CN111484520A - Ethylene diamine tetramethylene aluminum phosphonate flame retardant and preparation method and application thereof - Google Patents
Ethylene diamine tetramethylene aluminum phosphonate flame retardant and preparation method and application thereof Download PDFInfo
- Publication number
- CN111484520A CN111484520A CN201910078870.3A CN201910078870A CN111484520A CN 111484520 A CN111484520 A CN 111484520A CN 201910078870 A CN201910078870 A CN 201910078870A CN 111484520 A CN111484520 A CN 111484520A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- aluminum
- phosphonic acid
- tetramethylene phosphonic
- ethylene diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 155
- 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 143
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 title claims abstract description 13
- NCPIYHBOLXSJJR-UHFFFAOYSA-H [Al+3].[Al+3].[O-]P([O-])=O.[O-]P([O-])=O.[O-]P([O-])=O Chemical compound [Al+3].[Al+3].[O-]P([O-])=O.[O-]P([O-])=O.[O-]P([O-])=O NCPIYHBOLXSJJR-UHFFFAOYSA-H 0.000 title claims abstract description 12
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 229940120146 EDTMP Drugs 0.000 claims abstract description 64
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002861 polymer material Substances 0.000 claims abstract description 51
- -1 aluminum ions Chemical class 0.000 claims abstract description 45
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000000123 paper Substances 0.000 claims abstract description 26
- 239000002023 wood Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 229920001169 thermoplastic Polymers 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 13
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 9
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 8
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 229920000388 Polyphosphate Polymers 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000001205 polyphosphate Substances 0.000 claims description 6
- 235000011176 polyphosphates Nutrition 0.000 claims description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 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 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- IOGRQIWFIRKXQV-UHFFFAOYSA-K aluminum dipropylphosphinate Chemical compound C(CC)P([O-])(=O)CCC.[Al+3].C(CC)P([O-])(=O)CCC.C(CC)P([O-])(=O)CCC IOGRQIWFIRKXQV-UHFFFAOYSA-K 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 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 claims description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- WVLAZEHCUADXTN-UHFFFAOYSA-K aluminum butyl(ethyl)phosphinate Chemical compound [Al+3].CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC.CCCCP([O-])(=O)CC WVLAZEHCUADXTN-UHFFFAOYSA-K 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 claims description 2
- 239000004634 thermosetting polymer Substances 0.000 claims description 2
- SLKRGHBFYYVSLH-UHFFFAOYSA-K tris(dibutylphosphoryloxy)alumane Chemical compound [Al+3].CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC SLKRGHBFYYVSLH-UHFFFAOYSA-K 0.000 claims description 2
- BAWFMRPQYKKOLX-UHFFFAOYSA-B tetraaluminum;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O.[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O.[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O BAWFMRPQYKKOLX-UHFFFAOYSA-B 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 150000001450 anions Chemical class 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- BPSYZMLXRKCSJY-UHFFFAOYSA-N 1,3,2-dioxaphosphepan-2-ium 2-oxide Chemical compound O=[P+]1OCCCCO1 BPSYZMLXRKCSJY-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003365 glass fiber Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 3
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- DLXBSPPKDRUFHL-UHFFFAOYSA-N P1(OC(CCO1)N)=O.N1=C(N)N=C(N)N=C1N Chemical compound P1(OC(CCO1)N)=O.N1=C(N)N=C(N)N=C1N DLXBSPPKDRUFHL-UHFFFAOYSA-N 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229940010048 aluminum sulfate Drugs 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses an ethylene diamine tetramethylene phosphonic acid aluminum flame retardant, the structural formula of which is shown as the formula (I). The ethylene diamine tetramethylene phosphonic acid aluminum flame retardant has a stable molecular structure, each ethylene diamine tetramethylene phosphonic acid provides 6 monovalent anions to form salt with aluminum ions, has the advantages of high phosphorus content, good thermal stability, high flame retardant efficiency, high char yield, no halogen, environmental protection and the like, and can be widely applied to the fields of high polymer materials, wood, paper and the like as a phosphorus-nitrogen flame retardant. The invention also discloses a preparation method of the ethylene diamine tetramethylene aluminum phosphonate flame retardant, and the preparation method has the advantages of easily obtained raw materials, simple synthesis process, high yield and easy industrial production. The invention also discloses application of the flame retardant in high polymer materials, wood or paper. The invention also discloses a flame retardant composition containing the flame retardant. The invention also discloses a flame-retardant high polymer material containing the flame retardant composition.
Description
Technical Field
The invention belongs to the technical field of flame retardant application and synthesis, and particularly relates to an ethylene diamine tetramethylene aluminum phosphonate flame retardant, and a preparation method and application thereof.
Background
The polymer material has the characteristics of light weight, easy processing and forming and the like, and is widely applied to production and life. However, most of the high molecular materials are easy to burn, and the burning process is accompanied by the generation of toxic and harmful gases, so that the fire hazard is serious. In such an environment, it is particularly important to modify the flame retardancy of the polymer material. The flame retardant for the polymer material is usually selected from halogen-based, phosphorus-based, nitrogen-based, aluminum-magnesium-based, clay-based, boron-based, tin-based, intumescent, and silicon-based ones. At present, the flame-retardant high polymer material is mainly added with a brominated flame retardant, but the use amount is large. Although the high-efficiency flame-retardant effect can be ensured even if the addition amount is small, toxic and corrosive dense smoke can be generated, and great harm is caused to the environment and the health of human bodies. Therefore, the development of halogen-free flame retardants is increasing in various countries, and among them, halogen-free phosphorus-nitrogen flame retardants are one of the countermeasures. At high temperature, the halogen-free phosphorus-nitrogen flame retardant forms a compact carbon layer on the surface of the high polymer material, can isolate oxygen and heat, has low smoke generation amount, does not generate toxic or harmful gas, and has good flame retardant effect.
Phosphorus-nitrogen flame retardants, boron flame retardants, halogen flame retardants, and metal oxides or hydroxides such as aluminum, magnesium, and antimony are commonly used as the wood flame retardant. Flame retardant mechanisms of different types of flame retardants are different, and a compounding mode of several flame retardants is generally adopted. According to the development trend of wood flame retardants at home and abroad in recent years, research and development of long-acting flame retardants with low toxicity, low pollution, low moisture absorption and resistance to loss and multifunctional flame retardants with corrosion resistance, mildew resistance, insect resistance, dimensional stability and the like have been advanced. In addition to the above-mentioned characteristics, the effects of flame retardant treatment on the physical and mechanical properties such as wood strength and slab rubber strength must be considered in practical use, and the cost is also one of the factors that must be considered.
Paper is generally made of plant fibers, which are flammable substances. With the development of society, flame retardant paper using plant fiber as a main raw material, such as flame retardant packaging paper and paperboard, flame retardant decorative paper, flame retardant automobile filter paper and the like, is used in more and more fields, so that the research on the flame retardant of plant fiber paper has become a research hotspot in the field of special paper. The existing flame-retardant method for vegetable fiber paper is usually prepared by adding a flame retardant, such as adding a water-insoluble flame retardant into paper pulp to make flame-retardant paper, or using a surface sizing method, a coating method or an impregnation method and the like to enable the flame-retardant paper to have flame retardancy. The existing flame-retardant paper produced in China mainly has the defects of large addition amount of flame retardant, use of halogen-containing flame retardant, easy moisture absorption of the flame retardant and the like.
Phosphorus-containing flame retardants are often used in combination with nitrogen-based flame retardants. In patent CN1660857B, aluminum diethylphosphinate flame retardant uses melamine polyphosphate as a synergist. The compounded synergistic flame retardant is intermolecular, and the synergistic effect of phosphorus and nitrogen elements in the molecule draws attention of chemists. Ammonium polyphosphate (also called ammonium polyphosphate or condensed ammonium phosphate (APP for short) is a phosphorus-nitrogen flame retardant with excellent performance, has higher phosphorus content and nitrogen content, and has an intramolecular P-N synergistic effect. Patent CN104497041A discloses a compound of formula (ii) in which each aminotrimethylene phosphonic acid provides three monovalent anions, which with melamine form a melamine aminotrimethylene phosphonate. Patent CN106632468A discloses a compound of formula (III), each aminotrimethylene phosphonic acid providing a monovalent anion, which is reacted with a metal salt to give the aminotrimethylene phosphonic acid metal salt. Although both of these compounds have a certain flame retardancy, they have disadvantages such as a large amount of addition, low flame retardant efficiency, and low char yield. Patents CN102268814A and CN101487184A disclose the use of manganese, zinc or aluminum salts of ethylenediamine tetramethylene phosphonic acid as chelating agents in textile printing and dyeing auxiliaries. However, few reports have been made on aluminum ethylenediaminetetramethylenephosphonate as a flame retardant.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an aluminum ethylene diamine tetramethylene phosphonate flame retardant, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a flame retardant is aluminum ethylene diamine tetramethylene phosphonate, and the structural formula of the flame retardant is shown as the formula (I):
The invention synthesizes series of ethylene diamine tetramethylene phosphonic acid aluminum by reacting ethylene diamine tetramethylene phosphonic acid or acidic salt aqueous solution of ethylene diamine tetramethylene phosphonic acid with metal compound or aqueous solution thereof under different pH values, and obtains the compound with the structure shown as the formula (IV):
Wherein n is 1 to 8.
In the molecular structure of the compound (IV), each ethylenediamine tetramethylene phosphonic acid provides 1-8 univalent anions to react with aluminum ions.
Through a large number of synthesis and fire retardant screening studies, it is found that when n is 6, each ethylenediamine tetramethylene phosphonic acid has 2 undissociated hydrogen ions to provide 6 monovalent anions, and forms a stable chemical structure with 2 trivalent metal aluminum ions, and the flame retardant effect of the ethylenediamine tetramethylene phosphonic acid aluminum is the best, namely, the ethylenediamine tetramethylene phosphonic acid aluminum has the structure shown in formula (I), and the structure has the advantages of high phosphorus content, good thermal stability, high char yield, no halogen, green environmental protection and the like.
Preferred embodiments of the flame retardant of the present invention include at least one of the following (a) to (c):
(a) The particle size of the ethylene diamine tetramethylene aluminum phosphonate is D50-5 mu m-100 mu m;
(b) The tap bulk density of the ethylene diamine tetramethylene aluminum phosphonate is 0.4g/cm 3～0.9g/cm3；
(c) The angle of repose of the ethylene diamine tetramethylene aluminum phosphonate is 25-45 degrees.
The invention also aims to provide a preparation method of the flame retardant, which comprises the following steps:
(1) Reacting ethylene diamine tetramethylene phosphonic acid or the aqueous solution of the acid salt of the ethylene diamine tetramethylene phosphonic acid with the aqueous solution of the alkaline compound according to equivalent weight to obtain the aqueous solution of the alkali metal salt of the ethylene diamine tetramethylene phosphonic acid;
(2) And reacting the ethylene diamine tetramethylene phosphonic acid alkali metal salt aqueous solution with an aluminum metal compound or an aqueous solution thereof to prepare the ethylene diamine tetramethylene phosphonic acid aluminum.
As a preferred embodiment of the method for producing the flame retardant of the present invention, at least one of the following (d) to (f):
(d) In the step (1), at least one of the alkaline compounds sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acetate and potassium acetate;
(e) In the step (1), the acid salt of ethylenediamine tetramethylene phosphonic acid is at least one of ethylenediamine tetramethylene phosphonic acid monosodium salt, ethylenediamine tetramethylene phosphonic acid disodium salt, ethylenediamine tetramethylene phosphonic acid trisodium salt, ethylenediamine tetramethylene phosphonic acid tetrasodium salt, ethylenediamine tetramethylene phosphonic acid pentasodium salt, ethylenediamine tetramethylene phosphonic acid hexasodium salt, ethylenediamine tetramethylene phosphonic acid monopotassium salt, ethylenediamine tetramethylene phosphonic acid dipotassium salt, ethylenediamine tetramethylene phosphonic acid tripotassium salt, ethylenediamine tetramethylene phosphonic acid tetrapotassium salt, ethylenediamine tetramethylene phosphonic acid pentapotassium salt and ethylenediamine tetramethylene phosphonic acid hexapotassium salt;
(f) In the step (2), the aluminum metal compound is at least one of aluminum sulfate, aluminum chloride, aluminum acetate, aluminum nitrate, aluminum hydroxide and aluminum oxide.
The invention also aims to provide the application of the flame retardant in high polymer materials, wood or paper.
The invention also aims to provide a flame retardant composition comprising the flame retardant.
As a preferred embodiment of the flame retardant composition, the flame retardant composition comprises the following components in percentage by weight: 10-99.9% of flame retardant and 0.1-90% of additive.
As a more preferred embodiment of the flame retardant composition of the present invention, the flame retardant composition comprises the following components in weight percent: 20-70% of flame retardant and 30-80% of additive.
As a preferred embodiment of the flame retardant composition of the present invention, the additive is at least one of aluminum diethylphosphinate, aluminum dipropylphosphinate, aluminum dibutylphosphinate, aluminum ethylbutylphosphinate, aluminum hypophosphite, piperazine pyrophosphate, piperazine polyphosphate, melamine pyrophosphate, melamine polyphosphate, melamine cyanurate, guanidine, and dicyandiamide.
The invention also aims to provide a flame-retardant high polymer material, which comprises the flame retardant composition.
As a preferred embodiment of the flame retardant polymer material of the present invention, the flame retardant polymer material comprises the following components in percentage by weight: 1-50% of the flame retardant composition, 30-99% of a polymer, 0-60% of an auxiliary agent and 0-60% of a filler.
As a more preferable embodiment of the flame retardant polymer material of the present invention, the flame retardant polymer material comprises the following components in percentage by weight: 5-30% of the flame retardant composition, 40-95% of the polymer, 0-40% of the auxiliary agent and 0-40% of the filler.
As a preferred embodiment of the flame retardant polymer material of the present invention, the polymer is a thermoplastic polymer and/or a thermosetting polymer.
As a preferred embodiment of the flame retardant polymer material of the present invention, the thermoplastic polymer is at least one of polyester, polyamide and polyolefin.
In a more preferred embodiment of the flame retardant polymer material of the present invention, the thermoplastic polymer is at least one of nylon 66, polybutylene terephthalate, and polypropylene.
The invention has the beneficial effects that: the invention provides an ethylene diamine tetramethylene aluminum phosphonate flame retardant which has a stable molecular structure, each ethylene diamine tetramethylene phosphonic acid provides 6 monovalent anions to form salt with aluminum ions, has the advantages of high phosphorus content, good thermal stability, high flame retardant efficiency, high char yield, no halogen, environmental protection and the like, and can be widely applied to the fields of high polymer materials, wood, paper and the like as a phosphorus-nitrogen flame retardant. The invention also provides a preparation method of the ethylene diamine tetramethylene aluminum phosphonate flame retardant, and the preparation method has the advantages of easily obtained raw materials, simple synthesis process, high yield and easy industrial production. The invention also provides the application of the flame retardant in high polymer materials, wood or paper. The invention also provides a flame retardant composition containing the flame retardant. The invention also provides a flame-retardant high polymer material containing the flame retardant composition.
Drawings
FIG. 1 shows the structure of formula (I).
Detailed Description
The raw materials of the invention are all from commercial products.
The method for testing the particle size of the aluminum ethylene diamine tetramethylene phosphonate comprises the following steps:
The particle size distribution of the aluminum ethylenediaminetetramethylenephosphonate dispersed in the liquid phase was measured using a laser particle sizer. The specific operation is as follows: according to the particle size of the aluminum ethylenediamine tetramethylene phosphonate, 0.05g to 1.0g of a sample of the aluminum ethylenediamine tetramethylene phosphonate is put into a beaker, added with alcohol and water, dispersed by ultrasonic or stirring, and poured into a laser particle sizer to measure the particle size distribution of the aluminum ethylenediamine tetramethylene phosphonate. The particle size of the aluminum ethylene diamine tetramethylene phosphonate is evaluated according to D (10), D (50) and D (90) measured by a laser particle sizer.
The test method of the angle of repose of the aluminum ethylene diamine tetramethylene phosphonate comprises the following steps:
pouring the powder sample into a funnel, enabling the sample to fall on a round flat plate with the radius r below the round flat plate through the funnel, gradually stacking the powder until the powder cannot be stacked up continuously, measuring the stacking height h of the powder, and calculating the angle of repose α according to the formula (1).
tgα＝h/r (1)。
The method for testing the tap bulk density of the aluminum ethylenediamine tetramethylene phosphonate is determined by referring to GB/T20316.2-determination of bulk density.
The infrared absorption spectrum test method of the aluminum ethylenediamine tetramethylene phosphonate is determined by referring to the method of GB/T6040-2002 general rules of Infrared Spectroscopy.
The performance test of the flame-retardant high polymer material is carried out according to the following standards:
The tensile strength is GB/T1040-1992 test method for tensile property of plastics;
The bending strength is GB/T9341-2000 method for testing the bending performance of plastics;
Deflection GB/T9341-2000 method for testing bending property of plastics;
Notched impact strength: GB/T16420-1996 test method for small samples of plastic impact properties;
the combustion performance of the plastic is U L94 test.
The performance test of the flame-retardant wood is carried out according to the following standards:
Bonding strength: GB/T17657-1999 test method for physical and chemical properties of artificial board and facing artificial board;
Limiting oxygen index: GB/T2406-2009 oxygen index method for testing plastic combustion performance, GB50222-95 fire protection code for building interior decoration design stipulates that the oxygen index of grade B1 is not less than 48%;
Smoke density: GB/T8627-1999 Smoke Density test method for burning or decomposing building materials, the smoke Density level SDR is less than or equal to 75.
The performance test of the flame-retardant paper is carried out according to the following standards:
Combustion performance: GB/T14656-2009 flame retardant paper and paperboard burning performance test method;
Limiting oxygen index: GB/T2406-2009 "Plastic burning Performance test method oxygen index method", GB50222-95 "architectural interior decoration design fire code" stipulates that the B1 grade oxygen index is not less than 48%.
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: adding 9689g (10mol) of ethylenediamine tetramethylene phosphonic acid aqueous solution with the mass fraction of 45% into a reactor, neutralizing with 6000g (60mol) of NaOH aqueous solution with the mass fraction of 40%, stirring and heating to 90 ℃, adding 16650g (10mol) of aluminum sulfate octadecahydrate aqueous solution with the mass fraction of 40% within 60min, generating solid precipitate, cooling, filtering, washing with water and drying; 4714g of ethylenediamine tetramethylene phosphonic acid aluminum was obtained with a yield of 97.4%.
The particle size (mum) distribution of the product is as follows: d (10) 8.73; d (50): 25.93; d (90): 51.83;
Tap bulk density: 0.71g/cm 3；
Angle of repose: 34 degrees;
IR：463cm-1,604cm-1,777cm-1,1148cm-1,1437cm-1,1653cm-1,3034cm-1。
Example 2
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: adding 9689g (10mol) of ethylenediamine tetramethylene phosphonic acid aqueous solution with the mass fraction of 45% into a reactor, neutralizing with 8415g (60mol) of KOH aqueous solution with the mass fraction of 40%, stirring and heating to 90 ℃, adding 16650g (10mol) of aluminum sulfate octadecahydrate aqueous solution with the mass fraction of 40% within 60min, generating solid precipitate, cooling, filtering, washing with water and drying; 4680g of ethylenediamine tetramethylene phosphonic acid aluminum is obtained, and the yield is 96.7 percent.
The particle size (mum) distribution of the product is as follows: d (10): 16.82; d (50): 36.63; d (90): 71.93, respectively;
Tap bulk density: 0.79g/cm 3；
Angle of repose: 36 degrees;
IR：458cm-1,594cm-1,777cm-1,1147cm-1,1433cm-1,1651cm-1,3032cm-1。
Example 3
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: adding 9689g (10mol) of ethylenediamine tetramethylene phosphonic acid aqueous solution with the mass fraction of 45% into a reactor, neutralizing with 6000g (60mol) of NaOH aqueous solution with the mass fraction of 40%, stirring and heating to 90 ℃, adding aluminum chloride hexahydrate with the mass fraction of 40% into the reactor within 30min to prepare 12072g (20mol) of aqueous solution, generating solid precipitate, cooling, filtering, washing with water and drying; 4690g of ethylenediamine tetramethylene phosphonic acid aluminum is obtained, and the yield is 96.9 percent.
The particle size (mum) distribution of the product is as follows: d (10): 25.14; d (50): 60.01; d (90): 135.92, respectively;
Tap bulk density: 0.82g/cm 3；
Angle of repose: 39 degrees;
IR：463cm-1,600cm-1,779cm-1,1144cm-1,1435cm-1,1651cm-1,3030cm-1。
Example 4
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: 16229g (10mol) of ethylenediamine methylene phosphonic acid hexasodium aqueous solution with the mass fraction of 35% is added into a reactor, stirred and heated to 90 ℃, and 16650g (10mol) of octadecane water aluminum sulfate aqueous solution with the mass fraction of 40% is added within 120min to obtain 4613g of ethylenediamine tetramethylene phosphonic acid aluminum, and the yield is 95.3%.
The particle size (mum) distribution of the product is as follows: d (10): 22.85; d (50): 54.21; d (90): 111.84, respectively;
Tap bulk density of 0.75g/cm 3；
Angle of repose: 38 degrees;
IR：465cm-1,602cm-1,776cm-1,1140cm-1,1437cm-1,1653cm-1,3027cm-1。
Example 5
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: 14343g (10mol) of trisodium ethylenediamine tetramethylene phosphonate aqueous solution with the mass fraction of 35 percent is added into a reactor, 5610g (30mol) of KOH aqueous solution with the mass fraction of 30 percent is used for neutralization, the mixture is stirred and heated to 90 ℃, 16650g (10mol) of aluminum sulfate octadecahydrate aqueous solution with the mass fraction of 40 percent is added within 60min, and solid precipitate is generated, and the mixture is cooled, filtered, washed and dried; 4637g of ethylenediamine tetramethylene phosphonic acid aluminum is obtained, and the yield is 95.8%.
The particle size (mum) distribution of the product is as follows: d (10): 12.82; d (50): 29.59; d (90): 66.51, respectively;
Tap bulk density of 0.73g/cm 3；
Angle of repose: 31 degrees;
IR：462cm-1,601cm-1,777cm-1,1144cm-1,1436cm-1,1651cm-1,3029cm-1。
Example 6
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: 13086g (10mol) of ethylene diamine tetramethylene phosphonic acid monosodium salt aqueous solution with the mass fraction of 35% is added into a reactor, 6667g (50mol) of NaOH aqueous solution with the mass fraction of 30% is used for neutralization, the mixture is stirred and heated to 90 ℃, 16650g (10mol) of octadecane water aluminum sulfate aqueous solution with the mass fraction of 40% is added within 60min, solid precipitate is generated, the mixture is cooled, filtered, washed and dried, and the 4622g of ethylene diamine tetramethylene phosphonic acid aluminum is obtained, and the yield is 95.5%.
The particle size (mum) distribution of the product is as follows: d (10) is 8.97; d (50): 28.12; d (90): 55.84, respectively;
Tap bulk density of 0.71g/cm 3；
Angle of repose: 30 degrees;
IR：466cm-1,601cm-1,778cm-1,1148cm-1,1435cm-1,1655cm-1,3031cm-1。
Example 7
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: 14629g (10mol) of ethylene diamine tetramethylene phosphonic acid dipotassium aqueous solution with the mass fraction of 35% is added into a reactor, 6411g (40mol) of KOH aqueous solution with the mass fraction of 35% is used for neutralization, the mixture is stirred and heated to 90 ℃, 18757g (20mol) of aluminum nitrate nonahydrate aqueous solution with the mass fraction of 40% is added within 60min, solid precipitate is generated, the mixture is cooled, filtered, washed and dried, and 4574g of ethylene diamine tetramethylene phosphonic acid aluminum is obtained, and the yield is 94.5%.
The particle size (mum) distribution of the product is as follows: d (10): 10.98; d (50): 33.62; d (90): 81.66, respectively;
Tap bulk density: 0.74g/cm 3；
Angle of repose: 32 degrees;
IR：459cm-1,594cm-1,779cm-1,1149cm-1,1430cm-1,1650cm-1,3030cm-1。
Example 8
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: 16800g (10mol) of ethylene diamine tetramethylene phosphonic acid tetrapotassium water solution with the mass fraction of 35% is added into a reactor, 3206g (20mol) of KOH water solution with the mass fraction of 35% is used for neutralization, the mixture is stirred and heated to 90 ℃, 18757g (20mol) of aluminum nitrate nonahydrate water solution with the mass fraction of 40% is added within 60min, solid precipitate is generated, the mixture is cooled, filtered, washed and dried, and 4583g of ethylene diamine tetramethylene phosphonic acid aluminum is obtained, and the yield is 94.7%.
The particle size (mum) distribution of the product is as follows: d (10): 11.33; d (50): 35.83; d (90): 84.84;
Tap bulk density: 0.74g/cm 3；
Angle of repose: 33 °;
IR：459cm-1,593cm-1,776cm-1,1149cm-1,1436cm-1,1650cm-1,3033cm-1。
Example 9
The structural formula of the aluminum ethylene diamine tetramethylenephosphonate is shown as a formula (I), and the preparation method comprises the following steps: 17886g (10mol) of ethylene diamine tetramethylene phosphonic acid pentapotassium aqueous solution with the mass fraction of 35% is added into a reactor, the mixture is neutralized by 1333g (10mol) of NaOH aqueous solution with the mass fraction of 30%, the mixture is stirred and heated to 90 ℃, 12072g (20mol) of aluminum chloride hexahydrate aqueous solution with the mass fraction of 40% is added within 60min, solid precipitate is generated, the mixture is cooled, filtered, washed and dried, and 4613g of ethylene diamine tetramethylene phosphonic acid aluminum is obtained, and the yield is 95.3%.
The particle size (mum) distribution of the product is as follows: d (10): 11.73; d (50): 35.25; d (90): 84.12 of the total weight of the steel;
Tap bulk density of 0.74g/cm 3；
Angle of repose: 33 °;
IR：460cm-1,594cm-1,780cm-1,1145cm-1,1437cm-1,1650cm-1,3036cm-1。
Example 10
the aluminum ethylenediamine tetramethylene phosphonate obtained in example 1 and PBT are mixed according to the weight ratio of 35: 65 and extruded from a twin-screw extruder at 230-260 ℃ to prepare the flame-retardant thermoplastic polymer material, and the flame retardancy U L94 of the flame-retardant thermoplastic polymer material can reach V-2 grade after burning 3.0mm by sample preparation test.
Example 11
the aluminum ethylenediamine tetramethylene phosphonate obtained in example 2 was mixed with PA66 in a weight ratio of 35: 65 and extruded from a twin-screw extruder at 240-270 ℃ to give a flame-retardant thermoplastic polymer material, which was tested for flame retardancy U L94 to achieve a V-2 rating of 3.0mm on flame.
Example 12
the aluminum ethylenediamine tetramethylene phosphonate obtained in example 3 was mixed with PP in a weight ratio of 35: 65 and extruded from a twin-screw extruder at 170-200 ℃ to produce a flame-retardant thermoplastic polymer material, which was tested for flammability U L94 to achieve a V-2 rating at 3.0mm burn.
Example 13
The aluminum ethylenediaminetetramethylenephosphonate obtained in example 4 was mixed with aluminum diethylphosphinate, PBT and glass fiber in a weight ratio of 6:10:59:25 and extruded from a twin-screw extruder at 230-260 ℃ to prepare a flame-retardant thermoplastic polymer material.
Example 14
The aluminum ethylenediaminetetramethylenephosphonate obtained in example 5 was mixed with aluminum diethylphosphinate, PBT and glass fiber in a weight ratio of 8:8:59:25 and extruded from a twin-screw extruder at 230-260 ℃ to prepare a flame-retardant thermoplastic polymer material.
Example 15
The aluminum ethylenediaminetetramethylenephosphonate obtained in example 6 was mixed with aluminum diethylphosphinate, PBT, and glass fiber in a weight ratio of 10:6:59:25, and extruded from a twin-screw extruder at 230-260 ℃ to prepare a flame-retardant thermoplastic polymer material.
Example 16
The aluminum ethylenediaminetetramethylenephosphonate obtained in example 7 was mixed with aluminum hypophosphite, PBT and glass fiber in a weight ratio of 6:14:55:25 and extruded from a twin-screw extruder at 230-260 ℃ to prepare a flame-retardant thermoplastic polymer material.
Example 17
The aluminum ethylenediamine tetramethylene phosphonate obtained in example 8 was mixed with aluminum hypophosphite, PBT, and glass fiber in a weight ratio of 10:10:55:25, and extruded from a twin-screw extruder at 230-260 ℃ to prepare a flame retardant thermoplastic polymer material.
Example 18
The aluminum ethylenediaminetetramethylenephosphonate obtained in example 9 was mixed with aluminum hypophosphite, PBT, and glass fiber in a weight ratio of 14:6:55:25, and extruded from a twin-screw extruder at 230-260 ℃ to prepare a flame retardant thermoplastic polymer material.
Comparative example 1
Mixing aluminum diethylphosphinate, PBT and glass fiber according to the weight ratio of 16:59:25, and extruding from a double-screw extruder at 230-260 ℃ to prepare the flame-retardant thermoplastic polymer material.
Comparative example 2
Mixing aluminum hypophosphite, PBT and glass fiber according to the weight ratio of 20:55:25, and extruding the mixture from a double-screw extruder at 230-260 ℃ to obtain the flame-retardant thermoplastic polymer material.
The flame retardant thermoplastic polymer materials obtained in examples 13 to 18 and comparative examples 1 to 2 were sampled and tested for their combustion performance and mechanical properties, and the results are shown in table 1 below.
TABLE 1 PBT flame-retardant thermoplastic polymer material combustion performance and mechanical property parameter table
As can be seen from the test results in Table 1, the flame retardant effects of the PBT containing aluminum ethylenediaminetetramethylenephosphonate in examples 13 to 18 were superior to those of comparative examples 1 and 2, which did not contain aluminum ethylenediaminetetramethylenephosphonate, without changing the total amount of the flame retardant composition.
Example 19
The aluminum ethylenediaminetetramethylenephosphonate obtained in example 1 was mixed with aluminum dipropylenephosphinate, PA66, and glass fiber in a weight ratio of 6:14:55:25, and extruded from a twin-screw extruder at 240-270 ℃ to produce a flame-retardant thermoplastic polymer material.
Example 20
The aluminum ethylenediaminetetramethylenephosphonate obtained in example 2 was mixed with aluminum diethylphosphinate, PA66, and glass fiber in a weight ratio of 10:10:55:25, and extruded from a twin-screw extruder at 240-270 ℃ to produce a flame-retardant thermoplastic polymer material.
Example 21
Mixing the aluminum ethylenediamine tetramethylenephosphonate obtained in the example 3 with aluminum hypophosphite, PA66 and glass fiber in a weight ratio of 14: 6:55:25 and extruded from a twin-screw extruder at a temperature of 240-270 ℃ to obtain the flame retardant thermoplastic polymer material.
Comparative example 3
Mixing aluminum dipropylphosphinate, PA66 and glass fiber according to the weight ratio of 20:55:25, and extruding from a double-screw extruder at 240-270 ℃ to prepare the flame-retardant thermoplastic polymer material.
The polymer materials obtained in examples 19-21 and comparative example 3 were sampled and tested for combustion performance and mechanical properties, and the results are shown in table 2 below.
TABLE 2 flame retardant thermoplastic Polymer PA66 burn Performance and mechanical Properties parameter Table
As can be seen from the results in Table 2, the flame retarding effects of examples 19 to 21 of PA66 containing aluminum ethylenediaminetetramethylenephosphonate were superior to those of comparative example 3 containing no aluminum ethylenediaminetetramethylenephosphonate, without changing the total amount of the flame retardant composition.
Example 22
The weight ratio of the aluminum ethylenediamine tetramethylenephosphonate obtained in example 4 to the piperazine pyrophosphate and the PP is 15: 15:70 and extruding the mixture from a twin-screw extruder at a temperature of between 170 and 200 ℃ to obtain the flame-retardant thermoplastic polymer material.
Example 23
The weight ratio of the aluminum ethylenediamine tetramethylenephosphonate obtained in example 5 to the piperazine polyphosphate and the PP is 10: 20:70 and extruding the mixture from a twin-screw extruder at a temperature of between 170 and 200 ℃ to obtain the flame-retardant thermoplastic polymer material.
Comparative example 4
Mixing piperazine pyrophosphate and PP according to a weight ratio of 30:70, and extruding from a double-screw extruder at 170-200 ℃ to prepare the flame-retardant thermoplastic polymer material.
The polymer materials obtained in examples 22 and 23 and comparative example 4 were sampled and tested for their combustion and mechanical properties, and the results are shown in Table 3 below.
TABLE 3 flame retardant thermoplastic Polymer Material flammability and mechanical Properties parameter Table
As can be seen from the results in Table 3, the polymeric materials of examples 22 and 23 containing aluminum ethylenediaminetetramethylenephosphonate exhibited better flame retardant effects than comparative example 4 which did not contain aluminum ethylenediaminetetramethylenephosphonate.
Example 24
Mixing the aluminum ethylenediamine tetramethylenephosphonate obtained in the embodiment 1-9 with ammonium polyphosphate, spruce wood shavings and an adhesive for a particle board according to the weight ratio of 8: 7: 80:5 flame-retardant wood was prepared, and the wood without the flame retardant was comparative example 5, and the results of the performance test thereof are shown in the following table 4.
TABLE 4 flame retardant Wood Property parameter Table
| Group of | Bonding Strength (MPa) | Limiting oxygen index (%) | Smoke Density (SDR) |
| Example 1 | 1.02 | 50.4 | 40.87 |
| Example 2 | 1.05 | 49.3 | 41.39 |
| Example 3 | 1.03 | 48.7 | 40.69 |
| Example 4 | 1.07 | 49.9 | 40.19 |
| Example 5 | 1.04 | 50.3 | 41.83 |
| Example 6 | 1.08 | 48.9 | 42.39 |
| Example 7 | 1.05 | 49.3 | 40.59 |
| Example 8 | 1.07 | 50.0 | 41.07 |
| Example 9 | 1.03 | 49.7 | 42.85 |
| Comparative example 5 | 1.21 | 26.1 | 76.02 |
As can be seen from the test results in Table 4, the addition of the flame retardant aluminum ethylenediaminetetramethylenephosphonate can effectively exert the flame retardant effect.
Example 25
Mixing the aluminum ethylene diamine tetra-methylene phosphonate obtained in the examples 1-9 with white carbon black, calcium stearate, sodium carboxymethyl cellulose and water according to a weight ratio of 18:7:4: 1: 70 mixing and stirring uniformly to obtain a flame-retardant liquid, and coating the flame-retardant liquid on paper (quantitative: 70 g/m) by a coating machine 2) The flame-retardant paper is obtained by drying the single surface of the paper, the paper without the flame retardant is the comparative example 6, the combustion performance of the paper is tested by sample preparation, and the test results are shown in the following table 5.
TABLE 5 flame retardant paper Performance parameters Table
| Duration of afterflame(s) | Ignition time(s) | Charring length (mm) | Limiting oxygen index (%) | |
| Technical index | ≤5 | ≤60 | ≤115 | ≥32 |
| Example 1 | 0 | 1 | 18 | 36 |
| Example 2 | 0 | 2 | 19 | 34 |
| Example 3 | 0 | 1 | 19 | 34 |
| Example 4 | 0 | 1 | 18 | 36 |
| Example 5 | 0 | 2 | 20 | 33 |
| Example 6 | 0 | 1 | 21 | 35 |
| Example 7 | 0 | 2 | 18 | 34 |
| Example 8 | 0 | 2 | 20 | 36 |
| Example 9 | 0 | 2 | 21 | 34 |
| Comparative example 6 | 73 | 140 | Complete combustion | 21 |
As can be seen from the test results in Table 5, the addition of aluminum ethylenediaminetetramethylenephosphonate greatly improves the flame retardant effect of the paper.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (12)
1. The flame retardant is characterized by being ethylene diamine tetraacetic acid aluminum salt, and the structural formula of the flame retardant is shown as the formula (I):
2. The flame retardant according to claim 1, wherein at least one of the following (a) to (c):
(a) The particle size of the ethylene diamine tetramethylene aluminum phosphonate is D50-5 mu m-100 mu m;
(b) The tap bulk density of the ethylene diamine tetramethylene aluminum phosphonate is 0.4g/cm 3～0.9g/cm3；
(c) The angle of repose of the ethylene diamine tetramethylene aluminum phosphonate is 25-45 degrees.
3. The process for preparing a flame retardant according to claim 1 or 2, comprising the steps of:
(1) Reacting ethylene diamine tetramethylene phosphonic acid or the aqueous solution of the acid salt of the ethylene diamine tetramethylene phosphonic acid with the aqueous solution of the alkaline compound according to equivalent weight to obtain the aqueous solution of the alkali metal salt of the ethylene diamine tetramethylene phosphonic acid;
(2) And reacting the ethylene diamine tetramethylene phosphonic acid alkali metal salt aqueous solution with an aluminum metal compound or an aqueous solution thereof to prepare the ethylene diamine tetramethylene phosphonic acid aluminum.
4. The method for producing a flame retardant according to claim 3, wherein at least one of the following (d) to (f):
(d) In the step (1), at least one of the alkaline compounds sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acetate and potassium acetate;
(e) In the step (1), the acid salt of ethylenediamine tetramethylene phosphonic acid is at least one of ethylenediamine tetramethylene phosphonic acid monosodium salt, ethylenediamine tetramethylene phosphonic acid disodium salt, ethylenediamine tetramethylene phosphonic acid trisodium salt, ethylenediamine tetramethylene phosphonic acid tetrasodium salt, ethylenediamine tetramethylene phosphonic acid pentasodium salt, ethylenediamine tetramethylene phosphonic acid hexasodium salt, ethylenediamine tetramethylene phosphonic acid monopotassium salt, ethylenediamine tetramethylene phosphonic acid dipotassium salt, ethylenediamine tetramethylene phosphonic acid tripotassium salt, ethylenediamine tetramethylene phosphonic acid tetrapotassium salt, ethylenediamine tetramethylene phosphonic acid pentapotassium salt and ethylenediamine tetramethylene phosphonic acid hexapotassium salt;
(f) In the step (2), the aluminum metal compound is at least one of aluminum sulfate, aluminum chloride, aluminum acetate, aluminum nitrate, aluminum hydroxide and aluminum oxide.
5. Use of a flame retardant according to claim 1 or 2 in a polymeric material, wood or paper.
6. A flame retardant composition comprising the flame retardant of claim 1 or 2.
7. The flame retardant composition of claim 6, wherein the flame retardant composition comprises the following components in weight percent: 10 to 99.9% of the flame retardant of claim 1 or 2 and 0.1 to 90% of an additive; preferably, the flame retardant composition comprises the following components in percentage by weight: 20 to 70% of the flame retardant of claim 1 or 2 and 30 to 80% of the additive.
8. The flame retardant composition of claim 7, wherein the additive is at least one of aluminum diethylphosphinate, aluminum dipropylphosphinate, aluminum dibutylphosphinate, aluminum ethylbutylphosphinate, aluminum hypophosphite, piperazine pyrophosphate, piperazine polyphosphate, melamine pyrophosphate, melamine polyphosphate, melamine cyanurate, guanidine, and dicyandiamide.
9. A flame-retardant polymer material, comprising the flame retardant composition according to any one of claims 6 to 8.
10. The flame-retardant polymer material according to claim 9, wherein the flame-retardant polymer material comprises the following components in percentage by weight: 1-50% of the flame retardant composition of any one of claims 6-8, 30-99% of a polymer, 0-60% of an auxiliary agent and 0-60% of a filler; preferably, the flame-retardant polymer material comprises the following components in percentage by weight: 5-30% of the flame retardant composition of any one of claims 6-8, 40-95% of a polymer, 0-40% of an auxiliary agent and 0-40% of a filler.
11. The flame retardant polymer material according to claim 10, wherein the polymer is a thermoplastic polymer and/or a thermosetting polymer.
12. The flame retardant polymer material of claim 11, wherein the thermoplastic polymer is at least one of a polyester, a polyamide, and a polyolefin; preferably, the thermoplastic polymer is at least one of nylon 66, polybutylene terephthalate, and polypropylene.
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