-speed mixer according to a specified mass ratio, 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 polypropylene-based composition of the 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
A halogen-free flame-retardant polypropylene base masterbatch produced by a market general-purpose screw element double-screw extruder is composed of the following components in percentage by mass:
58.2% of random copolymer polypropylene, 39.5% of surface pretreatment flame retardant composition, 0.77% of cross-linking auxiliary TMPTMA, 0.03% of free radical initiator DBP, 0.2% of processing auxiliary hindered phenol antioxidant, 0.2% of phosphite antioxidant, 0.1% of dioctadecyl thiodipropionate and 1% of silicone master batch.
The preparation method comprises the following steps:
the technological parameters of melt extrusion by a single screw extruder are as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-190 ℃, the current of the main machine is 350-400A, the rotating speed of the main machine is 250rpm, the vacuum extraction pressure value of the metering section is about-0.5 MPa, the materials are premixed for 2min at 350r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 56:1.
Feeding random copolymer polypropylene, a crosslinking auxiliary agent and a free radical initiator in a main feeding port of a single screw extruder according to a specified mass ratio, plugging a natural exhaust port, carrying out melt blending by the single screw extruder to obtain pre-crosslinked polypropylene, and granulating after traction cooling to obtain particles.
The technological parameters of melt extrusion by a twin-screw extruder are 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 330-410A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, the materials are premixed for 3min at 750r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 48:1.
The pre-crosslinked random copolymer polypropylene, the processing aid and the surface pretreatment flame retardant composition are mixed uniformly in advance in a high-speed mixer according to a specified mass ratio, and fed at a main feeding port of a double-screw extruder. The kneading block combinations were produced from general grade modified polypropylene, reducing the use of 90 and 45 degree screw elements in the examples, melt blending by twin screw extruder to produce a polypropylene based composition of flame retardant composition, and pelletizing after traction cooling to produce pellets.
Comparative example 3
The halogen-free flame-retardant polypropylene base masterbatch which is not subjected to crosslinking treatment comprises the following components in percentage by mass:
59% of random copolymer polypropylene, 39.5% of flame retardant composition without surface pretreatment, 0.2% of processing aid hindered phenol antioxidant, 0.2% of phosphite antioxidant, 0.1% of dioctadecyl thiodipropionate and 1% of silicone master batch.
The preparation method comprises the following steps:
the technological parameters of melt extrusion by a single screw extruder are as follows: the temperature of the first area is 120-160 ℃, the temperature of the second area to the machine head is 170-190 ℃, the current of the main machine is 310-360A, the rotating speed of the main machine is 250rpm, the vacuum extraction pressure value of the metering section is about-0.5 MPa, the materials are premixed for 2min at 350r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 56:1.
Feeding the random copolymer polypropylene in a main feeding port of a single screw extruder, plugging a natural exhaust port, carrying out melt blending by the single screw extruder to obtain pre-crosslinked polypropylene, carrying out traction cooling, and granulating to obtain particles.
The technological parameters of melt extrusion by a twin-screw extruder are 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 340-420A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, the materials are premixed for 3min at 750r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 48:1.
The random copolymer polypropylene, the processing aid and the surface pretreatment flame retardant composition are mixed uniformly in advance in a high-speed mixer according to a specified mass ratio, and fed in 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 polypropylene-based composition of the 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
The universal halogen-free flame-retardant polypropylene base masterbatch without any treatment comprises the following components in percentage by mass:
59% of random copolymer polypropylene, 39.5% of flame retardant composition without surface pretreatment, 0.2% of processing aid hindered phenol antioxidant, 0.2% of phosphite antioxidant, 0.1% of dioctadecyl thiodipropionate and 1% of silicone master batch.
The preparation method comprises the following steps:
the technological parameters of melt extrusion by a twin-screw extruder are 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 370-450A, the rotating speed of the main machine is 450rpm, the vacuum extraction pressure value of the metering section is about-0.9 MPa, the materials are premixed for 3min at 750r/min in a high-speed mixer, and the length-diameter ratio of the double-screw extruder is 48:1.
The random copolymer polypropylene, the processing aid and the flame retardant composition with untreated surfaces are mixed uniformly in advance in a high-speed mixer according to a specified mass ratio, and fed at a main feeding port of a double-screw extruder. The kneading block combinations were produced from general grade modified polypropylene, reducing the use of 90 and 45 degree screw elements in the examples, melt blending by twin screw extruder to produce a polypropylene based composition of flame retardant composition, and pelletizing after traction cooling to produce pellets.
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;
(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) Melt strength: the test is carried out by using a Rheotens 71.97 type melt strength tester of GOTTFERT company, germany, the diameter of a die is 2mm, the temperature of the die is 230 ℃, the distance between the die and the upper edge of a stretching wheel is 40mm, the distance between the die and the center of the stretching wheel is 58mm, the gap between the stretching wheels is 0.4mm, and the stretching acceleration is 20mm/s 2 。
Table 1 results of performance testing of flame retardant polyolefin materials of examples and comparative examples
As can be seen from the test results of the examples and comparative examples in Table 1, the polyolefin-based compositions of the flame retardant compositions of examples 1 to 3 of the present invention have excellent tensile strength and notched impact strength, and the melt strength is excellent, and it is demonstrated that the flame retardant composition has high flame retarding efficiency from the fracture strain data, notched impact strength, water cut particle surface and plate appearance surface, and is excellent in dispersibility in polyolefin materials.
Example 1 in comparison to comparative example 1, the surface treated flame retardant composition was better in material mechanics, flame retardance and material and board surface than the non-performance treated flame retardant composition polyolefin-based composition.
Example 1 is compared with comparative example 2, which shows that the processing technology is important and has a large effect on dispersing the flame retardant.
In comparison of example 1 and comparative example 3, the melt strength of the polyolefin-based composition of the flame retardant composition was greatly improved upon crosslinking.
Example 1 shows that the surface treatment, processing and crosslinking treatment of the flame retardant composition are a significant improvement over comparative example 4.
The prepared flame retardant composition and the polyolefin-based composition thereof have the advantages in aspects of dispersibility, high melt strength, mechanical properties and the like, and mainly benefit from the application of polyolefin material crosslinking technology, self-made flame retardant composition preparation technology, application of flame retardant composition surface treatment technology and application of polyolefin master batch processing preparation technology of the flame retardant composition.
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 flame-retardant polyolefin composition and a preparation method thereof are characterized by comprising the compounding of a flame retardant composition and the surface treatment of the composition, and the preparation of a polyolefin-based composition thereof.
2. The flame retardant composition of claim 1, wherein the flame retardant composition is comprised of: 35-50% of flame retardant decabromodiphenyl ethane, 6-18% of flame retardant synergist antimonous oxide, 0.4-2% of anti-dripping agent polytetrafluoroethylene, 10-50% of flame retardant synergist magnesium silicate salt and 0.4-1% of fluorocarbon polymer.
3. The surface treatment of the flame retardant composition of claim 1, consisting of:
the component A is a flame retardant composition, and the mass percentage is 91-96%;
the component B is a coupling agent with the mass percentage of 0.5-2%, and is characterized in that the coupling agent is one or a mixture of more of a silane coupling agent, a maleic anhydride graft, a titanate coupling agent and an aluminate coupling agent;
the component C is a hyperdispersant, and the mass percentage of the hyperdispersant is 3-5%, and the composition is characterized in that the hyperdispersant is one or a mixture of a polyester hyperdispersant, a polyether hyperdispersant and a polyolefin hyperdispersant;
the component D is stearate, and the mass percentage is 0.5-2%, and is characterized in that the stearate is one or a mixture of more of magnesium stearate, calcium stearate, potassium stearate and zinc stearate.
4. The flame retardant composition surface treatment method according to claim 1, comprising:
adding the component A in proportion in a high-temperature spray gun, mixing at a low speed of 200-300r/min, setting the temperature of the high-temperature spray gun at 100-120 ℃ during uniform mixing, continuously spraying the component B mixture by the high-temperature spray gun for a certain time, adding the component C and the component D, increasing the rotating speed of the high-temperature spray gun to 600-1400r/min, mixing at a high speed for a certain time, and discharging for later use.
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 the flame retardant polyolefin composition of claim 1, in combination with the formulation:
53-58% of polyolefin resin by mass;
40-45% of the surface treatment flame retardant composition by mass percent;
0.2-2% of cross-linking auxiliary agent by mass percent;
0.02-0.1% of free radical initiator by mass percent;
the processing auxiliary agent accounts for 0.5 to 2 percent.
7. The flame retardant polyolefin composition of claim 6, wherein the crosslinking aid is one of trimethylolpropane trimethacrylate (TMPTMA), divinylbenzene (DVB), triallyl cyanurate (TAIC), polyethylene glycol dimethacrylate (MPL).
8. The flame retardant polyolefin composition according to claim 6, wherein the free radical initiator is one or a mixture of several of dicumyl peroxide (DCP), benzoyl Peroxide (BPO), di-tert-butyl peroxide (DBP) and Azobisisobutyronitrile (AIBN).
9. The flame retardant polyolefin composition according to claim 6, wherein the processing aid is one or a mixture of several of hindered phenolic antioxidants, phosphite antioxidants, dioctadecyl thiodipropionate, white oil, silicone masterbatch, erucamide, polypropylene wax and polyethylene wax.
10. The flame retardant polyolefin composition according to claims 5-8, which is prepared by a process comprising:
(1) Firstly, uniformly mixing polyolefin resin, a crosslinking auxiliary agent and a free radical initiator in a high-speed mixer according to certain mass ratio, adding the mixture into a single screw extruder with the length-diameter ratio of 56:1 for melt mixing extrusion, wherein the processing temperature is 120-190 ℃, a natural exhaust port is plugged, the vacuum extraction pressure value of a metering section is about-0.5 MPa, and granulating and drying are carried out to obtain the high-melt-strength matrix standby material.
(2) And then the high-melt-strength matrix standby material, the surface treatment flame retardant composition and the processing aid are mixed uniformly in advance in a high-speed mixer according to the mass proportion requirement, and are melted, mixed and extruded in a double-screw extruder with the length-diameter ratio of more than 40:1.
(3) 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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