CN115322441A - Method for producing aluminum hypophosphite flame retardant by using sodium hypophosphite mother solution - Google Patents
Method for producing aluminum hypophosphite flame retardant by using sodium hypophosphite mother solution Download PDFInfo
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- CN115322441A CN115322441A CN202211105149.7A CN202211105149A CN115322441A CN 115322441 A CN115322441 A CN 115322441A CN 202211105149 A CN202211105149 A CN 202211105149A CN 115322441 A CN115322441 A CN 115322441A
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- stirring
- flame retardant
- hypophosphite
- weight
- aluminum
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 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 83
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 title claims abstract description 77
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001379 sodium hypophosphite Inorganic materials 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000010413 mother solution Substances 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 24
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000005303 weighing Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 239000012065 filter cake Substances 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- IWZNIFKILUHTJK-UHFFFAOYSA-N 2-[[2,4,4,6,6-pentakis(2-cyanophenoxy)-1,3,5-triaza-2lambda5,4lambda5,6lambda5-triphosphacyclohexa-1,3,5-trien-2-yl]oxy]benzonitrile Chemical compound C(#N)C1=C(OP2(=NP(=NP(=N2)(OC2=C(C=CC=C2)C#N)OC2=C(C=CC=C2)C#N)(OC2=C(C=CC=C2)C#N)OC2=C(C=CC=C2)C#N)OC2=C(C=CC=C2)C#N)C=CC=C1 IWZNIFKILUHTJK-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 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 claims description 14
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003708 ampul Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 8
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 8
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 claims description 7
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 17
- NBITXRSWDMAPNH-UHFFFAOYSA-N C(C=C1)=CC=C1OP1N=PN=P[N]1 Chemical group C(C=C1)=CC=C1OP1N=PN=P[N]1 NBITXRSWDMAPNH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 35
- 238000012360 testing method Methods 0.000 description 31
- -1 hydrogen halides Chemical class 0.000 description 19
- 238000002485 combustion reaction Methods 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229920002627 poly(phosphazenes) Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000779 smoke 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
- 239000002253 acid Substances 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- NYYLKNDBZDKKAV-UHFFFAOYSA-N ClP1N=PN=P[N]1 Chemical compound ClP1N=PN=P[N]1 NYYLKNDBZDKKAV-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000001570 ionothermal synthesis Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/165—Hypophosphorous acid; Salts thereof
-
- 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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a method for producing an aluminum hypophosphite flame retardant by utilizing a sodium hypophosphite mother solution. The prepared phenoxyphosphazene covalent triazine composite material modifies aluminum hypophosphite, so that the compatibility of the phenoxyphosphazene covalent triazine composite material with a polymer is improved, the flame retardant effect can be improved due to the conjugate effect formed by the structure, and the highly crosslinked phenoxycyclotriphosphazene unit in the structure can prevent water molecules from entering the phenoxycyclotriphosphazene unit, so that the flame retardant has good hydrophobicity.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to a method for producing an aluminum hypophosphite flame retardant by utilizing a sodium hypophosphite mother solution.
Background
For many years, with the increasing trend of the application of materials developed by economy, the application of polymer materials is wider and wider, and the accompanying problem of flame retardance is more and more emphasized. However, based on the consideration of production cost and production technology, the proportion of the additive flame retardant reaches about 75 percent worldwide, and the reactive flame retardant cannot be applied in a large range due to the defects of complex production process and low yield. In addition, the issue of ecological safety has attracted attention all over the world, and halogen-containing flame retardants cause "secondary damage" to human life and property due to the generation of a large amount of smoke and a large amount of gases such as harmful and corrosive hydrogen halides during combustion. Therefore, the halogen-free flame retardant becomes a development trend, and has great significance for the research of low-toxicity and low-smoke halogen-free flame retardant.
Aluminum hypophosphite (Al) 2 (H 2 PO 2 ) 3 AHP) is used as a novel halogen-free flame retardant, and has the advantages of good thermal stability, good water resistance, obvious flame retardant effect, small influence on the mechanical properties of polymers and the like, so that the halogen-free flame retardant is used for flame retarding of engineering plastics such as acrylonitrile-butadiene-styrene copolymer (ABS), polybutylene terephthalate (PBT), nylon 6 (PA 6) and the like, and obtains good effect. AHP is widely applied in the fields of paint, rubber and plastics in recent years, and the added material has good thermal stability, flame retardance and processability due to the phosphorus content of 41.6 percent. AHP can be generally prepared by acid-base neutralization reaction of aluminium hydroxide and hypophosphorous acid in one step, the advantage of this method is that raw materials are simple and easy to get, does not need the separation of the intermediate product, the simple technological process, with low costs, the productive rate is high. But the defect is obvious, and the volatile toxicity of the hypophosphorous acid is high, so that the hypophosphorous acid has great harm to laboratory workers and the environment.
In the past years, AHP has been widely used as a novel efficient halogen-free phosphorus flame retardant in engineering plastics, such as PA, PU, ABS, PET, PBT, etc. However, AHP has some drawbacks, and as an additive flame retardant, it has poor compatibility with the substrate and poor thermal stability under high temperature processing, which has a fire risk, and at high temperature, AHP decomposes into phosphine gas, and spontaneous combustion occurs in air, and the combustion releases a large amount of heat, which in turn promotes the decomposition of AHP, thus forming a cycle and causing great damage; therefore, it is very necessary to reduce the hidden risk of AHP. In order to improve the dispersibility of AHP powder, improve the compatibility with high molecular materials, improve the flame retardant property, simultaneously improve the processability, the impact resistance and the thermodynamic property of polymers, further expand the application field of the polymers and carry out modification research on AHP, the modification research is very important.
The currently used modification methods mainly include ultra-fining, surface chemical modification and microencapsulation. The AHP superfine method comprises chemical direct synthesis and physical superfine grinding, and adopts proper measures to reduce the grain size of AHP grains as much as possible, enlarge the contact area between the AHP grains and a polymer matrix, ensure that the AHP grains can be uniformly dispersed into a high polymer, enhance the affinity with the polymer and improve the compatibility of the AHP grains and the polymer matrix, thereby achieving the purposes of reducing the dosage and improving the flame retardant effect. The surface chemical modification is to coat the particle surface by utilizing a surface chemical method, namely, adsorption or chemical reaction of functional groups in organic molecules or other inorganic gel molecules on the surface of the AHP powder, so that the particle surface is organized or changed in polarity, and thus, the surface modification is realized. The commonly used surface modifiers mainly comprise coupling agents (silane coupling agents, titanate coupling agents, aluminate coupling agents and the like) and anionic surfactants (higher fatty acids and derivatives thereof). The surface modification method of AHP is generally classified into a dry method and a wet method. Many coupling agents have poor water resistance and can be used by dissolving in an inert organic solvent only, so that a dry method is generally used. Anionic surfactants have good stability in water and are generally selected by a wet method. The dry modification process is simple, but the modification effect is poor; the wet modification effect is good, but the problems of loss of the modifier along with the solvent and cost increase exist. Different treatments have some impact on the interfacial and flame retardant properties of the article. Microencapsulation is a well-established technique that has applications in a wide variety of fields. The essence of microencapsulation is to wrap the fire retardant by organic or inorganic matters to form the microcapsule fire retardant; the microcapsule can endow the flame retardant core with the physical and chemical characteristics of a shell, and can greatly improve the compatibility of the flame retardant and a high polymer and the thermal stability of the flame retardant. Meanwhile, the microcapsule flame retardant is nontoxic and harmless in the production and use processes, does not generate dense smoke and toxic gas during combustion, and has no environmental pollution, so the microcapsule flame retardant becomes one of the research hotspots in the flame retardant field.
Patent CN 111961254A provides a preparation method of modified aluminum hypophosphite flame retardant, which comprises the following steps: in the kneader, aluminum hydroxide, hypophosphorous acid, a silane coupling agent and polyethylene are used as raw materials, aluminum hypophosphite is synthesized through neutralization reaction, and the modified aluminum hypophosphite flame retardant is obtained through thermal coating treatment of the silane coupling agent and the polyethylene. The preparation method has the advantages of high efficiency, low cost and easy operation. By adopting the method, the modified aluminum hypophosphite flame retardant with good water resistance and good material compatibility can be directly obtained under the environment-friendly synthesis process condition, the cost is reduced, and the comprehensive competitiveness of the modified aluminum hypophosphite flame retardant as a composite flame retardant is enhanced.
Patent CN 113308024A discloses an aluminum hypophosphite-polyphosphazene core-shell type flame retardant and a preparation method thereof: the preparation method comprises the following steps of dispersing aluminum hypophosphite microspheres in an organic solvent by ultrasonic waves uniformly, adding chlorocyclotriphosphazene and 4,4' -diaminodiphenyl sulfone, dropwise adding an acid binding agent, reacting under boiling point reflux, centrifugally collecting obtained products, washing, centrifuging and drying to obtain the aluminum hypophosphite-polyphosphazene microspheres. According to the invention, only a small amount of aluminum hypophosphite-polyphosphazene microsphere flame retardant is added into polyurethane, so that the flame-retardant and anti-dripping effects of the high polymer material can be obviously improved. The polyphosphazene-coated aluminum hypophosphite microsphere improves the flame retardant property of a high polymer material and reduces the addition amount of AHP, thereby reducing the cost and reducing the reduction of the mechanical property of the material. The polyphosphazene has good compatibility and is a high polymer, the polyphosphazene is used for coating aluminum hypophosphite, the flame retardant migration phenomenon cannot occur, and the polyphosphazene has good dispersibility and compatibility in a matrix material.
Most of chemical modification aiming at aluminum hypophosphite in the prior art is to add a silane coupling agent for grafting, but the method is very limited for improving the mechanical property of the polymer and is usually suitable for the contrary. The principle of modifying the aluminum hypophosphite by using the phosphazene derivative is that a macromolecular reticular structure is generated by using the reaction of a phosphorus-hydrogen bond and an aldehyde group in the phosphazene in the processing or combustion process, the performance of a polymer is improved, and the problems of high hygroscopicity, high smoke release amount, toxic phosphine release, poor compatibility and the like in the use process of the aluminum hypophosphite are solved. However, phosphazene derivatives absorb moisture and are very easily hydrolyzed, and acid substances are generated after hydrolysis, so that modification with them alone cannot ensure improvement in water resistance. Therefore, it is of great importance to develop a flame retardant capable of simultaneously improving the mechanical properties, water resistance and flame retardancy of polymers.
Disclosure of Invention
In view of the above defects in the prior art, the invention aims to provide an aluminum hypophosphite flame retardant which is more environment-friendly, has a good flame retardant effect and good water resistance, and a preparation method thereof.
The aluminum hypophosphite has high flame-retardant efficiency, but the aluminum hypophosphite has strong hygroscopicity and large polarity, so that the compatibility with materials is poor, the water resistance of the prepared flame-retardant material is poor, and after the aluminum hypophosphite is placed in a humid environment, the flame retardant migrates to the surface of the material, so that the flame retardance, the mechanics, the electrical property and the like of the material are influenced, the hydrophobic property of the aluminum hypophosphite is improved, the compatibility of the aluminum hypophosphite and the material is improved, and the aluminum hypophosphite has important scientific significance and application prospect on the flame-retardant efficiency of the material.
Hexachlorocyclotriphosphazene is the first phosphazene compound to be discovered, because hexachlorocyclotriphosphazene itself can be directly applied as a flame retardant additive. It is generally considered that the flame retardant mechanism of the phosphazene flame retardant has the gas phase flame retardant effect and also exerts the condensed phase flame retardant effect. However, the hexachlorocyclotriphosphazene absorbs moisture and is very easy to hydrolyze, and acid substances are generated after hydrolysis, so that the improvement of the water resistance cannot be guaranteed by singly modifying the hexachlorocyclotriphosphazene. The triazine derivative contains a large amount of nitrogen sources and tertiary amine structures, integrates the characteristics of carbon sources and expanding agents, is used as a carbon forming agent in the aspect of flame retardant modification of polymers, does not contain halogen and organic phosphorus elements, does not need to act with synergists such as antimony oxide and the like, and can generate an expanded carbon layer on the surface when high polymers containing the intumescent flame retardant are subjected to combustion thermal oxidation degradation. In the invention, the inventor firstly prepares hexa (cyanophenoxy) cyclotriphosphazene, then utilizes ionothermal synthesis to graft covalent triazine skeleton on the surface of the hexa (cyanophenoxy) cyclotriphosphazene to obtain phenoxyphosphazene covalent triazine composite material, and utilizes the composite material to chemically modify aluminum hypophosphite, the stable porous skeleton in the phenoxyphosphazene covalent triazine composite material can improve the compatibility of the aluminum hypophosphite in a polymer, and the N and P structures in the structure form a conjugated effect to ensure that the aluminum hypophosphite can be kept stable at high temperature, so that the flame retardant effect can be improved, and in addition, the structure has a highly crosslinked phenoxycyclotriphosphazene unit which can prevent water molecules from entering the phenoxyphosphazene unit, so that the flame retardant has better hydrophobicity.
The technical scheme of the invention is as follows:
a method for producing an aluminum hypophosphite flame retardant by using a sodium hypophosphite mother solution comprises the following steps:
s1, taking 50-80 parts by weight of sodium hypophosphite mother liquor, adding 3-5 parts by weight of calcium hypophosphite, stirring at room temperature for 2-4 hours until precipitation appears, filtering, and removing calcium phosphite precipitate to obtain filtrate;
s2, weighing 2-4 parts by weight of aluminum hydroxide, adding 10-15 parts by weight of water, dropwise adding 4-5 parts by weight of 98wt% concentrated sulfuric acid under stirring, heating to 100-110 ℃ after dropwise adding, stirring for 3-5 hours, and filtering after the reaction is finished to obtain a filtrate, namely an aluminum sulfate solution;
s3, adding the filtrate obtained in the step S1 into the aluminum sulfate solution obtained in the step S2 under stirring, heating to 80-90 ℃ after the addition is finished, stirring for 4-6 h, cooling to 40-60 ℃ after the reaction is finished, generating precipitates, filtering the reaction solution, adding 1-2 parts by weight of filter cake into water, washing, crushing and drying to obtain aluminum hypophosphite;
s4, weighing 1.1-2 parts by weight of 4-cyanophenol and 1.5-2 parts by weight of triethylamine, mixing to obtain a solution A, weighing 0.5-0.8 part by weight of hexachlorocyclotriphosphazene, adding into 30-50 parts by weight of tetrahydrofuran to obtain a solution B, adding the solution A into the solution B, heating to 60-70 ℃, carrying out reflux stirring for 20-24 h, concentrating after the reaction is finished, removing the solvent, adding 30-50 parts by weight of ethanol into the concentrate, heating to 70-80 ℃, carrying out reflux stirring for 2-4 h, cooling to 0-10 ℃, carrying out recrystallization, allowing precipitates to appear, filtering, and carrying out reduced pressure concentration on a filter cake to obtain hexa (cyanophenoxy) cyclotriphosphazene;
s5, weighing 0.5-0.6 part by weight of hexa (cyanophenoxy) cyclotriphosphazene and 0.08-0.1 part by weight of zinc chloride in the step S4, placing the hexa (cyanophenoxy) cyclotriphosphazene and 0.08-0.1 part by weight of zinc chloride into an ampoule bottle, vacuumizing and sealing the ampoule bottle, heating to 400-500 ℃, keeping the temperature for 40-50 h, cooling to room temperature after the reaction is finished, opening the ampoule bottle, crushing the obtained product, adding 1-2 parts by weight of 2mol/L HCl aqueous solution, stirring, filtering, washing a filter cake with water until the pH is neutral, respectively washing 2 times with 1-2 parts by weight of methanol and 1-2 parts by weight of dichloromethane, and drying the washed filter cake at 110-120 ℃ for 4-6 h to obtain the phenoxyphosphazene covalent triazine composite material;
s6, weighing 0.2-0.4 part by weight of the phenoxyphosphazene covalent triazine composite material in the step S5 and 4-8 parts by weight of aluminum hypophosphite in the step S3, uniformly mixing, stirring at 180-200 ℃ for 6-8 h, and obtaining the modified aluminum hypophosphite flame retardant after the reaction is finished.
Compared with the prior art, the invention has the beneficial effects that:
(1) The sodium hypophosphite mother liquor is recycled to produce the aluminum hypophosphite, so that the cost is reduced, and the method is green and environment-friendly;
(2) The phenoxyphosphazene covalent triazine composite material prepared by modifying the aluminum hypophosphite has a stable and firm skeleton structure and porosity, improves the compatibility of the aluminum hypophosphite in a high polymer material after being compounded with the aluminum hypophosphite, and can also help to improve the flame retardant property of the aluminum hypophosphite due to the thermal stability of the aluminum hypophosphite at high temperature;
(3) The prepared phenoxyphosphazene covalent triazine composite material modifies aluminum hypophosphite, so that the water resistance of the flame retardant is improved, and a good flame retardant effect can be realized under a humid condition.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
The parameters of part of the raw materials in the embodiment of the invention are as follows:
concentrated sulfuric acid, content: 98wt%, and alatin.
Hexachlorocyclotriphosphazene, cat No.: 1240028, purity: 98wt%, shanghai Haohong biomedical science and technology.
The sodium hypophosphite mother liquor contains about 60wt% of sodium hypophosphite, about 4wt% of sodium phosphite, about 0.2wt% of sodium sulfate and about 0.1wt% of sodium chloride.
Antioxidant JYANOX1010, shanghai Kayin chemical industry.
Comparative example 1
A method for producing an aluminum hypophosphite flame retardant by using a sodium hypophosphite mother solution comprises the following steps:
s1, taking 50kg of sodium hypophosphite mother liquor, adding 3kg of calcium hypophosphite, stirring at room temperature for 4h until a precipitate appears, filtering, and removing the calcium phosphite precipitate to obtain a filtrate;
s2, weighing 3kg of aluminum hydroxide, adding 10kg of water, dropwise adding 4.5kg of 98wt% concentrated sulfuric acid under stirring, after dropwise adding, heating to 100 ℃, stirring for 5 hours, and after the reaction is finished, filtering to obtain a filtrate, namely an aluminum sulfate solution;
s3, adding the filtrate obtained in the step S1 into the aluminum sulfate solution obtained in the step S2 under stirring, heating to 80 ℃ after the addition is finished, stirring for 6 hours, cooling to 40 ℃ after the reaction is finished, generating precipitates, filtering the reaction liquid, adding 2kg of filter cake into water, washing, crushing, and drying at 60 ℃ for 2 hours to obtain aluminum hypophosphite;
s4, weighing 1.1kg of 4-cyanophenol and 1.5kg of triethylamine, mixing to obtain a solution A, weighing 0.5kg of hexachlorocyclotriphosphazene, adding the hexachlorocyclotriphosphazene into 40L of tetrahydrofuran to obtain a solution B, adding the solution A into the solution B, heating to 70 ℃, refluxing and stirring for 24h, concentrating to remove the solvent after the reaction is finished, adding 35L of absolute ethyl alcohol into the concentrate, heating to 80 ℃, refluxing and stirring for 4h, cooling to 0 ℃, recrystallizing, wherein precipitates appear, filtering, and concentrating a filter cake at-0.9 MPa and 45 ℃ under reduced pressure to obtain hexa (cyanophenoxy) cyclotriphosphazene;
s5, weighing 0.2kg of hexa (cyanophenoxy) cyclotriphosphazene in the step S4 and 4kg of aluminum hypophosphite in the step S3, uniformly mixing, stirring at 200 ℃ for 8h, and obtaining the aluminum hypophosphite flame retardant after the reaction is finished.
Example 1
A method for producing an aluminum hypophosphite flame retardant by using a sodium hypophosphite mother solution comprises the following steps:
s1, taking 50kg of sodium hypophosphite mother liquor, adding 3kg of calcium hypophosphite, stirring at room temperature for 4 hours until precipitation appears, filtering, and removing calcium phosphite precipitation to obtain filtrate;
s2, weighing 3kg of aluminum hydroxide, adding 10kg of water, dropwise adding 4.5kg of 98wt% concentrated sulfuric acid under stirring, after dropwise adding, heating to 100 ℃, stirring for 5 hours, and after reaction, filtering to obtain a filtrate, namely an aluminum sulfate solution;
s3, adding the filtrate obtained in the step S1 into the aluminum sulfate solution obtained in the step S2 under stirring, heating to 80 ℃ after the addition is finished, stirring for 6 hours, cooling to 40 ℃ after the reaction is finished, generating precipitates, filtering the reaction liquid, adding 2kg of filter cake into water, washing, crushing, and drying at 60 ℃ for 2 hours to obtain aluminum hypophosphite;
s4, weighing 1.1kg of 4-cyanophenol and 1.5kg of triethylamine, mixing to obtain a solution A, weighing 0.5kg of hexachlorocyclotriphosphazene, adding the solution A into 40L of tetrahydrofuran to obtain a solution B, adding the solution A into the solution B, heating to 70 ℃, refluxing and stirring for 24h, concentrating to remove the solvent after the reaction is finished, adding 35L of absolute ethyl alcohol into the concentrate, heating to 80 ℃, refluxing and stirring for 4h, cooling to 0 ℃, recrystallizing, filtering, and concentrating a filter cake at-0.9MPa and 45 ℃ under reduced pressure to obtain hexa (cyanophenoxy) cyclotriphosphazene;
s5, weighing 0.5kg of hexa (cyanophenoxy) cyclotriphosphazene and 0.08kg of zinc chloride in the step S4, placing the hexa (cyanophenoxy) cyclotriphosphazene and the zinc chloride in an ampoule bottle, vacuumizing the ampoule bottle, sealing, heating to 400 ℃, keeping the temperature for 40h, cooling to room temperature after the reaction is finished, opening the ampoule bottle, crushing the obtained product, adding 1kg of 2mol/L HCl aqueous solution, stirring, filtering, washing a filter cake with water until the pH value is neutral, respectively washing the filter cake with 1.5L of methanol and 1.5L of dichloromethane for 2 times, and drying the washed filter cake at 110 ℃ for 4h to obtain the phenoxyphosphazene covalent triazine composite material;
s6, weighing 0.2kg of phenoxyphosphazene covalent triazine composite material in the step S5 and 4kg of aluminum hypophosphite in the step S3, uniformly mixing, stirring at 200 ℃ for 8h, and obtaining the aluminum hypophosphite flame retardant after the reaction is finished.
Example 2
A method for producing an aluminum hypophosphite flame retardant by using a sodium hypophosphite mother solution comprises the following steps:
s1, taking 50kg of sodium hypophosphite mother liquor, adding 3kg of calcium hypophosphite, stirring at room temperature for 4h until a precipitate appears, filtering, and removing the calcium phosphite precipitate to obtain a filtrate;
s2, weighing 3kg of aluminum hydroxide, adding 10kg of water, dropwise adding 4.5kg of 98wt% concentrated sulfuric acid under stirring, after dropwise adding, heating to 100 ℃, stirring for 5 hours, and after reaction, filtering to obtain a filtrate, namely an aluminum sulfate solution;
and S3, adding the filtrate obtained in the step S1 into the aluminum sulfate solution obtained in the step S2 under stirring, heating to 80 ℃ after the addition is finished, stirring for 6 hours, cooling to 40 ℃ after the reaction is finished, generating precipitates, filtering the reaction liquid, adding 2kg of filter cake into water, washing, crushing, and drying at 60 ℃ for 2 hours to obtain the aluminum hypophosphite flame retardant.
Example 3
A method for producing an aluminum hypophosphite flame retardant by using a sodium hypophosphite mother solution comprises the following steps:
s1, taking 50kg of sodium hypophosphite mother liquor, adding 3kg of calcium hypophosphite, stirring at room temperature for 4 hours until precipitation appears, filtering, and removing calcium phosphite precipitation to obtain filtrate;
s2, weighing 3kg of aluminum hydroxide, adding 10kg of water, dropwise adding 4.5kg of 98wt% concentrated sulfuric acid under stirring, after dropwise adding, heating to 100 ℃, stirring for 5 hours, and after reaction, filtering to obtain a filtrate, namely an aluminum sulfate solution;
s3, adding the filtrate obtained in the step S1 into the aluminum sulfate solution obtained in the step S2 under stirring, heating to 80 ℃ after the addition is finished, stirring for 6 hours, cooling to 40 ℃ after the reaction is finished, generating precipitates, filtering the reaction liquid, adding 2kg of filter cake into water, washing, crushing, and drying at 60 ℃ for 2 hours to obtain aluminum hypophosphite;
s4, weighing 0.2kg of hexachlorocyclotriphosphazene and 4kg of aluminum hypophosphite in the step S3, uniformly mixing, stirring at 200 ℃ for 8h, and obtaining the aluminum hypophosphite flame retardant after the reaction is finished.
Test example 1
The aluminum hypophosphite flame retardant prepared in the examples and the comparative examples is mixed with a polypropylene monomer to prepare a polypropylene composite material, and the specific preparation method comprises the following steps: 720g of polypropylene, 270g of aluminum hypophosphite flame retardant, 1010 g of antioxidant JYANOX and 5g of magnesium stearate are dried for 24 hours at 80 ℃ and then uniformly mixed, and the mixture is melted by a mixer, wherein the temperatures of a first zone and a second zone are respectively 170 ℃, the melt temperature is 170 ℃, the banburying time is set to be 6min, and the number of rotors is 30r/min. And (3) placing the materials which are subjected to banburying and uniformly mixed in a hot press at 170 +/-5 ℃ for heating for 8min, then raising the temperature to 10MPa, and fully exhausting. And hot pressing for 5min under the working pressure of 25MPa, and unloading and taking out the die after pressure maintaining and cooling for 2-3 min. The blank control was prepared in the same manner as the control except that no flame retardant was added. The prepared polypropylene composite material is subjected to flame retardancy test by adopting a vertical combustion test and a limited oxygen index test method, wherein the test method refers to a GB/T2408-2021 horizontal method and a vertical method for determining the combustion performance of plastics and a GB/T2406.2-2009 method for determining the combustion behavior by using an oxygen index method, part 2: room temperature test, vertical burning test refers to a method of preparing a sample strip of plastic products of a prescribed size according to relevant standards established in the state, and burning the sample strip under prescribed conditions. The sample size was: the length is 130mm, the width is 13mm, and the thickness is 3.2mm. The material is classified according to the burning time. Limiting Oxygen Index (LOI) test method: generally, at normal temperature, a sample prepared in advance is placed in a mixed gas of oxygen and nitrogen, and the volume percentage of the lowest oxygen concentration required for maintaining the combustion equilibrium is accurately determined. It is generally believed that: when the LOI is greater than 27, the material can generally be defined as a flame retardant material; when the LOI is greater than 22 but less than 27, this class of materials can be designated as pyrophoric materials; when the LOI is less than 22, the material is classified as a flammable material. Polypropylene materials are among the flammable materials. The test results are shown in Table 1.
TABLE 1 flame retardancy test
| Experimental protocol | Vertical combustion class | LOI index/%) |
| Comparative example 1 | V-1 | 28.5 |
| Example 1 | V-0 | 32.1 |
| Example 2 | V-1 | 23.7 |
| Example 3 | V-1 | 27.8 |
| Polypropylene material | Fail | 17.9 |
The test result shows that the LOI value of the pure polypropylene material is less than 22%, the pure polypropylene material is a flammable material, the flame retardant performance is improved after the flame retardant is added, and the flame retardant performance in the embodiment 1 is the most excellent, which is probably because the phenoxy phosphazene covalent triazine composite material is modified by aluminum hypophosphite, and a graphitized stable carbon structure is formed in the combustion process due to the stable skeleton structure of the phenoxy phosphazene covalent triazine composite material, so that the release of flammable gas and the attack of flame are blocked, and the protection of a bottom base material is facilitated. The surface of the residue of the composite material is reserved with a high content of P element after high-temperature combustion, and the flame-retardant element phosphorus and carbon are subjected to cross-linking reaction, so that the carbon layer is more stable, and the flame-retardant performance is better promoted. The triazine-based covalent skeleton promotes the formation of a non-combustible gas, such as CO, in the gas phase 2 And nitrogen-containing macromolecules, which play a role in flame retardance in a gas phase and can also be used as a char forming agent to retard the flame in a condensed phase to form a carbon protective layer with a relatively compact appearance and a microporous structure in the interior. The carbon layer structure can insulate heat and combustible gas and protect the material from being further corroded by fire. The effects are combined to improve the flame retardant property, so that the flame retardant property of the polyamide composite material prepared by the modified aluminum hypophosphite is obviously improved.
Test example 2
The mechanical properties of the flame retardants prepared in the examples and the comparative examples were measured by first preparing a polypropylene sample according to the method of test example 1, and the mechanical properties were measured by tensile properties, flexural properties, and impact strength. The definition of the tensile strength refers to the maximum tensile stress which can be borne by the sample when the sample strip to be tested is continuously stretched after being stressed and the phenomenon of breakage after the sample strip exceeds the bearing tensile limit is known under the action of the external tensile stress. The greater the tensile strength of the specimen, the more excellent the material exhibits excellent strength and toughness, and therefore its service properties are. In this chapter, the tensile properties of plastics are determined according to GB/T1040.1-2018 part 1: general rules the test pieces prepared by hot press molding were individually tested. The adopted test samples are dumbbell-shaped, the size of each test sample is 75mm multiplied by 10mm multiplied by 2mm, the test speed is 50mm/min, the surfaces of the test samples are kept flat and smooth, the outer surfaces of the test samples have no relevant defects such as burrs, fins and the like, the interior of the test samples have no serious defects such as bubbles, and meanwhile, the number of each group of test samples to be tested is determined to be 5, so that the scientificity of the test is increased. The calculation of tensile strength and elongation at break is shown in figure 1. The bending performance of a material mainly refers to the maximum bending load which the material can bear under the condition of external action. In this chapter, the specimens were tested according to GB/T9341-2008 determination of Plastic flexural Properties. The required sample size is 80mm × 10mm × 4mm, and the test speed is 5mm/min. The impact performance refers to the maximum impact load which the test piece can bear under the action of the outside so as to determine the impact strength of the material. The bending strength is calculated according to the formula 3. The impact strength can be used for analyzing and identifying the brittleness degree of various materials. The section 2 of the chapter is determined according to GB/T1043.2-2018 impact performance of plastic simple supported beams: instrumented impact test. The test was carried out using an electronic cantilever beam impact tester, the specimen being an a-notch, in which the energy of the pendulum is 5.5J, facing the notch of the specimen, and the specimen having dimensions 80mm × 10mm × 4mm. The impact strength is calculated as formula 4. The specific test results are shown in Table 2.
Delta = P/b d-formula 1
δ: tensile strength (MPa); p: a maximum load (N); b: specimen width (mm); d: specimen thickness (mm).
E＝(G﹣G 0 )/G 0 *100% -formula 2
E: elongation at break (%); g0: distance (mm) between original standard lines of the sample; g: the distance between the lines (mm) when the specimen broke.
σ f ＝(3P·L)/(2b·d 2 ) -formula 3
σ f : bending strength (MPa); p: breaking load or maximum load (N); l: span (mm); b: specimen width (mm). d: specimen thickness (mm).
ak＝A k /(b*d k )*10 3 -formula 4
a k : impact strength at the notch (KJ/m 2); ak: impact energy (J) that the notched specimen can absorb; b: specimen width (mm); dk: the thickness (mm) remaining after impact at the notch of the notched specimen.
Table 2 mechanical property test result table
According to mechanical property tests, the modification of aluminum hypophosphite can improve the mechanical property to a certain extent, which is probably due to the improvement of the compatibility after modification, while the mechanical property in the embodiment 1 is obviously improved because the phenoxy phosphazene covalent triazine composite material in the molecular structure contains a large amount of phenyl groups, the heterogeneous nucleation effect of the phenyl groups enables the crystallization area of the matrix to be more complete, the interfacial force between the flame retardant and the matrix enables the arrangement of molecular chain segments in amorphous areas to be more regular, and the mechanical property of the material is improved.
Test example 3
The flame retardants prepared in the control examples and examples were tested for water resistance by first preparing polypropylene samples according to the method of test example 1. The water resistance test of the polymer is an important basis for judging whether the polymer can maintain good performance in a humid environment. The specific operation is as follows: grouping and numbering the sample strips, and weighing the initial mass m of each sample strip 0 Arranging the sample strips in sequence, putting into 70 deg.C distilled water, decocting at constant temperature for 168 hr, changing the steaming feed water every 24 hr (from the first day to the fifth day), taking out the sample strips by the seventh day, wiping off water, placing in a vacuum drying oven, oven drying at 80 deg.C for 72 hr, taking out, cooling to room temperature, and weighing mass m 1 Calculating the mass loss rate (m) x /％)。m x ＝(m 0 ﹣m 1 )/m 0 *100%, the specific test results are shown in Table 3.
TABLE 3 Water resistance test results Table
| Experimental protocol | Mass loss rate/%) |
| Comparative example 1 | 0.97 |
| Example 1 | 0.51 |
| Example 2 | 1.26 |
| Example 3 | 1.21 |
| Polypropylene material | 1.34 |
It can be seen from the water resistance test that the aluminum hypophosphite in the embodiment 2 and the embodiment 3 is not modified and is modified by hexachlorocyclotriphosphazene, so that the hydrophilicity is strong, and the aluminum hypophosphite is easy to be extracted by water, while the aluminum hypophosphite in the embodiment 1 is modified by phenoxyphosphazene covalent triazine composite material, and due to the highly crosslinked phenoxycyclotriphosphazene unit in the structure, water molecules can be prevented from entering the aluminum hypophosphite, so that the hydrophobicity of the flame retardant is obviously improved, the aluminum hypophosphite is not easy to be extracted, the water resistance is enhanced, and the application of the polymer material under the humid condition has an important effect.
Claims (8)
1. A method for producing an aluminum hypophosphite flame retardant by using a sodium hypophosphite mother solution is characterized by comprising the following steps:
s1, taking sodium hypophosphite mother liquor, adding calcium hypophosphite, stirring at room temperature until a precipitate appears, filtering, and removing the calcium phosphite precipitate to obtain a filtrate;
s2, weighing aluminum hydroxide, adding water, dropwise adding concentrated sulfuric acid while stirring, heating and stirring after dropwise adding, and filtering after the reaction is finished to obtain a filtrate, namely an aluminum sulfate solution;
s3, adding the filtrate obtained in the step S1 into the aluminum sulfate solution obtained in the step S2 under stirring, heating and stirring after the addition is finished, cooling after the reaction is finished to generate precipitates, filtering the reaction liquid, washing a filter cake with water, crushing and drying to obtain aluminum hypophosphite;
s4, weighing 4-cyanophenol and triethylamine, mixing to obtain a solution A, weighing hexachlorocyclotriphosphazene, adding the hexachlorocyclotriphosphazene into tetrahydrofuran to obtain a solution B, adding the solution A into the solution B, heating to reflux, stirring, concentrating to remove the solvent after the reaction is finished, adding ethanol into the concentrate, heating to reflux, cooling to recrystallize after the stirring, wherein precipitates appear, filtering, and concentrating a filter cake under reduced pressure to obtain hexa (cyanophenoxy) cyclotriphosphazene;
s5, weighing the hexa (cyanophenoxy) cyclotriphosphazene and zinc chloride obtained in the step S4, placing the hexa (cyanophenoxy) cyclotriphosphazene and the zinc chloride into an ampoule bottle, vacuumizing the ampoule bottle, sealing, heating, preserving heat, cooling to room temperature after the reaction is finished, opening the ampoule bottle, crushing the obtained product, adding an HCl aqueous solution, stirring, filtering, washing a filter cake with water until the pH value is neutral, respectively washing with methanol and dichloromethane for 2 times, and drying the washed filter cake to obtain the phenoxyphosphazene covalent triazine composite material;
s6, weighing the phenoxyphosphazene covalent triazine composite material in the step S5 and the aluminum hypophosphite in the step S3, uniformly mixing, heating and stirring, and obtaining the modified aluminum hypophosphite flame retardant after the reaction is finished.
2. A method of producing an aluminum hypophosphite flame retardant as in claim 1, comprising the steps of:
s1, taking 50-80 parts by weight of sodium hypophosphite mother liquor, adding calcium hypophosphite, stirring at room temperature for 2-4 hours until precipitation appears, filtering, and removing calcium phosphite precipitation to obtain filtrate;
s2, weighing 2-4 parts by weight of aluminum hydroxide, adding 10-15 parts by weight of water, dropwise adding 98wt% concentrated sulfuric acid under stirring, after dropwise adding, heating to 100-110 ℃, stirring for 3-5 hours, and after the reaction is finished, filtering to obtain a filtrate, namely an aluminum sulfate solution;
s3, adding the filtrate obtained in the step S1 into the aluminum sulfate solution obtained in the step S2 under stirring, heating to 80-90 ℃ after the addition is finished, stirring for 4-6 h, cooling to 40-60 ℃ after the reaction is finished, generating precipitates, filtering the reaction solution, adding 1-2 parts by weight of filter cake into water, washing, crushing and drying to obtain aluminum hypophosphite;
s4, weighing 4-cyanophenol and triethylamine, mixing to obtain a solution A, weighing 0.5-0.8 part by weight of hexachlorocyclotriphosphazene, adding the solution A into 30-50 parts by weight of tetrahydrofuran to obtain a solution B, adding the solution A into the solution B, heating to 60-70 ℃, carrying out reflux stirring for 20-24 h, concentrating after the reaction is finished, removing the solvent, adding 30-50 parts by weight of ethanol into the concentrate, heating to 70-80 ℃, carrying out reflux stirring for 2-4 h, cooling to 0-10 ℃, carrying out recrystallization, allowing precipitates to appear, filtering, and carrying out reduced pressure concentration on a filter cake to obtain hexa (cyanophenoxy) cyclotriphosphazene;
s5, weighing 0.5-0.6 part by weight of hexa (cyanophenoxy) cyclotriphosphazene obtained in the step S4, mixing the hexa (cyanophenoxy) cyclotriphosphazene with zinc chloride, placing the mixture into an ampoule bottle, vacuumizing the ampoule bottle, sealing the ampoule bottle, heating to 400-500 ℃, keeping the temperature for 40-50 h, cooling to room temperature after the reaction is finished, opening the ampoule bottle, crushing the obtained product, adding 1-2 parts by weight of 2mol/L HCl aqueous solution, stirring, filtering, washing a filter cake with water until the pH is neutral, respectively washing 2 times with 1-2 parts by weight of methanol and 1-2 parts by weight of dichloromethane, and drying the washed filter cake at 110-120 ℃ for 4-6 h to obtain the phenoxyphosphazene covalent triazine composite material;
s6, weighing 0.2-0.4 part by weight of the phenoxyphosphazene covalent triazine composite material in the step S5 and the aluminum hypophosphite in the step S3, uniformly mixing, stirring at 180-200 ℃ for 6-8 h, and obtaining the modified aluminum hypophosphite flame retardant after the reaction is finished.
3. An aluminum hypophosphite flame retardant as defined in claim 1 or 2 wherein: the addition amount of the calcium hypophosphite in the step S1 is 3-5 parts by weight.
4. An aluminum hypophosphite flame retardant as defined in claim 1 or 2 wherein: the addition amount of the 98wt% concentrated sulfuric acid in the step S2 is 4 to 5 parts by weight.
5. An aluminum hypophosphite flame retardant as defined in claim 1 or 2 wherein: the addition amount of the 4-cyanophenol in the step S4 is 1.1 to 2 parts by weight.
6. An aluminum hypophosphite flame retardant as defined in claim 1 or 2 wherein: the addition amount of triethylamine in the step S4 is 1.5-2 parts by weight.
7. A method as set forth in claim 1 or 2 for producing an aluminum hypophosphite flame retardant, characterized in that: the addition amount of the zinc chloride in the step S5 is 0.08-0.1 part by weight.
8. A method as set forth in claim 1 or 2 for producing an aluminum hypophosphite flame retardant, characterized in that: and the addition amount of the aluminum hypophosphite in the step S6 is 4-8 parts by weight.
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