CN116854736A - 一种含磷化合物及其制备方法、及其用于制备抗老化阻燃聚氨酯 - Google Patents
一种含磷化合物及其制备方法、及其用于制备抗老化阻燃聚氨酯 Download PDFInfo
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- CN116854736A CN116854736A CN202310820572.3A CN202310820572A CN116854736A CN 116854736 A CN116854736 A CN 116854736A CN 202310820572 A CN202310820572 A CN 202310820572A CN 116854736 A CN116854736 A CN 116854736A
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- CN
- China
- Prior art keywords
- compound
- flame retardant
- reaction
- phosphine oxide
- trimethylol
- 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 58
- 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 57
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 26
- 239000004814 polyurethane Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000011574 phosphorus Substances 0.000 title abstract description 11
- 230000003712 anti-aging effect Effects 0.000 title abstract description 5
- -1 phosphonate phosphine oxide compound Chemical class 0.000 claims abstract description 36
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 38
- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 claims description 37
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000006260 foam Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000000746 purification Methods 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
- 238000003756 stirring Methods 0.000 claims description 4
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- LIQZZAPDGRFJIP-UHFFFAOYSA-L [dodecanoyloxy-bis(2-methylpropyl)stannyl] dodecanoate Chemical compound CC(C)C[Sn+2]CC(C)C.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O LIQZZAPDGRFJIP-UHFFFAOYSA-L 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 239000012974 tin catalyst Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 125000001544 thienyl group Chemical group 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 125000001041 indolyl group Chemical group 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 239000000779 smoke Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229920005830 Polyurethane Foam Polymers 0.000 description 9
- 239000011496 polyurethane foam Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003003 phosphines Chemical class 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- BOWOPMVHZHKSPM-UHFFFAOYSA-N n,n-dimethylacetamide;pyridine Chemical compound CN(C)C(C)=O.C1=CC=NC=C1 BOWOPMVHZHKSPM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002341 toxic gas Substances 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
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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- 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
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5304—Acyclic saturated phosphine oxides or thioxides
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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Abstract
本发明涉及一种含磷化合物及其制备方法,以及其用于制备抗老化阻燃聚氨酯,属于高分子材料合成领域。本发明提供一种化合物,其结构通式如式I所示。本发明制得一种新型结构的含膦阻燃剂三羟甲基膦酸酯氧化膦化合物,所得阻燃剂具有阻燃效能高、低烟无毒无卤的优点,并且与高分子材料的相容性好,不易迁移析出,产品较稳定,特别是具备长效阻燃的功能。
Description
技术领域
本发明涉及一种含磷化合物及其制备方法,以及其用于制备抗老化阻燃聚氨酯,属于高分子材料合成领域。
背景技术
聚氨酯硬质泡沫(RPUF)具有质量轻、比强度大、导热系数低、耐老化、耐化学腐蚀、黏结性能好等优点,是目前国际上应用最广泛的保温材料,被应用于建筑保温、冷库保温、轨道交通等诸多领域。然而,RPUF由大量易燃性碳氢链段组成,且密度低、比表面积大,其极限氧指数(LOI)仅为18-20%,极易被点燃,并伴随大量热量和HCN、CO等毒性气体释放,存在很大的火灾隐患。针对聚氨酯泡沫的易燃性问题,往往在其制备过程中以共混或共聚的方式引入阻燃剂,在RPUF燃烧分解初期,阻燃剂通过终止燃烧自由基链式反应、稀释可燃性气体浓度、阻碍热传递等方式实现RPUF的阻燃。另外,在面对野外苛刻的紫外环境,聚氨酯材料长期服役时自身也会加速老化,即使阻燃性能得以保持,但力学等其他关键性能也会下降严重,在铁路砟床等领域存在极大的应用挑战。
在无卤阻燃剂中,有机磷阻燃剂由于高效低毒、对环境无害及结构可调控而备受人们的青睐,陈明军等人发现以三羟甲基氧化磷(THPO)构筑的本征阻燃聚氨酯泡沫表现出难得的膨胀成炭行为,受到大量阻燃同行的关注(M.-J.Chen,C.-R.Chen,Y.Tan,J.-Q.Huang,X.-L.Wang,L.Chen,Y.-Z.Wang,Ind.Eng.Chem.Res.53(2014)1160–1171.),但目前基于此衍生的磷系阻燃剂在阻燃效能和力学性能还不令人满意,存在分子量低、阻燃效率低、不抗老化等缺点。
发明内容
针对上述缺陷,本发明基于三羟甲基氧化膦,以结构多样的膦氢化合物为反应原料,合成一类新型的含磷阻燃剂(简称PTMPOs),并将其应用于聚氨酯泡沫的制备中,得到具有阻燃和抗老化功能的聚氨酯硬质泡沫。
本发明的技术方案:
本发明要解决的第一个技术问题是提供一种化合物,其结构通式如式I所示:
式I中,R1、R2可为各类结构的烷基(C1-C30的直链或支链烷基)、芳基(C6-C30的直链或支链芳基)或氢。
进一步,所述R1、R2选自:甲基、甲氧基、乙基、乙氧基、丙基、异丙基、丁基,乙烯基、乙炔基、苯基、苄基、苯氧基、苯乙烯基、氨基、萘基、噻吩基、呋喃基、羟基、巯基或吲哚基等。
优选为甲基、甲氧基、乙基、乙氧基、苯基、苄基或苯氧基。
进一步,所述化合物选自下述结构式的物质:
本发明要解决的第二个技术问题是提供上述化合物的制备方法,所述制备方法为:在氮气或惰性气体保护下,先将无水的三羟甲基氧化膦、有机溶剂、缚酸剂和膦氢化合物在反应器中搅拌混匀;再于-20~25℃逐滴滴入四氯化碳,后升温至25~80℃下反应2~24h;反应结束后,经过纯化处理,得式I所示的化合物;其中,所述膦氢化合物选自:9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、亚磷酸二乙酯、α-磷氢二萘或二苯基膦氧。
进一步,所述制备方法为:先在无水的三羟甲基氧化膦中加入有机溶剂和缚酸剂,待三羟甲基氧化膦完全溶解后,加入膦氢化合物;然后将反应体系置于-20~25℃的环境中,逐滴滴入四氯化碳,后升温至25~80℃下反应2~24h;反应结束后,经过纯化处理得式I所示的化合物。
进一步,三羟甲基氧化膦和膦氢化合物摩尔比为:1:0.8~4。
进一步,所述有机溶剂包括极性溶剂、醇类溶剂、醚类溶剂、砜类溶剂或芳香类溶剂。
更进一步,所述有机溶剂选自:甲醇或乙醇等醇类溶剂;苯甲醚、乙醚和1,4-二氧六环等醚类溶剂;二甲基亚砜等砜类溶剂;甲苯或苯等芳香类溶剂;二氯甲烷、三氯甲烷等含卤极性溶剂;二甲苯、吡啶或氯苯等芳香极性溶剂、乙腈或丙腈等腈类溶剂以及N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等酰胺溶剂;优选吡啶、苯甲醚、氯苯和N,N-二甲基甲酰胺。
进一步,所述有机溶剂与三羟甲基氧化膦的用量比为:5~8mL:1g;即所述有机溶剂的体积毫升用量数为三羟甲基氧化膦质量克数的5~8倍。
进一步,所述缚酸剂包括:甲醇钠、三乙胺、吡啶、乙醇钠、、叔丁醇钾、叔丁醇钠、双(三甲基硅烷基)氨基钾、双(三甲基硅烷基)氨基锂、双(三甲基硅烷基)氨基钠、叔丁基锂等有机碱;或:氢化钠、氢氧化钠、氢氧化钾或碳酸铯等各类无机碱;优选为吡啶、三乙胺或甲醇钠。
进一步,所述缚酸剂与三羟甲基氧化膦的用量比为:1~6mL:1g;即所述缚酸剂的体积用量是三羟甲基氧化膦质量的1~6倍。
本发明中,有些缚酸剂即可做溶剂也可做碱,如吡啶、三乙胺等。
进一步,所述四氯化碳的体积用量是三羟甲基氧化膦质量的2~3倍;即所述四氯化碳与三羟甲基氧化膦的用量比为:2~3mL:1g。
进一步,所述纯化处理为:反应结束后,向反应液滴加弱碱溶液,使反应体系为中性;接着除去有机溶剂,然后经洗涤、过滤得滤液;最后经旋蒸、干燥制得式I所示得化合物。
本发明要解决的第三个技术问题是指出式I所示的化合物在阻燃剂中的用途,即其可作为聚合物的阻燃剂使用;优选为聚氨酯;更优选为聚氨酯硬质泡沫。
本发明要解决的第四个技术问题是提供一种阻燃聚氨酯材料,所述阻燃聚氨酯材料的原料包括阻燃剂,所述阻燃剂为式I所述的化合物。
进一步,所述阻燃聚氨酯材料中,阻燃剂添加量为5~40重量份;即阻燃剂添加量占聚氨酯质量的2.5wt%~20wt%。
进一步,所述阻燃聚氨酯材料的原料及其配比为:
聚醚多元醇100重量份,二异氰酸酯50~80重量份,阻燃剂5~40重量份,水2~3重量份,泡沫稳定剂2.5~4重量份,叔胺类催化剂0.2~0.4重量份,锡类催化剂0.3~0.1重量份,交联剂4~5重量份。
进一步,所述泡沫稳定剂选自:磺化貔麻油醇酸酯、烷基磺酸盐或聚二甲基硅氧烷-聚氧化烯烃共聚物,优选聚二甲基硅氧烷-聚氧化烯烃共聚物。
进一步,所述叔胺类催化剂选自:三乙烯二胺、N,N-二甲基环己胺、二甲基苄胺、三乙醇胺或N,N-二甲基氨基乙醇,优选三乙烯二胺。
进一步,所述锡类催化剂选自:二月桂酸二异丁基锡(T12)或辛酸亚锡或油酸亚锡,优选二月桂酸二异丁基锡(T12)
进一步,所述交联剂选自:三乙醇胺、二乙醇胺或乙醇胺,优选三乙醇胺
进一步,当阻燃剂添加量为10wt%时,所述阻燃聚氨酯材料的极限氧指数为26%。
本发明的有益效果:
1、本发明制得一种新型结构的含膦阻燃剂三羟甲基膦酸酯氧化膦化合物PTMPO(如式I所示),所得阻燃剂具有阻燃效能高、低烟无毒无卤的优点,并且与高分子材料的相容性好,不易迁移析出,产品较稳定,特别是具备长效阻燃的功能。
2、本发明三羟甲基膦酸酯氧化膦化合物PTMPOs的制备方法中,可将缚酸剂和有机溶剂统一,减少物料,具有良好的环境效益,又具有较好的经济效益。
3、本发明三羟甲基膦酸酯氧化膦化合物PTMPOs制备工艺采用不分离中间体的一锅法,具有高产率且原料廉价易得,及设备简单,便于操作,成本低廉,易于规模化转化和生产;有着较好的工业应用前景。
4、利用本发明方法制备的三羟甲基膦酸酯氧化膦化合物PTMPOs的收率为81%~92%,所得化合物不仅可作为有机合成中间体,因热稳定性优秀且含磷量高,适用范围广,特别适合用作聚氨酯的长效阻燃;所得阻燃材料的极限氧指数为26%。
5、本发明的制备方法中能够除去DOPO等原料,且对膦氢化合物没有特别的选择性,可选择DOPO、亚膦酸二乙酯或α-磷酰基二萘等膦氢化合物作为原料;存在广泛的适用性和操作简便性的优势。
附图说明
图1为膦氢化合物为DOPO制得的羟甲基膦酸酯氧化膦化合物(实施例1)的核磁谱图;图1表明,以氘代水作溶剂,δ4.70处为氘代水溶剂的H峰,δ7.93-6.65为3个DOPO上苯环上的Ar-H峰,δ4.29-3.40为3.72-3.98为O=P-O-CH2-P=O的亚甲基的H峰。
图2为R1、R2为膦氢化合物为DOPO制得的羟甲基膦酸酯氧化膦化合物(实施例1)的核磁谱图;图2表明,δ48.97和7.7分别为CH2-P=O,O-P=O上磷原子的吸收峰。
具体实施方式
下面结合实施例对本发明的具体实施方式做进一步的描述,并不因此将本发明限制在所述的实例范围之中。
实施例1:
在含有搅拌子的250mL的圆底烧瓶中加入三羟甲基氧化膦(0.033mol,4.63g),在80℃水浴中用油泵除去三羟甲基氧化膦中的水分,再加入30mL吡啶做有机溶剂和缚酸剂,待三羟甲基氧化膦完全溶解后,加入9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物DOPO(0.1mol,21.62g)转移至-20℃的低温恒温搅拌反应浴中。接着,将10mL四氯化碳通过恒压滴液漏斗逐滴加入,完毕后25℃继续反应24小时。反应结束后,用饱和碳酸氢钠溶液中和,接着减压蒸馏除去吡啶和水,用0℃冰水冷却过的无水乙醇洗涤除去DOPO和无机盐,抽滤得滤液,旋蒸除去乙醇,于60℃真空烘箱内干燥得到淡黄色固体,熔点为180±2℃,产率为92%。
实施例2:
在含有搅拌子的250mL的圆底烧瓶中加入三羟甲基氧化膦(0.05mol,7.0g),在80℃水浴中用油泵除去三羟甲基氧化膦中的水分,再加入30mLN,N-二甲基甲酰胺做有机溶剂和28mL三乙胺为缚酸剂,待三羟甲基氧化膦完全溶解后,加入9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物DOPO(0.1mol,21.62g)转移至-20℃的低温恒温搅拌反应浴中。接着,将10mL四氯化碳通过恒压滴液漏斗逐滴加入,完毕后25℃继续反应24小时。反应结束后,用饱和碳酸氢钠溶液中和,接着减压蒸馏除去吡啶和水,用0℃冰水冷却过的无水乙醇洗涤除去DOPO和无机盐,抽滤得滤液,旋蒸除去乙醇,于60℃真空烘箱内干燥得到淡黄色固体,熔点为180±2℃,产率为82%。
实施例3:
在含有搅拌子的250mL的圆底烧瓶中加入三羟甲基氧化膦(0.033mol,4.63g),在80℃水浴中用油泵除去三羟甲基氧化膦中的水分,再加入30mL吡啶做有机溶剂和缚酸剂,待三羟甲基氧化膦完全溶解后,加入亚磷酸二乙酯(0.1mol,13.8g)转移至-20℃的低温恒温搅拌反应浴中,接着,将10mL四氯化碳通过恒压滴液漏斗逐滴加入,完毕后25℃继续反应24小时,反应结束后,用饱和碳酸氢钠溶液中和,接着减压蒸馏除去吡啶和水,用0℃冰水冷却过的无水乙醇洗涤,抽滤得滤液,旋蒸除去乙醇,于60℃真空烘箱内干燥得到淡黄色固体,熔点为100±2℃,产率为89%。
实施例4:
在含有搅拌子的250mL的圆底烧瓶中加入三羟甲基氧化膦(0.033mol,4.63g),在80℃水浴中用油泵除去三羟甲基氧化膦中的水分,再加入30mL吡啶做有机溶剂和缚酸剂,待三羟甲基氧化膦完全溶解后,加入α-磷氢二萘(0.1mol,30.2g)转移至-20℃的低温恒温搅拌反应浴中,接着,将10mL四氯化碳通过恒压滴液漏斗逐滴加入,完毕后25℃继续反应24小时,反应结束后,用饱和碳酸氢钠溶液中和,接着减压蒸馏除去吡啶和水,用0℃冰水冷却过的无水乙醇洗涤,抽滤得滤液,旋蒸除去乙醇,于60℃真空烘箱内干燥得到淡黄色固体,熔点为200±2℃,产率为84%。
实施例5:
在含有搅拌子的250mL的圆底烧瓶中加入三羟甲基氧化膦(0.033mol,4.63g),在80℃水浴中用油泵除去三羟甲基氧化膦中的水分,再加入30mL氯苯做有机溶剂和吡啶做缚酸剂,待三羟甲基氧化膦完全溶解后,加入9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物DOPO(0.1mol,21.62g)转移至-20℃的低温恒温搅拌反应浴中,接着,将10mL四氯化碳通过恒压滴液漏斗逐滴加入,完毕后25℃继续反应24小时,反应结束后,用饱和碳酸氢钠溶液中和,接着减压蒸馏除去吡啶和水,用0℃冰水冷却过的无水乙醇洗涤除去DOPO和无机盐,抽滤得滤液,旋蒸除去乙醇,于60℃真空烘箱内干燥得到淡黄色固体,熔点为180±2℃,产率为90%
实施例6:
在含有搅拌子的250mL的圆底烧瓶中加入三羟甲基氧化膦(0.033mol,4.63g),在80℃水浴中用油泵除去三羟甲基氧化膦中的水分,再加入30mL苯甲醚做有机溶剂和(0.1mol,5.4g)甲醇钠做缚酸剂,待三羟甲基氧化膦完全溶解后,加入9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物DOPO(0.1mol,21.62g)转移至-20℃的低温恒温搅拌反应浴中,接着,将15mL四氯化碳通过恒压滴液漏斗逐滴加入,完毕后25℃继续反应24小时,反应结束后,用饱和碳酸氢钠溶液中和,接着减压蒸馏除去吡啶和水,用0℃冰水冷却过的无水乙醇洗涤除去DOPO和无机盐,抽滤得滤液,旋蒸除去乙醇,于60℃真空烘箱内干燥得到淡黄色固体,熔点为180±2℃,产率为84%
表1各实施例的原料及其用量
应用例1:
高回弹聚氨酯泡沫阻燃材料的制备(配方见表2):将20g阻燃剂THPO-DOPO(实施例1)和100g聚醚多元醇(330N)、2g蒸馏水(H2O)、4g泡沫稳定剂(DC-2525)、0.3g胺类催化剂(A-1)、0.3g二月桂酸二丁基锡(T12)和4.0g三乙醇胺(TEOA)混合后,机械搅拌4分钟,然后加入64.2g改性二异氰酸酯(MDI-2412),机械搅拌6秒钟,再迅速将样品倒入模具中。待泡沫生长完成后,将泡沫转入70℃烘箱中固化2h。固化完成后,将泡沫从模具中取出,切割成100*10*10cm3的长条泡沫。最后,所得阻燃材料参照GB/T2406.2-2009《塑料燃烧性能试验方法-氧指数法》测试样品的极限氧指数。
表2阻燃聚氨酯材料的配方表(重量份)
结果表明:当添加了本发明实施例1制得的阻燃剂THPO-DOPO,其添加量在最终所得聚氨酯阻燃材料中的质量占比为10wt%时,其极限氧指数已经达到26%的难燃级别;而在不添加任何阻燃剂的情况下,高回弹聚氨酯泡沫的极限氧指数只有18%,属于极易燃烧的范围;表明本发明制备的阻燃剂对高回弹聚氨酯泡沫有很好的阻燃效果。
应用例2
将应用例1中所得的阻燃高回弹聚氨酯泡沫阻燃材料,切割成100*10*10cm3的长条泡沫,放在200℃烘箱中持续烘烤2天,接着所得阻燃材料参照GB/T2406.2-2009《塑料燃烧性能试验方法-氧指数法》测试样品的极限氧指数,发现其极限氧指数仍可达到25%的难燃级别,且力学性能保持率高达90%,制备的阻燃剂对高回弹聚氨酯泡沫有较好的长效阻燃效果。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何不经过创造性劳动想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书所限定的保护范围为准。
Claims (10)
1.一种化合物,其特征在于,所述化合物的结构式如式I所示:
其中,R1、R2为C1-C30的直链或支链烷基、C6-C30的直链或支链芳基或氢。
2.根据权利要求1所述的一种化合物,其特征在于,所述R1、R2选自:甲基、甲氧基、乙基、乙氧基、丙基、异丙基、丁基,乙烯基、乙炔基、苯基、苄基、苯氧基、苯乙烯基、氨基、萘基、噻吩基、呋喃基、羟基、巯基或吲哚基;优选为甲基、甲氧基、乙基、乙氧基、苯基、苄基或苯氧基。
3.根据权利要求1或2所述的一种化合物,其特征在于,所述化合物为下述结构式的物质:
4.权利要求1~3任一项所述化合物的制备方法,其特征在于,所述制备方法为:在氮气或惰性气体保护下,先将无水的三羟甲基氧化膦、有机溶剂、缚酸剂和膦氢化合物在反应器中搅拌混匀;再于-20~25℃逐滴滴入四氯化碳,后升温至25~80℃下反应2~24h;反应结束后,经过纯化处理,得式I所示的化合物;其中,所述膦氢化合物选自:9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、亚磷酸二乙酯、α-磷氢二萘或二苯基膦氧。
5.根据权利要求4所述化合物的制备方法,其特征在于,所述制备方法为:先在无水的三羟甲基氧化膦中加入有机溶剂和缚酸剂,待三羟甲基氧化膦完全溶解后,加入膦氢化合物;然后将反应体系置于-20~25℃的环境中,逐滴滴入四氯化碳,后升温至25~80℃下反应2~24h;反应结束后,经过纯化处理得式I所示的化合物。
6.根据权利要求4或5所述化合物的制备方法,其特征在于,三羟甲基氧化膦和膦氢化合物摩尔比为:1:0.8~4;或:
所述有机溶剂与三羟甲基氧化膦的用量比为:5~8mL:1g;或:
所述缚酸剂与三羟甲基氧化膦的用量比为:1~6mL:1g;或:
所述四氯化碳与三羟甲基氧化膦的用量比为:2~3mL:1g。
7.根据权利要求4~6任一项所述化合物的制备方法,其特征在于,
所述有机溶剂包括极性溶剂、醇类溶剂、醚类溶剂、砜类溶剂或芳香类溶剂;
进一步,所述有机溶剂选自:甲醇、乙醇、苯甲醚、乙醚、1,4-二氧六环、二甲基亚砜、甲苯、苯、二氯甲烷、三氯甲烷、二甲苯、吡啶、氯苯、乙腈、丙腈、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺;优选为吡啶、苯甲醚、氯苯或N,N-二甲基甲酰胺;
进一步,所述缚酸剂包括:甲醇钠、三乙胺、吡啶、乙醇钠、、叔丁醇钾、叔丁醇钠、双(三甲基硅烷基)氨基钾、双(三甲基硅烷基)氨基锂、双(三甲基硅烷基)氨基钠、叔丁基锂、氢化钠、氢氧化钠、氢氧化钾或碳酸铯;优选为吡啶、三乙胺或甲醇钠。
8.根据权利要求4~7任一项所述化合物的制备方法,其特征在于,所述纯化处理为:反应结束后,向反应液滴加弱碱溶液,使反应体系为中性;接着除去有机溶剂,然后经洗涤、过滤得滤液;最后经旋蒸、干燥制得式I所示得化合物。
9.权利要求1~3任一项所述化合物在阻燃剂中的用途;
进一步,所述化合物用于阻燃聚氨酯;优选为聚氨酯硬质泡沫。
10.一种阻燃聚氨酯材料,其特征在于,所述阻燃聚氨酯材料的原料包括权利要求1~3任一项所述的化合物;
进一步,所述阻燃聚氨酯材料中,阻燃剂添加量为5~40重量份;即阻燃剂添加量占聚氨酯质量的2.5wt%~20wt%。
进一步,所述阻燃聚氨酯材料的原料及其配比为:
聚醚多元醇100重量份,二异氰酸酯50~80重量份,阻燃剂5~40重量份,水2~3重量份,泡沫稳定剂2.5~4重量份,叔胺类催化剂0.2~0.4重量份,锡类催化剂0.3~0.1重量份,交联剂4~5重量份。
进一步,所述泡沫稳定剂选自:磺化貔麻油醇酸酯、烷基磺酸盐或聚二甲基硅氧烷-聚氧化烯烃共聚物;所述叔胺类催化剂选自:三乙烯二胺、N,N-二甲基环己胺、二甲基苄胺、三乙醇胺或N,N-二甲基氨基乙醇;所述锡类催化剂选自:二月桂酸二异丁基锡、辛酸亚锡或油酸亚锡;所述交联剂选自:三乙醇胺、二乙醇胺或乙醇胺。
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