CN111825883A - Metal complex salts of polydialkylphosphinic acids and/or mixtures thereof, and use thereof - Google Patents
Metal complex salts of polydialkylphosphinic acids and/or mixtures thereof, and use thereof Download PDFInfo
- Publication number
- CN111825883A CN111825883A CN201910326976.0A CN201910326976A CN111825883A CN 111825883 A CN111825883 A CN 111825883A CN 201910326976 A CN201910326976 A CN 201910326976A CN 111825883 A CN111825883 A CN 111825883A
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- China
- Prior art keywords
- polymer
- flame retardant
- polydialkylphosphinic
- flame
- metal complex
- Prior art date
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- -1 Metal complex salts Chemical class 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000002253 acid Substances 0.000 title claims description 22
- 150000007513 acids Chemical class 0.000 title description 4
- 239000003063 flame retardant Substances 0.000 claims abstract description 86
- 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 claims abstract description 66
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 3
- 239000003822 epoxy resin Substances 0.000 claims abstract 2
- 239000004753 textile Substances 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000005504 styryl group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 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 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000012778 molding material Substances 0.000 claims description 2
- 150000002829 nitrogen Chemical class 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004634 thermosetting polymer Substances 0.000 claims 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- 229920006254 polymer film Polymers 0.000 claims 2
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 claims 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- 239000004110 Zinc silicate Substances 0.000 claims 1
- 229960000458 allantoin Drugs 0.000 claims 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229910001593 boehmite Inorganic materials 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000007859 condensation product Substances 0.000 claims 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- ZIWYFFIJXBGVMZ-UHFFFAOYSA-N dioxotin hydrate Chemical compound O.O=[Sn]=O ZIWYFFIJXBGVMZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims 1
- 238000002074 melt spinning Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- 229920005594 polymer fiber Polymers 0.000 claims 1
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 239000012779 reinforcing material Substances 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- 229910001887 tin oxide Inorganic materials 0.000 claims 1
- 239000002966 varnish Substances 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims 1
- 229940007718 zinc hydroxide Drugs 0.000 claims 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 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 claims 1
- 229910000165 zinc phosphate Inorganic materials 0.000 claims 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 claims 1
- 235000019352 zinc silicate Nutrition 0.000 claims 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 18
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 239000002905 metal composite material Substances 0.000 abstract description 15
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000002952 polymeric resin Substances 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 229920003002 synthetic resin Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229920006351 engineering plastic Polymers 0.000 description 8
- 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 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229940071538 aluminum sulfate tetradecahydrate Drugs 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- GUNGYIXTFIIJDK-UHFFFAOYSA-H dialuminum;trisulfate;tetradecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GUNGYIXTFIIJDK-UHFFFAOYSA-H 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CKGPKEALRYRVNN-UHFFFAOYSA-M sodium;butyl(ethyl)phosphinate Chemical compound [Na+].CCCCP([O-])(=O)CC CKGPKEALRYRVNN-UHFFFAOYSA-M 0.000 description 3
- LPFYDEANGXVAOA-UHFFFAOYSA-M sodium;diethylphosphinate Chemical compound [Na+].CCP([O-])(=O)CC LPFYDEANGXVAOA-UHFFFAOYSA-M 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- WVLAZEHCUADXTN-UHFFFAOYSA-K aluminum butyl(ethyl)phosphinate Chemical compound [Al+3].CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC WVLAZEHCUADXTN-UHFFFAOYSA-K 0.000 description 2
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- MQJUOTKNWSXWRK-UHFFFAOYSA-M sodium ethyl(hexyl)phosphinate Chemical compound CCCCCCP(=O)(CC)[O-].[Na+] MQJUOTKNWSXWRK-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GTOWTBKGCUDSNY-UHFFFAOYSA-K tris[[ethyl(methyl)phosphoryl]oxy]alumane Chemical class [Al+3].CCP(C)([O-])=O.CCP(C)([O-])=O.CCP(C)([O-])=O GTOWTBKGCUDSNY-UHFFFAOYSA-K 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- XDMYAHBAPIRGTQ-UHFFFAOYSA-K aluminum;methyl(propyl)phosphinate Chemical class [Al+3].CCCP(C)([O-])=O.CCCP(C)([O-])=O.CCCP(C)([O-])=O XDMYAHBAPIRGTQ-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical class CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- WMLXDIOQDFWKAO-UHFFFAOYSA-L zinc;methyl(phenyl)phosphinate Chemical compound [Zn+2].CP([O-])(=O)C1=CC=CC=C1.CP([O-])(=O)C1=CC=CC=C1 WMLXDIOQDFWKAO-UHFFFAOYSA-L 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)]
-
- 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
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- 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
- C08K3/38—Boron-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
- C08K5/49—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
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a flame retardant and a flame retardant synergist of a polydialkyl phosphinic acid metal composite salt and/or a mixture thereof shown as a formula (1), and application of the flame retardant and the flame retardant synergist in plastics, epoxy resin, paint, spinning and textiles. When the polydialkyl phosphinic acid metal composite salt and/or the mixture thereof is matched with polymer resin to manufacture a flame retardant material, the influence of the traditional alkyl phosphinic acid metal salt on the performance of the polymer material is greatly improved, and the corrosion to processing equipment is reduced.
Description
The technical field is as follows:
the invention relates to a polydialkyl phosphinic acid metal composite salt and/or a mixture thereof and application thereof. In particular to polydialkyl phosphinic acid metal composite salt and/or a mixture thereof, and application of the polydialkyl phosphinic acid metal composite salt as a halogen-free flame retardant and a flame-retardant synergist.
Background art:
most polymeric materials, such as polyolefins, polyesters, polycarbonates, polyamides, polyurethanes, epoxies, polyacrylates, and various other types of thermoplastic or thermoset plastic molding compounds, elastomeric materials, coatings, synthetic fibers, and the like, are generally composed primarily of relatively flammable, polymeric materials. For safety purposes, articles made from these materials are often required to meet certain safe flame retardant standards, and in order to meet these flame retardant standards, flame retardants, such as those comprising bromine-containing compounds and phosphorus-containing compounds, are typically added to the formulations used to make these materials in proportions. The phosphorus-containing compound flame retardant has relatively small influence on the environment, has high flame retardant efficiency, generates less smoke during the combustion of materials, is popular in the market, and becomes a trend for the development of the flame retardant industry in recent years. Most flame retardants containing phosphorus compounds, such as phosphates, have limited use in plastics, particularly engineering plastics, due to their low decomposition temperature, their migratory properties in the material and their relatively high volatility. One of the high temperature resistant flame retardants that can be used in engineering plastics is dialkylphosphinate.
Dialkyl phosphinates have been reported as flame retardants as early as the seventies, for example, U.S. Pat. Nos. 4,978,327,8322 disclose zinc methylphenylphosphinate and zirconium methylphenylphosphinate basic flame retardants, which are not very flame retardant effective and only increase the oxygen index (LOI) of the material by a few percent when used in polyester materials. Subsequent technical developments have focused mainly on zinc, calcium and aluminum salts of dialkylphosphinic acids, for example, patent EP0794220A1, DE19608008A1 disclose flame retardants with metal salts of aluminum methylethylphosphinate, aluminum methylpropylphosphinate and the like. The flame retardant efficiency of the short-chain dialkyl phosphinate is relatively high, and the flame retardant grade of V0 can be achieved when the short-chain dialkyl phosphinate is added into PBT by 20%. In addition, other dialkylphosphinic salts have been developed during this time, for example, EP794191 discloses a flame retardant of cyclic phosphinic salts, which also has very good flame retardant properties for PBT polyesters.
Later studies found that the synergistic effect of aluminum diethylphosphinate and aluminum methylethylphosphinate as flame retardants with other nitrogen-containing compounds such as Melamine Cyanurate (MCA) and melamine polyphosphate (MPP) further improved the flame retardant efficiency of dialkylphosphinate salts as flame retardants (patents US6255371B1, US6365071B 1). There are other flame retardant technologies such as aluminum methylmethoxyethyl phosphinate, in which the flame retardant efficiency is not improved despite the increased phosphorus content (patent EP971936A 1).
The wide market acceptance of this product is also achieved because of the synergistic effect of aluminum diethylphosphinate and nitrogen-containing compounds, which at the same time has led to a large number of new techniques for the synthesis and production of dialkyl phosphinate salts. Early patents for production and synthesis mainly used organic solvents as medium to react hypophosphorous acid or its alkali metal salt with olefins to obtain dialkylphosphinic acid or its alkali metal salt, and then to metathetically react dialkylphosphinic acid or its alkali metal salt with the corresponding metal compound to obtain the corresponding metal dialkylphosphinate salt (patent DE19752735, US6355832B 1). The synthesis techniques using organic solvents such as acetic acid as reaction medium often give the product solvent residues, which have negative effects on the materials (patent US7420007B2, US20060074157a 1). The main synthesis and manufacturing technologies at present mainly adopt water as a reaction medium to perform an addition reaction between hypophosphorous acid or an alkali metal salt thereof and olefin (patents US7635785B1, CN103951699B, US20050137418a 1).
Dialkylphosphinic salts, in particular aluminum diethylphosphinate, are currently one of the important flame retardants in many fields, in particular in the field of engineering plastics. However, because of their intrinsic properties, aluminum diethylphosphinate has been found in practical applications to lead to polymer degradation and to deterioration of the mechanical properties of the material even after high temperature processing, and because of their intrinsic properties, which often cause some corrosion of the production equipment, patent application US20070029532a1 describes in detail the decomposition of phosphorus-containing flame retardants during high temperature processing and the degradation of polymers and corrosion of equipment. To solve these problems engineers often add other nitrogen-free synergists to use. Patent US6547992B1 discloses a compounding technique of diethyl aluminum hypophosphite and zinc borate as stabilizers, which can reduce the degradation of the flame retardant to the polymer. Specially treated aluminum phosphite is also considered to be one of the effective synergists without nitrogen, and patent application US2014/0336325a1 discloses a compounding technique of high temperature resistant aluminum phosphite. The synergist compounding technology relieves the processing or material problems to a certain extent, but the synergists are used by physical mixing, the addition amount is high, and the flame retardant efficiency is often not met.
The present inventors have surprisingly found that when a short-chain metal dialkylphosphinate contains a small amount of long-chain alkylphosphinic acid groups, the metal polydialkylphosphinate as a flame retardant can improve mechanical properties of materials and corrosion of processing equipment, etc.
Different from the prior art, the corresponding components of the polydialkylphosphinic acid metal composite salt are combined with each other in a bonding mode in a bulk according to a certain molar ratio. The invention also relates to a mixture of the metal complex salts of polydialkylphosphinic acids of the invention described above. The mixture of these metal polydialkylphosphinates is distinguished from the physical mixture of the corresponding metal dialkylphosphinate salts in that the individual components of the metal polydialkylphosphinate complex are not added by mixing but remain in the product from the reaction mixture of the preparation process. The inventor finds that the polydialkyl phosphinic acid metal composite salt has the same flame retardant effect in glass fiber reinforced materials such as PBT, nylon 66, nylon 6T/66 and the like, and can reduce the decomposition of polymer molecules in the processing process, improve the mechanical property of the material and obviously improve the corrosion of equipment in the processing process.
The invention content is as follows:
the invention aims to provide a halogen-free flame retardant of polydialkyl phosphinic acid metal composite salt and a synergist used in combination with other flame retardants, which are used for manufacturing various flame-retardant molding compounds, flame-retardant thermosetting plastics, flame-retardant coatings, flame-retardant fibers, flame-retardant leather and the like, have good flame-retardant efficiency, maintain the mechanical properties of materials and reduce the corrosion to production equipment in the processing process.
It is another object of the present invention to provide a composition of a metal dialkylphosphinate complex salt and a thermoplastic or thermoset polymer useful in preparing flame retardant articles from the polymer.
It has been surprisingly found that the metal polydialkylphosphinate composite salt of the present invention, as a flame retardant and flame retardant synergist, has a flame retardant efficacy equivalent to or better than that of the pure dialkylphosphinate, and can reduce the degradation of the polymer during processing and reduce the corrosion to equipment. The flame retardant can be used independently, and can also be used as a flame retardant synergist to be used together with the flame retardant in a flame retardant mixture. Generally, the flame retardant mixture is mixed with the polymer to be flame-retardant-treated by kneading and extrusion together with other polymer additives. The resulting polymer mixture is flame-retardant and is usually processed further later into polymer molding materials or polymer shaped bodies, etc. The processing is carried out at a relatively high temperature at which the polymer is present in molten form and can significantly exceed 320 ℃ in a short time. The flame retardants and synergists employed must be able to withstand this temperature without decomposition. Compared with the common aluminum dialkyl phosphinate, the metal composite salt of the polydialkyl phosphinate is stable in the processing process, does not cause polymer degradation in the processing process, and reduces corrosion to equipment in the processing process.
When the multi-diethyl phosphinic acid metal composite salt contains a small amount of long-chain dialkyl phosphinic acid groups, the composite salt serving as a plastic flame retardant or flame retardant synergist has higher flame retardant efficiency than the corresponding pure diethyl phosphinic acid salt, reduces the degradation effect on polymers and reduces the corrosion on processing equipment.
Therefore, the metal composite salt of dialkyl phosphinic acid-alkyl phosphorous acid related by the invention overcomes the defects of the prior art and is characterized in that the chemical formula is as follows:
wherein R1, R2, R3, R4, R5 and R6 are the same or different and are H, or linear or branched C1-C8 saturated alkyl, or linear or branched C2-C12 unsaturated alkenyl or C6-C18 aryl, or organic groups containing carboxyl, hydroxyl, amine, ester, amide, epoxy or halogenated.
Wherein M is Ca, Mg, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn metal cation and/or protonated nitrogen base.
Wherein
m is the ion valence number of the metal cation
y: x is an arbitrary number from 0.005 to 0.15
z: x is an arbitrary number from 0.005 to 0.15
Wherein m is x + y + Z.
I.e. wherein the total number of valencies of the metal cation M is equal to the total number of valencies of the anion of the polydialkylphosphinate.
Preferably, wherein R1, R2, R3, R4 and R5 are selected from hydrogen, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and styryl.
Particularly preferably, wherein R1, R2 are selected from H, ethyl, R3, R4, R5 are selected from ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, styryl,
preferably, the first and second electrodes are formed of a metal,
m is Ca, Mg, Zn, Al,
preferably, the first and second electrodes are formed of a metal,
y: x is any number from 0.005 to 0.075
z: x is any number from 0.005 to 0.075
Wherein m is x + y + z
Preferably, the present invention relates to a polydialkylphosphinic acid metal complex salt having a particle size of 0.1 to 1000. mu.m, a solubility in water of 0.01 to 10g/l, a bulk density of 80 to 800g/l and a residual moisture of 0.1 to 5%.
The preparation of the metal polydialkylphosphinate complex salt of the present invention can be achieved by the following method, comprising the steps of:
carrying out double decomposition reaction on polydialkyl phosphinic acid or the mixture of polydialkyl phosphinic acid alkali metal salts and an aqueous solution of a metal compound in an aqueous medium solution to obtain the corresponding polydialkyl phosphinic acid metal composite salt. The metal compound comprises Mg, Ca, Zn, Al, Ti, Fe, Sn and Zr. The aqueous medium solution herein is a solution comprising 50 to 100% water and 0 to 50% reaction-modifying additives. Preferably, the aqueous medium solution is a solution comprising 80 to 100% water and 0 to 20% reaction-modifying additives. The reaction control additive herein comprises inorganic acids, acid salts, carbonic acid, alkali, electrolytes.
The aqueous medium solution is a solution comprising 95 to 100% water, 0 to 5% of a reaction-regulating additive.
The polydialkyl phosphinate is an alkali metal salt, particularly a sodium salt thereof.
The equivalent ratio of the mixture of the alkali metal salt of polydialkylphosphinic acid to the metal compound used in the metathesis reaction of the above-mentioned preparation process is from 1.5: 1 to 1: 2, and preferably, the equivalent ratio of the mixture of alkali metal salt of dialkylphosphinic acid and alkali metal alkylphosphite to the metal compound used is from 1.2: 1 to 1: 1.2.
The metal compound of the preparation method is the metal compound of Mg, Ca, Zn and Al,
the above-mentioned metal polydialkylphosphinic acid composite salt is preferably aluminum diethylphosphinate-ethylpropylphosphinate-ethylbutylphosphinate, aluminum diethylphosphinate-ethylisopropylphosphinate-ethylisobutylphosphinate, aluminum diethylphosphinate-ethylisobutylphosphinate, or aluminum diethylphosphinate-ethylisobutylphosphinate.
The ratio of each dialkylphosphinate of the metal polydialkylphosphinate composite salt of the present invention may be prepared by chemical synthesis according to design.
The polydialkyl phosphinic acid metal composite salt can be used as a flame retardant and a flame retardant synergist for engineering plastics, particularly for flame retardance of polyester PBT, polyamide PA6, PA66, PA6T/66 and the like. The composition compounded by the polydialkyl phosphinic acid metal composite salt and the polymer engineering plastic can be used for obtaining a corresponding flame-retardant engineering plastic product through heating extrusion/injection molding.
The invention also provides the application of the molding composition of the engineering plastic containing the polydialkyl phosphinic acid metal composite salt as the flame retardant and the flame-retardant synergist in the flame-retardant thermoplastic engineering plastic
The specific implementation mode is as follows:
the preparation method and the use of the metal polydialkylphosphinate complex salt of the present invention will be further described in the following examples. The scope of the present invention is not limited to the enumerated cases.
Example 1: preparation of aluminum diethylphosphinate (comparative)
1490g (14mol) of sodium hypophosphite monohydrate and 35 g of concentrated sulfuric acid, and 7.5kg of deionized water were charged into a 16 liter, jacketed, enamel pressure reactor and dissolved. After the solution had been heated to 100 ℃ ethylene was introduced into the reactor via a pressure-reducing valve, so that the ethylene pressure was saturated at 6 bar. Then 300 g of water and 16 g (0.06mol) of an aqueous solution of potassium persulfate were added dropwise to the reactor with continuous stirring at a steady dropping rate over a period of 6 hours, during which the reactor was kept under stirring with the ethylene pressure kept constant at 6 bar and the temperature maintained at 100 ℃ and 110 ℃. After the end of the dropwise addition, the reaction was continued for 1 hour, after which the ethylene was discharged, reduced to atmospheric pressure and the temperature was lowered to 90 ℃. Then, 3000 g of a solution containing 46% aluminum sulfate tetradecahydrate was added dropwise to the reaction solution obtained above at a stable rate over one hour with stirring, and the obtained precipitate was filtered, washed with hot water, and finally vacuum-dried at 130 ℃. 1723 g of solid product are obtained (yield 94.6%). By using31The product was examined by P NMR and found to contain 99.1% of aluminum diethylphosphinate, 0.4% of aluminum ethylbutylphosphinate, and 0.5% of others.
As a result, 99.1% of aluminum diethylphosphinate, 0.4% of aluminum ethylbutylphosphinate, and 0.5% of the others were contained.
Example 2: preparation of diethyl phosphinic acid-ethyl propyl phosphinic acid-ethyl butyl aluminum phosphinate composite salt
1490g (14mol) of sodium hypophosphite monohydrate and 35 g of concentrated sulfuric acid, and 7.5kg of deionized water were charged into a 16 liter, jacketed, enamel pressure reactor and dissolved. After the solution was heated to 100 ℃, an ethylene-propylene mixed gas containing 4% propylene was introduced into the reaction vessel through a pressure reducing valve so that the gas pressure became saturated at 6 bar. An aqueous solution of 300 g of water and 16 g (0.06mol) of potassium persulfate was then added in stable drops with continuous stirring in the reactorThe acceleration is dropped into the reaction kettle within 6 hours, during which the reaction kettle is kept stirring, the ethylene-propylene gas pressure is constant at 6 bar, and the temperature is maintained between 100 ℃ and 110 ℃. After the end of the dropwise addition, the reaction was continued for 1 hour, then ethylene-propylene was discharged, the pressure was reduced to normal pressure, and the temperature was lowered to 90 ℃.31The PNMR detected the resulting clear liquid and found to contain 95.7% of sodium diethylphosphinate, 3.4% of sodium ethylpropylphosphinate, 0.5% of sodium ethylbutylphosphinate, and the other 0.4%.
3000 g of a solution containing 46% of aluminum sulfate tetradecahydrate was added dropwise to the reaction solution obtained above at a constant rate over one hour with stirring, and the obtained precipitate was filtered, washed with hot water, and finally vacuum-dried at 130 ℃. 1681 g of solid product are obtained (yield 92.3%).
Example 3: preparation of aluminum diethylphosphinate-ethylbutylphosphinate-ethylhexylphosphinate
1490g (14mol) of sodium hypophosphite monohydrate and 7.5kg of acetic acid were charged into a 16-liter enamel autoclave equipped with a jacket and dissolved therein. After the solution was heated to 85 ℃, an ethylene-butene-hexene ternary mixture gas containing 3% butene and 2% vaporized hexene was introduced into the reactor through a pressure reducing valve to saturate the gas at 5 bar. 250ml of water and 56 g of azobisimidepropane dihydrochloride aqueous solution are then added dropwise to the reaction vessel with constant stirring over 4 hours, during which the reaction vessel is kept under stirring at a temperature of between 85 and 95 ℃ and the ethylene-butene-hexene gas pressure is kept constant at 5 bar. After the end of the dropwise addition, the reaction was continued for 2 hours, and then ethylene-propylene-hexene was discharged and reduced to normal pressure.31The transparent liquid obtained was examined by P NMR, and found to contain 94.6% of sodium diethylphosphinate, 3.4% of sodium ethylbutylphosphinate, 1.6% of sodium ethylhexylphosphinate, and the balance 0.4%.
The product of the above reaction was subjected to removal of acetic acid on a rotary evaporator and then dissolved with 7.5kg of deionized water. 3000 g of a solution containing 46% of aluminum sulfate tetradecahydrate was added dropwise to the reaction solution obtained above at a constant rate over one hour with stirring, and the obtained precipitate was filtered, washed repeatedly with hot water, then with acetone, and finally vacuum-dried at 130 ℃. 1665 g (91.3% yield) of solid product are obtained.
Example 4: preparation of aluminum diethylphosphinate-ethylbutylphosphinate-ethylhexylphosphinate
1490g (14mol) of sodium hypophosphite monohydrate and 7.5kg of acetic acid were charged into a 16-liter enamel autoclave equipped with a jacket and dissolved therein. After the solution was heated to 85 ℃, the ethylene-butene-hexene ternary mixture containing 2% butene and 3% vaporized hexene was introduced into the reactor through a pressure reducing valve to saturate the gas at 5 bar. 250ml of water and 56 g of azobisimidepropane dihydrochloride aqueous solution are then added dropwise to the reaction vessel with constant stirring over 4 hours, during which the reaction vessel is kept under stirring at a temperature of between 85 and 95 ℃ and the ethylene-butene gas-hexene gas pressure is kept constant at 5 bar. After the completion of the dropwise addition, the reaction was continued for 2 hours, and then ethylene-propylene-hexene gas was discharged and the pressure was reduced to normal pressure.31The transparent liquid obtained was examined by P NMR to find that it contained 93.5% of sodium diethylphosphinate, 3.2% of sodium ethylbutylphosphinate, 2.8% of sodium ethylhexylphosphinate, and the balance 0.5%.
The product of the above reaction was subjected to removal of acetic acid on a rotary evaporator and then dissolved with 7.5kg of deionized water. 3000 g of a solution containing 46% of aluminum sulfate tetradecahydrate was added dropwise to the reaction solution obtained above at a constant rate over one hour with stirring, and the obtained precipitate was filtered, washed repeatedly with hot water, then with acetone, and finally vacuum-dried at 130 ℃. 1671 g of solid product are obtained (yield 91.4%).
Examples 5 to 8 applications of flame retardants
The raw materials and sources adopted by the embodiment of the invention are as follows:
(1) nylon 66 resin, EPR27, Pingshan horse
(2) Glass fiber, ECS301UW, Chongqing International composite Co., Ltd
(3) MPP, Melapur 200 from BASF
(4) Zinc borate, Firebake ZB, available from US Borax
(5) Antioxidant Irganox 1098 from BASF
Plastic specimen preparation and testing
The flame retardant and polymer chips were mixed in the proportions indicated in table one and then strand, water cooled, and cut into pellets using a twin screw pelletizer at a temperature range of 280 ℃. And (3) drying the polymer granules with the flame retardant, and performing injection molding at 285 ℃ by using a single-screw injection molding machine.
And (3) flame retardant test: the vertical flame retardant test was performed according to the UL94 standard.
Notched impact strength: the impact of the flame retardant on the polymeric material during processing can be evaluated by evaluating the notched impact strength of the injection molded specimens, the lower the notched impact strength of the material, indicating that the more severe the molecular decomposition of the material during processing, the greater the negative impact of the flame retardant on the material. The test conditions of the melt index are carried out according to the national standard GB/T1843-2008.
And (3) equipment corrosion index testing: the corrosion of the flame retardant to equipment during processing can be expressed by a corrosion index, and the higher the corrosion index, the more serious the corrosion of the material to the equipment during processing is. The equipment corrosion index consisted of a die block with a 12x15x3mm extrusion orifice mounted in the die of an injection molding machine, and the weight loss at the die orifice was measured after 25 kg of molding compound was injected through the die block at a certain temperature.
The test results of the embodiment are shown in table one.
Watch 1
From the results in Table one, it can be seen that flame retardant materials formulated with the products of examples 2-4 of the present invention and PA66 have improved notched impact strength and corrosion resistance to equipment.
Claims (10)
1. A polydialkyl phosphinic acid metal complex salt and/or mixture thereof, wherein the chemical composition is as shown in formula (1):
wherein R1, R2, R3, R4 and R5 are the same or different and are H, or linear chain or branched chain C1-C8 saturated alkyl, or linear chain or branched chain C2-C12 unsaturated alkenyl or C6-C18 aryl, or organic groups containing carboxyl, hydroxyl, amine, ester, amide, epoxy or halogenated.
Wherein M is Ca, Mg, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn metal cation and/or protonated nitrogen base.
Wherein
m is the ion valence number of the metal cation
y: x is an arbitrary number from 0.005 to 0.15
z: x is an arbitrary number from 0.005 to 0.15
Wherein m is x + y + Z.
2. The polydialkylphosphinic acid metal complex salt and/or mixture of salts as claimed in claim 1 wherein R1, R2, R3, R4, R5 are selected from hydrogen, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, styryl.
3. The polydialkylphosphinic acid metal complex salt and/or mixture of salts as claimed in claims 1 to 2 wherein R1, R2 are selected from H, ethyl, R3, R4, R5 are selected from ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, styryl.
4. A polydialkylphosphinic acid metal complex salt and/or mixtures thereof as claimed in any one of claims 1 or 3 wherein M is Ca, Mg, Zn, Al metal cation and/or mixture of metal cations.
5. The polydialkylphosphinic acid metal complex salt and/or mixture thereof as claimed in any one of claims 1 to 3 wherein
y: x is any number from 0.005 to 0.075
z: x is any number from 0.005 to 0.075
Wherein m is x + y + z.
6. The polydialkylphosphinic acid metal complex salt and/or mixture thereof as claimed in any one of claims 1 to 4, characterised in that it has a particle size of 0.1 to 1000 μm, a solubility in water of 0.01 to 10g/L, a bulk density of 80 to 800g/L and a residual moisture of 0.1 to 5%.
7. Use of a polydialkylphosphinic acid metal complex salt and/or mixtures thereof as claimed in any one of claims 1 to 5 as a flame retardant or flame retardant synergist.
8. Use of the polydialkylphosphinic acid metal complex salts and/or mixtures thereof as claimed in any one of claims 1 to 5, as flame retardants for varnishes and foamed coatings, for wood and other cellulose-containing products, as reactive and/or nonreactive flame retardants for polymers, for the preparation of flame-retardant thermoplastic or thermosetting polymer moulding materials, for the preparation of flame-retardant polymer mouldings and/or for equipping flame retardants by polyester melt spinning and fiber textiles and mixed fabrics with flame retardants and/or for epoxy resins, and as synergists in flame retardant mixtures and flame retardants.
9. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers comprising from 0.1 to 45% by weight of a polydialkylphosphinic acid metal complex salt and/or a mixture thereof as claimed in any of claims 1 to 5, from 55 to 99.9% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, from 0 to 55% by weight of additives and from 0 to 30% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.
10. Flame retardant thermoplastic or thermoset polymer moulding material, polymer moulded bodies, polymer films, polymer filaments and polymer fibres according to any of claims 8 to 9, characterised in that the flame retardant is a polydialkylphosphinic acid metal complex salt and a flame retardant synergist, wherein the synergist is: condensation products of melamine and/or reaction products of melamine with phosphoric acid and/or reaction products of melamine with polyphosphoric acid or mixtures thereof and/or polycondensation products of melamine with cyanuric acid or mixtures thereof; a nitrogen-containing phosphate of the formula (NH4) y H3-y PO4 or (NH4 PO3) z, wherein y is equal to 1 to 3 and z is equal to 1 to 10,000; benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, dicyandiamide and/or guanidine; magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate and/or zinc stannate, zinc phosphate.
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| CN114806601A (en) * | 2022-05-10 | 2022-07-29 | 江苏利思德新材料有限公司 | Alkyl phosphinate composition and preparation method and application thereof |
| WO2023168790A1 (en) * | 2022-03-10 | 2023-09-14 | 江苏利思德新材料有限公司 | Aluminum diethylphosphinate crystal with low fine powder content, and preparation method therefor and use thereof |
| WO2023168791A1 (en) * | 2022-03-10 | 2023-09-14 | 江苏利思德新材料有限公司 | Halogen-free flame retardant composition and application thereof |
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| WO2024060020A1 (en) * | 2022-09-20 | 2024-03-28 | 中国科学院宁波材料技术与工程研究所 | Dialkyl phosphinic acid hybrid salt, preparation method therefor, and use thereof |
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