CN112028932A - 一种二烷基次膦酸酯阻燃剂及其制备方法和应用 - Google Patents
一种二烷基次膦酸酯阻燃剂及其制备方法和应用 Download PDFInfo
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- CN112028932A CN112028932A CN202011031998.3A CN202011031998A CN112028932A CN 112028932 A CN112028932 A CN 112028932A CN 202011031998 A CN202011031998 A CN 202011031998A CN 112028932 A CN112028932 A CN 112028932A
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- Prior art keywords
- flame retardant
- reaction
- catalyst
- hydrogen
- acid
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 64
- 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 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- -1 phosphinic acid acyl halide Chemical class 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims abstract description 8
- 125000005997 bromomethyl group Chemical group 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 2
- 229940046149 ferrous bromide Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-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
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 13
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 6
- KGENPKAWPRUNIG-UHFFFAOYSA-N 1-[chloro(ethyl)phosphoryl]ethane Chemical compound CCP(Cl)(=O)CC KGENPKAWPRUNIG-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
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- 238000013112 stability test Methods 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-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
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- UHQXTUYYLOVMDB-UHFFFAOYSA-N 1-[bromo(butyl)phosphoryl]butane Chemical compound CCCCP(Br)(=O)CCCC UHQXTUYYLOVMDB-UHFFFAOYSA-N 0.000 description 1
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- BXIBVJRBYMVNRW-UHFFFAOYSA-N 1-[bromo(propyl)phosphoryl]propane Chemical compound CCCP(Br)(=O)CCC BXIBVJRBYMVNRW-UHFFFAOYSA-N 0.000 description 1
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- FKTWHPRHZDOJRC-UHFFFAOYSA-N 1-[chloro(2-methylpropyl)phosphoryl]-2-methylpropane Chemical compound CC(C)CP(Cl)(=O)CC(C)C FKTWHPRHZDOJRC-UHFFFAOYSA-N 0.000 description 1
- UURSVZMTFRQAFX-UHFFFAOYSA-N 1-[chloro(propyl)phosphoryl]propane Chemical compound CCCP(Cl)(=O)CCC UURSVZMTFRQAFX-UHFFFAOYSA-N 0.000 description 1
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- NHCKBRCJXVNYJA-UHFFFAOYSA-N 2-[butan-2-yl(chloro)phosphoryl]butane Chemical compound CCC(C)P(Cl)(=O)C(C)CC NHCKBRCJXVNYJA-UHFFFAOYSA-N 0.000 description 1
- ICKHJNMKQISCQZ-UHFFFAOYSA-N 2-[chloro(propan-2-yl)phosphoryl]propane Chemical compound CC(C)P(Cl)(=O)C(C)C ICKHJNMKQISCQZ-UHFFFAOYSA-N 0.000 description 1
- MRJHDJDCKDZZOC-UHFFFAOYSA-N 2-[tert-butyl(chloro)phosphoryl]-2-methylpropane Chemical compound CC(C)(C)P(Cl)(=O)C(C)(C)C MRJHDJDCKDZZOC-UHFFFAOYSA-N 0.000 description 1
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
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- 239000007983 Tris buffer Substances 0.000 description 1
- OPAQIMUKVFWWHE-UHFFFAOYSA-N [bromo(methyl)phosphoryl]methane Chemical compound CP(C)(Br)=O OPAQIMUKVFWWHE-UHFFFAOYSA-N 0.000 description 1
- CVNMBKFJYRAHPO-UHFFFAOYSA-N [chloro(methyl)phosphoryl]methane Chemical compound CP(C)(Cl)=O CVNMBKFJYRAHPO-UHFFFAOYSA-N 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 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 description 1
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- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
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- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
Description
技术领域
本发明涉及阻燃剂技术领域,具体涉及一种二烷基次膦酸酯阻燃剂及其制备方法和应用。
背景技术
磷酸酯是有机磷系阻燃剂的主要品种,它具有阻燃效果持久,与聚合物基材相容性好,耐水,耐候等优点,因而在聚氨酯,环氧树脂,聚碳酸酯,不饱和树脂等高分子材料中应用广泛。传统的磷酸酯大多以三氯化磷,三氯氧磷,五氧化二磷等与相应的含有羟基,氨基,环氧基团的化合物反应而成。如常见的磷酸三乙酯(TEP)、磷酸三丁酯(TDP)、磷酸三苯酯(TPP)、磷酸三(二甲苯)酯(TXP)、磷酸三(α-氯乙基)酯(TCEP)、磷酸三(l,3-二氯-2-丙基)酯(TDCPP)、磷酸三(2-氯异丙基)酯(TCPP)等。该类阻燃剂在家居,建材,电子电器等诸多领域中已获得广泛的应用(如公开号为CN102775839A、CN106633794A的专利技术等)。
传统的磷酸酯分子结构中大多含有P-O-C键,长时间存储,该类阻燃剂会面临酸值升高,甚至阻燃剂在聚合物表面析出,阻燃性能降低,材料机械性能恶化等问题,这给磷酸酯类阻燃剂的应用带来困扰。另一方面,部分磷酸酯阻燃剂,分子结构中虽然含有较为稳定的P-C键,降低了磷酸酯的水解,返酸等现象。如甲基膦酸二甲酯(DMMP),乙基磷酸二乙酯(DEEP)等。但该类阻燃剂为国际禁化武组织重点监控的化学品,其生产、使用、流通均受到严格的管制,给该类阻燃剂的大规模推广使用,带来不便。
发明内容
针对上述技术问题和克服传统磷酸酯阻燃剂的不足,本发明提供了一种二烷基次膦酸酯阻燃剂,相较于传统的磷酸酯阻燃剂,它具有储存稳定,不返酸,磷含量高,阻燃效率高等优点;且分子中同时含有两个P-C键,不属于国际禁化武组织重点监控的化学品,生产及推广使用方便。
一种二烷基次膦酸酯阻燃剂,结构式如下式(I)所示:
式(I)中,R1、R2分别独立的选自C1-C4的烷基,R3选自氢、氯甲基、溴甲基中的一种,R4选自氯、溴、甲基中的一种,R5选自氢、氯、溴、甲基中的一种。
本发明还提供了所述的二烷基次膦酸酯阻燃剂的优选制备方法,以二烷基次膦酸酰卤和环氧化合物为原料,在催化剂作用下50-100℃反应得到所述二烷基次膦酸酯阻燃剂,反应式如下所示:
反应式中,R1、R2分别独立的选自C1-C4的烷基,Ra选自氯、溴中的一种,Rb选自氢、甲基、氯甲基中的一种,R3选自氢、氯甲基、溴甲基中的一种,R4选自氯、溴、甲基中的一种,R5选自氢、氯、溴、甲基中的一种;
所述催化剂为碱土金属卤化物、第三主族卤化物、过渡金属卤化物或酸催化剂中的一种。
本发明制备方法中,所述原料、催化剂的混合方式可以是任意形式。包括二烷基次膦酸酰卤和环氧化合物先混合,然后加热到特定的反应温度。也可以是先在体系中加入二烷基次膦酸酰卤,加热到特定的反应温度,然后慢慢滴加环氧化合物。也可以是先在体系中加入环氧化合物,加热到特定的反应温度,然后慢慢加入二烷基次膦酸酰卤。催化剂可以在反应开始前一并或分别加入,也可以在反应过程中分批加入或连续加入。
本发明制备方法中,反应结束,可以通过现有的方法提纯产物。譬如过滤,洗涤等方法。优选地,反应结束后产物经过滤,碱洗,水洗,提纯,得到成品二烷基次膦酸酯阻燃剂。此处所述的碱洗可以是氢氧化钠溶液,氢氧化钾溶液,碳酸钠溶液中的一种,其质量浓度可以是0.5wt%-3wt%;此处所述的提纯可以为蒸馏,蒸发;如减压蒸馏,常压蒸馏,降膜蒸发等操作工艺。
作为优选,所述制备方法具体包括:将催化剂加入到二烷基次膦酸酰卤中,开启搅拌,惰性气体保护下升温至50-100℃,然后缓慢加入环氧化合物,加入完毕后,持续保温反应,所得产物经过滤、碱洗、水洗、提纯,即得成品二烷基次膦酸酯阻燃剂。产率不低于95%。
所述惰性气体可以是稀有气体、氮气等。
所述加入环氧化合物的时间一般控制在2~3h。
所述制备方法中,环氧化合物一般过量。所述二烷基次膦酸酰卤和环氧化合物的摩尔比优选为1:1.01-1.50,进一步优选为1:1.01-1.20。
催化剂用量可根据需要进行调控。所述催化剂质量优选为二烷基次膦酸酰卤质量的0.1%-10.0%,进一步优选为二烷基次膦酸酰卤质量的0.1%-5.0%。
所述制备方法中,所述反应的压力优选不小于一个大气压,即为常压或大于一个大气压。进一步优选,所述反应在大于一个大气压的压力下进行,可以促进反应的快速进行。
本领域技术人员可以根据实际需要,选择反应时间。可选地,反应时间长短可调,决定于催化剂、反应温度、所需的反应程度。通常情况下,反应速度较快在约0.5小时至8小时就可完成反应;可选地,反应时间为1小时至5小时。
所述制备方法中,所述反应的温度优选为60-100℃。
所述制备方法中,所述催化剂优选包括碘化铁、溴化铁、氯化铁、氯化亚铁、溴化亚铁、氯化镍、溴化镍、三氯化铝、三溴化铝、氯化镁、四氯化钛、烷基磺酸、芳基磺酸、三氟化硼中的至少一种。
本发明中,所述的二烷基次膦酸酰卤,包括二烷基次膦酸酰氯,二烷基次膦酸酰溴;所述的烷基为C1-C4的烷基。具体优选为:二甲基次膦酸酰氯,二甲基次膦酸酰溴,二乙基次膦酸酰氯,二乙基次膦酸酰溴,二正丙基次膦酸酰氯,二正丙基次膦酸酰溴,二异丙基次膦酸酰氯,二异丙基次膦酸酰溴,二正丁基次膦酸酰氯,二正丁基次膦酸酰溴,二仲丁基次膦酸酰氯,二仲丁基次膦酸酰溴,二异丁基次膦酸酰氯,二异丁基次膦酸酰溴,二叔丁基次膦酸酰氯,二叔丁基次膦酸酰溴。
所述的二烷基次膦酰卤可由二烷基次膦酸经卤化反应后制得。具体包括如下两个步骤:
1)二烷基次膦酸的制备。通常由次磷酸钠与C2-C4的烯烃为原料,先制备得到二烷基次磷酸钠,然后二烷基次磷酸钠与相应的酸,如硫酸,盐酸,硝酸,乙酸等反应后二烷基次膦酸。
2)二烷基次膦酸酰卤的制备。二烷基次膦酸与卤化试剂反应后制备得到。此处所用的卤化试剂包括氯化亚砜,三氯化磷,五氯化磷,三溴化磷,五溴化磷;优选为氯化亚砜,三氯化磷,五氯化磷,三溴化磷。
本发明中,所用的环氧化合物,包括环氧乙烷,环氧丙烷,环氧氯丙烷。即:当Rb为氢时,所述的环氧化合物为环氧乙烷;当Rb为甲基时,所述的环氧化合物为环氧丙烷;当Rb为氯甲基时,所述的环氧化合物为环氧氯丙烷。
本发明制备方法可以为间歇式或连续式进行。连续式工艺中可采用一系列的反应装置,如管道式反应器进行反应。反应结束后分离产物和原材料,将过量的环氧化合物返回到原料罐中实现连续反应。间歇式反应可采用一系列的反应装置,如反应釜进行反应。反应结束后分离产物和原材料,将过量的环氧化合物返回到原料罐中实现间歇反应。
本发明还提供了一种阻燃型聚氨酯材料,包括所述的二烷基次膦酸酯阻燃剂。所述聚氨酯材料包括硬质聚氨酯材料及软质聚氨酯材料。
本领域技术人员可以根据实际需要,将所述二烷基次膦酸酯阻燃剂单独使用或者与其它阻燃剂混合后使用。此处所述的其它阻燃剂包括:(a)磷酸酯阻燃剂,如磷酸三乙酯(TEP),磷酸三丁酯(TBP),磷酸三辛酯,磷酸三苯酯(TPP),磷酸三(二甲苯)酯(TXP),三(2-氯异丙基)磷酸酯(TCPP)、三(2-氯乙基)磷酸酯(TCEP)、3-三(二氯丙基)磷酸酯(TDCPP);(b)含氮阻燃剂,如聚磷酸铵,氰尿酸三聚氰胺,聚磷酸三聚氰胺等;(c)烷基次磷酸盐,如二乙基次膦酸铝;根据不同的聚氨酯应用体系,选择不同的阻燃剂用量。通常情况下,以阻燃型聚氨酯材料原料中聚醚多元醇总质量为100份计,所述二烷基次膦酸酯阻燃剂用量在3-35质量份之间。可选地,所述二烷基次膦酸酯阻燃剂用量在3-25质量份之间。
本发明中,C1-C4等均指基团中所包含的碳原子数。
本发明中,“烷基”是由烷烃化合物分子上失去任意一个氢原子所形成的基团。所述烷烃化合物包括直链烷烃、支链烷烃。
本发明与现有技术相比,主要优点包括:
1、提供了具有式(I)的二烷基次膦酸酯阻燃剂及其制备方法。该阻燃剂分子中含有稳定的P-C键结构,其储存稳定性好。存储及使用过程中,酸值稳定,不返酸;且该阻燃剂磷含量高,具有较高阻燃效率。
2、该二烷基次膦酸酯的制备,采用二烷基次膦酸酰卤和环氧化合物为原料一步法合成。反应过程操作方便;反应收率高。
3、利用本发明的阻燃剂可以用来制备阻燃聚氨酯材料,该阻燃剂单独使用或者与其它阻燃剂混合后使用。含有该阻燃剂的聚氨酯材料具有良好的阻燃性能。
附图说明
图1为本发明实施例1所得产物的核磁共振磷谱示意图;
图2为本发明实施例1所得产物的核磁共振氢谱示意图;
图3为本发明实施例2所得产物的核磁共振磷谱示意图;
图4为本发明实施例2所得产物的核磁共振氢谱示意图;
图5为本发明实施例3所得产物的核磁共振磷谱示意图;
图6为本发明实施例3所得产物的核磁共振氢谱示意图。
具体实施方式
下面结合附图及具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法,通常按照常规条件,或按照制造厂商所建议的条件。
如无特别说明,原料均通过商业途径购买。
核磁共振(NMR)测试:所用型号为AVANCE DMX 400MHz,瑞士Bruker公司;测试方法为:
1H NMR,以CDCl3为溶剂,四甲基硅烷内标;
31P NMR,以氘代氯仿为溶剂,85%磷酸外标,扫描次数为64次;
酸值测定:采用0.01mmol/L的KOH甲醇溶液直接滴定,以溴百里酚蓝为指示剂;酸值用每克产品消耗的氢氧化钾的质量(mg)表示。
储存稳定性测定:取一定量的磷酸酯,置于80℃,80%的恒温恒湿箱中,储存168h后,测试酸值。
以下实施例中,产率的计算方法为:(产物重量/产物理论重量)×100%。
实施例1制备具有式(II)结构的化合物
向装有搅拌器、温度计的压力釜中加入281.0g(2mol)二乙基次膦酸酰氯,0.281g三氯化铝,开启搅拌,通入氮气置换三次,升温至60-70℃,缓慢加入88.9g(2.02mol)环氧乙烷,约两小时内加完,保温搅拌2小时后开启真空,脱去未反应完的环氧乙烷。产物经过滤,碱洗,蒸馏提纯,得产品354.3g。产率95.7%。产物核磁共振磷谱图、核磁共振氢谱图分别如图1、2所示。
实施例2制备具有式(III)结构的化合物
向装有搅拌器、温度计的压力釜中加入281.0g(2mol)二乙基次膦酸酰氯,3.8g三氯化铝,开启搅拌,通入氮气置换三次后升温至80℃,缓慢加入140.0g环氧丙烷,约三小时内加完,保温搅拌2.5小时后开启真空,脱去未反应完的环氧丙烷。过滤,碱洗,蒸馏提纯,得产品393.1g。产率99.3%。产物核磁共振磷谱图、核磁共振氢谱图分别如图3、4所示。
实施例3制备具有式(IV)结构的化合物
向装有搅拌器、温度计,回流冷凝器四口烧瓶中加入281.0g(2mol)二乙基次膦酸酰氯,14.4g氯化镁,开启搅拌,通入氮气置换三次后升温至100℃,缓慢滴入190.0g环氧氯丙烷,约三小时内加完,保温搅拌3小时后,开启真空,脱去未反应完的环氧氯丙烷,结束反应。过滤,碱洗,再次过滤提纯,得产品452.4g。产率97.0%。产物核磁共振磷谱图、核磁共振氢谱图分别如图5、6所示。
表1分别列出了实施例1~3中所得产物,储存稳定性测试实验结果;作为对比,表中还列出了常见的阻燃剂磷酸三乙酯(TEP)、磷酸三(2-氯异丙基)酯(TCPP)、甲基磷酸二甲酯(DMMP)、乙基磷酸二乙酯(DEEP)在80℃,80%湿度下,储存168小时的稳定性测试结果;详见表1。
表1阻燃剂酸值测试结果
序号 | 化合物 | 酸值(mgKOH/g) |
1 | 实施例1 | 0.38 |
2 | 实施例2 | 0.50 |
3 | 实施例3 | 0.62 |
4 | TEP | 10.6 |
5 | TCPP | 15.8 |
6 | DMMP | 5.8 |
7 | DEEP | 8.3 |
实施例4制备阻燃型聚氨酯材料
将实施例1~3制备的二烷基次膦酸酯阻燃剂用于制备聚氨酯泡沫,其具体操作过程为:
在杯子A中加入聚醚多元醇,二乙醇胺,阻燃剂,水,胺类催化剂,有机锡催化剂和硅油;在杯子B中称取甲苯二异氰酸酯(TDI);杯子A中物料高速搅拌20秒,将杯B中加入杯A中,继续高速搅拌10秒,将混合后液体迅速导入15cm×15cm×20cm的盒子中,待泡沫不再升起后,继续熟化,制得聚氨酯泡沫。
具体配方及阻燃性能列于下表2中。
表2聚氨酯发泡配方
原料名称 | 用量/g |
聚醚多元醇330N | 70 |
聚醚多元醇POP-H45 | 30 |
水 | 2.3 |
二乙醇胺 | 1.5 |
硅油(Y-10366) | 0.8 |
胺类催化剂 | 0.15 |
有机锡催化剂 | 0.1 |
甲苯二异氰酸酯(TDI) | 31 |
阻燃剂 | 27 |
按表2配方准备各原料并发泡,将制得的泡沫切割成12mm×12mm×200mm的样条,每五根一组,并测试氧指数。作为对比,同时将实施例1~3制备的二烷基次膦酸酯阻燃剂与常见的阻燃剂磷酸三乙酯(TEP)、磷酸三(2-氯异丙基)酯(TCPP)、甲基磷酸二甲酯(DMMP)、乙基磷酸二乙酯(DEEP)进行复配,同等操作步骤和条件下发泡,测试氧指数;结果见表3。
表3阻燃剂的极限氧指数测试结果
序号 | 化合物 | 氧指数(LOI) |
1 | 实施例1 | 28 |
2 | 实施例2 | 27 |
3 | 实施例3 | 27 |
4 | 17g实施例1+10g TEP | 25 |
5 | 10g实施例1+17g TCPP | 23 |
6 | 15g实施例2+12g DEEP | 23 |
7 | 14g实施例3+13g DEEP | 24 |
此外应理解,在阅读了本发明的上述描述内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (10)
3.根据权利要求2所述的制备方法,其特征在于,具体包括:将催化剂加入到二烷基次膦酸酰卤中,开启搅拌,惰性气体保护下升温至50-100℃,然后缓慢加入环氧化合物,加入完毕后,持续保温反应,所得产物经过滤、碱洗、水洗、提纯,即得成品二烷基次膦酸酯阻燃剂。
4.根据权利要求2或3所述的制备方法,其特征在于,所述二烷基次膦酸酰卤和环氧化合物的摩尔比为1:1.01-1.50。
5.根据权利要求2或3所述的制备方法,其特征在于,所述催化剂质量为二烷基次膦酸酰卤质量的0.1%-10.0%。
6.根据权利要求2或3所述的制备方法,其特征在于,所述反应的压力不小于一个大气压。
7.根据权利要求2或3所述的制备方法,其特征在于,所述反应的温度为60-100℃。
8.根据权利要求2或3所述的制备方法,其特征在于,所述催化剂包括碘化铁、溴化铁、氯化铁、氯化亚铁、溴化亚铁、氯化镍、溴化镍、三氯化铝、三溴化铝、氯化镁、四氯化钛、烷基磺酸、芳基磺酸、三氟化硼中的至少一种。
9.根据权利要求2或3所述的制备方法,其特征在于,所述制备方法为间歇式或者连续式进行。
10.一种阻燃型聚氨酯材料,其特征在于,包括如权利要求1所述的二烷基次膦酸酯阻燃剂。
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