CN114874265A - Rare earth flame-retardant complex and preparation method and application thereof - Google Patents
Rare earth flame-retardant complex and preparation method and application thereof Download PDFInfo
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- CN114874265A CN114874265A CN202210502882.6A CN202210502882A CN114874265A CN 114874265 A CN114874265 A CN 114874265A CN 202210502882 A CN202210502882 A CN 202210502882A CN 114874265 A CN114874265 A CN 114874265A
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- retardant
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- phosphate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 27
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000010668 complexation reaction Methods 0.000 title description 2
- -1 coatings Polymers 0.000 claims abstract description 19
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 18
- 239000002861 polymer material Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 5
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 238000001035 drying Methods 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
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- YASRHLDAFCMIPB-UHFFFAOYSA-N (1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]octan-4-yl)methanol Chemical compound C1OP2(=O)OCC1(CO)CO2 YASRHLDAFCMIPB-UHFFFAOYSA-N 0.000 claims description 2
- HEORQRHVQJVWEH-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) dihydrogen phosphate Chemical compound OCC(C)(C)COP(O)(O)=O HEORQRHVQJVWEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 2
- LCANECIWPMDASZ-UHFFFAOYSA-N 2-isocyanatoethanol Chemical compound OCCN=C=O LCANECIWPMDASZ-UHFFFAOYSA-N 0.000 claims description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229910003472 fullerene Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960001954 piperazine phosphate Drugs 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 229920005594 polymer fiber Polymers 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000013022 formulation composition Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 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 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a rare earth flame-retardant complex, a preparation method and application thereof, and the structural formula is
Ln is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy. The invention has excellent flame-retardant synergistic performance and is combined with phosphorus-nitrogen seriesThe flame retardant is matched, so that the flame retardant efficiency of the phosphorus-nitrogen flame retardant can be effectively improved, and the addition amount of the phosphorus-nitrogen flame retardant is reduced. The rare earth flame-retardant complex can be applied to the fields of engineering plastics, polymer films, polymer fibers, coatings, rubber and the like, and the flame retardant property of the product is improved.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a rare earth flame-retardant complex and a preparation method and application thereof.
Background
In recent years, polymer materials have been widely used in many fields such as electronic and electrical products, high-speed rail ships, aerospace and the like due to advantages such as light weight, high strength and easy processing. However, most of the high polymer materials are composed of C, H, O and other elements, and belong to intrinsic flammable and combustible materials, so that the high polymer materials are easy to cause property loss due to fire. In addition, the high molecular material can generate a large amount of smoke and toxic gas during combustion, thereby causing great threat to the life health of people. Therefore, the flame retardant modification of the high polymer material has important significance for widening the application field and protecting the life and health of people.
In the current technology, the flame retardant mainly includes an intumescent flame retardant, a halogen flame retardant, a nitrogen flame retardant, a phosphorus flame retardant, a metal hydroxide flame retardant, and the like. Halogen flame retardants mainly comprise chlorine-based flame retardants and bromine-based flame retardants, but have some negative effects on health, the environment, and the properties of final products, so that it has been a trend of development that the applications of halogen flame retardants are gradually limited. Flame retardants such as intumescent flame retardants, nitrogen flame retardants, and phosphorus flame retardants, although containing no halogen, have low flame retardant efficiency, require a large proportion to exert a flame retardant effect, and have a large influence on the performance and processability of products. Similar problems exist with metal hydroxide flame retardants.
Along with the improvement of the green environmental awareness of people, China also puts forward higher and higher requirements on the macromolecular flame retardant, similar to the RoHS requirements and the REACH list of the European Union. Therefore, the development of a novel halogen-free, low-smoke, high-efficiency flame retardant and flame retardant technology is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a rare earth flame-retardant complex.
The invention also aims to provide a preparation method of the rare earth flame-retardant complex.
The invention also aims to provide a flame-retardant polymer material.
The technical scheme of the invention is as follows:
a rare earth flame-retardant complex with a structural formula of
Ln is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy.
In a preferred embodiment of the invention, Ln is Ce or La.
The preparation method of the rare earth flame-retardant complex comprises the following steps:
(1) adding Ln (NO) 3 ) 3 ·6H 2 Dissolving O in deionized water to obtain solution A, and adding DDP ([ (6-oxo-6H-dibenzo [ c, e ])][1，2]Oxaphosphohexa-6-yl) methyl]Succinic acid) is dispersed in deionized water to obtain suspension B; (2) adding 10-25% ammonia water solution into the suspension B until DDP is completely dissolved to obtain solution C with pH of 6-8;
(3) dropwise adding the solution A into the solution C, continuously stirring at 30-50 ℃, continuously reacting at room temperature for 0.5-3h after dropwise adding is finished, performing centrifugal treatment, and fully washing with deionized water to obtain a solid product;
(4) and (3) drying the solid product at 90-120 ℃ in vacuum to constant weight to obtain the rare earth flame-retardant complex.
In a preferred embodiment of the invention, Ln (NO) is present in the solution A 3 ) 3 ·6H 2 The proportion of O and deionized water is 1-5 mmol: 10-50 mL; in the suspension B, the ratio of DDP to deionized water is 1-5 mmol: 10-50 mL.
Further preferably, said Ln (NO) 3 ) 3 ·6H 2 The mol ratio of O to DDP is 1: 1-3.
The flame-retardant high polymer material comprises the rare earth flame-retardant complex, a high polymer material, a halogen-free flame retardant, an anti-dripping agent and a processing aid.
In a preferred embodiment of the invention, the mass percentages of the rare earth flame-retardant complex, the high polymer material, the halogen-free flame retardant, the anti-dripping agent and the processing aid are 0.2-3%, 79.0-92.6%, 7-17%, 0.1-0.5% and 0.1-0.5% in sequence.
In a preferred embodiment of the present invention, the polymer material is selected from at least one of polyethylene, polypropylene, polyoxymethylene, polycarbonate, polyamide, polyester, acrylonitrile-butadiene-styrene copolymer, polyurethane, polymethyl methacrylate, polyphenylene sulfide, polyphenylene oxide, polystyrene, ethylene-vinyl acetate copolymer, ethylene-propylene-diene monomer rubber, natural rubber, and epoxy resin.
In a preferred embodiment of the present invention, the halogen-free flame retardant is selected from the group consisting of ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melamine cyanurate, bis (diphenyl) phosphate, m-phenylene bis (diphenyl) phosphate, dimethyl methylphosphonate, triphenyl phosphate, aluminum phosphite, aluminum diethylphosphinate, 2-carboxyethylphenylphosphinic acid, piperazine phosphate, piperazine pyrophosphate, dimethyl methylphosphonate, tris (neopentyl glycol phosphate) methylamine, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane, [ 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane ] phosphate melamine salt, melamine cyanurate salt, and mixtures thereof, At least one of [ 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane ] phenylsilane, 9-10-dihydro-oxa-10-phosphaphenanthrene-10-oxide, and 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.
In a preferred embodiment of the invention, the anti-dripping agent is selected from the group consisting of polytetrafluoroethylene, fullerene, graphene, halloysite nanotubes, silicon carbide whiskers, hexaphenoxycyclotriphosphazene, and 13, 5, 5-tetrafluoro-1, 3-diphenoxycyclotriphosphazene
At least one of (1).
In a preferred embodiment of the present invention, the processing aid is selected from at least one of EBS, antioxidant 1010, pentaerythritol, tris (2-hydroxyethyl) isocyanate.
The rare earth flame-retardant complex can be applied to the fields of engineering plastics, polymer films, polymer fibers, coatings, rubber and the like, and the flame retardant property of the product is improved.
The invention has the beneficial effects that:
1. the invention has excellent flame-retardant synergistic performance, and can effectively improve the flame-retardant efficiency of the phosphorus-nitrogen flame retardant and reduce the addition amount of the phosphorus-nitrogen flame retardant when being matched with the phosphorus-nitrogen flame retardant.
2. The invention has less synthesis steps, is simple and easy to operate; the energy consumption is low, and high temperature and high pressure are not needed; the reaction time is short, and the reaction yield is high; the reaction process does not use organic solvent, and belongs to a green and environment-friendly preparation method.
3. The flame-retardant high polymer material disclosed by the invention is high in flame-retardant grade and excellent in mechanical property.
Drawings
FIG. 1 is a scanning electron micrograph of La @ DDP prepared in examples 1 to 2 of the present invention.
FIG. 2 shows IR spectra of La @ DDP prepared in examples 1-2 of the present invention.
FIG. 3 is a thermogravimetric plot of La @ DDP prepared in examples 1 through 2 of the present invention.
FIG. 4 is a digital photograph, a scanning electron micrograph, and an EDS spectrum of a combustion residual carbon analysis of comparative example 7 and example 7 according to the present invention (comparative example 7(a, b, c, d); example 7(e, f, g, h)).
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Adding La (NO) 3 ) 3 ·6H 2 Dissolving O (1mmo1) in 10mL of deionized water to obtain a solution A, and dispersing DDP (1mmol) in 10mL of deionized water to obtain a suspension B;
(2) to suspension B, 10% aqueous ammonia was added until complete dissolution of DDP to give solution C, pH about 6.
(3) Transferring the solution C to a three-neck flask, dropwise adding the solution A into the solution C through a dropping funnel, continuously stirring at 30 ℃, continuously reacting at room temperature for 0.5h after dropwise adding, performing centrifugal treatment, and washing for at least 3 times by using deionized water to obtain a solid product;
(4) and (3) drying the solid product at 90 ℃ in vacuum to constant weight to obtain the rare earth flame-retardant complex La @ DDP shown in figures 1 to 3.
The yield of the obtained rare earth flame-retardant complex La @ DDP is 99.0%.
Example 2
(1) Adding La (NO) 3 ) 3 ·6H 2 Dissolving O (1mmol) in 10mL of deionized water to obtain a solution A, and dispersing DDP (1.5mmol) in 20mL of deionized water to obtain a suspension B;
(2) to suspension B, 10% aqueous ammonia was added until complete dissolution of DDP to give solution C, pH about 7.
(3) Transferring the solution C to a three-neck flask, dropwise adding the solution A into the solution C through a dropping funnel, continuously stirring at 30 ℃, continuously reacting at room temperature for 1h after dropwise adding, performing centrifugal treatment, and washing with deionized water for at least 3 times to obtain a solid product;
(4) and (3) drying the solid product at 90 ℃ in vacuum to constant weight to obtain the rare earth flame-retardant complex La @ DDP shown in figures 1 to 3.
The yield of the obtained rare earth flame-retardant complex La @ DDP is 98.2%.
Example 3
(1) Adding Ce (NO) 3 ) 3 ·6H 2 Dissolving O (1mmol) in 10mL of deionized water to obtain a solution A, and dispersing DDP (3mmol) in 30mL of deionized water to obtain a suspension B;
(2) to suspension B, 10% aqueous ammonia was added until complete dissolution of DDP to give solution C, pH about 7.
(3) Transferring the solution C to a three-neck flask, dropwise adding the solution A into the solution C through a dropping funnel, continuously stirring at 40 ℃, continuously reacting at room temperature for 2 hours after dropwise adding, performing centrifugal treatment, and washing with deionized water for at least 3 times to obtain a solid product;
(4) and (3) carrying out vacuum drying on the solid product at the temperature of 90 ℃ to constant weight to obtain the rare earth flame-retardant complex Ce @ DDP.
The yield of the obtained rare earth flame-retardant complex Ce @ DDP is 97.5.
Example 4
(1) Mixing Y (NO) 3 ) 3 ·6H 2 Dissolving O (1mmol) in 10mL of deionized water to obtain a solution A, and dispersing DDP (3mmol) in 30mL of deionized water to obtain a suspension B;
(2) to suspension B was added 15% aqueous ammonia solution until the DDP was completely dissolved, giving solution C, pH about 8.
(3) Transferring the solution C to a three-neck flask, dropwise adding the solution A into the solution C through a dropping funnel, continuously stirring at 40 ℃, continuously reacting at room temperature for 2 hours after dropwise adding, performing centrifugal treatment, and washing with deionized water for at least 3 times to obtain a solid product;
(4) and (3) carrying out vacuum drying on the solid product at the temperature of 90 ℃ to constant weight to obtain the rare earth flame-retardant complex Ce @ DDP.
The yield of the obtained rare earth flame-retardant complex Y @ DDP is 97.0%.
Example 5
The La @ DDP prepared in the embodiment 1 is applied to a flame-retardant polymer, and comprises the following specific components: polypropylene: 92.6%, La @ DDP: 0.2% ammonium polyphosphate: 7.0%, hexaphenoxycyclotriphosphazene: 0.1%, EBS: 0.1 percent.
Weighing the raw materials according to the proportion, and putting the raw materials into a high-speed mixer for uniform mixing to form a premix; adding the premix into a double-screw extruder for melt extrusion, carrying out bracing granulation, and finally drying to obtain the flame-retardant polymer material based on the rare earth flame-retardant complex, and carrying out related performance tests.
Examples 6 to 14 and comparative examples 1 to 7
Examples 6-14 and comparative examples 1-7 were prepared as in example 5, with the specific formulation compositions shown in Table 1, and the La @ DDP and Ce @ DDP were prepared as in examples 1 and 3, respectively. The comparison example 7 and the comparison example 7 are shown in fig. 4.
TABLE 1 formulation compositions of examples 5-14 and comparative examples 1-7
TABLE 2 summary of the properties of examples 5-14 and comparative examples 1-6
From examples 1-4, it can be seen that the rare earth flame-retardant complex prepared by the invention has the advantages of simple preparation method and high yield. As can be seen from the data of example 7 and comparative example 1/2/3 in Table 2, the rare earth flame-retardant complex and the halogen-free flame retardant have good synergistic effect, and can greatly improve the flame-retardant efficiency, so that the V-0 flame-retardant grade can be achieved by only needing less addition proportion. The anti-dripping agent of the invention can effectively prevent the dripping phenomenon generated when the polymer is burnt. The compound flame-retardant system can simultaneously play a flame-retardant role in gas phase and condensed phase. In the condensed phase, on the one hand, degradation products such as phosphoric acid and polyphosphoric acid generated by decomposition of the halogen-free flame retardant at high temperature catalyze formation of a carbon layer, and remain in the form of P ═ O and P — O — C in the carbon layer. On the other hand, rare earth ions and oxides thereof generated by the decomposition of La @ DDP at high temperature have the capability of catalyzing esterification and ester exchange reactions. Phosphate obtained by decomposing the halogen-free flame retardant can further react with carbonate through ester exchange under the catalysis of La, so that a more compact three-dimensional network carbon layer structure is formed, the transfer of heat and oxygen to a bottom layer matrix is reduced, and combustible volatile matters are also reduced from entering a gas phase. In the gas phase, the gas generated by decomposing the halogen-free flame retardant dilutes oxygen and combustible gas, phosphorus-containing free radicals are released in the La @ DDP thermal decomposition process and diffuse to the gas phase, and the combustion is interrupted and inhibited by quenching high-activity free radicals such as OH, H and the like generated by the breakage of a high molecular chain, so that the degradation process of the polymer is slowed down. Thus, under the dual action of both condensed phase and vapor phase flame retardation, continuous dense highly graphitized carbon residue is produced, which facilitates a reduction in heat and oxygen transfer, ultimately slowing or even preventing the combustion process.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A rare earth flame-retardant complex is characterized in that: the structural formula is
Ln is selected from Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy.
2. The rare earth flame retardant complex of claim 1, wherein: and Ln is Ce or La.
3. A process for preparing a rare earth flame retardant complex according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) ln (NO) 3 ) 3 ·6H 2 Dissolving O in deionized water to obtain solution A, and dispersing DDP in deionized waterObtaining a suspension B; (2) adding 10-25% ammonia water solution into the suspension B until DDP is completely dissolved to obtain solution C with pH of 6-8;
(3) dropwise adding the solution A into the solution C, continuously stirring at 30-50 ℃, continuously reacting at room temperature for 0.5-3h after dropwise adding is finished, performing centrifugal treatment, and fully washing with deionized water to obtain a solid product;
(4) and (3) drying the solid product at 90-120 ℃ in vacuum to constant weight to obtain the rare earth flame-retardant complex.
4. The method of claim 3, wherein: in the solution A, Ln (NO) 3 ) 3 ·6H 2 The proportion of O and deionized water is 1-5 mmol: 10-50 mL; in the suspension B, the ratio of DPP to deionized water is 1-5 mmol: 10-50 mL.
5. The method of claim 4, wherein: ln (NO) as defined above 3 ) 3 ·6H 2 The molar ratio of O to DPP is 1: 1-3.
6. A flame-retardant polymer material is characterized in that: the raw materials of the rare earth flame-retardant complex comprise the rare earth flame-retardant complex as described in claim 1 or 2, a high molecular material, a halogen-free flame retardant, an anti-dripping agent and a processing aid.
7. The flame-retardant polymer material according to claim 6, wherein: the high polymer material is selected from at least one of polyethylene, polypropylene, polyformaldehyde, polycarbonate, polyamide, polyester, acrylonitrile-butadiene-styrene copolymer, polyurethane, polymethyl methacrylate, polyphenylene sulfide, polyphenyl ether, polystyrene, ethylene-vinyl acetate copolymer, ethylene propylene diene monomer, natural rubber and epoxy resin.
8. The flame-retardant polymer material according to claim 6, wherein: the halogen-free flame retardant is selected from ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melamine cyanurate, bis (diphenyl) phosphate, m-phenylene bis (diphenyl) phosphate, dimethyl methylphosphonate, triphenyl phosphate, aluminum phosphite, diethyl aluminum hypophosphite, 2-carboxyethylphenyl hypophosphorous acid, piperazine phosphate, piperazine pyrophosphate, dimethyl methylphosphonate, tris (neopentyl glycol phosphate) methylamine, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane, [ 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane ] phosphate melamine salt, [ 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo (2, 2, 2) octane ] phenylsilane, 9-10-dihydro-oxa-10-phosphaphenanthrene-10-oxide and 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.
9. The flame-retardant polymer material according to claim 6, wherein: the anti-dripping agent is at least one selected from polytetrafluoroethylene, fullerene, graphene, halloysite nanotubes, silicon carbide whiskers, hexaphenoxycyclotriphosphazene and 1, 3, 5, 5-tetrafluoro-1, 3-diphenoxycyclotriphosphazene.
10. The flame-retardant polymer material according to claim 6, wherein: the processing aid is at least one of EBS, an antioxidant 1010, pentaerythritol and tris (2-hydroxyethyl) isocyanate.
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