FR2998816A1 - ION EXCHANGE RESIN HAVING CHELATING PROPERTIES, PROCESS FOR PREPARING SAME AND USES THEREOF - Google Patents

Abstract

The invention relates to an ion exchange resin with chelating properties which is obtained by polycondensation in basic medium: at least one first phenolic monomer, chelating, which corresponds to the general formula (I) below: in where m = 0, 1, 2 or 3; n = 0, 1 or 2; R1, R2, R3, R4, R5 are H, -OH, C1-C10 alkyl or alkoxy, aryl, -SO3H, -COOR with R = H or C1-C10 alkyl, -P (O) (OR ) (OR ') or -C (O) NRR' with R and R '= H and / or C1 to C10 alkyl; with the proviso that at least one of R1 to R5 = -OH and at least two of R1 to R5 = H; at least one second phenolic monomer, which does not correspond to the general formula (I); and formaldehyde. The invention also relates to a process for preparing this resin and to the uses of said resin. Applications: decontamination of an aqueous medium with cesium and / or strontium, in particular in the nuclear industry.

Description

The invention relates to the field of radionuclide decontamination of aqueous media in which these radionuclides are present in small amounts. EXAMPLES OF ION EXCHANGING RESIN WITH CHELATING PROPERTIES, ITS PREPARATION PROCESS AND USES More specifically, the invention relates to an ion exchange resin, of the formo-phenolic type, which has chelating properties, which has a selectivity to both cesium and strontium and which is therefore as such, particularly adapted to coextract (that is to say, extract in a grouped manner) these two elements of an aqueous medium in which they are located, this aqueous medium can be a freshwater medium or a seawater environment.

The invention also relates to a process for preparing this resin as well as to uses of said resin. The invention is likely to find applications in all situations where it may be desirable to decontaminate an aqueous medium of cesium and / or strontium and, in particular, in the nuclear industry to treat aqueous liquid effluents containing one of the following: and / or the other of these two elements, which are likely to be produced by nuclear installations, either as part of their normal operation (for example, in the context of an activity of reprocessing spent nuclear fuel) or accidentally. STATE OF THE PRIOR ART Irradiated nuclear fuel reprocessing plants produce so-called low and intermediate-level aqueous liquid effluents (FA-MA), which contain a number of radionuclides resulting from nuclear fission and corrosion of fuel cladding. , and which therefore need to be processed to extract these radionuclides. To the effluents resulting from the reprocessing of the irradiated nuclear fuels are added the effluents of washing of the contaminated equipment as well as the effluents related to possible nuclear incidents. Cesium 137 and strontium 90 are among the radionuclides whose extraction is more specifically targeted because they are abundant in irradiated nuclear fuel (and of which in the aqueous liquid effluents resulting from the reprocessing of these fuels) and their period of approximately 30 years makes them particularly radiotoxic. Moreover, this period is too long for the decay to take place within a reasonable time interval.

At present, the decontamination of aqueous effluents FA-MA is generally carried out by means of purification systems based on the use of ion exchange resins (sulfonic, carboxylic, formo-phenolic, ...) or by processes of coprecipitation. These two types of treatment have limitations, namely that co-precipitation generates large volumes of waste in the form of sludge and thus leads to large volumes of storage, while the ion exchange resins currently used have a low ability to extract metal ions in a grouped manner. However, the possibility of extracting radionuclides in a grouped manner from aqueous liquid effluents is a key point for treating these effluents while producing a minimum of waste.

It is known that formo-phenolic polymer resins, which are also known as phenol-formaldehyde resins and which are obtained by the polycondensation of phenolic compounds and formaldehyde, typically in a basic medium, can be used to extract cesium and strontium from an aqueous saline medium. It is also known that it is possible to modulate the selectivity of formo-phenolic resins with respect to cesium ions or strontium ions (that is to say their ability to extract preferentially this type of ions). playing on the nature of the phenolic compound from which they are prepared. It has thus been shown that the use of resorcinol and 3,5-dihydroxybenzoic acid (or α-resorcylic acid) tends to increase the selectivity of formo-phenolic resins towards cesium (SK Samanta et al. Sep. Sci. Technol., 27 (2), 255-267 (1992), reference [1]), whereas the use of catechol or of a phenol / iminodiacetic acid mixture tends to increase their strontium selectivity (SK Samanta et al., Racliochim Acta, 57, 201-205 (1992), reference [2]). More recently, it has been proposed to incorporate a compound with chelating or complexing properties in formophenolic resins in order to increase their selectivity towards target ions. Thus: - Favre-Réguillon et al. (Sep. Sci.Technol., 36 (3), 367-379 (2001), reference [3]) incorporated a crown ether (dibenzo [18] crown-6 or dibenzo [24] -coron-8) in resin resins based on resorcinol and formaldehyde and have studied the ability of the resins thus obtained to extract lithium, sodium, potassium, rubidium and cesium from an aqueous medium; K.A. K. Ebraheem et al. (Sep. Sci.Technol., 35 (13), 2115-2125 (2000), reference [4]) incorporated 8-hydroxyquinoline in bisphenol A and formaldehyde resins, and studied the behavior of resins thus obtained with respect to lanthanum, cerium, neodymium, samarium and gadolinium; - Mr. Draye et al. (Sep. Sci., Technol., 35 (8), 1117-1132 (2000), reference [5]) have also incorporated 8-hydroxyquinoline but in phenol, catechol or resorcinol resins, and formaldehyde and were interested in the behavior of resins thus obtained vis-à-vis lanthanum and europium; while - K. Singh and R. Gupta (J. Indion Chem Soc., 79, 447-449 (2002), reference [6]) incorporated diethylenetriaminepentaacetic acid (DTPA) in a resin-based of phenol and formaldehyde and analyzed the sorption capacities of this resin vis-à-vis 19 different types of metal ions (Ag, Co, Pb, Al, La, In, Pt, Zr, Th, etc.) but of which neither cesium nor strontium is part. In references [3] to [5], the crown ethers and 8-hydroxyquinoline act as co-monomers in the polycondensation of phenolic compounds and formaldehyde so that they become an integral part of the matrices. polymers forming the resins.

On the other hand, this is not the case of the DTPA in reference [6] which, because it has no reactive center capable of reacting with formaldehyde, does not participate in the polycondensation reaction. Thus, the DTPA is present in the polymer matrix forming the resin without being immobilized on this matrix, which, taking into account the solubility of this compound in the aqueous phase, may lead to its release by the resin during the use of the latter in an aqueous medium and, therefore, to an alteration, even a loss, of its chelating properties. In view of the foregoing, the inventors have set themselves the goal of supplying new ion exchange resins with chelating properties, which are selective both with respect to cesium and strontium and thus make it possible to extract in a group manner these two elements of an aqueous medium, and whose chelating properties are not likely to be altered during use. The inventors have also set themselves the goal that the synthesis of these resins is simple to implement and can be achieved at costs compatible with their use on an industrial scale. PRESENTATION OF THE INVENTION These and other objects are achieved by the present invention which proposes, firstly, an ion exchange resin with chelating properties, of formo-phenolic type, which is obtained by polycondensation in basic medium: at least one first phenolic monomer, chelating, which corresponds to the following general formula (I): ## STR1 ## in which: m is 0, 1, 2 or 3, n is 0, 1 or 2, R1, R2, R3, R4, R5 independently of one another are hydrogen, -OH, C1-C10 alkyl, C1-C10 alkoxy; aryloxy, aryloxy, -SO3H, -COOR wherein R is hydrogen or C1-C10 alkyl, -P (O) (OR) or a -C (O) NRR 'group in which R and R' independently of one another represent a hydrogen atom or a C1-C10 alkyl group; with the proviso that at least one of R1 to R5 is -OH and at least two of R1 to R5 are hydrogen; at least one second phenolic monomer, which does not correspond to the general formula (I) above; and - formaldehyde.

Thus, the resin according to the invention is a formophenolic type resin which is functionalized with chelating groups derived from ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTPA) or acid. triethylene tetramine hexaacetic acid (HTTA) but in which the chelating groups are an integral part of the polymer matrix of the resin since the latter is obtained by condensation of a first phenolic monomer carrying these chelating groups, a second phenolic monomer and formaldehyde . Unexpectedly, this resin has been shown to have a selectivity, not only towards cesium but also towards strontium, as will be demonstrated in Example 3 below. In the foregoing and the following, the term "C1-C10 alkyl group" means any alkyl group, linear or branched, which is formed by at least one carbon atom and at most ten carbon atoms such as a methyl, ethyl, propyl group such as n-propyl or isopropyl, butyl such as n-butyl, sec-butyl, isobutyl or tert-butyl, pentyl as n-pentyl, sec-pentyl or isopentyl, hexyl as n-hexyl or isohexyl, heptyl such as n-heptyl or isoheptyl, octyl as n-octyl or isooctyl, nonyl as n-nonyl or isononyl, decyl as n-decyl or isodecyl, etc .; ; "C1-C10 alkoxy group" means any linear or branched O-alkyl group which is formed by at least one carbon atom and at most ten carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, butoxy such as n-butoxy, sec-butoxy or isobutoxy, pentoxy as n-pentoxy, sec-pentoxy or isopentoxy, hexoxy as n-hexoxy or isohexoxy, heptoxy as n-heptoxy or isoheptoxy, octoxy as n-octoxy or isooctoxy, nonoxy such as n-nonoxy or isononoxy, decoxy as n-decoxy or isodecoxy, etc .; "Aryl group" means any group derived from an arene, that is to say from a hydrocarbon whose formula is derived from benzene, such as a phenyl, benzyl, naphthyl, o-tolyl or m-tolyl group; p-tolyl, o-xylyl, m-xylyl, p-xylyl, phenethyl, etc .; and "aryloxy group" means any O-aryl group wherein the aryl group is as defined above such as, for example, phenoxy, benzyloxy, naphthyloxy, o-tolyloxy, m-tolyloxy, p-tolyloxy , o-xylyloxy, m-xylyloxy, p-xylyloxy, phenethyloxy, etc. In the context of the invention, it is preferable to use alkyl and alkoxy groups which comprise from 1 to 6 carbon atoms, aryl groups which are chosen from phenyl, benzyl and phenethyl groups, the phenyl group being especially preferred - and aryloxy groups which are selected from phenoxy, benzyloxy and phenethyloxy, phenyloxy being most preferred. According to the invention, the first phenolic monomer preferably corresponds to the general formula (I) above in which R 3 represents a group -OH, R 1 and R 5 both represent a hydrogen atom, while m, n, R2 and R4 have the same meaning as before. More preferably, it is preferred that the first phenolic monomer has the above general formula (I) wherein m is 2, R 3 is -OH, R 1, R 2 and R 5 are all hydrogen, R 4 is a hydrogen atom or a -OH group, while has the same meaning as above. Phenolic monomers, which correspond to the above general formula (I) wherein m is 2, R3 is -OH, R1, R2, R4 and R5 are all four hydrogen, while n is 0 or 1, are very particularly preferred. According to the invention, the second phenolic monomer can be any phenolic compound which is capable of conducting, by condensation with formaldehyde, a formophenolic resin provided that this compound does not meet the general formula (I) below. before. In other words, it can be any compound which comprises at least one benzene ring at least one carbon atom of which bears an -OH group and at least two carbon atoms of which carry a hydrogen atom but which do not does not meet the general formula (I) above. The second phenolic monomer preferably comprises 1 to 4 benzene rings, which can either be connected two by two through a vertex or via an atom, for example oxygen, or a group, by -CH2- or -C (CH3) 2-, forming a bridge, or be joined to each other, each of these benzene cycles having at least one carbon atom carrying a -OH group and at least two atoms of carbon carriers of a hydrogen atom.

Thus, by way of non-limiting example, the second phenolic monomer can be chosen from phenol, catechol (or 1,2-dihydroxybenzene), resorcinol (or 1,3-dihydroxybenzene), hydroquinone (or 1,4-dihydroxybenzene), hydroxyquinol (or 1,2,4-trihydroxybenzene), phloroglucinol (or 1,3,5-trihydroxybenzene), pyrogallol (or 1,2,3-trihydroxybenzene), benzenetetrol ( or 1,2,3,5-tetrahydroxybenzene), cresols (m-, o- and p-cresol), xylenols (2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6 xylenol, 3,4-xylenol and 3,5-xylenol), hydroxybenzoic acids (2-hydroxybenzoic acid, 3-hydroxybenzoic acid and 4-hydroxybenzoic acid), dihydroxybenzoic acids (2,3-dihydroxybenzoic acid, acid 2, 4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid and α-resorcylic acid), trihydroxybenzoic acids (pyrogallol carboxylic acid, 2,3,5-trihydroxybenzoic acid 2,3,6-trihydroxybenzoic acid, 2,4,5-trihydroxybenzoic acid, phloroglucinic acid and gallic acid), mono-, di- or trihydroxybenzene sulfonic acids (4-hydroxybenzene sulfonic acid, 1,2-dihydroxybenzene sulfonic acid, 2,5-dihydroxybenzene sulfonic acid, 3,4-dihydroxybenzene sulfonic acid, etc.), mono-, di- or trihydroxybenzene phosphonic acids (4-hydroxybenzene phosphonic acid, 1,2-dihydroxybenzene phosphonic acid, 3,4-acid dihydroxybenzene phosphonic acid, etc.), mono-, di- or trihalogenophenols (2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,3-difluorophenol, 2,4-difluorophenol, 2,5-difluorophenol, 2,6-difluorophenol, difluorophenol, 3,4-difluorophenol, 2,3,4-trifluorophenol, 2,3,6-trifluorophenol, 2,4,6-trifluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,3- dichlorophenol, 2,4-dichlorophenol, 2,5-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 2,3,4-trichlorophenol, 2,3,6-trichlorophenol, 2 , 4,6-trichlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,3-dibromophenol, 2,4-dibromophenol, 2,5-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 2 , 3,4-tribromophenol, 2,3,6-tribromophenol, 2,4,6-tribromophenol, etc.), bisphenol A, phenylphenols (m-phenylphenol, o-phenylphenol and p-phenylphenol), hydroxybenzo-ethercreams (4-hydroxybenzo-15-crown-5,6-hydroxybenzo-15-crown-5,4-hydroxybenzo-18-crown-6,6-hydroxybenzo-18-crown-6, etc.), the calix [n] arenes (calix [4] resorcinarene, calix [4] hydroquinone, calix [4] arene, calix [6] arene, calix [8] arene, etc.) and mixtures thereof. According to the invention, the second phenolic monomer is preferably chosen from dihydroxybenzenes (cathecol, resorcinol and hydroquinone) and calix [4] resorcinarene, resorcinol being very particularly preferred. The resin according to the invention may in particular be obtained by a process which comprises: a) the preparation of a reaction medium comprising the first and second phenolic monomers, formaldehyde and a strong base; and b) applying a heat treatment to the reaction medium thus prepared to obtain the formation of the resin by polycondensation of the first and second phenolic monomers and formaldehyde.

According to the invention, step a) may in particular be carried out by: dissolving the first and second phenolic monomers in an aqueous solution of the strong base; then addition of formaldehyde to the basic solution of phenolic monomers thus obtained. In step a), use is preferably made of: a molar ratio between the first phenolic monomer and the second phenolic monomer which is between 0.1 and 5 and, more preferably, between 0.5 and 2; a molar ratio between formaldehyde and the first and second phenolic monomers which is between 2 and 10 and, more preferably, between 2 and 4; a molar ratio between the strong base and the first and second phenolic monomers which is between 0.5 and 2.5 and more preferably between 1 and 2; and a molar ratio of water (which is present in the aqueous solution of strong base) to the first and second phenolic monomers which is between 25 and 500 and more preferably between 50 and 150.

The strong base is preferably a metal hydroxide such as an alkali metal hydroxide of the lithium hydroxide, sodium hydroxide, potassium hydroxide or cesium hydroxide type, or a hydroxide of an alkaline earth metal of calcium hydroxide type, strontium hydroxide or barium hydroxide. Sodium hydroxide is most preferred.

In step b), the heat treatment preferably consists in heating the reaction medium to a temperature of between 95 ° C. and 130 ° C. and, more preferably, between 95 ° C. and 110 ° C., for 16 hours at 96 hours and, better still, 48 to 96 hours. According to the invention, the process may advantageously furthermore comprise the reduction of the resin obtained in stage b) in the form of particles, for example by grinding, these particles preferably measuring from 0.05 to 1 mm, washing the particles thus obtained with aqueous solutions, for example alternately acidic and basic, and drying the particles thus washed, for example in an oven. An ion exchange resin is thus obtained, which has chelating properties and is ready to be used for extracting cesium or strontium from an aqueous medium containing one of these elements, or even more to extract these two elements grouped together if they are both present in the same aqueous medium. Also, the subject of the invention is also the use of an ion exchange resin with chelating properties, as defined above, for extracting cesium and / or strontium from an aqueous medium in which one and / or the other of these elements are present. Preferably, the resin is used to co-extract cesium and strontium from an aqueous medium in which these two elements are present.

According to the invention, the aqueous medium is preferably an industrial aqueous liquid effluent and, in particular, an aqueous liquid effluent from the nuclear industry such as, for example, a low and medium activity effluent resulting from the reprocessing of irradiated nuclear fuel, or any other aqueous liquid effluent containing radio-contaminants.

The extraction of cesium and / or strontium from an aqueous medium, whether it be a freshwater or seawater medium, using a resin according to the invention is extremely simple to implement since it is sufficient to put this resin in contact with the aqueous medium, for example in a stirred reactor or in a column, for a time sufficient to allow cesium and / or strontium to be complexed by the resin, and then separate the resin from the aqueous medium. It should be noted that the first phenolic monomer of general formula (I) can be obtained by reaction of a compound of general formula (II) below: ## STR2 ## Wherein n is 0, 1 or 2, with a compound of the following general formula (III): (III) wherein m is 0, 1, 2 or 3 and R1, R2, R3, R4, R5 represent independently of one another a hydrogen atom, an -OH group, a C1-C10 alkyl group, a C1-C10 alkoxy group, an aryl group, an aryloxy group, a -503H group, a -COOR group in which R represents a hydrogen atom or a C1-C10 alkyl group, a -P (O) (OR) group or a -C (O) NRR 'group in which R and R' represent independently of one another a hydrogen atom or a C1-C10 alkyl group, with the proviso that at least one of R1 to R5 is -OH and at least two of R1 to R5 are a hydrogen atom, using prot operating glasses adapted from those described in the literature (S. Lauren et al., Fur. J. Inorg. Chem., 2061-2067 (2007), reference [7]; N. N. Parac-Vogt et al., J. Alloy Compd., 374 (1-2), 325-329 (2004), reference [8]; A. Leydier et al., Tetrahedron, 68, 1163-1170 (2012), reference [9]). Other features and advantages of the invention will appear better on reading the additional description which follows, which relates to an exemplary synthesis of compounds suitable for use as first phenolic monomers in the synthesis of ion exchange resins according to the invention, to an exemplary synthesis of ion exchange resins according to the invention, as well as an example of demonstration of the ability of the resins thus synthesized to selectively extract cesium and strontium from a liquid effluent. Of course, these examples are given as an illustration of the subject of the invention and do not constitute in any way a limitation of this object.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 represents, in graphic form, the values of the distribution coefficient (KD in ml / g) and the extraction percentage (E) obtained for strontium during tests consisting of extracting cesium and strontium an aqueous solution simulating a seawater diluted to 200 ppm sodium and doped with cesium and strontium, at a concentration of 10 -4 M, with two resins according to the invention (ETRF-Na and DTRF-Na) and by varying the amount of resin used from 0.5 g to 25 g / l of aqueous solution. FIG. 2 shows, in graphical form, the values of the distribution coefficient (KD in ml / g) and the extraction percentage (E) obtained for cesium in tests consisting in extracting cesium and strontium from a solution aqueous solution simulating a seawater diluted to 200 ppm sodium and doped with cesium and strontium, at a concentration of 10 -4 M, with two resins according to the invention (ETRF-Na and DTRF-Na) and by varying the amount of resin used from 0.5 g to 25 g / l of aqueous solution.

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS EXAMPLE 1 SYNTHESIS OF COMPOUNDS SUITABLE FOR USE AS FIRST PHENOLIC MONOMERS Four compounds are synthesized which can be used as first phenolic monomers in the synthesis of resins according to the invention.

These compounds are respectively called EDTA-bisTyramide, EDTA-bisDopamide, DTPA-bisTyramide and DTPA-bisDopamide in the following.

They correspond to the general formula (I) above in which: m = 2, R 3 = -OH, R 1 = R 2 = R 4 = R 5 = H and n = 0 for EDTA-m = 2, R 3 = R4 = -OH, R1 = R2 = R5 = H and n = 0 for EDTA- - m = 2, R3 = -OH, R1 = R2 = R4 = R5 = H and n = 1 for DTPA- - m = 2, R3 = R4 = -OH, R1 = R2 = R5 = H and n = 1 for the DTPAIls thus correspond to the particular formula (la) below: bisTyramide; bisDopamide; bisTyramide; and bisDopamide.

Wherein R4 represents a hydrogen atom or an -OH group, while n is 0 or 1.n is 0 or 1. These four compounds are obtained by reaction of a compound of general formula (II) above in which n is 0 or 1, with a compound of general formula (III) above in which m = 2, R3 = R4 = -OH and R1 = R2 = R5 = H, in which case it is tyramine, or m = 2, R3 = R4 = -OH, R1 = R2 = R5 = H, in which case it is dopamine.

For this purpose, to a solution of the compound of general formula (II) in which n is 0 (1.281 g, 5 mmol), or the compound of general formula (II) in which n is 1 (1.786 g, 5 mmol), in anhydrous dimethylformamide (DMF) are added 12.5 mmol of tyramine (ie 1.715 g of tyramine) or of dopamine (or 2.37 g of dopamine). The reaction mixture is heated at 60 ° C under nitrogen flow for 24 hours. Then, a small amount (0.25 g) of ascorbic acid is added to the reaction mixture to prevent oxidation. After removal of the solvent under reduced pressure, the products are dissolved in ethanol (32 ml for the two products resulting from the condensation with dopamine and 65 ml for the two products resulting from the condensation with tyramine), then precipitated in diethyl ether (150 mL). The precipitates are filtered and then washed with diethyl ether before drying in vacuo. The returns are in all cases of the order of 80%. Nuclear Magnetic Resonance Characterization of Proton and Carbon 13 (1H-NMR and 1-3C NMR), Fourier Transform Infrared Spectroscopy (FTIR), Electrospray Mass Spectroscopy (MS-ES) and Mass Spectroscopy high resolution (SM-HR) of the compounds thus obtained are given below. EDTA-bis-tetramidine: 1H NMR (DMSO-d6, 400MHZ, 25 ° C) δ (ppm): 8.03 (t, 1H, CH2CONH), 6.99 (d, 2H, Ar-H), 6.68; (d, 2H, Ar-H), 3.35 (s, 2H, NCH 2 C (O) NH), 3.25 (t, 2H, NCH 2 CH 2 Ar), 3.22 (s, 2H, NCH 2 CO 2 H), 2.59. (t, 2H, NCH2CH2N), 2.51 (t, 2H, NHCH2CH2Ar); 13 C NMR (DMSO-d6, 100 MHz, 25 ° C) δ (ppm): 172.5 (C = O), 170.16 (C = O), 155.6 (ArC), 129.4 (ArCH) 115.3 (ArCH), 57.47 (CH2), 55.33 (CH2), 52.25 (CH2), 39.64 (CH2), 34.41 (CH2); IRTF: ν = 3191 cm -1 (OH), ν = 2972 cm -1 (aromatic CH), ν = 2902 cm -1 (CH 2), ν = 1732 cm -1 (C = O acid), v = 1652 cm -1 (C = 0 amide I), v = 1604 cm -1 (C = C), ν = 1519 cm -1 (C = O amide II), ν = 1193 cm -1 (OH); ), v = 814 cm -1 (aromatic CH); Found 5M-ES: 531.2 ([M + Hr); HRMS found: 531.2462 ([M + H]); Mcalc. : 530.2377.

EDTA-bis-dopamide: 1 H NMR (D 2 O, 400 MH 2 O, 25 ° C) δ (ppm): 6.82-6.55 (m, 3H, Ar-H), 3.51 (s, NCH 2 C (O) NH) , 3.46 (s, NCH2CO2H), 3.39 (t, 2H, NCH2CH2Ar), 3.11 (t, NCH2CH2N), 2.63 (t, 2H, NHCH2CH2Ar); 13 C NMR (D 2 O, 100 MH 2 O, 25 ° C) δ (ppm): 171.43 (C = O), 168.13 (C = O), 143.77 (ArC), 142.29 (ArC), 131, 75 (ArC), 121.1 (ArCH), 116.52 (ArCH), 116.47 (ArCH), 56.33 (CH2), 54.93 (CH2), 51.1 (CH2), 40.37 (CH2), 36.87 (CH2); IRTF: ν = 3188 cm -1 (OH) broad, ν = 3027 cm -1 (aromatic CH), ν = 2946 cm -1 (CH 2), ν = 1735 cm -1 (C = O acid) , v = 1651 cm -1 (C = 0 amide 0, v = 1603 cm -1 (C = C), v = 1519 cm -1 (C = O amide II), v = 119 cm -1 (OH); v = 813 cm-1- (aromatic CH); 5M-ES found 563.2 ([M + H]), found: 563.2384 ([m + H]), McAlp .: 562.2275; DTPA-bis (tri) amide: 1H NMR (DMSO-d6, 400 MHz, 25 ° C) (ppm): 8.13 (t, 2H, CH2CONH), 6.99 (dd, 4H, Ar-H), 6, 7 (dd, 4H, Ar-H), 3.5 (s, 2H, NCH 2 COOH), 3.48 (s, 4H, NCH 2 C (O) NH), 3.25 (m, 8H, NCH 2 CO 2 H & NCH 2 CH 2 N), 3.01 (4H, NHCH2CH2Ar), 2.86 (4H, NHCH2CH2Ar), 2.61 (t, 4H, NCH2CH2N), 13 C NMR (DMSO-d6, 100 MHZ, 25 ° C) δ (ppm): 172, 71 (C = O), 170.03 (C = O), 169.19 (C = O), 156.18 (ArC), 155.62 (ArC), 129.42 (ArCH), 115.35 ( ArCH), 66.98 (CH2), 57.44 (CH2), 55.23 (CH2), 52.17 (CH2), 50.46 (CH2), 39.23 (CH2), 34.34 (CH2) FTIR: ν = 3217 cm -1 (OH), ν = 2972 cm -1 (aromatic CH), ν = 2901 cm -1 (CH 2), ν = 1722 cm -1 (C = O acid) ), v = 1639 cm -1 (C = O amide I), ν = 1616 cm -1 (C = C), ν = 1515 cm -1 ( C = 0 amide II), ν = 1231 cm -1 (OH), ν = 825 cm -1 (aromatic C-H); 5M-ES found: 632.2 ([M + H]); MS-HR found: 632.2935 ([M + H]) M - calc. 631.2853. DTPA-bis-dopamide: 1 H NMR (D 2 O, 400 MH 2 O, 25 ° C) δ (ppm): 6.68 (d, 2H, Ar-H), 6.55 (d, 2H, Ar-H), 6.5 (dd, 2H, Ar-H), 3.88 (s, 2H, NCH2C (O) NH), 3.76 (s, 2H, NCH2CO2H), 3.52 (s, 1H, NCH2CO2H), 3.33 (t, 2H, NCH2CH2N), 3.14 (t, NHCH2CH2Ar), 3.11 (t, NHCH2CH2Ar), 2.60 (t, 2H, NCH2CH2N); 13 C NMR (D 2 O, 100 MH 2 O, 25 ° C) δ (ppm): 172.54 (C = O), 169.87 (C = O), 166.36 (C = O), 143.77 (ArC) , 142.93 (ArC), 131.72 (ArC), 121.13 (ArCH), 116.54 (ArCH), 116.05 (ArCH), 56.27 (CH2), 55.41 (CH2), 52.18 (CH 2), 50.03 (CH 2), 40.56 (CH 2), 36.86 (CH 2), 33.67 (CH 2); IRTF: ν = 3211 cm -1 (OH), ν = 3039 cm -1 (aromatic CH), ν = 2963 cm -1 (CH 2), ν = 1729 cm -1 (C = 0 acid), v = 1652 cm -1 (C = O amide I), v = 1603 cm -1 (C = C), ν = 1519 cm -1 (C = O amide II), ν = 1194 cm -1 (OH); ), v = 814 cm -1 (aromatic CH); 5M-ES found: 664.3 ([M + H]); Found: 664.2830 ([M + H]) M - calc. 663.2752.

These compounds are used as phenolic monomers with chelating properties in the synthesis of resins according to the invention without additional purification. EXAMPLE 2 RESIN SYNTHESIS ACCORDING TO THE INVENTION Resins according to the invention are synthesized using: one of the compounds synthesized in Example 1 above as the first phenolic monomer; resorcinol, catechol or calix [4] resorcinarene as the second phenolic monomer; - formaldehyde; - sodium hydroxide (NaOH) or cesium hydroxide (C50H) as a strong base; and a chelating monomer / phenol monomer / formaldehyde / strong base / H 2 O molar ratio of 0.5 / 0.5 / 2.5 / 1.5 / 100. The chelating monomer (0.5 mmol) and the phenolic monomer (0.5 mmol) are first solubilized in a solution of NaOH or CsOH (1.5 mmol in 100 mmol H 2 O). The resulting solution is stirred at room temperature or at 0 ° C and formaldehyde (2.5 mmol) is added to this solution. The reaction mixture is stirred for 24 hours after which it is heated in an oven under air at 100 ° C for 96 hours. After caking and hardening of this mixture, it is recovered, crushed (particle size between 0.05 and 1 mm), washed and conditioned by subjecting it to 3 washing cycles each comprising a washing with a solution of 1M HCl followed by washing with 1M NaOH solution and then dried under air at 80 ° C for 24 hours.

The twenty-two resins which are presented in Table I below are thus synthesized, in which the first and second phenolic monomers as well as the strong base having been used for the synthesis of each of them are also indicated.

Table I Resin First monomer Second monomer Phenolic phenolic base ETRF-Na EDRF-Na DTRF-Na DDRF-Na EDTA-bisTyramide EDTA-bisDopamide DTPA-bisTyramide DTPA-bis-Dopamide Resorcinol Resorcinol Resorcinol Resorcinol NaOH NaOH NaOH NaOH ETCF-Na EDTA-bisTyramide Catholol NaOH EDCF-Na EDTA-bis-dopamide Cathecol NaOH ETCRF-Na EDCRF-Na DTCRF-Na DDCRF-Na EDTA-bisTyramide EDTA-bis-Dopamide DTPA-bisTyramide DTPA-bis-dopamide Calix [4] resorcinarene Calix [4] resorcinarene Calix [4] resorcinarene Calix [4] ] resorcinarene NaOH NaOH NaOH NaOH ETRF-Cs EDRF-Cs DTRF-Cs DDRF-Cs EDTA-bisTyramide EDTA-bisDopamide DTPA-bisTyramide DTPA-bisDopamide Resorcinol Resorcinol Resorcinol Resorcinol CsOH CsOH CsOH CsOH ETCF-Cs EDCF-Cs DTCF-Cs DDCF-Cs EDTA-bisTyramide EDTA-bisDopamide DTPA-bisTyramide DTPA-bisDopamide Cathol Cathol Cathol Cathol CsOH CsOH CsOH CsOH ETCRF-Cs EDCRF-Cs DTCRF-Cs DDCRF-Cs EDTA-bisTyramide EDTA-bis-Dopamide DTPA-bisTyramide DTPA-bis-dopamide Calix [4] resorc inarene Calix [4] resorcinarene Calix [4] resorcinarene Calix [4] resorcinarene CsOH CsOH CsOH CsOH By way of example, the characterizations by 1-3C NMR of the solid, FTIR and by elemental analysis of the ETRF-Na and DTRF-Na resins are given below.

ETRF-Na: 13C NMR MAS 6 (ppm): 177.3 (C = O), 171.1 (C = O), 150.7 (ArC), 127.5 (ArCH), 117.1 (ArCH) , 58.4 (CH2), 54.34 (CH2), 41.1 (CH2), 40.4 (CH2), 32.9 (CH2), 32 (CH2); IRTF: ν = 3241 cm -1 (OH), ν = 2947 cm -1 (CH 2), ν = 2897 cm -1 (aromatic CH), ν = 2838 cm -1 (CH 2), v = 1648 cm -1 (COQ / C = O amide I), v = 1582 cm -1 (C = O amide II / C = C), ν = 1233 cm -1 (CO), ν = 1120 cm -1 - (OH), ν = 820 cm -1 (aromatic CH); Elemental analysis: C: 51.67%, N: 8.31%, 0: 30.54%, Na: 9.08%.

DTRF-Na: 13C NMR MAS 6 (ppm): 177.8 (C = O), 171.5 (C = O), 151.1 (ArC), 127.9 (ArCH), 117.6 (ArCH) , 58.9 (CH2), 54.1 (CH2), 41.3 (CH2), 40.2 (CH2), 32.8 (CH2), 32 (CH2); IRTF: ν = 3305 cm -1 (OH), ν = 2940 cm -1 (CH 2), ν = 2917 cm -1 (aromatic CH), ν = 1651 cm -1 (C 0 -C 1) = 0. amide 1), v = 1582 cm -1 (C = O amide II / C = C), v = 1234 cm -1 (C-O), ν = 1110 cm-1 (OH), ν = 824 cm -1 ( Aromatic CH); Elemental analysis: C: 55.03%, N: 8.40%, 0: 27.27%, Na: 9.02%. EXAMPLE 3: SELECTIVE EXTRACTION OF CÉSIUM AND STRONTIUM BY RESINS ACCORDING TO THE INVENTION The ability of the resins according to the invention to selectively extract cesium and strontium from an aqueous liquid effluent is assessed by extraction tests which are in batch mode, using aqueous aqueous effluents, three different aqueous solutions, hereinafter referred to as solutions 1, 2 and 3, respectively, and consisting of: solution 1: ultrapure water (water milliQTM) doped with cesium and strontium (in the form of CsCl and SrCl2 chlorides) at a concentration of 10-4 M; solution 2: a solution simulating a seawater diluted to 200 ppm (parts per million) of sodium and doped with cesium and strontium (in the form of CsCl and SrCl 2 chlorides) at a concentration of 10 -4 M; solution 3: a solution simulating a seawater diluted to 200 ppm of sodium and 25 ppm of calcium, doped with cesium and strontium (in the form of chlorides CsCl and SrCl2) at a concentration of 10-4 M. These tests consist to contact a certain amount of resin with a certain volume of solution 1, 2 or 3, to leave the mixture stirring at 25 ° C for 24 hours and then, after decantation, to take the supernatant, to filter (on a 0.22um cellulose acetate membrane) and to measure the concentration of the various cations present in the filtrate by atomic emission spectrometry (ICPAES) and ion chromatography.

For each cation, the distribution coefficient, denoted KD and expressed in ml / g, which represents the ratio between the amount of this cation present in the resin and the quantity of this cation remaining in solution after extraction, and which is determined by the following formula: Ci-Cf xV = (FD-1) xV KD - Cf mm with: Ci = initial concentration of the cation in solution (in mg / L); Cf = concentration of the cation in solution after extraction (in mg / L); V = volume of solution (in mL); m = mass of resin (in mg); FD = decontamination factor = -Ci; and Cf - the percentage of extraction, denoted E, which is determined by the formula: E = Ci-Cf x100 Ci with: Ci = initial concentration of the cation in solution (in mg / l); Cf = concentration of the cation in solution after extraction (in mg / L). Tables II and III below show the values of KD, E and FD obtained, respectively for cesium and strontium, with the twenty-two resins synthesized in example 2 and solutions 1 and 2, and using 1 g of resin per L of solution. Table II Cesium Resin Solution 1 Solution 2 (H2O + Cs + Sr) (H2O + Na + Cs + Sr) KD E FD KD E FD (mL / g) (%) (mL / g) (%) ETRF-Na 4319 , 2 81,352 5,4 399.5 28,751 1,4 ETRF-Cs 4559,3 82,159 5,6 375.9 27,517 1,4 DTRF-Na 3772,8 79,048 4,8 467.4 31,851 1.5 DTRF-Cs 1975.4 68.286 3.2 185 16.783 1.2 EDRF-Na 3192.5 77.022 4.4 275.8 22.453 1.3 EDRF-Cs 2834.9 76.682 4.3 135.3 13.568 1.2 DDRF-Na 2485 , 6 77,145 4,4 224.6 23,371 1,3 DDRF-Cs 3352.7 77,878 4,5 212.7 18,256 1,2 ETCF-Na 2537.5 74,804 4,287.2 25,151 1,3 ETCF-Cs 1192, 2 58,452 2,4 115,8 12,024 1,1 DTCF-Cs 3066 76,3 4,2 217,7 18,607 1,2 EDCF-Na 2164 70,791 3,4 269 23,154 1,3 EDCF-Cs 2018 68,548 3.2 271.5 22.673 1.3 DDC-Fs 2481.9 71.483 3.5 138 12.237 1.1 F CFR-N 3368.7 79.483 4.9 250.7 22.379 1.3 F CFR-Cs 2505.4 72.266 3.6 276 , 8 22.351 1.3 DTCRF-Na 4466.3 82.424 5.7 499 34.38 1.5 DTCRF-Cs 4711.9 82.483 5.7 836.9 45.561 1.8 EDCRF-Na 2595.3 72.186 3.6 290.4 22.508 1.3 EDCRF-Cs 2940.7 77.024 4.4 352.4 28.659 1.4 DDCRF-Na 2562.2 75.146 4 315, 2 27,112 1,4 DDCRF-Cs 2955,9 75,455 4.1 417.9 30,294 1,4 Table III Strontium Solution 1 Solution 2 Resin (H 2 O + Cs + Sr) (H 2 O + Na + Cs + Sr) (1 g / L) KD E FD KD E FD (mL / g) (%) (mL / g) (%) ETRF-Na> 32835> 97.1> 34.2> 34318> 97.2> 35.7 ETRF-Cs > 32836> 97.1> 34.2> 32175> 97.0> 33.5 DTRF-Na 33164 97.1 34.2> 34661> 97.2 35.7 DTRF-Cs> 30426> 97.1> 34 , 2> 29814> 97.0> 33.5 EDRF-Na> 38746> 97.5> 39.7> 33011> 97.2> 35.7 EDRF-Cs> 28590> 97.1> 34.2> 28015 > 97.0> 33.5 DDRF-Na> 35883> 97.3> 36.9> 31247> 97.0> 33.5 DDRF-Cs> 31585> 97.1> 34.2> 30950> 97.0 > 33.5 ETCF-Na> 28346> 97.1> 34.2> 27775> 97.0> 33.5 ETCF-Cs> 32654> 97.5> 39.5> 27540> 97.0> 33.5 DTCF-Cs> 36696> 97.5> 39.5> 31736> 97.1> 34.3 EDCF-Na> 29611> 97.1> 34.2> 29015> 97.0> 33.5 EDCF-Cs> 35677> 97.5> 39.5> 25094> 96.4> 28.1 DDCF-Cs 17365 94.6 18.5> 25696 96.3 26.9 FTE-NA> 28838> 97.1> 34.2 > 28258> 97.0> 33.5 ETCRF-Cs> 37049> 97.5> 39.5> 32041> 97.1 > 34.3 DTCRF-Na> 31585> 97.1> 34.2> 30950> 97.0> 33.5 DTCRF-Cs> 38531> 97.5> 39.5> 33323> 97.1> 34.3 EDCRF-Na> 38531> 97.5> 39.5> 32498> 97.0> 33.5 EDCRF-Cs 28430 97.0 33.4> 26483 96.8 31.2 DDCRF-Na 9995 92.2 12, 8> 12616 93.7 15.9 DDCRF-Cs 15620 94.0 17.2> 11099 92.0 12.5 Table IV below shows the KD and E values obtained for strontium, with ETRF resins -Na and DTRF-Na synthesized in Example 2 above and solutions 2 and 3, varying the amount of resin used per L solution from 0.5 g to 25 g.

Table IV Resin Solution 2 Solution 3 (H2O + Na + Cs + Sr) (H2O + Na + Ca + Cs + Sr) KD E KD E (mL / g) (%) (mL / g) (%) ETRF-Na (g / L)> 59241> 96.9 58.5 3.0 0.5 1> 34318> 97.2> 7891> 90.4 2.5> 12503> 96.9> 3668> 90.4> 6251 > 96.9> 1863> 90.4> 3098> 96.9> 931> 90.4 25> 1257> 96.9> 492> 90.4 DTRF-Na (g / L)> 59800> 96.9 1142 , 0 41.1 0.5 1> 34661> 97.2> 7512> 90.4 2.5 8423 95.5> 3611> 90.4 5 2747 93.3> 1848> 90.4 10 1220 92.5 > 939> 90.4 25 390 90.7> 375> 90.4 Figure 1 represents, in graphical form, the results presented in Table IV above for solution 2, while Figure 2 represents, also 5 in graphic form, the KD and E values obtained for cesium, with the ETRF-Na and DTRF-Na resins synthesized in Example 2 above and the solution 2, by varying the amount of resin used by L solution (from 0.5 g to 25 g) These tables and figures show that regardless of the composition of the aqueous solution having tee used to perform the extraction tests are obtained 10 distribution coefficients and extraction of very high percentages (> 97% in almost all cases) for strontium. The presence of calcium, which has the same behavior in aqueous solution and the same charge as strontium, affects only very little the efficiency of strontium decontamination with KD and E values of the same order of magnitude as in the absence of calcium (see Table IV above). Strontium is therefore very efficiently extracted from the different aqueous solutions, whatever the nature of these.

As for cesium, it is very efficiently co-extracted with strontium from a sodium-free aqueous solution (see Table II above). The presence of sodium leads to a significant decrease in the efficiency of cesium extraction highlighting Cs / Na competition. However, as shown in FIG. 2, an increase in the concentration of resin in the aqueous solution to be decontaminated makes it possible to overcome this problem since, for a resin concentration of 25 g / l, results are obtained in terms of efficiency of the order of 85%. BIBLIOGRAPHIC REFERENCES [1] S. K. Samanta et al., Sep. Sci. Technol., 27 (2), 255-267 (1992) [2] S. K. Samanta et al., Radiochem. Acta, 57, 201-205 (1992) [3] A. Favre-Reguillon et al., Sep. Sci. Technol., 36 (3), 367-379 (2001) [4] K. A. K. Ebraheem et al., Sep. Sci. Technol., 35 (13), 2115-2125 (2000) [5] M. Draye et al., Sep. Sci. Technol., 35 (8), 1117-1132 (2000) [6] K. Singh and R. Gupta, J. Indian. Chem. Soc., 79, 447-449 (2002) [7] S. Lauren et al., Fur. J. Inorg. Chem., 2061-2067 (2007) [8] TN Parac-Vogt et al., J. Alloy Compd., 374 (1-2), 325-329 (2004) [9] A. Leydier et al., Tetrahedron , 68, 1163-1170 (2012)

Claims (16)

REVENDICATIONS1. An ion exchange resin with chelating properties, of the formophenolic type, which is obtained by polycondensation in basic medium: of at least one first phenolic monomer, chelating, which corresponds to the following general formula (I): o (N) embedded image in which: m is 0, 1, 2 or 3, n is 0, 1 or 2, R1, R2, R3, R4, R5 represent independently from each other a hydrogen atom, a -OH group, a C1-C10 alkyl group, a C1-C8 alkoxy group, an aryl group, -SO3H group, a -COOR group in which R represents an atom of hydrogen or a C1-C10 alkyl group, a -P (O) (OR) group or a -C (O) NRR 'group in which R and R' independently represent one of the groups another a hydrogen atom or a C1-C10 alkyl group; with the proviso that at least one of R1 to R5 is -OH and at least two of R1 to R5 are hydrogen; at least one second phenolic monomer, which does not correspond to the general formula (I); and - formaldehyde.SP 53096 SL 25 The resin of claim 1, wherein the first phenolic monomer has the general formula (I) wherein R 3 is -OH, R 1 and R 5 are both hydrogen, and m, n, R2 and R4 have the same meaning as before. The resin according to claim 2, wherein the first phenolic monomer has the general formula (I) wherein m is 2, R3 is -OH, R1, R2 and R5 are all 3 hydrogen, R4 represents a hydrogen atom or a -OH group, while it has the same meaning as above. The resin according to claim 3, wherein the first phenolic monomer has the general formula (I) wherein m is 2, R3 is -OH, R1, R2, R4 and R5 are all four hydrogen , while n is 0 or 1. 5. A resin according to any one of claims 1 to 4, wherein the second phenolic monomer comprises from 1 to 4 benzene rings, each of these rings having at least one carbon atom which bears a group -OH and at least two atoms of carbon that carry a hydrogen atom. 6. Resin according to claim 5, wherein the second phenolic monomer is chosen from phenol, catechol, resorcinol, hydroquinone, hydroxyquinol, phloroglucinol, pyrogallol, benzenetetrol, cresols, xylenols, mono-, di- or trihydroxybenzoic acids, mono- or di- or trihydroxybenzene sulfonic acids, mono-, di- or trihydroxybenzene phosphonic acids, mono-, di- or trihalogenophenols, bisphenol A, phenylphenols, hydroxybenzoethercouronnes and calix [n] arenes. 7. The resin of claim 6, wherein the second phenolic monomer is selected from catechol, resorcinol, hydroquinone and calix [4] resorcinarene. Process for the synthesis of an ion exchange resin with chelating properties, as defined in any one of claims 1 to 7, which comprises: a) the preparation of a reaction medium comprising the first and second phenolic monomers formaldehyde and a strong base; and b) applying a heat treatment to the reaction medium thus prepared to obtain the formation of the resin by polycondensation of the first and second phenolic monomers and formaldehyde. The process of claim 8, wherein step a) comprises: solubilizing the first and second phenolic monomers in an aqueous solution of the strong base; then - the addition of formaldehyde to the basic solution of phenolic monomers thus obtained. 10. The method of claim 8 or claim 9, wherein is used in step a) a molar ratio between the first phenolic monomer and the second phenolic monomer which is between 0.1 and 5. 11. A method according to any one of claims 8 to 10, wherein is used in step a) a molar ratio between formaldehyde and the first and second phenolic monomers which is between 2 and 10. 12. Process according to any one of claims 8 to 11, wherein is used in step a) a molar ratio between the strong base and the first and second phenolic monomers which is between 0.5 and 2.5. 13. A process according to any one of claims 8 to 12, wherein the heat treatment of step b) comprises heating the reaction medium at a temperature between 95 ° C and 130 ° C for 16 hours to 96 hours . 14. Use of an ion exchange resin with chelating properties, as defined in any one of claims 1 to 7, for extracting cesium and / or strontium from an aqueous medium in which the one and / or either of these elements are present. 15. Use according to claim 14, wherein the resin is used to co-extract cesium and strontium from an aqueous medium in which both of these elements are present. 15 16. Use according to claim 14 or claim 15, wherein the aqueous medium is an industrial aqueous liquid effluent and, preferably, an aqueous liquid effluent from the nuclear industry. o