Novel formo-phenolic resins, process for the preparation thereof, and use of same in the extraction of uranium from water

Patent metadata

Field	Value
Publication number	US-2023398517-A1
Application number	US-202118250415-A
Country	US
Kind code	A1
Filing date	Oct 26, 2021
Priority date	Oct 26, 2020
Publication date	Dec 14, 2023
Grant date	—

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.

First claim

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) v , wherein R′″ represents an atom of hydrogen, a linear or branched C 1 to C 9 alkyl group, an aryl group, a heteroaryl group, a linear or branched C 1 to C 9 -alkylearyl group, a linear or branched C 1 to C 9 -heteroalkyl-aryl group,
a linear or branched C 1 to C 9 -alkylheteroaryl, a linear or branched C 1 to C 9 -alkyl-aryl-C 1 to C 9 alkyl group, a linear or branched C 1 to C 9 -alkyl-heteroaryl-C 1 to C 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:

wherein:
at least one of the R 1 to R 5 substituents represents an —OH group or a salt form,
and
at least one of the R 1 to R 5 substituents represents a hydrogen atom,
and wherein:
q is 0, 1, 2 or 3,
R 1 , R 2 , R 3 , R 4 and R 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 2 ,
—SH,
linear or branched C 1 to C 10 alkyl,
linear or branched C 1 to C 10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O,
aryl,
linear or branched C 1 to C 10 alkylaryl,
linear or branched C 1 to C 10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S,
halogen, in particular F or Cl,
branched or unbranched C 3 to C 10 cycloalkyl,
—C(O)OR wherein R represents a hydrogen atom or a C 1 to C 10 alkyl group,
—P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C 1 to C 10 alkyl group, or a —C(O)NRR′ group wherein R and R′ represent independently of each other a hydrogen atom or a C 1 to C 10 alkyl group,

L is a linker chosen from one of the following structures:

wherein
m is 0, 1, 2, 3, 4 or 5,
p is 0 or 1,
A represents a —CH 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 a , R b , R c , and R d represent independently
a group chosen from:
—OH, or a salified form, in particular chosen from —ONa, —OK, —OLi, et-OCs,
—NH 2 ,
—SH,
linear or branched C 1 to C 10 alkyl,
linear or branched C 1 to C 10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O,
aryl,
linear or branched C 1 to C 10 alkylaryl,
linear or branched C 1 to C 10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S,
halogen, in particular F or Cl,
branched or unbranched C 3 to C 10 cycloalkyl,
—C(O)OR wherein R represents a hydrogen atom or a C 1 to C 10 alkyl group,
—P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C 1 to C 10 alkyl group, or a —C(O) NRR′ group wherein R and R′ are independently hydrogen or C 1 to C 10 alkyl, and

wherein the chelating monomer units of Formula 6-A have the following structure:

wherein:
at least one of the R 6 to R 10 substituents represents an —OH group or a salified form, and
at least one of the R 6 to R 10 substituents represents a hydrogen atom,
and wherein:
q and L are as defined above top for Formula 1-A,
R 6 , R 7 , R 1 , R 9 and R 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 2 ,
—SH,
linear or branched C 1 to C 10 alkyl,
linear or branched C 1 to C 10 heteroalkyl, the heteroatom being chosen in particular from O, N, S and N═O,
aryl,
linear or branched C 1 to C 10 alkylaryl,
linear or branched C 1 to C 10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S,
halogen, in particular F or Cl,
branched or unbranched C 3 to C 10 cycloalkyl,
—C(O)OR wherein R represents a hydrogen atom or a C 1 to C 10 alkyl group,
—P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C 1 to C 10 alkyl group, or a —C(O)NRR′ group wherein R and R′ are independently hydrogen or C 1 to C 10 alkyl, and

wherein the monomer units of Formula 7-A have the following structure:

wherein:
at least one of the R 11 to R 16 substituents represents an —OH group or a salt form, and
at least two of the R 11 to R 16 substituents represent a hydrogen atom,
and wherein:
—R 11 , R 12 , R 13 , R 14 , R 15 and R 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 2 ,
—SH,
linear or branched C 1 to C 10 alkyl,
linear or branched C 1 to C 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 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 16 , said monomer unit of Formula 7-A being in particular a naphthol,
linear or branched C 1 to C 10 alkylaryl,
linear or branched C 1 to C 10 heteroalkylaryl, the heteroatom being chosen in particular from O, N and S,
halogen, in particular F or Cl,
branched or unbranched C 3 to C 10 cycloalkyl,
—C(O)OR wherein R represents a hydrogen atom or a C 1 to C 10 alkyl group,
—P(O)(OR)(OR′) wherein R and R′ independently represent a hydrogen atom, a C 1 to C 10 alkyl group, or a —C(O)NRR′ group wherein R and R′ are independently of each other a hydrogen atom or a C 1 to C 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 1 to C 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 1 to C 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 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 1 to R 5 substituents represents an —OH group or a salified form, and at least o

Assignees

• Centre Nat Rech Scient
• Univ De Montpellier Um
• Commissariat A Lenergie Atomique Et Aux Energies Alternatives Cea
• Ecole Nat Superieure De Chimie De Montpellier Enscm

Inventors

• Pellet-Rostaing Stéphane
• Arrachart Guilhem
• Mossand Guillaume
• Leydier Antoine

Classifications

• B01J20/267 Primary

  Cross-linked polymers · CPC title

• C08G8/20

  with polyhydric phenols · CPC title

• C08G8/10

  with phenol · CPC title

• C08G8/24 Primary

  with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20 · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title