CN101778853A - 稀土有机磷酸盐在有机溶剂中的溶液的制备方法 - Google Patents
稀土有机磷酸盐在有机溶剂中的溶液的制备方法 Download PDFInfo
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- CN101778853A CN101778853A CN200880102348A CN200880102348A CN101778853A CN 101778853 A CN101778853 A CN 101778853A CN 200880102348 A CN200880102348 A CN 200880102348A CN 200880102348 A CN200880102348 A CN 200880102348A CN 101778853 A CN101778853 A CN 101778853A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 38
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000003960 organic solvent Substances 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- -1 rare-earth compound Chemical class 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 4
- 235000019253 formic acid Nutrition 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- 229910052779 Neodymium Inorganic materials 0.000 claims description 22
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical group [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 3
- 235000011054 acetic acid Nutrition 0.000 abstract 1
- 150000001243 acetic acids Chemical class 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 150000004674 formic acids Chemical class 0.000 abstract 1
- 235000011167 hydrochloric acid Nutrition 0.000 abstract 1
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 150000004672 propanoic acids Chemical class 0.000 abstract 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 62
- 239000000243 solution Substances 0.000 description 42
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 31
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 235000011007 phosphoric acid Nutrition 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000005352 clarification Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- WPBLFRYFCLYQRD-UHFFFAOYSA-N bis(2-ethylhexyl) hydrogen phosphate;neodymium Chemical compound [Nd].CCCCC(CC)COP(O)(=O)OCC(CC)CCCC WPBLFRYFCLYQRD-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl 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
- C07F9/30—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)]
- C07F9/304—Aromatic acids (P-C aromatic linkage)
-
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- 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)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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- 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)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3834—Aromatic acids (P-C aromatic linkage)
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- 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
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- 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
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
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- 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
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- 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
- C07F9/4084—Esters with hydroxyaryl compounds
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- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
本发明的稀土有机磷酸盐在有机溶剂中的溶液的制备方法在于,在选自水、硝酸、盐酸、乙酸、甲酸和丙酸以及这些酸的稀土盐的促进剂存在下,在该溶剂中使选自稀土的氧化物、氢氧化物、碳酸盐和羟基碳酸盐的稀土化合物与有机含磷酸反应。促进剂的使用使得可以简化该方法、降低反应时间并获得残余固体含量可以低的溶液。
Description
技术领域
本发明涉及稀土有机磷酸盐在有机溶剂中的溶液的制备方法。
背景技术
稀土有机磷酸盐的溶液尤其用作二烯聚合催化剂的制备原料。
通过侵蚀稀土的无机盐制备稀土有机磷酸盐的溶液通常是困难的。因为,这要么需要大量过量的有机磷酸以完全溶解稀土的无机盐,造成产品中存在残余酸,其存在对于应用是不期望的;要么需要很长的、与工业应用不相容的反应时间。此外,如此得到的溶液通常具有高粘度(>15000cPs),这使得几乎不可能进行产物中存在的残余固体的任何过滤操作。
因此,重要的是提出这样一种方法,该方法使得可以在工业条件下获得具有低含量的固体形式的稀土无机盐并且还具有可接受的残余酸度的溶液。
发明内容
本发明的目的因而是提供这样的方法。
为此,用于制备稀土有机磷酸盐在有机溶剂中的溶液的本发明方法是这样的类型:其中在所述溶剂存在下,使选自稀土的氧化物、氢氧化物、碳酸盐和羟基碳酸盐的稀土化合物与有机含磷酸反应,并且其特征在于该反应在选自水、硝酸、盐酸、乙酸、甲酸和丙酸以及这些酸的稀土盐的促进剂存在下进行。
根据本发明使用促进剂使得尤其可以简化该方法、降低反应时间并获得残余固体含量可以低的溶液。
通过阅读以下说明以及各个具体但非限制性的、用于说明的实施例,本发明的其它特征、细节和优点将更加完整地呈现。
稀土指的是钇和周期表中原子序数在57和71之间(含端点)的元素构成的组中的元素。
本发明方法特别适用于选自钕、镧、镨、钐和铈的稀土的有机磷酸盐的制备。
本发明方法涉及稀土化合物与有机含磷酸的反应。
作为稀土化合物,使用以上提及的那些。其中,优选使用氧化物。
有机含磷酸可以更具体地选自磷酸的单酯或二酯、膦酸和次膦酸。
磷酸的单酯或二酯可以分别对应于式(RO)PO(OH)2和(RO)(R’O)PO(OH),其中R和R’相同或不同,代表烷基或芳基。
作为例子,R和R’可以是正丁基、异丁基、戊烷基(pentyle)、戊基(amyle)、异戊基、2,2-二甲基己基、2-乙基己基、1-乙基己基、辛基、壬基、癸基、2,2-二甲基辛基、甲苯基、壬基苯基。
有机含磷酸也可以选自通式(RO)R’P(O)(OH)和RP(O)(OH)2的膦酸,其中R和R’相同或不同,代表烷基或芳基。作为例子,R和R’可以是正丁基、异丁基、戊烷基、戊基、异戊基、2,2-二甲基己基、2-乙基己基、1-乙基己基、辛基、壬基、癸基、2,2-二甲基辛基、甲苯基、壬基苯基。
有机含磷酸还可以选自通式R(R’)P(O)OH和R(H)P(O)OH的次膦酸,其中R和R’相同或不同,代表烷基或芳基。作为例子,R和R’可以是正丁基、异丁基、戊烷基、戊基、异戊基、2,2-二甲基己基、2-乙基己基、1-乙基己基、辛基、壬基、癸基、2,2-二甲基辛基、甲苯基、壬基苯基。
当然,可以使用上述有机含磷酸的混合物。
本发明的基本特征在于稀土化合物和有机含磷酸之间的反应在以上所给类型的促进剂的存在下进行。
该反应通常通过将稀土化合物、有机含磷酸和促进剂在有机溶剂中混合而进行。
使用的有机溶剂通常是烃溶剂,更具体是脂族、脂环族甚至芳香族溶剂。
该溶剂可以选自己烷、环己烷、甲基环己烷、庚烷、甲基戊烷、甲基环戊烷、戊烷、3-甲基戊烷、2-甲基戊烷、2,3-二甲基戊烷及它们的异构体、甲苯和二甲苯及其混合物。优选己烷、环己烷、甲基环己烷、它们的异构体和它们的混合物。可商购的烃溶剂为Exxon提供的己烷Exxon提供的庚烷Exxon提供的ISOPAR-和ISOPAR-Exxon提供的SOLVENTPhilips提供的MINERAL SPIRITSBASF提供的环己烷以及Total Fluides提供的甲基环己烷。
下面将具体说明使用的促进剂的量。可以注意到,通常,最小量是从该量开始促进剂可以起作用的量,即使得反应收率可接受的量。当反应结束时的反应介质不再呈现混浊性时,该收率是可接受的。因而,该量对于本领域技术人员是可以容易地确定的。最大量通常不关键,并且可以根据工业约束条件进行确定。下面给出的量仅仅是作为说明性的例子,因此应当理解为处于最小量和最大量之间。
当促进剂是水时,以水/稀土摩尔比表示,使用的水量通常在约1和约500之间,更具体地在1和300之间,再具体地在5和100之间。根据一种优选的实施方案,该比值为至少25,更具体地为至少50,再具体地为至少90,以上所给数值的上限值也可适用此实施方案。
当促进剂是酸时,以酸/稀土摩尔比表示,使用的酸的量通常在约0.005和约0.2之间,更具体地在0.005和0.1之间,再具体地在0.005和0.06之间。
可以注意到,可以使用纯酸或者以浓溶液或稀溶液使用。
如上所述,促进剂可以是稀土的硝酸盐、氯化物、乙酸盐、甲酸盐或丙酸盐。在这种情况下,以盐/稀土摩尔比表示,盐的量通常在约0.005和约0.2之间,更具体地在0.005和0.1之间。
稀土化合物和有机含磷酸在促进剂存在下的反应通常在至少60℃的温度下进行,更具体地在80℃和100℃之间。然而高于100℃的温度是可以的。
该侵蚀的持续时间可以在宽的限度内变化,例如在1和6小时之间,实际上它可以在1和2小时之间。
优选地,该反应在惰性气氛例如氮气下进行,以避免溶液被空气中的氧污染。
在反应结束时,得到稀土有机磷酸盐的溶液。
该溶液可以任选地用水洗涤,以除去残余的酸。该洗涤可以通过将该有机溶液与水混合、搅拌、沉降然后分离水相与有机相来进行。
该溶液也可以任选地进行蒸馏以除去残余的水。这样,可以获得水含量至多500ppm、更具体地至多100ppm的溶液。以水/稀土摩尔比表示,该水含量可以为至多0.2,更具体地为至多0.04。
以有机含磷酸/稀土摩尔比表示,残余酸度可以为至多0.75,更具体地至多0.6,再具体地至多0.4。
在仅有很少量的起始稀土化合物存在于溶液中的情况下,反应的收率高。该溶液实际上具有澄清外观。获得的收率通常为至少95%,可以达到100%的收率。
通过向溶液中加入选自醇、羧酸或磷酸的化合物,可以调整溶液的粘度。作为非限制性的例子,可以列举乙醇、乙二醇、丙二醇、二丙二醇、乙酸、丙酸。
如上所述,通过本发明方法得到的稀土有机磷酸盐溶液可以用于制备二烯如丁二烯和异戊二烯的聚合催化剂。
具体实施方式
现在将给出实施例。
实施例1
在预先用氩气惰性化的反应器中,加入3.03g含有72.4重量%的钕的氧化钕、17.39g二(2-乙基己基)磷酸(DEHPA)、80g甲基环己烷(MCH)和25.9g水。将该混合物搅拌并升温至95℃,直到固体完全消失,即在该例中为1小时。将该混合物冷却并沉降。因而从该混合物中除去22.5g水。然后用Dean Stark型装置蒸馏水/MCH恒沸物。从而得到二(2-乙基己基)磷酸钕在MCH中的溶液84g。
该溶液具有如下特征:澄清外观,溶液中钕的含量为2.65%,用DEHPA重量百分比表示的残余游离酸度为2.2%,水含量为382ppm。在该例中,摩尔比为DEHPA/Nd=0.37,水/Nd=0.11。侵蚀收率为100%。
实施例2
在预先用氩气惰性化的反应器中,加入3.03g含有72.4重量%的钕的氧化钕、17.39g二(2-乙基己基)磷酸(DEHPA)、80g甲基环己烷(MCH)和1.8ml 0.5mo l/l的硝酸。该硝酸的量相当于相对于钕的0.06摩尔当量的HNO3。将该混合物搅拌并升温至80℃,直到不再能用视觉分辨出固体的存在,即在该例中为3小时。将该混合物冷却。相继用20g水洗涤3次以除去残余的硝酸。每次洗涤包含30分钟的搅拌阶段和随后的同样30分钟的沉降阶段,除了最后一次沉降持续12小时。因而相继回收18g、18g然后23g水。然后用Dean Stark型装置蒸馏水/MCH恒沸物。从而得到二(2-乙基己基)磷酸钕在MCH中的溶液100g。
该溶液具有如下特征:澄清外观,溶液中钕的含量为2.15%,用DEHPA重量百分比表示的残余游离酸度为3.0%,水含量为72ppm。在该例中,摩尔比为DEHPA/Nd=0.62,水/Nd=0.03。侵蚀收率为98%。
实施例3
在预先用氩气惰性化的反应器中,加入3.03g含有72.4重量%的钕的氧化钕、17.39g二(2-乙基己基)磷酸(DEHPA)、80g甲基环己烷(MCH)和0.9ml 1mol/l的盐酸。该盐酸的量相当于相对于钕的0.06摩尔当量的HCl。将该混合物搅拌并升温至80℃,持续3小时。将该混合物冷却。相继用20g水洗涤3次以除去残余的盐酸。每次洗涤包含30分钟的搅拌阶段和随后的同样30分钟的沉降阶段,除了最后一次沉降持续12小时。然后用Dean Stark型装置蒸馏水/MCH恒沸物。从而得到二(2-乙基己基)磷酸钕在MCH中的澄清溶液。
该溶液具有如下特征:澄清外观,溶液中钕的含量为2.25%,用DEHPA重量百分比表示的残余游离酸度为2.85%,水含量为249ppm。在该例中,摩尔比为DEHPA/Nd=0.56,水/Nd=0.09。侵蚀收率为100%。
实施例4
在预先用氩气惰性化的反应器中,加入2.88g含有72.4重量%的钕的氧化钕、0.53g含有24.4重量%的钕的硝酸钕水溶液、17.39g二(2-乙基己基)磷酸(DEHPA)和80g甲基环己烷(MCH)。将该混合物搅拌并升温至80℃,直到固体完全消失,即在该例中为1小时。将该混合物冷却。相继用20g水洗涤3次以除去无机残余物。每次洗涤包含30分钟的搅拌阶段和随后的同样30分钟的沉降阶段,除了最后一次沉降持续12小时。然后用Dean Stark型装置蒸馏水/MCH恒沸物。从而得到二(2-乙基己基)磷酸钕在MCH中的澄清溶液。
该溶液具有如下特征:澄清外观,溶液中钕的含量为2.1%,用DEHPA重量百分比表示的残余游离酸度为3.2%,水含量为369ppm。在该例中,摩尔比为DEHPA/Nd=0.68,水/Nd=0.14。侵蚀收率为99%。
实施例5
在预先用氩气惰性化的反应器中,加入2.88g含有72.4重量%的钕的氧化钕、0.58g含有22.2重量%的钕的氯化钕水溶液、17.39g二(2-乙基己基)磷酸(DEHPA)和80g甲基环己烷(MCH)。将该混合物搅拌并升温至80℃,持续5小时。将该混合物冷却。相继用20g水洗涤3次以除去无机残余物。每次洗涤包含30分钟的搅拌阶段和随后的同样30分钟的沉降阶段,除了最后一次沉降持续12小时。然后用Dean Stark型装置蒸馏水/MCH恒沸物。从而得到二(2-乙基己基)磷酸钕在MCH中的澄清溶液。
该溶液具有如下特征:澄清外观,溶液中钕的含量为2.05%,用DEHPA重量百分比表示的残余游离酸度为3.3%,水含量为406ppm。在该例中,摩尔比为DEHPA/Nd=0.72,水/Nd=0.16。侵蚀收率为98%。
实施例6
在预先用氩气惰性化的反应器中,加入3.03g含有72.4重量%的钕的氧化钕、16.15g二(2-乙基己基)磷酸(DEHPA)、80g甲基环己烷(MCH)和1.8ml 0.5mol/l的硝酸。该硝酸的量相当于相对于钕的0.06摩尔当量的HNO3。将该混合物搅拌并升温至80℃,直到不再能用视觉分辨出固体的存在,即在该例中为3小时。将该混合物冷却。相继用20g水洗涤3次以除去无机残余物。每次洗涤包含30分钟的搅拌阶段和随后的同样30分钟的沉降阶段。因而回收了20g、19.5g然后19.5g。然后用Dean Stark型装置蒸馏水/MCH恒沸物。从而得到二(2-乙基己基)磷酸钕在MCH中的澄清外观的溶液。该溶液具有如下特征:溶液中钕的含量为2.05%,用DEHPA重量百分比表示的残余游离酸度为1.59%,水含量为209ppm。在该例中,摩尔比为DEHPA/Nd=0.34,水/Nd=0.08。侵蚀收率为95%。
实施例7
在预先用氩气惰性化的反应器中,加入3.03g含有72.4重量%的钕的氧化钕、17.39g二(2-乙基己基)磷酸(DEHPA)、80g甲基环己烷(MCH)和0.054g 99.8%的乙酸。该乙酸的量相当于相对于钕的0.06摩尔当量的CH3COOH。将该混合物搅拌并升温至80℃,直到不再能用视觉分辨出固体的存在,即在该例中为1小时。将该混合物冷却。相继用20g水洗涤3次以除去无机残余物。每次洗涤包含30分钟的搅拌阶段和随后的同样30分钟的沉降阶段,除了最后一次沉降持续一夜。因而回收了16g、24.2g然后17.1g。然后用Dean Stark型装置蒸馏水/MCH恒沸物。从而得到二(2-乙基己基)磷酸钕在MCH中的澄清外观的溶液。该溶液具有如下特征:溶液中钕的含量为2.3%,用DEHPA重量百分比表示的残余游离酸度为2.65%,水含量为77ppm。在该例中,摩尔比为DEHPA/Nd=0.51,水/Nd=0.026。侵蚀收率为100%。
Claims (6)
1.稀土有机磷酸盐在有机溶剂中的溶液的制备方法,其中在所述溶剂存在下,使选自稀土的氧化物、氢氧化物、碳酸盐和羟基碳酸盐的稀土化合物与有机含磷酸反应,其特征在于该反应在选自水、硝酸、盐酸、乙酸、甲酸和丙酸以及这些酸的稀土盐的促进剂存在下进行。
2.根据权利要求1的方法,其特征在于使用选自磷酸的单酯或二酯、膦酸和次膦酸的有机含磷酸。
3.根据权利要求1或2的方法,其特征在于使用烃溶剂,更具体是脂族或脂环族溶剂。
4.根据以上权利要求之一的方法,其特征在于制备选自钕、镧、镨、钐和铈的稀土的有机磷酸盐。
5.根据以上权利要求之一的方法,其特征在于在至少60℃的温度下进行稀土化合物与有机含磷酸的反应。
6.根据以上权利要求之一的方法,其特征在于使用氧化物作为与有机含磷酸反应的稀土化合物。
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FR2945803B1 (fr) * | 2009-05-19 | 2011-07-29 | Michelin Soc Tech | Procede de synthese d'un organophosphate de terre rare et son utilisation pour la preparation d'un systeme calalytique "preforme" |
RU2534012C1 (ru) * | 2013-07-17 | 2014-11-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский химико-технологический университет имени Д.И. Менделеева" | Способ получения лантаноидной соли ди-(2-этилгексил)фосфорной кислоты |
KR101656126B1 (ko) * | 2013-09-30 | 2016-09-08 | 주식회사 엘지화학 | 신규한 네오디뮴 화합물 및 이를 포함하는 디엔 중합용 촉매 |
RU2540083C1 (ru) * | 2013-11-13 | 2015-01-27 | Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" (ФГУП "НИИСК") | Способ получения раствора диалкилфосфата гадолиния-компонента катализаторов (со) полимеризации сопряженных диенов |
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US3702233A (en) * | 1971-08-11 | 1972-11-07 | Gte Sylvania Inc | Yttrium purification |
US4449134A (en) * | 1982-04-19 | 1984-05-15 | Xerox Corporation | Composite ink jet drivers |
US6197713B1 (en) * | 1997-12-19 | 2001-03-06 | Bridgestone Corporation | Use of Lewis acids for the breakdown of gelatinous rare earth compounds in hydrocarbon solutions |
JP3010039B1 (ja) * | 1998-08-18 | 2000-02-14 | 奇美実業股▲分▼有限公司 | ランタニド系金属カルボン酸塩の製造方法、及びそのジエン系単量体の重合用触媒としての使用 |
DE60008515T2 (de) * | 1999-04-26 | 2004-12-16 | Rhodia Electronics And Catalysis Inc., Shelton | Stabile lösungen von seltenenerden tris(organophosphor-derivaten) |
US6767927B1 (en) * | 1999-04-26 | 2004-07-27 | Rhodia Rare Earths Inc. | Synthesis of stable solutions of rare earth tris (organophosphate) in hydrocarbon solvents |
WO2003097708A1 (fr) * | 2002-05-16 | 2003-11-27 | Societe De Technologie Michelin | Systeme catalytique pour preparer des polybutadienes et procede de preparation |
US7906631B2 (en) * | 2007-10-15 | 2011-03-15 | Bridgestone Corporation | Method of producing rare earth salt of dialkyl phosphate or dioleyl phosphate |
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2007
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- 2008-07-08 RU RU2010108164/04A patent/RU2441013C2/ru active
- 2008-07-08 US US12/671,323 patent/US8404821B2/en active Active
- 2008-07-08 EP EP08774893.5A patent/EP2178887B1/fr active Active
- 2008-07-08 JP JP2010519403A patent/JP5394379B2/ja active Active
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- 2008-07-08 CN CN2008801023484A patent/CN101778853B/zh active Active
- 2008-07-08 KR KR1020107002659A patent/KR101239493B1/ko active IP Right Grant
- 2008-07-08 PL PL08774893T patent/PL2178887T3/pl unknown
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CN116023533A (zh) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | 膦酸酯钕溶液及其制备方法和应用 |
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BRPI0814019A2 (pt) | 2015-02-03 |
PL2178887T3 (pl) | 2015-11-30 |
KR20100031761A (ko) | 2010-03-24 |
RU2010108164A (ru) | 2011-09-20 |
RU2441013C2 (ru) | 2012-01-27 |
US20100280264A1 (en) | 2010-11-04 |
JP2010535729A (ja) | 2010-11-25 |
WO2009019100A1 (fr) | 2009-02-12 |
ZA201000825B (en) | 2010-10-27 |
EP2178887B1 (fr) | 2015-06-03 |
CN103145756A (zh) | 2013-06-12 |
BRPI0814019B1 (pt) | 2017-06-13 |
KR101239493B1 (ko) | 2013-03-06 |
EP2178887A1 (fr) | 2010-04-28 |
FR2919871B1 (fr) | 2010-04-23 |
CN103145756B (zh) | 2015-05-27 |
JP5394379B2 (ja) | 2014-01-22 |
US8404821B2 (en) | 2013-03-26 |
CN101778853B (zh) | 2013-03-06 |
FR2919871A1 (fr) | 2009-02-13 |
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