NOVEL FORMO-PHENOLIC RESINS, PROCESS FOR THE PREPARATION THEREOF, AND USE OF SAME IN THE EXTRACTION OF URANIUM FROM WATER

Abstract

The subject matter of the present invention consists of formo-phenolic resins, a method for the preparation thereof, and the use of same in the extraction of uranium from an aqueous sample. The present invention also relates to novel formo-phenolic resins.

Claims

1-17. (canceled)

18. A method for preparing a crosslinked formo-phenolic resin, said method comprising a step of heating a reaction medium comprising: 100% chelating monomer units of Formula 1-A, or 100% chelating monomer units of Formula 6-A, or a mixture of chelating monomer units of Formula 1-A and Formula 6-A, or a mixture of monomer units of Formula 1-A and Formula 7-A, or a mixture of monomer units of Formula 6-A and Formula 7-A, or a mixture of monomer units of Formula 1-A, of Formula 6-A, and of Formula 7-A, and an aldehyde having the structure R′″—(CHO).sub.v, wherein R′″ represents an atom of hydrogen, a linear or branched C.sub.1 to C.sub.9 alkyl group, an aryl group, a heteroaryl group, a linear or branched C.sub.1 to C.sub.9-alkylearyl group, a linear or branched C.sub.1 to C.sub.9-heteroalkyl-aryl group, a linear or branched C.sub.1 to C.sub.9-alkylheteroaryl, a linear or branched C.sub.1 to C.sub.9-alkyl-aryl-C.sub.1 to C.sub.9 alkyl group, a linear or branched C.sub.1 to C.sub.9-alkyl-heteroaryl-C.sub.1 to C.sub.9-alkyl, and wherein v represents 1 or 2, in particular formaldehyde, in particular in the form of formaldehyde, paraformaldehyde, or 1,3,5-trioxane, and a base, and optionally a solvent, wherein the chelating monomer units of Formula 1-A have the following structure: ##STR00091## wherein: at least one of the R.sup.1 to R.sup.5 substituents represents an —OH group or a salt form, and at least one of the R.sup.1 to R.sup.5 substituents represents a hydrogen atom, and wherein: q is 0, 1, 2 or 3, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ represent independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, L is a linker chosen from one of the following structures: ##STR00092## wherein m is 0, 1, 2, 3, 4 or 5, p is 0 or 1, A represents a —CH.sub.2 group, a —CH—OH group, an oxygen atom, an —NH— group, an N-oxide group or a sulfur atom, E represents a CH group, a C—OH group, an oxygen atom, a nitrogen atom, an N-oxide group or a sulfur atom, R.sub.a, R.sub.b, R.sub.c, and R.sub.d represent independently a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, et-OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O) NRR′ group wherein R and R′ are independently hydrogen or C.sub.1 to C.sub.10 alkyl, and wherein the chelating monomer units of Formula 6-A have the following structure: ##STR00093## wherein: at least one of the R.sup.6 to R.sup.10 substituents represents an —OH group or a salified form, and at least one of the R.sup.6 to R.sup.10 substituents represents a hydrogen atom, and wherein: q and L are as defined above top for Formula 1-A, R.sup.6, R.sup.7, R.sup.1, R.sup.9 and R.sup.10 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ are independently hydrogen or C.sub.1 to C.sub.10 alkyl, and wherein the monomer units of Formula 7-A have the following structure: ##STR00094## wherein: at least one of the R.sup.11 to R.sup.16 substituents represents an —OH group or a salt form, and at least two of the R.sup.11 to R.sup.16 substituents represent a hydrogen atom, and wherein: —R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, or polyaryl with 1 to 4 aromatic rings, if R.sup.15 represents an aryl or polyaryl group, said aryl or polyaryl group may be fused with the monomer unit of Formula 7-A at position R.sup.16, said monomer unit of Formula 7-A being in particular a naphthol, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ are independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, and wherein from 2 to 8 monomer units of Formula 7-A can be linked together by a linear or branched C.sub.1 to C.sub.10 alkyl group, said monomer unit of Formula 7-A being in particular a calixarene comprising from 2 to 8 monomer units of Formula 7-A, or wherein from 2 to 4 monomer units of Formula 7-A may be linked to each other by a linear or branched C.sub.1 to C.sub.10 heteroalkyl group, the heteroatom being in particular 0, the said monomer unit of Formula 7-A being in particular a crown ether comprising from 2 to 4 monomer units of Formula 7-A, to obtain a crosslinked formo-phenolic resin consisting of a polymer containing monomer units linked together by a —R″-group, in particular by a —(CH.sub.2)-group.

19. The method for preparing a crosslinked formo-phenolic resin according to claim 18, wherein the chelating monomer units are of Formula 1-A, said chelating monomer units of Formula 1-A being able to be mixed with at least one of the monomer units of Formulas 6-A and 7-A, said Formula 1-A being such that: at least one of the R.sup.1 to R.sup.5 substituents represents an —OH group or a salified form, and at least one of the R.sup.1 to R.sup.5 substituents represents a hydrogen atom, and q is 0, 1, 2 or 3, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, L is a linker chosen from one of the following structures: ##STR00095## wherein m is 0, 1, 2, 3, 4 or 5, p is 0 or 1, A represents a —CH.sub.2 group, E represents a CH group, or a C—OH group, R.sub.a, R.sub.b, R.sub.c, and R.sub.a represent independently -a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, and/or wherein the chelating monomer units are of Formula 6-A, said chelating monomer units of Formula 6-A being able to be mixed with at least one of the monomer units of Formulas 1-A and 7-A, said Formula 6-A being such that: at least one of the R.sup.6 to R.sup.10 substituents represents an —OH group or a salified form, and at least one of the R.sup.6 to R.sup.10 substituents represents a hydrogen atom, and q is 0, 1, 2 or 3, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, L is a linker chosen from one of the following structures: ##STR00096## wherein: m is 0, 1, 2, 3, 4 or 5, p is 0 or 1, A represents a —CH.sub.2 group, E represents a CH group, or a C—OH group, R.sub.a, R.sub.b, R.sub.c, and R.sub.d represent independently a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, and/or wherein the monomer units are of Formula 7-A, said monomer units of Formula 7-A being mixed with at least one of the monomer units of Formula 1-A and 6-A, said Formula 7-A being such that: at least one of the R.sup.11 to R.sup.16 substituents represents an —OH group or a salified form, and at least two of the R.sup.11 to R.sup.16 substituents represent a hydrogen atom, and R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being 0, aryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, halogen, in particular F or Cl.

20. The method according to claim 18, wherein the base is a strong base, chosen in particular from lithium hydroxide, sodium hydroxide, potassium hydroxide or cesium hydroxide, in particular sodium hydroxide, and/or the solvent is water, and/or the heating step is carried out at a temperature between 80° C. and 150° C., and/or the heating step is carried out for a time ranging from 16 to 96 hours.

21. The method according to claim 18, further comprising, after the heating step, at least one washing step, said washing step being carried out in particular with: an aqueous solution of a strong base, in particular sodium hydroxide, then water, to obtain a formo-phenolic resin wherein the —OH groups are salified, in particular in the —ONa form, or an aqueous solution of a strong base, in particular sodium hydroxide, then an aqueous solution of hydrochloric acid, then water, to obtain a formo-phenolic resin comprising —OH groups, and/or further comprising, after the heating step, or after the washing step, a drying step, in particular in an oven at a temperature of 80° C., for 24 hours, to obtain a dried formo-phenolic resin, and/or further comprising, after the heating step, after the washing step, or after the drying step, a grinding step, to obtain a ground formo-phenolic resin.

22. A cross-linked formo-phenolic resin as obtained by the method according to claim 18.

23. A cross-linked formo-phenolic resin, consisting of a polymer containing monomer units linked together by one or more —R″— group(s), wherein R″ represents a linear or branched C.sub.1-C.sub.10-alkyl group, a linear or branched C.sub.1 to C.sub.10 alkylaryl group, a linear or branched C.sub.1 to C.sub.10-alkylaryl C.sub.1 to C.sub.10-alkyl group, a linear or branched C.sub.1 to C.sub.10-alkyl-heteroaryl-C.sub.1 to C.sub.10-alkyl group, said monomer units being: either chelating monomer units of Formula 1-B: ##STR00097## wherein: at least one of the R.sup.1 to R.sup.5 substituents represents an —OH group or a salified form, and at least one of the R.sup.1 to R.sup.5 substituents represent a hydrogen atom, and wherein: q is 0, 1, 2 or 3, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ represent independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, L is a linker chosen from one of the following structures: ##STR00098## wherein m is 0, 1, 2, 3, 4 or 5, p is 0 or 1, A represents a —CH.sub.2 group, a —CH—OH group, an oxygen atom, an —NH— group, a N-oxide group or a sulfur atom, E represents a CH group, a C—OH group, an oxygen atom, a nitrogen atom, a N-oxide group or a sulfur atom, R.sub.a, R.sub.b, R.sub.c, and R.sub.d represent independently a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ represent independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, or chelating monomer units of Formula 6-B: ##STR00099## wherein: at least one of the R.sup.6 to R.sup.10 substituents represents an —OH group or a salt form, and at least one of the R.sup.6 to R.sup.10 substituents represent a hydrogen atom, and wherein: q and L are as defined above for Formula 1-B, R.sup.6, R.sup.7, R.sup.1, R.sup.9 and R.sup.10 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ independently of each other represent a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, and optionally monomer units of Formula 7-B: ##STR00100## wherein: at least one of the R.sup.11 to R.sup.16 substituents represents an —OH group or a salt form, and at least two of the R.sup.11 to R.sup.16 substituents represent a hydrogen atom, wherein: —R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, or polyaryl of 1 to 4 aromatic rings, if R.sup.15 represents an aryl or polyaryl group, said aryl or polyaryl group can be fused with the monomer unit of Formula 7-B at the R.sup.16 position, said monomer unit of Formula 7-B being in particular a naphthol, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ represent independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, and wherein from 2 to 8 monomer units of Formula 7-B can be linked together by a linear or branched C.sub.1 to C.sub.10 alkyl group, said monomer unit of Formula 7-B being in particular a calixarene comprising from 2 to 8 monomer units of Formula 7-B, or wherein from 2 to 4 monomer units of Formula 7-B can be linked together by a linear or branched C.sub.1 to C.sub.10 heteroalkyl group, the heteroatom being in particular 0, said monomer unit of Formula 7-B being in particular a crown ether comprising from 2 to 4 monomer units of Formula 7-B, or one of at least two any of the monomer units of Formula 1-B, 6-B and 7-B, wherein the structure of Formula 7-B does not correspond to the structure of Formula 1-B or 6-B, said group —R″— being located: either between two chelating monomer units of Formula 1-B, on at least one carbon atom of the monomer unit carrying a R.sup.1 to R.sup.5 substituent which represents a hydrogen atom, or between two chelating monomer units of Formula 6-B, on at least one carbon atom of the monomer unit carrying a R.sup.6 to R.sup.10 substituent which represents a hydrogen atom, or between a chelating monomer unit of Formula 1-B, on at least one carbon atom of the monomer unit carrying a R.sup.1 to R.sup.5 substituent which represents a hydrogen atom, and at least one carbon atom of the monomer unit of Formula 6-B carrying a R.sup.6 to R.sup.10 substituent which represents a hydrogen atom, or between a chelating monomer unit of Formula 1-B, on at least one carbon atom of the monomer unit carrying a R.sup.1 to R.sup.5 substituent which represents a hydrogen, and at least one carbon atom of the monomer unit of Formula 7-B carrying a R.sup.11 to R.sup.16 substituent which represents a hydrogen atom, or between a chelating monomer unit of Formula 6-B, on at least one carbon atom of the monomer unit carrying a R.sup.6 to R.sup.10 substituent which represents a hydrogen atom, and at least one carbon atom of the monomer unit of Formula 7-B carrying a R.sup.11 to R.sup.16 substituent which represents a hydrogen atom.

24. The phenolic-formaldehyde resin according to claim 23, wherein the chelating monomer units are of Formula 1-B wherein: at least one of the R.sup.1 to R.sup.5 substituent represents an —OH group or a salt form, and at least one of the R.sup.1 to R.sup.5 substituent represents a of hydrogen, and wherein: q is 0, 1, 2 or 3, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, L is a linker chosen from one of the following structures: ##STR00101## wherein m is 0, 1, 2, 3, 4 or 5, p is 0 or 1, A represents a —CH.sub.2 group, -E represents a CH group, or a C—OH group, R.sub.a, R.sub.b, R.sub.c, and R.sub.d represent independently a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, said chelating monomer units of Formula 1-B may be mixed with at least one of the monomer units of Formulas 6-B and 7-B, and/or wherein the chelating monomer units are of Formula 6-B wherein: at least one of the R.sup.6 to R.sup.10 substituent represents an —OH group or a salified form, and at least one of the R.sup.6 to R.sup.10 substituents represent a hydrogen atom, and wherein q is 0, 1, 2 or 3, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, -L is a linker chosen from one of the following structures: ##STR00102## wherein m is 0, 1, 2, 3, 4 or 5, p is 0 or 1, A represents a —CH.sub.2 group, E represents a CH group, or a C—OH group, R.sub.a, R.sub.b, R.sub.c, and R.sub.d represent independently a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, said chelating monomer units of Formula 6-B may be mixed with at least one of the monomer units of Formulas 1-B and 7-B, and/or wherein the monomer units are of Formula 7-B wherein: at least one of the R.sup.11 to R.sup.16 substituents represents an —OH group or a salified form, and at least two of the R.sup.11 to R.sup.16 substituents represent a hydrogen atom, and wherein: R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being 0, aryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, halogen, in particular F or Cl, linear or branched C.sub.1 to C.sub.10 alkylaryl, halogen, in particular F or Cl, said monomer units of Formula 7-B are mixed with at least one of the monomer units of Formula 1-B and 6-B.

25. The formo-phenolic resin according to claim 23, wherein the chelating monomer units of Formula 1-B have the structure of Formula 8-B, 9-B, 10-B, 11-B, 12-B 13-B, 14-B or ##STR00103## ##STR00104## R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, L and q being as defined in claim 23, in particular the structure of Formula 16-B, 17-B or 18-B: ##STR00105## Formulas 8-B, 9-B, 13-B, 14-B, 15-B, 16-B, 17-B and 18-B wherein the —OH groups are in particular in a salified form, in particular in the form —ONa, and/or wherein the chelating monomer units of Formula 6 have the structure of Formula 19-B: ##STR00106## L, q, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 being as defined in claim 23, in particular the structure of Formula 22-B: ##STR00107## Formulas 19-B, 21-B and 22-B wherein the —OH groups are in particular in a salified form, in particular in the —ONa form, and/or wherein the monomer units of Formula 7 have the structure of Formula 23-B, 24-B, 25-B or 26-B: ##STR00108## R.sup.11, R.sup.12, R.sup.14, R.sup.15 and R.sup.16 being as defined in claim 23, in particular the structure of Formula 27-B, 28-B, or 29-B: ##STR00109## Formulas 23-B, 24-B, 25-B, 26-B, 27-B, 28-B and 29-B wherein the —OH groups are in particular in a salified form, in particular in the —ONa form.

26. The formo-phenolic resin according to claim 23, wherein the polymer consists of: 100% chelating monomer units of Formula 1-B.

27. A method for extracting uranium, in particular in an ionic form, in particular in the form of UO.sub.2.sup.2+, comprising: a step of bringing into contact a formo-phenolic resin, with an aqueous solution comprising uranium, said aqueous solution being in particular sea water, and said formo-phenolic resin consisting of a polymer containing monomer units bonded together by one or more —R″ group(s), in particular by one or more —(CH.sub.2)-group (s), wherein R″ represents a —(CH.sub.2)— group, a linear or branched —(CH)—C.sub.1 to C.sub.10-alkyl group, a —(CH)-aryl group, a —(CH)-heteroaryl group, a linear or branched —(CH)—(C.sub.1 to C.sub.10) alkylaryl group, a linear or branched —(CH)—(C.sub.1 to C.sub.10-alkyl)heteroaryl, a-(CH)-aryl-(CH)— group, a linear or branched-(CH)—(C.sub.1 to C.sub.10-alkyl)-aryl-(C.sub.1 to C.sub.10-alkyl)-(CH)-group, a-(CH)-heteroaryl-(CH), a linear or branched (CH)—(C.sub.1 to C.sub.10-alkyl)-heteroaryl-(C.sub.1 to C.sub.10-alkyl)-(CH)-group, said monomer units being: either chelating monomer units of Formula 1 ##STR00110## wherein: at least one of the R.sup.1 to R.sup.5 substituents represents an —OH group or a salt form, and at least one of the R.sup.1 to R.sup.5 substituents represents a hydrogen atom, and wherein: q is 0, 1, 2 or 3, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, heteroaryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O) NRR′ group wherein R and R′ represent independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, L is a linker chosen from one of the following structures: ##STR00111## wherein: m is 0, 1, 2, 3, 4 or 5, up is 0 or 1, A represents a —CH.sub.2 group, a —CH—OH group, an oxygen atom, an —NH— group, a N-oxide group or a sulfur atom, E represents a CH group, a C—OH group, an oxygen atom, a nitrogen atom, a N-oxide group or a sulfur atom, R.sub.a, R.sub.b, R.sub.c, and R.sub.d independently represent a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and OCs, —NH2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, heteroaryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ represent independently of each other a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ represent independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, or chelating monomer units of Formula 6 ##STR00112## wherein: at least one of the R.sup.6 to R.sup.10 substituents represents an —OH group or a salified form, and at least one of the R.sup.6 to R.sup.10 substituents represents a hydrogen atom, and wherein: q and L are as defined above for Formula 1, R.sup.6, R.sup.7, R.sup.1, R.sup.9 and R.sup.10 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl, heteroaryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, branched or unbranched C.sub.3 to C.sub.10 cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O) NRR′ group wherein R and R′ represent independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, or monomer units of Formula 7: ##STR00113## wherein: at least one of the R.sup.11 to R.sup.16 substituents represents an —OH group, or a salt form, and at least two of the R.sup.11 to R.sup.16 substituents represent a hydrogen atom, and wherein: —R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 independently represent: a hydrogen atom, or a group chosen from: —OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, and —OCs, —NH.sub.2, —SH, linear or branched C.sub.1 to C.sub.10 alkyl, linear or branched C.sub.1 to C.sub.10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O, aryl or polyaryl with 1 to 4 aromatic rings, if R.sup.15 represents an aryl or polyaryl group, said aryl or polyaryl group can be fused with the monomer unit of Formula 7 at position R.sup.16, said monomer unit of Formula 7 being in particular a naphthol, heteroaryl, linear or branched C.sub.1 to C.sub.10 alkylaryl, linear or branched C.sub.1 to C.sub.10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S, halogen, in particular F or Cl, linear or branched C.sub.1 to C.sub.10 alkylaryl, branched or unbranched C.sub.3 to C.sub.10cycloalkyl, —C(O)OR wherein R represents a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, —P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C.sub.1 to C.sub.10 alkyl group, or a —C(O)NRR′ group wherein R and R′ are independently of each other a hydrogen atom or a C.sub.1 to C.sub.10 alkyl group, and wherein from 2 to 8 monomer units of Formula 7 can be linked together by a linear or branched C.sub.1 to C.sub.10 alkyl group, said monomer unit of Formula 7 being in particular a calixarene comprising from 2 to 8 monomer units of Formula 7, or wherein from 2 to 4 monomer units of Formula 7 can be linked together by a linear or branched C.sub.1 to C.sub.10 heteroalkyl group, the heteroatom being in particular 0, the said monomer unit of Formula 7 being in particular a crown ether comprising from 2 to 4 monomer units of Formula 7, or a mixture of at least two of any of the monomer units of Formulas 1, 6 and 7, wherein the structure of Formula 7 does not correspond to the structure of Formula 1 or 6, provided that if the resin consists exclusively of monomer units of Formula 7, at least two of the R.sup.11 to R.sup.16 substituent represent a group other than a hydrogen atom, said —R′— group being located: either between two chelating monomer units of Formula 1, on at least one carbon atom of the monomer unit carrying a R.sup.1 to R.sup.5 substituent which represents a hydrogen atom, or between two chelating monomer units of Formula 6, on at least one carbon atom of the monomer unit carrying a R.sup.6 to R.sup.10 substituent which represents a hydrogen atom, or between two monomer units of Formula 7, on at least one carbon atom of the monomer unit carrying a R.sup.11 to R.sup.16 substituent which represents a hydrogen atom, or between a chelating monomer unit of Formula 1, on at least one carbon atom of the monomer unit carrying a R.sup.1 to R.sup.5 substituent which represents a hydrogen atom, and at least one carbon atom of the monomer unit of Formula 6 carrying a R.sup.6 to R.sup.10 substituent which represents a hydrogen atom, or between a chelating monomer unit of Formula 1, on at least one carbon atom of the monomer unit carrying a R.sup.1 to R.sup.5 substituent which represents a hydrogen atom, and at least one carbon atom of the monomer unit of Formula 7 carrying a R.sup.11 to R.sup.16 substituent which represents a hydrogen atom, or between a chelating monomer unit of Formula 6, on at least one carbon atom of the monomer unit carrying a R.sup.6 to R.sup.10 substituent which represents a hydrogen atom, and at least one carbon atom of the monomer unit of Formula 7 carrying a R.sup.11 to R.sup.16 substituent which represents a hydrogen atom.

28. The method for extracting uranium according to claim 27, further comprising, after the contacting step, a uranium recovery step, said recovery step being carried out in particular by eluting the formo-phenolic resin with an aqueous alkaline solution, and optionally a step for regenerating the formo-phenolic resin. phenolic, in particular by washing the formo-phenolic resin with: an aqueous solution of soda, then water, or an aqueous solution of soda, then an aqueous solution of hydrochloric acid, then water, to obtain a regenerated formo-phenolic resin.

29. The method for extracting uranium according to claim 27, wherein: the formo-phenolic resin has a Q.sub.ads uranium adsorption capacity greater than 5 mg/g, and/or the percentage of uranium E extraction is greater than 10, and/or the distribution coefficient Ka is greater than 100 mL/g, and/or the FS.sub.U/M separation factor is greater than 2, where U is uranium and M is the competing metal.

30. The formo-phenolic resin according to claim 23, wherein the polymer consists of: 100% chelating monomer units of Formula 6-B.

31. The formo-phenolic resin according to claim 23, wherein the polymer consists of: a mixture of chelating monomer units of Formula 1-B and chelating monomer units of Formula 6-B.

32. The formo-phenolic resin according to claim 23, wherein the polymer consists of: a mixture of chelating monomer units of Formula 1-B and monomer units of Formula 7-B.

33. The formo-phenolic resin according to claim 23, wherein the polymer consists of: a mixture of chelating monomer units of Formula 6-B and monomer units of Formula 7-B.

34. The formo-phenolic resin according to claim 23, wherein the polymer consists of: a mixture of chelating monomer units of Formula 1-B, chelating monomer units of Formula 6-B, and monomer units of Formula 7-B.

Description

Example 1: Synthesis of Chelating Monomer Units of Formula 1

[1023] The chelating monomers of Formula 1 were obtained according to General Scheme 1:

##STR00078##

Example 1A: Synthesis of Methylated Bis-Catecholamides—Stage 1

[1024] To a solution of 2,3-dimethoxybenzoic acid (2.2 eq.) in anhydrous dichloromethane (0.8 M) was added dropwise oxalyl chloride (3 eq.) at room temperature.

[1025] A few drops of anhydrous 7V,7V-dimethylformamide were added and the medium was stirred for 2 h, until the end of the evolution of HCl. After evaporation of the solvents and residual oxalyl chloride, the residue was redissolved in anhydrous dichloromethane (0.8 M) and added dropwise to a solution of diamine (1 eq) and triethylamine (2.5 eq.) in anhydrous dichloromethane (0.8 M).

[1026] After 17 hours of stirring, the medium was washed twice with an aqueous solution of 1 M HCl, a saturated aqueous solution of NaCl, then dried over MgSO.sub.4 and evaporated under reduced pressure.

[1027] The residue obtained is purified by flash chromatography on silica gel using a cyclohexane/ethyl acetate gradient ranging from a ratio of 8/2 v/v to a ratio of 2/8 v/v in order to obtain a methylated bis-catecholamide in the form of a thick colorless oil with a yield of between 86% and 100%.

[1028] The following compounds were obtained:

N,N′-(cyclohexane-1,3-diylbis(methylene))bis(2,3-dimethoxybenzamide)

[1029] ##STR00079##

[1030] RMN .sup.1H (CD.sub.2Cl.sub.2, 400 MHz, 25° C.) δ (ppm): 8.02 (te, 1.5H), 7.96 (te, 0.5H), 7.60 (dd, J=7.9, 1.6 Hz, 1.5H), 7.57 (dd, J=8.0, 1.7 Hz, 0.5H), 7.12 (q, J=8.0 Hz, 2H), 7.04 (dd, J=8.1, 1.6 Hz, 2H), 3.87 (s, 6H), 3.86 (s, 6H), 3.39 (t, J=6.6 Hz, 1H), 3.30 (t, J=6.2 Hz, 3H), 1.90 (d, J=12.7 Hz, 1H), 1.83 (d, J=11.4 Hz, 2H), 1.70-1.53 (m, 3H), 1.41-1.25 (m, 2H), 1.03-0.84 (m, 2H);

[1031] RMN .sup.13C (CD.sub.2Cl.sub.2, 100 MHz, 25° C.) δ (ppm): 165.11, 153.13, 147.87, 127.38, 124.52, 122.81, 115.52, 61.54, 56.35, 46.23, 43.97, 38.29, 35.67, 33.55, 33.15, 31.20, 29.82, 25.83, 21.07.

N,N′-(pentane-1,5-diyl)bis(2,3-dimethoxybenzamide)

[1032] ##STR00080##

[1033] RMN .sup.1H (CD.sub.2Cl.sub.2, 400 MHz, 25° C.) δ (ppm): 7.96 (se, 2H), 7.59 (d, J=7.9 Hz, 2H), 7.13 (t, J=7.9 Hz, 2H), 7.05 (d, J=7.9 Hz, 2H), 3.87 (s, 6H), 3.86 (s, 6H), 3.44 (q, J=6.4 Hz, 4H), 1.67 (quint, J=7.3 Hz, 4H), 1.54-1.45 (m, 2H);

[1034] RMN .sup.13C (CD.sub.2C.sub.2, 100 MHz, 25° C.) δ (ppm): 165.12, 153.15, 147.90, 127.41, 124.54, 122.75, 115.51, 61.48, 56.36, 39.82, 29.76, 24.94.

N,N′-(1,3-phenylene bis(methylene))bis(2,3-dimethoxybenzamide)

[1035] ##STR00081##

[1036] RMN .sup.1H (CD.sub.2Cl.sub.2, 400 MHz, 25° C.) δ (ppm): 8.33 (se, 2H), 7.64 (d, J=7.9 Hz, 2H), 7.35-7.27 (m, 4H), 7.14 (t, J=7.9 Hz, 2H), 7.07 (d, J=8.0 Hz, 2H), 4.63 (d, J=5.7 Hz, 4H), 3.87 (s, 6H), 3.81 (s, 6H);

[1037] RMN .sup.13C (CD.sub.2Cl.sub.2, 100 MHz, 25° C.) δ (ppm): 165.26, 153.19, 148.08, 139.89, 129.24, 127.06, 126.88, 126.70, 124.59, 122.91, 115.82, 61.58, 56.40, 43.86.

Example 1B: Synthesis of Bis-Catecholamides—Stage 2

[1038] To a solution of methylated bis-catecholamide synthesized in example IA (1 eq.) in anhydrous dichloromethane (0.08 M) was added dropwise BBr.sub.3 (7 eq.) with vigorous stirring at 0° C. The solution obtained (yellow or orange depending on the precursor) was stirred for 18 hours at room temperature then carefully added to crushed ice with vigorous stirring until the end of the hydrolysis.

[1039] The precipitate thus obtained was filtered, washed three times with ice water, and once with cold dichloromethane, then dissolved in methanol under reflux.

[1040] The solution was poured into water to precipitate the product.

[1041] The precipitate was filtered, washed three times with water and dried in order to obtain a phenolic monomer of Formula 1 in the form of a grey, beige or pink powder depending on the nature of the precursor with a yield of between 85% and 94%.

[1042] The following compounds were obtained:

N,N′-(cyclohexane-1,3-diylbis(methylene))bis(2,3-dihydroxybenzamide)—CYCAM

[1043] ##STR00082##

[1044] RMN .sup.1H (CD.sub.3OD, 400 MHz, 25° C.) δ (ppm): 7.20 (d, J=8.2 Hz, 2H), 6.92 (d, J=7.8 Hz, 2H), 6.68 (t, J=8.1 Hz, 2H), 4.86 (s, 6H), 3.21 (d, J=6.8 Hz, 4H), 1.87-1.76 (m, 3H), 1.66-1.53 (m, 3H), 1.33-1.21 (m, 2H), 0.90 (qd, J=12.8, 2.9 Hz, 2H);

[1045] RMN .sup.13C(CD.sub.3OD, 100 MHz, 25° C.) δ (ppm): 171.42, 150.05, 147.26, 119.59, 119.52, 118.70, 116.92, 46.71, 44.40, 38.95, 36.29, 34.06, 31.84, 30.43, 26.49.

N,N′-(pentane-1,5-diyl)bis(2,3-dihydroxybenzamide)-5-LICAM

[1046] ##STR00083##

[1047] RMN .sup.1H (CD.sub.3OD, 400 MHz, 25° C.) δ (ppm): 7.19 (dd, J=8.1, 1.1 Hz, 2H), 6.91 (dd, J=7.9, 1.1 Hz, 2H), 6.70 (t, J=8.0 Hz, 2H), 4.93 (s, 6H), 3.39 (t, J=7.1 Hz, 4H), 1.67 (quint, J=7.4 Hz, 4H), 1.50-1.42 (m, 2H);

[1048] RMN .sup.1C(CD.sub.3OD, 100 MHz, 25° C.) δ (ppm): 171.47, 150.22, 147.30, 119.53, 118.59, 40.35, 30.08, 25.36.

N,N′-(1,3-phenylenebis(methylene))bis(2,3-dihydroxybenzamide)-m-BENZCAM

[1049] ##STR00084##

[1050] RMN .sup.1H (CD.sub.3OD, 400 MHz, 25° C.) δ (ppm): 7.35-7.21 (m, 6H), 6.92 (dd, J=7.9, 1.1 Hz, 2H), 6.70 (t, J=8.0 Hz, 2H), 4.93 (s, 6H), 4.56 (s, 4H);

[1051] RMN .sup.13C(CD.sub.3OD, 100 MHz, 25° C.) δ (ppm): 171.46, 150.29, 147.31, 140.37, 129.76, 127.39, 127.31, 119.68, 119.63, 118.70, 116.68, 43.87.

Example 2: Synthesis of the Chelating Monomer Units of Formula 6

[1052] The chelating monomers of Formula 6 were obtained according to General Scheme 2

##STR00085##

Example 2A: Synthesis of Isophthalic Acid—Stage 1

[1053] ##STR00086##

[1054] To a solution of 2,6-dimethylanisole (1 eq.) in water (0.22 M) was added KMnO.sub.4 (2.1 eq.).

[1055] The solution was heated for 4 hours under reflux.

[1056] Another quantity of KMnO.sub.4 (2.1 eq.) was added and the reflux is maintained for an additional 2.5 hours.

[1057] The reaction medium was then left stirring for 17 hours at room temperature and then filtered through celite.

[1058] The precipitate was washed twice with hot water and the filtrate was concentrated under reduced pressure to one third of the initial volume.

[1059] The solution thus obtained was acidified to a pH of 2.5 by adding a concentrated solution of HCl. The precipitate thus obtained was filtered, washed with water and dried to obtain 2-methoxyisophthalic acid in the form of a white powder with a yield of 73%.

[1060] RMN .sup.1H (DMSO-d6, 400 MHz, 25° C.) δ (ppm): 13.10 (s, 2H), 7.81 (d, J=7.7 Hz, 2H), 7.25 (t, J=7.7 Hz, 1H), 3.80 (s, 3H); RMN .sup.13C (DMSO-d6, 100 MHz, 25° C.) δ (ppm): 167.03, 157.74, 133.50, 127.76, 123.60, 62.98.

Example 2B: Synthesis of Dimethoxybenzamide/V-Boc—Stage 2

[1061] ##STR00087##

[1062] To a solution of 2,3-dimethoxybenzoic acid (1.1 eq.) in anhydrous dichloromethane (0.4 M) was added oxalyl chloride (1.5 eq.).

[1063] After adding a few drops of N,N-dimethylformamide, the medium was stirred for 2 hours until the end of the release of HCl. After evaporation of the solvents and the residual oxalyl chloride, the residue was dissolved again in anhydrous dichloromethane (0.4 M) and added dropwise to a solution of N-Boc-ethylenediamine (1 eq.) and triethylamine (1.3 eq.) in anhydrous dichloromethane (0.4 M).

[1064] After 20 hours of stirring at room temperature, the medium was washed twice with an aqueous solution of 1 M HCl, a saturated solution of NaCl, then dried with MgSO.sub.4 and evaporated under reduced pressure.

[1065] The residue was purified by flash chromatography on silica gel with a gradient of dichloromethane/ethyl acetate from 10/0 to 4/6 in order to obtain the (2-(2,3-dimethoxybenzamido)ethyl)carbamate of tert-butyl in the form of a thick colorless oil with a yield of 93%.

[1066] RMN .sup.1H (CD.sub.2Cl.sub.2, 400 MHz, 25° C.) δ (ppm): 8.17 (s, 1H), 7.60 (d, J=7.9 Hz, 1H), 7.14 (t, J=7.9 Hz, 1H), 7.06 (d, J=7.8 Hz, 1H), 5.02 (se, 1H), 3.89 (s, 3H), 3.88 (s, 3H), 3.53 (q, J=5.9 Hz, 2H), 3.32 (t, J=5.9 Hz, 2H), 1.40 (s, 9H);

[1067] RMN .sup.13C (CD.sub.2C.sub.2, 100 MHz, 25° C.) δ (ppm): 166.00, 156.41, 153.18, 148.08, 126.98, 124.54, 122.74, 115.81, 79.36, 61.53, 56.39, 41.27, 40.07, 28.46.

Example 2C: Synthesis of Dimethoxybenzamide—Stage 3

[1068] ##STR00088##

[1069] To a solution of (2-(2,3-dimethoxybenzamido)ethyl)carbamate of tert-butyl (1 eq.), synthesized according to Example 2B, in dichloromethane (0.13 M) at 0° C. was added a solution of trifluoroacetic acid (20 eq.) in dichloromethane (3 M).

[1070] The solution thus obtained was stirred for 3 hours at room temperature then washed twice with an aqueous solution of NaOH until a pH>10 was obtained, a saturated solution of NaCl, water then evaporated under reduced pressure in order to obtain N-(2-aminoethyl)-2,3-dimethoxybenzamide in the form of an orange oil with a yield of 95%.

[1071] RMN .sup.1H (CD.sub.2Cl.sub.2, 400 MHz, 25° C.) δ (ppm): 8.26 (se, 1H), 7.60 (d, J=7.8 Hz, 1H), 7.13 (t, J=8.0 Hz, 1H), 7.05 (d, J=7.9 Hz, 1H), 3.89 (s, 3H), 3.87 (s, 3H), 3.46 (q, J=5.9 Hz, 2H), 2.89 (t, J=5.9 Hz, 2H), 1.47 (s, 2H);

[1072] RMN .sup.13C (CD.sub.2Cl.sub.2, 100 MHz, 25° C.) δ (ppm): 165.39, 153.21, 148.03, 124.49, 122.73, 115.57, 61.52, 56.37, 42.81, 41.96.

Example 2D: Synthesis of Methylated Isophthalamide-Bis-Catecholamide—Stage 4

[1073] ##STR00089##

[1074] To a solution of 2-methoxyisophthalic acid, synthesized according to example 2A, (1 eq.) and hydrated HOBT (2.1 eq.) in THE (0.05 M) was added dropwise a solution of DCC (2.1 eq.) in THE (0.23 M) at 0° C. then the medium was stirred for four hours at room temperature.

[1075] The precipitate thus formed was filtered off and the filtrate was added dropwise to a solution of A-(2-aminoethyl)-2,3-dimethoxybenzamide (2.1 eq.) previously synthesized in THE (0.11 M) at 0° C. then the medium was stirred for twenty-four hours at room temperature.

[1076] Dichloromethane was then added to the reaction medium and the latter was washed twice with an aqueous solution of 1 M NaOH and water.

[1077] The organic phase was dried with MgSO.sub.4 and then concentrated under vacuum.

[1078] The residue was purified by flash chromatography on silica gel using a gradient of dichloromethane/methanol from 100/0 to 97/3 in order to obtain N.sup.1,N.sup.3-bis(2-(2,3-dimethoxybenzamido)ethyl)-2-methoxyisophthalamide in the form of a white powder with a yield of 97%.

[1079] RMN .sup.1H (CD.sub.2Cl.sub.2, 400 MHz, 25° C.) δ (ppm): 8.28 (se, 2H), 8.00 (d, J=7.7 Hz, 2H), 7.77 (se, 2H), 7.59 (dd, J=7.9, 1.7 Hz, 2H), 7.26 (t, J=7.7 Hz, 1H), 7.13 (t, J=7.9 Hz, 2H), 7.06 (dd, J=8.2, 1.6 Hz, 2H), 3.86 (s, 6H), 3.85 (s, 6H), 3.76 (s, 3H), 3.71-3.67 (m, 8H);

[1080] RMN .sup.13C (CD.sub.2Cl.sub.2, 100 MHz, 25° C.) δ (ppm): 166.13, 165.75, 156.59, 153.16, 148.08, 134.35, 128.49, 126.80, 125.09, 124.55, 122.65, 115.86, 63.78, 61.55, 56.36, 40.59, 39.84.

Example 2E: Synthesis of Isophthalamide-Bis-Catecholamide-IPACAM—Stage 5

[1081] ##STR00090##

[1082] To a solution of N.sup.1,N.sup.3-bis(2-(2,3-dimethoxybenzamido)ethyl)-2-methoxyisophthalamide, synthesized according to Example 2D (1 eq.) in anhydrous dichloromethane (0.08 M) was added dropwise drop of BBr.sub.3 (9 eq.) with vigorous stirring at 0° C. The solution thus obtained was stirred for three days at room temperature and then carefully added to crushed ice with vigorous stirring until the end of the hydrolysis.

[1083] The precipitate thus obtained was filtered, washed three times with water and then dissolved in methanol under reflux.

[1084] The solution was added to water to precipitate the product.

[1085] The precipitate was filtered, washed three times with water and dried to obtain the phenolic monomer IPACAM, in the form of a beige powder with a yield of 95%.

[1086] RMN .sup.1H (CD.sub.3OD, 400 MHz, 25° C.) δ (ppm): 7.96 (d, J=7.9 Hz, 2H), 7.18 (dd, J=8.0, 0.9 Hz, 2H), 6.96-6.90 (m, 3H), 6.69 (t, J=8.0 Hz, 2H), 4.94 (s, 9H), 3.63 (s, 8H);

[1087] RMN .sup.13C(CD.sub.3OD, 100 MHz, 25° C.) δ (ppm): 172.08, 170.07, 161.40, 150.38, 147.31, 134.09, 119.69, 119.57, 119.26, 118.62, 116.54, 40.42, 40.17.

Example 3: Synthesis of Formo-Phenolic Resins

[1088] Formo-phenolic resins have been synthesized using: [1089] one of the chelating monomers synthesized in Example 1 or in Example 2 above as first phenolic monomer or as sole phenolic monomer, [1090] phenol, catechol or resorcinol as second phenolic monomer or as sole phenolic monomer, [1091] formaldehyde as an aldehyde, [1092] an aqueous solution of sodium hydroxide as a strong base, [1093] and water, with [1094] A chelating monomer/phenolic monomer/strong base/H2O/formaldehyde molar ratio of 0/1/1.5/100/2.5 when the resin contains only phenol as monomer, of 1/0/3/100/3.75, 0.5/0.5/3/100/3.75, 0.34/0.66/3/100/3.75 when the resin contains partly or only IPACAM, and 1/0/3/100/2.5, 0.5/0.5/3/100/2.5, 0.34/0.66/3/100/2.5 and 0/1/3/100/2.5 in all other cases.

[1095] A mixture of chelating monomer and phenolic monomer, or only chelating monomer, or only phenolic monomer was first dissolved in a NaOH solution with stirring.

[1096] Then, water is added in order to reach 100 equivalents with respect to the mixture of chelating monomer and phenolic monomer, or only to the chelating monomer, or only to the phenolic monomer.

[1097] The resulting solution was stirred and then the formaldehyde was added.

[1098] The reaction mixture was kept under stirring for 24 hours, after which it was transferred to a container with a wide neck and a flat bottom, such as a beaker, and then heated in a ventilated oven at 100° C. for 96 hours.

[1099] After solidification and then hardening of this mixture, the resin thus formed was recovered, ground using a ball mill and then washed.

[1100] Two types of successive washes were used depending on the form of resin to be obtained.

[1101] In all cases, the solutions used were added to the resin at a concentration of 40 mL/g of resin: [1102] 0.1 M NaOH, 0.1 M HCl, then twice water to keep the resin in the protonated —OH form, [1103] 0.1 M NaOH, then water three times in order to keep the resin in the deprotonated form [1104] —ONa.

[1105] The resins thus washed were dried in a ventilated oven at 80° C. for 24 hours.

[1106] After drying, the resins were dispersed using a mortar and then dried again at 80° C. for 5 hours after which they were stored.

[1107] Twenty-six resins presented in Table 1 were thus synthesized.

[1108] The nature and the molar ratio of the various monomers used as well as the form wherein the resin was preserved after washing are also indicated.

TABLE-US-00001 TABLE 1 First phenolic Molar Second phenolic Molar Resin Name of the resin monomer ratio monomer ratio form CYCAM100-H CYCAM 1 — — —OH 5-LICAM100-H 5-LICAM 1 — — —OH m-BENZCAM100-H m-BENZCAM 1 — — —OH IPACAM100-H IPACAM 1 — — —OH IPACAM100-Na IPACAM 1 — — —ONa CYCAM50-P50-H CYCAM 0.5 Phenol 0.5 —OH CYCAM34-P66-H CYCAM 0.34 Phenol 0.66 —OH IPACAM50-P50-H IPACAM 0.5 Phenol 0.5 —OH IPACAM34-P66-H IPACAM 0.34 Phenol 0.66 —OH IPACAM50-C50-H IPACAM 0.5 Catechol 0.5 —OH IPACAM50-C50-Na IPACAM 0.5 Catechol 0.5 —ONa IPACAM34-C66-H IPACAM 0.34 Catechol 0.66 —OH IPACAM34-C66-Na IPACAM 0.34 Catechol 0.66 —ONa 5-LICAM50-R50-H 5-LICAM 0.5 Resorcinol 0.5 —OH 5-LICAM50-R50-Na 5-LICAM 0.5 Resorcinol 0.5 —ONa 5-LICAM34-R66-H 5-LICAM 0.34 Resorcinol 0.66 —OH 5-LICAM34-R66-Na 5-LICAM 0.34 Resorcinol 0.66 —ONa m-BENZCAM50-R50-H m-BENZCAM 0.5 Resorcinol 0.5 —OH m-BENZCAM50-R50-Na m-BENZCAM 0.5 Resorcinol 0.5 —ONa m-BENZCAM34-R66-H m-BENZCAM 0.34 Resorcinol 0.66 —OH m-BENZCAM34-R66-Na m-BENZCAM 0.34 Resorcinol 0.66 —ONa P100-H — — Phenol 1 —OH C100-H — — Catechol 1 —OH C100-Na — — Catechol 1 —ONa R100-H — — Resorcinol 1 —OH R100-Na — — Resorcinol 1 —ONa

[1109] The resins in Table 1 were characterized by elemental analysis.

[1110] By way of example, the elemental analysis results for the m-BENZCAM100-H, m-BENZCAM50-R50-H and m-BENZCAM34-R66-H resins are given below.

[1111] m-BENZCAM100-H:

[1112] Elemental analysis: C: 57.36%, H: 4.34%, N: 6.03%.

[1113] m-BENZCAM50-R50-H:

[1114] Elemental analysis: C: 56.79%, H: 4.39%, N: 4.56%.

[1115] m-BENZCAM34-R66-H:

[1116] Elemental analysis: C: 56.12%, H: 4.47%, N: 3.53%.

Example 4: Selective Extraction of Uranium by Resins According to the Invention

[1117] The ability of the resins to selectively extract uranium from seawater was determined by extraction tests carried out in discontinuous mode (batch), using, as aqueous solution, three different solutions, respectively referred to below solutions 1, 2 and 3, and consisting of: [1118] Solution 1: a solution simulating seawater doped with 50 ppm in uranium (1.9.10.sup.−4 M in uranyl) and 60 ppm in carbonates (1.0.10.sup.−3M) at a pH of 8.25±0.1. [1119] Solution 2: a solution simulating seawater doped with 200 ppm in uranium (7.4.10.sup.−4M in uranyl) and 226 ppm in carbonates (3.8.10.3M) at a pH of 8.25±0.1 [1120] Solution 3: a solution simulating seawater doped with 50 ppm in uranium (1.9.10-.sup.4M in uranyl), 100 ppm in strontium (1.2.10.3M), 200 ppm in sodium (8.7.10.3M), 200 ppm in potassium (5.2.10.sup.−M), 200 ppm in calcium (5.1.10.sup.−3M), 200 ppm in magnesium (8.4.10.sup.−3M) and 60 ppm in carbonates (1.0.10.sup.−3M) at a pH of 8.25±0.1. [1121] Solution 4: a solution corresponding to water from the Rhône doped with 50 ppm in uranium (1.9.10.sup.−4M in uranyl). [1122] These tests consist in bringing a certain quantity of resin into contact with a certain volume of solution 1, 2 or 3, in leaving the mixture under stirring at 22° C. for 15 hours, then, after centrifugation, in removing the supernatant, in filtering (on a 0.22 μm cellulose acetate membrane) and in measuring the concentration of the various cations present in the filtrate by atomic emission spectrometry with induction coupled plasma (ICP-AES) or by mass spectrometry with plasma coupled by induction (ICP-MS) when the uranium concentrations are very low and difficult to measure by ICP-AES. [1123] Thus, for each cation were determined: [1124] The adsorption capacity, noted Q.sub.ads and expressed in mg of extracted metal/g of resin, which represents the quantity of this cation present in the resin, and which was determined by the following formula:

[00005] $\begin{matrix} Q_{ads} = (C_{i} - C_{f}) .Math. \frac{V}{m} & Formule 1 \end{matrix}$ [1125] The percentage of extraction, noted E and expressed in %, which represents the percentage of cation extracted by the resin compared to the initial quantity of cation, and which was determined by the following formula:

[00006] $\begin{matrix} E = \frac{C_{i} - C_{f}}{C_{i}} .Math. 100 & Formule 2 \end{matrix}$ [1126] The distribution coefficient, noted K.sub.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 was determined by the following formula:

[00007] $\begin{matrix} K_{D} = \frac{C_{i} - C_{f}}{C_{f}} .Math. \frac{V}{m} .Math. 1000 & Formule 3 \end{matrix}$ [1127] The separation factor, denoted FS.sub.U/M, where M represents a competing metal, which represents the ratio between the K.sub.D of uranium and the K.sub.D of another metal, which makes it possible to quantify the selectivity of a resin to be extracted uranium with respect to another metal, and which was determined by the following formula:

[00008] $\begin{matrix} {FS}_{U / M} = \frac{K_{D_{U}}}{K_{D_{M}}} & Formule 4 \end{matrix}$

avec:
C.sub.i=initial concentration of the cation in solution (mg/L),
C.sub.f=concentration of the cation in solution after extraction (mg/L),
V=volume of solution (mL),
m=mass of resin (mg).

[1128] Table 2 below presents the Q.sub.ads, E and K.sub.D values obtained for uranium with twenty-four resins synthesized in example 3 and solutions 1 and 2 for Vim ratios equal to 1 and 4.

TABLE-US-00002 TABLE 2 Solution 1 Solution 2 Q.sub.ads E K.sub.D Q.sub.ads E K.sub.D Name of the resin V/m (mg/g) (%) (mL/g) (mg/g) (%) (mL/g) CYCAM100-H 1 19.3 38 615 5-LICAM100-H 1 22.5 44 794 5.8 3 29 m-BENZCAM100-H 1 >50.3 >99 >100000 199.5 99 68855 4 — — — 354.2 44 3110 IPACAM100-H 1 26.3 52 1071 IPACAM100-Na 1 88.3 46 869 CYCAM50-P50-H 1 30.3 60 1485 CYCAM34-P66-H 1 42.7 84 5273 IPACAM50-P50-H 1 23.6 46 866 IPACAM34-P66-H 1 30.0 59 1442 IPACAM50-C50-H 1 16.8 9 97 IPACAM50-C50-Na 1 78.0 41 697 IPACAM34-C66-H 1 36.7 19 240 IPACAM34-C66-Na 1 84.0 44 794 5-LICAM50-R50-H 1 50.2 99 84223 199.8 99 76326 5-LICAM50-R50-Na 4 — — — 353.1 44 3093 5-LICAM34-R66-H 1 50.1 99 75662 200.0 99 81629 5-LICAM34-R66-Na 4 — — — 408.5 50 4073 m-BENZCAM50-R50-H 1 >50.3 >99 >100000 200.1 99 85587 m-BENZCAM50-R50-Na 4 — — — 418.4 52 4276 m-BENZCAM34-R66-H 1 >50.3 >99 >100000 200.4 99 97367 m-BENZCAM34-R66-Na 4 — — — 446.2 55 4908 P100-H 1 45.1 89 7919 C100-H 1 >50.3 >99 >100000 128.5 68 2092 4 — — — 143.0 19 928 R100-H 1 46.9 92 12216

[1129] Table 3 below presents the values of Q.sub.ads, E and K.sub.D obtained for uranium as well as the values of FS.sub.U/M (where M is a competing cation) obtained with the twenty-six resins synthesized in Example 3 and solution 3 for a V/m ratio equal to 1.

TABLE-US-00003 TABLE 3 Solution 3 Q.sub.ads U E U K.sub.D U Name of the resin (mg/g) (%) (mL/g) FS.sub.U/Sr FS.sub.U/Ca FS.sub.U/Mg FS.sub.U/Na FS.sub.U/K CYCAM100-H 11.6 22 287 13 7 13 12 12 5-LICAM100-H 7.2 14 160 10 5 11 8 7 m-BENZCAM100-H 26.1 50 997 12 7 36 86 90 IPACAM100-H 16.1 31 445 19 10 19 20 20 IPACAM100-Na 48.7 99 73730 825 355 754 6615 7212 CYCAM50-P50-H 17.7 34 512 30 10 33 36 38 CYCAM34-P66-H 17.1 33 487 27 13 28 31 33 IPACAM50-P50-H 16.1 31 445 20 11 19 19 19 IPACAM34-P66-H 20.0 38 621 26 13 25 26 27 IPACAM50-C50-H 28.9 59 1416 53 31 78 190 178 IPACAM50-C50-Na 48.2 98 43038 577 302 627 3343 3467 IPACAM34-C66-H 46.3 94 15235 335 264 547 1542 1590 IPACAM34-C66-Na 48.5 98 60270 851 471 1043 6335 6333 5-LICAM50-R50-H 50.5 97 28950 346 206 683 1704 1798 5-LICAM50-R50-Na 49.2 100 518179 4237 2548 7435 36015 37041 5-LICAM34-R66-H 51.0 98 39202 392 259 810 1984 2038 5-LICAM34-R66-Na 49.2 100 327813 2422 1556 5204 29388 30491 m-BENZCAM50-R50-H 45.3 87 6526 80 48 202 574 589 m-BENZCAM50-R50-Na 49.0 99 178353 1450 899 3100 20659 19556 m-BENZCAM34-R66-H 50.5 97 29385 323 209 914 3568 3167 m-BENZCAM34-R66-Na 49.1 100 213443 1530 1026 3690 25275 22135 P100-H 1.4 3 27 2 1 1 2 2 C100-H 51.4 98 62348 973 677 2216 6014 5186 C100-Na 44.2 90 8626 76 59 185 1321 841 R100-H 30.4 58 1385 34 20 58 62 41 R100-Na 18.9 38 619 7 5 15 35 30

TABLE-US-00004 TABLE 4 Solution 4 Name of the resin Q.sub.ads U (mg/g) E U (%) K.sub.D U (mL/g) m-BENZCAM50-R50-H 19.4 95 18036 m-BENZCAM34-R66-H 22.8 97 39809

[1130] Table 4 These results show that formo-phenolic resins have a good affinity for uranium.

[1131] This affinity is greater when the resins contain a chelating monomer and even greater when they are in the deprotonated —ONa form.

[1132] In the presence of competing metals, the resins retain their good affinity for uranium.

[1133] In this case, the resins not only have a very good affinity for uranium, but also excellent selectivity with respect to all the competing metals tested.

[1134] For example, in the absence of competing metals, the m-BENZCAM34-R66-H resin makes it possible to extract almost half of its mass in uranium (Q.sub.ads=446.2 mg/g).

[1135] This excellent affinity is preserved in the presence of competing metals (E=97%) with excellent selectivities.

[1136] In the presence of competing metals, the resin that seems to stand out from the others is 5-LICAM50-R50-Na with 100% uranium extraction, a uranium adsorption capacity of 49.2 mg/g and separation factors between 2548 and 37041.

[1137] This resin is indeed a striking example of the importance of adding a chelating phenolic monomer within the resin in order to increase the selectivity, since the RI 00-Na resin, containing only resorcinol, has separation only between 5 and 35.

[1138] These results, in terms of load capacity and selectivity, have never been achieved in the literature by other types of materials, for the extraction of uranium from seawater, by solid-liquid extraction.

NOVEL FORMO-PHENOLIC RESINS, PROCESS FOR THE PREPARATION THEREOF, AND USE OF SAME IN THE EXTRACTION OF URANIUM FROM WATER

Inventors

Cpc classification

Classification Explorer

C08G8/20

CHEMISTRY; METALLURGY

Classification Explorer

B01J20/3475

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

G21F9/12

PHYSICS

Classification Explorer

B01J20/3021

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

B01J20/3425

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

B01J20/3085

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

C08G8/10

CHEMISTRY; METALLURGY

Classification Explorer

B01J20/267

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

C08G8/24

CHEMISTRY; METALLURGY

International classification

Classification Explorer

B01J20/26

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

C08G8/20

CHEMISTRY; METALLURGY

Classification Explorer

C08G8/10

CHEMISTRY; METALLURGY

Classification Explorer

C08G8/24

CHEMISTRY; METALLURGY

Classification Explorer

B01J20/30

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

B01J20/34

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

G21F9/12

PHYSICS

Abstract

Claims

Description