CN112321638B - 单烷基亚膦酸二烷基酯、二烷基膦酸酯及其金属盐的制备方法 - Google Patents
单烷基亚膦酸二烷基酯、二烷基膦酸酯及其金属盐的制备方法 Download PDFInfo
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- CN112321638B CN112321638B CN202011146863.1A CN202011146863A CN112321638B CN 112321638 B CN112321638 B CN 112321638B CN 202011146863 A CN202011146863 A CN 202011146863A CN 112321638 B CN112321638 B CN 112321638B
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- 229910052751 metal Chemical class 0.000 title claims abstract description 18
- 239000002184 metal Chemical class 0.000 title claims abstract description 18
- 150000003839 salts Chemical class 0.000 title claims abstract description 15
- 230000008569 process Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 150000008282 halocarbons Chemical class 0.000 claims description 9
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- 238000004519 manufacturing process Methods 0.000 claims description 6
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005052 trichlorosilane Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000005048 methyldichlorosilane Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- BZLZKLMROPIZSR-UHFFFAOYSA-N triphenylsilicon Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)C1=CC=CC=C1 BZLZKLMROPIZSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004754 hydrosilicons Chemical class 0.000 claims 1
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- 150000007513 acids Chemical class 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
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- 239000000460 chlorine Substances 0.000 abstract description 2
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- 238000009833 condensation Methods 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- YBXFAVVDFPWMPR-UHFFFAOYSA-N diethoxy(ethyl)phosphane Chemical compound CCOP(CC)OCC YBXFAVVDFPWMPR-UHFFFAOYSA-N 0.000 description 6
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- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- GQAXWUVTNDQEQR-UHFFFAOYSA-N 1-diethylphosphoryloxyethane Chemical compound CCOP(=O)(CC)CC GQAXWUVTNDQEQR-UHFFFAOYSA-N 0.000 description 2
- YLXGYLLBXARBDE-UHFFFAOYSA-N 6-methylheptylphosphonic acid Chemical compound CC(C)CCCCCP(O)(O)=O YLXGYLLBXARBDE-UHFFFAOYSA-N 0.000 description 2
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- 239000005977 Ethylene Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 150000001350 alkyl halides Chemical class 0.000 description 2
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 2
- GBNVBFGHGMAMDH-UHFFFAOYSA-N bis(6-methylheptyl)phosphinic acid Chemical compound CC(C)CCCCCP(O)(=O)CCCCCC(C)C GBNVBFGHGMAMDH-UHFFFAOYSA-N 0.000 description 2
- ZXMSTCRBSAVFDO-UHFFFAOYSA-N dimethoxy(methyl)phosphane Chemical compound COP(C)OC ZXMSTCRBSAVFDO-UHFFFAOYSA-N 0.000 description 2
- HAXBLJDZJKJLHZ-UHFFFAOYSA-N dimethylphosphoryloxymethane Chemical compound COP(C)(C)=O HAXBLJDZJKJLHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BXZAHARWAYSGTO-UHFFFAOYSA-K [Al+3].CCP([O-])=O.CCP([O-])=O.CCP([O-])=O Chemical compound [Al+3].CCP([O-])=O.CCP([O-])=O.CCP([O-])=O BXZAHARWAYSGTO-UHFFFAOYSA-K 0.000 description 1
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-M dimethylphosphinate Chemical compound CP(C)([O-])=O GOJNABIZVJCYFL-UHFFFAOYSA-M 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005648 named reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
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- 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
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
- C07F9/4816—Acyclic saturated acids or derivatices 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
-
- 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
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4866—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the ester moiety containing a substituent or structure which is considered as characteristic
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- Health & Medical Sciences (AREA)
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- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
技术领域
本发明涉及膦酸酯合成技术领域,具体的说是一种单烷基亚膦酸二烷基酯、二烷基膦酸酯及其金属盐的制备方法。
背景技术
二烷基次膦酸铝和锌是具有良好热稳定性和阻燃性的无卤阻燃剂,现已作为溴系阻燃剂的替代物而广泛用于聚酰胺和聚酯的阻燃。二烷基次膦酸也是非常重要的稀土萃取剂,如 Cyanex272二(2,4,4-三甲基戊基)次膦酸是性能优异的有色金属分离萃取剂,用于萃取分离镍、钴、稀土等效果显著。二烷基次膦酸及其盐可以通过各种方法加以制备。
目前二烷基次膦酸及其衍生物制备的主流方法主要有三种:傅克反应法、格氏试剂法和自由基加成法。
傅克反应(Friedel-Crafts)是有机合成中经典的人名反应,AlCl3就是其中最常用的催化剂之一。它具有优异的催化性能,特别是针对芳环取代、烷烃异构化、酰基化等反应。
Horold等人利用AlCl3催化黄磷与氯代烷反应,再经氧化、水解得到二烷基膦酸。
Wefering等人将黄磷溶于甲苯经AlCl3催化在高压釜中与一氯甲烷反应,再以氢氧化钾碱性溶液加入到反应体系中,最后水洗得到目标烷基次膦酸盐。John.D等人是以三氯化磷为原料,引入AlCl3和硝基甲烷进入混合溶液中,萃取得烷基次膦酸盐。虽然AlCl3催化反应法原理简单,但效率低及产物难以分离,产率低,在实际应用中一直受到限制。
格氏试剂法均以卤代烃RX为原料,与镁等活泼金属在有机溶液中制得格氏试剂,通式为(RMgX),再与含P=O键的磷类物质反应制得二烷基次膦酸盐。清华大学贾彩等人用格氏试剂加成法合成了二烷己基二硫代次膦酸。柴生勇等人同样利用格氏试剂法合成了二烷基次膦酸盐。其中后者利用RX和镁条制得RMgX后,通过与亚膦酸二酯亲核加成反应得到二烷基氧化磷,最后经氧化、酸化得到二烷基次膦酸盐。格氏试剂合成法具有合成工艺简单、操作方便、产品纯等优点,适用于小规模的生产。但是格氏试剂成本较高,限制了大规模生产。
自由基加成法常用于双键加成反应,德国科莱恩公司已经通过自由基加成法将二烷基次磷酸盐的合成运用到工业生产中。此方法的优势为:原理简单、反应效率高、针对性强、产物纯度较高。科莱恩公司以一水合次磷酸钠和乙烯为原料,高压下通过醋酸溶剂将二者混合,引入偶氮类引发剂,升温制得二乙基次膦酸,最后经氢氧化铝或磷酸铝反应制得AlPi。虽然自由基加成法的原料简单易得,成本低廉,但是反应温度和压力高,反应时间长,控制难,容易得到单烷基取代的次膦酸或长链烷烃的次膦酸,导致得到的二烷基次膦酸盐的热稳定性下降,在塑料中的阻燃效果变差或萃取的效率变低。
此外,专利号为CN201510137169.6的专利中,采用烷基次膦酸二烷基酯在温度60~120℃及含碘类催化剂作用下制备二烷基次膦酸烷基酯。该方法具有收率高、操作简单、副产物可以回收利用、无环境污染等优点。但是该专利没有公开原料烷基次膦酸二烷基酯的制备方法,然而烷基次膦酸二烷基酯的制备也存在技术障碍,实际生产中,烷基次膦酸二烷基酯一般是由格氏试剂的方法得到,对反应条件要求高,反应路线如下:
而且该专利方法制备二烷基次膦酸盐时采用了大量的有机溶剂,增加了有机污染物的排放。
发明内容
针对现有技术中烷基次膦酸二烷基酯的制备反应条件要求高的技术问题,本发明主要为了解决上述问题,在温和条件下制得烷基次膦酸二烷基酯,进而用于制备二烷基次膦酸酯及其酸和盐,解决制备二烷基次膦酸酯时,傅克反应法使用大量AlCl3造成副产物较多后处理繁琐;格氏试剂法需要无水无氧操作苛刻条件以及很高的原材料成本造价高而难以商品化;自由基加成法需要长时间的高温高压以及由此带来的单烷基化和烯烃聚合的副产物导致产品纯度下降的问题。本发明不仅可以降低二烷基次膦酸酯及其衍生物的生产成本,同时使反应过程易于控制,避免采取高温高压长时间反应,提高产品纯度与收率。
本发明采用单烷基膦酸二烷基酯与含硅氢还原剂反应制备单烷基亚膦酸二烷基酯,然后进行催化异构化反应得到二烷基膦酸烷基酯。二烷基膦酸烷基酯酸化后,得到二烷基次膦酸溶液,二烷基次膦酸酯溶液与金属盐反应即可得到相应的二烷基次膦酸盐。
本发明的第一目的在于提供一种单烷基亚膦酸二烷基酯的制备方法,包括步骤:
单烷基膦酸二烷基酯在含硅氢还原剂的作用下反应得到单烷基亚膦酸二烷基酯;反应式如下:
其中各R1独立地为碳原子数1~10的烷基,所述烷基为直链烷基和含有支链的烷基;
所述含硅氢还原剂为含氯和/或含氢的硅烷。
所述含硅氢还原剂的硅原子还连有取代基,所述取代基选自芳基、烷氧基、烷烃基中的一种或多种。所述芳基为苯基或取代的苯基,优选苯基。所述烷氧基为碳原子数1~10的烷氧基,包括直链烷基和含有支链的烷氧基,优选甲氧基或乙氧基。所述烷烃基为碳原子数1~10 的烷基,包括直链烷基和含有支链的烷基,优选甲基、乙基、丙级或异丙基。
优选的,所述含硅氢还原剂为三氯氢硅烷、六氯二硅烷、苯基三氢硅烷、二苯基二氢硅烷、三苯基氢硅烷、甲氧基三氢硅烷、二甲氧基二氢硅烷、甲基二氯硅烷中的一种或多种。更优选甲氧基三氢硅烷。
所述含硅氢还原剂的用量,与所述含硅氢还原剂的氢含量有关,一般来说含硅氢还原剂的氢的摩尔比例等于或适当高于单烷基膦酸二烷基酯,优选的,所述含硅氢还原剂的氢含量与所述单烷基膦酸二烷基酯的摩尔比可设为1~2∶1,更优选1.0~1.2∶1。比如,若所述含硅氢还原剂中含有一个氢,优选所述含硅氢还原剂与单烷基膦酸二烷基酯的摩尔比可设为 1~2∶1,更优选1.0~1.2∶1;再比如,若所述含硅氢还原剂中含有两个氢,所述含硅氢还原剂与单烷基膦酸二烷基酯的摩尔比可设为1~2∶2,更优选1.0~1.2∶2;再比如,若所述含硅氢还原剂中含有三个氢,所述含硅氢还原剂与单烷基膦酸二烷基酯的摩尔比可设为1~2∶3,更优选1.0~1.2∶3。
例外的,六氯二硅烷虽然不含有氢,但是其还原效果相当于含有一个氢的硅烷。
优选的,反应还加入了有机胺类催化剂。
有机胺类催化剂主要作用是与含硅还原剂形成络合物,降低反应温度,提高产率。
优选的,所述有机胺类催化剂和所述含硅氢还原剂的摩尔比为0.9~1.1∶1,更优选1∶1。
优选的,所述有机胺类催化剂为三乙胺,二乙胺,二甲基苯胺中的一种或多种。
进一步的,加入有机胺类催化剂时,会生产盐,因此可加入有机溶剂来提升反应速度。优选的,有机溶剂采用苯、甲苯、四氢呋喃或者类似性质的溶剂。
优选的,具体操作为:在惰性气体保护,0~30℃优选5~25℃条件下,向所述含硅氢还原剂中滴加单烷基膦酸二烷基酯,滴加完毕后逐步升温至70~120℃优选80~100℃至反应完毕,然后减压蒸馏得到单烷基亚膦酸二烷基酯。
或者优选的,具体操作为:在惰性气体保护,0~30℃优选5~25℃条件下,向所述含硅氢还原剂和所述有机胺类催化剂的混合物中滴加单烷基膦酸二烷基酯,滴加完毕后逐步升温至 70~120℃优选80~100℃至反应完毕,然后减压蒸馏得到单烷基亚膦酸二烷基酯。
或者优选的,具体操作为:在惰性气体保护,0~30℃优选5~25℃条件下,向所述含硅氢还原剂、所述有机胺类催化剂和有机溶剂的混合物中滴加单烷基膦酸二烷基酯,滴加完毕后逐步升温至70~120℃优选80~100℃至反应完毕,然后减压蒸馏得到单烷基亚膦酸二烷基酯。
本发明的第二目的在于提供一种二烷基膦酸烷基酯的制备方法,其包括步骤:
(a)通过如上所述的方法制备单烷基亚膦酸二烷基酯;
(b)单烷基亚膦酸二烷基酯在卤代烃的催化作用下进行异构化反应,得到二烷基膦酸烷基酯;
反应式如下:
其中各R1独立地为碳原子数1~10的烷基,所述烷基为直链烷基和含有支链的烷基,X 为F、Cl、Br或I。
步骤(b)中,卤代烷R1X是催化剂,少量的就可以引发,R1X的R1存在进入产物结构的可能,因此,最终的产物中少量会含有卤代烷R1X的R1结构。
优选的,步骤(b)中,所述卤代烃为含碳原子数为1~10的卤代烃,所述单烷基亚磷酸二烷基酯与卤代烃的摩尔比为1000∶10~40;所述异构化反应的反应温度为60~250℃优选 100~150℃,反应时间为0.5~16小时。
本发明的第三目的在于提供一种二烷基膦酸烷基酯金属盐的制备方法,其包括步骤:
(A)通过如上所述的方法制备二烷基膦酸烷基酯;
(B)步骤(A)制得的二烷基膦酸烷基酯在酸性条件下水解后与金属盐溶液进行水热反应,得到二烷基次膦酸金属盐;金属盐的金属元素为Ce、La、Al、Zn、Ni、Ca、Mg或Fe。
优选的,所述水热反应温度为80~160℃优选90~110℃,反应时间为0.5~8小时。
发明的积极进步效果在于:
本发明主要公开了采用单烷基膦酸二烷基酯与含硅氢还原剂反应制备单烷基亚膦酸二烷基酯,然后进行催化异构化反应得到二烷基膦酸烷基酯。二烷基膦酸烷基酯酸化后,得到二烷基次膦酸溶液,二烷基次膦酸酯溶液与金属盐反应即可得到相应的二烷基次膦酸盐。
本发明以单烷基膦酸二烷基酯为原料,与含硅氢还原剂反应制得单烷基亚膦酸二烷基酯,不涉及需要苛刻反应条件及高昂的格氏试剂,工艺条件温和,后处理简单,转化率高,在工业化中易于实现。
本发明以单烷基亚膦酸二烷基酯异构化制备二烷基膦酸烷基酯,工艺条件温和,在工业化中易于实现,不涉及需要苛刻反应条件及高昂的格氏试剂,也不涉及需要在高温高压条件才反应的烯烃类气体如乙烯之类易燃易爆气体的使用,后处理简单易行产品纯度高达 98-99%,二烷基膦酸烷基酯可水解得到的二烷基次膦酸,可以应用于金属离子或稀土的萃取,不需要进行额外的提纯。应用本发明方法既可以制备高含磷量的二甲基次膦酸盐,也可以制备含有长链或支链烷烃的二烷基次膦酸,应用在金属离子萃取剂方面,具有非常强的使用价值。
附图说明
图1是乙基次膦酸铝的SEM图。
具体实施方式
以下结合具体实施例和附图对本发明做进一步的说明。应理解,以下实施例仅用于说明本发明而非用于限定本发明的范围。
实施例1二甲基次膦酸甲酯的制备
在装有冷凝回流装置、滴加装置和通入氮气的1L反应釜中,加入还原剂苯基硅烷2mol,在5℃下滴加3mol甲基膦酸二甲酯,滴加完毕后逐步升温到90℃,保持约1小时,然后在氮气氛下减蒸馏得到产物甲基亚膦酸二甲酯,产率约为92%(wt)。然后在装有冷凝回流装置、滴加装置和通入氮气的反应釜中,加入化合物甲基亚膦酸二甲酯,滴加卤代烃碘甲烷,并升温到120℃,回流反应4小时后减压蒸馏得到产物二甲基次磷酸甲酯,产率约为95%(wt)。
实施例2二异辛基次膦酸膦酸的制备
在装有冷凝回流装置、滴加装置和通入氮气的1L反应釜中,加入还原剂三氯硅烷3mol 和三乙胺3mol,在25℃下滴加2mol异辛基膦酸二异辛酯(此化合物可以在市场上购买或自制,自制方法为:由亚膦酸三异辛酯经过Arbuzov重排得到),滴加完毕后逐步升温到100℃,保持约2小时,然后在氮气氛下减蒸馏得到产物异辛基亚膦酸二异辛酯,产率约为87%(wt)。然后在装有冷凝回流装置、滴加装置和通入氮气的反应釜中,加入化合物异辛基亚膦酸二异辛酯,滴加5克溴代异辛烷烃,并升温到150℃,回流反应8小时后减压蒸馏得到产物二异辛基次磷酸异辛酯,产率约为93%(wt)。最后将二异辛基次膦酸异辛酯加入到稀硫酸中加热至100℃进行水解,6小时后水解完全,得到二异辛基次膦酸。
实施例3乙基亚膦酸二乙酯的制备
在装有冷凝回流装置、滴加装置和通入氮气的1L反应釜中,加入还原剂六氯硅烷3mol,在10℃下滴加3mol乙基膦酸二乙酯,滴加完毕后逐步升温到80℃,保持约3小时,然后在氮气氛下减蒸馏得到产物乙基亚膦酸二乙酯,产率约为84%(wt)。然后在装有冷凝回流装置、滴加装置和通入氮气的反应釜中,加入乙基亚膦酸二乙酯,升温至130℃,滴加入4克溴乙烷作为催化剂,反应10小时,得到二乙基次膦酸乙酯,产率约为92%(wt)。最后将二乙基次膦酸乙酯加入到适量稀硫酸中加热至101℃进行水解,7小时后水解完全,调节pH值至6.5,然后加入等当量的是硫酸铝,在加压的条件120℃下进行水热反应4H然后过滤,水洗,干燥即得具有棒状的二乙基次膦酸铝(SEM图如图1所示)。
实施例4乙基亚膦酸二乙酯的制备
在装有冷凝回流装置、滴加装置和通入氮气的1L反应釜中,加入还原剂六氯硅烷3mol、 3mol三乙胺和400mL苯,在10℃下滴加3mol乙基膦酸二乙酯,滴加完毕后逐步升温到80℃,保持约3小时,然后在氮气氛下减蒸馏得到产物乙基亚膦酸二乙酯,产率约为87%(wt)。
实施例5乙基亚膦酸二乙酯的制备
在装有冷凝回流装置、滴加装置和通入氮气的1L反应釜中,加入还原剂甲氧基三氢硅烷 1mol、3mol三乙胺和400mL苯,在10℃下滴加3mol乙基膦酸二乙酯,滴加完毕后逐步升温到80℃,保持约3小时,然后在氮气氛下减蒸馏得到产物乙基亚膦酸二乙酯,产率约为89% (wt)。
Claims (7)
2.根据权利要求1所述的方法,其特征在于,所述含硅氢还原剂的氢含量与所述单烷基膦酸二烷基酯的摩尔比可设为1~2∶1。
3.根据权利要求1所述的方法,其特征在于,所述有机胺类催化剂和所述还原剂的摩尔比为0.9~1.1∶1。
4.根据权利要求1或3所述的方法,其特征在于,具体操作为:在惰性气体保护,0~30℃条件下,向所述还原剂和所述有机胺类催化剂的混合物中滴加单烷基膦酸二烷基酯,滴加完毕后逐步升温至70~120℃至反应完毕,然后减压蒸馏得到单烷基亚膦酸二烷基酯。
6.根据权利要求5所述的方法,其特征在于,步骤(b)中,所述卤代烃为含碳原子数为1~10的卤代烃,所述单烷基亚磷酸二烷基酯与卤代烃的摩尔比为1000∶10~40;所述异构化反应的反应温度为60~250℃,反应时间为0.5~16小时。
7.一种二烷基次膦酸烷基酯金属盐的制备方法,其特征在于,其包括步骤:
(A)通过权利要求5-6任一项所述的方法制备二烷基次膦酸烷基酯;
(B)步骤(A)制得的二烷基次膦酸烷基酯在酸性条件下水解后与金属盐溶液进行水热反应,得到二烷基次膦酸金属盐;金属盐的金属元素为Ce、La、Al、Zn、Ni、Ca、Mg或Fe。
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