CN117903554A - Halogen-free flame-retardant master batch, preparation method thereof and high-strength halogen-free flame-retardant TPV injection molding material - Google Patents
Halogen-free flame-retardant master batch, preparation method thereof and high-strength halogen-free flame-retardant TPV injection molding material Download PDFInfo
- Publication number
- CN117903554A CN117903554A CN202410077816.8A CN202410077816A CN117903554A CN 117903554 A CN117903554 A CN 117903554A CN 202410077816 A CN202410077816 A CN 202410077816A CN 117903554 A CN117903554 A CN 117903554A
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- CN
- China
- Prior art keywords
- flame retardant
- halogen
- free flame
- injection molding
- retardant
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 198
- 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 171
- 238000001746 injection moulding Methods 0.000 title claims abstract description 94
- 239000012778 molding material Substances 0.000 title claims abstract description 74
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000004743 Polypropylene Substances 0.000 claims abstract description 83
- -1 polypropylene Polymers 0.000 claims abstract description 62
- 229920001155 polypropylene Polymers 0.000 claims abstract description 58
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 claims abstract description 17
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 16
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 16
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 16
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008117 stearic acid Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- 229910002804 graphite Inorganic materials 0.000 claims description 31
- 239000010439 graphite Substances 0.000 claims description 31
- 229920002943 EPDM rubber Polymers 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 17
- 239000003607 modifier Substances 0.000 claims description 17
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 15
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 239000004611 light stabiliser Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 6
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 229920001195 polyisoprene Polymers 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 229920002857 polybutadiene 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 3
- 239000004413 injection moulding compound Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 26
- 230000007547 defect Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 60
- 230000002829 reductive effect Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 22
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- 230000000052 comparative effect Effects 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group 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 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- FCHGUOSEXNGSMK-UHFFFAOYSA-N 1-tert-butylperoxy-2,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1C(C)C FCHGUOSEXNGSMK-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VOQFZENYFWLTBF-UHFFFAOYSA-N 2,4-ditert-butyl-6-(5-chloro-2H-benzotriazol-4-yl)phenol Chemical compound CC(C)(C)c1cc(c(O)c(c1)C(C)(C)C)-c1c(Cl)ccc2[nH]nnc12 VOQFZENYFWLTBF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
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- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical group [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
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- 125000000962 organic group Chemical group 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
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- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
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Abstract
The application relates to the technical field of high polymer materials, and particularly discloses a halogen-free flame-retardant master batch, a preparation method thereof and a high-strength halogen-free flame-retardant TPV injection molding material. A halogen-free flame retardant master batch comprises a modified flame retardant, grafted PP and grafted PE, wherein the modified flame retardant comprises magnesium hydroxide, aluminum hydroxide, nitrogen-phosphorus flame retardant, polypropylene, POE, stearic acid and liquid polyolefin; the preparation method comprises the following steps: mixing magnesium hydroxide, aluminum hydroxide, nitrogen-phosphorus flame retardant, polypropylene, POE, stearic acid and liquid polyolefin, extruding and granulating to obtain a modified flame retardant; and mixing the modified flame retardant with grafted PP and grafted PE, extruding and granulating to obtain the halogen-free flame retardant master batch. The halogen-free flame-retardant master batch is used for preparing the TPV injection molding material, and has the advantages of good compatibility in the TPV injection molding material, uniform dispersion, excellent mechanical property of the TPV injection molding material, good flame-retardant effect and difficult defect generation during injection molding.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a halogen-free flame-retardant master batch, a preparation method thereof and a high-strength halogen-free flame-retardant TPV injection molding material.
Background
TPV material is a thermoplastic elastomer prepared by dispersing EPDM rubber into PP material by adopting a dynamic vulcanization method, has good ageing resistance, dielectric property, mechanical property and stable processing property, has high toughness of rubber and plasticity of plastic, and is widely applied in the industries of automobiles, household appliances, cables and the like, but has low oxygen index and poor flame retardance because a large amount of softening oil is flushed into rubber in the processing process, thus limiting the use of partial fields. The current research on the flame retardant direction of TPVs is mature, especially in the halogen-containing direction, but halogen-containing flame retardants are not friendly to the environment.
The halogen-free flame retardant is various, mainly comprises phosphorus and metal oxide, wherein aluminum hydroxide is a non-toxic and pollution-free flame retardant without secondary pollution, can be matched with various synergistic flame retardants, is added more, is not easy to generate bending and whitening phenomena, has good smoke suppression and flame retarding effects, is low in cost and easy to obtain materials, can be decomposed to generate magnesium oxide, and improves fire resistance.
However, the halogen-free flame retardant has the problem of poor compatibility with the TPV matrix, the lower flame retardant addition amount leads to poor flame retardant effect, the higher flame retardant addition amount leads to poor fluidity of the TPE material, and the special structural characteristics thereof lead to the difficulty of the flame retardant entering a fully crosslinked rubber-plastic system, lead to the difficulty of injection molding of the TPV material and also influence the mechanical property of injection molded products.
In view of the above related art, the inventors have found that a flame retardant having good compatibility with TPV is to be studied, which can improve the flame retardant effect of TPV without affecting the mechanical strength and injection molding effect thereof.
Disclosure of Invention
In order to improve the compatibility of injection molding materials and TPV materials and improve the mechanical strength, injection molding effect and flame retardance of the TPV materials, the application provides a halogen-free flame-retardant master batch, a preparation method thereof and a high-strength halogen-free flame-retardant TPV injection molding material.
In a first aspect, the application provides a halogen-free flame-retardant master batch, which adopts the following technical scheme:
The halogen-free flame retardant master batch comprises 25-30wt% of modified flame retardant, 12-16wt% of grafted PP based on the modified flame retardant, 230-250wt% of magnesium hydroxide based on the polypropylene, 130-150wt% of aluminum hydroxide based on the polypropylene, 90-100deg.C% of nitrogen-phosphorus based flame retardant, 20-25wt% of POE based on the modified flame retardant, 8-10wt% of stearic acid based on the modified flame retardant, and 8-10wt% of liquid polyolefin.
By adopting the technical scheme, the aluminum hydroxide is a non-toxic and pollution-free flame retardant without secondary pollution, can be matched with a plurality of synergistic flame retardants for use, is not easy to generate bending and whitening phenomena after being added, has good smoke suppression and flame retarding effects, is low in price and easy to obtain materials, can be decomposed to generate magnesium oxide, improves fire resistance, can form a relatively stable carbon layer in the reburning process, thereby preventing heat transfer, and simultaneously can prevent contact between oxygen and carbon, and the addition of polypropylene in the flame retardant can lead the magnesium hydroxide, the aluminum hydroxide and nitrogen-phosphorus flame retardants to be in dispersibility in TPV materials, and can lead the soft chain curling structure of octene and crystallized ethylene chains in POE to be used as physical crosslinking points, so that the flame retardant has excellent toughness and good processability and can improve the mechanical strength of the halogen-free flame retardant master batch; the liquid polyolefin can improve the surface wettability of the halogen-free flame retardant, and improve the dispersibility of the halogen-free flame retardant in the TPV material and the compatibility of the halogen-free flame retardant with a rubber matrix; the modified aluminum hydroxide, magnesium hydroxide, nitrogen-phosphorus flame retardant, such as polypropylene, POE, liquid polyolefin and the like, are blended with grafted PP and grafted PE, and when the grafted PP is mixed with a TPV material, the compatibility between ethylene propylene diene monomer and polypropylene can be improved, and the dispersibility of halogen-free flame retardant master batch is improved, so that the TPV injection molding material has high flame retardance, good mechanical property and fluidity, and excellent injection molding property.
Optionally, the nitrogen-phosphorus flame retardant is at least one selected from triazine char former, melamine cyanurate and ammonium polyphosphate.
By adopting the technical scheme, the nitrogen-phosphorus flame retardant can protect the polymer, isolate hot oxygen and reduce smoke density and toxic gas.
Optionally, the nitrogen-phosphorus flame retardant comprises a triazine char former, melamine cyanurate and ammonium polyphosphate in a mass ratio of 1:0.3-0.5:0.3-0.5.
By adopting the technical scheme, the three flame retardants with the dosage ratio can better play a flame-retardant protection effect on the TPV injection molding material.
Optionally, the liquid polyolefin is selected from at least one of liquid polybutadiene, liquid polyisoprene, maleic anhydride modified liquid polybutadiene, hydroxylated liquid polyisoprene.
Optionally, the polypropylene has a melt index of 1.9-26g/10min.
Through adopting above-mentioned technical scheme, the polypropylene melt index that uses is big, and the flow velocity is big, when moulding plastics, is impacted to the outside of injection molding product to prevent that fire-retardant master batch mobility is relatively poor, wrap up in the centre of the sample of moulding plastics by the better part of mobility, be difficult to reach better flame retardant efficiency.
In a second aspect, the application provides a preparation method of halogen-free flame-retardant master batch, which adopts the following technical scheme:
the preparation method of the halogen-free flame-retardant master batch comprises the following steps:
mixing magnesium hydroxide, aluminum hydroxide, nitrogen-phosphorus flame retardant, polypropylene, POE, stearic acid and liquid polyolefin, extruding and granulating at 155-165 ℃ to prepare modified flame retardant;
and mixing the modified flame retardant with grafted PP and grafted PE, and extruding and granulating at 140-180 ℃ to obtain the halogen-free flame retardant master batch.
By adopting the technical scheme, magnesium hydroxide, aluminum hydroxide and the like are mixed with polypropylene, liquid polyolefin, POE and stearic acid, extruded and granulated to prepare the modified flame retardant, grafting adopts grafted PP and grafted PE for further modification treatment, and when the halogen-free flame retardant master batch, ethylene propylene diene monomer, polypropylene and the like are used for preparing TPV injection molding materials, the grafted PP and the grafted PE can effectively improve the compatibility of the flame retardant and each raw material of the TPV, the dispersibility and the fluidity, and further improve the flame retardance, the mechanical strength and the injection molding effect.
In a third aspect, the application provides a high-strength halogen-free flame retardant TPV injection molding material, which adopts the following technical scheme: a high-strength halogen-free flame-retardant TPV injection molding material comprises halogen-free flame-retardant master batch, ethylene propylene diene monomer, polypropylene, plasticizer, flow modifier, antioxidant, inorganic filler, lubricant, cross-linking agent, cross-linking auxiliary agent and light stabilizer, wherein the additive amount of the halogen-free flame-retardant master batch is 40-50wt%, the additive amount of the polypropylene is 15-25wt%, the additive amount of the plasticizer is 30-35wt%, the additive amount of the flow modifier is 2-4wt%, the additive amount of the antioxidant is 0.05-0.15wt%, the additive amount of the inorganic filler is 10-15wt%, the additive amount of the lubricant is 0.3-0.4wt%, the additive amount of the cross-linking agent is 0.05-2wt%, the additive amount of the cross-linking auxiliary agent is 0.03-3wt%, and the additive amount of the light stabilizer is 0.01-0.5wt%.
By adopting the technical scheme, the ethylene propylene diene monomer rubber particles are uniformly dispersed in the polypropylene continuous phase, the dispersibility of the flame retardant in the TPV injection molding material can be improved by grafting the PP, the polypropylene and other raw materials in the halogen-free flame retardant master batch, the mechanical property and the flame retardant effect are further improved, and the flowability of the TPV injection molding material is good in a molten state by adding the flow modifier, so that the optimal tensile strength, elongation at break and melt strength can be achieved, the difficulty and the energy consumption of the TPV injection molding are greatly reduced, the defects in the injection molding process are reduced, and the production efficiency is improved.
Optionally, the flow modifier is at least one selected from polyurethane resin Texin 270, vedamemepoe VM8880, and flow modifier M-80.
Optionally, the crosslinking agent is selected from at least one of diisopropylbenzene peroxide, 1, 4-bis (tert-butylperoxy diisopropyl) benzene, 1, 3-bis (tert-butylperoxy diisopropyl) benzene, 2, 5-dimethyl-2, 5-bis-tert-butylhexane peroxide (bis-di-penta), and phenolic resin.
The auxiliary cross-linking agent is at least one selected from triallyl cyanurate, triallyl isocyanurate, N' -phenyl bismaleimide, ethylene glycol dimethacrylate, trimethylol propyl methacrylate, trimethylol propyl triacrylate and allyl methacrylate.
The light stabilizer is at least one selected from 2-hydroxy-4-methoxybenzophenone, 2' -dihydroxy-4-methoxybenzophenone, 2 (2-hydroxy-3 ',5' -di-tert-butylphenyl) -5-chlorobenzotriazole and bis (2, 6-tetramethylpiperidine) sebacate.
Optionally, the lubricant is at least one selected from calcium stearate Cast (BS 3818), N-N ethylene bis stearamide EBS, pentaerythritol stearate PETS.
Optionally, the plasticizer is selected from at least one of white oil 70N, paraffinic oil 312, and naphthenic oil 4010.
Optionally, the inorganic filler is selected from at least one of talc, calcium carbonate and wollastonite.
Optionally, the high-strength halogen-free flame retardant TPV injection molding material is also added with flame retardant synergist, and the addition amount of the flame retardant synergist is 0.8-1.5wt% based on ethylene propylene diene monomer rubber.
By adopting the technical scheme, when the TPV injection molding material is prepared into products such as cable materials, the service life of the TPV material is reduced due to the existence of the pH value of the external environment, so that the corrosion resistance of the TPV material can be improved by adding a certain amount of preservative.
Optionally, the preparation method of the flame retardant synergist comprises the following steps:
Dispersing expandable graphite in distilled water, performing ultrasonic dispersion for 20-30min, adding zirconium oxychloride, continuing ultrasonic treatment for 20-30min, adding ammonia water until the pH is 9.5, standing for 0.5-1h, performing suction filtration and washing on the precipitate, mixing with deionized water, reacting for 10-11h at 180-190 ℃, performing suction filtration, washing and drying to obtain a premix, wherein the molar ratio of the zirconium oxychloride to the expandable graphite is 1.2-1.6:1;
Mixing the premix with silicon resin, mixing boric acid, heating to 95-100 ℃, reacting for 6-7h, filtering, washing, drying,
Preparing an intermediate, wherein the mass ratio of the premix to the silicone resin to the boric acid is 1:0.5-0.7:0.2-0.5;
Blending, extruding and granulating the intermediate, polypropylene and maleic anhydride grafted polypropylene, wherein the mass ratio of the intermediate to the polypropylene to the maleic anhydride grafted polypropylene is 1:0.3-0.5:0.1-0.2.
According to the technical scheme, the expandable graphite is a graphite sheet manufactured by treating natural graphite in nature with strong acid such as concentrated sulfuric acid and concentrated nitric acid, has a sheet structure, van der Waals force between sheets is overlapped with each other to form a complete and continuous sheet structure, and when the expandable graphite is combusted, interlayer substances become gas, so that the sheets of the graphite are pushed to pull the distance between the sheets, and the expandable graphite rapidly expands into corn-shaped worm structures after combustion to form thicker porous carbon layers and consume a large amount of heat, so that the effect of blocking oxygen and heat transfer is achieved, and when the expandable graphite is subjected to high heat and combustion, water vapor is released to easily cause nonflammable gas to be diluted, flammable gas is reduced, and the degree of combustion is reduced; zirconium oxychloride forms zirconium oxide under the action of ammonia water, the zirconium oxide is a high-temperature-resistant oxide, and has the characteristics of excellent physical and chemical properties, such as good heat resistance, wear resistance, corrosion resistance and the like, and the two-dimensional expandable graphite sheet layer and zero-dimensional zirconium oxide particles form a composite hybrid material, so that the composite hybrid material has the excellent properties of the two materials, also has different new properties of a single component, can more effectively fill injection molding materials, and reduces the permeation channel of corrosive media; the molecular chain of the silicon resin is an inorganic structure of Si-O bond, the side chain is an organic group, the silicon resin has excellent heat resistance, lubricity, compatibility and the like, meanwhile, the toughness and elasticity of a high polymer material are realized, boric acid is a polybasic acid containing 3 hydroxyl groups, the silicon resin has better heat resistance, and is a preservative, the silicon resin and the silicon resin form silicon-boron resin which can play a role together with a premix to inhibit the pyrolysis of the TPV injection molding material, and the silicon-boron resin can stabilize a carbon layer, strengthen the strength of the carbon layer and further strengthen the corrosion resistance of the TPV material; under the action of maleic anhydride grafted polypropylene, the intermediate has good dispersibility in polypropylene, expandable graphite and zirconia can fill micropores in the injection molding material, namely corrosion medium is prevented from penetrating through the micropores, and the intermediate has good interfacial compatibility with polypropylene, ethylene propylene diene monomer and the like, so that the intermediate has good interfacial compatibility with the injection molding material, the flame retardant synergist can be effectively combined in the injection molding material, the capability of the flame retardant synergist for preventing the corrosion medium from penetrating in the injection molding material is enhanced, and the corrosion resistance of the injection molding material is improved.
In a third aspect, the application provides a preparation method of a high-strength halogen-free flame retardant TPV injection molding material, which adopts the following technical scheme:
a preparation method of a high-strength halogen-free flame retardant TPV injection molding material comprises the following steps:
Adding the halogen-free flame-retardant master batch into ethylene propylene diene monomer, uniformly mixing at 140-200 ℃, adding polypropylene, a cross-linking agent, a co-cross-linking agent, a flow modifier, a light stabilizer, an antioxidant, an inorganic filler, an antioxidant, a lubricant and a plasticizer, and dynamically vulcanizing to obtain the high-strength halogen-free flame-retardant TPV injection molding material.
By adopting the technical scheme, the halogen-free flame-retardant master batch and the ethylene propylene diene monomer are mixed, so that the halogen-free flame-retardant master batch is fully dispersed in the ethylene propylene diene monomer, then raw materials such as polypropylene are added, and along with the crosslinking of the ethylene propylene diene monomer and the polypropylene, the flame retardant is coated in a crosslinked rubber-plastic system, so that the flame retardant effect of the TPV injection molding material is good, and the flame retardant does not influence the injection molding effect.
In summary, the application has the following beneficial effects:
1. According to the application, the magnesium hydroxide, the aluminum hydroxide, the nitrogen-phosphorus flame retardant, the polypropylene, the liquid polyolefin and the like are adopted to prepare the flame retardant, the modified flame retardant is blended with the grafted PP and the grafted PE, and the halogen-free flame retardant with a specific proportion is modified through a two-step process, so that the flame retardant is fully mixed in a TPV matrix, V0-level flame retardance is realized, mechanical properties such as tensile strength of the material and the like are improved, defects in an injection molding process are reduced, and production efficiency is improved.
2. According to the application, the halogen-free flame-retardant master batch is preferably mixed with the ethylene propylene diene monomer, and then raw materials such as polypropylene are added, so that the halogen-free flame-retardant master batch is fully dispersed in the ethylene propylene diene monomer, and when the polypropylene is crosslinked with the ethylene propylene diene monomer, the halogen-free flame-retardant master batch can enter a crosslinking system, so that the processability is not influenced, the injection molding pressure and the injection molding difficulty are reduced, the defects in the injection molding process are reduced, the compatibility between interfaces is reduced, and the mechanical property and the flame-retardant effect of the composite material are improved.
3. In the application, the expandable graphite, zirconium oxychloride, silicon resin, boric acid, polypropylene and the like are preferably adopted to prepare the flame retardant synergist, zirconium oxide particles are loaded on the expandable graphite, so that the penetration of corrosive medium is reduced, the heat resistance and flame retardant effect can be further improved, in addition, silicon resin and boric acid can form silicon-boron resin on the expandable graphite loaded with zirconium oxide, so that the corrosion resistance is improved, the heat resistance and flame retardant effect is enhanced, and finally, the polypropylene and maleic anhydride grafted polypropylene are utilized to improve the dispersibility and compatibility of the raw materials such as zirconium oxide, the expandable graphite, the silicon-boron resin, ethylene propylene diene monomer and the like.
Detailed Description
The following examples illustrate the application in further detail.
Preparation examples 1 to 7 of flame retardant synergists
The expandable graphite particle size in the preparation example of the flame retardant synergist is 80 meshes, the expandable graphite particle size is selected from Qingdao rock-sea carbon materials, the density of polypropylene is 0.922g/cm 3, the melt index is 1.9g/10min, the expandable graphite particle size is selected from Tianjin combination 6012, the maleic anhydride grafted polypropylene is selected from DuPont, model 353D in U.S., and the preparation method of the silicone resin is as follows: 12g of deionized water and 24g of absolute ethyl alcohol are mixed, 0.3g of citric acid is added, ultrasonic treatment is carried out until the citric acid is dissolved, 18g of vinyltrimethoxysilane and 6g of dimethyldimethoxysilane are added, and the mixture is stirred at 40 ℃ for reaction for 8 hours and aged for 24 hours.
Preparation example 1: (1) Dispersing 20g of expandable graphite in 50mL of distilled water, performing ultrasonic dispersion for 20min, adding zirconium oxychloride, continuing ultrasonic treatment for 20min, adding ammonia water with the concentration of 0.5mol/L until the pH value is 9.5, standing for 0.5h, removing supernatant to obtain precipitate, performing suction filtration and washing on the precipitate until no chloride ions are detected by using 0.1mol/L of silver nitrate solution, mixing with 75mL of deionized water, placing the mixture into a reaction kettle, heating the reaction kettle to 180 ℃ at the filling degree of 80%, performing heat preservation reaction for 11h at the speed of 4 ℃/min, performing suction filtration, washing and drying to obtain a premix, wherein the mol ratio of zirconium oxychloride to the expandable graphite is 1.6:1;
(2) Mixing 20g of the premix obtained in the step (1) with silicon resin and boric acid, heating to 95 ℃, reacting for 7 hours, carrying out suction filtration, washing, and drying at 80 ℃ for 24 hours to obtain an intermediate, wherein the mass ratio of the premix to the silicon resin to the boric acid is 1:0.5:0.2;
(3) 10g of intermediate is mixed with polypropylene and maleic anhydride grafted polypropylene, extruded and granulated at 160 ℃, and the mass ratio of the intermediate to the polypropylene to the maleic anhydride grafted polypropylene is 1:0.5:0.2.
Preparation example 2: (1) Dispersing 20g of expandable graphite in 50mL of distilled water, performing ultrasonic dispersion for 30min, adding zirconium oxychloride, continuing ultrasonic treatment for 30min, adding ammonia water with the concentration of 0.5mol/L until the pH value is 9.5, standing for 1h, removing supernatant to obtain precipitate, performing suction filtration and washing on the precipitate until no chloride ions are detected by using 0.1mol/L of silver nitrate solution, then mixing with 75mL of deionized water, placing the mixture into a reaction kettle, heating the reaction kettle to 190 ℃ at the speed of 4 ℃/min, performing heat preservation reaction for 10h, performing suction filtration, washing and drying to obtain a premix, wherein the molar ratio of the zirconium oxychloride to the expandable graphite is 1.2:1;
(2) Mixing 20g of the premix obtained in the step (1) with silicon resin and boric acid, heating to 100 ℃, reacting for 6 hours, carrying out suction filtration, washing, and drying at 80 ℃ for 24 hours to obtain an intermediate, wherein the mass ratio of the premix to the silicon resin to the boric acid is 1:0.7:0.5; (3) 10g of intermediate is mixed with polypropylene and maleic anhydride grafted polypropylene, extruded and granulated at 160 ℃, and the mass ratio of the intermediate to the polypropylene to the maleic anhydride grafted polypropylene is 1:0.3:0.1.
Preparation example 3: (1) Mixing 20g of expandable graphite with silicon resin and boric acid, heating to 95 ℃, reacting for 7 hours, carrying out suction filtration, washing, and drying at 80 ℃ for 24 hours to obtain an intermediate, wherein the mass ratio of the premix to the silicon resin to the boric acid is 1:0.5:0.2;
(2) 10g of intermediate is mixed with polypropylene and maleic anhydride grafted polypropylene, extruded and granulated at 160 ℃, and the mass ratio of the intermediate to the polypropylene to the maleic anhydride grafted polypropylene is 1:0.5:0.2.
Preparation example 4: (1) Dispersing 20g of expandable graphite in 50mL of distilled water, performing ultrasonic dispersion for 20min, adding zirconium oxychloride, continuing ultrasonic treatment for 20min, adding ammonia water with the concentration of 0.5mol/L until the pH value is 9.5, standing for 0.5h, removing supernatant to obtain precipitate, performing suction filtration and washing on the precipitate until no chloride ions are detected by using 0.1mol/L of silver nitrate solution, mixing with 75mL of deionized water, placing the mixture into a reaction kettle, heating the reaction kettle to 180 ℃ at the filling degree of 80%, performing heat preservation reaction for 11h at the speed of 4 ℃/min, performing suction filtration, washing and drying to obtain a premix, wherein the mol ratio of zirconium oxychloride to the expandable graphite is 1.6:1;
(2) 10g of the premix is mixed with polypropylene and maleic anhydride grafted polypropylene, extruded and granulated at 160 ℃, and the mass ratio of the intermediate to the polypropylene to the maleic anhydride grafted polypropylene is 1:0.5:0.2.
Preparation example 5: the difference from preparation example 1 is that boric acid was not added in step (2).
Preparation example 6: the difference from preparation example 1 is that step (3) was not performed, and an intermediate was used as a flame retardant synergist.
Preparation example 7: mixing 20g of expandable graphite dispersion with silicon resin, mixing boric acid, heating to 95 ℃, reacting for 7 hours, carrying out suction filtration, washing, and drying at 80 ℃ for 24 hours to obtain an intermediate, wherein the mass ratio of the premix, the silicon resin and the boric acid is 1:0.5:0.2.
Examples
Example 1: the halogen-free flame retardant master batch comprises a modified flame retardant, grafted PP and grafted PE, wherein the dosages of the three raw materials are shown in table 1, the grafted PP is maleic anhydride grafted PP, the density is 0.953g/cm 3, the melt index is 10g/10min, the density of the grafted PE is 0.92g/cm 3, the melt index is 1.6g/10min, the grafted PE is selected from DuPont 353D, the chemical grade of Japanese three-well is NF408, the raw materials and the dosages of the modified flame retardant are shown in table 1, the density of polypropylene is 0.922g/cm 3, the melt index is 1.9g/10min, the grafted PP is selected from Tianjin joint 6012, the magnesium hydroxide is selected from Yabao, the model is H5IV, the aluminum hydroxide is selected from Shandong-Tepitai, the model is HT-205, the triazine char former is IFR-TCA, the density of POE is 0.868g/cm 3, the melt index is 0.5g/10min, the modified flame retardant is selected from DuPoison's 8150, the stearic acid is Indonesia 8, the liquid is LIS is liquid poly 1838, the LIS is a liquid Litschet elastomer is selected from Lim 30, and the model of Vision Mary, and the Vision's elastic grade is 30.
The preparation method of the halogen-free flame-retardant master batch comprises the following steps:
mixing magnesium hydroxide, aluminum hydroxide, nitrogen-phosphorus flame retardant, polypropylene, POE, stearic acid and liquid polyolefin for 15min, extruding and granulating at 160 ℃ to prepare modified flame retardant;
And mixing the modified flame retardant with grafted PP and grafted PE, and extruding and granulating at 160 ℃ to obtain the halogen-free flame retardant master batch.
TABLE 1
Examples 2-3: the difference between the halogen-free flame retardant master batch and the example 1 is that the raw materials are shown in Table 1.
Comparative example
Comparative example 1: the difference between the halogen-free flame retardant master batch and the example 1 is that the raw materials of the modified flame retardant are shown in the table 1.
Comparative example 2: the halogen-free flame retardant master batch differs from example 1 in that no liquid polyolefin is added to the modified flame retardant.
Comparative example 3: the halogen-free flame retardant master batch is different from example 1 in that no polypropylene is added to the modified flame retardant.
Comparative example 4: the halogen-free flame-retardant master batch is different from the example 1 in that the halogen-free flame-retardant master batch is prepared by adopting the following raw materials and methods: adding the following raw materials into an extruder, extruding and granulating at 160 ℃ to obtain halogen-free flame-retardant master batch, wherein the raw materials are used in the following amounts: 50kg of magnesium hydroxide, 30kg of aluminum hydroxide, 10kg of triazine char-forming agent, 5kg of melamine cyanurate, 5kg of ammonium polyphosphate, 20kg of polypropylene of model 6012, 5kg of POE of model 8150, 2kg of stearic acid, 2kg of liquid polyisoprene, 40kg of grafted PP of model 353D and 20kg of grafted PE of model DGDB-3485.
Comparative example 5: the halogen-free flame retardant master batch differs from example 1 in that an equivalent amount of silane coupling agent KH550 is used in the modified flame retardant instead of the liquid polyolefin.
Application example
Application example 1: the high-strength halogen-free flame-retardant TPV injection molding material comprises the following raw materials in parts by weight: 30kg of the halogen-free flame retardant master batch prepared in the example 1, 60kg of ethylene propylene diene rubber, 10kg of polypropylene, 20kg of plasticizer, 2kg of flow modifier, 0.05kg of antioxidant, 0.05kg of light stabilizer, 8kg of inorganic filler, 0.2kg of lubricant, 1.2kg of cross-linking agent and 1.8kg of cross-linking auxiliary agent, wherein ethylene content of ethylene propylene diene monomer is 65.9% and is selected from medium petrochemical three-well chemical, model is 3092M, density of polypropylene is 0.922g/cm 3, melt index is 1.9g/10min, plasticizer is white oil 70N, flow modifier is polyurethane resin Texin270, antioxidant is antioxidant 1010 and antioxidant 168 in mass ratio of 1:1, light stabilizer is Basoff 2020, inorganic filler is talcum powder, lubricant comprises calcium stearate and erucamide in mass ratio of 1:1, cross-linking agent is DCP, and auxiliary cross-linking agent is triisopropyl isocyanate.
The preparation method of the high-strength halogen-free flame retardant TPV injection molding material comprises the following steps:
Adding halogen-free flame retardant master batch into ethylene propylene diene monomer rubber, uniformly mixing at 140-200 ℃, adding polypropylene, a cross-linking agent, a co-cross-linking agent, a flow modifier, a light stabilizer, an antioxidant, an inorganic filler, an antioxidant, a lubricant and a plasticizer, and dynamically vulcanizing to obtain the high-strength halogen-free flame retardant TPV injection molding material, wherein the temperature of each region is 160 ℃ in one region, 170 ℃ in two regions, 180 ℃ in three regions, 180 ℃ in four regions, 190 ℃ in five regions, 190 ℃ in six regions, 190 ℃ in seven regions, 190 ℃ in eight regions, 190 ℃ in nine regions, 190 ℃ in ten regions, 190 ℃ in eleven regions, 190 ℃ in twelve regions, 190 ℃ in thirteen regions, and 190 ℃ in the machine head.
Application example 2: the high-strength halogen-free flame-retardant TPV injection molding material is different from application example 1 in that the halogen-free flame-retardant master batch is prepared from example 2.
Application example 3: the high-strength halogen-free flame-retardant TPV injection molding material is different from application example 1 in that a halogen-free flame-retardant master batch is prepared in example 3.
Application example 4: the high-strength halogen-free flame-retardant TPV injection molding material is different from the application example 1 in that the halogen-free flame-retardant master batch is prepared from the comparative example 1.
Application example 5: the high-strength halogen-free flame-retardant TPV injection molding material is different from the application example 1 in that the halogen-free flame-retardant master batch is prepared from comparative example 2.
Application example 6: the high-strength halogen-free flame-retardant TPV injection molding material is different from the application example 1 in that the halogen-free flame-retardant master batch is prepared from comparative example 3.
Application example 7: a high-strength halogen-free flame-retardant TPV injection molding material is different from application example 1 in that a halogen-free flame-retardant master batch is prepared from comparative example 4.
Application example 8: a high-strength halogen-free flame-retardant TPV injection molding material is different from application example 1 in that a halogen-free flame-retardant master batch is prepared from comparative example 5.
Application example 9: the high-strength halogen-free flame-retardant TPV injection molding material is different from application example 1 in that grafted PP and grafted PE in the halogen-free flame-retardant master batch are not blended with a modified flame retardant for granulation, but the grafted PP, the grafted PE and the modified flame retardant are blended with ethylene propylene diene rubber, polypropylene, a crosslinking agent, a crosslinking assistant agent, a flow modifier, a light stabilizer, an antioxidant, an inorganic filler, an antioxidant, a lubricant and a plasticizer for dynamic vulcanization.
Application example 10: a high-strength halogen-free flame retardant TPV injection molding material is different from application example 1 in that no flow modifier is added.
Application example 11: a high-strength halogen-free flame retardant TPV injection molding material is different from application example 1 in that the flow modifier is M-80.
Application example 12: the high-strength halogen-free flame retardant TPV injection molding material is different from the application example 1 in that the injection molding material is prepared by the following method:
43kg of ethylene propylene diene rubber with the model number of 3092M, 9.8kg of polypropylene, 14kg of white oil 70N, 5.6kg of talcum powder, 0.035kg of antioxidant 1010/0.035kg of light stabilizer 2020, 0.07kg of erucamide and 1.4kg of polyurethane resin Texin 270 are mixed for 5min at 160 ℃ to prepare TPV particles;
72.94kgTPV particles are mixed with 7.63kg of magnesium hydroxide H5V, 4.578kg of aluminum hydroxide HT-205, 1.526kg of triazine char-forming agent, 0.763kg of melamine cyanurate, 0.763kg of ammonium polyphosphate, 0.763kg of POE with model 8150, 5.6kg of grafted PP with model 353D and 2.8kg of grafted PE with model DGDB-3485, extruded and granulated to obtain the halogen-free flame-retardant TPV, wherein the temperature of each region is one region 160 ℃, two regions 170 ℃, three regions 180 ℃, four regions 180 ℃, five regions 190 ℃, six regions 190 ℃, seven regions 190 ℃, eight regions 190 ℃, nine regions 190 ℃, ten regions 190 ℃, eleven regions 190 ℃, twelve regions 190 ℃, thirteen regions 190 ℃, and the temperature of a machine head 190 ℃.
Application example 13: the high-strength halogen-free flame-retardant TPV injection molding material is different from application example 1 in that a flame-retardant synergist accounting for 1.5 weight percent of the ethylene propylene diene monomer is also added, and the flame-retardant synergist is prepared by preparation example 1.
Application example 14: the high-strength halogen-free flame-retardant TPV injection molding material is different from application example 1 in that a flame-retardant synergist accounting for 0.8 weight percent of the ethylene propylene diene monomer is also added, and the flame-retardant synergist is prepared by preparation example 2.
Application example 15: a high-strength halogen-free flame-retardant TPV injection molding material is different from application example 13 in that a flame-retardant synergist is prepared from preparation example 3.
Application example 16: a high-strength halogen-free flame-retardant TPV injection molding material is different from application example 13 in that a flame-retardant synergist is prepared from preparation example 4.
Application example 17: a high-strength halogen-free flame retardant TPV injection molding material is different from application example 13 in that a flame retardant synergist is prepared from preparation example 5.
Application example 18: a high-strength halogen-free flame retardant TPV injection molding material is different from application example 13 in that a flame retardant synergist is prepared from preparation example 6.
Application example 19: a high-strength halogen-free flame-retardant TPV injection molding material is different from application example 13 in that a flame-retardant synergist is prepared from preparation example 7.
Application example 20: the high-strength halogen-free flame-retardant TPV injection molding material is different from application example 13 in that the flame-retardant synergist is expandable graphite.
Performance test
TPV molding compounds were prepared according to the method in the application example, and performance tests were performed with reference to the following method, and the test results are recorded in Table 2.
1. Hardness: the test was conducted according to ASTM D2240, standard test method for hardness of Durometer.
2. Vertical tensile strength: the test was carried out according to GB/T528-2009 "determination of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber".
3. Elongation at break in vertical direction: the test was carried out according to GB/T528-2009 "determination of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber".
4. Oxygen index: the detection is carried out according to GB/T2406-2008 oxygen index method of plastic combustion performance test method.
5. Flame retardant rating: the detection is carried out according to GB/T2408-1996 horizontal method and vertical method of test method of Plastic Combustion Performance.
6. Melt mass flow rate: the measurements were carried out according to GB/T3682.1-2000 determination of the melt mass flow rate and the melt volume flow rate of thermoplastics.
7. Injection molding surface: the sample is injection molded into a square plate with the thickness of 60mm multiplied by 1 mm;
8. corrosion resistance: the test piece was immersed in 10% hydrochloric acid and 10% sodium hydroxide solution for 30 days, and then the change rate of the tensile strength before and after the immersion was measured.
TABLE 2
The halogen-free flame-retardant master batches prepared in the application examples 1 and 2 are respectively different in raw material dosage, and are vulcanized with materials such as ethylene propylene diene monomer, polypropylene and the like to form the injection molding material, and the flame retardant can be fully mixed in a matrix, so that the mechanical property and flame retardant effect of the injection molding material are good, and the injection molding material has proper fluidity, so that the injection molding surface is free of defects.
In application example 3, only one nitrogen-phosphorus flame retardant, which is a triazine char-forming agent, was used, and the flame retardant effect was reduced as compared with application example 1.
The halogen-free flame retardant master batch prepared in application example 4 and comparative example 1 was used, the amounts of the raw materials in the modified flame retardant were different, and the tensile strength and the elongation at break of the injection molding material prepared in application example 4 were reduced, and the flame retardant grade was lowered as shown in Table 2.
The halogen-free flame retardant master batches prepared in the application examples 5 and 6 respectively adopt the comparative examples 2 and 3, the phase transition is carried out between the comparative examples 2 and 3 and the example 1, the liquid polyolefin and the polypropylene are not added in the modified flame retardant respectively, the tensile strength and the elongation at break of the injection molding materials prepared in the application examples 5 and 6 are reduced, the corrosion resistance is weakened, and the flame retardant effect is reduced.
In comparative example 7, the halogen-free flame retardant master batch prepared in comparative example 4 was used, and the grafted PP and the grafted PE were blended and extruded with the raw materials of the modified flame retardants such as magnesium hydroxide, aluminum hydroxide, etc., compared with application example 1, the tensile strength and elongation at break of the injection molding material in application example 7 were significantly reduced, and the flame retardant effect was poor, the melt flow rate was slow, and the injection molding effect was poor.
The halogen-free flame retardant master batch prepared in application example 8 adopts the silane coupling agent to replace liquid polyolefin, and compared with application example 1, the mechanical property and flame retardant effect of the injection molding material are reduced, and the corrosion resistance effect is reduced.
The modified flame retardant in the halogen-free flame retardant master batch in application example 9 is prepared by blending and vulcanizing the modified flame retardant, the grafted PP, the grafted PE, the ethylene propylene diene monomer, the polypropylene and other raw materials without using grafted PP and grafted PE for blending and granulating, and compared with application example 1, the injection molding material in application example 9 has the advantages that the flame retardant grade is good, but the tensile strength and the breaking elongation are obviously reduced, the melt mass flow rate is reduced, and the breaking occurs on the injection molding surface.
In application example 10, no flow modifier was added, and in application example 11, the flow modifier was M-80, as compared with application example 1, and the mechanical properties of the injection molding materials prepared in application example 10 and application example 11 were lowered, the flame retardant effect was weakened, and the quality of the injection molding surface was deteriorated.
The TPV material is prepared by adopting a conventional method in application example 12, and then the flame retardant containing magnesium hydroxide and aluminum hydroxide, grafted PP, grafted PE and the like are blended and vulcanized, so that compared with application example 1, the injection molding material prepared in application example 12 has high hardness, low tensile strength and elongation at break, low melt mass flow rate, rough surface after injection molding and short-mouth and material breakage phenomena.
In application examples 13 and 14, compared with application example 1, a certain amount of flame retardant synergist was added, and it is shown in table 2 that the oxygen index of the injection molding materials prepared in application examples 13 and 14 was increased, the flame retardant effect was improved, and the tensile strength change rate was reduced and the corrosion resistance was increased after soaking in hydrochloric acid.
Application example 15 using the flame retardant synergist of preparation example 3, the tensile strength change rate of the injection molding material prepared in application example 15 was smaller than that of application example 12, indicating that the corrosion resistance was reduced, compared with preparation example 1, without supporting zirconia between the layers of expandable graphite.
In application example 16, the flame retardant synergist prepared in preparation example 4 was used, and compared with preparation example 1, the flame retardant synergist prepared in application example 17 was prepared in preparation example 5, boric acid was not added in application example 5, and the oxygen index of the injection molding materials prepared in application example 16 and application example 17 was reduced as compared with application example 13, and the tensile strength change rate was increased and the corrosion resistance was deteriorated.
The flame retardant synergist in application example 18 was prepared from preparation example 6, and polypropylene and maleic anhydride grafted polypropylene are not added in application example 6, and compared with application example 13, the tensile strength and elongation at break of the injection molding material prepared in application example 18 are reduced, which indicates that polypropylene and maleic anhydride grafted polypropylene can improve the compatibility of the flame retardant synergist with each component in the injection molding material, and prevent the mechanical strength of the injection molding material from being affected by the addition of the preservative.
The preservative of application example 19 was prepared in preparation example 7, and expandable graphite was treated with boric acid and silicone resin to prepare a flame retardant synergist, and the oxygen index of the injection molding material prepared in application example 19 was lowered and the anticorrosive effect was reduced as compared with application example 13.
The flame retardant synergist in application example 20 is expandable graphite, and the anticorrosive effect and the flame retardant effect of the injection molding material prepared in application example 20 are inferior to those of application example 13.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The halogen-free flame retardant master batch is characterized by comprising 25-30wt% of modified flame retardant, 12-16wt% of grafted PE (polypropylene), 230-250wt% of magnesium hydroxide, 130-150wt% of aluminum hydroxide, 90-100deg.wt% of nitrogen-phosphorus flame retardant, 20-25wt% of POE, 8-10wt% of stearic acid and 8-10wt% of liquid polyolefin.
2. The halogen-free flame retardant masterbatch of claim 1, wherein: the nitrogen-phosphorus flame retardant is at least one selected from triazine char-forming agent, melamine cyanurate and ammonium polyphosphate.
3. The halogen-free flame retardant masterbatch of claim 2, wherein: the nitrogen-phosphorus flame retardant comprises a triazine charring agent, melamine cyanurate and ammonium polyphosphate in a mass ratio of 1:0.3-0.5:0.3-0.5.
4. The halogen-free flame retardant masterbatch of claim 1, wherein: the liquid polyolefin is at least one selected from liquid polybutadiene, liquid polyisoprene, maleic anhydride modified liquid polybutadiene and hydroxylated liquid polyisoprene.
5. The halogen-free flame retardant masterbatch of claim 1, wherein: the melt index of the polypropylene is 1.9-26g/10min.
6. The method for preparing the halogen-free flame retardant master batch according to any one of claims 1 to 5, which is characterized in that: the method comprises the following steps:
mixing magnesium hydroxide, aluminum hydroxide, nitrogen-phosphorus flame retardant, polypropylene, POE, stearic acid and liquid polyolefin, extruding and granulating at 155-165 ℃ to prepare modified flame retardant;
and mixing the modified flame retardant with grafted PP and grafted PE, and extruding and granulating at 140-180 ℃ to obtain the halogen-free flame retardant master batch.
7. The high-strength halogen-free flame-retardant TPV injection molding material is characterized by comprising the halogen-free flame-retardant master batch, ethylene propylene diene monomer, polypropylene, a plasticizer, a flow modifier, an antioxidant, an inorganic filler, a lubricant, a crosslinking agent, a crosslinking aid and a light stabilizer according to any one of claims 1-5, wherein the additive amount of the halogen-free flame-retardant master batch is 40-50wt%, the additive amount of the polypropylene is 15-25wt%, the additive amount of the plasticizer is 30-35wt%, the additive amount of the flow modifier is 2-4wt%, the additive amount of the antioxidant is 0.05-0.15wt%, the additive amount of the inorganic filler is 10-15wt%, the additive amount of the lubricant is 0.3-0.4wt%, the additive amount of the crosslinking agent is 0.05-2wt%, the additive amount of the crosslinking aid is 0.03-3wt% and the additive amount of the light stabilizer is 0.01-0.5wt% based on the ethylene propylene diene monomer.
8. The high-strength halogen-free flame retardant TPV injection molding compound of claim 7, wherein: the high-strength halogen-free flame retardant TPV injection molding material is also added with flame retardant synergist, and the addition amount of the flame retardant synergist is 0.8-1.5wt% based on ethylene propylene diene monomer rubber.
9. The high-strength halogen-free flame retardant TPV injection molding compound of claim 7, wherein: the preparation method of the flame retardant synergist comprises the following steps:
Dispersing expandable graphite in distilled water, performing ultrasonic dispersion for 20-30min, adding zirconium oxychloride, continuing ultrasonic treatment for 20-30min, adding ammonia water until the pH is 9.5, standing for 0.5-1h, performing suction filtration and washing on the precipitate, mixing with deionized water, reacting for 10-11h at 180-190 ℃, performing suction filtration, washing and drying to obtain a premix, wherein the molar ratio of the zirconium oxychloride to the expandable graphite is 1.2-1.6:1;
Mixing the premix with silicon resin and boric acid, heating to 95-100 ℃, reacting for 6-7 hours, and performing suction filtration, washing and drying to obtain an intermediate, wherein the mass ratio of the premix to the silicon resin to the boric acid is 1:0.5-0.7:0.2-0.5;
Blending, extruding and granulating the intermediate, polypropylene and maleic anhydride grafted polypropylene, wherein the mass ratio of the intermediate to the polypropylene to the maleic anhydride grafted polypropylene is 1:0.3-0.5:0.1-0.2.
10. The method for preparing the high-strength halogen-free flame retardant TPV injection molding material according to any one of claims 7-9, which is characterized in that: the method comprises the following steps:
Adding the halogen-free flame-retardant master batch into ethylene propylene diene monomer, uniformly mixing at 140-200 ℃, adding polypropylene, a cross-linking agent, a co-cross-linking agent, a flow modifier, a light stabilizer, an antioxidant, an inorganic filler, an antioxidant, a lubricant and a plasticizer, and dynamically vulcanizing to obtain the high-strength halogen-free flame-retardant TPV injection molding material.
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| CN119505163A (en) * | 2025-01-21 | 2025-02-25 | 上海丕优材料科技有限公司 | Flame retardant polyurethane foam material and preparation method thereof |
| CN120865645A (en) * | 2025-09-25 | 2025-10-31 | 江阴市得宝新材料科技有限公司 | Halogen-free flame-retardant high-load polypropylene master batch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN119505163A (en) * | 2025-01-21 | 2025-02-25 | 上海丕优材料科技有限公司 | Flame retardant polyurethane foam material and preparation method thereof |
| CN120865645A (en) * | 2025-09-25 | 2025-10-31 | 江阴市得宝新材料科技有限公司 | Halogen-free flame-retardant high-load polypropylene master batch |
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