CN114524843A - 一种端羟基反应型阻燃剂及其制备方法 - Google Patents
一种端羟基反应型阻燃剂及其制备方法 Download PDFInfo
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- CN114524843A CN114524843A CN202210180674.9A CN202210180674A CN114524843A CN 114524843 A CN114524843 A CN 114524843A CN 202210180674 A CN202210180674 A CN 202210180674A CN 114524843 A CN114524843 A CN 114524843A
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- flame retardant
- reactive flame
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- dihydric alcohol
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 22
- 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 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 24
- -1 alkyl phosphonic acid diol ester Chemical class 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 11
- HPUPGAFDTWIMBR-UHFFFAOYSA-N [methyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(C)OC1=CC=CC=C1 HPUPGAFDTWIMBR-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical group 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000005690 diesters Chemical class 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
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000006757 chemical reactions by type Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 claims description 2
- YWDFOLFVOVCBIU-UHFFFAOYSA-N 1-dimethoxyphosphorylpropane Chemical compound CCCP(=O)(OC)OC YWDFOLFVOVCBIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- UHMQAIKRVPHZGY-UHFFFAOYSA-N [ethyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(CC)OC1=CC=CC=C1 UHMQAIKRVPHZGY-UHFFFAOYSA-N 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 238000005809 transesterification reaction Methods 0.000 abstract description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- WOURXYYHORRGQO-UHFFFAOYSA-N Tri(3-chloropropyl) phosphate Chemical compound ClCCCOP(=O)(OCCCCl)OCCCCl WOURXYYHORRGQO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000004032 superbase Substances 0.000 description 2
- 150000007525 superbases Chemical class 0.000 description 2
- ZNJCLRGMOCIUIY-UHFFFAOYSA-N tris(2,2-dichloropropyl) phosphate Chemical compound CC(Cl)(Cl)COP(=O)(OCC(C)(Cl)Cl)OCC(C)(Cl)Cl ZNJCLRGMOCIUIY-UHFFFAOYSA-N 0.000 description 2
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NPNBLTJGRBYCJB-UHFFFAOYSA-N 1-[butoxy(methyl)phosphoryl]oxybutane Chemical compound CCCCOP(C)(=O)OCCCC NPNBLTJGRBYCJB-UHFFFAOYSA-N 0.000 description 1
- ISSNMMCUMAXLBE-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol methylphosphonic acid Chemical compound CP(O)(O)=O.C(COCCO)O ISSNMMCUMAXLBE-UHFFFAOYSA-N 0.000 description 1
- RSYULXLIWNALGV-UHFFFAOYSA-N COP(=O)OCCO Chemical compound COP(=O)OCCO RSYULXLIWNALGV-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 229920002842 oligophosphate Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Polymers OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
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)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- 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)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fireproofing Substances (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明属于阻燃剂技术领域，具体为一种端羟基反应型阻燃剂的制备方法，其特征在于所述反应型阻燃剂为烷基膦酸二元醇酯，结构式为：
Description
技术领域
本发明属于阻燃剂技术领域，具体涉及一种端羟基反应型阻燃剂及其制备方法。
背景技术
聚氨酯泡沫是目前世界上用途最广，用量最大的高分子材料之一。其广泛用于家具，汽车，坐垫，外墙及管道保温，矿山等制造行业。但由于聚氨酯泡沫材料在空气中极易燃烧，在未经过处理的情况下，极限氧指数LOI只有17。而添加阻燃剂可以有效降低聚氨酯材料的可燃性，并减小燃烧中有毒气体的浓烟的释放。传统的添加型阻燃剂如磷酸三(氯丙基)酯(TCPP)、磷酸三(2，2-二氯丙基)酯(TDCPP)、磷酸三(氯乙基)酯(TCEP)可以提供良好的阻燃性，但这些含卤素的小分子阻燃剂容易从聚氨酯材料中析出，随着时间的推移可能失去原有的阻燃性。并且卤素阻燃剂在燃烧时本身就会产生大量有毒浓烟，因此含卤素的添加型阻燃剂在一些行业中将会受到越来越多的限制。
中国苏州科技学院专利CN102604112A采取三氯氧磷与乙醇先预先反应，再通过二元醇聚合的方法制造低聚磷酸酯。江苏雅克化工专利CN101293896A采用类似工艺。而山东兄弟科技股份有限公司专利CN101899160B也采取相似的工艺，但采用二元醇封端，聚磷酸酯的端羟基从而制得反应型阻燃多元醇。由于磷酸酯普遍在水中有较大的溶解性，上述三篇专利所述的方法均存在氯化氢难以去除干净，阻燃剂酸值过大导致无法在聚氨酯中使用的情况。
德国科莱恩专利US5985965采用五氧化二磷与磷酸三乙酯缩合反应得到长链P-O-P结构的聚合体，再引入羟基化合物例如水或二元醇将长链断开形成末端为P-OH的短链结构，再通过环氧乙烷乙氧基化，从而制得端羟基乙基齐聚磷酸酯。此工艺技术壁垒高，反应聚合度难以掌控，并且由于五氧化二磷的强脱水性，物料颜色极易变黑，而原料之一的环氧乙烷又存在易燃易爆的风险，给工业大生产带来了一定的难度。
亚磷酸酯由于没有磷氧双键的存在，反应活性远高于磷酸酯，反应较好发生。美国专利 US3855360及US6043305采用亚磷酸酯为原料，通过二元醇酯交换反应聚合，而后再用催化剂通过阿布佐夫反应，将低聚亚磷酸酯转化为膦酸酯的工艺。但由于亚磷酸酯活性太大，如果三个磷氧键被全部酯交换，则无法通过下一步阿布佐夫反应转化为膦酸酯。亚磷酸酯阻燃性欠佳，并且通常伴有难为的异味。并且阿布佐夫是放热剧烈的反应，通常难以控制放热温度，给工艺带来了一定的危险性。
膦酸酯与磷酸酯相比，化合物中含有P-C键，其耐水解性，耐溶剂性及耐热性远高于P-O -R键，同时P-C在化学反应中大部分情况下不会参与反应，因此能参与反应的结构被固定在了两个基团，这就给了膦酸酯很好的可塑性。在聚氨酯泡沫中往往带有双官能度的端羟基反应基团才能取得最好的效果。陈星宇，段佳君等人以甲基膦酸二甲酯为原料以金属氧化物为催化剂合成了聚甲基膦酸乙二醇酯。程超，孙才英等人以甲基膦酸二甲酯为原料，以离子液体做催化剂与碘甲烷合成了反应型的聚甲基膦酸乙二醇酯。此二人工艺均存在酸值过大的情况(50～370mgKOH/g)。
发明内容
由于甲基膦酸二甲酯极其稳定难以被酯交换，必须使用超强碱催化剂在较高的温度下才能使之与多元醇发生酯交换，而超强碱与高温同时会对甲基膦酸二甲酯进行破坏，因此往往存在酯交换后酸值过大的情况。
经本公司研究发现，相较于较难发生酯交换反应的甲基膦酸二甲酯，甲基膦酸二苯酯的苯基是较容易被酯交换反应置换下的基团。同时苯基耐温性好且稳定，产品的最终结构好控制。本发明以工业化为目的，从安全，环保，及相，产品收率及产品质量等角度，通过甲基膦酸二苯酯与二元醇酯交换反应，制成一种全新的反应型阻燃剂。工艺简单安全节能。
反应型膦酸酯多元醇的反应过程及结构，如下所示：
其中R为C1-C4的无卤烷基；
Ar为甲基、乙基、或者芳基；
而R2为C1-C5的亚烷基或中间含有一个氧原子的C1-C8的亚烷基。
合成过程：
将烷基膦酸二酯与二元醇混合，加热至80-180℃，在催化剂及在氮气保护的环境下酯交换反应，不断蒸出副产物苯酚，最终得到端羟基反应型烷基膦酸二元醇酯。此过程中所述的烷基膦酸二酯选自以下合物的一种或多种：甲基膦酸二甲酯，乙基膦酸二乙酯，丙基膦酸二甲酯，甲基膦酸二苯酯，乙基膦酸二苯酯。优选甲基膦酸二苯酯。
此过程中所述的二元醇选自以下合物的一种或多种：乙二醇，二乙二醇，二丙二醇，1，3-丙二醇，1，4-丁二醇，1，5-戊二醇。优选二乙二醇与二丙二醇。
此过程中所述的催化剂的组分自以下路易斯酸或路易斯碱的一种或多种：三氯化铝，二氯化镁，四氯化钛，三氯化铁，氯化锌，辛酸亚锡，钛酸四丁酯，钛酸四异丙酯，三乙胺，1，8-二氮杂双环[5.4.0]十一碳-7-烯，三乙烯二胺，4-二甲氨基吡啶，氢氧化钠，氢氧化钾，碳酸钾，碳酸钠，甲醇钠，乙醇钠，甲醇锂，叔丁醇钠。
此过程中催化剂用量为烷基膦酸二酯用量的1.0～3.0‰。
具体应用举例
以下实施例进一步说明。
实施例1：甲基膦酸二乙二醇酯
使用磁力搅拌导热油锅，1000ml的三口瓶中，通入氮气隔绝空气，加入248g甲基膦酸二苯酯(1mole)，212g二乙二醇(2mole)，2.5g氢氧化钠。升温至150度保温2小时开始减压蒸馏，蒸出副产物苯酚。反应容器负压保持在0.08-0.1Mpa。在取得馏分理论质量的60％时，升温至180度，继续减压蒸馏，直至再无明显的苯酚被蒸出。得到无色略带浑浊的液体，测得酸值2.97mgKOH/g，羟值 397mgKOH/g(理论411mgKOH/g)，磷含量11.14％(理论11.39％)。
实施例2：甲基膦酸二丙二醇酯
使用磁力搅拌导热油锅，1000ml的三口瓶中，通入氮气隔绝空气，加入248g甲基膦酸二苯酯 (1mole)，268g一缩二丙二醇(2mole)，2.5g氢氧化钠。升温至150度保温2小时开始减压蒸馏，蒸出副产物苯酚。反应容器负压保持在0.08-0.1Mpa。在取得馏分理论质量的60％时，升温至180度，继续减压蒸馏，直至再无明显的苯酚被蒸出。得到微黄透明液体，测得酸值1.44mgKOH/g，羟值 335mgKOH/g(理论342mgKOH/g)，磷含量9.36％(理论9.45％)。
实施例3：甲基膦酸二丁醇酯
使用磁力搅拌导热油锅，1000ml的三口瓶中，通入氮气隔绝空气，加入248g甲基膦酸二苯酯 (1mole)，180g 1，4-丁二醇(2mole)，2.5g氢氧化钠。升温至150度保温2小时开始减压蒸馏，蒸出副产物苯酚。反应容器负压保持在0.08-0.1Mpa。在取得馏分理论质量的60％时，升温至180度，继续减压蒸馏，直至再无明显的苯酚被蒸出。得到无色略浑浊的液体，测得酸值8.65mgKOH/g，羟值 442mgKOH/g(理论467mgKOH/g)，磷含量12.67％(理论12.92％)。将物料降温升温至60度，在 1小时内缓慢通入气体环氧乙烷。结束后减压蒸馏去除物料中残留的环氧乙烷。测得酸值 0.55mgKOH/g，羟值472mgKOH/g，磷含量为12.22％。
Claims (10)
1.一种端羟基反应型阻燃剂及其制备方法，其特征在于所述反应型阻燃剂为烷基膦酸二元醇酯，结构式为：
其中R1为C1-C4的烷基，R2为C1-C8的亚烷基或中间含有一个氧原子的C1-C8的亚烷基。
2.根据权利要求1所述的一种端羟基反应型阻燃剂的制备方法，其特征包括以下步骤：
将烷基膦酸二酯与二元醇混合，加热至80-180℃，在催化剂及在氮气保护的环境下进行酯交换反应，不断蒸出副产物，最终得到端羟基反应型烷基膦酸二元醇酯。
3.根据权利要求1所述的制备方法，其特征在于：所述的烷基膦酸二酯选自以下化合物的一种或多种：甲基膦酸二甲酯，乙基膦酸二乙酯，丙基膦酸二甲酯，甲基膦酸二苯酯，乙基膦酸二苯酯。
4.根据权利要求1或2所述的制备方法，其特征在于：优选甲基膦酸二苯酯。
5.根据权利要求1所述的制备方法，其特征在于：所述的二元醇选自以下化合物的一种或多种：乙二醇，二乙二醇，二丙二醇，1，3-丙二醇，1，4-丁二醇，1，5-戊二醇。
6.根据权利要求1或5所述的制备方法，其特征在于：优选二乙二醇与二丙二醇。
7.根据权利要求1和2所述的制备方法，其特征在于：所述的催化剂的组分来自以下路易斯酸或路易斯碱的一种或多种：三氯化铝，二氯化镁，四氯化钛，三氯化铁，氯化锌，辛酸亚锡，钛酸四丁酯，钛酸四异丙酯，三乙胺，1，8-二氮杂双环[5.4.0]十一碳-7-烯，三乙烯二胺，4-二甲氨基吡啶。
8.根据权利要求1和2所述的制备方法，其特征在于：所述的催化剂的组分来自以下金属氧化物的一种或多种：氢氧化钠，氢氧化钾，碳酸钾，碳酸钠，甲醇钠，乙醇钠，甲醇锂，叔丁醇钠。
9.根据权利要求1或7或8，其特征在于：所添加的催化剂用量为烷基膦酸二酯用量的1.0～3.0‰。
10.根据权利要求1所述的制备方法，其特征在于：烷基磷酸二酯与二元醇的比例为1∶2～2.5。
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