CN104981473A - 作为阻燃材料的吖嗪金属磷酸盐 - Google Patents
作为阻燃材料的吖嗪金属磷酸盐 Download PDFInfo
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- CN104981473A CN104981473A CN201280077344.1A CN201280077344A CN104981473A CN 104981473 A CN104981473 A CN 104981473A CN 201280077344 A CN201280077344 A CN 201280077344A CN 104981473 A CN104981473 A CN 104981473A
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- Prior art keywords
- metal
- formula
- melamine
- zinc
- mixture
- Prior art date
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003063 flame retardant Substances 0.000 title claims abstract description 32
- 229910001463 metal phosphate Inorganic materials 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 24
- 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 abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 99
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 58
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 46
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 40
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims description 64
- -1 hydrocalumite Chemical compound 0.000 claims description 58
- 239000011777 magnesium Substances 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 229910052782 aluminium Inorganic materials 0.000 claims description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 235000011007 phosphoric acid Nutrition 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- WMXBGWKUWMQWAL-UHFFFAOYSA-H trizinc 1,3,5-triazine-2,4,6-triamine diphosphate Chemical compound N1=C(N)N=C(N)N=C1N.P(=O)([O-])([O-])[O-].[Zn+2].P(=O)([O-])([O-])[O-].[Zn+2].[Zn+2] WMXBGWKUWMQWAL-UHFFFAOYSA-H 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920000388 Polyphosphate Polymers 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 239000001205 polyphosphate Substances 0.000 claims description 10
- 235000011176 polyphosphates Nutrition 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 9
- 150000004692 metal hydroxides Chemical class 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 9
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 8
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000004800 polyvinyl chloride Substances 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 claims description 7
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 claims description 7
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 7
- 238000005496 tempering Methods 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229940071182 stannate Drugs 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- CYQFCXCEBYINGO-IAGOWNOFSA-N delta1-THC Chemical group C1=C(C)CC[C@H]2C(C)(C)OC3=CC(CCCCC)=CC(O)=C3[C@@H]21 CYQFCXCEBYINGO-IAGOWNOFSA-N 0.000 claims description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920003987 resole Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000005402 stannate group Chemical group 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 239000011155 wood-plastic composite Substances 0.000 claims description 4
- BISHACNKZIBDFM-UHFFFAOYSA-N 5-amino-1h-pyrimidine-2,4-dione Chemical compound NC1=CNC(=O)NC1=O BISHACNKZIBDFM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 239000004640 Melamine resin Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920001587 Wood-plastic composite Polymers 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- JHXVRRJXCDAINK-UHFFFAOYSA-N NC(=O)N.N#CC#N Chemical compound NC(=O)N.N#CC#N JHXVRRJXCDAINK-UHFFFAOYSA-N 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 229910052599 brucite Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 claims description 2
- CGNKSELPNJJTSM-UHFFFAOYSA-N phenylphosphonous acid Chemical class OP(O)C1=CC=CC=C1 CGNKSELPNJJTSM-UHFFFAOYSA-N 0.000 claims description 2
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical group NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 3
- 239000010457 zeolite Substances 0.000 claims 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims 1
- VFGRNTYELNYSKJ-UHFFFAOYSA-N 6-amino-1,3-dimethylpyrimidine-2,4-dione Chemical compound CN1C(N)=CC(=O)N(C)C1=O VFGRNTYELNYSKJ-UHFFFAOYSA-N 0.000 claims 1
- NCHZSYFYQPCAMA-UHFFFAOYSA-N C1(=CC=CC=C1)P.N1=C(N)N=C(N)N=C1N Chemical compound C1(=CC=CC=C1)P.N1=C(N)N=C(N)N=C1N NCHZSYFYQPCAMA-UHFFFAOYSA-N 0.000 claims 1
- 208000035389 Ring chromosome 6 syndrome Diseases 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- OMUGFZNEOIWQOD-UHFFFAOYSA-N boric acid;zinc Chemical compound [Zn].OB(O)O OMUGFZNEOIWQOD-UHFFFAOYSA-N 0.000 claims 1
- 239000000123 paper Substances 0.000 claims 1
- 229940059574 pentaerithrityl Drugs 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 229920000580 poly(melamine) Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 25
- 239000004411 aluminium Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920006324 polyoxymethylene Polymers 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229930040373 Paraformaldehyde Natural products 0.000 description 5
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000005340 bisphosphate group Chemical group 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920006380 polyphenylene oxide Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 239000004794 expanded polystyrene Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- 229920002689 polyvinyl acetate Polymers 0.000 description 1
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- 238000007363 ring formation reaction Methods 0.000 description 1
- 102220157709 rs144942998 Human genes 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- XGFPOHQJFNFBKA-UHFFFAOYSA-B tetraaluminum;phosphonato phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O XGFPOHQJFNFBKA-UHFFFAOYSA-B 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- GUXKHZAUXJHDDU-UHFFFAOYSA-H trizinc guanidine diphosphate Chemical compound P(=O)([O-])([O-])[O-].[Zn+2].NC(=N)N.P(=O)([O-])([O-])[O-].[Zn+2].[Zn+2] GUXKHZAUXJHDDU-UHFFFAOYSA-H 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 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
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Abstract
本发明涉及吖嗪金属磷酸盐、含有其的组合物、其制备方法以及其作为阻燃剂的应用。典型代表物是(A-H)(+)[MtPO4](-)·2H2O和(Mel-H)(+)[AlP2O7](-)(其中A=蜜胺或胍,Mel=蜜胺以及Mt=Mg或Zn)。
Description
本发明涉及吖嗪金属磷酸盐、含有吖嗪金属磷酸盐的组合物、其制备方法以及其作为膨胀型含金属阻燃剂的应用。典型代表物是(A-H)(+)[MtPO4](-)·2H2O和(Mel-H)(+)[AIP2O7](-)(其中A=蜜胺或胍,Mel=蜜胺而Mt=Mg或Zn)。
发明背景及技术目标
已知膨胀型材料具有阻燃作用,这是由于在受到强热时,例如在火焰作用下,该类材料发泡形成不易燃烧的绝缘层,并在此情况下抑制熔融的可能燃烧的材料的滴落。
由EP 2183314B1已知膨胀型含金属蜜胺磷酸盐。然而这些磷酸盐具有缺少热稳定性的缺点。因此,例如其中描述的铝盐[(Mel-H)]3 (+)[Al(HPO4)3](3-)在280-300℃的热处理下生成1摩尔的蜜胺和2摩尔的水,形成[(Mel-H)]2 (+)[AlP3O10](2-)。类似的情况适用于[(Mel-H)]2 (+)[MgP2O7](2-)。此外,其中描述的产物仅可以以多步方法获得。这些化合物也都具有不利的模量(蜜胺/金属比例)3或2。
同样已知胺金属磷酸盐,如例如Inorg.Chem.,2005,44,658-665和Crystal Growth and Design(晶体生长与设计),2002,2(6),665-673中所述的,但由于其烷基胺含量,其热稳定性不令人满意,并因此不适于作为阻燃剂。
Inorg.Chem.,2001,40,895-899中描述了亚磷酸氰基胍(双氰胺)锌(cyanoguanidine(dicyandiamide)zinc phosphite),其中模量(氰基胍/锌比例)是1。该出版物中未出现磷酸胍锌(guanidine zinc phosphate)。亚磷酸氨基胍锌在Intern.J.of Inorg.Mater.,2001,3,1033-1038中有描述,其中模量(氨基胍/锌比例)是2:3。该合成同样是水热法进行的。该文献中未出现磷酸氨基胍锌。JCS Dalton Trans.2001,2459-2461中公开了亚磷酸胍锌,其中模量(胍/锌比例)是2。未描述模量为1的磷酸胍锌。
Chem.Mater.,1997,9,1837-1846中也公开了磷酸胍锌。然而,这些是水热法制备的,且还需要长的反应时间。另外,这些磷酸盐的模量(胍/锌比例)是0.5、2和3,并因此与本发明的模量无例外地都为1的吖嗪金属盐明显不同。
无金属膨胀型蜜胺磷酸盐同样是已知的。因此,例如在WO 00/02869、EP 1789475、WO 97/44377和EP 0974588中已描述了许多制备蜜胺多磷酸盐的方法。然而,根据这些方法制备耗费时间,且由于反应温度高(340-400℃),这些方法与非常高的能耗有关。另外,使用尿素作为其它添加剂。
已上市的基于蜜胺多磷酸盐的制剂在EP1537173B1中有描述。
另外,已有基于蜜胺例如基于3,9-二氢-2,4,8,10-四氧杂-3,9-二磷杂螺环[5,5]-十一烷3,9-二氧化物的蜜胺盐(MAP)和基于双(1-氧代-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷-4-基甲醇)磷酸盐的蜜胺盐(melabis)的膨胀型阻燃系统。
“Fire Retardancy of Polymeric Materials(聚合材料的阻燃性)”,第二版(2010),编辑:C.Wilkie,A.B.Morgan,CRS出版社,FL,USA的第129-162页第6章中描述了其它膨胀型系统。
“Flame Retardants for Plastics and Textiles(塑料和织物的阻燃剂)”,(2009),作者:E.Weil和S.Levchik,Hanser Verlag,Munich的第85-119页第5和6章中详细描述了聚酰胺(PA)和热塑性聚酯(PET/PBT)的阻燃剂。
然而,现有技术中描述的阻燃剂有以下缺点,其阻燃效果常常不令人满意,不可用于塑料或者仅可在一定条件下用于塑料,特别是电气电子领域的热塑性塑料和弹性体。另外,一些含磷阻燃剂影响导电性,且因此例如可能负面地改变电气元件中具有阻燃剂的热塑性塑料的特性。
尽管现有技术已知大量出版物,仍持续地需要具有优化的特性和改善的环境相容性的阻燃剂。
因此本发明的一个目的是提供更有效的阻燃剂,与现有技术中已知的阻燃剂相比,其尤其具有更好的一些次级特性,譬如较低的酸性(pH值较高),从而腐蚀性较低以及导电性较低。
具体而言,本发明的一个目的是提供具有高度固有(热)稳定性且在掺入阻燃剂之后赋予聚合物优良机械特性的阻燃剂。
因此本发明的一个目的是提供这种阻燃剂。这些也应是容易得到的。发明详述
吖嗪金属磷酸盐
在本发明中,由于提供通式[I]的吖嗪金属磷酸盐令人惊喜地实现了该目的:
[(A-H)(+)[Mm+(PO4)x (3-)(P2O7)y (4-)](-)·pH2O]z [I]
其中(A-H)(+)选自式(I)的蜜胺-H、式(II)的蜜白胺-H、R是甲基或苯基的式(III)的胍胺以及R是氢或胺的式(IV)的(氨基)胍-H。
M是金属或金属氧化物,选自Cu、Mg、Ca、Zn、Mn、Fe、Co、Ni、TiO、ZrO、VO、B、Si、Al、Sb、La、Ti、Zr、Ce、Bi和Sn。
m=2或3,
x和y彼此独立,各是0或1。
P是0-4的整数,以及
Z是>5的整数,
其中1+m=3x+4y。
这些化合物优选由非水热途径制备,且模量(吖嗪/金属比例)是1。
本发明的吖嗪金属磷酸盐典型地是(配位)聚合物,且如蜜胺磷酸锌和蜜胺磷酸铝的实施例所示,可用交替(磷酸盐)PO4和Zn(OP)4四面体或(二磷酸盐)P2O7和Al(OP)4四面体(结构Ia和Ib)来配制:
优选的化合物是,例如:
(A-H)(+)[MtPO4](-)·pH2O,其中A是蜜胺、胍或氨基胍,Mt是Mg或Zn,以及p是0-4;
(A-H)(+)[AlP2O7](-),其中A是蜜胺、胍或氨基胍;
(A-H)(+)[MtPO4](-)·pH2O,其中A是蜜白胺、乙酰胍胺或苯并胍胺,Mt是Mg或Zn,以及p是0-4;
(A-H)(+)[AlP2O7](-)·pH2O,其中A是蜜白胺、乙酰胍胺或苯并胍胺,以及p是0-4;
(A-H)(+)[MtPO4](-)·pH2O,其中A是蜜胺、胍或氨基胍,Mt是Sn、TiO或ZrO,以及p是0-4;
(A-H)(+)[AlP2O7](-)·pH2O,其中A是蜜胺、胍或氨基胍,Mt是Ce、Sb或Bi,以及p是0-4;
事实令人惊喜地表明,本发明的吖嗪金属磷酸盐比阻燃剂中使用的常规化合物更热稳定。另外,其可以简单地以单步法制备。其制备方法节能且经济,因为无需单独制备金属磷酸二氢盐。这是特别有利的,因为在大部分情况中,金属磷酸二氢盐仅是热时储存稳定的,且在室温下一段时间后,倾向于形成沉淀。然而,这些沉淀很难再重新溶解。
含吖嗪金属磷酸盐的组合物
还意外地发现了,可通过提供已加入增效剂或共组分的组合物来进一步优化吖嗪金属磷酸盐在阻燃效果和膨胀行为方面的作用性。这些其它组分可以是含金属的或无金属的。
因此本发明还提供一种组合物,其包含上述吖嗪金属磷酸盐(组分(i))、与组分(i)不同的其它含金属组分(ii)以及可选的无金属组分(iii)。
所述其它含金属组分(ii)可包含特别是金属氢氧化物、金属磷酸盐、金属焦磷酸盐、水滑石、水铝钙石、阳离子或阴离子改性的有机粘土、锡酸盐或钼酸盐、金属硼酸盐或式(V)或(VI)的金属亚膦酸盐,或式(VII)的金属膦酸盐,
其中R1和R2彼此独立,各是氢、直链或支链C1-C6-烷基或苯基;Mt1是Ca、Mg、Zn或Al;m=2或3;以及Mt是Ca、Mg、Zn、Al、Sn、Zr、TiO、ZrO、Ce、MoO、WO2、VO、Mn、Bi或Sb,D=O或S,以及n是2或3。
水滑石和水铝钙石具有例如组成Mg6Al2(OH)16CO3和Ca4Al2(OH)12CO3。对本领域技术人员来说,有机粘土是基于阳离子交换的亲有机物质改性的粘土矿物质(主要是蒙脱石),例如三乙醇牛脂铵蒙脱石和三乙醇牛脂铵水辉石,如Dr.G.Beyer;Konf.Fire Resistance in Plastics,2007中所述。阴离子有机粘土是基于与碱金属松脂酸盐、不饱和与饱和脂肪酸盐以及长链烷基取代的磺酸盐和硫酸盐阴离子交换的亲有机物质改性水滑石。
金属氧化物优选是三氧化二锑、四氧化二锑、五氧化二锑或氧化锌。
对于金属磷酸盐,优选的是金属焦磷酸盐。特别优选的是焦磷酸铝和焦磷酸锌、三磷酸锌和三磷酸铝、偏磷酸铝和偏磷酸锌,以及正磷酸铝和正磷酸锌。
在阳离子或阴离子改性的有机粘土中,特别优选用烷基硫酸盐或脂肪酸羧酸盐改性的水滑石或用长链季铵改性的粘土矿物质。
在金属氢氧化物的情况中,优选氢氧化镁(水镁石)、氢氧化铝(ATH,三水铝矿)或水合氧化铝(勃姆石)以及水菱镁矿和水锌矿。除三水铝矿和勃姆石之外,还提及氢氧化铝的其它变体即三羟铝石(bayerite)、三斜水铝石(nordstrandite)和水铝石(diaspore)组成。
此外,优选的钼酸盐或锡酸盐是七钼酸铵、八钼酸铵、锡酸锌或羟基锡酸锌或其混合物。这些盐也可作为降烟剂,并因此在本发明的阻燃剂中具有特别有利的性质。
来自金属硼酸盐类的优选的是碱金属硼酸盐、碱土金属硼酸盐或硼酸锌。还提到的有硼酸铝、硼酸钡、硼酸钙、硼酸镁、硼酸锰、硼酸蜜胺、硼酸钾、硼磷酸锌或其混合物。
金属亚膦酸盐是优选的盐,其中Mt1选自Ca、Mg、Zn和Al。优选的金属亚膦酸盐为苯基亚膦酸盐、二乙基(甲基,乙基)亚膦酸盐,特别是与上述金属结合的那些。
次磷酸盐中,Mg、Ca、Zn和Al盐是特别优选的。
优选的金属亚膦酸盐(VI)和金属膦酸盐(VII)是Mt选自Ca、Mg、Zn和Al的盐。特别优选的是使用在不使用碱金属氢氧化物的情况下,在水中由6H-二苄基[c,e][1,2]氧磷杂环6-氧化物(6H-dibenz[c,e][1,2]oxaphosphorin 6-oxide)[CAS No.:35948-25-5)制备的金属亚膦酸盐(VI)。还特别优选使用例如通过前体(VI)的热环化获得的金属膦酸盐(VII)。非常特别优选的是膦酸锌或膦酸铵和硫代膦酸盐(VII)。优选地,由(硫代)膦酸制备(硫代)膦酸盐(CAS No.:36240-31-0和CASNo.:62839-09-2)。所有磷前体作为商业产品可得。
所述无金属(共)组分(本发明的组合物的组分(iii))具体包含WO 2010/063623中所述的红磷、低聚磷酸酯、低聚膦酸酯、环状膦酸酯、硫代焦磷酸酯、蜜胺正磷酸盐或蜜胺焦磷酸盐、二蜜胺磷酸盐、蜜白胺(多磷酸盐)、蜜勒胺、多磷酸铵、蜜胺苯基磷酸盐及其单酯盐,WO 2010/057851中所述的蜜胺苯基亚膦酸盐,WO 2009/034023中所述的羟基烷基氧化膦,四羟甲基季鏻盐和磷杂环戊烷(氧化物)或磷杂环戊二烯衍生物,以及哌嗪作为桥结构(member)的双磷酰胺酯(bisphosphorramidate)或亚膦酸酯,NOR-HALS化合物类(非碱性氨基醚受阻胺光稳定剂)及其混合物。
对于其它额外组分,优选蜜胺多磷酸盐、双蜜胺二磷酸锌、双蜜胺二磷酸镁或双蜜胺三磷酸铝。
低聚磷酸酯中,优选式(VIII)或式(IX)的磷酸酯,
其中,每个R独立地是氢、C1-C4-烷基或羟基,n=1-3,以及o=1-10。特别优选的是Rn=H且间苯二酚或对苯二酚作为桥结构的组成以及Rn=H且双酚A或双酚F作为桥结构的组成的低聚物。
优选式(X)的低聚膦酸酯,
其中R3是甲基或苯基,x=1-20,在每种情况中,R独立地是氢、C1-C4-烷基或羟基,n=1-3,以及o是1-10。
特别优选的是Rn=H且间苯二酚或对苯二酚作为桥构件的组成的低聚物。
此外,优选式(XI)的环状膦酸酯:
其中R3是甲基或苯基,R是氢、C1-C4-烷基或羟基,以及y是0-2。
特别优选双[(5-乙基-2-甲基-1,3,2-二氧磷杂环己烷-5-基)甲基]甲基膦酸酯P,P’-二氧化物(bis[(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)methyl]methylphosphonate P,P’-dioxide)。
还优选式(XII)的硫代焦磷酸酯
其中,每个R1和R2独立地是氢或C1-C4-烷基。
特别优选2,2’-氧代双[5,5-二甲基-1,3,2-二氧磷杂环己烷]2,2’-二硫化物(2,2’-oxybis[5,5-dimethyl-1,3,2-dioxaphosphorinan]2,2’-disulfide)。
羟烷基膦氧化物中,优选异丁基双羟甲基膦氧化物和其与环氧树脂的组合,如WO-A 2009/034023中所述。
四羟烷基季鏻盐中,特别优选四羟甲基季鏻盐。
磷杂环戊烷或磷杂环戊二烯衍生物中,特别优选EP 1024166中所述的二氢磷杂环戊二烯(氧化物)衍生物和磷杂环戊烷(氧化物)衍生物及其盐。
双磷酰胺酯中,特别优选哌嗪作为桥结构的双-二-邻甲苄基酯。
同样特别优选的是亚膦酸酯如下式示出的苯单苯基酯(benzenemonophenyl ester)衍生物或9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(6H-二苯并(c,e)(1,2)-氧磷杂己环-6-酮)衍生物:
X=(CH2)y,其中y=2-18。
其中,R是C1-C4-烷基,n是1-6,以及x是1-3。特别优选的是如下所示的式(XIII)、(XIV)或(XV)的化合物。
双-9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(6H-二苯并(c,e)(1,2)-氧磷杂己环6-氧化物)化合物(式XV)和10-苄基-9-氧杂-10-磷杂菲-10-氧化物,CAS No.:113504-81-7。这些化合物的制备方法在Russ.J.Org.Chem.2004,40(12),1831-35中有描述。适用于本发明的目的的其它9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(6H-二苯并(c,e)(1,2)-氧磷杂己环6-氧化物)衍生物在US 8101678 B2和US 8236881 B2中有描述。
也可以使用二氢氧杂磷杂蒽氧化物(酮)代替9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(6H-二苯并(c,e)(1,2)-氧磷杂己环-6-氧化物)。WO-A 2008/119693中可找到概述。
NOR-HALS化合物中,优选以下化合物:
其中R’=CH3、n-C4H9或c-C6H11,
其中R’=CH3、n-C4H9或c-C6H11,
其中R’=CH3、n-C4H9或c-C6H11,
其中R’=CH3、n-C4H9或c-C6H11,
其中R’=CH3、n-C4H9或c-C6H11。
另外,同样优选的是多元醇、氨基尿嘧啶、POSS化合物、三羟乙基异氰尿酸酯、氰脲酸蜜胺酯、可膨胀石墨或其混合物。POSS化合物(多面体齐聚倍半硅氧烷)和其衍生物在POLYMER,vol.46,pp.7855-7866中有更详细的描述。此处特别优选基于甲基硅氧烷的POSS衍生物。
此外,具有哌嗪-1,4-二基桥结构和吗啉-1-基端基的三羟乙基异氰尿酸酯聚对苯二甲酸二醇酯(trishydroxyethyl isocyanurate polyterephthalate)也可以存在于本发明的阻燃剂中。
此外,以下添加剂可以存在于本发明的阻燃剂中:双吖嗪季戊四醇二磷酸盐、六芳氧基三磷腈、聚芳氧基磷腈以及硅氧烷,例如通式(R2SiO)r或(RSiO1.5)r的硅氧烷。
两种或多种上述化合物的混合物一般而言也存在于本发明的混合物中。
特别优选的是两种的组合,诸如:
—MZP或MAP2(蜜胺磷酸锌/蜜胺二磷酸铝)以及按照式(VI)的二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁(Mg(2’-hydroxy[1,1’-biphenyl-2-yl-2-phosphinate])2)CAS No.:[165597-56-8]、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌(Zn(2’-hydroxy[1,1’-biphenyl-2-yl-2-phosphinate])2)CAS No.:[139005-99-5]、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝(Al(2’-hydroxy[1,1’-biphenyl-2-yl-2-phosphinate])3)CAS No.:[145826-41-1];按照式(VII)的二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁(Mg(10-oxy-9,10-dihydro-9-oxaphosphaphenanthrene 10-oxidate)2)CASNo.:[147025-23-8]、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌(Zn(10-oxy-9,10-dihydro-9-oxaphosphaphenanthrene 10-oxidate)2)CASNo.:[69151-14-0]、三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝(Al(10-oxy-9,10-dihydro-9-oxaphosphaphenanthrene 10-oxidate)3)CASNo.:[121166-84-5]、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)钙(Ca(10-oxy-9,10-dihydro-9-oxaphosphaphenanthrene 10-oxidate)2)CASNo.:[144722-45-2]。
—M2ZP2或M2AP3(双蜜胺二磷酸锌/双蜜胺三磷酸铝)以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝。
非常特别优选的是三种的组合,诸如:
—MZP或MAP2(蜜胺磷酸锌/蜜胺二磷酸铝)以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝;以及硼酸锌。
—M2ZP2或M2AP3(双蜜胺二磷酸锌/双蜜胺三磷酸铝)以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝;以及硼酸锌。
—MZP或MAP2(蜜胺磷酸锌/蜜胺二磷酸铝)以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝;以及锡酸锌。
—M2ZP2或M2AP3(双蜜胺二磷酸锌/双蜜胺三磷酸铝)以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝;以及锡酸锌。
—MZP或MAP2(蜜胺磷酸锌/蜜胺二磷酸铝)以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝;以及勃姆石。
—M2ZP2或M2AP3(双蜜胺二磷酸锌/双蜜胺三磷酸铝)以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝;以及勃姆石。
—MZP+MPP以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝。
—MAP2+MPP以及二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])镁、二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌、三(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])铝、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)镁、二(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)锌或三(10-氧-9,10-二氢-9-氧杂磷杂菲-10-氧化合)铝。
本发明的吖嗪金属磷酸盐的用途
本发明的一具体实施方案提供了本发明的吖嗪金属磷酸盐作为阻燃剂在聚合物或聚合物混合物中的的用途。因此本发明进一步提供了如上所述的额外含有聚合物或聚合物混合物的组合物。优选首先生产包含组分(i)、(ii)和可选的(iii)的上述组合物,并将该组合物并入所述聚合物或聚合物混合物中。
本发明还提供了生产阻燃聚合物模塑组合物的方法,其特征在于在混合装置(compounding apparatus)中于升温下用聚合物熔融物中的聚合物颗粒(polymer pellet)和可能的添加剂使本发明的稳定阻燃剂均质化,接着取出均质化聚合物链(polymer strand),冷却并制粒。例如在对流恒温烤箱中于90℃下将所得颗粒干燥。
优选地,所述混合装置选自单螺杆挤出机、多区螺杆(multizone screw)或双螺杆挤出机。适合的混合装置是单螺杆挤出机,例如来自汉诺威市(Hanover)的Berstorff GmbH和/或纽伦堡(Nuremberg)的Leistritz;具有三层螺杆和/或短压缩螺杆的多层螺杆挤出机,混炼挤出机例如来自Coperion Buss Compounding Systems,CH-Pratteln,如MDK/E46-11D,和/或实验室捏合机(来自瑞士Buss的L=11D的MDK);双螺杆挤出机,例如来自Coperion Werner Pfleiderer GmbH&Co.KG.Stuttgart(ZSK 25,ZSK 30,ZSK 40,ZSK 58,ZSK MEGA混合机40,50,58,70,92,119,177,250,320,350,380)和/或来自汉诺威市(Hanover)Berstorff GmbH、纽伦堡(Nuremberg)Leistritz Extrusionstechnik GmbH;环形挤出机,例如来自劳芬(Laufen)的3+Extruder GmbH,其具有绕静芯旋转的3-12个小螺杆的环;和/或例如来自波鸿(Bochum)Entex的行星齿轮式挤出机,和/或脱挥发挤出机和/或级联挤出机和/或美利弗(Maillefer)螺杆;具有反转双螺杆的混合机,例如来自Krauss-Maffei Berstorff的Complex 37或70型。
所述聚合物通常是热塑性的,优选选自聚酰胺、聚碳酸酯、聚烯烃、聚苯乙烯、聚酯、聚氯乙烯、聚乙烯醇、ABS和聚氨酯,或是热固性的,优选选自环氧树脂(含硬化剂)、酚醛树脂和蜜胺树脂。
还可使用两种或多种聚合物的混合物,特别是热塑性塑料和/或热固性塑料,其中本发明的吖嗪金属磷酸盐用作阻燃剂。
这种聚合物的实例是:
—单烯和二烯的聚合物,例如聚丙烯、聚异丁烯、聚-1-丁烯、聚-4-甲基-1-戊烯、聚乙烯基环己烷、聚异戊二烯或聚丁二烯,以及环烯例如环戊烯或降冰片烯和聚乙烯的(也是交联的)聚合物,所述聚乙烯例如高密度聚乙烯(HDPE)或高分子量高密度聚乙烯(HDPE-HMW)、具有超高分子量的高密度聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)以及线性低密度聚乙烯(LLDPE)、(VLDPE)和(ULDPE),还有乙烯和乙酸乙烯酯的共聚物(EVA);
—聚苯乙烯、聚(对甲基苯乙烯)、聚(α-甲基苯乙烯)
—聚丁二烯-苯乙烯或聚丁二烯和(甲基)丙烯腈的共聚物和接枝共聚物,例如ABS和MBS;
—含卤素聚合物,如聚氯丁二烯、聚氯乙烯(PVC);聚偏二氯乙烯(PVDC)、氯乙烯-偏二氯乙烯、氯乙烯-乙酸乙酯或氯乙烯-乙酸乙酯的共聚物;
—聚(甲基)丙烯酸酯、聚甲基丙烯酸甲酯(PMMA)、聚丙烯酰胺和聚丙烯腈(PAN);
—不饱和醇和胺或酰基衍生物或其缩醛的聚合物,例如聚乙烯醇(PVA)、聚乙酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯或聚马来酸乙烯酯、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙基酯和聚烯丙基蜜胺;
—环醚的均聚物和共聚物,例如聚烷撑乙二醇、聚环氧乙烷、聚环氧丙烷以及其与双缩水甘油醚的共聚物;
—聚缩醛,如聚甲醛(POM)以及聚氨酯和丙烯酸酯改性的聚缩醛;
—聚苯醚和聚苯硫醚以及其与苯乙烯聚合物或聚酰胺的混合物;
—由二胺和二羧酸和/或由氨基羧酸衍生的聚酰胺和共聚酰胺或对应内酰胺,例如聚酰胺4、聚酰胺6、聚酰胺6/6、聚酰胺6/10、聚酰胺6/9、聚酰胺6/12、聚酰胺12/12、聚酰胺11、聚酰胺12,由间二甲苯二胺和己二酸衍生的聚芳酰胺,以及由EPDM或ABS改性的共聚多酰胺。聚酰胺和共聚酰胺的实例衍生自ε-己内酰胺、己二酸、癸二酸、十二烷酸、间苯二甲酸、对苯二甲酸、己二胺、四甲撑二胺、2-甲基戊甲撑二胺、2,2,4-三甲基六甲撑二胺、2,4,4-三甲基六甲撑二胺、间二甲苯二胺或双(3-甲基-4-氨基环己基)甲烷;
—聚脲、聚酰亚胺、聚酰胺亚胺、聚醚酰亚胺、聚酯酰亚胺、聚乙内酰脲(polyhydantoin)和聚苯并咪唑;
—由二羧酸和二元醇和/或羟基羧酸衍生的聚酯或对应内酯,例如聚对苯二甲酸乙二酯、聚对苯二甲酸丙二酯、聚对苯二甲酸丁二酯、聚对苯二甲酸-1,4-二甲基环己酯、聚萘二甲酸亚烷基酯(PAN)和聚对羟基苯甲酸酯、聚乳酸酯和聚乙醇酸酯;
—聚碳酸酯和聚酯碳酸酯;
—聚酮;
—上述聚合物的混合物或合金,例如PP/EPDM、PA/EPDM或ABS、PVC/EVA、PVC/ABS、PBC/MBS、PC/ABS、PBTP/ABS、PC/AS、PC/PBT、PVC/CPE、PVC/丙烯酸酯、POM/热塑性PUR、PC/热塑性PUR、POM/丙烯酸酯、POM/MBS、PPO/HIPS、PPO/PA6.6以及共聚物、PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC,和TPE-O、TPE-S和TPE-E;
—热固性塑料如PF、MF或UF或其混合物;
—环氧树脂—热塑性塑料和热固性塑料;
—酚醛树脂;
—木塑复合材料(WPC)和基于PLA、PHB和淀粉的聚合物。
在聚合物或聚合物混合物中,由吖嗪金属磷酸盐(组分(i))和额外的含金属组分(ii)以及可选的无金属组分(iii)组成的本发明的阻燃制剂,其浓度基于该聚合物或聚合物混合物优选为0.1-60wt%。组合物中吖嗪金属磷酸盐(i)与共组分(ii)和可选的(iii)的组分比的范围优选为1:1-1:4。
本发明的优选实施方案中,本发明的聚合物材料还可含有填充剂,所述填充剂优选选自金属氢氧化物和/或金属氧化物,优选为碱土金属氢氧化物,例如氢氧化镁和氢氧化铝;硅酸盐优选页硅酸盐,诸如膨润土、高岭土、白云母、叶蜡石、白铁矿和滑石;或其它材料如钙硅石、二氧化硅如石英、云母、长石;以及二氧化钛、碱土金属硅酸盐和碱金属硅酸盐;碳酸盐,优选碳酸钙,以及滑石、粘土、云母、硅藻土、硫酸钙、硫酸钡、黄铁矿、玻璃纤维、玻璃颗粒、玻璃珠和玻璃球、木粉、纤维粉、炭黑、石墨、白垩和色素。
这些填充剂可赋予聚合物材料其它所需性质。具体而言,例如,可通过用玻璃纤维加固来提高机械稳定性,或可通过加入染料使聚合物着色。
在另一实施方案中,聚合物材料可含有其它添加剂如抗氧化剂、光稳定剂、加工助剂、成核剂、抗静电剂、润滑剂如硬脂酸钙和硬脂酸锌、增粘剂、抗冲击改性剂、特别是相容剂和分散剂。
此外,除本发明的吖嗪金属磷酸盐之外,还可向聚合物加入泡沫形成剂。泡沫形成剂优选是蜜胺、蜜胺-甲醛树脂、尿素衍生物如尿素、硫脲、胍胺、苯并胍胺、乙酰胍胺和琥珀酰胍胺、双氰胺、胍和氨基磺酸胍、以及其它胍盐或尿囊素和甘脲。
另外,含有本发明的吖嗪金属磷酸盐的聚合物还可含有流滴剂(antidripping agent),特别是基于聚四氟乙烯的流滴剂。这种流滴剂的浓度基于待加工的聚合物优选为0.01-15wt%。
制备本发明的吖嗪金属磷酸盐的方法
本发明还提供了通过使吖嗪起始材料(A)与金属氧化物起始材料(B)和正磷酸(C)反应来制备上述本发明的吖嗪金属磷酸盐的方法,其中,所述吖嗪起始材料(A)选自式(I-H)的蜜胺、式(II-H)的蜜白胺、式(III-H)的胍胺和式(IV-H)的碳酸(氢)胍,所述金属氧化物起始材料(B)选自金属氧化物、金属氢氧化物和/或金属碳酸盐。
优选的吖嗪起始材料是蜜胺、胍胺和蜜白胺。优选的金属氧化物选自MgO、ZnO、Al2O3和SnO、ZrO2,优选的金属氢氧化物选自Mg(OH)2、Zn(OH)2、Al(OH)3、Ce(OH)3和Bi(OH)3,(碱性)金属碳酸盐优选选自CaCO3、MgCO3、碱性碳酸镁(水菱镁矿)、碱性碳酸锌和碱性碳酸锆。
特别优选的是Mg(OH)2、ZnO、Al(OH)3和碱性碳酸锌。一般而言,两种或多种上述化合物的混合物也可用作吖嗪起始材料(A)和/或用作金属氧化物起始材料(B)。
所述方法常包括以下步骤:
(a)首先加入吖嗪组分(A)和金属氧化物起始材料(B)(即金属(氢)氧化物或(碱性)金属碳酸盐)的含水悬浮液,
(b)加入正磷酸,
(c)加热至优选的60-80℃,
(d)分离产物,以及
(e)可选地,干燥至恒重,和/或通常在250-300℃下回火。
所述方法优选包括摩尔比为(1-3):(1):(1-3)的组分(A-1至A-4):(B):(C)的反应,具体而言,原因在于确保额外的蜜胺磷酸盐或(氨基)胍磷酸盐是在原位形成。
特别优选的是,在步骤(a)后进行制粒工序。可优选地在喷雾干燥器、喷雾制粒机(顶喷或底喷逆流法)、流化床制粒机或在桨式混合机或水平干燥机中作为喷雾团聚进行,同时除去引入的水直到获得所需残留含水量。可通过将式(I)的吖嗪金属磷酸盐的含水悬浮液在通常的70-80℃下喷雾干燥,或由组分(A)和(B)的进料混合物作为流化床开始喷雾制粒,将组分(C)喷到流化床上,接着干燥来进行制粒。使流化床温度保持恒定在范围70-80℃内,同时将颗粒干燥并形成自由流动的无粉尘颗粒状材料。残留水含量为约0.5-1%。
通常于220-350℃,优选250-300℃下进行反应产物的回火。
实施例
以下实施例用于说明本发明,用实施例1-6的化合物描述本发明的方法,实施例1-4还描述新化合物。实施例7是比较例。实施例8描述了本发明的化合物作为阻燃剂的用途。
实施例1:蜜胺磷酸镁二水合物(MMP)的合成
C3H7N6O4PMg·2H2O(MW:282.5)
边搅拌边将127.4g(1.01mol)蜜胺和58.3g(1.0mol)氢氧化镁悬浮于1.5升水中。搅拌下向该悬浮液中滴加115.3g(1.0mol)正磷酸(85%的强度)作为稀释水溶液。于60℃搅拌1小时后,形成大量沉淀。接着将混合物再搅拌60分钟,冷却至室温,将形成的白色沉淀抽滤出,用水洗涤,并于120℃下干燥至恒重。
产率:253.0g,相当于理论的90%。
元素分析:
实施例2:蜜胺磷酸锌二水合物(MZP)的合成
C3H7N6O4PZn·2H2O(MW=323.5)
边搅拌边将2547g(20.2mol)蜜胺和1628g(20.0mol)氧化锌悬浮于20升水中。搅拌下向该悬浮液中滴加2306g(20.0mol)正磷酸(85%的强度)作为稀释水溶液。于60℃搅拌1小时后,形成大量沉淀。接着将混合物再搅拌60分钟,冷却至室温,将形成的白色沉淀抽滤出,用水洗涤,并于120℃下干燥至恒重(产物2-I)。
产率:6042.0g,相当于理论的93.4%。
元素分析:
于290℃下将以这种方式获得的产物2-I回火4小时(产物2-II),
失重:10.4%。C3H7N6O4PZn(分子量:287.5)。
元素分析:
实施例3:蜜胺磷酸镁半水合物(GMP)的合成
CH6N3O4PMg·0.5H2O(MW=188.4)
边搅拌边将91.0g(0.505mol)碳酸二胍和58.3g(1.0mol)氢氧化镁悬浮于1.5升水中。搅拌下向该悬浮液中滴加115.3g(1.0mol)正磷酸(85%的强度)作为稀释水溶液。于35℃搅拌1小时后,形成白色沉淀。接着将混合物再搅拌60分钟,冷却至室温,将形成的白色沉淀抽滤出,用水洗涤,并于120℃下干燥至恒重。
产率:109.1g,相当于理论的58%。
实施例4:磷酸胍锌(GZP)的合成
CH6N3O4PZn(MW=220.4)
边搅拌边将91.0g(0.505mol)碳酸二胍和81.4g(1.0mol)氧化锌悬浮于1.5升水中。搅拌下向该悬浮液中滴加115.3g(1.0mol)正磷酸(85%的强度)作为稀释水溶液。于60℃搅拌1小时后,形成大量沉淀。
接着将混合物再搅拌60分钟,冷却至室温,将形成的白色沉淀抽滤出,用水洗涤,并于120℃下干燥至恒重。
产率:185.0g,相当于理论的84%。
实施例5:双蜜胺二磷酸锌单水合物(M2ZP2)的合成
C6H16N12O8P2Zn·H2O(MW=529.6)
边搅拌边将2547g(20.2mol)蜜胺和814g(10.0mol)氧化锌悬浮于15升水中。搅拌下向该悬浮液中滴加2306g(20.0mol)正磷酸(85%的强度)作为稀释水溶液。于60℃搅拌1小时后,形成大量沉淀。接着将混合物再搅拌60分钟,冷却至室温,将形成的白色沉淀抽滤出,用水洗涤,并于120℃下干燥至恒重(产物5-I)。
产率:5118g,相当于理论的96.6%。
于290℃下将以这种方式获得的产物5-I回火4小时(产物5-II)。
失重:7.3%,生成双蜜胺二磷酸锌。
元素分析:
实施例6:由喷雾法合成双蜜胺二磷酸锌单水合物(M2ZP2)
C6H16N12O8P2Zn·H2O(MW=529.6)
边搅拌边将2547g(20.2mol)蜜胺和814g(10.0mol)ZnO置于来自GLATT GmbH的GPCG 3.1流化床制粒机中。通过空气流连续流化固体床,向其上喷洒由1000ml水中2306g(20.0mol)正磷酸产生的溶液。将流化床温度保持恒定在范围70-80℃中,同时干燥颗粒并形成自由流动的无粉尘颗粒材料。主级分(>80%)的粒径范围为200-400μm。残余含水量为约0.5-1%。产率:定量。
于290℃下将以这种方式获得的产物6-I回火4小时(产物6-II)。
失重:8.0%,生成双蜜胺二磷酸锌。
元素分析:
比较例7:二蜜胺焦磷酸锌酸的合成
[Mel-H]+ 2[ZnP2O7]2-(如EP2183314B1中所述)
步骤I:制备双磷酸二氢锌
于搅拌下,在约500ml水中使81.37g(1mol)ZnO与230.6g(2mol)正磷酸(85%的强度)反应。于90℃搅拌2小时后,ZnO已反应。
步骤II:双磷酸二氢锌与蜜胺反应
将252.2g蜜胺悬浮于约500ml水中。边搅拌边加入双磷酸二氢锌(步骤I),滤出产物,并于120℃干燥。
产率:503.0g,相当于理论的95%。
步骤III:于300℃下将来自步骤II的200g产物回火3小时。失重:6.5%。
过滤后,在室温下对实验产物(实施例1-7)测定10%的强度的含水悬浮液的pH测量值和导电率。此外,使用Netzsch STA 409仪进行TGA/DSC测量(升温速率:10K/min;N2/50)(见表1)。
表1:实验产物的性质数据
*按EP2183314B1中所述的制备
进一步检验作为阻燃剂的以下锌化合物:(见表2)
表2:锌化合物的物理性质
与产物7的导电率值相比,本发明的产物2、4和5表现出改善的导电率值。300℃下的失重也比比较产物7的情况低。
实施例8:(用作PA中的阻燃剂)
材料:PA 6.6(Durethan A30S;来自LANXESS);玻璃纤维(671;10μm×4mm;来自John Manville);蜜胺多磷酸盐MPP(Melapur 200;来自BASF),二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌(Zn(2’-hydroxy[1,1’-biphenyl-2-yl-2-phosphinate])2,内部产物(in-houseproduct)),双蜜胺二磷酸锌(实施例5)。
在Leistritz ZSE 27HP-44D双螺杆挤出机上将组分混合并制粒。通过注射成型由这些颗粒制造符合标准的测试样品(d=1.6mm)。按照UL-94测试进行燃烧测试。在表3中示出结果。
表3:阻燃测试
组分 | A | B |
PA 6.6 | 47.5% | 48.0% |
玻璃纤维 | 30.0% | 30.0% |
阻燃组分: | ||
二(2’-羟基[1,1’-联苯-2-基-2-亚膦酸])锌 | 12.5% | 12.0% |
MPP | -- | 10.0% |
M2ZP2 | 10.0% | -- |
UL-94测试 | V-0 | V-0 |
Claims (28)
1.通式[I]的吖嗪金属磷酸盐,
[(A-H)(+)[Mm+(PO4)x (3-)(P2O7)y (4-)](-)·pH2O]z [I]
其中,(A-H)(+)选自式(I-H)的(蜜胺-H)+、式(II-H)的(蜜白胺-H)+、R是甲基或苯基的式(III-H)的(胍胺-H)+以及R’是氢或氨基的式(IV-H)的[(氨基)胍-H]+,
M=Cu、Mg、Ca、Zn、Mn、Fe、Co、Ni、TiO、ZrO、VO、B、Si、Al、Sb、La、Ti、Zr、Ce、Bi或Sn,
m=2或3,
x和y彼此独立,各是0或1,
p是0-4的整数,以及
z是>5的整数,
其中1+m=3x+4y。
2.一种组合物,包括:
(i)如权利要求1所述的吖嗪金属磷酸盐,
(ii)与组分(i)不同的含金属组分,以及
(iii)可选的无金属组分。
3.如权利要求2所述的组合物,其特征在于,所述含金属组分(ii)选自金属氢氧化物、金属磷酸盐、金属焦磷酸盐、双蜜胺二磷酸锌、双蜜胺二磷酸镁、双蜜胺三磷酸铝、水滑石、水铝钙石、沸石优选沸石X或沸石Y、阳离子或阴离子改性的有机粘土、锡酸盐或钼酸盐、金属硼酸盐或式(V)或(VI)的金属亚膦酸盐、式(VII)的金属膦酸盐或其混合物,
其中R1和R2彼此独立,各是氢、直链或支链C1-C6-烷基或苯基;Mt1是Ca、Mg、Zn或Al;m=2或3;以及Mt是Ca、Mg、Zn、Al、Sn、Zr、TiO、ZrO、Ce、MoO、WO2、VO、Mn、Bi或Sb,D=O或S,以及n是2或3。
4.如权利要求3所述的组合物,其特征在于,所述金属氢氧化物选自氢氧化镁(水镁石)、氢氧化铝(ATH,三水铝石)、水合氧化铝(勃姆石)或其混合物。
5.如权利要求3所述的组合物,其特征在于,所述钼酸盐或锡酸盐选自七钼酸铵、八钼酸铵、锡酸锌、羟基锡酸锌或其混合物。
6.如权利要求3所述的组合物,其特征在于,所述金属硼酸盐选自碱金属硼酸盐、碱土金属硼酸盐、硼酸锌或其混合物,优选硼酸锌。
7.如权利要求3所述的组合物,其特征在于,式(V)或(VI)的金属亚膦酸盐选自次磷酸盐、苯基亚膦酸盐、二乙基(甲基,乙基)亚膦酸盐或其混合物,其中Mt=Ca、Mg、Zn或Al,Mt1和/或M优选是Zn或Al。
8.如权利要求3所述的组合物,其特征在于,式(VI)的金属亚膦酸盐和式(VII)的金属膦酸盐中的Mt是Ca、Ce、Mg、Zn或Al。
9.如权利要求2所述的组合物,其特征在于,所述无金属组分(iii)选自红磷、低聚磷酸酯、低聚膦酸酯、环状膦酸酯、硫代焦磷酸酯、蜜胺正磷酸盐、蜜白胺、蜜勒胺、蜜胺苯基亚膦酸盐、单聚、低聚和多聚蜜胺苯基膦酸盐、多磷酸铵、羟基烷基氧化膦、四羟烷基季鏻盐、磷杂环戊烷(氧化物)衍生物或二氢磷杂环戊二烯(氧化物)衍生物、亚膦酸酯或其混合物。
10.如权利要求9所述的组合物,其特征在于,所加蜜胺正磷酸盐选自蜜胺焦磷酸盐、蜜胺多磷酸盐或其混合物。
11.如权利要求9所述的组合物,其特征在于,所述低聚磷酸酯对应于式(VIII)、(IX),和/或所述低聚膦酸酯对应于式(X),
其中各R独立地是氢、C1-C4-烷基或羟基,R3是甲基或苯基,x是1-20的整数,n=1、2或3,以及o是1-10的整数。
12.如权利要求9所述的组合物,其特征在于,所述环状膦酸酯对应于式(XI),
其中R是氢、C1-C4-烷基或羟基,R3是甲基或苯基,以及y=0或2。
13.如权利要求9所述的组合物,其特征在于,所述硫代焦磷酸酯对应于式(XII),
其中R1和R2各独立地是氢、C1-C4-烷基或羟基。
14.如权利要求9所述的组合物,其特征在于,所述亚膦酸酯选自苯单苯基酯衍生物、式(XIII)或(XIV)的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物或6H-二苯并(c,e)(1,2)-氧磷杂己环-6-酮衍生物和10-苄基-9-氧杂-10-磷杂菲-10-氧化物或其混合物:
15.如权利要求9所述的组合物,其特征在于,所述组分(iii)还包含多元醇、氨基尿嘧啶、POSS化合物、NOR-HALS衍生物、三羟乙基异氰尿酸酯、氰脲酸蜜胺酯、可膨胀石墨或其混合物。
16.如权利要求15所述的组合物,其特征在于,所述多元醇选自季戊四醇、二季戊四醇和/或三季戊四醇,所述氨基尿嘧啶是1,3-二甲基-6-氨基尿嘧啶,以及所述POSS化合物基于甲基硅氧烷。
17.如权利要求2-16中任一项所述的组合物,还包含聚合物或聚合物混合物,其特征在于,所述聚合物或聚合物混合物中的组分(i)和(ii)的总浓度基于所述聚合物或聚合物混合物为0.1-60wt%。
18.如权利要求17所述的组合物,其特征在于,所述聚合物是热塑性的,优选选自聚酰胺、聚碳酸酯、聚烯烃、聚苯乙烯、聚酯、聚氯乙烯、聚乙烯醇、ABS和聚氨酯、基于聚乳酸和/或淀粉的生物聚合物,或是热固性的,优选选自环氧树脂、酚醛树脂和蜜胺树脂,或是两种或多种这些聚合物的聚合物混合物。
19.制备通式[I]的吖嗪金属磷酸盐的方法,
[(A-H)(+)[Mm+(PO4)x (3-)(P2O7)y (4-)](-)·pH2O]z [I]
其中,(A-H)(+)选自式(I-H)的(蜜胺-H)+、式(II-H)的(蜜白胺-H)+、R是甲基或苯基的式(III-H)的(胍胺-H)+以及R’是氢或氨基的式(IV-H)的[(氨基)胍-H]+,
M=Cu、Mg、Ca、Zn、Mn、Fe、Co、Ni、TiO、ZrO、VO、B、Si、Al、Sb、La、Ti、Zr、Ce、Bi或Sn,
m=2或3,
x和y彼此独立,各是0或1,
p是0-4的整数,以及
z是>5的整数,
其中1+m=3x+4y,
所述方法通过使吖嗪起始材料(A)与金属氧化物起始材料(B)和正磷酸(C)反应来进行,
其中,所述吖嗪起始材料(A)选自式(I-H)的蜜胺、式(II-H)的蜜白胺、式(III-H)的胍胺以及式(IV-H)的碳酸(氢)胍,所述金属氧化物起始材料(B)选自金属氧化物、金属氢氧化物和/或金属碳酸盐,
20.如权利要求19所述的方法,其特征在于,所述胍胺是乙酰胍胺或苯并胍胺。
21.如权利要求19或20所述的方法,其特征在于,组分(B)中,所述金属氧化物或金属氢氧化物的金属是Cu、Mg、Ca、Zn、Mn、Fe、Co、Ni、Ti、Zr、VO、B、Si、Al、Sb、La、Ce、Bi或Sn,以及所述碱性金属碳酸盐或金属碳酸盐的金属是Zn、Mg、Zr或Cu。
22.如权利要求19-21中任一项所述的方法,其特征在于,首先在水中加入组分(A)和(B)作为混合物,优选作为悬浮液,并加入正磷酸(C)。
23.如权利要求19-22中任一项所述的方法,其特征在于,所述反应在20-90℃,优选在30-70℃下进行。
24.如权利要求19-23中任一项所述的方法,其特征在于,组分(A):(B):(C)以摩尔比(1-3):(1):(1-3)存在,同时吖嗪磷酸盐还在化学计量1:1:1以外额外存在。
25.如权利要求19-24中任一项所述的方法,其特征在于,其在卧式或立式混合机,优选桨式混合机、制粒机或喷雾干燥器中进行。
26.如权利要求19-25中任一项所述的方法,其特征在于,所述反应产物在220-350℃,优选250-300℃下回火。
27.如权利要求1-18中任一项所述的组合物作为聚合物或聚合物混合物、纸张、织物或木塑复合材料(WPC)中的阻燃剂的应用。
28.如权利要求27中所述的应用,其特征在于,所述聚合物是热塑性的,优选选自聚酰胺、聚碳酸酯、聚烯烃、聚苯乙烯、聚酯、聚氯乙烯、聚乙烯醇、ABS和聚氨酯、基于聚乳酸和/或淀粉的生物聚合物,或是热固性的,优选选自环氧树脂、酚醛树脂和蜜胺树脂。
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CN107828204A (zh) * | 2017-11-22 | 2018-03-23 | 江苏利思德新材料有限公司 | 一种聚氨酯用无卤阻燃复配体系及其在无卤阻燃聚氨酯中的应用 |
CN107936297A (zh) * | 2017-11-22 | 2018-04-20 | 江苏利思德新材料有限公司 | 玻纤增强尼龙用无卤阻燃复配体系及其在无卤阻燃玻纤增强尼龙材料中的应用 |
CN109651825A (zh) * | 2018-12-04 | 2019-04-19 | 厦门大学 | 一种含磷硅氮的金属离子络合物阻燃剂及其制备方法与应用 |
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CN107828204A (zh) * | 2017-11-22 | 2018-03-23 | 江苏利思德新材料有限公司 | 一种聚氨酯用无卤阻燃复配体系及其在无卤阻燃聚氨酯中的应用 |
CN107936297A (zh) * | 2017-11-22 | 2018-04-20 | 江苏利思德新材料有限公司 | 玻纤增强尼龙用无卤阻燃复配体系及其在无卤阻燃玻纤增强尼龙材料中的应用 |
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CN109651825A (zh) * | 2018-12-04 | 2019-04-19 | 厦门大学 | 一种含磷硅氮的金属离子络合物阻燃剂及其制备方法与应用 |
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