WO2014101346A1 - 一种复合阻燃剂及其应用 - Google Patents
一种复合阻燃剂及其应用 Download PDFInfo
- Publication number
- WO2014101346A1 WO2014101346A1 PCT/CN2013/071851 CN2013071851W WO2014101346A1 WO 2014101346 A1 WO2014101346 A1 WO 2014101346A1 CN 2013071851 W CN2013071851 W CN 2013071851W WO 2014101346 A1 WO2014101346 A1 WO 2014101346A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ammonium
- flame retardant
- aluminum
- composite flame
- calcium
- Prior art date
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 98
- 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 95
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 150000003863 ammonium salts Chemical group 0.000 claims abstract description 5
- -1 Aliphatic carboxylate Chemical class 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229940090948 ammonium benzoate Drugs 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 3
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- ZLANTYQNMVCEHC-UHFFFAOYSA-N [Ca].[PH2](OCC)=O Chemical compound [Ca].[PH2](OCC)=O ZLANTYQNMVCEHC-UHFFFAOYSA-N 0.000 claims description 2
- YMHVBCADCUZNKP-UHFFFAOYSA-M [NH4+].[Ca+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Ca+].[O-]S([O-])(=O)=O YMHVBCADCUZNKP-UHFFFAOYSA-M 0.000 claims description 2
- NFTAXEWFOFZEAY-UHFFFAOYSA-N [PH2](OCC)=O.[Mg] Chemical compound [PH2](OCC)=O.[Mg] NFTAXEWFOFZEAY-UHFFFAOYSA-N 0.000 claims description 2
- KMMOYCFLDNKPOC-UHFFFAOYSA-N [PH2](OCCC)=O.[Ca] Chemical compound [PH2](OCCC)=O.[Ca] KMMOYCFLDNKPOC-UHFFFAOYSA-N 0.000 claims description 2
- GRCOGTLCPHYXFO-UHFFFAOYSA-N [PH2](OCCC)=O.[Mg] Chemical compound [PH2](OCCC)=O.[Mg] GRCOGTLCPHYXFO-UHFFFAOYSA-N 0.000 claims description 2
- IOGRQIWFIRKXQV-UHFFFAOYSA-K aluminum dipropylphosphinate Chemical compound C(CC)P([O-])(=O)CCC.[Al+3].C(CC)P([O-])(=O)CCC.C(CC)P([O-])(=O)CCC IOGRQIWFIRKXQV-UHFFFAOYSA-K 0.000 claims 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 claims description 2
- QVKQNISQFCPYGN-UHFFFAOYSA-K aluminum;dimethylphosphinate Chemical compound [Al+3].CP(C)([O-])=O.CP(C)([O-])=O.CP(C)([O-])=O QVKQNISQFCPYGN-UHFFFAOYSA-K 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- PQILKFQDIYPBKI-UHFFFAOYSA-N azane;2-phenylacetic acid Chemical compound [NH4+].[O-]C(=O)CC1=CC=CC=C1 PQILKFQDIYPBKI-UHFFFAOYSA-N 0.000 claims description 2
- IPRCVFMLNWMMLD-UHFFFAOYSA-N azane;benzene-1,3-dicarboxylic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)C1=CC=CC(C([O-])=O)=C1 IPRCVFMLNWMMLD-UHFFFAOYSA-N 0.000 claims description 2
- CHCFOMQHQIQBLZ-UHFFFAOYSA-N azane;phthalic acid Chemical compound N.N.OC(=O)C1=CC=CC=C1C(O)=O CHCFOMQHQIQBLZ-UHFFFAOYSA-N 0.000 claims description 2
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 claims description 2
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 2
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 2
- DONULGYRZAGJQH-UHFFFAOYSA-L calcium;dimethylphosphinate Chemical compound [Ca+2].CP(C)([O-])=O.CP(C)([O-])=O DONULGYRZAGJQH-UHFFFAOYSA-L 0.000 claims description 2
- OYLGLPVAKCEIKU-UHFFFAOYSA-N diazanium;sulfonato sulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OS([O-])(=O)=O OYLGLPVAKCEIKU-UHFFFAOYSA-N 0.000 claims description 2
- WRMGSHJRBULEMY-UHFFFAOYSA-L diethylphosphinate iron(2+) Chemical compound C(C)P([O-])(=O)CC.[Fe+2].C(C)P([O-])(=O)CC WRMGSHJRBULEMY-UHFFFAOYSA-L 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012747 synergistic agent Substances 0.000 claims description 2
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- SLKRGHBFYYVSLH-UHFFFAOYSA-K tris(dibutylphosphoryloxy)alumane Chemical compound [Al+3].CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC SLKRGHBFYYVSLH-UHFFFAOYSA-K 0.000 claims description 2
- OTOSBXURLCNNDV-UHFFFAOYSA-K tris(dipentylphosphoryloxy)alumane Chemical compound CCCCCP(=O)(CCCCC)O[Al](OP(=O)(CCCCC)CCCCC)OP(=O)(CCCCC)CCCCC OTOSBXURLCNNDV-UHFFFAOYSA-K 0.000 claims description 2
- QCZYHDUNHYLTAG-UHFFFAOYSA-L C(C)P([O-])=O.[Mg+2].C(C)P([O-])=O Chemical compound C(C)P([O-])=O.[Mg+2].C(C)P([O-])=O QCZYHDUNHYLTAG-UHFFFAOYSA-L 0.000 claims 1
- HZCDANOFLILNSA-UHFFFAOYSA-N Dimethyl hydrogen phosphite Chemical compound COP(=O)OC HZCDANOFLILNSA-UHFFFAOYSA-N 0.000 claims 1
- FDPPRGFSWMXMAW-UHFFFAOYSA-K aluminum butyl(methyl)phosphinate Chemical compound [Al+3].CCCCP(C)([O-])=O.CCCCP(C)([O-])=O.CCCCP(C)([O-])=O FDPPRGFSWMXMAW-UHFFFAOYSA-K 0.000 claims 1
- HFWIMCKIKFOFGA-UHFFFAOYSA-K aluminum;ethyl(propyl)phosphinate Chemical compound [Al+3].CCCP([O-])(=O)CC.CCCP([O-])(=O)CC.CCCP([O-])(=O)CC HFWIMCKIKFOFGA-UHFFFAOYSA-K 0.000 claims 1
- XDMYAHBAPIRGTQ-UHFFFAOYSA-K aluminum;methyl(propyl)phosphinate Chemical compound [Al+3].CCCP(C)([O-])=O.CCCP(C)([O-])=O.CCCP(C)([O-])=O XDMYAHBAPIRGTQ-UHFFFAOYSA-K 0.000 claims 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims 1
- ZZTCCAPMZLDHFM-UHFFFAOYSA-N ammonium thioglycolate Chemical compound [NH4+].[O-]C(=O)CS ZZTCCAPMZLDHFM-UHFFFAOYSA-N 0.000 claims 1
- 229910001871 ammonium zinc sulfate Inorganic materials 0.000 claims 1
- XSOHCQBMTDEBAD-UHFFFAOYSA-N azane Chemical compound N.N.N XSOHCQBMTDEBAD-UHFFFAOYSA-N 0.000 claims 1
- QOYTTYBESIGTCR-UHFFFAOYSA-N azane ethyl formate Chemical compound C(=O)OCC.N QOYTTYBESIGTCR-UHFFFAOYSA-N 0.000 claims 1
- GJDOTWYVTBUQDM-UHFFFAOYSA-N azanium 2-(4-methylphenyl)acetate Chemical compound CC1=CC=C(C=C1)CC(=O)[O-].[NH4+] GJDOTWYVTBUQDM-UHFFFAOYSA-N 0.000 claims 1
- GGHVJPZGYLCBPB-UHFFFAOYSA-N azanium 3-ethylbenzoate Chemical compound C(C)C=1C=C(C=CC1)C(=O)[O-].[NH4+] GGHVJPZGYLCBPB-UHFFFAOYSA-N 0.000 claims 1
- DRYHXHUXMMIMPH-UHFFFAOYSA-L calcium;diethylphosphinate Chemical compound [Ca+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DRYHXHUXMMIMPH-UHFFFAOYSA-L 0.000 claims 1
- TXGQALXWGNPMKD-UHFFFAOYSA-L diazanium;zinc;disulfate;hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O TXGQALXWGNPMKD-UHFFFAOYSA-L 0.000 claims 1
- XAURQBXQKXQJGF-UHFFFAOYSA-L dimethylphosphinate iron(2+) Chemical compound CP(=O)(C)[O-].CP(=O)(C)[O-].[Fe+2] XAURQBXQKXQJGF-UHFFFAOYSA-L 0.000 claims 1
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229930003658 monoterpene Natural products 0.000 claims 1
- 235000002577 monoterpenes Nutrition 0.000 claims 1
- GTOWTBKGCUDSNY-UHFFFAOYSA-K tris[[ethyl(methyl)phosphoryl]oxy]alumane Chemical compound [Al+3].CCP(C)([O-])=O.CCP(C)([O-])=O.CCP(C)([O-])=O GTOWTBKGCUDSNY-UHFFFAOYSA-K 0.000 claims 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QUVZQNAFNYSQIH-UHFFFAOYSA-N [Bi].[Br] Chemical compound [Bi].[Br] QUVZQNAFNYSQIH-UHFFFAOYSA-N 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002829 nitrogen Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- PDAXJVMXHHATAJ-UHFFFAOYSA-N CCCCO[PH2]=O Chemical compound CCCCO[PH2]=O PDAXJVMXHHATAJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IHSZURPWPOXDOF-UHFFFAOYSA-N [PH2](O)=O.C(C)[Ca]CC Chemical compound [PH2](O)=O.C(C)[Ca]CC IHSZURPWPOXDOF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ILZAWBYGLWGBHA-UHFFFAOYSA-N azane phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1.N ILZAWBYGLWGBHA-UHFFFAOYSA-N 0.000 description 1
- VRXUNFOOILCQQO-UHFFFAOYSA-N azanium 2-(2-methylphenyl)acetate Chemical compound CC1=C(C=CC=C1)CC(=O)[O-].[NH4+] VRXUNFOOILCQQO-UHFFFAOYSA-N 0.000 description 1
- YTAWNXJTQUFFKN-UHFFFAOYSA-N azanium 2-(3-methylphenyl)acetate Chemical compound CC=1C=C(C=CC1)CC(=O)[O-].[NH4+] YTAWNXJTQUFFKN-UHFFFAOYSA-N 0.000 description 1
- QZUWHZSCOCALIT-UHFFFAOYSA-N azanium 4-ethylbenzoate Chemical compound C(C)C1=CC=C(C=C1)C(=O)[O-].[NH4+] QZUWHZSCOCALIT-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- FFPQSNUAVYJZDH-UHFFFAOYSA-N diazanium;terephthalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 FFPQSNUAVYJZDH-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- HHYXZVYUIJDJAH-UHFFFAOYSA-L magnesium;diethylphosphinate Chemical compound [Mg+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC HHYXZVYUIJDJAH-UHFFFAOYSA-L 0.000 description 1
- MKNUZASDTKBRNE-UHFFFAOYSA-L magnesium;dimethylphosphinate Chemical compound [Mg+2].CP(C)([O-])=O.CP(C)([O-])=O MKNUZASDTKBRNE-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ILMYTDDXICIZAE-UHFFFAOYSA-K tris(dihexylphosphoryloxy)alumane Chemical compound CCCCCCP(=O)(CCCCCC)O[Al](OP(=O)(CCCCCC)CCCCCC)OP(=O)(CCCCCC)CCCCCC ILMYTDDXICIZAE-UHFFFAOYSA-K 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- MXMCTPBQIJWVBA-UHFFFAOYSA-L zinc;dimethylphosphinate Chemical compound [Zn+2].CP(C)([O-])=O.CP(C)([O-])=O MXMCTPBQIJWVBA-UHFFFAOYSA-L 0.000 description 1
- CZPRKINNVBONSF-UHFFFAOYSA-M zinc;dioxido(oxo)phosphanium Chemical compound [Zn+2].[O-][P+]([O-])=O CZPRKINNVBONSF-UHFFFAOYSA-M 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
- C07F9/4816—Acyclic saturated acids or derivatices which can have further substituents on alkyl
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
- C08K2003/3054—Ammonium sulfates
Definitions
- the invention relates to the field of polymer flame retardant, in particular to a composite flame retardant and application thereof. Background technique
- the existing flame-retardant modified polymer whether it is a thermoplastic resin matrix or a thermosetting resin matrix, needs to select phosphorus, nitrogen or a compounding system thereof in order to meet the requirements of non-halogenation.
- the most common phosphorus-containing flame retardants and their compositions are mainly micro-gelatinized red phosphorus, phosphate ester, and intumescent flame retardant system mainly composed of ammonium polyphosphate.
- These flame retardant systems can meet the flame retardant requirements of certain specific polymers, and these flame retardant systems are flame retardant by solid camera.
- the phosphorus-containing flame retardant with solid-phase flame retardant mechanism and its compound flame retardant system have the disadvantages of low flame retardancy and selectivity.
- the phosphinate is a kind of phosphorus-containing flame retardant which can act on the gas phase. Therefore, the applicable resin matrix range is equivalent to the bromine-bismuth compound flame retardant system, but the flame retarding efficiency is also low, and the compounding is not required. For synergists, 20-30% by weight is required to achieve UL 94 V-0 flame retardancy.
- Patent CN 1660857 B and CN 100348653 C disclose a composition of a fluorenylphosphinate complex with an amine-containing cyclic structure synergist, although these synergists have a certain degree of synergy, but The degree of synergy is limited, and therefore the amount of phosphinate is still high, greatly increasing the cost of the composition. Summary of the invention
- the object of the present invention is to provide a novel composite flame retardant which overcomes the deficiencies of the prior art and which can greatly improve the flame retardant efficiency of the flame retardant by rational selection of the synergist.
- Another object of the present invention is to provide an application of the composite flame retardant.
- Another object of the present invention is to provide a flame-retardant molding composition containing the composite flame retardant.
- a composite flame retardant comprising the following components in terms of weight percent:
- the flame retardant has the structure represented by the formula (I):
- M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and Or a protonated nitrogen reduction, wherein m is 1, 2, 3 or 4; the synergist is an ammonium salt containing at least one N + ;
- the additive is a char former and/or a stabilizer.
- a composite flame retardant composed of the following components by weight:
- the flame retardant has a knot represented by formula (I)
- M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K And/or a protonated nitrogen base, wherein m is 1, 2, 3 or 4; the synergist is an ammonium salt containing at least one N + .
- the carbon-forming agent is a carbon-forming agent commonly used in the field, and the function thereof is to help the matrix resin form a stable and strong carbon residence during the combustion process, thereby achieving the flame-retardant effect of the oxygen barrier, the carbon-forming agent It is selected from the group consisting of pentaerythritol, pentaerythritol ester, novolac, cellulose, etc. or a mixture of these.
- the stabilizer is a stabilizer commonly used in the art, and the function thereof is to improve the stability of the composite flame retardant composed of the phosphine (phosphoric acid) flame retardant and the synergist during processing and molding,
- the stabilizer is selected from the group consisting of magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, zinc borate, zinc stannate, zinc hydroxystannate, and the like, or a mixture of these.
- the weight percentage of the flame retardant and the synergist is:
- the synergistic agent has a thermal decomposition temperature of 180 ° C or higher.
- the negative ion of the synergist is S0 4 2 —, HS0 4 , S 2 0 7 2 —, Br—, Cr, C1—C3 aliphatic carboxylate or C7—C10 aromatic carboxylate.
- the synergist is ammonium sulfate, ammonium aluminum sulfate, magnesium sulfate, ammonium ammonium sulfate, calcium ammonium sulfate, ammonium iron sulfate, Ammonium hydrogen sulfate, ammonium pyrophosphate, ammonium chloride, ammonium bromide, ammonium formate, ammonium acetate, ammonium propionate, ammonium isopropylate, ammonium benzoate, ammonium phenylacetate, ammonium phthalate, ammonium isophthalate , ammonium terephthalate, ammonium phenylpropionate, ammonium 2-methylphenylacetate, ammonium 3-methylphenylacetate, ammonium 4-methyl hexanoate, ammonium 2-based benzoate, 3-ethylbenzene Ammonium formate, ammonium 4-ethylbenzoate.
- the synergist is sulfuric acid, sulfuric acid, 4, ammonium hydrogen sulfate, ammonium pyrophosphate, ammonium chloride or ammonium bromide.
- 1 ⁇ and may be hydrogen or a C1 to C6 alkyl group at the same time or at different times.
- M is Al, Mg, Ca, Zn, Sn or Fe.
- the flame retardant is aluminum hypophosphite, magnesium hypophosphite, calcium hypophosphite, iron hypophosphite, aluminum diethylphosphinate, magnesium diethylphosphinate, zinc diethyl linalate, diethyl Calcium phosphinate, iron diethylphosphinate, aluminum dimethylphosphinate, magnesium dimethylphosphinate, zinc dimethylphosphinate, calcium dimethylphosphinate, dimethyl Iron phosphonate, aluminum dipropyl phosphinate, aluminum dibutylphosphinate, aluminum dipentylphosphinate, aluminum bishexylphosphinate, aluminum decyl phosphinate, decyl propyl phosphine Aluminum acid, aluminum methyl phosphinate, aluminum ethyl propyl phosphinate, aluminum ethyl butyl phosphinate, aluminum monomethylphosphinate, aluminum monoethylphosphinate, aluminum
- the preparation method of the composite flame retardant comprises the following steps: respectively, the flame retardant, the synergist and/or the additive are weighed according to the design weight ratio, and then added to the mixer and uniformly mixed.
- the resin component in the flame retardant molding composition is a thermoplastic resin or a thermosetting resin.
- the thermoplastic/thermosetting resin may be composed of a single thermoplastic/thermosetting resin, or a plastic alloy composed of two or more thermoplastic resins or composed of two or more thermosetting resins.
- the present invention has the following beneficial effects:
- the composite flame retardant of the invention can greatly improve the flame retardant efficiency of the hypophosphite or alkyl phosphinate flame retardant by adding a suitable synergist, and greatly reduce the resistance of the hypophosphite or alkyl phosphinate.
- the amount of fuel used can greatly improve the flame retardant efficiency of the hypophosphite or alkyl phosphinate flame retardant by adding a suitable synergist, and greatly reduce the resistance of the hypophosphite or alkyl phosphinate. The amount of fuel used. detailed description
- hypophosphite used in the examples was purchased from Wuhan Dazhou Chemical Industry Co., Ltd.;
- Dialkyl phosphinate purchased from Clariant, Germany;
- Ammonium sulfate purchased from Yueyang Baoqing Chemical Co., Ltd.
- Ammonium chloride purchased from Zhuzhou Jianghai Environmental Protection Industry Co., Ltd.
- Ammonium bromide purchased from Suzhou Zhongda Chemical
- Ammonium pyrosulfate purchased from Beijing Hengye Zhongyuan Chemical Co., Ltd.;
- Ammonium aluminum sulfate purchased from Wuhan Jinnuo Chemical Co., Ltd.;
- Ammonium formate purchased from Shanghai Jincheng Chemical Co., Ltd.;
- Ammonium benzoate purchased from Shanghai Jincheng Chemical Co., Ltd.;
- Zinc Oxide Rubber Grade Zinc Oxide, Weifang Longda Zinc Industry Co., Ltd.;
- PC FN 1900, Japan's light
- PBT TH6100, Xinjiang Lanshan Weihe Polyester Co., Ltd.;
- PA YH800, Yueyang Stone 4 ⁇
- TPU 1185, Bayer Chemicals
- Epoxy resin E-55, Baling Petrochemical
- Extrusion processing performance judgment standard Whether the extruded strip has foaming, discoloration, surface roughness, etc. during the granulation process by the naked eye, and the extrusion is determined according to the foaming, discoloration and surface roughness of the extruded strand Processing performance.
- the extrusion processing performance is good; when the strip has little foaming, slight discoloration, and the surface is not rough, the extrusion processing performance is slightly decomposed; When the strands are less foamed, slightly discolored, and the surface is slightly roughened, but still acceptable, the extrusion processability is partially decomposed.
- Ammonium sulfate 80 - - 85 - - 50 - 50 Ammonium chloride - 80 - 70 50 - - - Ammonium benzoate - 85 - - - - - 50 -- Linear phenolic 5 - - - - - - - - - zinc oxide - - 5 - - - - - - - Application example
- a flame retardant PBT composition was prepared in the formulation listed in Table 4, which consisted of 75 parts of PBT and 25 parts of a composite flame retardant.
- the composite flame retardant was selected according to the type of Table 4, and the flame retardant property was tested. .
- the preparation method of the flame-retardant PBT composition is prepared in accordance with the preparation method of the existing flame-retardant PBT composition.
- a flame-retardant molding composition was prepared in the formulation listed in Table 5, the flame-retardant molding composition consisting of 80 parts of the resin composition and 20 parts of the composite flame retardant, and the resin and the composite flame retardant were selected according to the types of Table 5. And test its flame retardant properties.
- the preparation method of the flame-retardant molding composition is prepared by referring to a preparation method of a conventional flame-retardant molding composition prepared from various resins.
- the composite flame retardant of the present invention has a wide range of applicable systems and can be used for preparing a flame retardant thermoplastic molding composition or a flame retardant thermosetting molding composition.
- the above is only the embodiment of the present invention, and thus does not limit the scope of the patent of the present invention. Any equivalent structure or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied to other related technical fields, The same is included in the scope of patent protection of the present invention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Fireproofing Substances (AREA)
Abstract
本发明公开一种复合阻燃剂及其应用。所述复合阻燃剂包括如下按重量百分比计算的组分:阻燃剂15~99%;协效剂1~85%;其他添加剂0~25%;所述协效剂为至少含有一个NH4
+的铵盐;所述添加剂为成炭剂和/或稳定剂。本发明所述复合阻燃剂通过加入合适的协效剂,可以大幅提高次磷酸盐或烷基次膦酸盐阻燃剂的阻燃效率,大大减少次磷酸盐或烷基次膦酸盐阻燃剂的用量。
Description
说 明 书 一种复合阻燃剂及其应用
技术领域
本发明涉及聚合物阻燃领域, 特别涉及一种复合阻燃剂及其应用。 背景技术
现有的阻燃改性聚合物, 无论是热塑性树脂基体或者热固性树脂基体, 为了满足无卤化 的要求, 需要选择含磷、 氮或其复配体系。 现在使用最普遍的含磷阻燃剂及其组合物主要有 微胶嚢化红磷、 磷酸酯、 以聚磷酸铵为主体的膨胀型阻燃体系等。 这些阻燃体系, 可以对应 的满足某一些特定聚合物的阻燃要求, 并且, 这些阻燃体系, 都是通过固相机理来实现阻燃。 与传统溴-锑复配阻燃体系比较, 固相阻燃机理的含磷阻燃剂及其复配阻燃体系, 具有阻燃效 率低、 适用范围有选择性等缺点。
次膦酸盐是一类可以作用于气相的含磷阻燃剂, 因而, 其适用的树脂基体范围和溴 -锑复 配阻燃体系相当, 但同样存在阻燃效率低的问题, 不复配协效剂时, 需添加 20-30 重量%才 可以达到 UL 94 V-0 级阻燃。 专利 CN 1660857 B 和 CN 100348653 C公开了一种垸基次膦 酸盐复配含胺基环状结构协效剂的组合物, 尽管这些协效剂能起到一定程度的协效作用, 但 是其协效程度有限, 并且因此次膦酸盐的用量依然较高, 大大增大了组合物的成本。 发明内容
本发明的发明目的, 是为了克服现有技术的不足, 提供一种新的复合阻燃剂, 该复合阻 燃剂通过对协效剂的合理选择, 可以大幅提高阻燃剂的阻燃效率。
本发明的另一目的, 在于提供所述复合阻燃剂的应用。
本发明的另一目的, 在于提供一种含有所述复合阻燃剂的阻燃模塑组合物。
本发明的上述 3的, 通过如下技术方案予以实现:
一种复合阻燃剂, 所述复合阻燃剂包括如下按重量百分比计算的组分:
阻燃剂 15~99%;
协效剂 1~85%;
添加剂 0~25%;
( I )
其中, 和 可同时或不同时为氢或垸基, M为 Mg、 Ca、 Al、 Sb、 Sn、 Ge、 Ti、 Fe、 Zr、 Zn、 Ce、 Bi、 Sr、 Mn、 Li、 Na、 K和 /或是质子化氮减, 其中 m是 1、 2、 3或 4; 所述协效剂为至少含有一个 N +的铵盐;
所述添加剂为成炭剂和 /或稳定剂。
一种复合阻燃剂, 所述复合阻燃剂由如下按重量百分比计算的组分组成:
阻燃剂 15-99%;
协效剂 1-85%;
( I )
其中, 和 可同时或不同时为氢或: ¾基, M为 Mg、 Ca、 Al、 Sb、 Sn、 Ge、 Ti、 Fe、 Zr、 Zn、 Ce、 Bi、 Sr、 Mn、 Li、 Na、 K和/或是质子化氮碱, 其中 m是 1、 2、 3或 4; 所述协效剂为至少含有一个 N +的铵盐。
其中, 所述成炭剂为本领域常用的成炭剂, 其作用是帮助基体树脂在燃烧过程中形成稳 定、 坚固的炭居, 从而达到隔氧隔质的阻燃作用, 所述成炭剂选自季戊四醇、 季戊四醇酯、 线性酚醛、 纤维素等或这些物质的混合物。
其中, 所述稳定剂为为本领域常用的稳定剂, 其作用是改善次膦(磷) 酸盐阻燃剂及其 协效剂组成的复合阻燃剂在加工和成型过程中的稳定性, 所述稳定剂选自氧化镁、 氧化钙、 氧化铝、 氧化锌、 氧化锰、 氧化锡、 硼酸锌、 锡酸锌、 羟基锡酸锌等或这些物质的混合物。
其中, 所述复合阻燃剂中, 阻燃剂与协效剂的重量百分比为:
阻燃剂 25~50%;
协效剂 50~75<¾。
其中, 所述协效剂的热分解温度在 180°C以上。
其中, 所述协效剂的负离子为 S04 2—, HS04 , S207 2-、 Br―、 Cr、 C1~C3的脂肪族羧酸根 或 C7~C10的芳香族羧酸根。
其中, 所述协效剂为硫酸铵、 硫酸铵铝、 硫酸按镁、 硫酸铵锌、 硫酸铵钙、 硫酸铵铁、
硫酸氢铵、 焦硫酸铵、 氯化铵、 溴化铵、 甲酸铵、 乙酸铵、 丙酸铵、 异丙酸铵、 苯甲酸铵、 苯乙酸铵、 邻苯二甲酸铵、 间苯二甲酸銨、 对苯二曱酸铵、 苯丙酸铵、 2-甲基苯乙酸铵、 3- 甲基苯乙酸铵、 4-甲基笨己酸铵、 2- 基苯甲酸铵、 3-乙基苯甲酸铵、 4-乙基苯甲酸铵。
其中, 所述协效剂为硫酸按、 硫酸楼 4§、 硫酸氢铵、 焦硫酸铵、 氯化铵或溴化铵。
其中, 所述阻燃剂中, 1^和 可同时或不同时为氢或 C1~C6的烷基。
其中, 所述阻燃剂中, M为 Al、 Mg、 Ca、 Zn、 Sn或 Fe。
其中, 所述阻燃剂为次磷酸铝、 次磷酸镁、 次磷酸钙、 次磷酸铁、 二乙基次膦酸铝、 二 乙基次膦酸镁、 二乙基次麟酸锌、 二乙基次膦酸钙、 二乙基次膦酸铁、 二甲基次膦酸铝、 二 甲基次膦酸镁、 二甲基次膦酸锌、 二甲基次膦酸钙、 二甲基次膦酸铁、 二丙基次膦酸铝、 二 丁基次膦酸鋁、 二戊基次膦酸铝、 二己基次膦酸铝、 曱基乙基次膦酸铝、 曱基丙基次膦酸铝、 甲基丁基次膦酸铝、 乙基丙基次膦酸铝、 乙基丁基次膦酸铝、 单甲基次膦酸铝、 单乙基次膦 酸铝、 单丙基次膦酸铝、 单丁基次膦酸铝、 单戊基次膦酸铝、 单己基次膦酸铝、 单甲基次膦 酸镁、 单乙基次膦酸镁、 单丙基次膦酸镁、 单丁基次膦酸镁、 单甲基次膦酸钙、 单乙基次膦 酸钙、 单丙基次膦酸钙、 单丁基次膦酸钙。
所述复合阻燃剂的制备方法, 包括如下步骤: 按照设计重量比例分别称取阻燃剂、 协效 剂和/或添加剂, 再加入混合器中混合均匀。
所述复合阻燃剂在制备阻燃模塑组合物中的应用。
所述阻燃模塑组合物中的树脂组分为热塑性树脂或热固性树脂。 所述的热塑性 /热固性树 脂可以是由单独一种热塑性 /热固性树脂组成, 或者是由两种以上热塑性树脂组成或由两种以 上热固性树脂组成的塑料合金。
与现有技术相比, 本发明具有如下有益效果:
本发明所述复合阻燃剂通过加入合适的协效剂, 可以大幅提高次磷酸盐或烷基次膦酸盐 阻燃剂的阻燃效率, 大大减少次磷酸盐或烷基次膦酸盐阻燃剂的用量。 具体实施方式
下面结合一些具体实施方式对本发明复合阻燃剂、 制备方法及其应用做进一步描述。 具 体实施例为进一步详细说明本发明, 非限定本发明的保护范围。
本发明的实施例采用以下原料:
实施例中所用到的次磷酸盐, 购自武汉大洲化工;
二烷基次膦酸盐, 购自德国科莱恩;
硫酸铵, 购自岳阳市宝庆化工有限公司;
氯化铵, 购自株洲江海环保实业有限公司;
溴化铵, 购自苏州市中达化工;
焦硫酸铵 , 购自北京恒业中远化工有限公司;
硫酸铵铝, 购自武汉金诺化工有限公司;
甲酸銨, 购自上海金成化工有限公司;
苯曱酸铵, 购自上海金成化工有限公司;
线性酚 PF-204, 桓台县永汇化工有限公司;
氧化锌: 橡胶级氧化锌, 潍坊龙达锌业有限公司;
PC: FN 1900, 日本出光;
PBT: TH6100, 新疆蓝山屯河聚酯有限公司;
PA: YH800, 岳阳石 4乜;
TPU: 1185, 拜耳化工;
环氧树脂: E-55, 巴陵石化;
合金: PC/ABS 合金, ABS, 3904, 上海高桥石化;
组合物垂直燃烧等级判定标准: UL-94;
挤出加工性能判定标准: 通过肉眼观 出造粒过程中, 挤出的料条是否有发泡、 变色、 表面粗糙等情况出现, 根据挤出料条发泡、 变色、 表面粗糙程度判定挤出加工性能。 料条不 出现发泡、 变色、 表面粗糙等情况时, 挤出加工性能为好; 料条出现极少发泡、 轻微变色、 表面不变粗槌等情况时, 挤出加工性能为轻微分解; 料条出现较少发泡、 轻微变色、 表面稍 变粗糙等情况但仍可接受时, 挤出加工性能为部分分解。
以下以具体实施例的方式加以说明, 所述原料均为重量份。 制备实施例 按表 1~3记载的重量份分别称取阻燃剂、协效剂和 /或添加剂,再加入混合器中混合均匀。, 制备实施例 1~18及对比例 1~6的复合阻燃剂。 表 1
实施例 实施例 实施例 实施例 实施例 实施例 实施例 实施例 实施例
1 2 3 4 5 6 7 8 9 二乙基次 15 25 15 15 50 50 50 50 99
雜 石克酸按 85 - - - - - - - 1 溴化铵 - 75 - - 50 - - - - 甲酸铵 - - 85 - - - - - - 苯甲酸铵 - - - 85 - - 50 - - 焦硫酸铵 - - - - - 50 - - - 硫酸铵铝 - - - - - - - 50 - 表 2
实施例 实施例 实施例 实施例 实施例 实施例 实施例 实施例 实施例
10 11 12 13 14 15 16 17 18 二乙基次
15 - - - 30 - - 50 - 膦酸铝
次磷酸铝 - 15 - - - 50 - - - 二乙基次
- - 15 - - - - - 50 膦酸锌
二丁基次
- - - 15 - - 50 - - 膦酸铝
硫酸銨 80 - - 85 - - 50 - 50 氯化铵 - - 80 - 70 50 - - - 苯甲酸銨 - 85 - - - - - 50 --
线性酚醛 5 - - - - - - - - 氧化锌 - - 5 - - - - - - 应用实施例
以表 4所列配方制备阻燃 PBT组合物, 所述阻燃 PBT组合物由 75份 PBT和 25份复合 阻燃剂组成, 复合阻燃剂按表 4的种类选择, 并检测其阻燃性能。 所述阻燃 PBT组合物的制 备方法参照现有的阻燃 PBT组合物的制备方法制备。
表 4
从应用对比例 1~6的结果可以看出, 当采用现有的 MCA/MPP复配得到的复合阻燃剂的 阻燃效果不佳, 从应用对比例 5和 6还看出, 当复合阻燃剂中, 阻燃剂的添加量太低时, 也
不能达到理想的阻燃效果。 以表 5所列配方制备阻燃模塑组合物, 所述阻燃模塑組合物由 80份树脂组合物和 20份 复合阻燃剂组成, 树脂及复合阻燃剂按表 5的种类选择, 并检测其阻燃性能。 所述阻燃模塑 组合物的制备方法参照现有的各种树脂制备成阻燃模塑组合物的制备方法制备。
表 5
从应用实施例 1~24可以看出,本发明所述的复合阻燃剂的适用体系广泛,可以用于制备 阻燃热塑性模塑组合物或阻燃热固性模塑组合物。 以上所述仅为本发明的实施例, 并非因此限制本发明的专利范围, 凡是利用本发明说明 书内容所作的等效结构或等效流程变换, 或直接或间接运用在其他相关的技术领域, 均同理 包括在本发明的专利保护范围内。
Claims
1、 一种复合阻燃剂, 其特征在于, 所述复合阻燃剂包括如下按重量百分比计算的组分: 阻燃剂 15~99%;
协效剂 1~85%;
添加剂 0~25%;
( I )
其中, 和 可同时或不同时为氢或 基, M为 Mg、 Ca、 Al、 Sb、 Sn、 Ge、 Ti、 Fe、 Zr、 Zn、 Ce、 Bi、 Sr、 Mn、 Li、 Na、 K和 /或是廣子化氮减, 其中 m是 1、 2、 3或 4;
所述协效剂为至少含有一个 N¾+的铵盐;
所述添加剂为成炭剂和 /或稳定剂。
2、一种复合阻燃剂,其特征在于,所述复合阻燃剂由如下按重量百分比计算的组分組成: 阻燃剂 15~99%;
协效剂 1~85%;
( I )
其中, 和 可同时或不同时为氢或垸基, M为 Mg、 Ca、 Al、 Sb、 Sn、 Ge、 Ti、 Fe、 Zr、 Zn、 Ce、 Bi、 Sr、 Mn、 Li、 Na、 K和/或是庸子化氮碱, 其中 m是 1、 2、 3或 4;
所述协效剂为至少含有一个 N +的铵盐。
3、 如权利要求 1或 2所述复合阻燃剂, 其特征在于, 所述复合阻燃剂中, 阻燃剂与协效 剂的重量百分比为:
阻燃剂 25~50%;
协效剂 50~75%。
4、 如权利要求 1或 2所述复合阻燃剂, 其特征在于, 所述协效剂的热分解温度在 180 °C 以上。
5、如权利要求 1或 2所述复合阻燃剂 ,其特征在于,所述协效剂的负离子为 S04 2—、 HS04、 S207 2—、 Br -、 Cl—、 C1 C3的脂肪族羧酸根或 C7~C10的芳香族羧酸根。
6、 如权利要求 1或 2所述复合阻燃剂, 其特征在于, 所述协效剂为硫酸铵、 硫酸铵铝、 硫酸铵镁、 硫酸铵锌、 硫酸铵钙、 硫酸铵铁、 硫酸氢铵、 焦硫酸铵、 氯化铵、 溴化铵、 甲酸 銨、 乙酸銨、 丙酸銨、 异丙酸铵、 苯甲酸銨、 苯乙酸銨、 邻苯二甲酸銨、 间苯二甲酸銨、 对 笨二甲酸铵、 笨丙酸铵、 2-曱基笨乙酸铵、 3-曱基笨乙酸铵、 4-甲基苯乙酸铵、 2-乙基笨甲酸 铵、 3-乙基苯甲酸铵和 /或 4-乙基苯甲 S铵。
7、 如权利要求 1或 2所述复合阻燃剂, 其特征在于, 所述阻燃剂中, 和 可同时或 不同时为氢或 C1~C6的烷基。
8、如权利要求 1或 2所述复合阻燃剂, 其特征在于,所述阻燃剂为次磷酸铝、次磷酸镁、 次磷酸钙、 次磷酸铁、 二乙基次膦酸铝、 二乙基次膦酸镁、 二乙基次膦酸锌、 二乙基次膦酸 钙、 二乙基次膦酸铁、 二甲基次膦酸铝、 二甲基次膦酸 4美、 二甲基次膦酸辞、 二甲基次膦酸 钙、 二甲基次膦酸铁、 二丙基次膦酸铝、 二丁基次膦酸铝、 二戊基次膦酸铝、 二己基次膦酸 铝、 甲基乙基次膦酸铝、 甲基丙基次膦酸铝、 甲基丁基次膦酸铝、 乙基丙基次膦酸铝、 乙基 丁基次膦酸铝、 单曱基次膦酸铝、 单乙基次膦酸铝、 单丙基次膦酸铝、 单丁基次膦酸铝、 单 戊基次膦酸铝、 单己基次膦酸铝、 单甲基次膦酸镁、 单乙基次膦酸镁、 单丙基次膦酸镁、 单 丁基次膦酸镁、 单甲基次膦酸钙、 单乙基次膦酸钙、 单丙基次膦酸钙和 /或单丁基次膦酸钙。
9、 权利要求 1~8任意一项权利要求所述复合阻燃剂在制备阻燃模塑组合物中的应用。
10、 如权利要求 9所述应用, 其特征在于, 所述阻燃模塑组合物中的树脂组分为热塑性 树脂或热固性树脂。
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