WO2006123051A2 - Para-tertio-butylcalix[6]arenes portant des fonctions triacides en positions 2, 4 et 6 , membranes liquides supportees et materiaux supports les comportant et leurs utilisations - Google Patents
Para-tertio-butylcalix[6]arenes portant des fonctions triacides en positions 2, 4 et 6 , membranes liquides supportees et materiaux supports les comportant et leurs utilisations Download PDFInfo
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- WO2006123051A2 WO2006123051A2 PCT/FR2006/001105 FR2006001105W WO2006123051A2 WO 2006123051 A2 WO2006123051 A2 WO 2006123051A2 FR 2006001105 W FR2006001105 W FR 2006001105W WO 2006123051 A2 WO2006123051 A2 WO 2006123051A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/72—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings and other rings
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the radioactive compounds are present in very different physicochemical forms, generating different toxicities and therefore very different risks of exposure of the personnel.
- the analytical technique of reference is the spectrometry ⁇ . Due to the short path of the ⁇ particles in the material, it is impossible to directly measure uranium, americium and plutonium in the urine, it is therefore necessary to manufacture a thin film source for each of the actinides. This involves a first step of mineralization of the sample followed by a chemical purification that isolates the actinides from the urinary matrix and separates them from each other, in order to limit the spectral interferences.
- the present invention relates to a new family of para-tert-butyl compounds calix [6] arenes of formula (IA) or (IB)
- R1, R3 and R5, identical or different, represent, each independently:
- a hydrogen atom, or halogen (ii). an acetyl, amino, phosphate, nitro, sulfate, carboxy, carboxylic, thiocarboxy, carbamate, thiocarbamate radical, (iii). a linear or branched alkyl, having 1 to 60, preferably 1 to 30 carbon atoms, optionally substituted, optionally having at least one ethylenic or acetylenic unsaturation, (iv). cycloalkyl having 3 to 12 carbon atoms, optionally substituted, optionally having at least one ethylenic or acetylenic unsaturation, (v).
- radicals (ii) to (v) which may be substituted by halogen atoms, organometallic compounds, alcohols, amines, carboxylic, sulphonic, sulfuric, phosphoric, phosphonic or hydroxamic acid or carboxylic acid functions, carbamates, thiocarbamates, ethers thiols, epoxides, thioepoxides, isocyanates, isothiocyanates or a carbon of these radicals may be replaced by a heteroatom of nitrogen, sulfur, phosphorus, oxygen, boron, arsenic; (vi) a polymer selected from the group consisting of polystyrenes, copolymers of chloro- and / or bromomethylstyrene and divinylbenzene, polyethers, polyacrylamides, polygly
- R1, R3 and R5 not simultaneously representing CH 3 in (IA) and (IB),
- R1, R3 and R5 do not simultaneously represent CH 2 COOH in (IA), and R1, R3 and R5 do not simultaneously represent CH 2 CONHOH in (IB).
- two of R1, R3 and R5 represent hydrogen or methyl, the third being chosen from (vi) a polymer selected from the group comprising polystyrenes, copolymers chloro and / or bromomethylstyrene and divinylbenzene, polyethers, polyacrylamides, polyglycidyl methacrylates, dextrans, and agaroses.
- the para-tert-butyl calix [6] arenes of the invention are compounds of formula (IA) or (IB) in which R 1, R 3 and R 5 are identical and preferably they represent a hydrogen.
- the invention also relates to supported liquid membranes comprising a para-tert-butyl calix [6] arene of formula (IA) or (IB)
- radicals (ii) to (v) which may be substituted by halogen atoms, organometallic compounds, alcohols, amines, carboxylic, sulphonic, sulfuric, phosphoric, phosphonic or hydroxamic acid or ester functional groups, carbamates, thiocarbamates, ethers , thiols, epoxides, thioepoxides, isocyanates, isothiocyanates or carbon of these radicals can be replaced by a heteroatom of nitrogen, sulfur, phosphorus, oxygen, boron, arsenic;
- the organic solvent according to the invention has a boiling point greater than 60 ° C., so as to limit the evaporation of said solvent during storage. It must also have good solubility properties vis-à-vis the calixarenes of the invention.
- solvents although this list is not exhaustive, are toluene, xylene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, 1,4-diisopropylbenzene, hexylbenzene, kerosene.
- tetrahydropyran 1,2,3,4-tetrahydronaphthalene
- pentanol and higher homologous alcohols for example diethylene glycol dibutyl ether, esters such as methyl benzoate, ethers such as orthonitrophenyl pentyl ether or nitrophenyl octyl ether.
- solubilities in mol / l of compound IA in various solvents are the following: at 25 ° C. 1,2-dichorobenzene: 3.13 ⁇ 10 -3 M, chlorobutane: 1.6 ⁇ M 3 M, isooctane: 1.25 10 -3 M, isobutyl acetate: 1.75 10 -3 M, t-butyl acetate: 5.25 -3 M, isoamyl benzoate: 2.40 ⁇ 10 -3 M acetate acetate benzyl: 3.7 1 10.
- the support materials constituting the supported liquid membranes of the invention are of mineral origin selected from the group comprising silica gels, oxides, such as alumina, zirconia or titanium oxide, or of organic origin selected from the group consisting of polystyrene-divinylbenzenes, polyethers, polyacrylamides, polyglycidyl methacrylates, or of organo-mineral origin selected from the group consisting of silica / dextran or hydroxyapatite / agarose composites, and mixtures thereof.
- the support is in particulate form, the particle size varying between 10 nm and 10 mm, preferably between 10 and 50 microns and the pore diameter varying between 10 and 5000 ⁇ , preferably between 100 and 500 ⁇ .
- the invention also relates to the liquid membranes contained in the supported liquid membranes, that is to say on the para-tert-butyl calix [6] arenes of formulas (IA) and (IB), dissolved in a solvent the solvent being an organic solvent insoluble in water as described above.
- the invention also relates to a support material which is a para-tert-butyl calix [6] arene of formula (IIA) or (HB)
- R'1, R '3 and R' 5 identical or different, represent, each independently:
- a linear or branched alkyl having 1 to 60, preferably 1 to 30 carbon atoms, optionally substituted, optionally having at least one ethylenic or acetylenic unsaturation
- a cycloalkyl having from 3 to 12 carbon atoms, optionally substituted, optionally having at least one ethylenic or acetylenic unsaturation
- radicals (ii) to (v) which may be substituted by halogen atoms, organometallic compounds, alcohols, amines, carboxylic, sulphonic, sulfuric, phosphoric, phosphonic or hydroxamic acid or carboxylic acid functions, carbamates, thiocarbamates, ethers thiols, epoxides, thioepoxides, isocyanates, isothiocyanates or a carbon of these radicals may be replaced by a heteroatom of nitrogen, sulfur, phosphorus, oxygen, boron, arsenic;
- SPACER being a divalent radical selected from the group consisting of C1-C60, preferably C1-C30, alkyl, C1-C60 alkylarylene, aryl C1-C60alkylene, aryl C1-C60 alkyl) -aryls
- the divalent radical may be substituted by halogen atoms, organometallics, alcohols, amines, acids, esters, carbamates, thiocarbamates, ethers, thiols, epoxides, thioepoxides, isocyanates, isothiocyanates , or a carbon of this divalent radical which can be replaced by a heteroatom of nitrogen, sulfur, phosphorus, oxygen, boron, arsenic; the support being chosen from supports of mineral or organic or organo-mineral origin, preferably particulate, whose particle size varies between 10 nm and 10 mm, preferably between 10 and 50 microns and whose pore diameter
- a support material is constitutive of the stationary phase of a chromatographic column.
- the support is of mineral origin chosen from the group comprising a silica gel, oxides, such as alumina, zirconia or titanium oxide, or of organic origin chosen from the group comprising polystyrene-divinylbenzene, polyethers, polyacrylamides, polyglycidyl methacrylates or of organo-mineral origin selected from the group consisting of silica / dextran or hydroxyapatite / agarose composites.
- a silica gel oxides, such as alumina, zirconia or titanium oxide
- organic origin chosen from the group comprising polystyrene-divinylbenzene, polyethers, polyacrylamides, polyglycidyl methacrylates or of organo-mineral origin selected from the group consisting of silica / dextran or hydroxyapatite / agarose composites.
- This support comes from a support comprising reactive chemical functions, said chemical functions being organic or inorganic, for example the chloride functions of carboxylic acids, amines, aldehydes, thiols, sulfochloride, isocyanate, metal halide, without this list is not exhaustive.
- functionalized particulate supports are the copolymer of [5- (4-chloromethyl) phenyl] pentylstyrene and divinylbenzene as well as the copolymer of [5- (4-bromomethyl) phenyl] pentylstyrene and of divinylbenzene, and the copolymer of 4-chloromethyl-styrene and divinylbenzene.
- They may be in the form of spherical or irregular solid particles whose particle size is variable as well as the porosity. Different commercial grades are available such as Stratospheres TM resins sold by Aldrich.
- the compound of formula (b) is then optionally subsequently modified, by saponification or by substitution of the carboxylic acid ethyl ester functions, to yield compounds of formulas A or B.
- the compound of formula (b) may also be partially or totally demethylated, to yield compounds of general formulas (cl), (c2) or (c3).
- the compounds of formulas (cl) or (c2) or (c3) are then modified by chemical modification of the hydroxyls to lead on the one hand to compounds of general formula (IA) by saponification of ethyl esters or on the other hand to compounds of general formula (IB) for obtaining hydroxamic acid functional groups from ethyl esters.
- the compounds of formula (cl) or (c2) or (c3) can then be directly reacted with suitably functionalized supports, to lead to covalent grafting reactions via the activation of their free phenolic hydroxyls, to lead on the one hand to support materials of general formula (HA) by saponification of ethyl esters or on the other hand to support materials of general formula (IIB) for obtaining hydroxamic acid functions from ethyl esters.
- a support material according to the invention can also be represented as follows:
- the process consists in synthesizing at first a common precursor comprising acid ester functions io
- the acetone is then evaporated to dryness under vacuum from a laminar pump, water bath regulated at 60 ° C.
- the solid dry residue obtained is solubilized in chloroform.
- water is added and the biphasic medium is stirred vigorously and then acidified with 12M concentrated hydrochloric acid.
- the lower organic phase is then recovered by decantation and then washed with water until neutrality of the washing water contained in the upper phase.
- the lower organic phase is then dried over anhydrous sodium sulphate and then filtered.
- the clear organic phase is concentrated to dryness, water bath at 60 ° C. under a laminar vacuum.
- the dry residue is then purified by low pressure chromatography on chromatographic grade silica gel.
- the eluent used is pure synthetic methylene chloride stabilized with amylene.
- the purity of the various fractions is monitored in methylene chloride / ethanol 95/5 by TLC on virgin silica plates.
- Fractions containing the symmetrical compound 1,3,5-trimethoxy-p-tert-butylcalix [6] arene mono-stain TLC (revelation by iodine vapor) are combined and then concentrated to dryness.
- the residue is used as it is in the next step.
- the process consists of synthesizing the common precursor comprising carboxylic acid ester functional groups at the 2,4- and 6-positions and trimethoxy functions at the 1,3 and 5 positions, by modifying all the phenolic hydroxyls of the compound obtained previously, and labeled in positions 2,4 and 6, positions 1,3 and 5 being protected by methoxy groups.
- the product obtained in the preceding example (formula (a)) is dissolved in anhydrous DMF (dimethylformamide) (dried over sodium hydride), under a nitrogen atmosphere. A very large excess of cesium carbonate is added and the suspension obtained is stirred for 4 hours under nitrogen.
- the process consists of partially or totally demethylating the common precursor of formula (b), comprising carboxylic acid ester functional groups at the 2, 4 and 6 positions and both the phenolic and methoxy hydroxyl functional groups at the 1-position. , 3 and 5 (compounds (cl) or (c2)), or only phenolic hydroxyl groups at the 1, 3 and 5 positions (compound (c3)).
- the compound of formula (b), obtained above is dissolved in anhydrous chloroform previously dried over sodium hydride. The medium is stirred under a nitrogen atmosphere and then trimethylsilyl iodide
- the lower chloroform phase is evaporated to dryness under vacuum of a laminar pump, water bath regulated at 60 ° C. after drying over anhydrous sodium sulphate.
- the dry residue obtained is then purified by low pressure chromatography on chrotnatographic silica gel.
- the eluent used is toluene / ethyl acetate 90/10.
- the purity of the various fractions is controlled in Toluene / ethyl acetate 90/10 by TLC on virgin silica plates deposited on a polyester support.
- the fractions containing compounds (c1) or (c2) or (c3) are combined and separately dried under the previously described evaporation conditions. Each residue of dryness is used as it is for possible subsequent chemical modifications.
- the method comprises synthesizing a compound of general formula (d1) or (d2) or
- a compound of formula (cl) or (c2) or (c3) obtained above is dissolved in anhydrous DMF (dimethylformamide) (dried over sodium hydride), under a nitrogen atmosphere. A very large excess of cesium carbonate is added and the suspension obtained is stirred for 4 hours under nitrogen. A very large excess of halide, the organic residue of which represents the group R 1 or R 3 or R 5, is then cast over 5 minutes on the reaction suspension and the strongly stirred medium is brought gradually to reflux for 24 hours, under nitrogen bubbling. ⁇ _ .
- the DMF is evaporated to dryness under vacuum from a laminar pump, a water bath regulated at 80 ° C. The solid dry residue obtained is solubilized in chloroform.
- the lower chloroform phase is evaporated to dryness under vacuum of a laminar pump, water bath regulated at 60 ° C. after drying over anhydrous sodium sulphate.
- the dry residue obtained is then purified by low pressure chromatography on chromatographic grade silica gel.
- the eluent used is the toluene / ethyl acetate mixture
- the purity of the various fractions is controlled in the Toluene / ethyl acetate mixture 90/10 by TLC on virgin silica plates deposited on a polyester support.
- fractions containing the compound (d1) or (d2) or (d3) are combined and separately dried under the previously described evaporation conditions.
- the dry residue is used as is for possible subsequent chemical modifications.
- the process consists in covalently grafting, on a support, a compound of formula (cl) or (c2) or (c3) or (d1) or (d2) or (d3) having d ester functions.
- carboxylic acid in position 2, 4 and 6 and both phenolic and methoxy hydroxyl functional groups in positions 1 and / or 3 (compounds
- a compound of formula (cl) or (c2) or (c3) or (d1) or (d2) or (d3) is dissolved in anhydrous dimethylformamide previously dried over sodium hydride.
- the medium is stirred under nitrogen until complete dissolution.
- Cesium carbonate in a very large excess is then added and a commercial resin of known and quantified functionality, said functionality being chosen to be able to react on a phenolic hydroxyl or on a group R 1 and / or R 3 and / or R 5, and the reaction medium is carried for 72 hours at 60 ° C. under nitrogen bubbling.
- a compound of general formula (a) or ((cl)) or (c2) or (c3) or (d1) or (d2) or (d3) or a compound obtained using the process is used. described in part E. Said compound is dissolved or suspended in ethanol. An aqueous solution of potassium hydroxide, in very large excess relative to the stoichiometry counted on the number of ethyl ester groups to be saponified, is added and the medium (solution or suspension) is heated for 4 hours at reflux.
- the suspension is filtered and the precipitate (or the support) is washed with water until neutral pH of the filtration water, then with ethanol.
- the solid is dried at 40 ° C. under vacuum to constant weight.
- Said compound is dissolved or suspended in THF.
- a second solution is then added, comprising scale potash previously dissolved in a methanol / THF mixture and maintained at + 5 ° C.
- the medium (solution or suspension) is stirred for 7 days at ambient temperature under a nitrogen atmosphere.
- reaction mass is evaporated to dryness, water bath at 60 ° C. under vacuum.
- reaction mass is evaporated to dryness, water bath at 60 ° C. under vacuum.
- the invention also relates to the use of a supported liquid membrane as described above and / or a support material according to the invention for selective complexation and analysis of uranium elements, americium and plutonium or other radioelements in their cationic form.
- the invention also relates to the use of a supported liquid membrane and / or a support material according to the invention to remove a mixture of at least two constituents, chosen from the group comprising organic and inorganic molecules. or organo-mineral, at least a portion of one of these constituents, or to separate said constituents by a chromatrographic method.
- the supported liquid membranes and the support materials of the invention are particularly suitable for exclusion chromatography. They allow the detection and the separation of minute quantities of product, in particular the separation of uranium and / or plutonium and / or americium with contents of the order of ImBq / 1.
- Carrier material containing -3,5-dimethoxy-2,4,6-tri-carboxylic acid-p-tert-butylcalix [6] arene
- the solid dry residue obtained is solubilized in 5.0 l of chloroform. After dissolution, 1.0 l of water are added and the two-phase medium is stirred vigorously. 0.1 l of concentrated hydrochloric acid 12M are slowly added as a function of the evolution of carbon dioxide. The organic phase is then washed 5 times with 1.0 l of water and then dried over 200 g of anhydrous sodium sulphate. After filtration, the organic phase is concentrated to dryness, the bath at 60 ° C. under a laminar vacuum. 250 g of placing residue dry are obtained which are then purified by low pressure chromatography on 15 kg of silica gel
- the DMF is evaporated to dryness under vacuum from a laminar pump, a water bath regulated at 80 ° C.
- the solid dry residue obtained is solubilized in 2.0 l of chloroform. After dissolution, 0.5 l of water are added and the two-phase medium is stirred vigorously. 20 ml of 12M concentrated hydrochloric acid are slowly added as a function of the evolution of carbon dioxide. The organic phase is then washed 5 times with 0.5 l of water and then dried over 20 g of anhydrous sodium sulphate. After filtration, the organic phase is concentrated to dryness, the bath at 60 ° C. under a laminar vacuum. The residue is taken up in 300 ml of ethanol. A white suspension is obtained. The solid is recovered by filtration and washing with 3 times 40 ml of ethanol, and then dried at 40 ° C. under vacuum in an oven.
- the reaction is stopped by adding 2 l of water. 100 ml of 1M HCl are added and the red organic phase is recovered. It is washed twice with 1 liter of water. The chloroform phase is evaporated to dryness under vacuum of a laminar pump, water bath regulated at 60 ° C. after drying with 200 g of anhydrous sodium sulphate. 27.2 g of dry residue are obtained which are then purified by low pressure chromatography on 3 kg of silica gel 40-200 ⁇ va (60 ⁇ pore). The eluent used is a toluene / ethyl acetate 90/10 (20 l). The purity of the various fractions is controlled in the Toluene / ethyl acetate mixture 90/10 by TLC on virgin silica plates deposited on a polyester support.
- reaction suspension is cooled and then 12 ml of 12M HCl are added.
- the pH of the suspension is 1.
- the suspension is filtered and then washed with 8 times 100 ml of water and then with ethanol (3 times 50 ml).
- reaction suspension is evaporated to dryness, water bath at 60 ° C. under vacuum.
- residue is taken up in methylene chloride / acetic acid 50 ml / 10 ml and stirred for 4 hours.
- the reaction mass is dried in a water bath at 60 ° C. under vacuum.
- the dry residue is taken up in 20 ml of dichloromethane.
- the expected product precipitates in the form of a white solid.
- Example 1-2 In a 250 ml glass reactor, equipped with a condenser, are introduced 5.9 g of product (white powder) obtained in Example 1-2 (4.00 mmol) and 150 ml of ethanol. A solution previously prepared (and maintained at +5 ° C.) of flake potash (12 g at 100%, ie 214 mmol) in 150 ml of water is added all at once to the reactor. The reaction medium is heated for 4 hours under nitrogen bubbling.
- the aqueous solution containing americium is then passed over the Column (fixation step)
- the fixed americium is finally eluted with a 2M HNO 3 solution (elution step). Solutions flow by natural gravitation.
- Americium is measured by alpha spectrometry in each solution at the bottom of the column. The results of the measurements make it possible to calculate the binding efficiency and the elution yield of americium.
- the conditioning, fixing and rinsing steps are identical to those described in Example 4.
- the fixed uranium is eluted with an HNO 3 IM solution.
- the uranium is measured by alpha spectrometry or mass spectrometry (ICP-MS) in each solution at the bottom of the column. The measurement results are used to calculate the fixation yield and the elution yield of uranium.
- the uranium present at a concentration of 5.10 6 g / l in urine is fixed by means of the calixarenes of the invention.
- 1 g of supported liquid membrane of Example 3 packed in column is used.
- a preliminary step of mineralization of the urine is carried out by heating by microwaves.
- the mineralization residue is taken up in a 2M HNO 3 solution, and then the pH of the solution is adjusted to 4 before the column pass.
- 100 mg of column-conditioned carrier material of Example 1-5 is used The conditioning, fixing, rinsing and elution steps are identical to those described in Example 4
- the plutonium is measured by alpha spectrometry or mass spectrometry (ICP-MS) in each columnar solution and the measurement results are used to calculate the fixation yield and the plutonium elution yield.
- ICP-MS mass spectrometry
- Example 1-3 In a 250 ml glass reactor, equipped with a condenser, are introduced 5.03 g of product (white powder) obtained in Example 1-3, when carrying out a second test identical to the previous one. (4.00 mmol) and 150 ml of ethanol. A solution previously prepared (and maintained at +5 ° C.) of flake potash (12 g at 100%, ie 214 mmol) in 150 ml of water is added all at once to the reactor. The reaction medium is heated for 4 hours under nitrogen oiling.
- the uranium is measured and the results are expressed as in the previous examples.
- 1 g of the supported liquid membrane obtained above, packed in column are used
- the conditioning, fixing, rinsing and elution steps are identical to those described in Example 4 , the conditioning and rinsing solutions being adjusted to pH 3.
- the thorium is measured by alpha spectrometry or by mass spectrometry (ICP-MS) in each solution at the bottom of the column and the results are expressed as in the previous examples.
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/914,861 US20090095681A1 (en) | 2005-05-17 | 2006-05-16 | P-tert-butylcalix[6]arenes with triacidic functions at 2, 4 and 6, supported liquid membranes and support materials comprising the same and use thereof |
JP2008511751A JP4814318B2 (ja) | 2005-05-17 | 2006-05-16 | 2位、4位および6位に三酸官能基(triacidicfunction)を有するp−tert−ブチルカリックス[6]アレーン、それを含む支持された液体膜および支持材料、ならびにその使用 |
EP06755491A EP1885682A2 (fr) | 2005-05-17 | 2006-05-16 | Para - tertio - butylcalix [6]arenes portant des fonctions triacides en positions 2, 4 et 6 , membranes liquides supportees et materiaux supports les comportant et leurs utilisations |
BRPI0610823-7A BRPI0610823A2 (pt) | 2005-05-17 | 2006-05-16 | para-terc-butilcalix[6]arenos que portam funções triácidos nas posições 2, 4 e 6, membranas lìquidas suportadas e materiais suportes que os compreendem e suas utilizações |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0504944 | 2005-05-17 | ||
FR0504944A FR2885901B1 (fr) | 2005-05-17 | 2005-05-17 | Para-tertio-butylcalix(6)arenes portant des fonctions triacides en positions 2,4 et 6, membranes liquides supportees et materiaux supports les comportant et leurs utilisations |
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WO2006123051A2 true WO2006123051A2 (fr) | 2006-11-23 |
WO2006123051A3 WO2006123051A3 (fr) | 2007-01-25 |
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PCT/FR2006/001105 WO2006123051A2 (fr) | 2005-05-17 | 2006-05-16 | Para-tertio-butylcalix[6]arenes portant des fonctions triacides en positions 2, 4 et 6 , membranes liquides supportees et materiaux supports les comportant et leurs utilisations |
Country Status (9)
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US (1) | US20090095681A1 (fr) |
EP (2) | EP2263995A1 (fr) |
JP (1) | JP4814318B2 (fr) |
CN (1) | CN101175709A (fr) |
BR (1) | BRPI0610823A2 (fr) |
FR (1) | FR2885901B1 (fr) |
RU (1) | RU2422432C2 (fr) |
WO (1) | WO2006123051A2 (fr) |
ZA (1) | ZA200709962B (fr) |
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US20110281948A1 (en) * | 2008-12-17 | 2011-11-17 | Institut De Radioprotection Et De Surete Nucleaire | Cosmetic and pharmaceutical formulations of calixarene molecules |
CN103242193A (zh) * | 2013-05-17 | 2013-08-14 | 南华大学 | 一种羟肟化杯[6]芳烃高效铀萃取剂的制备及其用途 |
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US8636830B2 (en) * | 2010-06-11 | 2014-01-28 | William Marsh Rice University | Aliphatic amine based nanocarbons for the absorption of carbon dioxide |
CN102140089B (zh) * | 2011-02-23 | 2013-05-22 | 大连民族学院 | 硫代杯[8]芳烃二乙基乙酰胺及其合成方法和用途 |
RU2480451C1 (ru) * | 2012-03-21 | 2013-04-27 | Федеральное государственное бюджетное учреждение науки Институт органической и физической химии им. А.Е. Арбузова Казанского научного центра Российской академии наук | Производное тетраметилоксифенилкаликс[4]арена для сорбции азо-красителей из водных растворов |
RU2540603C2 (ru) * | 2013-02-26 | 2015-02-10 | Общество с ограниченной ответственностью "Сорбент-Технологии" (ООО "Сорбент-Технологии") | СОСТАВ ЭКСТРАКЦИОННО-ХРОМАТОГРАФИЧЕСКОГО МАТЕРИАЛА ДЛЯ СЕЛЕКТИВНОГО ВЫДЕЛЕНИЯ U(VI), Th(IV), Np(IV) и Pu (IV) ИЗ АЗОТНОКИСЛЫХ РАСТВОРОВ |
CN104016884A (zh) * | 2014-06-05 | 2014-09-03 | 南华大学 | 一种杯芳烃衍生物的合成方法 |
US10232342B2 (en) | 2015-07-01 | 2019-03-19 | William Marsh Rice University | Method, synthesis, activation procedure and characterization of an oxygen rich activated porous carbon sorbent for selective removal of carbon dioxide with ultra high capacity |
ITUB20153049A1 (it) * | 2015-08-10 | 2017-02-10 | Eni Spa | Composti metallici di calixareni, composizioni detergenti che li contengono e loro impiego in composizioni lubrificanti |
RU2731016C1 (ru) * | 2020-02-11 | 2020-08-28 | Акционерное общество "Радиевый институт имени В.Г. Хлопина" | Экстракционная смесь для выделения цезия и америция из щелочных растворов |
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-
2006
- 2006-05-16 ZA ZA200709962A patent/ZA200709962B/xx unknown
- 2006-05-16 CN CNA200680017162XA patent/CN101175709A/zh active Pending
- 2006-05-16 EP EP10184117A patent/EP2263995A1/fr not_active Ceased
- 2006-05-16 JP JP2008511751A patent/JP4814318B2/ja not_active Expired - Fee Related
- 2006-05-16 EP EP06755491A patent/EP1885682A2/fr not_active Withdrawn
- 2006-05-16 RU RU2007146695/04A patent/RU2422432C2/ru not_active IP Right Cessation
- 2006-05-16 BR BRPI0610823-7A patent/BRPI0610823A2/pt not_active IP Right Cessation
- 2006-05-16 WO PCT/FR2006/001105 patent/WO2006123051A2/fr active Application Filing
- 2006-05-16 US US11/914,861 patent/US20090095681A1/en not_active Abandoned
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EP1295861A2 (fr) * | 2001-09-24 | 2003-03-26 | Synaptec GmbH | Calix(6)arenes, procédé de leur préparation et leur utilisation |
DE10210115A1 (de) * | 2002-03-08 | 2003-09-18 | Deutsches Textilforschzentrum | Mit Calixarenen ausgerüstete textile Materialien, Verfahren zu ihrer Herstellung und ihre Verwendung |
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Cited By (5)
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US20110281948A1 (en) * | 2008-12-17 | 2011-11-17 | Institut De Radioprotection Et De Surete Nucleaire | Cosmetic and pharmaceutical formulations of calixarene molecules |
JP2012512232A (ja) * | 2008-12-17 | 2012-05-31 | アンスティテュート デュ ラジオプロテクシオン エ デュ スロテ ヌークレア | カリックスアレーン分子の化粧用製剤および医薬製剤 |
US8987334B2 (en) * | 2008-12-17 | 2015-03-24 | Institut De Radioprotection Et De Surete Nucleaire | Cosmetic and pharmaceutical formulations of calixarene molecules |
CN103242193A (zh) * | 2013-05-17 | 2013-08-14 | 南华大学 | 一种羟肟化杯[6]芳烃高效铀萃取剂的制备及其用途 |
CN103242193B (zh) * | 2013-05-17 | 2015-04-01 | 南华大学 | 一种羟肟化杯[6]芳烃高效铀萃取剂的制备及其用途 |
Also Published As
Publication number | Publication date |
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RU2007146695A (ru) | 2009-06-27 |
US20090095681A1 (en) | 2009-04-16 |
JP4814318B2 (ja) | 2011-11-16 |
BRPI0610823A2 (pt) | 2010-09-14 |
WO2006123051A3 (fr) | 2007-01-25 |
EP1885682A2 (fr) | 2008-02-13 |
JP2008545645A (ja) | 2008-12-18 |
CN101175709A (zh) | 2008-05-07 |
FR2885901A1 (fr) | 2006-11-24 |
RU2422432C2 (ru) | 2011-06-27 |
EP2263995A1 (fr) | 2010-12-22 |
FR2885901B1 (fr) | 2008-02-29 |
ZA200709962B (en) | 2009-03-25 |
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