CN114058122A - Flame-retardant polypropylene resin - Google Patents
Flame-retardant polypropylene resin Download PDFInfo
- Publication number
- CN114058122A CN114058122A CN202111523899.1A CN202111523899A CN114058122A CN 114058122 A CN114058122 A CN 114058122A CN 202111523899 A CN202111523899 A CN 202111523899A CN 114058122 A CN114058122 A CN 114058122A
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- CN
- China
- Prior art keywords
- flame
- retardant
- polypropylene resin
- flame retardant
- phosphorus
- Prior art date
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- 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 241
- 239000003063 flame retardant Substances 0.000 title claims abstract description 224
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 144
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 144
- -1 polypropylene Polymers 0.000 title claims abstract description 139
- 229920005989 resin Polymers 0.000 title claims abstract description 101
- 239000011347 resin Substances 0.000 title claims abstract description 101
- 239000003999 initiator Substances 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 47
- 239000011574 phosphorus Substances 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 24
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004595 color masterbatch Substances 0.000 claims abstract description 19
- 238000009835 boiling Methods 0.000 claims abstract description 18
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 15
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical class CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 6
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 claims description 6
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 claims description 5
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 claims description 5
- PVKCVCDTYNNNOG-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrobromide Chemical compound [Br-].NC1=NC(N)=[NH+]C(N)=N1 PVKCVCDTYNNNOG-UHFFFAOYSA-N 0.000 claims description 4
- LXIZRZRTWSDLKK-UHFFFAOYSA-N 1,3-dibromo-5-[2-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]propan-2-yl]-2-(2,3-dibromopropoxy)benzene Chemical compound C=1C(Br)=C(OCC(Br)CBr)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 LXIZRZRTWSDLKK-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- YVVYMSXDQGDASK-UHFFFAOYSA-N 1,2,3-tribromo-4-[2-(2,3,4-tribromophenoxy)ethoxy]benzene Chemical compound BrC1=C(Br)C(Br)=CC=C1OCCOC1=CC=C(Br)C(Br)=C1Br YVVYMSXDQGDASK-UHFFFAOYSA-N 0.000 claims description 3
- XUMFBUWGVLTWTH-UHFFFAOYSA-N 1,2-dibromo-3-(2,3-dibromo-2-methylpropoxy)-2-methylpropane Chemical compound BrCC(Br)(C)COCC(C)(Br)CBr XUMFBUWGVLTWTH-UHFFFAOYSA-N 0.000 claims description 3
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 claims description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- QBFHSEQNGHSFLZ-UHFFFAOYSA-N 2,4,6-tris(2,3,4-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=C(Br)C(Br)=CC=C1OC1=NC(OC=2C(=C(Br)C(Br)=CC=2)Br)=NC(OC=2C(=C(Br)C(Br)=CC=2)Br)=N1 QBFHSEQNGHSFLZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 238000002485 combustion reaction Methods 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000007246 mechanism Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 6
- 229940064002 calcium hypophosphite Drugs 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical group C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 3
- 229920005606 polypropylene copolymer Polymers 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- HLQNQYKRKYSHOH-UHFFFAOYSA-N [Br].[N].[P] Chemical compound [Br].[N].[P] HLQNQYKRKYSHOH-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HOHPOKYCMNKQJS-UHFFFAOYSA-N [P].[Br] Chemical compound [P].[Br] HOHPOKYCMNKQJS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a flame-retardant polypropylene resin which comprises, by weight, 100 parts of polypropylene, 1-5 parts of a phosphorus-bromine-initiator ternary system flame retardant, 0-5 parts of a processing aid and 0-5 parts of a color master batch; the phosphorus-bromine-initiator ternary system flame retardant is prepared by compounding a bromine flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the bromine flame retardant A to the phosphorus flame retardant B to the initiator C is 1: 0.5-20: 0.1-5; the chemical structure of the phosphorus flame retardant B is
In the formula, X is O or S, R1Is hydrogen, alkyl or alkoxy, R2Is a metal ion or an alkyl group, R3Is a metal ion or an alkyl group, and R2And R3Not simultaneously being alkyl. The flame-retardant polypropylene resin has a high limit oxygen index vertical combustion grade, has a gas-phase flame-retardant mechanism, a condensed-phase flame-retardant mechanism and a catalytic char formation effect, and has good boiling resistance and precipitation resistance.
Description
Technical Field
The invention belongs to the technical field of polypropylene resin, and relates to flame-retardant polypropylene resin.
Background
The polypropylene (PP) fiber has the advantages of light weight, electric insulation, wear resistance, corrosion resistance, high strength, good heat retention and the like, and is widely applied to the fields of decoration, garment materials, medical treatment and health, industry and the like. However, polypropylene has a relatively low ignition point and a relatively low ignition point, belongs to a flammable material, and has a limited oxygen index of only 17.4%. The wide application of polypropylene products makes the flame retardant property of polypropylene increasingly receive attention, and the development of flame retardant polypropylene resin which is easy for industrial production and has good mechanical property becomes a trend of industry development.
The catalytic carbonization of inorganic metal ions has been proved to have good flame-retardant auxiliary effect, which can promote the formation of a compact carbon protective layer on the surface of a polymer substrate and isolate the mass transfer between the polymer and oxygen and heatCan react to further achieve the purpose of self-extinguishing of the material. However, polypropylene materials are composed of only hydrocarbon nitrogen and have the chemical formula (C)3H6)nThe polypropylene is a high polymer material which is extremely difficult to form carbon, so that flame retardant modification of polypropylene is usually only focused on gas phase flame retardant action, and the catalytic action of forming carbon through a substrate is rarely involved. This phenomenon is limited by the nature of the material itself, and it is difficult to find a good flame retardant system suitable for polyolefin materials with both gas phase flame retardant effect and catalytic char formation effect.
Therefore, the development of a flame-retardant polypropylene resin which has the advantages of small addition amount of a flame retardant, good flame-retardant performance and high efficiency, and has the functions of gas-phase flame-retardant, condensed-phase flame-retardant and catalytic char formation is a technical problem which is urgently needed to be solved at present.
Disclosure of Invention
The present invention has been made to solve the above problems occurring in the prior art, and an object of the present invention is to provide a flame retardant polypropylene resin.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the flame-retardant polypropylene resin comprises, by weight, 100 parts of polypropylene, 1-5 parts of a phosphorus-bromine-initiator ternary system flame retardant, 0-5 parts of a processing aid and 0-5 parts of a color master batch; the phosphorus-bromine-initiator ternary system flame retardant is added by at least 1 part for achieving the using effect, and is added by at most 5 parts for lower bromine content;
the phosphorus-bromine-initiator ternary system flame retardant is prepared by compounding a bromine flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the bromine flame retardant A to the phosphorus flame retardant B to the initiator C is 1: 0.5-20: 0.1-5; the flame retardant is a bromine-phosphorus-initiator ternary system, the mass ratio of the three systems has the best synergistic effect within the range, if the bromine is too little or too much, the gas-phase flame retardant effect of the flame retardant is influenced, similarly, the phosphorus flame retardant mainly plays a role in condensed phase flame retardant, if the bromine is too little, the phosphorus flame retardant has more burning molten drops and poor flame retardant effect, if the bromine is too much, the phosphorus flame retardant and the bromine flame retardant are in antagonism, the initiator generates free radicals to play a role in synergistic flame retardant, if the phosphorus flame retardant is too little, the phosphorus flame retardant does not play a role, and if the phosphorus flame retardant is too much, the free radicals initiate the degradation of a matrix to accelerate and weaken the function of the flame retardant;
the chemical structure of the phosphorus flame retardant B is shown as a formula (I);
in the formula, X is O (oxygen) or S (sulfur), R1Is hydrogen, alkyl or alkoxy, R2Is a metal ion or an alkyl group, R3Is a metal ion or an alkyl group, and R2And R3Not both being alkyl, i.e. R2、R3May be the same or different metals, respectively, or one may be a metal and the other may be an alkyl group.
As a preferred technical scheme:
the flame-retardant polypropylene resin has the limit oxygen index of more than or equal to 29 percent, the burning molten droppings are brittle carbon slag, the vertical burning grade is V-0 grade, the flame-retardant polypropylene resin is steamed and boiled in boiling water for 72 hours, the surface of a product does not separate out (the test method refers to UL746C evaluation immersion test for plastics used in electric appliances), and the limit oxygen index does not decrease after continuous baking at 120 ℃ for 168 hours (the test method refers to the test method of flame retardant precipitation performance in thermoplastic plastic products of China Union of Petroleum and chemical industries). The flame-retardant polypropylene resin prepared by adopting the phosphorus-nitrogen-bromine flame-retardant system in the prior art has white spots on the inner surface after being cooked for 24 hours by boiling water, and the flame-retardant performance basically disappears after continuously working for 72 hours at 120 ℃.
The flame-retardant polypropylene resin is prepared from polypropylene, polypropylene copolymer or a mixture of polypropylene homopolymer and polypropylene copolymer, wherein the melt index of the polypropylene homopolymer or the polypropylene copolymer is 2-80 g/10 min. The melt index was measured at a test temperature of 230 ℃ under a weight (including a plunger) of 2.16Kg, and the melt index of the polypropylene matrix resin for spinning was also adjusted by adding a molecular weight modifier (e.g., t-butyl peroxide, di-t-butyl peroxide, dicumyl peroxide, paraquat, and poly paraquat).
The flame-retardant polypropylene resin comprises one or more of decabromodiphenylethane, tris (2, 3-dibromopropyl) isocyanurate, 2,4, 6-tris (tribromophenoxy) -1, 3, 5-triazine, 1, 2-bis (tribromophenoxy) ethane, tetrabromobisphenol A-bis (2, 3-dibromopropyl) ether, tetrabromobisphenol S-bis (2, 3-dibromopropyl) ether, tetrabromobisphenol A-bis (2, 3-dibromo-2-methylpropyl) ether, tetrabromobisphenol A epoxy resin with a relative molecular mass of 5000-100000, melamine hydrobromide, tris (tribromoneopentyl) phosphate and N, N' -ethylenebistetrabromophthalimide.
The initiator C is more than one of a compound with a structure shown in a formula (II) and a compound with a structure shown in a formula (III);
in the formula, R4、R5Are the same or different alkyl groups.
In the flame-retardant polypropylene resin, the compound with the structure shown in the formula (II) is generated by coupling reaction of mixed diisopropylbenzene, wherein the mass ratio of o-diisopropylbenzene, m-diisopropylbenzene and p-diisopropylbenzene in the mixed diisopropylbenzene is 0-1: 0.1-30: 0.1-50 (the reaction can be carried out under the proportion to obtain a product with a required structure).
The flame-retardant polypropylene resin is prepared by melt blending polypropylene, a phosphorus-bromine-initiator ternary system flame retardant, a processing aid and color master batches.
The melt blending temperature of the flame-retardant polypropylene resin is 180-230 ℃.
The mechanism of the invention is as follows:
in the phosphorus-nitrogen-bromine flame-retardant system consisting of melamine hydrobromide, inorganic aluminum hypophosphite and paraquat in the prior art, bromine and low-valence phosphorus (positive valence) are subjected to oxidation reduction under the action of an initiator to generate bromine free radical for flame retardance, so that the flame-retardant effect is achieved in a gas-phase environment. The flame-retardant mechanism can quickly take away heat when the polymer is burnt, so that the aim of extinguishing combustion is fulfilled. However, the combustion products in this case are molten unburnt polypropylene droplets, which can lead to flame spread. Therefore, the vertical burning grade of the polypropylene material of the existing phosphorus-bromine flame retardant system can only be V-2 grade under the condition of 1-5 wt% of addition amount.
The phosphorus-bromine-initiator system adopted by the invention selects a phosphorus-containing flame retardant which is different from the existing system and contains metal ions, namely a phosphorus-containing compound with a structure shown as a formula (I), and on one hand, compared with a monovalent phosphorus flame retardant, phosphorus in the molecular structure of the compound has more electron binding sites and higher reaction activity (the outermost layer of monovalent phosphorus is arranged into a semi-stable structure with four electrons occupying one electron sublayer). Under the action of an initiator, phosphorus element reacts with free radicals generated by the initiator, so that not only are new phosphorus-containing free radicals generated, but also more active electrons are released, the active electrons attack weak binding sites of a bromine compound (brominated flame retardant A) and generate chemical bond breakage, bromine in the bromine compound is promoted to be converted into bromine free radicals, and free radicals with flame retardance at low energy with higher concentration than that of the traditional phosphorus flame retardant are generated, so that a good gas-phase flame retardant effect is achieved, and the flame retardant efficiency is high; on the other hand, when the metal elements on the phosphorus flame retardant are combusted, the phosphorus flame retardant can catalyze the polymer matrix to generate a large amount of carbon slag, the carbon slag is gathered on the surface of the matrix and wraps the periphery of the polypropylene melt and drops along with the combustion of the polypropylene, and the carbon slag is dense and thick, so that the thermal oxygen degradation reaction of the polymer can be shielded, the flame is completely extinguished in the dropping process of the melt drops, and the flame diffusion threat is avoided, so that the corresponding vertical combustion grade is improved to V-0 grade.
In addition, by using the mixture obtained by coupling and polymerizing diisopropylbenzene and/or an azo compound as an initiator, in addition to stopping a combustion chain reaction in a gas phase, so that the polymer has the gas-phase flame-retardant effect, the initiator can generate free radicals in a condensed phase to prevent the thermal-oxidative degradation of polypropylene. When the two free radicals have the flame retardant effect, firstly, the thermal degradation in a condensed phase is reduced to a lower degree, and simultaneously, the combustible chain reaction generated by the thermal degradation of the lower degree is terminated by the initiator free radicals in a gas phase environment, namely, the two free radicals are matched with each other in a gas phase and a solid phase to prevent the combustion reaction from being carried out, so that the gas-solid synergistic flame retardant effect is realized.
The flame-retardant polypropylene resin prepared by the invention has the advantages that the flame retardant is gathered and distributed in a polypropylene base material by taking a phosphorus-containing flame retardant as a center and is not easy to migrate under the action of thermal oxygen except the functions of gas-phase flame-retardant effect, condensed-phase flame-retardant effect and catalytic carbonization, so that the flame-retardant polypropylene resin has good flame-retardant durability, the surface is not separated out after being boiled in boiling water for 72 hours, and the limited oxygen index is not reduced after being continuously baked at 120 ℃ for 168 hours.
Has the advantages that:
(1) the flame-retardant polypropylene resin disclosed by the invention is simple in preparation process, low in cost and suitable for industrialization;
(2) the flame-retardant polypropylene resin has higher limit oxygen index vertical combustion grade, and has a gas-phase flame-retardant mechanism, a condensed-phase flame-retardant mechanism and a catalytic char formation effect;
(3) the flame retardant polypropylene resin has the advantages of less flame retardant addition amount, good mechanical property and wide application range;
(4) the flame retardance of the flame-retardant polypropylene has durability, the surface of a product is not separated after the product is boiled in boiling water for 72 hours, and the oxygen index of the material is not reduced after the product is continuously baked for 168 hours at 120 ℃.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The invention can select adding or not adding processing agent and color master batch according to actual requirements. The processing aid used in the invention is a common plastic processing aid, comprising a toughening agent, a reinforcing agent, a filler, a lubricant and the like, the color master batch is a common color master batch of a polypropylene carrier, the color is black, yellow, red, green and a mixed color thereof, and the color and the brand conform to the specification of HG/T4668-one 2014 polypropylene (PP) color master batch.
Example 1
The preparation method of the flame-retardant polypropylene resin comprises the following steps:
(1) preparing raw materials:
homo-polypropylene with a melt index of 30g/10 min;
phosphorus-bromine-initiator ternary system flame retardant: the flame retardant is prepared by compounding a brominated flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the brominated flame retardant A to the phosphorus flame retardant B to the initiator C is 1:0.5: 0.1; wherein, the bromine flame retardant A is tris (2, 3-dibromopropyl) isocyanurate, and the phosphorus flame retardant B is
The initiator C is prepared by the following method: weighing 100 g of mixed diisopropylbenzene (the mass ratio of o-diisopropylbenzene to m-diisopropylbenzene to p-diisopropylbenzene is 0.5:10:25) and 45 g of tert-butyl peroxide, putting the mixed diisopropylbenzene and the tert-butyl peroxide into a three-neck flask with a reflux condenser and a nitrogen guide pipe, adding 1 g of zinc chloride, introducing nitrogen for protection, heating to 100-120 ℃, stirring for reaction for 6 hours, heating to reflux for continuous reaction for 10 hours, cooling to normal temperature after the reaction is finished, washing with purified water for 3 times, leaving an organic phase, distilling at normal pressure, distilling at reduced pressure to remove unreacted liquid, and cooling to normal temperature to obtain 35 g of paste for later use. Confirming the structure as a target object through infrared, nuclear magnetic resonance and element analysis;
(2) and (2) melting and blending 100 parts of polypropylene prepared in the step (1) and 1 part of phosphorus-bromine-initiator ternary system flame retardant by weight to prepare the flame-retardant polypropylene resin, wherein the temperature of melting and blending is 200 ℃.
The ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 29.5 percent, the vertical combustion level is V-0 level, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Comparative example 1
A flame-retardant polypropylene resin, the preparation method of which is substantially the same as that of example 1, except that the phosphorus flame retardant B in the phosphorus-bromine-initiator ternary system flame retardant is replaced with calcium hypophosphite.
The ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 27.5 percent, the vertical combustion level is V-2 level, the inner surface of the flame-retardant polypropylene resin is separated out after the flame-retardant polypropylene resin is steamed and boiled in boiling water for 24 hours, and the ultimate oxygen index is reduced to 24 percent after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Comparing example 1 with comparative example 1, it can be seen that after the phosphorus flame retardant of the present invention is replaced by calcium hypophosphite, the limiting oxygen index, the vertical burning grade, the migration resistance, the flame retardant durability and the like are all significantly reduced, because calcium hypophosphite is an inorganic rigid particle, and agglomeration and stress concentration occur in polypropylene, which leads to significant reduction of the flame retardant performance. In addition, the compatibility between calcium hypophosphite and polypropylene is poor, the calcium hypophosphite is easy to migrate under the action of hot oxygen, and the flame retardant durability and migration resistance are both inferior to those of the calcium hypophosphite.
Example 2
The preparation method of the flame-retardant polypropylene resin comprises the following steps:
(1) preparing raw materials:
homo-polypropylene with a melt index of 50g/10 min;
phosphorus-bromine-initiator ternary system flame retardant: the flame retardant is prepared by compounding a brominated flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the brominated flame retardant A to the phosphorus flame retardant B to the initiator C is 1:1: 1; wherein the bromine flame retardant A is 1, 2-di (tribromophenoxy) ethane, and the phosphorus flame retardant B is
The initiator C is prepared by the following method: weighing 100 g of mixed diisopropylbenzene (the mass ratio of o-diisopropylbenzene to m-diisopropylbenzene to p-diisopropylbenzene is 0:0.1:50) and 45 g of tert-butyl peroxide, putting the mixture into a three-neck flask with a reflux condenser and a nitrogen guide pipe, adding 1 g of zinc chloride, introducing nitrogen for protection, heating to 100-120 DEG CStirring and reacting for 6 hours, heating to reflux and continuing to react for 10 hours, cooling to normal temperature after the reaction is finished, washing for 3 times by purified water, distilling the remaining organic phase at normal pressure, then distilling under reduced pressure to remove unreacted liquid, and cooling to normal temperature to obtain 35 g of paste for later use. Confirming the structure as a target object through infrared, nuclear magnetic resonance and element analysis;
processing aids (tougheners, brand CMG 9801);
color masterbatch (red masterbatch, brand PP 350);
(2) and (2) melting and blending 100 parts of polypropylene prepared in the step (1), 1 part of phosphorus-bromine-initiator ternary system flame retardant, 1 part of processing aid and 1 part of color master batch according to parts by weight to prepare the flame-retardant polypropylene resin, wherein the temperature of melting and blending is 205 ℃.
The ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 30%, the vertical burning grade is V-0 grade, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Example 3
The preparation method of the flame-retardant polypropylene resin comprises the following steps:
(1) preparing raw materials:
homo-polypropylene with a melt index of 80g/10 min;
phosphorus-bromine-initiator ternary system flame retardant: the flame retardant is prepared by compounding a brominated flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the brominated flame retardant A to the phosphorus flame retardant B to the initiator C is 1:2: 1; wherein the bromine flame retardant A is tetrabromobisphenol A-bis (2, 3-dibromopropyl) ether, and the phosphorus flame retardant B is
The initiator C is prepared by the following method: weighing 100 g of mixed diisopropylbenzene (the mass ratio of o-diisopropylbenzene to m-diisopropylbenzene to p-diisopropylbenzene is 0.5:10:25) and 45 g of tert-butyl peroxide, putting the mixture into a three-neck flask with a reflux condenser and a nitrogen guide tube, adding 1 g of zinc chloride, introducing nitrogen for protection, heating to 100-120 ℃, stirring for reacting for 6 hours, heating to reflux, and then continuing to refluxAnd (3) continuing the reaction for 10 hours, cooling to normal temperature after the reaction is finished, washing for 3 times by using purified water, remaining an organic phase, distilling at normal pressure, then distilling at reduced pressure to remove unreacted liquid, and cooling to normal temperature to obtain 35 g of paste for later use. Confirming the structure as a target object through infrared, nuclear magnetic resonance and element analysis;
processing aids (reinforcing agents, brand TMY-4A);
color masterbatch (yellow masterbatch, brand PP 150);
(2) and (2) melting and blending 100 parts of polypropylene prepared in the step (1), 2 parts of phosphorus-bromine-initiator ternary system flame retardant, 2 parts of processing aid and 2 parts of color master batch according to parts by weight to prepare the flame-retardant polypropylene resin, wherein the temperature of melting and blending is 208 ℃.
The ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 29 percent, the vertical burning grade is V-0 grade, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Example 4
The preparation method of the flame-retardant polypropylene resin comprises the following steps:
(1) preparing raw materials:
ethylene propylene copolymer polypropylene having a melt index of 50g/10min (trade name EP 380T);
phosphorus-bromine-initiator ternary system flame retardant: the flame retardant is prepared by compounding a brominated flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the brominated flame retardant A to the phosphorus flame retardant B to the initiator C is 1:10: 5; wherein the bromine flame retardant A is tetrabromobisphenol S-bis (2, 3-dibromopropyl) ether, and the phosphorus flame retardant B is
The structural formula of the initiator C is
Processing aids (reinforcing agents, brand TMY-4A);
color masterbatch (black masterbatch, brand PP 050);
(2) and (2) melting and blending 100 parts of polypropylene prepared in the step (1), 3 parts of phosphorus-bromine-initiator ternary system flame retardant, 3 parts of processing aid and 3 parts of color master batch according to parts by weight to prepare the flame-retardant polypropylene resin, wherein the temperature of melting and blending is 210 ℃.
The ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 33%, the vertical burning grade is V-0 grade, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Example 5
The preparation method of the flame-retardant polypropylene resin comprises the following steps:
(1) preparing raw materials:
ethylene propylene copolymer polypropylene having a melt index of 50g/10min (trade name EP 380T);
phosphorus-bromine-initiator ternary system flame retardant: the flame retardant is prepared by compounding a brominated flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the brominated flame retardant A to the phosphorus flame retardant B to the initiator C is 1:20: 5; wherein the bromine flame retardant A is tetrabromobisphenol A-bis (2, 3-dibromo-2-methylpropyl) ether, and the phosphorus flame retardant B is
The structural formula of the initiator C is
Processing aids (mold release agents, designation AC 617A);
color masterbatch (black masterbatch, brand PP 050);
(2) and (2) melting and blending 100 parts of polypropylene prepared in the step (1), 3 parts of phosphorus-bromine-initiator ternary system flame retardant, 3 parts of processing aid and 4 parts of color master batch according to parts by weight to prepare the flame-retardant polypropylene resin, wherein the temperature of melting and blending is 215 ℃.
The ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 29 percent, the vertical burning grade is V-0 grade, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Example 6
The preparation method of the flame-retardant polypropylene resin comprises the following steps:
(1) preparing raw materials:
a mixture of homopolypropylene having a melt index of 50g/10min and ethylene propylene copolypropylene (trade name EP380T) having a melt index of 50g/10min in a mass ratio of 1: 1;
phosphorus-bromine-initiator ternary system flame retardant: the flame retardant is prepared by compounding a brominated flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the brominated flame retardant A to the phosphorus flame retardant B to the initiator C is 1:2: 5; wherein, the bromine flame retardant A is tetrabromobisphenol A epoxy resin with the relative molecular mass of 20000, and the phosphorus flame retardant B is
The structural formula of the initiator C is
Processing aids (lubricants, designation YY-5031);
color masterbatch (black masterbatch, brand PP 050);
(2) and (2) melting and blending 100 parts of polypropylene prepared in the step (1), 5 parts of phosphorus-bromine-initiator ternary system flame retardant, 5 parts of processing aid and 5 parts of color master batch according to parts by weight to prepare the flame-retardant polypropylene resin, wherein the temperature of melting and blending is 220 ℃.
The ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 29 percent, the vertical burning grade is V-0 grade, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Example 7
A preparation method of flame-retardant polypropylene resin is basically the same as that in example 1, except that a brominated flame retardant A is replaced by tris (tribromoneopentyl) phosphate (trade name FR-370), the ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 30%, the vertical combustion level is V-0 level, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Example 8
A preparation method of a flame-retardant polypropylene resin is basically the same as that in example 1, except that a brominated flame retardant A is replaced by a mixture of tetrabromobisphenol A-bis (2, 3-dibromopropyl) ether and tris (tribromoneopentyl) phosphate (trade name FR-370) in a mass ratio of 1:1, the ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 29%, the vertical combustion grade is V-0, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is cooked for 72 hours by boiling water, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Example 9
A preparation method of flame-retardant polypropylene resin is basically the same as that in example 1, except that a brominated flame retardant A is replaced by decabromodiphenylethane, the ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 32%, the vertical burning grade is V-0 grade, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Example 10
A preparation method of flame-retardant polypropylene resin is basically the same as that in example 1, except that a bromine flame retardant A is replaced by melamine hydrobromide, the ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 32.5%, the vertical combustion level is V-0, the surface of the flame-retardant polypropylene resin is not separated out after being boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after being continuously baked at 120 ℃ for 168 hours.
Example 11
A preparation method of a flame-retardant polypropylene resin is basically the same as that in example 1, except that a brominated flame retardant A is replaced by N, N' -ethylenebistetrabromophthalimide, polypropylene is an ethylene-propylene copolymer, the trademark K8003, and the melt index is 2.5g/10 min. The ultimate oxygen index of the finally prepared flame-retardant polypropylene resin is 29.5 percent, the vertical combustion level is V-0 level, the surface of the flame-retardant polypropylene resin is not separated out after the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, and the ultimate oxygen index is not reduced after the flame-retardant polypropylene resin is continuously baked at 120 ℃ for 168 hours.
Claims (8)
1. A flame-retardant polypropylene resin characterized by: the flame-retardant polypropylene resin consists of 100 parts by weight of polypropylene, 1-5 parts by weight of phosphorus-bromine-initiator ternary system flame retardant, 0-5 parts by weight of processing aid and 0-5 parts by weight of color master batch;
the phosphorus-bromine-initiator ternary system flame retardant is prepared by compounding a bromine flame retardant A, a phosphorus flame retardant B and an initiator C, wherein the mass ratio of the bromine flame retardant A to the phosphorus flame retardant B to the initiator C is 1: 0.5-20: 0.1-5;
the chemical structure of the phosphorus flame retardant B is shown as a formula (I);
in the formula, X is O or S, R1Is hydrogen, alkyl or alkoxy, R2Is a metal ion or an alkyl group, R3Is a metal ion or an alkyl group, and R2And R3Not simultaneously being alkyl.
2. The flame-retardant polypropylene resin of claim 1, wherein the limited oxygen index of the flame-retardant polypropylene resin is not less than 29%, the vertical burning level is V-0, the flame-retardant polypropylene resin is boiled in boiling water for 72 hours, the surface of the flame-retardant polypropylene resin is not separated out, and the limited oxygen index is not reduced after continuous baking at 120 ℃ for 168 hours.
3. The flame retardant polypropylene resin according to claim 1, wherein the polypropylene is homo-polypropylene, co-polypropylene or a mixture thereof, and the melt index of the homo-polypropylene or the co-polypropylene is 2-80 g/10 min.
4. The flame retardant polypropylene resin according to claim 1, wherein the brominated flame retardant A is one or more selected from decabromodiphenylethane, tris (2, 3-dibromopropyl) isocyanurate, 2,4, 6-tris (tribromophenoxy) -1, 3, 5-triazine, 1, 2-bis (tribromophenoxy) ethane, tetrabromobisphenol A-bis (2, 3-dibromopropyl) ether, tetrabromobisphenol S-bis (2, 3-dibromopropyl) ether, tetrabromobisphenol A-bis (2, 3-dibromo-2-methylpropyl) ether, tetrabromobisphenol A epoxy resin having a relative molecular mass of 5000 to 100000, melamine hydrobromide, tris (tribromoneopentyl) phosphate and N, N' -ethylenebistetrabromophthalimide.
5. The flame retardant polypropylene resin according to claim 1, wherein the initiator C is one or more of a compound having a structure represented by formula (II) and a compound having a structure represented by formula (III);
in the formula, R4、R5Are the same or different alkyl groups.
6. The flame retardant polypropylene resin according to claim 5, wherein the compound having the structure represented by formula (II) is generated by coupling reaction of mixed diisopropylbenzenes, wherein the mass ratio of o-diisopropylbenzene, m-diisopropylbenzene and p-diisopropylbenzene in the mixed diisopropylbenzenes is 0-1: 0.1-30: 0.1-50.
7. The flame-retardant polypropylene resin according to any one of claims 1 to 6, wherein the flame-retardant polypropylene resin is prepared by melt blending polypropylene, a phosphorus-bromine-initiator ternary system flame retardant, a processing aid and a color master batch.
8. The flame retardant polypropylene resin according to claim 7, wherein the melt blending temperature is 180 to 230 ℃.
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| CN115960416A (en) * | 2022-12-20 | 2023-04-14 | 银禧工程塑料（东莞）有限公司 | Low-shrinkage, low-warpage and high-oxygen-index antibacterial polypropylene composite material and preparation method thereof |
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