EP1373142A1 - Composes d'addition de terre rare ou de gallium, procedes pour leur preparation et leur utilisation comme catalyseur - Google Patents

Composes d'addition de terre rare ou de gallium, procedes pour leur preparation et leur utilisation comme catalyseur

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Publication number
EP1373142A1
EP1373142A1 EP01972229A EP01972229A EP1373142A1 EP 1373142 A1 EP1373142 A1 EP 1373142A1 EP 01972229 A EP01972229 A EP 01972229A EP 01972229 A EP01972229 A EP 01972229A EP 1373142 A1 EP1373142 A1 EP 1373142A1
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EP
European Patent Office
Prior art keywords
compound
rare earth
gallium
aliphatic
halide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01972229A
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German (de)
English (en)
French (fr)
Inventor
Thomas Mathivet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Electronics and Catalysis SAS
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Rhodia Electronics and Catalysis SAS
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Filing date
Publication date
Priority claimed from FR0012582A external-priority patent/FR2814737B1/fr
Priority claimed from FR0014863A external-priority patent/FR2816945B1/fr
Application filed by Rhodia Electronics and Catalysis SAS filed Critical Rhodia Electronics and Catalysis SAS
Publication of EP1373142A1 publication Critical patent/EP1373142A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/128—Mixtures of organometallic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/253—Halides
    • C01F17/271—Chlorides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/32—Gallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/37—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/38—Lanthanides other than lanthanum

Definitions

  • the present invention relates to an addition compound of a carboxylic acid and a halide or a rare earth or gallium halocarboxylate, an anhydrous addition compound of a rare earth halide or gallium and a nitrogen or oxygen donor compound, their methods of preparation and their use as a catalyst.
  • the compounds based on rare earths and in particular the halides of anhydrous rare earths, in particular chlorides, are very advantageous compounds for their use as catalyst elements for the polymerization of dienes such as butadiene.
  • the preparation of these compounds is not easy.
  • a rare earth carboxylate can be prepared by reaction of a rare earth carboxylate with a halogenated organometallic compound for example AIEt 2 CI or A EtsC to give the halogen rare earth compound for example chloride.
  • a halogenated organometallic compound for example AIEt 2 CI or A EtsC
  • this halogenated compound is reacted with another organometallic compound such as AI (iBu) 3 to give the catalytically active species.
  • AI (iBu) 3 organometallic compound
  • This preparation process is a complex implementation because the organometallic complexes of aluminum are pyrophoric and the rare earth carboxylates can be in the form of very high viscosity solutions.
  • anhydrous rare earth chloride by simple thermal dehydration of a hydrated rare earth chloride such as the hexahydrate salt.
  • a hydrated rare earth chloride such as the hexahydrate salt.
  • the last molecule of water can react with rare earth chloride to form a rare earth oxychloride in a significant proportion, for example greater than 10%, and this oxychloride is very frequently undesirable in chloride applications.
  • Other methods involving the drying of hydrated rare earth chloride in the presence of ammonium chloride and then sublimation of the latter generally lead to a product polluted by the drying agent.
  • the invention relates to a first process which is a process for the preparation of an addition compound of a carboxylic acid and a rare earth halide or gallium or a rare earth halocarboxylate or gallium of the same acid, which is characterized in that it reacts with HX, X denoting a halogen, and in a solvent chosen from alkanes, cyclanes, aromatic solvents and their mixtures, a rare earth carboxylate or of gallium, the reaction being carried out with an atomic ratio X rare earth or gallium less than 3 in the case of the preparation of a halocarboxylate.
  • the invention also relates, as a new product, to an addition compound of a carboxylic acid and a rare earth or gallium halide or a rare earth or gallium halocarbox
  • a nitrogen or oxygen donor compound free of water and chosen from linear and cyclic aliphatic ether-oxides, aliphatic glycol ethers, aliphatic ketones, aliphatic amides, aliphatic nitriles , aliphatic sulfoxides and hexamethylphosphotriamide whereby an addition compound of the rare earth or gallium halide and of said nitrogen or oxygen donor compound is precipitated.
  • the invention finally relates to the anhydrous compound for adding a rare earth halide or gallium and a nitrogen or oxygen donor compound and which is capable of being obtained by the process which has just been described above.
  • the second method of the invention makes it possible to obtain a compound based on a rare earth halide and anhydrous and high purity gallium. This process is simple, it does not require the use of reagents in large excess and avoids significant effluents. In addition, the carboxylic acid produced during the reaction as well as the solvent can be easily recycled. Finally, it is not no need to use rare earth salts and anhydrous nitrogen or oxygen donors. It is also possible to use industrial solvents containing water.
  • rare earth in the present description the elements of the group consisting of scandium, yttrium and the elements of the periodic classification with atomic number included inclusively between 57 and 71.
  • X denotes a halogen say fluorine, chlorine, bromine and iodine.
  • the first type of compound of the invention that is to say the compound of addition of a carboxylic acid and a rare earth or gallium halide or a rare earth or gallium halocarboxylate, will d 'first be described.
  • rare earth or gallium halocarboxylate is meant in the present description a product which can be represented for example by the global formula (1) MX n A 3 . n without prejudging chemical bonds between the different elements.
  • the compound of the invention can be represented for example by the formula (2):
  • M denotes here a trivalent rare earth or gallium
  • A the anionic part of a carboxylic acid (AH denoting the carboxylic acid), X a halogen as defined above, n verifying the relationship
  • x is a number greater than 0 and which generally ranges from 0 to 3 inclusive.
  • the compound of the invention can be in a polymerized form in which case it can be represented by formula (3): [MXnA 3- n. xAH] p
  • M can be more particularly neodymium, praseodymium, lanthanum, gadolinium, samarium or cerium.
  • X can be more particularly chlorine, bromine and iodine and even more particularly chlorine.
  • the carboxylic acid can in particular be an aiiphatic, cycloaliphatic or aromatic acid, saturated or unsaturated, with a linear or branched chain.
  • it is an acid having at least 6 atoms of carbon, more particularly of a C 6 -C 32 acid and even more particularly of Ce to C-i ⁇ .
  • the carboxylic acid can be chosen from those comprising a ternary or quaternary carbon atom.
  • a ternary or quaternary carbon atom there may be mentioned as isopentanoic acid, hexanoic acid, 2-ethylhexanoic acid, 2-ethylbutyric 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 Mention may very particularly be made of neodecanoic acid. By this is meant 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 addition compound of the invention is generally in the form of a solution in a solvent.
  • This solvent is chosen from alkanes, cyclanes and aromatic solvents and their mixtures.
  • 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 also 2,3 -diméthylbutane. Mention may also be made of the halogenated derivatives of these alkanes and cyclanes such as dichloromethane or chloroform.
  • aromatic solvents there may be mentioned more particularly benzene, ethyl-benzene, toluene and xylene. Halogen derivatives of aromatic solvents can also be used, such as chlorobenzene.
  • n in formula (2) which represents the value of the halogen / rare earth or gallium atomic ratio, is less than 3. More particularly , n can be between 0.1 (terminal included) and 3 and even more particularly between 1 and 2 (terminals included).
  • the solution of the addition compound of the invention has a viscosity which is low, generally close to that of the solvent. There are thus generally solutions of viscosity less than 100cPs and preferably less than 50cPs.
  • the water content of this same solution is generally less than 100 ppm, more particularly at most 500 ppm and even more particularly less than 200 ppm.
  • the solutions obtained are also very stable. No settling of solid matter is observed after a period of at least three months.
  • the solutions may have a high concentration of rare earth or gallium, for example at least 10% by mass of rare earth or gallium carboxylate, this concentration possibly reaching 60%.
  • the invention also relates to a catalyst which results from the reaction with an organometallic compound of the addition compound as described above.
  • This organometallic compound can be a compound of aluminum, magnesium or lithium. Mention may in particular be made of dialkylmagnesians such as, for example, dibutylmagnesium. More particularly, the compound can be a compound of formula AIRR'R "where R, R ', R" are identical or different and represent a hydrocarbon radical containing 1 to 20 carbon atoms approximately, one or two of R, R' or R "may be a hydrogen atom. Among these compounds, mention may be made of trialkylaluminium, triarylaluminium, dialkylaluminium hydrides, diarylaluminium hydrides, alkylarylaluminium hydrides, monoalkylaluminium dihydrides, and monoarylaluminium dihydrides.
  • the reaction of the organometallic compound and of the addition compound takes place in a manner known per se, in particular over a wide temperature range which can range from approximately 0 ° C. to approximately 150 ° C. and preferably from approximately 25 ° C. at 80 ° C.
  • the reaction is carried out with stirring, for example over a period of a few minutes to about 2 hours.
  • the reaction product is recovered by distillation under reduced pressure or by filtration or decantation, it is optionally washed with a dry hydrocarbon such as n-heptane.
  • the catalyst can be used for the polymerization or copolymerization of unsaturated compounds, in particular 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.
  • the catalyst obtained with an organomagnesium or an organolithium can be used very particularly for the stereospecific trans polymerization of butadiene.
  • the catalyst obtained with an organoaluminum compound can be used very particularly for the stereospecific cis polymerization of butadiene.
  • the addition compound of the invention is obtained by reacting a rare earth or gallium carboxylate with HX and in a solvent chosen from alkanes, cyclanes, aromatic solvents and their mixtures, this solvent being as defined above.
  • the rare earth carboxylates used as starting materials are those corresponding to the carboxylic acids defined above.
  • carboxylates soluble in the abovementioned solvent are used.
  • starting carboxylates capable of being used in the process of the invention mention may in particular be made of the liquid compositions of rare earth carboxylates described in patent application WO 99/54335.
  • a rare earth or anhydrous starting gallium carboxylate is used.
  • anhydrous carboxylate is meant a carboxylate whose water content is at most 500 ppm, preferably at most 200 ppm and even more preferably at most 100 ppm.
  • HX is preferably used in gaseous form and in this case the reaction implemented in the process is a liquid-gas reaction.
  • the reaction can be carried out at low HX pressures.
  • HX can also be used in solution in an anhydrous organic solvent.
  • solvent for HX mention may be made of those given above, that is to say the alkanes and cyclanes, the aromatic solvents and their halogen derivatives.
  • the reaction with HX is usually carried out at room temperature (from 10 ° C to 25 ° C for example).
  • the reaction with HX takes place at or near stoichiometry.
  • the reaction is carried out using quantities of reagents such that the atomic ratio XI rare earth or gallium is less than 3.
  • This reaction produces a compound which remains in solution in the solvent of the reaction medium and which is an addition compound of a rare earth halide or gallium and the acid corresponding to the salt of the rare earth or gallium, c 'is to say of a carboxylic acid as defined above.
  • the reaction can be written as below:
  • the invention also relates to a second process which is a process for preparing an anhydrous compound for adding a neodymium or cerium halide and a nitrogen or oxygen donor compound and which will now be described .
  • This process uses the addition compound of a carboxylic acid and a rare earth or gallium halide which has been described above. This is why, this process comprises a first stage which consists in preparing this addition compound and in which one reacts with HX, X denoting a halogen, and in a solvent chosen from alkanes, cyclanes and aromatic solvents and mixtures thereof, a rare earth or gallium carboxylate. Everything that was said above about this step also applies here.
  • This second method also includes a second step.
  • This second step consists in adding to the medium obtained at the end of the first step a nitrogen or oxygen donor compound. It should be noted here that it is not necessary for this donor compound to be free of water. It is however possible to use an anhydrous donor compound, here an anhydrous is understood to mean a product which has a water content of at most 100 ppm, more particularly at most 50 ppm and even more particularly at most 20 ppm.
  • This compound can first of all be chosen from linear and cyclic aliphatic ether oxides.
  • linear ones those generally having a number of carbon atoms of at most 4 are used.
  • cyclics there may be mentioned more particularly, tetrahydrofuran (THF),
  • the compound can also be chosen from ethers of aliphatic glycols.
  • ethers of aliphatic glycols there may be mentioned 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 2-methoxyethylether (diglyme).
  • the compound can also be chosen from aliphatic ketones. Use may more particularly be made of saturated aliphatic ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone.
  • Aliphatic amides can also constitute compounds which can be used in the context of the present invention, such as dimethylformamide.
  • Aliphatic nitriles such as
  • the compound can also be chosen from aliphatic sulfoxides such as dimethyl sulfoxide.
  • the addition of the nitrogen or oxygen donor compound is preferably carried out under inert gas, for example under argon, and at ambient temperature.
  • the quantity of this donor compound may in particular be between 10 and 50, quantity expressed by the molar ratio of nitrogen or oxygen donor compound / compound of addition of the rare earth halide or gallium and the acid (MX 3 , xAH for example).
  • the addition of the nitrogen or oxygen donor compound results in the precipitation of a rare earth or gallium halide addition compound and said nitrogen or oxygen donor compound.
  • the reaction can be written as follows:
  • the precipitate is separated from the reaction medium by any suitable means. It can be washed with a solvent of the same type as that used for the reaction medium. It can also be dried under vacuum and at room temperature for example.
  • the invention relates to a more specific process for the preparation of an anhydrous compound based on a neodymium or cerium halide.
  • This process is of the same type as that which has just been described, but we used in the second stage of ethanol. Everything that has been said elsewhere in the description of the general process, in particular for the second step, also applies to this specific process.
  • the invention relates, as a new product, to a compound of a second type, that is to say the compound for adding the rare earth halide or gallium and the nitrogen or oxygen donor compound capable of 'be obtained by the second method of the invention which has just been described.
  • This addition compound has a water content of less than
  • this second addition compound also has a rare earth or gallium oxyhalide content of at most 1000 ppm. Generally, the compound does not contain AH acid as defined above.
  • This second addition compound can consist of particles of average size between 1 ⁇ m and 100 ⁇ m, this size being measured by implementing a laser technique with a CILAS type device.
  • the rare earth can be more particularly neodymium, praseodyme, lanthanum, gadolinium, samarium or cerium and the halide can be more particularly chlorine.
  • the second anhydrous compound of the invention can be used as part of a catalyst for the polymerization or copolymerization of unsaturated compounds, in particular dienes. Mention may be made, as unsaturated compounds more particularly, of ethylene, propylene, butadiene and styrene. It can also be used as part of a catalyst for the acylation of aromatic compounds.
  • the invention therefore also relates to catalysts of the aforementioned type comprising the anhydrous compound of the invention.
  • the catalysts generally also contain organic aluminum compounds.
  • This second compound can also be used as a starting product for the preparation of organometallic complexes of rare earths, such as alcoholates, amides and lanthanocenes. Examples will now be given.
  • This example relates to a compound of the second type of the invention, ie an anhydrous compound for the addition of a neodymium versatate and THF.
  • a compound of the second type of the invention ie an anhydrous compound for the addition of a neodymium versatate and THF.
  • the water content (Karl Fisher) of this solid is 210 ppm, the neodymium content (measured by complexometry) is 36.3%, the chloride content (measured by argentimetry) is 27.0% and that of oxychloride NdOCI (measured by acid consumption) is less than 1000ppm.
  • This product has the formula NdCI 3 , 2THF. The yield is 96%.
  • This example relates to a compound of the second type of the invention, ie an anhydrous compound for the addition of a lanthanum neodecanoate and THF.
  • a compound of the second type of the invention ie an anhydrous compound for the addition of a lanthanum neodecanoate and THF.
  • a reflux condenser connected to an oil bubbler is adapted to the flask containing the anhydrous solution.
  • This example relates to a compound of the second type of the invention, that is to say an anhydrous compound for adding a cerium neodecanoate and THF. 0 In a 2 ⁇ 0ml two-way balloon fitted with an argon inlet, place
  • a Dean-Stark is fitted on the flask and distilled to a water content of 4 ⁇ ppm (measured by the Karl Fisher technique).
  • a reflux condenser connected to an oil bubbler is adapted to the flask containing the anhydrous solution.
  • a bubbling tube fitted with a porosity frit 1 is also fitted on the second tube of the balloon. The installation is purged with helium for 10 minutes, then with hydrogen chloride for ⁇ minutes.
  • the HCl is boiled in the solution at a flow rate of ⁇ Oml / min for 48 minutes under a pressure of 1 bar (HCl volume: 2.0 I, 0.0861 mol), ⁇ Under argon, 20 ml of anhydrous THF are then added to the syringe.
  • This example relates to a compound of the second type of the invention, that is to say an anhydrous compound for adding a samarium neodecanoate and
  • the gas line is purged with helium for 10 minutes, then purged with hydrogen chloride for ⁇ minutes.
  • the compound obtained has the formula SmCl 3 (THF) 2 .
  • the yield is 83%.
  • EXAMPLE ⁇ 0 This example relates to a compound of the second type of the invention, that is to say an anhydrous compound of addition of a neodymium neodecanoate and of THF.
  • a reflux condenser connected to an oil bubbler is adapted to the flask containing the anhydrous solution.
  • a bubbling tube fitted with a porosity frit 1 is fitted to the second tube of the balloon.
  • the gas line is purged with helium for 10 minutes, then purged with hydrogen chloride for ⁇ minutes.
  • This example relates to a compound of the second type of the invention, that is to say an anhydrous compound of addition of a neodymium neodecanoate and of ⁇ THF.
  • a reflux condenser connected to an oil bubbler is adapted to the flask containing the anhydrous solution.
  • a bubbling tube fitted with a porosity frit 1 is fitted to the second tube of the balloon.
  • the gas line is purged with helium for 10 minutes, then purged with hydrogen chloride for ⁇ minutes.
  • This example relates to a compound of the second type of the invention, that is to say an anhydrous compound for adding a neodymium neodecanoate and ⁇ dioxane.
  • a reflux condenser connected to an oil bubbler is adapted to the flask containing the anhydrous solution.
  • a bubbling tube fitted with a porosity frit 1 is fitted to the second tube of the balloon.
  • the gas line is purged with helium for 10 minutes, then purged with hydrogen chloride for ⁇ minutes.
  • This example relates to a compound of the second type of the invention, ie an anhydrous compound for the addition of a lanthanum neodecanoate and THF.
  • a compound of the second type of the invention ie an anhydrous compound for the addition of a lanthanum neodecanoate and THF.
  • a reflux condenser connected to an oil bubbler is adapted to the flask containing the anhydrous solution.
  • a bubbling tube fitted with a porosity frit 1 is fitted to the second tubing of the balloon.
  • the gas line is purged with helium for 10 minutes, then purged with hydrogen chloride for ⁇ minutes.
  • This example shows that the process of the invention can be carried out with industrial hexane containing water.
  • This example relates to a compound of the first type of the invention, that is to say an addition compound of a neodymium chloroversatate.
  • ⁇ In a 2icol0ml two-way balloon fitted with an argon inlet, place
  • This example relates to a compound of the first type of the invention, that is to say an addition compound of a neodymium chloroversatate.
  • a compound of the first type of the invention that is to say an addition compound of a neodymium chloroversatate.
  • This example relates to a compound of the first type of the invention, that is to say an addition compound of a neodymium chloroversatate.
  • a Dean-Stark is fitted on the flask and distilled to a water content of 1 ⁇ ppm (measured by Karl Fischer).
  • This example relates to the use as a catalyst of a compound of the first type of the invention.
  • This example relates to the use as a catalyst of a compound of the first type of the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerization Catalysts (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Catalysts (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Furan Compounds (AREA)
EP01972229A 2000-10-03 2001-09-28 Composes d'addition de terre rare ou de gallium, procedes pour leur preparation et leur utilisation comme catalyseur Withdrawn EP1373142A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR0012582 2000-10-03
FR0012582A FR2814737B1 (fr) 2000-10-03 2000-10-03 Compose anhydre a base d'un halogenure de terre rare ou de gallium, son procede de preparation et son utilisation comme catalyseur
FR0014863A FR2816945B1 (fr) 2000-11-17 2000-11-17 Compose d'addition d'un acide carboxylique et d'un halogenocarboxylate de terre rare ou de gallium, son procede de preparation et son utilisation
FR0014863 2000-11-17
PCT/FR2001/003017 WO2002028776A1 (fr) 2000-10-03 2001-09-28 Composes d'addition de terre rare ou de gallium, procedes pour leur preparation et leur utilisation comme catalyseur

Publications (1)

Publication Number Publication Date
EP1373142A1 true EP1373142A1 (fr) 2004-01-02

Family

ID=26212658

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01972229A Withdrawn EP1373142A1 (fr) 2000-10-03 2001-09-28 Composes d'addition de terre rare ou de gallium, procedes pour leur preparation et leur utilisation comme catalyseur

Country Status (8)

Country Link
US (1) US20070259772A1 (ko)
EP (1) EP1373142A1 (ko)
JP (2) JP2004510725A (ko)
KR (1) KR100550178B1 (ko)
CN (1) CN100447088C (ko)
AU (1) AU2001292010A1 (ko)
CA (1) CA2424925A1 (ko)
WO (1) WO2002028776A1 (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110014107A1 (en) * 2008-09-17 2011-01-20 Pai Ganesh Gurpur Process For Preparing Anhydrous Rare Earth Metal Halides
CN103665218B (zh) * 2012-09-12 2016-04-27 中国石油化工股份有限公司 一种聚异戊二烯及其制备方法和橡胶组合物
CN103539190B (zh) * 2013-08-21 2015-08-12 内蒙古工业大学 一种形貌可控的LaOCl纳米材料的制备方法
CN112552321B (zh) * 2020-12-10 2023-12-12 合肥安德科铭半导体科技有限公司 一种含镧有机化合物及其应用

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
FR2698290B1 (fr) * 1992-11-23 1995-03-24 Michelin & Cie Catalyseur de polymérisation de dioléfines, son procédé de préparation et son application à la préparation de polymères.
US5362459A (en) * 1993-05-17 1994-11-08 Pure-Etch Co. Neodymium recovery process
GB9319945D0 (en) * 1993-09-28 1993-11-17 Solvay Interox Ltd Oxidation of alkylaromatic compounds
DE19512127A1 (de) * 1995-04-04 1996-10-10 Bayer Ag Neuer Katalysator für die Gasphasenpolymerisation von konjugierten Dienen
US6111082A (en) * 1998-04-17 2000-08-29 Rhodia Rare Earths Inc. Stable concentrated rare earth carboxylate liquids
KR100290437B1 (ko) * 1998-10-07 2001-09-22 박찬구 연속식 1,3-부타디엔 중합에 적합한 니오디뮴할로겐 착화합물의제조방법
FR2799394A1 (fr) * 1999-10-11 2001-04-13 Michelin Soc Tech Catalyseur solide supporte utilisable pour la polymerisation de dienes conjugues, son procede de preparation et procede de polymerisation de dienes conjugues utilisant ce catalyseur
KR100352764B1 (ko) * 2000-03-16 2002-09-16 금호석유화학 주식회사 신규한 단분자 니오디뮴 카르복실레이트 화합물 및 이를포함하는 디엔 중합용 촉매

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0228776A1 *

Also Published As

Publication number Publication date
KR100550178B1 (ko) 2006-02-10
JP2008297302A (ja) 2008-12-11
JP2004510725A (ja) 2004-04-08
CA2424925A1 (fr) 2002-04-11
CN100447088C (zh) 2008-12-31
CN1471494A (zh) 2004-01-28
KR20030059172A (ko) 2003-07-07
AU2001292010A1 (en) 2002-04-15
US20070259772A1 (en) 2007-11-08
WO2002028776A1 (fr) 2002-04-11

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