WO2002076992A1 - Preparation d'une solution stable de carboxylate de terre rare - Google Patents
Preparation d'une solution stable de carboxylate de terre rare Download PDFInfo
- Publication number
- WO2002076992A1 WO2002076992A1 PCT/FR2002/000993 FR0200993W WO02076992A1 WO 2002076992 A1 WO2002076992 A1 WO 2002076992A1 FR 0200993 W FR0200993 W FR 0200993W WO 02076992 A1 WO02076992 A1 WO 02076992A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solution
- rare earth
- acid
- added
- additive
- Prior art date
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 30
- -1 rare-earth carboxylate Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 6
- 150000002009 diols Chemical class 0.000 claims abstract description 5
- 150000001408 amides Chemical class 0.000 claims abstract description 4
- 150000001414 amino alcohols Chemical class 0.000 claims abstract description 4
- 150000004072 triols Chemical class 0.000 claims abstract description 4
- 150000001734 carboxylic acid salts Chemical class 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 15
- 238000010533 azeotropic distillation Methods 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 5
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium 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
- 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
- 238000004821 distillation Methods 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims 1
- 230000003019 stabilising effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 67
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000007942 carboxylates Chemical class 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012045 crude solution Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CASCCINXYVTVRI-UHFFFAOYSA-M sodium;7,7-dimethyloctanoate Chemical compound [Na+].CC(C)(C)CCCCCC([O-])=O CASCCINXYVTVRI-UHFFFAOYSA-M 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004146 Propane-1,2-diol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
Definitions
- the present invention relates to a process for the preparation of a stable solution of rare earth carboxylate.
- catalysts based on rare earths are used in the polymerization processes of olefins for example for the polymerization of butadiene. These catalysts are prepared from solutions of rare earth carboxylate in an organic solvent. These solutions can have a certain instability, especially those at high concentration. After a few days or weeks of storage, a precipitate or cloudiness may appear in the solutions as well as an increase in viscosity.
- the object of the present invention is to increase the stability of rare earth carboxylate solutions.
- the process for the preparation of a stable solution of rare earth carboxylate according to the invention is of the type in which a carboxylic acid or a salt thereof is reacted with a rare earth compound in the presence of a solvent, whereby a solution of a rare earth carboxylate is obtained in said solvent, and it is characterized in that, in order to stabilize said solution thus obtained, at least one stabilizing additive chosen from the group consisting is added thereto by carboxylic acids, diols or triols, amides and amino alcohols, and having a number of carbon atoms of at most 4.
- rare earth in the present description the elements of the group consisting of scandium, ytt ⁇ um and the elements of the periodic classification of atomic number included inclusively between 57 and 71.
- the present invention applies very particularly to solutions for which the rare earth is neodymium, praseodymium, lanthanum, gadolinium, samarium or cerium.
- the carboxylates are prepared by reacting a rare earth compound with a carboxylic acid or a salt thereof according to known methods.
- the carboxylic acid used can in particular be an aliphatic, cycloaliphatic or aromatic acid, saturated or unsaturated, with a linear or branched chain.
- acids having at least 6 carbon atoms are used, more particularly those in Ce to C32 and even more particularly those in Ce to de.
- isopentanoic acid hexanoic acid, 2-ethyl hexanoic acid, 2-ethyl butyric acid, nonanoic acid, isononanoic acid, acid decanoic, octanoic acid, isooctanoic acid, neodecanoic acid, undecylenic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid and naphthenic acids .
- neodecanoic acid mixtures of branched carboxylic acids generally having approximately 10 carbon atoms and an acid number of approximately 310 to approximately 325 mg KOH / g sold by Shell under the brand “Versatic 10" (generally called versatic acid) or by Exxon under the brand name "Neodecanoic acid”.
- the carboxylate can be prepared by reacting a carboxylic acid of the above type with a rare earth oxide in an organic solvent.
- This solvent can be chosen from alkanes, cyclanes and aromatic solvents and their mixtures. Preferably, this solvent is chosen from those which can form an azeotrope with water.
- alkanes and cyclanes mention may be made more particularly of hexane, cyclohexane, pentane, cyclopentane, heptane and their derivatives and isomers such as methyl-pentane, methyl-cyclopentane or else 2,3 -diméthylbutane. It is also possible to use the halogenated derivatives of these alkanes and cyclanes such as dichloromethane or chloroform.
- aromatic solvents mention may be made more particularly of benzene, ethylbenzene, toluene and xylene. Halogen derivatives of aromatic solvents can also be used, such as chlorobenzene.
- the carboxylate can also be prepared by reacting a salt of a carboxylic acid of the type described above with a rare earth salt.
- the salt of the carboxylic acid can be a salt of an alkali, an alkaline earth or of ammonium and it is obtained firstly by reaction in water of the acid with the corresponding base.
- the pH of the solution thus obtained can be between 7.5 and 12 for example, more particularly between 9 and 10.
- the solution of the salt of the carboxylic acid is reacted with the rare earth salt.
- the rare earth salt can in particular be a nitrate. This reaction is carried out in an organic solvent and an organic phase is thus obtained containing the rare earth carboxylate and an aqueous phase.
- the aqueous phase is separated from the organic phase by any known means and the rare earth carboxylate solution is thus obtained.
- This solution can be washed one or more times with water.
- the water content of the organic solution can be adjusted by azeotropic distillation, to obtain for example a water content of at most 1000 ppm by weight.
- the free acidity of the solution can be variable, for example it can be between 0.5% and 2% by weight (expressed as% by weight of acid). It can also be adjusted according to the use for which this solution is intended.
- the invention applies in particular to concentrated solutions, that is to say having a concentration which can be between 6% and 13% by weight of rare earth metal.
- additives can first of all be chosen from carboxylic acids, more particularly from saturated aliphatic acids. Propanoic acid can be used very particularly. These additives can also be chosen from diols or triols. As an additive of this type, there may be mentioned propane 1-2 diol as well as propane triol.
- Formamide HCO-NH 2
- additives can finally be chosen from amino alcohols such as, for example, monoethanolamine or diethanolamine.
- the additives are added to the rare earth carboxylate solution, preferably after washing thereof.
- the addition of the stabilizer can be done either before or after this distillation.
- the amount of additive added can be between 0.1% and 2% by weight of additive relative to the carboxylate solution and more particularly between 0.5% and 1.5%.
- the carboxylate solution can be used in the preparation of catalytic compounds intended for the polymerization or the copolymerization of unsaturated compounds, in particular of dienes.
- unsaturated compounds mention may be made of ethylene, butadiene 1-3, isoprene, trans-pentadiene 1-3; trans-hexadiene 1-3, trans-methyl-2 pentadiene 1 -3; trans-methyl-3 pentadiene 1-3, dimethyl 2-3 butadiene 1-3.
- a sodium neodecanoate solution with a pH between 9.0 and 10.0 (25 ° C) is prepared by mixing 62.3 g of neodecanoic acid , 40g of water and about 28.8g of aqueous sodium hydroxide solution at 50% by weight of sodium hydroxide.
- the organic phase is washed 3 times with 150 ml of water. 199 g of crude solution of neodymium neodecanoate are obtained with 1.0% free acidity (expressed as% by weight of neodecanoic acid) and 1.3% water. The yield is greater than 99%.
- neodecanoic acid is added to adjust the free acidity of the solution to approximately 3% (expressed as a percentage by weight of neodecanoic acid).
- the solution is only stable for a few hours. Indeed, the solution becomes cloudy, then large precipitates form very quickly, a sharp increase in viscosity is also observed.
- Example 1 The procedure described in Example 1 is repeated identically, except that before the azeotropic distillation, 1.8 g of formamide (0.9% by weight of the solution) are added.
- Neodecanoic acid is also added in order to adjust the free acidity of the solution to approximately 3% (expressed as a percentage by weight of neodecanoic acid).
- the viscosity of the solution is less than 30 cPs. This solution is stable for at least 12 months. Its viscosity remains constant and the formation of solid deposits is not observed.
- Example 1 The procedure described in Example 1 is repeated identically, except that before the azeotropic distillation, 1.8 g of propane-1, 2-diol (0.9% by weight of the solution) are added. Neodecanoic acid is also added in order to adjust the free acidity of the solution to approximately 3% (expressed as a percentage by weight of neodecanoic acid).
- Example 1 The procedure described in Example 1 is repeated identically, except that before the azeotropic distillation, 1.8 g of glycerol (0.9% by weight of the solution) are added. We also add neodecanoic acid to to adjust the free acidity of the solution to approximately 3% (expressed as a percentage by weight of neodecanoic acid).
- the viscosity of the solution is less than 30 cPs. This solution is stable for at least 12 months. Its viscosity remains constant and the formation of solid deposits is not observed.
- Example 2 The procedure described in Example 1 is repeated identically, except that before the azeotropic distillation, 1.2 g of propanoic acid (0.6% by weight of the solution) are added. Neodecanoic acid is also added in order to adjust the free acidity of the solution to around 3%
- the solution is only stable for a few hours. Indeed, the solution becomes very viscous and then solidifies.
- Example 6 The procedure described in Example 6 is repeated identically, except that before the azeotropic distillation, propanoic acid is added so that the product contains 1.1% by weight. Toluene is also added in order to adjust the neodymium concentration to approximately 10% and neodecanoic acid in order to adjust the free acidity of the solution to approximately 4% (expressed as a percentage by weight of neodecanoic acid).
- the viscosity of the solution is less than 30 cPs. This solution is stable for at least 6 months. Its viscosity remains constant and the formation of solid deposits is not observed.
- Example 6 The procedure described in Example 6 is repeated identically, except that before the azeotropic distillation, propanoic acid is added so that the product contains 0.6% by weight. Toluene is also added in order to adjust the neodymium concentration to approximately 6.6% and neodecanoic acid in order to adjust the free acidity of the solution to approximately 2.5% (expressed as a percentage by weight of neodecanoic acid).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0104013A FR2822469B1 (fr) | 2001-03-26 | 2001-03-26 | Procede de preparation d'une solution stable de carboxylate de terre rare |
FR0104013 | 2001-03-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002076992A1 true WO2002076992A1 (fr) | 2002-10-03 |
Family
ID=8861518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/000993 WO2002076992A1 (fr) | 2001-03-26 | 2002-03-21 | Preparation d'une solution stable de carboxylate de terre rare |
Country Status (2)
Country | Link |
---|---|
FR (1) | FR2822469B1 (fr) |
WO (1) | WO2002076992A1 (fr) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5731381A (en) * | 1996-11-01 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Termination of gas phase polymerizations of conjugated dienes, vinyl-substituted aromatic compounds and mixtures thereof |
US6111082A (en) * | 1998-04-17 | 2000-08-29 | Rhodia Rare Earths Inc. | Stable concentrated rare earth carboxylate liquids |
-
2001
- 2001-03-26 FR FR0104013A patent/FR2822469B1/fr not_active Expired - Fee Related
-
2002
- 2002-03-21 WO PCT/FR2002/000993 patent/WO2002076992A1/fr not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5731381A (en) * | 1996-11-01 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Termination of gas phase polymerizations of conjugated dienes, vinyl-substituted aromatic compounds and mixtures thereof |
US6111082A (en) * | 1998-04-17 | 2000-08-29 | Rhodia Rare Earths Inc. | Stable concentrated rare earth carboxylate liquids |
Also Published As
Publication number | Publication date |
---|---|
FR2822469B1 (fr) | 2004-07-30 |
FR2822469A1 (fr) | 2002-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0112219B1 (fr) | Compositions organométalliques mixtes comprenant des éléments du groupe des lanthanides et du manganèse ou des éléments du groupe du fer, procédé de préparation et applications desdites compositions comme additifs pour combustibles ou carburants | |
WO2013017786A1 (fr) | Procede de preparation d'amino-acides ou esters comprenant une etape de metathese | |
EP2099739A1 (fr) | Procede de synthese d'esters (meth)acryliques catalyse par un titanate de polyol. | |
EP0668257B1 (fr) | Catalyseur et procédé d'hydrogénation du benzène utilisant ledit catalyseur | |
EP1633700B1 (fr) | Procede de preparation de dinitriles | |
CA1303014C (fr) | Systemes catalytiques perfectionnes a duree de vie et de conservation prolongees pour la metathese d'olefines | |
EP1362029A1 (fr) | Procede de preparation d'un peroxyester | |
EP0331556A2 (fr) | Nouveau procédé de préparation de l'acide éthylène-diamine-N-N'-bis (ortho-hydroxyphénylacétique) et de dérivés de celui-ci | |
CA1067911A (fr) | Procede de preparation de monomeres acryliques destines a la fabrication de floculants cationiques | |
WO2002076992A1 (fr) | Preparation d'une solution stable de carboxylate de terre rare | |
EP1976831B1 (fr) | Compositions a base de (meth)acrylates d'alkylimidazolidone | |
EP0449693B1 (fr) | Catalyseur et procédé pour la synthèse d'esters carboxyliques saturés | |
EP0663238B1 (fr) | Procédé de préparation d'un catalyseur d'hydrogénation soluble en phase liquide organique | |
EP0095431B1 (fr) | Procédé de préparation d'esters par carbonylation de composés monooléfiniques | |
CA2087665C (fr) | Procede d'activation de support a base de chlorure de magnesium entrant dans la fabrication de la composante catalytique de polymerisation de l'ethylene | |
EP1226135B1 (fr) | Procede de preparation d'un derive du thiophene | |
EP0323332B1 (fr) | Perfectionnement à la production d'alcools tertiaires et secondaires par l'action d'un composé organique halogéné et du manganèse sur un composé porteur d'un groupe carbonyle | |
WO2006082200A1 (fr) | Procédé direct de préparation d'amino-alcools ou d'alcools utilisant le borohydrure d'halogénozinc | |
CA2449121A1 (fr) | Procede d'hemihydrogenation de dinitriles en aminonitriles | |
EP1250312B1 (fr) | Procede d'hydrocyanation de composes organiques insatures | |
FR2816945A1 (fr) | Compose d'addition d'un acide carboxylique et d'un halogenocarboxylate de terre rare ou de gallium, son procede de preparation et son utilisation | |
FR2814737A1 (fr) | Compose anhydre a base d'un halogenure de terre rare ou de gallium, son procede de preparation et son utilisation comme catalyseur | |
EP1172385A1 (fr) | Procédé pour la polymérisation des alpha-oléfines | |
BE648455A (fr) | ||
EP0325072A1 (fr) | Perfectionnement à la préparation d'alcools tertiaires et secondaires par l'action d'un composé organo-manganeux sur un composé porteur de groupe carbonyle |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
122 | Ep: pct application non-entry in european phase | ||
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |