WO2014086788A1

WO2014086788A1 - Ion exchange resin having chelating properties, method for preparing same and uses thereof

Info

Publication number: WO2014086788A1
Application number: PCT/EP2013/075406
Authority: WO
Inventors: Stéphane PELLET-ROSTAING; Guilhem ARRACHART; Ahmad KENAAN; Stéphanie GRACIA; Raphaël TURGIS; Véronique Dubois
Original assignee: Commissariat à l'énergie atomique et aux énergies alternatives; Centre National De La Recherche Scientifique; Universite Montpellier 2 Sciences Et Techniques
Priority date: 2012-12-04
Filing date: 2013-12-03
Publication date: 2014-06-12
Also published as: FR2998816A1; FR2998816B1; EP2928604A1

Abstract

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

Description

ION EXCHANGE RESIN HAVING CHELATING PROPERTIES, ITS METHOD OF

PREPARATION AND ITS USES

DESCRIPTION TECHNICAL FIELD

The invention relates to the field of radionuclide decontamination of aqueous media in which these radionuclides are present in small amounts.

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 which affect the environment. one and / or the other of these two elements, which are likely to be produced by nuclear facilities, either as part of their normal operation (for example, in the context of an activity of reprocessing spent nuclear fuel) either 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 therefore need to be treated for 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 fuels (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). by 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]), while the use of catechol or of a phenol / iminodiacetic acid mixture tends to increase their selectivity with respect to strontium (SK Samanta et al., Radiochem 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.

So :

- 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. Indian. Chem. Soc., 79, 447-449 (2002), reference [6]) incorporated diethylenetriaminepentaacetic acid (DTPA) in a phenol-formaldehyde-based resin and analyzed the sorption capacities of this resin vis-a-vis 19 different types of metal ions (Ag, Co, Pb, Al, La, I n, Pt, Zr,

Th, etc.) but of which neither cesium nor strontium are part.

In references [3] to [5], crown ethers and 8-hydroxyquinoline act as co-monomers in the polycondensation of phenolic compounds and formaldehyde so that they are then part of the polymer matrices 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 purpose of the inventors is to provide new ion exchange resins with chelating properties that are selective both for cesium and strontium and In this way, these two elements of an aqueous medium can be grouped together and their chelating properties are not likely to be altered during use.

The goal of the inventors is also that the synthesis of these resins is simple to implement and can be achieved at costs compatible with their use on an industrial scale.

STATEMENT OF THE INVENTION

These and other objects are achieved by the present invention which proposes, firstly, an ion exchange resin having 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):

(D in which :

* m is 0, 1, 2 or 3,

* n is 0, 1 or 2,

* Ri, R2, R3, R _4, R 5 represent independently each other a hydrogen atom, -OH, an alkyl group in Ci to Ci _0, alkoxy, Ci to Ci ₀ aryl, an aryloxy group, a -SO ₃ H group, a -COOR group in which R represents a hydrogen atom or a C ₁ -C 10 alkyl group, a -P (O) (OR) (OR ') group or a -C (O) NRR 'group in which R and R' are, independently of each other, a hydrogen atom or a C ₁ -C 10 alkyl group; with the proviso that at least one of R 1 to R ₅ is -OH and at least two of R 1 to R ₅ 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 what precedes and what follows, we mean by:

"C ₁ -C ₁₀ 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 or propyl group such as π-propyl or isopropyl, butyl such as π-butyl, sec-butyl, isobutyl or ieri-butyl, pentyl as π-pentyl, sec-pentyl or isopentyl, hexyl as π-hexyl or isohexyl, heptyl as π-heptyl or isoheptyl, octyl as π-octyl or isooctyl, nonyl as n-nonyl or isononyl, decyl as π-decyl or isodecyl, etc. ;

"C ₁ -C ₁₀ 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 a methoxy, ethoxy or propoxy group; , isopropoxy, butoxy such as π-butoxy, sec-butoxy or isobutoxy, pentoxy as π-pentoxy, sec-pentoxy or iso-pentoxy, hexoxy as π-hexoxy or isohexoxy, heptoxy as π-heptoxy or isoheptoxy, octoxy as π-octoxy or isooctoxy, nonoxy such as π-nonoxy or isononoxy, decoxy as π-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 by

"Aryloxy group" means any O-aryl group in which 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 -OH group, Ri and R ₅ both represent a hydrogen atom, while m, n, R ₂ and R ₄ have the same meaning as above.

More preferably, it is preferred that the first phenolic monomer corresponds to the general formula (I) above wherein m is 2, R ₃ is -OH, R 1, R ₂ and R ₅ all represent a hydrogen atom, R ₄ represents a hydrogen atom or a -OH group, while n has the same meaning as above.

Phenolic monomers, which correspond to the above general formula (I) in which m is 2, R ₃ represents a group -OH, R 1, R ₂ , R ₄ and R ₅ all represent a hydrogen atom, while n is 0 or 1, are most 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 -CH ₂ - or -C (CH ₃ ) ₂ -, forming a bridge, or be contiguous to each other, each of these benzene rings having at least one carbon atom carrying a -OH group and at least two carbon atoms carrying 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 (acid pyrogallolcarboxylic 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 (acid 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, acid 1,2-dihydroxybenzene phosphonic acid, 3,4-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, 3,4-difluorophenol, 2,3,4-trifluorophenol, 2,3,6-trifluorophenol, 2,4,6-trifluorophenol, 2-chlorophenol, 3-chloro phenol, 4-chlorophenol, 2,3-dichlorophenol, 2,4-dichlorophenol, 2,5-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophen N, 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), hydroxybenzoethercreams (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 their mixtures.

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) preparing a reaction medium comprising the first and second phenolic monomers, formaldehyde and a strong base; and

b) the application of a heat treatment to the reaction medium thus prepared to obtain the formation of the resin by polycondensation of the first and second phenol 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 between the water (which is present in the aqueous solution of strong base) and 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 type, sodium hydroxide, potassium hydroxide or cesium hydroxide, or an alkaline earth metal hydroxide 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, the 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:

in which n is 0, 1 or 2, with a compound of general formula (III) below:

(I I I)

wherein m is 0, 1, 2 or 3 and R _lr R _2, R 3, R _4, R 5 represent independently each other a hydrogen atom, -OH, an alkyl group in Ci to Ci _0, a alkoxy Ci-Ci _0, an aryl group, an aryloxy group, an -S0 ₃ H group, a -COOR group wherein R represents a hydrogen atom or an alkyl group C1 to _0, a group -P (O) (OR) (OR ') or a group -C (O) NRR' in which R and R 'independently of one another represent a hydrogen atom or a C ₁ -C 10 alkyl group ; with the proviso that at least one of R 1 to R ₅ is -OH and at least two of R 1 to R ₅ are hydrogen; using procedures adapted from those described in the literature (Lauren et al., Eur J. Inorg Chem., 2061-2067 (2007), reference [7], TN Parac-Vogt et al. 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 to 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 only by way of illustration of the object 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 (K _D in ml / g) and of the extraction percentage (E) obtained for strontium during tests consisting in extracting cesium and strontium from a 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 represents, in graphical form, the values of the distribution coefficient (K _D in ml / g) and of the extraction percentage (E) obtained for cesium in tests consisting in extracting cesium and strontium from a 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 quantity 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 suitable for use 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-bis-pyramide;

m = 2, R ₃ = R ₄ = -OH, R 1 = R ₂ = R ₅ = H and n = 0 for EDTA-bis-polyamide;

m = 2, R ₃ = -OH, R 1 = R ₂ = R ₄ = R ₅ = H and n = 1 for DTPA-bis-pyramide; and

m = 2, R ₃ = R ₄ = -OH, R 1 = R ₂ = R ₅ = H and n = 1 for DTPA-bis-dopamide.

They therefore correspond to the following special formula (I-a):

(the)

wherein R ₄ represents a hydrogen atom or an -OH group, while n is 0 or ln 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, R ₃ = R ₄ = -OH and R 1 = R ₂ = R ₅ = H, in which case it is tyramine, or m = 2, R ₃ = R ₄ = -OH, R 1 = R ₂ = R ₅ = 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 (DM F) 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 a stream of nitrogen 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%.

Proton and carbon 13 nuclear magnetic resonance characterization ( ¹ H NMR and ¹³ C NMR), Fourier transform infrared spectroscopy (FTIR), electrospray mass spectroscopy (MS-ES) and high-level mass spectroscopy resolution (MS-HR) of the compounds thus obtained are given below.

EDTA-bisTyramide:

¹ H NMR (DMSO-d 6, 400 MH ² O, 25 ° C.) δ (ppm): 8.03 (t, 1H, CH ₂ CONH), 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, NCH ₂ CH ₂ N), 2.51 (t, 2H, NHCH ₂ CH ₂ Ar);

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 (CH ₂ ), 55.33 (CH ₂ ), 52.25 (CH ₂ ), 39.64 (CH ₂ ), 34.41 (CH ₂ );

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), ν = 1652 cm ^-1 (C = O amide I), v = 1604 cm ^-1 (C = C), v = 1519 cm ^-1 (C = O amide II), V = 1193 cm ^-1 (OH), ν = 814 cm ^-1 (aromatic CH);

SM-ES found: 531.2 ([M + H] ⁺ ); HRMS found: 531.2462 ([M + H] ⁺ ); M _{co / c} . ; 530.2377. EDTA-bisDopamide:

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, NCH ₂ CO ₂ H), 3.39 (t, 2H, NCH ₂ CH ₂ Ar), 3.11 (t, NCH ₂ CH ₂ N), 2.63 (t, 2H). NHCH ₂ CH ₂ Ar); 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 (CH ₂ ), 54.93 (CH ₂ ), 51.1 ( CH ₂ ), 40.37 (CH ₂ ), 36.87 (CH ₂ );

IRTF: ν = 3188 cm ^-1 (OH) broad, v = 3027 cm ¹ (aromatic CH), ν = 2946 cm ¹ (CH ₂ ), ν = 1735 cm ^-1 (C = O acid), ν = 1651 cm ¹ (C = 0 amide I), v = 1603 cm ^-1 (C = C), v = 1519 cm ^-1 (C = O amide II), ν = 1191 cm ^-1 (OH), ν = 813 cm ^-1 ^"1 (aromatic CH);

MS-ES found: 563.2 ([M + H] ⁺ ); HRMS found: 563.2384 ([M + H] ⁺ ); M _{co / c} . ; 562.2275. DTPA-bisTyramide:

¹ H NMR (DMSO-d 6, 400 MH ² O, 25 ° C.) δ (ppm): 8.13 (t, 2H, CH ₂ CONH), 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, NHCH ₂ CH ₂ Ar), 2.86 (4H, NHCH ₂ CH ₂ Ar), 2.61 (t, 4H, NCH ₂ CH ₂ N) ;

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 (CH ₂ ), 57.44 (CH ₂ ), 55.23 (CH ₂ ), 52 17 (CH ₂ ), 50.46 (CH ₂ ), 39.23 (CH ₂ ), 34.34 (CH ₂ );

IRTF: ν = 3217 cm ^-1 (OH), ν = 2972 cm ^-1 (aromatic CH), ν = 2901 cm ^-1 (CH ₂ ), ν = 1722 cm ^-1 (C = O acid), ν = 1639 cm ^-1 (C = 0 amide I), v = 1616 cm ^-1 (C = C), v = 1515 cm ^-1 (C = O amide II), V = 1231 cm ^-1 (OH), ν = 825 cm ^-1 (aromatic CH);

MS-ES found: 632.2 ([M + H] ⁺ ); MS-HR found: 632.2935 ([M + H] ⁺ ); M _{co / c} . ; 631.2853.

DTPA-bisDopamide:

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, NCH ₂ C (O) NH), 3.76 (s, 2H, NCH ₂ CO ₂ H), 3.52 (s, 1H, NCH) ₂ C0 ₂ H), 3.33 (t, 2H, NCH ₂ CH ₂ N), 3.14 (t, NHCH ₂ CH ₂ Ar), 3.11 (t, NHCH ₂ CH ₂ Ar), 2.60 (t, 2H, NCH ₂ CH ₂ N);

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 (CH ₂ ), 55.41 (CH ₂ ), 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 ), V = 1729 cm ^-1 (C = O acid), ν = 1652 cm ^-1 (C = 0 amide I), v = 1603 cm ^-1 (C = C), v = 1519 cm ^-1 (C = O amide II), V = 1194 cm ^-1 (OH), v = 814 cm ^-1 (aromatic CH);

MS-ES found: 664.3 ([M + H] ⁺ ); HRMS found: 664.2830 ([M + H] ⁺ ); M _{co / c} . ; 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 Synthesis of Resins 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 (CsOH) as a strong base; and

a chelating monomer / phenol monomer / formaldehyde / strong base / H ₂ 0 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 0). 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

By way of examples, the ¹³ C NMR characterizations of the solid, FTIR and elemental analysis of the ETRF-Na and DTRF-Na resins are given below. ETRF-Na:

NMR ¹³ C MASδ (ppm): 177.3 (C = O), 171.1 (C = O), 150.7 (ArC), 127.5 (ArCH), 117.1 (ArCH), 58, 4 (CH ₂ ), 54.34 (CH ₂ ), 41.1 (CH ₂ ), 40.4 (CH ₂ ), 32.9 (CH ₂ ), 32 (CH ₂ );

FTIR: v = 3241 cm ^"1 (OH), v = 2947 ^{cm" 1} (CH ₂₎ v = 2897 cm ^"1 (aromatic CH), v = 2838 ^{cm" 1} (CH ₂₎ v = 1648 cm ^{" 1} (COO ^"/ C = 0 amide I), v = 1582 ^{cm" 1} (C = 0 amide ll / C = C), v = 1233 cm ^"1 (C-0), v = 1120 ^{cm" 1} (OH ), v = 820 cm ^-1 (aromatic CH);

Elemental analysis: C: 51.67%, N: 8.31%, 0: 30.54%, Na: 9.08%. DTRF-Na:

NMR ¹³ C MASδ (ppm): 177.8 (C = O), 171.5 (C = O), 151.1 (ArC), 127.9 (ArCH), 117.6 (ArCH), 58, 9 (CH ₂ ), 54.1 (CH ₂ ), 41.3 (CH ₂ ), 40.2 (CH ₂ ), 32.8 (CH ₂ ), 32 (CH ₂ );

FTIR: v = 3305 cm ^"1 (OH), v = 2940 ^{cm" 1} (CH ₂₎ v = 2917 cm ^"1 (aromatic CH), v = 1651 ^{cm" 1} (COO ^"/ C = 0 amide I) v = 1582 cm- ¹ (C = O-amide II / C = C), v = 1234 cm- ¹ (CO), 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 carried out in batch mode, using, as aqueous liquid effluents. , three different aqueous solutions, hereinafter referred to as solutions 1, 2 and 3 respectively, and consisting of:

solution 1: ultrapure water (milli-Q ™ water) doped with cesium and strontium (in the form of CsCl and SrCl ₂ chlorides) at a concentration of 10 ^-4 M;

solution 2: a solution simulating a seawater diluted at 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 with 200 ppm of sodium and 25 ppm of calcium, doped with cesium and strontium (in the form of chlorides CsCl and SrCl ₂ ) at a concentration of 10 ^-4 M.

These tests involve contacting a certain quantity of resin with a certain volume of solution 1, 2 or 3, allowing the mixture to stir at 25 ° C. for 24 hours and then, after decantation, to take the supernatant, to filter it. (on a 0.22μιη cellulose acetate membrane) and to measure the concentration of the various cations present in the filtrate by atomic emission spectrometry (ICP-AES) and ion chromatography.

It is thus determined for each cation:

the coefficient of distribution, denoted K _D and expressed in ml / g, which represents the ratio between the quantity 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 :

K _{D =} ^ L _X ! _{= (FD} - _{1) X}

Cf m m

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);

This

FD = decontamination factor = -; and

Cf

the extraction percentage, denoted E, which is determined by the formula:

E = I ^ L _X100

This

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 K _D , E and FD values obtained for cesium and strontium respectively, 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 I I

Solution 1 Solution 2

(H ₂ O + Cs + Sr) (H ₂ O + Na + Cs + Sr)

Resin

K _D E Ko E

FD 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

DDCF-Cs 2481.9 71.483 3.5 138 12.237 1.1

ETCRF-Na 3368.7 79.483 4.9 250.7 22.379 1.3

ETCRF-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

Table IV below shows the K _D and E values obtained for strontium, with the ETRF-Na and DTRF-Na resins synthesized in Example 2 above and solutions 2 and 3, by varying the amount of resin used per L solution of 0.5 g to 25 g. Table IV

FIG. 1 represents, in graphic form, the results presented in Table IV above for solution 2, while FIG. 2 represents, also in graphical form, the K _D and E values obtained for cesium, with the ETRF-Na and DTRF-Na resins synthesized in Example 2 above and the solution 2, made it vary the amount of resin used per L of solution (from 0.5 g to 25 g)

These tables and figures show that, regardless of the composition of the aqueous solution that was used to carry out the extraction tests, very high distribution coefficients and extraction percentages (> 97% in almost all case) for strontium.

The presence of calcium, which has the same behavior in aqueous solution and the same load as strontium, affects only very little the effectiveness of the decontamination of strontium with K _D 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 regards cesium, it is very effectively co-extracted with strontium from a sodium-free aqueous solution (see Table I I 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-Réguillon 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] Mr. 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., Eur. J. Inorg. Chem., 2061-2067 (2007)

[8] N. N. Parac-Vogt et al., J. Alloy Compd., 374 (1-2), 325-329 (2004)

[9] A. Leydier et al., Tetrahedron, 68, 1163-1170 (2012)

Claims

1. An ion exchange resin with chelating properties, of formphenol type, which is obtained by polycondensation in a basic medium:

at least one first phenolic monomer, chelating, which corresponds to the following eneral formula (I):

(D

in which :

* m is 0, 1, 2 or 3,

* n is 0, 1 or 2,

* Ri, R2, R3, R _4, R 5 represent independently each other a hydrogen atom, -OH, an alkyl group in Ci to Ci _0, alkoxy, Ci to Ci ₀ aryl, a group -SO ₃ H, a group -COOR in which R represents a hydrogen atom or a C ₁ -C 10 alkyl group, a group -P (O) (OR) (OR ') or a -C group (0) NRR 'wherein R and R' independently of one another a hydrogen atom or an alkyl group Ci-Ci _0; with the proviso that at least one of R 1 to R ₅ is -OH and at least two of R 1 to R ₅ are hydrogen;

at least one second phenolic monomer, which does not correspond to the general formula (I); and

- formaldehyde.

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 , R ₂ and R ₄ have the same meaning as before.

3. The resin of claim 2, wherein the first phenolic monomer has the general formula (I) wherein m is 2, R ₃ is -OH, R 1, R ₂ and R ₅ are all three atoms. hydrogen, R ₄ 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, R ₃ is -OH, R 1, R ₂ , R ₄ and R ₅ are all four hydrogen atom, 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.

A process for synthesizing an ion exchange resin with chelating properties, as defined in any one of claims 1 to 7, which comprises:

b) the application of 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 method 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.

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.