CN111777798A - Aluminum diethylenetriamine penta (methylene phosphonic acid) flame retardant and preparation method and application thereof - Google Patents
Aluminum diethylenetriamine penta (methylene phosphonic acid) flame retardant and preparation method and application thereof Download PDFInfo
- Publication number
- CN111777798A CN111777798A CN201910268986.3A CN201910268986A CN111777798A CN 111777798 A CN111777798 A CN 111777798A CN 201910268986 A CN201910268986 A CN 201910268986A CN 111777798 A CN111777798 A CN 111777798A
- Authority
- CN
- China
- Prior art keywords
- aluminum
- flame retardant
- diethylenetriamine
- diethylenetriamine pentamethylene
- phosphonic acid
- 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.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 159
- 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 146
- -1 Aluminum diethylenetriamine Chemical compound 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000002861 polymer material Substances 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 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 12
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 65
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 229920001169 thermoplastic Polymers 0.000 claims description 30
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical class OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 8
- 229910001377 aluminum hypophosphite Inorganic materials 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
- 239000002253 acid Chemical class 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
- 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 5
- 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
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 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 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
- RSXFVIHGHLSFCP-UHFFFAOYSA-N NCCNCCN.[Na].[Na].[Na] Chemical compound NCCNCCN.[Na].[Na].[Na] RSXFVIHGHLSFCP-UHFFFAOYSA-N 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
- FUKAZHDJZGBSRX-UHFFFAOYSA-N NCCNCCN.[K] Chemical compound NCCNCCN.[K] FUKAZHDJZGBSRX-UHFFFAOYSA-N 0.000 claims description 2
- KIQNQRYJTRXVNB-UHFFFAOYSA-N NCCNCCN.[K].[K] Chemical compound NCCNCCN.[K].[K] KIQNQRYJTRXVNB-UHFFFAOYSA-N 0.000 claims description 2
- LFUMYYHFEVFSIB-UHFFFAOYSA-N NCCNCCN.[Na].[Na].[Na].[Na].[Na].[Na].[Na] Chemical compound NCCNCCN.[Na].[Na].[Na].[Na].[Na].[Na].[Na] LFUMYYHFEVFSIB-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
- OQRDSLOUOFIGSC-UHFFFAOYSA-N [Na].[Na].[Na].[Na].[Na].NCCNCCN Chemical compound [Na].[Na].[Na].[Na].[Na].NCCNCCN OQRDSLOUOFIGSC-UHFFFAOYSA-N 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
- GVVGQWPLZQAOSX-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;sodium Chemical compound [Na].NCCNCCN GVVGQWPLZQAOSX-UHFFFAOYSA-N 0.000 claims description 2
- NZHHNTCPCRNLRB-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;sodium Chemical compound [Na].[Na].NCCNCCN NZHHNTCPCRNLRB-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
- 238000000034 method Methods 0.000 abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- 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
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- MQNVHUZWFZKETG-UHFFFAOYSA-N P1(OCCCCCO1)=O.NCCNCCN Chemical compound P1(OCCCCCO1)=O.NCCNCCN MQNVHUZWFZKETG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000009826 distribution Methods 0.000 description 13
- 239000003365 glass fiber Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
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- 239000000779 smoke Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- 239000000835 fiber Substances 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 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 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
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 3
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 238000011160 research Methods 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
- 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
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 229940038384 octadecane Drugs 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AAAFJGRHSQZEKX-UHFFFAOYSA-N NCCNCCN.[Ca] Chemical compound NCCNCCN.[Ca] AAAFJGRHSQZEKX-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
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- 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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- SPXGIKNZDDYFOQ-UHFFFAOYSA-N [Mg].NCCNCCN Chemical compound [Mg].NCCNCCN SPXGIKNZDDYFOQ-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
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- 238000004458 analytical method Methods 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Images
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
- 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
- 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
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Abstract
The invention discloses an aluminum diethylenetriamine pentamethylene phosphonate flame retardant, the structural formula of which is shown as a formula (I). The aluminum diethylenetriamine pentamethylene phosphonate flame retardant has a stable molecular structure, each diethylenetriamine pentamethylene phosphonate provides 8 univalent 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 aluminum diethylenetriamine pentamethylenephosphonate 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 aluminum diethylenetriamine pentamethylenephosphonate 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 characteristics, the flame retardant effect and the influence of the flame retardant treatment on the physical and mechanical properties such as the strength of wood or the strength of a plywood sheet must be considered in practice, and the cost is 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. German patent DE19532208A discloses the use of metal salts of diethylenetriamine pentamethylenephosphonic acid as coolant lubricants for metal working. Patent WO2007128745A discloses the use of magnesium diethylenetriamine pentamethylenephosphonate as an additive in textile detergents. GB2157279A discloses the use of calcium diethylenetriamine pentamethylenephosphonate as a flame retardant additive in drilling cements. However, few reports have been made on aluminum diethylenetriamine pentamethylenephosphonic acid as a flame retardant.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an aluminum diethylenetriamine pentamethylene 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 diethylenetriamine pentamethylene phosphonate, and the structural formula of the flame retardant is shown as the formula (I):
the invention synthesizes a series of aluminum diethylenetriamine pentamethylene phosphonate by reacting the aqueous solution of diethylenetriamine pentamethylene phosphonic acid or the acid salt of the diethylenetriamine pentamethylene phosphonic acid with a metal compound or the aqueous solution thereof under different pH values, and obtains a compound with a structure shown in a formula (IV):
wherein n is 1 to 10.
In the molecular structure of the compound (IV), each diethylenetriamine pentamethylene phosphonic acid provides 1 to 10 univalent anions to react with aluminum ions.
Through a large number of synthetic and fire retardant screening researches, the aluminum diethylenetriamine pentamethylene phosphonate with the structure (I) has the best fire retardant effect, high phosphorus content, good thermal stability, high char yield, no halogen, greenness, environmental protection and the like when n is 8. The compound with the structure (I) is prepared by reacting diethylenetriamine pentamethylene phosphonic acid or an acid salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid with an aqueous solution of an alkaline compound according to equivalent weight to obtain a diethylenetriamine pentamethylene phosphonic acid metal salt aqueous solution, and reacting with an aluminum metal compound or an aqueous solution thereof. The structure is characterized in that each diethylenetriamine pentamethylene phosphonic acid has 2 undissociated hydrogen ions to provide 8 univalent anions, and forms a stable chemical structure with trivalent metal aluminum ions.
Preferred embodiments of the flame retardant include at least one of the following (a) to (c):
(a) the particle size of the aluminum diethylenetriamine pentamethylene phosphonate is D50-5 mu m-100 mu m;
(b) the tap bulk density of the aluminum diethylenetriamine pentamethylene phosphonate is 0.4g/cm3～0.9g/cm3；
(c) The angle of repose of the aluminum diethylenetriamine pentamethylene 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 diethylenetriamine pentamethylene phosphonic acid or an acid salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid with an aqueous solution of an alkaline compound according to equivalent weight to obtain an alkali metal salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid;
(2) reacting the aqueous solution of the alkali metal salt of diethylenetriamine pentamethylene phosphonic acid with the aluminum metal compound or the aqueous solution of the aluminum metal compound to prepare the aluminum diethylenetriamine pentamethylene phosphonic acid.
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), the alkaline compound is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acetate or potassium acetate;
(e) in the step (1), the acid salt of diethylenetriamine pentamethylene phosphonic acid is monosodium diethylenetriamine pentamethylene phosphonic acid, disodium diethylenetriamine pentamethylene phosphonic acid, trisodium diethylenetriamine pentamethylene phosphonic acid, tetrasodium diethylenetriamine pentamethylene phosphonic acid, pentasodium diethylenetriamine pentamethylene phosphonic acid, hexasodium diethylenetriamine pentamethylene phosphonic acid, heptasodium diethylenetriamine pentamethylene phosphonic acid, octasodium diethylenetriamine pentamethylene phosphonic acid, at least one of monopotassium diethylenetriamine pentamethylenephosphonic acid, dipotassium diethylenetriamine pentamethylenephosphonic acid, tripotassium diethylenetriamine pentamethylenephosphonic acid, tetrapotassium diethylenetriamine pentamethylenephosphonic acid, pentapotassium diethylenetriamine pentamethylenephosphonic acid, hexapotassium diethylenetriamine pentamethylenephosphonic acid, heptapotassium diethylenetriamine pentamethylenephosphonic acid, and octapotassium diethylenetriamine pentamethylenephosphonic acid;
(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 which comprises 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 the flame retardant and 0.1-90% of the 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 the flame retardant and 30-80% of the 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 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 a polymer, 0-40% of an auxiliary agent and 0-40% of a 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.
As a 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 aluminum diethylenetriamine pentamethylene phosphonate flame retardant which has a stable molecular structure, each diethylenetriamine pentamethylene phosphonate provides 8 univalent anions to form salt with aluminum ions, and the aluminum diethylenetriamine pentamethylene phosphonate flame retardant 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 aluminum diethylenetriamine pentamethylenephosphonate 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 diethylenetriamine pentamethylene phosphonate comprises the following steps:
the particle size distribution of aluminum diethylenetriamine pentamethylenephosphonate dispersed in the liquid phase was measured by a laser particle sizer. The specific operation is as follows: according to the particle size of the aluminum diethylenetriamine pentamethylene phosphonate, 0.05g to 1.0g of the aluminum diethylenetriamine pentamethylene 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 diethylenetriamine pentamethylene phosphonate. The particle size of the aluminum diethylenetriamine pentamethylene 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 diethylenetriamine pentamethylene phosphonate comprises the following steps:
and 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, and gradually piling the powder until the powder cannot be piled up continuously. The powder bulk height h is measured and the angle of repose α is calculated according to the formula (1).
tgα＝h/r (1)。
The tapped bulk density test method of the aluminum diethylenetriamine pentamethylene phosphonate is determined by referring to GB/T20316.2-determination of bulk density.
The infrared absorption spectrum testing method of the aluminum diethylenetriamine pentamethylene phosphonate is determined by referring to the method of GB/T6040-2002 'general rule on infrared spectrum analysis methods'.
The performance test of the flame-retardant high polymer material is carried out according to the following standards:
tensile strength: GB/T1040 + 1992 test methods for tensile Properties of plastics;
bending strength: GB/T9341-2000 method for testing bending property 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 is UL94 test for the combustion performance of plastics.
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 boards and facing artificial boards;
limiting oxygen index: GB/T2406-2009 oxygen index method for testing the combustion performance of plastics, GB 50222-95 fire protection code for interior decoration design of buildings stipulates that the oxygen index of grade B1 is not less than 48%;
smoke density: GB/T8627 and 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 and 2009 'Plastic burning Performance test method oxygen index method', GB 50222-95 'architectural interior decoration design fire protection 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 diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: adding 12738g (10mol) of diethylenetriamine pentamethylene phosphonic acid aqueous solution with the mass fraction of 45% into a reactor, neutralizing with 8000g (80mol) of NaOH aqueous solution with the mass fraction of 40%, stirring and heating to 90 ℃, adding 22200g (13.33mol) of aluminum sulfate octadecahydrate aqueous solution with the mass fraction of 40% within 60min, generating solid precipitate, cooling, filtering, washing and drying; 6187g of diethylenetriamine pentamethylene aluminum phosphonate is obtained, and the yield is 97.1%.
The particle size (mum) distribution of the product is as follows: d (10) is 8.20; d (50): 26.75; d (90): 52.52;
tap bulk density: 0.72g/cm3；
Angle of repose: 34 degrees;
IR：453cm-1,573cm-1,781cm-1,1142cm-1,1466cm-1,1649cm-1,2820cm-1,2880cm-1,3032cm-1。
example 2
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: 12738g (10mol) of diethylenetriamine pentamethylene phosphonic acid aqueous solution with the mass fraction of 45% is added into a reactor, 11220g (80mol) of KOH aqueous solution with the mass fraction of 40% is used for neutralization, the mixture is stirred and heated to 90 ℃, 22200g (13.33mol) of aluminum sulfate octadecahydrate aqueous solution with the mass fraction of 40% is added within 60min, solid precipitate is generated, and the solid precipitate is cooled, filtered, washed and dried; 6111g of aluminum diethylenetriamine pentamethylene phosphonate is obtained, and the yield is 95.9 percent.
The particle size (mum) distribution of the product is as follows: d (10): 15.49; d (50): 37.27; d (90): 73.39;
tap bulk density: 0.78g/cm3；
Angle of repose: 36 degrees;
IR：453cm-1,573cm-1,781cm-1,1142cm-1,1466cm-1,1649cm-1,2820cm-1,2880cm-1,3032cm-1。
example 3
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: adding 12738g (10mol) of diethylenetriamine pentamethylene phosphonic acid aqueous solution with the mass fraction of 45% into a reactor, neutralizing with 8000g (80mol) 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% within 30min to prepare 16095g (26.67mol) of aqueous solution, generating solid precipitate, cooling, filtering, washing with water and drying; 6130g of aluminum diethylenetriamine pentamethylene phosphonate is obtained, and the yield is 96.2 percent.
The particle size (mum) distribution of the product is as follows: d (10): 24.42; d (50): 61.48; d (90): 134.23;
tap bulk density: 0.81g/cm3；
Angle of repose: 39 degrees;
IR：450cm-1,576cm-1,780cm-1,1140cm-1,1468cm-1,1650cm-1,2818cm-1,2882cm-1,3031cm-1。
example 4
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: 17006g (10mol) of 35% by mass of diethylenetriamine pentamethylenephosphonic acid monosodium solution is added into a reactor, 9333g (70mol) of 30% by mass of NaOH solution is used for neutralization, the mixture is stirred and heated to 90 ℃, 22200g (13.33mol) of 40% by mass of octadecane water aluminum sulfate solution is added within 60min, solid precipitate is generated, and the mixture is cooled, filtered, washed and dried to obtain 6187g of diethylenetriamine pentamethylenephosphonic acid aluminum, wherein the yield is 97.1%.
The particle size (mum) distribution of the product is as follows: d (10) is 8.97; d (50): 28.12; d (90): 55.84;
tap bulk density of 0.71g/cm3；
Angle of repose: 30 degrees;
IR：451cm-1,578cm-1,782cm-1,1139cm-1,1465cm-1,1652cm-1,2817cm-1,2883cm-1,3030cm-1。
example 5
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: 18263g (10mol) of trisodium diethylenetriamine pentamethylene phosphonic acid aqueous solution with the mass fraction of 35% is added into a reactor, 9350g (50mol) of KOH aqueous solution with the mass fraction of 30% is used for neutralization, the mixture is stirred and heated to 90 ℃, 22200g (13.33mol) of aluminum sulfate octadecahydrate aqueous solution with the mass fraction of 40% is added within 60min, solid precipitate is generated, and the solid precipitate is cooled, filtered, washed and dried; 6149g of aluminum diethylenetriamine pentamethylene phosphonate is obtained, and the yield is 96.5 percent.
The particle size (mum) distribution of the product is as follows: d (10): 12.91; d (50) is 30.16; d (90): 67.03;
tap bulk density of 0.73g/cm3；
Angle of repose: 32 degrees;
IR：454cm-1,574cm-1,782cm-1,1140cm-1,1467cm-1,1650cm-1,2821cm-1,2881cm-1,3031cm-1。
example 6
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: adding 19520g (10mol) of 35% by mass of diethylenetriamine pentamethylene phosphonic acid pentasodium aqueous solution into a reactor, neutralizing with 5610g (30mol) of 30% by mass of KOH aqueous solution, stirring and heating to 90 ℃, adding 22200g (13.33mol) of 40% by mass of octadecane water aluminum sulfate aqueous solution within 60min to generate solid precipitate, cooling, filtering, washing and drying; the yield of the aluminum diethylenetriamine pentamethylene phosphonate 6079g is 95.4 percent.
The particle size (mum) distribution of the product is as follows: d (10): 15.62; d (50): 36.61; d (90): 78.50;
tap bulk density of 0.75g/cm3；
Angle of repose: 34 degrees;
IR：455cm-1,581cm-1,784cm-1,1145cm-1,1482cm-1,1651cm-1,2820cm-1,2883cm-1,3033cm-1。
example 7
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: adding 20777g (10mol) of 35 mass percent of diethylenetriamine pentamethylene phosphonic acid heptasodium water solution into a reactor, neutralizing with 1870g (10mol) of 30 mass percent KOH water solution, stirring and heating to 90 ℃, adding 22200g (13.33mol) of 40 mass percent octadecahydrate aluminum sulfate water solution within 60min to generate solid precipitate, cooling, filtering, washing and drying; 6111g of aluminum diethylenetriamine pentamethylene phosphonate is obtained, and the yield is 95.9 percent.
The particle size (mum) distribution of the product is as follows: d (10): 14.02; d (50): 31.32; d (90): 68.82;
tap bulk density: 0.73g/cm3；
Angle of repose: 31 degrees;
IR：453cm-1,575cm-1,783cm-1,1142cm-1,1469cm-1,1652cm-1,2820cm-1,2880cm-1,3033cm-1。
example 8
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: 18549g (10mol) of dipotassium diethylenetriamine pentamethylene phosphonate with the mass fraction of 35% is added into a reactor, 9617g (60mol) of KOH aqueous solution with the mass fraction of 35% is used for neutralization, the mixture is stirred and heated to 90 ℃, 25009g (26.67mol) of aluminum nitrate nonahydrate aqueous solution with the mass fraction of 40% is added within 60min, solid precipitate is generated, and the solid precipitate is cooled, filtered, washed and dried to obtain 6047g of aluminum diethylenetriamine pentamethylene phosphonate, wherein the yield is 94.9%.
The particle size (mum) distribution of the product is as follows: d (10): 11.22; d (50): 33.72; d (90): 82.52;
tap bulk density of 0.74g/cm3；
Angle of repose: 32 degrees;
IR：454cm-1,579cm-1,785cm-1,1135cm-1,1466cm-1,1652cm-1,2818cm-1,2883cm-1,3032cm-1。
example 9
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: adding 20720g (10mol) of 35% by mass of diethylenetriamine penta-methylene phosphonic acid tetrapotassium water solution into a reactor, neutralizing with 6411g (40mol) of 35% by mass of KOH water solution, stirring and heating to 90 ℃, adding 25009g (26.67mol) of 40% by mass of aluminum nitrate nonahydrate water solution within 60min to generate solid precipitate, cooling, filtering, washing with water, and drying to obtain 6066g of diethylenetriamine penta-methylene phosphonic acid aluminum, wherein the yield is 95.2%.
The particle size (mum) distribution of the product is as follows: d (10): 12.31; d (50): 36.21; d (90): 85.65;
tap bulk density of 0.74g/cm3；
Angle of repose: 33 °;
IR：452cm-1,579cm-1,785cm-1,1136cm-1,1468cm-1,1650cm-1,2819cm-1,2882cm-1,3031cm-1。
example 10
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: 22891g (10mol) of diethylenetriamine pentamethylene phosphonic acid hexapotassium aqueous solution with the mass fraction of 35% is added into a reactor, 2667g (20mol) of NaOH aqueous solution with the mass fraction of 30% is used for neutralization, the mixture is stirred and heated to 90 ℃, 16095g (26.67mol) of aluminum chloride hexahydrate with the mass fraction of 40% is added within 60min, solid precipitate is generated, and the mixture is cooled, filtered, washed and dried to obtain 6098g of diethylenetriamine pentamethylene phosphonic acid aluminum, and the yield is 95.7%.
The particle size (mum) distribution of the product is as follows: d (10): 12.73; d (50): 35.29; d (90): 84.83;
tap bulk density of 0.74g/cm3；
Angle of repose: 33 °;
IR：454cm-1,573cm-1,780cm-1,1142cm-1,1466cm-1,1650cm-1,2821cm-1,2879cm-1,3031cm-1。
example 11
The structural formula of the aluminum diethylenetriamine pentamethylene phosphonate is shown as a formula (I), and the preparation method comprises the following steps: 25063g (10mol) of octapotassium diethylenetriamine pentamethylene phosphonate with the mass fraction of 35% is added into a reactor, the reactor is stirred and heated to 90 ℃, 16095g (26.67mol) of aluminum chloride hexahydrate with the mass fraction of 40% is added within 60min, solid precipitate is generated, the mixture is cooled, filtered, washed and dried, and 6123g of aluminum diethylenetriamine pentamethylene phosphonate is obtained, and the yield is 96.1%.
The particle size (mum) distribution of the product is as follows: d (10): 24.21; d (50): 62.42; d (90): 136.87;
tap bulk density: 0.81g/cm3；
Angle of repose: 39 degrees;
IR：451cm-1,576cm-1,782cm-1,1140cm-1,1466cm-1,1649cm-1,2818cm-1,2880cm-1,3030cm-1。
example 12
The aluminum diethylenetriamine pentamethylene phosphonate obtained in the example 1 and PBT are mixed according to the weight ratio of 35: 65, extruding the mixture from a twin-screw extruder at the temperature of 230 ℃ and 260 ℃ to prepare the flame-retardant thermoplastic polymer material, and testing the flame retardancy of the flame-retardant thermoplastic polymer material by a sample preparation test, wherein the flame retardancy of the flame-retardant thermoplastic polymer material can reach V-2 grade by 3.0mm of UL 94.
Example 13
Mixing the aluminum diethylenetriamine pentamethylene phosphonate obtained in the example 2 with PA66 according to the weight ratio of 35: 65, extruding the mixture from a double-screw extruder at the temperature of 240-270 ℃ to prepare the flame-retardant thermoplastic polymer material, and testing the combustion performance of the sample by UL94 to reach V-2 grade after 3.0mm combustion.
Example 14
Mixing the aluminum diethylenetriamine pentamethylene phosphonate obtained in the example 3 and PP according to the weight ratio of 35: 65, extruding the mixture from a double-screw extruder at the temperature of 170-200 ℃ to prepare the flame-retardant thermoplastic polymer material, and testing the combustion performance of the sample to achieve the V-2 grade by UL94 combustion of 3.0 mm.
Example 15
The aluminum diethylenetriamine pentamethylene phosphonate obtained in the example 4 is mixed with the aluminum diethylphosphinate, PBT and glass fiber according to the weight ratio of 6:10:59:25, and extruded from a double-screw extruder at the temperature of 230-260 ℃ to prepare the flame-retardant thermoplastic polymer material.
Example 16
The aluminum diethylenetriamine pentamethylene phosphonate obtained in the example 5 is mixed with the aluminum diethylphosphinate, PBT and glass fiber according to the weight ratio of 8:8:59:25, and extruded from a twin-screw extruder at the temperature of 230 ℃ and 260 ℃ to prepare the flame-retardant thermoplastic polymer material.
Example 17
The aluminum diethylenetriamine pentamethylene phosphonate obtained in the example 6, the aluminum diethylphosphinate, the PBT and the glass fiber are mixed according to the weight ratio of 10:6:59:25, and are extruded from a double-screw extruder at the temperature of 230-260 ℃ to prepare the flame-retardant thermoplastic polymer material.
Example 18
The aluminum diethylenetriamine pentamethylene phosphonate obtained in example 7 is mixed with aluminum hypophosphite, PBT and glass fiber according to the 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 19
The aluminum diethylenetriamine pentamethylene phosphonate obtained in the example 8 is mixed with aluminum hypophosphite, PBT and glass fiber according to the weight ratio of 10:10:55:25, and extruded from a double-screw extruder at the temperature of 230-260 ℃ to prepare a flame-retardant thermoplastic polymer material.
Example 20
The aluminum diethylenetriamine pentamethylene phosphonate obtained in example 9 is mixed with aluminum hypophosphite, PBT and glass fiber according to the 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
Aluminum hypophosphite, PBT and glass fiber are mixed according to the weight ratio of 20:55:25, and are extruded from a double-screw extruder at 230-260 ℃ to prepare the flame-retardant thermoplastic polymer material.
Example 21
The flame retardant thermoplastic polymer materials obtained in examples 15 to 20 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
From the test results in table 1, it can be seen that, under the condition that the total amount of the flame retardant composition is not changed, the PBT containing the diethylenetriamine pentamethylene aluminum phosphonate in the examples 15-20 has better flame retardant effect than the PBT containing the diethylenetriamine pentamethylene aluminum phosphonate in the comparative examples 1 and 2.
Example 22
The aluminum diethylenetriamine pentamethylene phosphonate obtained in example 10 was mixed with aluminum dipropylphosphinate, PA66 and glass fiber in a weight ratio of 6:14:55:25, and extruded from a twin-screw extruder at a temperature of 240 ℃ and 270 ℃ to obtain a flame-retardant thermoplastic polymer material.
Example 23
The aluminum diethylenetriamine pentamethylene phosphonate obtained in example 11 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 a temperature of 240 ℃ and 270 ℃ to obtain a flame-retardant thermoplastic polymer material.
Example 24
The aluminum diethylenetriamine pentamethylene phosphonate obtained in example 1 is mixed with aluminum hypophosphite, PA66 and glass fiber according to the weight ratio of 14:6:55:25, and extruded from a twin-screw extruder at the temperature of 240-270 ℃ to prepare a 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 the temperature of 240 ℃ and 270 ℃ to prepare the flame-retardant thermoplastic polymer material.
Example 25
The polymer materials obtained in examples 22-24 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 22 to 24 of PA66 containing aluminum diethylenetriamine pentamethylenephosphonate were superior to those of comparative example 3 containing no aluminum diethylenetriamine pentamethylenephosphonate, without changing the total amount of the flame retardant composition.
Example 26
The aluminum diethylenetriamine pentamethylenephosphonate obtained in example 2 was mixed with piperazine pyrophosphate and PP in a weight ratio of 15:15:70 and extruded from a twin-screw extruder at 170 ℃ and 200 ℃ to prepare a flame-retardant thermoplastic polymer material.
Example 27
The aluminum diethylenetriamine pentamethylene phosphonate obtained in the example 3 is mixed with the piperazine polyphosphate and PP according to the weight ratio of 10:20:70, and extruded from a twin-screw extruder at 170-200 ℃ to prepare the flame-retardant thermoplastic polymer material.
Comparative example 4
The flame-retardant thermoplastic polymer material is prepared by mixing piperazine pyrophosphate and PP according to the weight ratio of 30:70 and extruding the mixture from a double-screw extruder at the temperature of 170-200 ℃.
The polymer materials obtained in examples 26 and 27 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, 23 containing aluminum diethylenetriamine pentamethylenephosphonate exhibited better flame retardant effects than comparative example 4, which did not contain aluminum diethylenetriamine pentamethylenephosphonate.
Example 28
The aluminum diethylenetriamine pentamethylene phosphonate obtained in the examples 1 to 11, ammonium polyphosphate, spruce wood shavings and adhesive for particle boards are prepared into flame-retardant wood according to the weight ratio of 8:7:80:5, the wood without the flame retardant is the comparative example 5, and the performance test results 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 | 1.03 | 50.3 | 40.89 |
| Example 2 | 1.04 | 49.7 | 41.26 |
| Example 3 | 1.05 | 48.9 | 40.27 |
| Example 4 | 1.04 | 49.3 | 40.83 |
| Example 5 | 1.07 | 50.0 | 41.83 |
| Example 6 | 1.03 | 49.1 | 42.21 |
| Example 7 | 1.08 | 49.7 | 40.78 |
| Example 8 | 1.05 | 50.2 | 41.01 |
| Example 9 | 1.06 | 49.5 | 42.22 |
| Example 10 | 1.03 | 49.2 | 42.38 |
| Example 11 | 1.06 | 49.8 | 41.90 |
| Comparative example 5 | 1.23 | 26.2 | 75.93 |
From the test results in table 4, it can be seen that the addition of the flame retardant aluminum diethylenetriamine pentamethylenephosphonate can effectively exert the flame retardant effect.
Example 29
The aluminum diethylenetriamine pentamethylene phosphonate obtained in the examples 1 to 11, white carbon black, calcium stearate, sodium carboxymethylcellulose and water are uniformly mixed and stirred according to the weight ratio of 18:7:4:1:70 to obtain the flame-retardant liquid, and the flame-retardant liquid is coated on paper (fixed amount: 70 g/m) by a coating machine2) 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
From the test results in table 5, it can be seen that the addition of aluminum diethylenetriamine pentamethylenephosphonate 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 aluminum diethylenetriamine pentamethylene phosphonate, 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 aluminum diethylenetriamine pentamethylene phosphonate is D50-5 mu m-100 mu m;
(b) the tap bulk density of the aluminum diethylenetriamine pentamethylene phosphonate is 0.4g/cm3～0.9g/cm3；
(c) The angle of repose of the aluminum diethylenetriamine pentamethylene 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 diethylenetriamine pentamethylene phosphonic acid or an acid salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid with an aqueous solution of an alkaline compound according to equivalent weight to obtain an alkali metal salt aqueous solution of diethylenetriamine pentamethylene phosphonic acid;
(2) reacting the aqueous solution of the alkali metal salt of diethylenetriamine pentamethylene phosphonic acid with the aluminum metal compound or the aqueous solution of the aluminum metal compound to prepare the aluminum diethylenetriamine pentamethylene phosphonic acid.
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), the alkaline compound is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acetate and potassium acetate;
(e) in the step (1), the acid salt of diethylenetriamine pentamethylene phosphonic acid is monosodium diethylenetriamine pentamethylene phosphonic acid, disodium diethylenetriamine pentamethylene phosphonic acid, trisodium diethylenetriamine pentamethylene phosphonic acid, tetrasodium diethylenetriamine pentamethylene phosphonic acid, pentasodium diethylenetriamine pentamethylene phosphonic acid, hexasodium diethylenetriamine pentamethylene phosphonic acid, heptasodium diethylenetriamine pentamethylene phosphonic acid, octasodium diethylenetriamine pentamethylene phosphonic acid, at least one of monopotassium diethylenetriamine pentamethylenephosphonic acid, dipotassium diethylenetriamine pentamethylenephosphonic acid, tripotassium diethylenetriamine pentamethylenephosphonic acid, tetrapotassium diethylenetriamine pentamethylenephosphonic acid, pentapotassium diethylenetriamine pentamethylenephosphonic acid, hexapotassium diethylenetriamine pentamethylenephosphonic acid, heptapotassium diethylenetriamine pentamethylenephosphonic acid, and octapotassium diethylenetriamine pentamethylenephosphonic acid;
(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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