CN117720773A - Modified flame retardant and preparation method and application thereof - Google Patents
Modified flame retardant and preparation method and application thereof Download PDFInfo
- Publication number
- CN117720773A CN117720773A CN202311793204.0A CN202311793204A CN117720773A CN 117720773 A CN117720773 A CN 117720773A CN 202311793204 A CN202311793204 A CN 202311793204A CN 117720773 A CN117720773 A CN 117720773A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- layer
- nitrogen
- modified
- tannic acid
- Prior art date
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class 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 172
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 129
- 239000010410 layer Substances 0.000 claims abstract description 94
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 59
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 59
- 229920002258 tannic acid Polymers 0.000 claims abstract description 59
- 229940033123 tannic acid Drugs 0.000 claims abstract description 59
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 59
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 58
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- -1 polyethylene Polymers 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011247 coating layer Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- 229920000768 polyamine Polymers 0.000 claims abstract description 8
- 229920000573 polyethylene Polymers 0.000 claims abstract description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 230000009920 chelation Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229920000388 Polyphosphate Polymers 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000001205 polyphosphate Substances 0.000 claims description 12
- 235000011176 polyphosphates Nutrition 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 7
- 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 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001462 antimony Chemical class 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical class [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000729 poly(L-lysine) polymer Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical class [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 14
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 13
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical class CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
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- 238000001228 spectrum Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
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- 239000003963 antioxidant agent Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
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- 230000004580 weight loss Effects 0.000 description 5
- 239000013522 chelant Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical class [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
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- 150000002367 halogens Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 description 1
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- OCFSGVNHPVWWKD-UHFFFAOYSA-N butylaluminum Chemical compound [Al].[CH2]CCC OCFSGVNHPVWWKD-UHFFFAOYSA-N 0.000 description 1
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- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BBIDBFWZMCTRNP-UHFFFAOYSA-N ethylalumane Chemical compound CC[AlH2] BBIDBFWZMCTRNP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 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
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- 229920001864 tannin Polymers 0.000 description 1
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- 150000007970 thio esters Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
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- 229960001763 zinc sulfate Drugs 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified flame retardant and a preparation method and application thereof, wherein the modified flame retardant comprises a granular flame retardant and a coating layer coated on the granular flame retardant, the coating layer comprises a nitrogen-containing layer, a tannic acid layer and a metal salt layer which are sequentially arranged, nitrogen-containing substances in the nitrogen-containing layer are one or a combination of more than one of polycationic electrolyte containing nitrogen, polyethylene polyamine with carbon number more than or equal to 4 and polyethyleneimine, tannic acid in the tannic acid layer and metal ions in the metal salt layer can be subjected to chelation to form a chelating structure, and a coating procedure of the nitrogen-containing layer, a coating procedure of the tannic acid layer and a coating procedure of the metal salt layer are sequentially carried out during preparation; the modified flame retardant disclosed by the invention has the advantages of good thermal stability, low preparation process operation difficulty, low preparation energy consumption and the like on the basis of excellent flame retardant property, is suitable for a high-temperature processing process, is applied to plastics, and can effectively improve the flame retardance of plastics.
Description
Technical Field
The invention relates to the field of flame retardant materials, in particular to a modified flame retardant and a preparation method and application thereof.
Background
Along with the continuous development of high polymer materials, various flame retardants capable of reducing the combustibility and flammability of polymers are widely researched and applied, and the flame retardants are in the stage of vigorous development, so that the flame retardant materials are widely applied to the fields of electronic appliances, transportation, aerospace and the like. The flame retardant is various in variety and mainly comprises halogen flame retardant, phosphorus flame retardant, nitrogen flame retardant and the like, but with the continuous improvement of environmental requirements, the halogen flame retardant gradually leaves the market, and meanwhile, the phosphorus flame retardant, the nitrogen flame retardant, the phosphorus-nitrogen mixed flame retardant and the like with better flame retardant effect have larger application and development space, and the phosphorus flame retardant has the advantages of two-phase flame retardance, low smoke and toxicity, small addition amount and the like, thus the flame retardant occupies a larger scale in the market, and the flame retardant application market is also continuously expanded.
However, phosphorus flame retardants have a great deal of problems during use. Adding a large amount of powder flame retardant into plastics can deteriorate the mechanical properties of the plastics and influence the comprehensive properties of the materials; part of the flame retardant can release smoke dust and gas in the processing process to cause environmental pollution; the dispersibility of the flame retardant in the material is poor, the compatibility with the material is poor, and the flame retardant efficiency and the comprehensive performance of the material are affected; part of the flame retardant has poor high-temperature heat stability and is difficult to apply to a high-temperature processing process, thereby influencing the flame retardant effect.
Aiming at the problems, the prior art is improved, for example, chinese patent CN107778530B discloses a preparation method of a micro-encapsulation surface modification flame retardant of a mussel-like material, which takes a mixed solution of formaldehyde aqueous solution, melamine, urea, sodium carbonate, ammonium polyphosphate, sodium dodecyl sulfate, the mussel-like material and the like as a coating layer, specifically, firstly, urea formaldehyde modified melamine resin is prepared for coating, then a tannic acid iron complex is coated, and micro-encapsulation is formed on the surface of the flame retardant for flame retardant surface modification, so that the char formation of the material is enhanced; however, in the patent, on one hand, special urea-formaldehyde modified melamine resin needs to be matched for coating, so that the dependence is strong, the process is complex, and the urea-formaldehyde modified melamine resin needs high-temperature reaction and high-temperature coating, so that the energy consumption is high; on the other hand, the ideal flame-retardant effect can be obtained only by carrying out the operation of coating the iron tannins for many times, and the process steps are increased, so that the method is not beneficial to industrial application. As another example, chinese patent CN104558690a discloses an organosilicon coated modified phosphines/phosphates flame retardant, in which silanes with different structures are subjected to hydrolysis reaction on the surface of phosphines/phosphates solid particles, and the phosphines/phosphates are subjected to organosilicon coated modification by chemical reaction, so that the water resistance and electrical properties of the phosphines/phosphates flame retardant polymer are improved, but the thermal stability of the material is still to be improved. As another example, chinese patent CN113621179a discloses a surface-modified zinc alkyl phosphinate flame retardant and modified polycarbonate based thereon, wherein the surface of the C1-2 zinc alkyl phosphinate is modified by using a silane coupling agent, and the carbon residue of the obtained modified flame retardant is improved, but the thermal stability of the material is still to be improved. As another example, chinese patent CN115260594B discloses a modified phosphorus-containing flame retardant, which includes a phosphorus-containing flame retardant and a coating layer coated on the phosphorus-containing flame retardant, the coating layer including a polyelectrolyte layer and a polyurethane layer sequentially coated on the phosphorus-containing flame retardant; the polyurethane in the polyurethane layer is selected from one or a combination of more of polyether polyurethane, polyester polyurethane and polyether polyester mixed polyurethane; the polyurethane in the polyurethane layer is solidified polyurethane; the cured polyurethane is obtained by curing polyurethane and a curing agent; the curing agent is selected from one or a combination of two of diisocyanate and polyisocyanate, and although the heat resistance of the phosphorus-containing flame retardant is improved, the heat resistance is required to be further improved so as to be suitable for preparing flame retardant materials at higher processing temperature, and in particular, the modified phosphorus-containing flame retardant needs to be heated at high temperature in the preparation process, and even needs to be cured at a temperature of up to 85 ℃, so that the energy consumption is high.
Disclosure of Invention
The invention aims to overcome one or more defects in the prior art and provide a novel modified flame retardant which has good thermal stability and low preparation process operation difficulty on the basis of excellent flame retardant property.
The invention also provides a preparation method of the modified flame retardant.
The invention also provides application of the modified flame retardant in preparation of flame retardant materials, wherein the flame retardant materials comprise high-molecular flame retardant materials.
In order to achieve the above purpose, the invention adopts a technical scheme that: the modified flame retardant comprises a granular flame retardant and a coating layer coated on the granular flame retardant, wherein the coating layer comprises a nitrogen-containing layer, a tannic acid layer and a metal salt layer which are sequentially arranged, nitrogen-containing substances in the nitrogen-containing layer are one or a combination of more than or equal to 4 of polycation electrolyte containing nitrogen, polyethylene polyamine with carbon number and polyethylene imine, and tannic acid in the tannic acid layer and metal ions in the metal salt layer can be chelated to form a chelating structure.
According to some preferred and specific aspects of the present invention, the nitrogen-containing polycationic electrolyte comprises a combination of one or more selected from polydiallyldimethyl ammonium chloride, polyvinylpyridine, chitosan, polyacrylamide hydrochloride N-methyl-N-vinylacetamide, poly-L-lysine hydrochloride.
According to the invention, the polyethylene polyamine has the structure of formula (I):
in the formula (I), n is 1-20.
In some embodiments, n is 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, etc.
According to some preferred and specific aspects of the present invention, the polyethylene polyamine is one or a combination of more selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine.
According to some preferred aspects of the present invention, the metal salt in the metal salt layer is a combination of one or more selected from the group consisting of iron salt, zinc salt, magnesium salt, calcium salt, cobalt salt, aluminum salt, arsenic salt, and antimony salt.
Further, the acid radical of the metal salt is selected from sulfate, acetate, nitrate or halogen ions. The halogen ion includes chloride ion, bromide ion, iodide ion, and the like.
Preferably, the metal salt is selected to be soluble in water.
According to some preferred aspects of the invention, the metal ion of the metal salt comprises Co 2+ 、Zn 2+ 、Mg 2+ 、Al 3+ 、As 3 + 、Sb 3+ 、Ca 2+ One or more combinations thereof. In practical application, the metal ions can form a stable chelate structure with tannic acid, so that stable combination between a tannic acid layer and a metal salt layer is facilitated, a denser coating structure is formed, a certain flame retardant effect can be achieved in the combustion process, and the flame retardant performance can be further improved.
In some embodiments, the metal salt includes, but is not limited to, iron trichloride, iron dichloride, zinc chloride, zinc sulfate, zinc nitrate, magnesium sulfate, magnesium nitrate, magnesium chloride, calcium nitrate, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt sulfate, aluminum chloride, aluminum nitrate, arsenic chloride, antimony sulfate, antimony nitrate, antimony chloride, and the like.
According to some preferred aspects of the present invention, the mass ratio of the particulate flame retardant, the nitrogen-containing layer, the tannic acid layer, and the metal salt layer is 100-800:1-10:0.1-15.
According to some preferred aspects of the present invention, the coating layer further includes a silane coupling agent layer formed on the metal salt layer, and compatibility between the flame retardant and the polymer material may be further improved.
Further, the mass ratio of the granular flame retardant to the silane coupling agent layer is 100-800:0.1-20.
According to some preferred and specific aspects of the invention, the method of preparing the coating layer comprises:
coating the nitrogen-containing layer on the granular flame retardant to form a first intermediate;
then mixing the first intermediate with tannic acid in a solvent to form a tannic acid layer on the nitrogen-containing layer to form a second intermediate;
then mixing the second intermediate with a metal salt in a solvent to form the metal salt layer on the tannic acid layer;
and selectively forming the silane coupling agent layer on the metal salt.
In some embodiments of the present invention, in preparing the coating layer, the particulate flame retardant is dispersed in a solvent in the presence of a dispersing agent to form a dispersion solution, then a nitrogen-containing substance is added, mixed and stirred to form the nitrogen-containing layer coated on the particulate flame retardant, then tannic acid is added, mixed and stirred to form the tannic acid layer coated on the nitrogen-containing layer, then a metal salt is added, mixed and stirred to form the metal salt layer coated on the tannic acid layer, and then a silane coupling agent is optionally added, mixed and stirred.
Further, the silane coupling agent in the silane coupling agent layer is one or a combination of more selected from vinyl trimethoxy silane, vinyl triethoxy silane, gamma-aminopropyl trimethoxy silane, dimethylphenyl silane, phenyl triethoxy silane, octyl trimethoxy silane and n-octyl triethoxy silane.
In some embodiments of the invention, the solvent is a combination of one or more selected from the group consisting of water, ethanol, propanol, acetone.
In some embodiments of the invention, the particulate flame retardant comprises a nitrogen-containing flame retardant or a phosphorus-containing flame retardant.
Further, the phosphorus-containing flame retardant includes, but is not limited to, one or more combinations that may be hypophosphite, alkyl hypophosphite, phosphite, polyphosphate, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof.
In some embodiments, the alkyl group in the alkyl hypophosphite is a C1-C6 alkyl group. Further, the alkyl hypophosphite is one or a combination of more selected from diethyl aluminum hypophosphite, diethyl zinc hypophosphite, monoethyl aluminum hypophosphite, monoethyl zinc hypophosphite, dibutyl zinc hypophosphite, butyl aluminum hypophosphite and butyl zinc hypophosphite.
Further, the nitrogen-containing flame retardant includes, but is not limited to, one or more combinations selected from melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, ammonium polyphosphate, pyrophosphate.
The invention provides another technical scheme that: the preparation method of the modified flame retardant comprises a coating process of a nitrogen-containing layer, a coating process of a tannic acid layer and a coating process of a metal salt layer and a coating process of a selective silane coupling agent layer are sequentially carried out on the granular flame retardant.
According to some preferred and specific aspects of the present invention, the coating process is performed in the presence of a dispersant in a solvent.
In some embodiments of the present invention, the dispersant includes, but is not limited to, a surfactant selected from one or more of anionic surfactants, nonionic surfactants, and cationic surfactants.
Further, the anionic surfactant is selected from one or more of sulfonate, sulfate, phosphate.
Further, the nonionic surfactant is selected from one or a combination of more of alkylphenol ethoxylates, fatty acid polyoxyethylene esters and alkyl alcohol amides.
Further, the cationic surfactant is selected from one or more of fatty amine salt, polyethylene polyamine salt and quaternary ammonium salt.
In some embodiments of the invention, the solvent is selected from one or more of deionized water, ethanol, propanol, acetone.
In some embodiments of the invention, the mass ratio of the particulate flame retardant to the solvent is from 1:1 to 1:8.
In some embodiments of the invention, the dispersant is present in the solvent at a mass concentration of 0.1 to 5g/L.
According to the invention, the preparation temperature of the modified flame retardant can be relatively low, the energy consumption requirement is low, and the coating process can be controlled to be carried out at 10-30 ℃. Preferably, it can be carried out at 20-30 ℃. According to a specific aspect of the present invention, the coating process may be performed at room temperature.
According to the invention, each coating process is independently completed and then the next coating process is carried out according to the sequence of the coating processes.
According to a specific aspect of the invention, an embodiment for preparing the modified flame retardant comprises: dispersing the granular flame retardant and the dispersing agent into a solvent, adding a nitrogen-containing substance, stirring for 0.5-1 h at the temperature of 20-80 ℃; adding tannic acid into the solution after the operation, stirring for 0.5-5 h at the temperature of 20-80 ℃; adding a metal salt solution into the solution after the operation, stirring for 0.5-5 h at the temperature of 20-80 ℃; and adding a silane coupling agent into the solution after the operation, stirring for 0.5-3 hours at the temperature of 20-80 ℃ to obtain the modified flame retardant.
In some embodiments, the coating materials may be added dropwise, or in portions, or in one portion.
In some embodiments of the invention, the preparation method further comprises a post-treatment step after coating is completed, which comprises centrifugation, water washing, and drying.
The invention provides another technical scheme that: a flame retardant additive comprising the modified flame retardant described above.
Further, the flame retardant additive further comprises a combination of one or more of zinc borate, melamine polyphosphate, and melamine cyanurate.
According to some preferred and specific aspects of the invention, the flame retardant additive consists of the modified flame retardant, zinc borate, melamine polyphosphate and melamine cyanurate.
Further, the mass ratio of the modified flame retardant to the zinc borate to the melamine polyphosphate to the melamine cyanurate is 8-15:0.1-2:2.5-4:3.5-5.
The invention provides another technical scheme that: the modified flame retardant, or the application of the flame retardant additive in preparing flame retardant materials.
In some embodiments of the present invention, the flame retardant material is a flame retardant polymeric material comprising a resin matrix and the modified flame retardant described above or the flame retardant additive described above.
Further, the resin matrix may be polyamide, polyurethane, polyolefin, or the like.
The flame-retardant polymer material is a halogen-free flame-retardant material.
In some embodiments of the present invention, the halogen-free flame retardant material is a halogen-free flame retardant polyamide comprising, in parts by mass: 45-85 parts of polyamide, 5-12 parts of modified flame retardant, 2-10 parts of other flame retardants, 0.3-3 parts of toughening agent, 0.2-4 parts of antioxidant and 0-3.5 parts of coupling agent.
In some embodiments of the invention, the polyamide is selected from the group consisting of one or more of PA6, PA66, PA-612, PA-12, PA-6T, and PA-9T; the other flame retardant is selected from one or a combination of more of zinc borate, melamine polyphosphate and melamine cyanurate; the toughening agent is selected from one or two of POE grafted maleic anhydride and EPDM grafted maleic anhydride; the antioxidant is selected from one or more of phenolic antioxidants 1098, 1076, 1010, 1024, 2246, BHT, phosphorus antioxidants 168, 636, 626, 686, thio ester antioxidants DLTP, DSTP and composite antioxidants 215, 225; the coupling agent is selected from one or more of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
based on the defects of complex preparation process, high energy consumption, improved temperature resistance of the modified flame retardant, and the like existing in the prior art, the invention innovatively proposes that a nitrogen-containing substance which is provided with a hydrophobic chain segment and can be positively charged is firstly used for forming a nitrogen-containing layer on the surface of a granular flame retardant, and then a tannic acid layer and a metal salt layer are sequentially coated, wherein firstly, the granular flame retardant is generally hydrophobic, the specific nitrogen-containing substance can be mutually close due to the hydrophobic interaction between the hydrophobic chain segment and the granular flame retardant, and further can be better coated on the surface of the granular flame retardant, secondly, the nitrogen-containing layer contains a large amount of nitrogen sources, a large amount of nitrogen can be generated in the flame retardant process, and further a similar inert atmosphere can be formed to prevent oxygen from contacting with the combustible substance, the occurrence of combustion reaction is reduced, the third tannic acid has electronegativity, when the tannic acid is coated on the nitrogen-containing layer, the tannic acid can realize excellent and uniform coating effect on the nitrogen-containing layer due to the attraction of positive and negative charges, the structural stability of the coating layer is improved, the storage, the transportation or the processing of the modified flame retardant are facilitated, the fourth tannic acid has a large number of benzene ring structures, the hardness of the coating structure can be improved, the thermal stability of the coating structure can also be improved, the high-temperature processing performance of the flame retardant is improved, the fifth metal salt layer is arranged, when the tannic acid layer is contacted with the tannic acid layer, the two layers are relatively independent, the connection and the stability between the two independent layers can be realized through the chelation of metal ions and the tannic acid, and the very stable chelating coating structure can be constructed, part of metal ions can also play a role in synergistic flame retardance.
In addition, the modified flame retardant does not need to be prepared at high temperature, so that the energy consumption and the cost of purchasing related heating equipment are greatly reduced, and the process is simple and easy to operate, thereby being beneficial to industrial application.
Drawings
FIG. 1 is an SEM spectrum (scale bar 30 μm) of unmodified aluminum diethylphosphinate according to an embodiment of the present invention;
FIG. 2 is a SEM spectrum (scale 4 μm) of unmodified aluminum diethylphosphinate according to an embodiment of the present invention;
FIG. 3 is an SEM spectrum (scale bar 10 μm) of modified aluminum diethylphosphinate obtained in example 1 according to the present invention;
FIG. 4 is an SEM spectrum (scale 3 μm) of modified aluminum diethylphosphinate obtained in example 1 of the present invention;
FIG. 5 is a graph showing isothermal adsorption and desorption of nitrogen from modified and unmodified aluminum diethylphosphinates obtained in example 1 according to the present invention;
FIG. 6 is an EDS spectrum of unmodified aluminum diethylphosphinate in an embodiment of the present invention;
FIG. 7 is an EDS spectrum of modified aluminum diethylphosphinate obtained in example 1 of the present invention.
Detailed Description
The invention mainly comprises the following conception: the preparation method has the advantages that the specific coating raw materials are selected, the multi-level construction is carried out on the surface layer of the granular flame retardant, the layers are mutually independent and can be mutually and tightly combined through different acting forces, so that the unique effects of the different raw materials are realized and are used together to synergistically improve the high-temperature stability, flame retardance and other performances of the integral flame retardant.
Further, the invention provides a modified flame retardant which comprises a granular flame retardant and a coating layer coated on the granular flame retardant, wherein the coating layer comprises a nitrogen-containing layer, a tannic acid layer and a metal salt layer which are sequentially arranged.
Wherein the nitrogen-containing substance in the nitrogen-containing layer is one or a combination of more than one selected from a polycation electrolyte containing nitrogen, polyethylene polyamine with carbon number more than or equal to 4 and polyethyleneimine, and the nitrogen-containing substance not only contains a nitrogen source but also has electropositivity, for example, can have positive charge in water, and especially can also have a hydrophobic chain segment, so that the nitrogen-containing substance is favorable for rapidly and uniformly coating the surface of the granular flame retardant with the same hydrophobicity through hydrophobic interaction force.
In the invention, tannic acid in the tannic acid layer and metal ions in the metal salt layer can be chelated to form a chelate structure, and the tannic acid has a chemical formula of C 76 H 52 O 46 The structure of the composition contains a large amount of benzene rings and hydroxyl groups, and the metal salt is selected from salts of metal cations capable of chelating tannic acid, and more preferably Fe 2+ 、Fe 3+ 、Co 2 + 、Zn 2+ 、Mg 2+ 、Al 3+ 、As 3+ 、Sb 3+ 、Ca 2+ Plasma salts.
The modified flame retardant has better dispersion stability in flame retardant materials, particularly high polymer materials, and further preferably, a silane coupling agent layer can be additionally arranged on the outer surface of the metal salt layer, so that the dispersibility and compatibility of the whole flame retardant in the high polymer materials can be further improved.
The above-described aspects are further described below in conjunction with specific embodiments; it should be understood that these embodiments are provided to illustrate the basic principles, main features and advantages of the present invention, and that the present invention is not limited by the scope of the following embodiments; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
All starting materials are commercially available or prepared by methods conventional in the art, not specifically described in the examples below.
Example 1
The embodiment provides a modified diethyl aluminum hypophosphite and a preparation method thereof, wherein the preparation method comprises the following steps:
0.3g of sodium dodecylbenzenesulfonate was dissolved in 1.2L of water to obtain an aqueous solution, and 400g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring at room temperature for 6h to obtain a mixed solution. To this was added 0.3g of polydiallyl dimethyl ammonium chloride (PDDA, aba Ding Shiji) and stirred at room temperature for 0.5h. Then, 0.1g of tannic acid was added thereto and stirred at room temperature for 1 hour. Then, 0.1g of ferric trichloride was added thereto, and the mixture was stirred at room temperature for 0.5h. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the modified diethyl aluminum hypophosphite.
Example 2
The embodiment provides a modified diethyl aluminum hypophosphite and a preparation method thereof, wherein the preparation method comprises the following steps:
dissolving 0.5g alkylphenol ethoxylate in 1.5L water to obtain aqueous solution, adding 500g diethyl aluminum hypophosphite (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) into the aqueous solution under high speed stirring 3 ) Stirring was carried out at room temperature for 4 hours to obtain a mixed solution. To this was added 0.3g of polyethylenimine (PEI, aba Ding Shiji) and stirred at room temperature for 0.5h. Then, 0.3g of tannic acid was added thereto and stirred at room temperature for 1 hour. 0.2g of aluminum sulfate was added thereto, and the mixture was stirred at room temperature for 0.5h. Finally, 0.5g of vinyltrimethoxysilane was added thereto and stirred at room temperature for 1 hour. Centrifuging to remove water after the reaction is finished, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain modified diethyl hypophosphorous acidAluminum.
Example 3
The embodiment provides a modified diethyl aluminum hypophosphite and a preparation method thereof, wherein the preparation method comprises the following steps:
0.5g of dodecyltrimethylammonium chloride was dissolved in 1.5L of water to obtain an aqueous solution, and 500g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring was carried out at room temperature for 4 hours to obtain a mixed solution. To this was added 2g of tetraethylenepentamine and stirred at room temperature for 0.5h. Then, 0.5g of tannic acid was added thereto and stirred at room temperature for 1 hour. 0.5g of aluminum sulfate was added thereto, and the mixture was stirred at room temperature for 0.5h. Finally, 0.5g of phenyltriethoxysilane was added and stirred at room temperature for 1h. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the modified diethyl aluminum hypophosphite.
Example 4
This example provides a modified melamine polyphosphate, the preparation process of this example being substantially the same as that of example 1, except that: the aluminum diethylphosphinate of example 1 (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) 3 ) Replaced by melamine polyphosphate (D50 of 2.83 microns, D95 of 24.1 microns, bulk density of 0.4 g/cm) 3 )。
Example 5
This example provides a modified melamine cyanurate, the process of which is substantially the same as in example 2, except that: the aluminum diethylphosphinate of example 2 (D50 of 26.2 microns, D95 of 62.3 microns, bulk density of 0.7 g/cm) 3 ) Replaced by melamine cyanurate (D50 9.28 microns, D95 38.7 microns, bulk density 0.4 g/cm) 3 )。
Example 6
The present example provides a modified aluminum phosphite, the preparation process of this example is basically the same as that of example 3, and the difference is that: the aluminum diethylphosphinate of example 3 (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) 3 ) Substituted by aluminium phosphite (D50 is18.3 microns, D95 of 58.3 microns, bulk density of 0.7g/cm 3 )。
Example 7
This example provides a modified melamine polyphosphate, the preparation process of this example being substantially the same as that of example 1, except that: the ferric trichloride in example 1 was replaced with an equivalent molar amount of cobalt nitrate.
Comparative example 1
This comparative example provides a modified aluminum diethylphosphinate, which is prepared as follows:
0.5g of dodecyltrimethylammonium chloride was dissolved in 1.5L of water to obtain an aqueous solution, and 500g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring was carried out at room temperature for 4 hours to obtain a mixed solution. To this was added 0.5g of tannic acid, and the mixture was stirred at room temperature for 1 hour. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the modified diethyl aluminum hypophosphite.
Comparative example 2
This comparative example provides a modified aluminum diethylphosphinate, which is prepared as follows:
0.5g of dodecyltrimethylammonium chloride was dissolved in 1.5L of water to obtain an aqueous solution, and 500g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring was carried out at room temperature for 4 hours to obtain a mixed solution. To this was added 0.5g of phenyltriethoxysilane, and the mixture was stirred at room temperature for 1 hour. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the modified diethyl aluminum hypophosphite.
Comparative example 3
This comparative example provides a modified aluminum diethylphosphinate, which differs substantially from example 1 only in that: the process of coating polydiallyl dimethyl ammonium chloride is not performed.
The preparation method comprises the following steps:
0.3g of sodium dodecylbenzenesulfonate was dissolved in 1.2L of waterTo the aqueous solution, 400g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) was added with stirring at high speed 3 ) Stirring at room temperature for 6h to obtain a mixed solution. To this was added 0.1g of tannic acid, and the mixture was stirred at room temperature for 1 hour. Then, 0.1g of ferric trichloride was added thereto, and the mixture was stirred at room temperature for 0.5h. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the modified diethyl aluminum hypophosphite.
Comparative example 4
This comparative example provides a modified aluminum diethylphosphinate, which differs substantially from example 1 only in that: and adding ferric trichloride immediately after the tannic acid is added, so that the tannic acid is not fully coated to form a tannic acid layer.
The preparation method comprises the following steps:
0.3g of sodium dodecylbenzenesulfonate was dissolved in 1.2L of water to obtain an aqueous solution, and 400g of aluminum diethylphosphinate (D50 of 26.2 μm, D95 of 62.3 μm, bulk density of 0.7 g/cm) was added to the aqueous solution under high-speed stirring 3 ) Stirring at room temperature for 6h to obtain a mixed solution. To this was added 0.3g of polydiallyl dimethyl ammonium chloride (PDDA, aba Ding Shiji) and stirred at room temperature for 0.5h. Then, 0.1g of tannic acid was added thereto, and immediately after the addition, 0.1g of iron trichloride was added thereto, followed by stirring at room temperature for 1.5 hours. And after the reaction is finished, centrifuging to remove water, centrifuging for three times, washing with water, and drying in an oven at 120 ℃ to obtain the modified diethyl aluminum hypophosphite.
Performance test 1
(1) Characterization and comparison of SEM, BET data, EDS for the coated sample and the sample before coating
Fig. 1 and fig. 2 are SEM spectra of unmodified aluminum diethyl hypophosphite under different scale dimensions, and fig. 3 and fig. 4 are SEM spectra of modified aluminum diethyl hypophosphite under different scale dimensions obtained after coating in example 1, and it can be seen from characterization results of SEM that the surface of a sample is uniformly coated, so that the surface structure of the sample is changed.
The modified aluminum diethylphosphinate and unmodified aluminum diethylphosphinate obtained in example 1 were measuredAs shown in FIG. 5, the specific surface area of unmodified aluminum diethylphosphinate was 2.1791m by calculating BET data 2 G, average pore size 58.0857nm; example 1 coated modified aluminum diethylphosphinate having a specific surface area of 4.4283m 2 The average pore diameter per gram was 24.0853nm. The specific surface area of the coated sample is increased, the average pore diameter is decreased, and the coating agent forms effective and uniform coating on the surface of the flame retardant, so that the interfacial compatibility between the flame retardant powder and the flame retardant material is improved, and the mechanical property of the flame retardant material is improved.
As can be seen from the EDS spectra of FIG. 6 and FIG. 7, the coated sample surface has iron element (FIG. 7), and the unmodified sample surface has no iron element (FIG. 6), which proves that the modifier is coated on the sample surface.
(2) The thermal weight loss temperature at 2% mass of thermal weight loss was tested by thermal weight loss analysis TGA (heating rate 10 ℃/min), and the specific results are shown in table 1.
TABLE 1
As can be seen from table 1, in the modified examples according to the method of the present invention, the thermal weight loss temperature after modification is significantly improved compared with that before modification, and it can be seen that the thermal stability of the flame retardant is significantly improved, while in the comparative example 1, in which only tannic acid modification and only the comparative example 2 are used, the thermal weight loss temperature of the flame retardant is hardly increased, and in the comparative example 3, although a certain chelate coating structure is realized on the surface of the flame retardant particles, the coating effect is not ideal, and the ideal coating effect cannot be achieved, so that the thermal stability is limited, and in the comparative example 4, in which ferric trichloride is added immediately after tannic acid addition, the thermal stability of the obtained modified aluminum diethylphosphinate is hardly increased, and analysis shows that: the method is characterized in that ferric trichloride is added to the horse after the tannic acid is added, so that the tannic acid is not coated on the surfaces of the flame-retardant particles, and under the competitive reaction, the tannic acid and iron ions are preferentially chelated to form chelates, so that the tannic acid is difficult to coat on the surfaces of the flame-retardant particles, and the coating effect is poor.
(3) The modified flame retardant powders obtained in examples 1 to 7 and comparative examples 1 to 4 were transferred to an oven, warmed up from room temperature to 320 ℃ (about 1 hour for use), then taken out after standing at 320 ℃ for 0.5 hour, and the change rate of the mass of the modified flame retardant powders before and after heating was measured to reflect the thermal stability of the powders, and specific results are shown in table 2.
TABLE 2
Application examples 1 to 7 and application comparative examples 1 to 4
The modified flame retardant powders obtained in examples 1 to 7 and comparative examples 1 to 4 were used in flame retardance of PA66 (purchased from Chongqing Huafeng chinlon fiber Co., ltd.), and the preparation process of the flame retardant PA66 material was as follows: the modified flame retardant powder obtained in examples 1-7 and comparative examples 1-4 and other raw materials (see table 3) are independently weighed according to parts by weight, poured into a high-speed mixer to be mixed, stirred for 15 minutes under the condition of 1200r/min, and granulated by a double screw extruder after sample discharging to obtain halogen-free flame retardant reinforced PA66 material, and then dried and injection molded into standard samples;
wherein the extrusion process parameters of the twin-screw extruder are as follows:
temperature distribution of processing extruder
Host screw speed: 180n/min, feeding rotation speed: 7.8Hz, host current: 29A
The injection molding process parameters are as follows: flame-retardant PA66 standard sample preparation: t1=255 ℃, t2=260 ℃, t3=260 ℃, nozzle 270 ℃, clamping force 105MPa, melt back pressure 0MPa, melt distance 62mm, melt back distance 6mm. Heating temperature of the die temperature machine: 120 ℃.
TABLE 3 Table 3
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Performance test 2
The mechanical properties and flame retardant properties of the halogen-free flame retardant reinforced PA66 material of application examples 1-7 and application comparative examples 1-4 were tested by respectively using the methods of impact strength (GB/T1843-2008), bending strength (GB/T9341-2008), tensile strength (GB/T1040.2-2006), oxygen index (GB/T2406.2-2009), vertical burning (GB/T2408-2008), glow wire ignition temperature GWIT (GB/T5169.13-2013) of the material, and the like, and the results are shown in Table 4.
TABLE 4 Table 4
As can be seen from table 4, the use of comparative example 1 with only tannic acid coated flame retardant particles of comparative example 1 for polyamide materials resulted in very poor dispersion, resulting in poor flame retardance and mechanical properties of the materials; although the flame retardant particles coated with silane alone in comparative example 2 were improved in flame retardance compared with comparative example 1, the improvement was limited and the flame retardant properties were still unsatisfactory; application comparative example 3, which is the best of the four application comparative examples, may benefit from the formation of a small amount of chelate coating on the surface of the flame retardant particles, but the coating effect is still poor, and the improvement of flame retardant and mechanical properties is insufficient; the application of the modified aluminum diethylphosphinate of comparative example 4 in comparative example 4, as shown above, resulted in poor dispersibility in the resin material, and the practice showed that the mechanical properties and flame retardant properties were poor as compared with example 1.
Meanwhile, referring to the above, the flame retardant has a good flame retardant effect when a lower part of flame retardant is added, and is beneficial to industrial application.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (21)
1. A modified flame retardant comprising a particulate flame retardant and a coating layer coated on the particulate flame retardant, characterized in that: the coating layer comprises a nitrogen-containing layer, a tannic acid layer and a metal salt layer which are sequentially arranged, wherein nitrogen-containing substances in the nitrogen-containing layer are selected from one or more of a polycation electrolyte containing nitrogen, polyethylene polyamine with carbon number more than or equal to 4 and polyethylene imine, and tannic acid in the tannic acid layer and metal ions in the metal salt layer can be subjected to chelation to form a chelating structure.
2. The modified flame retardant of claim 1, wherein: the metal salt in the metal salt layer is one or a combination of a plurality of iron salt, zinc salt, magnesium salt, calcium salt, cobalt salt, aluminum salt, arsenic salt and antimony salt.
3. The modified flame retardant of claim 2, wherein: the acid radical of the metal salt is selected from sulfate radical, acetate radical, nitrate radical or halogen ion.
4. A modified flame retardant according to any one of claims 1 to 3, wherein: the metal ion of the metal salt comprises Co 2+ 、Zn 2+ 、Mg 2+ 、Al 3+ 、As 3+ 、Sb 3+ 、Ca 2+ One or more combinations thereof.
5. The modified flame retardant of claim 1, wherein: the nitrogen-containing polycation electrolyte comprises one or more selected from polydiallyl dimethyl ammonium chloride, polyvinyl pyridine, chitosan, polyacrylamide hydrochloride N-methyl-N-vinylacetamide and poly-L-lysine hydrochloride.
6. The modified flame retardant of claim 1, wherein: the polyethylene polyamine has a structure represented by formula (I):
in the formula (I), n is 1-20.
7. The modified flame retardant of claim 1, wherein: the mass ratio of the granular flame retardant to the nitrogen-containing layer to the tannic acid layer to the metal salt layer is 100-800:1-10:0.1-15.
8. The modified flame retardant of claim 1, wherein: the coating layer also comprises a silane coupling agent layer formed on the metal salt layer, wherein the mass ratio of the granular flame retardant to the silane coupling agent layer is 100-800:0.1-20.
9. The modified flame retardant of claim 1, wherein: the method for preparing the coating layer comprises the following steps:
coating the nitrogen-containing layer on the granular flame retardant to form a first intermediate;
then mixing the first intermediate with tannic acid in a solvent to form a tannic acid layer on the nitrogen-containing layer to form a second intermediate;
then mixing the second intermediate with a metal salt in a solvent to form the metal salt layer on the tannic acid layer;
and selectively forming the silane coupling agent layer on the metal salt.
10. The modified flame retardant of claim 9, wherein: in the process of preparing the coating layer, dispersing the granular flame retardant in a solvent in the presence of a dispersing agent to form a dispersion solution, then adding a nitrogen-containing substance, mixing and stirring to form the nitrogen-containing layer coated on the granular flame retardant, then adding tannic acid, mixing and stirring to form the tannic acid layer coated on the nitrogen-containing layer, then adding metal salt, mixing and stirring to form the metal salt layer coated on the tannic acid layer, then optionally adding a silane coupling agent, mixing and stirring.
11. The modified flame retardant of any of claims 8-10, wherein: the silane coupling agent in the silane coupling agent layer is one or a combination of more selected from vinyl trimethoxy silane, vinyl triethoxy silane, gamma-aminopropyl trimethoxy silane, dimethyl phenyl silane, phenyl triethoxy silane, octyl trimethoxy silane and n-octyl triethoxy silane.
12. The modified flame retardant according to claim 9 or 10, characterized in that: the solvent is one or a combination of more selected from water, ethanol, propanol and acetone.
13. The modified flame retardant of claim 1, wherein: the particulate flame retardant includes a nitrogen-containing flame retardant or a phosphorus-containing flame retardant.
14. A process for the preparation of a modified flame retardant as claimed in any of claims 1 to 13, characterized in that: the preparation method comprises a coating process of a nitrogen-containing layer, a coating process of a tannic acid layer and a coating process of a metal salt layer and a coating process of a selective silane coupling agent layer are sequentially carried out on the granular flame retardant.
15. The method for preparing the modified flame retardant according to claim 14, wherein: the coating step is performed in a solvent in the presence of a dispersant.
16. The method for preparing the modified flame retardant according to claim 14, wherein: the coating process is controlled to be carried out at the temperature of 10-30 ℃.
17. The method for preparing the modified flame retardant according to claim 14, wherein: and according to the sequence of the coating processes, after each coating process is independently finished, the next coating process is carried out.
18. A flame retardant additive comprising the modified flame retardant of any of claims 1-13.
19. The flame retardant additive of claim 18 further comprising a combination of one or more of zinc borate, melamine polyphosphate, and melamine cyanurate.
20. The flame retardant additive of claim 19, wherein the flame retardant additive is composed of the modified flame retardant, zinc borate, melamine polyphosphate and melamine cyanurate, and the mass ratio of the modified flame retardant, the zinc borate, the melamine polyphosphate and the melamine cyanurate is 8-15:0.1-2:2.5-4:3.5-5.
21. Use of a modified flame retardant according to any of claims 1 to 13, or a flame retardant additive according to any of claims 18 to 20, in the preparation of a flame retardant material.
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