CN115558181A - 一种阻燃母粒及其制备方法与应用 - Google Patents
一种阻燃母粒及其制备方法与应用 Download PDFInfo
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- CN115558181A CN115558181A CN202211207146.4A CN202211207146A CN115558181A CN 115558181 A CN115558181 A CN 115558181A CN 202211207146 A CN202211207146 A CN 202211207146A CN 115558181 A CN115558181 A CN 115558181A
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- flame retardant
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- master batch
- antioxidant
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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 169
- 239000003063 flame retardant Substances 0.000 title claims abstract description 162
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 polyethylene Polymers 0.000 claims abstract description 64
- 239000004698 Polyethylene Substances 0.000 claims abstract description 51
- 229920000573 polyethylene Polymers 0.000 claims abstract description 51
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000004611 light stabiliser Substances 0.000 claims abstract description 15
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229920001903 high density polyethylene Polymers 0.000 claims description 6
- 239000004700 high-density polyethylene Substances 0.000 claims description 6
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 6
- 229920001684 low density polyethylene Polymers 0.000 claims description 6
- 239000004702 low-density polyethylene Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 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 5
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000004605 External Lubricant Substances 0.000 claims description 4
- 239000004610 Internal Lubricant Substances 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical group 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 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 3
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 3
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- GRKDVZMVHOLESV-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(COC(=O)C=C)C(Br)=C1Br GRKDVZMVHOLESV-UHFFFAOYSA-N 0.000 claims description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- IGOLLIYZEGOLRR-UHFFFAOYSA-N 1,4-bis(tribromomethyl)benzene Chemical group BrC(Br)(Br)C1=CC=C(C(Br)(Br)Br)C=C1 IGOLLIYZEGOLRR-UHFFFAOYSA-N 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005997 bromomethyl group Chemical group 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 3
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical class [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 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
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 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 compound 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 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
- GYKKGOMJFMCRIN-UHFFFAOYSA-L zinc;ethyl(methyl)phosphinate Chemical compound [Zn+2].CCP(C)([O-])=O.CCP(C)([O-])=O GYKKGOMJFMCRIN-UHFFFAOYSA-L 0.000 description 1
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- 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
- C08J3/223—Packed additives
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- 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
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- 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
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- 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
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- 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
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- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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Abstract
本发明公开了一种阻燃母粒及其制备方法与应用,涉及阻燃材料技术领域。本发明所述阻燃母粒包含如下重量份的成分:聚烯烃树脂40~75份、阻燃剂20~55份、润滑剂0.1~5份、抗氧剂0.2~0.7份和光稳定剂0~0.5份;所述阻燃剂为溴系阻燃剂和阻燃剂A两种阻燃剂的复配物或溴系阻燃剂、阻燃剂A和阻燃剂B三种阻燃剂的复配物;所述阻燃剂A为包含‑O‑P=O‑和‑P‑C‑结构的阻燃剂,所述阻燃剂B为卤代磷酸酯类阻燃剂;所述阻燃剂A、阻燃剂B具有熔点。以本发明所述阻燃母粒制备的聚乙烯薄膜具有优异的阻燃性能及力学性能,同时能保持膜的透明性,适合于建筑包装、大棚养殖、轨道交通等防火要求高的场合。
Description
技术领域
本发明涉及阻燃材料技术领域,尤其涉及一种阻燃母粒及其制备方法与应用。
背景技术
聚乙烯薄膜是产量最大、应用范围最广的塑料薄膜之一,被广泛应用于建筑业、农业、包装、电子电器、光伏等领域。一般来说,暖棚养殖、建筑材料和屋面防水层等都需要包裹聚乙烯薄膜;暖棚养殖必须配置照明灯具等潜在火源,而一旦发生火灾,造成重大损失;建筑防水薄膜、光伏胶膜同样需要良好的防火性能,防止火焰沿着材料表面蔓延。因此想扩大其应用领域,需要对其进行阻燃改性处理。
常用的聚乙烯薄膜,如LLDPE、HDPE、MLLDPE材料,极易燃烧,氧指数为18;聚乙烯阻燃改性出现了卤系、无机系、氮磷系膨胀型等各具特色的阻燃剂产品。其中卤系阻燃剂是目前全世界产量最大的阻燃产品,具有添加量小、阻燃效果显著的优点。在与三氧化二锑复配使用时烟量大,薄膜点燃后容易流滴,造成二次伤害;无机系阻燃剂公认具有安全、无毒、防滴落、抑烟、价格低廉的优点,但须大量添加才能获得显著的阻燃效果,造成加工性能差,膜的强度低等问题。以P-N型为主的膨胀型阻燃剂,以聚合物脱水成碳隔绝热量、氧气达到阻燃目的,但应用在薄膜中,薄膜的厚度小,所形成炭层薄,无法达到量好的自熄性能,同时添加量大,对产品的透明度、韧性影响大。
中国专利201810636223.5公开了以四溴双酚A双(2,3-二溴丙基)醚0.5-10份;磷系阻燃剂0.5-10份;阻燃协效剂0.1-2份。所选用的聚磷酸盐为无机阻燃剂,没有熔点,无法保证膜制品的透明性,阻燃剂颗粒在膜制品中的分散较差。所选用的阻燃协效剂为联枯类化合物,在聚丙烯中能产生自由基提高阻燃性,但由于聚乙烯中没有叔碳结构,阻燃效率提升不明显;因此亟需寻找一种阻燃效果好,燃烧无滴落且同时能保持膜制品透明性的阻燃母粒。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种阻燃母粒及其制备方法与应用。所述阻燃母粒具有良好的阻燃性能,应用于聚乙烯薄膜中可以克服现有聚乙烯薄膜难以兼顾阻燃剂和透明性的技术难题,并且对聚乙烯薄膜的力学性能不会产生明显的影响。
为实现上述目的,本发明所采取的技术方案为:
一种阻燃母粒,所述阻燃母粒包含如下重量份的成分:聚烯烃树脂40~75份、阻燃剂20~55份、润滑剂0.1~5份、抗氧剂0.2~0.7份和光稳定剂0~0.5份;所述阻燃剂为溴系阻燃剂和阻燃剂A两种阻燃剂的复配物或溴系阻燃剂、阻燃剂A和阻燃剂B三种阻燃剂的复配物;所述阻燃剂A为包含-O-P=O-和-P-C-结构的阻燃剂,所述阻燃剂B为卤代磷酸酯类阻燃剂;所述阻燃剂A、阻燃剂B具有熔点。
本发明通过选用溴系阻燃剂和磷系阻燃剂复配,并对磷系阻燃剂的种类进行筛选,其中磷系阻燃剂在聚合物分解阶段,脱水碳化从而减少聚合物因热分解而产生的可燃性气体数量,在凝聚相抑制了聚合物裂解反应,同时燃烧时形成PO·自由基,与溴系阻燃剂在高温分解成自由基Br·共同作用,与火焰区域的H原子结合,起到了抑制火焰的作用;可以避免现有溴锑阻燃剂燃烧时产生大量黑烟,燃烧时易滴落、造成二次伤害的问题;相比于镁铝阻燃剂和磷氮阻燃剂,阻燃效率更高,在少量添加时即可大幅提高由所述母粒制备的聚乙烯薄膜的阻燃性能,对膜的加工及力学性能影响较小,制备出的聚乙烯薄膜具有良好的阻燃性、透明度高。
优选地,所述聚烯烃树脂包含LLDPE、LDPE、HDPE中的至少一种;所述LLDPE、LDPE、HDPE的熔融指数为0.05~50g/10min(测试标准为GB/T3682-2006,条件:190℃*2.16kg)。当聚烯烃树脂满足上述要求时,其加工性能更好,材料的透明性更优。
优选地,所述阻燃母粒中还含有N-烷氧基受阻胺阻燃增效剂0.1~3份。
N-烷氧基受阻胺阻燃增效剂在热分解时形成烷氧、氮氧等自由基,抑制燃烧过程中自由基的产生,并且可以与溴系阻燃剂作用,使Br·更容易释放,提升溴系阻燃剂的阻燃性能,另外,N-烷氧基受阻胺阻燃协效剂与磷系阻燃剂、聚合物之间的自由基反应加速了体系凝聚相中的反应,极大地提高了阻燃效率。当磷系阻燃剂中含有-O-P=O-和-P-C结构时,三者具有最优的协同阻燃作用,燃烧时间可控制在20s内。
优选地,所述阻燃母粒包含如下重量份的成分:聚烯烃树脂55~65份、阻燃剂30~40份、润滑剂0.5~1份、抗氧剂0.2~0.5份、光稳定剂0.1~0.3份和N-烷氧基受阻胺阻燃增效剂0.2~0.5份。当各组分的配比符合上述限定时,以所述阻燃母粒制备的聚乙烯薄膜的阻燃性能相对更好,并且透明度均可以达到85以上。
优选地,所述阻燃剂中溴系阻燃剂的重量份为18~25份、包含-O-P=O-和-P-C-结构的阻燃剂的重量份为10~15份、卤代磷酸酯类阻燃剂的重量份为0~5份。各阻燃剂的配比会影响其在聚合物中的阻燃效果,只有当各成分的配比符合上述限定时,才能保证所述阻燃母粒中各成分之间具有协同作用。
优选地,所述溴系阻燃剂为2,4,6-三(2,4,6-三溴苯氧基)-1,3,5-三嗪、四溴双酚A双(2,3-二溴丙基)醚、八溴S醚、六溴对二甲苯、丙烯酸五溴苄酯、三聚氰胺氢溴酸盐中的至少一种,所述溴系阻燃剂中溴的质量百分含量为38%~83%;所述阻燃剂A为烷基次膦酸盐、烷基次膦酸、芳基次膦酸中的至少一种;所述阻燃剂B为三(三溴新戊基)磷酸酯、2,2-二(溴甲基)-1,3-二[(2-溴丙基-2-氯丙基)磷酸酯]丙烷中的至少一种。
进一步优选地,所述溴系阻燃剂为三聚氰胺氢溴酸盐、八溴S醚中的至少一种;所述阻燃剂A为苯基次膦酸;所述阻燃剂B为三(三溴新戊基)磷酸酯。将以上述阻燃剂制备的阻燃母粒用于聚乙烯薄膜中可以保证聚乙烯薄膜的透明度可达95以上,燃烧时间可以控制在5s内,不会发生滴落。
优选地,所述润滑剂为内润滑剂、外润滑剂中的至少一种,所述内润滑剂为聚乙烯蜡、氧化聚乙烯蜡、聚丙烯蜡、乙撑双硬脂酸酰胺、季戊四醇硬脂酸酯中的至少一种,所述外润滑剂为硬脂酸、硬脂酸钙、硬脂酸丁酯、硬脂酸甘油酯、硅酮润滑脂、芥酸酰胺、油酸酰胺中的至少一种;所述抗氧剂为酚类抗氧剂、亚磷酸酯类抗氧剂、硫醚类抗氧剂、金属盐抗氧剂中的至少一种;所述光稳定剂为光稳定剂944、光稳定剂622、光稳定剂770中的至少一种。
同时,本发明还公开了一种所述阻燃母粒的制备方法,所述制备方法包括如下步骤:
(1)按配方将各组分混合均匀,得到混合料;
(2)将混合料加入挤出机中,熔融共混、挤出,得到所述阻燃母粒。
优选地,所述挤出机中各区温度为100~200℃,所述螺杆的转速为100~500rpm。
此外,本发明还公开了一种透明聚乙烯薄膜,所述阻燃母粒在所述透明聚乙烯薄膜中的重量百分含量为5%~20%,所述透明聚乙烯薄膜可通过熔融吹塑或挤出流延制备而成。
相比于现有技术,本发明的有益效果为:
本发明通过对阻燃剂的成分进行选择,以溴系阻燃剂和阻燃剂A或溴系阻燃剂与阻燃剂A、阻燃剂B复配制备出了具有良好阻燃性的阻燃母粒,并且所述阻燃母粒应用于聚乙烯薄膜中不会对产品的力学性能、透明度产生较大的影响,仅需添加少量即可使聚乙烯薄膜具有UL94 VTM-0的阻燃效果,并且无滴落,聚乙烯薄膜的透明度可达80以上。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。
实施例及对比例中使用的原料如下:
HDPE:齐鲁石化6098,MI为0.08g/10min;
LLDPE:大庆石化7042,MI为2g/10min;
LDPE:燕山石化LD600,MI为2g/10min;
2,4,6-三(2,4,6-三溴苯氧基)-1,3,5-三嗪:山东默锐化学FR245;
八溴S醚:山东兄弟化工,GREATBAY XZ-6600;
三聚氰胺氢溴酸盐:湖南美莱珀,M-108H;
二乙基次膦酸锌:科莱恩化工,OP950;
苯基次膦酸:湖北双焱化工;
次磷酸铝:日光东成,4138B;
甲基乙基次膦酸锌:广东喜嘉新材料,MPZ;
二乙基次膦酸铝:科莱恩化工,OP935;
三(三溴新戊基)磷酸酯:山东日兴新材料,FR-370;
乙撑双硬脂酸酰胺:日本花王,EBFF;
氧化聚乙烯蜡:Honeywell,AC-6A蜡;
抗氧剂1010:北京极易化工;
抗氧剂168:北京极易化工;
光稳定剂944:南京华立明化工;
Nor116:BASF;
光稳定剂770:北京天罡助剂。
上述MI值参考GB/T 3682-2006,在190℃*2.16kg条件下测得。
实施例1~15
本发明所述阻燃母粒的实施例,实施例1~15的配方如表1所示,制备方法如下:
(1)按配方称取各组分,以混合器将各组分混合均匀,得到混合料;
(2)将混合料加入挤出机的喂料斗中,熔融共混、挤出造粒,得到所述阻燃母粒;其中,挤出机中各段温度为110℃、140℃、150℃、160℃、170℃、180℃、190℃、180℃、170℃、160℃、160℃、180℃,螺杆直径为Φ52,螺杆长径比为48:1,螺杆转速为300rpm。
表1(重量份)
对比例1
一种阻燃母粒,所述阻燃母粒与实施例3的区别仅在于,以次磷酸铝替代苯基次膦酸。
对比例2
一种阻燃母粒,所述阻燃母粒与实施例3的区别仅在于,以二乙基次膦酸铝替代苯基次膦酸。
将实施例1~15和对比例1~2分别制备成聚乙烯薄膜,记为聚乙烯薄膜1~17,制备方法如下:将制备的母粒加入对应的基材(与母粒中使用的基体树脂相同)中,待混合均匀后,加入挤出机料仓,进行流延膜制备,膜的厚度为0.17±0.01mm;母粒在膜中的含量为10wt%。
对聚乙烯薄膜的透明度、阻燃性能以及力学性能进行测试,测试结果如表2所示。
透明度测试方法:GB/T 2410-2008透明塑料透光率和雾度试验方法。
阻燃性测试方法:UL94 VTM薄膜垂直燃烧测试。
拉伸强度试验方法:GB/T 1040.3-2006塑料拉伸性能的测定第3部分:薄膜和薄片的试验条件。
表2性能对比
项目 | UL94 | 燃烧时间 | 是否滴落 | 透明度 | 拉伸强度/MPa |
聚乙烯薄膜1 | VTM-0 | 7s | 否 | 88 | 27.2 |
聚乙烯薄膜2 | VTM-0 | 6s | 否 | 90 | 17 |
聚乙烯薄膜3 | VTM-0 | 2s | 否 | 97 | 26.5 |
聚乙烯薄膜4 | VTM-0 | 4s | 否 | 95 | 16.5 |
聚乙烯薄膜5 | VTM-0 | 6s | 否 | 92 | 25.0 |
聚乙烯薄膜6 | VTM-0 | 5s | 否 | 93 | 26.0 |
聚乙烯薄膜7 | VTM-0 | 9.5s | 否 | 92 | 25.5 |
聚乙烯薄膜8 | VTM-0 | 9.7s | 否 | 91 | 27.0 |
聚乙烯薄膜9 | VTM-1 | 12s | 否 | 90 | 24.5 |
聚乙烯薄膜10 | VTM-0 | 4s | 否 | 95 | 26.5 |
聚乙烯薄膜11 | VTM-1 | 15s | 否 | 90 | 22.0 |
聚乙烯薄膜12 | VTM-0 | 5s | 否 | 94 | 23.5 |
聚乙烯薄膜13 | VTM-0 | 4s | 否 | 98 | 25 |
聚乙烯薄膜14 | VTM-1 | 11s | 否 | 91 | 24.5 |
聚乙烯薄膜15 | VTM-1 | 17s | 否 | 84 | 21.0 |
聚乙烯薄膜16 | VTM-2 | 18s | 是 | 60 | 18.0 |
聚乙烯薄膜17 | VTM-2 | 18s | 是 | 45 | 17.5 |
由表2可知,聚乙烯薄膜1~15均可以达到UL94 VTM-1阻燃等级,并且透明度可以达到84以上,具有良好的阻燃性以及透明性。聚乙烯薄膜16~17的透明度较低,并且容易造成应力集中,强度低于20MPa。
聚乙烯薄膜16使用的次磷酸铝不含-O-P=O-和-P-C-两种结构,阻燃不能满足VTM-1要求,燃烧时间较长,存在滴落现象。聚乙烯薄膜17所选用的二乙基次磷酸,不能满足VTM-1要求,燃烧超时、有滴落。
实施例3、5、6中各成分的用量都在优选范围内,制备的聚乙烯薄膜阻燃性能较好,同时还具有良好的透明性以及力学性能。实施例9、11所选用的阻燃剂为非优选阻燃剂,因此,制备的聚乙烯薄膜的燃烧时间超过10s,不能达到VTM-0等级;实施例7、8、14中不含有Nor116,燃烧时间明显更长,可见该增效剂能缩短燃烧时间。实施例11中虽然含有Nor116,但阻燃剂A为非优选阻燃剂,其阻燃性能比实施例14更差,该结果表明,Nor116并非与任何磷系或溴系阻燃剂都具有良好的协同阻燃作用。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,但并不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种阻燃母粒,其特征在于,包含如下重量份的成分:聚烯烃树脂40~75份、阻燃剂20~55份、润滑剂0.1~5份、抗氧剂0.2~0.7份和光稳定剂0~0.5份;所述阻燃剂为溴系阻燃剂和阻燃剂A两种阻燃剂的复配物或溴系阻燃剂、阻燃剂A和阻燃剂B三种阻燃剂的复配物;所述阻燃剂A为包含-O-P=O-和-P-C-结构的阻燃剂,所述阻燃剂B为卤代磷酸酯类阻燃剂;所述阻燃剂A、阻燃剂B具有熔点。
2.如权利要求1所述的阻燃母粒,其特征在于,所述聚烯烃树脂为LLDPE、LDPE、HDPE中的至少一种;所述LLDPE、LDPE、HDPE的熔融指数为0.05~50g/10min。
3.如权利要求1所述的阻燃母粒,其特征在于,所述阻燃母粒还包含N-烷氧基受阻胺阻燃增效剂0.1~3份。
4.如权利要求3所述的阻燃母粒,其特征在于,所述阻燃母粒包含如下重量份的成分:聚烯烃树脂55~65份、阻燃剂30~40份、润滑剂0.5~1份、抗氧剂0.2~0.5份、光稳定剂0.1~0.3份和N-烷氧基受阻胺阻燃增效剂0.2~0.5份。
5.如权利要求4所述的阻燃母粒,其特征在于,所述阻燃剂中溴系阻燃剂的重量份为18~25份、包含-O-P=O-和-P-C-结构的阻燃剂的重量份为10~15份、卤代磷酸酯类阻燃剂的重量份为0~5份。
6.如权利要求1所述的阻燃母粒,其特征在于,所述溴系阻燃剂为2,4,6-三(2,4,6-三溴苯氧基)-1,3,5-三嗪、四溴双酚A双(2,3-二溴丙基)醚、八溴S醚、六溴对二甲苯、丙烯酸五溴苄酯、三聚氰胺氢溴酸盐中的至少一种;所述阻燃剂A为烷基次膦酸盐、烷基次膦酸、芳基次膦酸中的至少一种;所述阻燃剂B为三(三溴新戊基)磷酸酯、2,2-二(溴甲基)-1,3-二[(2-溴丙基-2-氯丙基)磷酸酯]丙烷中的至少一种。
7.如权利要求6所述的阻燃母粒,其特征在于,所述溴系阻燃剂为三聚氰胺氢溴酸盐、八溴S醚中的至少一种;所述阻燃剂A为苯基次膦酸。
8.如权利要求1所述的阻燃母粒,其特征在于,所述润滑剂为内润滑剂和外润滑剂中的至少一种,所述内润滑剂为聚乙烯蜡、氧化聚乙烯蜡、聚丙烯蜡、乙撑双硬脂酸酰胺、季戊四醇硬脂酸酯中的至少一种,所述外润滑剂为硬脂酸、硬脂酸钙、硬脂酸丁酯、硬脂酸甘油酯、硅酮润滑脂、芥酸酰胺、油酸酰胺中的至少一种;所述抗氧剂为酚类抗氧剂、亚磷酸酯类抗氧剂、硫醚类抗氧剂、金属盐抗氧剂中的至少一种;所述光稳定剂为光稳定剂944、光稳定剂622、光稳定剂770中的至少一种。
9.一种如权利要求1~8任一项所述阻燃母粒的制备方法,其特征在于,包括如下步骤:
(1)按配方将各组分混合均匀,得到混合料;
(2)将混合料加入挤出机中,熔融共混、挤出,得到所述阻燃母粒。
10.一种透明聚乙烯薄膜,其特征在于,含有如权利要求1~8任一项所述阻燃母粒,所述阻燃母粒在所述透明聚乙烯薄膜中的重量百分含量为5%~20%。
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