EP3126343A1 - Novel complexes for the separation of cations - Google Patents
Novel complexes for the separation of cationsInfo
- Publication number
- EP3126343A1 EP3126343A1 EP15717009.3A EP15717009A EP3126343A1 EP 3126343 A1 EP3126343 A1 EP 3126343A1 EP 15717009 A EP15717009 A EP 15717009A EP 3126343 A1 EP3126343 A1 EP 3126343A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- crosslinking
- chosen
- sulphate
- sulphonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000926 separation method Methods 0.000 title description 7
- 150000001768 cations Chemical class 0.000 title description 3
- 239000000463 material Substances 0.000 claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 150000002739 metals Chemical class 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 44
- 230000000536 complexating effect Effects 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 238000004132 cross linking Methods 0.000 claims description 93
- 229920000642 polymer Polymers 0.000 claims description 64
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 claims description 53
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 37
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 125000000524 functional group Chemical group 0.000 claims description 31
- 150000003573 thiols Chemical class 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
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- 125000003118 aryl group Chemical group 0.000 claims description 24
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- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 claims description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 21
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 20
- -1 platinoids Chemical compound 0.000 claims description 20
- 125000006239 protecting group Chemical group 0.000 claims description 20
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- 125000004076 pyridyl group Chemical group 0.000 claims description 16
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- 125000002541 furyl group Chemical group 0.000 claims description 15
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- 229910052787 antimony Inorganic materials 0.000 claims description 7
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- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 7
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- 239000011777 magnesium Substances 0.000 claims description 7
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- 125000004434 sulfur atom Chemical group 0.000 claims description 7
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- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
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- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
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- 125000006850 spacer group Chemical group 0.000 claims description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
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- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
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- 229920001721 polyimide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
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- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3882—Arylalkanephosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4021—Esters of aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08L39/08—Homopolymers or copolymers of vinyl-pyridine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
Definitions
- the present invention provides complexes comprising a matrix-structured material having rare earth complexing domains or strategic metals, their method of preparation, and their use for extracting or separating rare earths or strategic metals in an aqueous or organic medium.
- Strategic metals are metals considered critical for the development of European industry, especially for the new technology industry. Although there is no official list of strategic metals, antimony, indium, beryllium, magnesium, cobalt, niobium, platinoids, gallium, germanium, tantalum, tungsten, Molybdenum, titanium, mercury, cesium, lithium, strontium and rare earths, especially lanthanides, are generally considered strategic metals.
- rare earths Due to their unique electronic and optical properties, rare earths are essential elements in the new technologies industry, particularly for the electronics, automotive, clean energy and aerospace sectors, but also of defense. Although, contrary to popular belief, rare earths are relatively widespread in the earth's crust, rare earth mining remains very expensive and inefficient because of its low concentration in mineral deposits and the fact that it is difficult to separate them from each other.
- Beer et al. J. Chem Soc, Dalton Trans., 1998, 2783-2785 describe Tantagel® S NH 2 resins functionalized by cali [4] arenes substituted with 1-acid 3-diethyl amide, the latter being grafted onto resins. via the functional group: -O-CH 2 -CH 2 -NH 2 .
- Pathak and Rao (Analytica Chimica Acta., 1996, vol 335, no.3, 283-290) also disclose a styrene-divinylbenzene copolymer resin functionalized with calixarenes (p-tert-butylcalix [8] arene ).
- No. 6,342,634 discloses soluble acid amides, especially acid amides in which two calixarenes are linked by a diamine, and styrene-divinylbenzene copolymer resins physisorbent said acid-amides.
- EP 1 481 402 discloses a method for separating metals, such as 90 Y and 90 Sr, in an aqueous solution, using an ion exchanger comprising a carbon or graphite substrate impregnated with a hydrophobic chelating extractant having affinities different, at a selective pH, for the metals to be separated.
- an ion exchanger comprising a carbon or graphite substrate impregnated with a hydrophobic chelating extractant having affinities different, at a selective pH, for the metals to be separated.
- the regeneration of such an exchanger can be performed only under acidic conditions with the application of large volumes of acidic solutions, which damages the environment.
- US 2009/0093664 discloses a carbon nanotube, on which are covalently bound extractants of lanthanides or actinides, for the recovery and separation of lanthanides and actinides. Due to the low fluid velocity to traverse the die, this method is not fast enough and is therefore incompatible with industrial use.
- the extraction capacity of this complex is limited to a low concentration of the metals to be extracted, due, at the same time, to the deformation, during the electrochemical grafting, of the cavities for metals of interest close to the support, the high density of the grafted calixarenes and the hydrophobic nature of the complexing film, which prevents the access of the metals of interest to the calixarenes close to the support.
- the inventors have succeeded in synthesizing new materials capable of overcoming the technical defects of the prior art.
- Said materials can form a thick layer up to 1 micron, while the electrochemical grafting, as described previously in the international application WO 2013/124831, allows to deposit a layer of calixarenes of at most 100 nm on a support.
- the complexing cavities in a material according to the invention are distributed in 3 dimensions and in a homogeneous manner, which allows i) to have a larger quantity of molecules-cages (and therefore a larger capture capacity of metals), and (ii) cavities even at depth to be accessible to the metals of interest.
- the specific surface area of a material of the invention can be up to 1000 times greater than that of resins functionalized by calixarenes after their crosslinking. Due to its very high specific surface area, the extraction time of rare earths by a material of the invention is considerably reduced compared to the resins conventionally used for the extraction of rare earths. These particular physicochemical properties confer on these materials a high retention capacity of the metals of interest and consequently allow said materials to be used on an industrial scale for the extraction and / or separation of the different strategic metals, in particular different rare earths.
- the subject of the present invention is a new complex comprising (i) a solid support and (ii) a solid material, with a matrix and homogeneous structure, having a structuring element and a crosslinking element, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said organic solvent, at least one of the two elements carrying or forming a complexing domain of strategic metals consisting of rare earths, antimony, indium, beryllium, magnesium, cobalt, niobium, platinoids, gallium, germanium, tantalum, tungsten, molybdenum, titanium, mercury, cesium, lithium and strontium,
- Said structuring element and said crosslinking element being formed, independently of one another, by at least one entity selected from the group consisting of: (a) a polymer consisting of monomers, said polymer possibly bearing at least one coordinating group, advantageously a phosphate group,
- an aryl group or a substituted aryl group such as a tosyl group or a diazonium group
- aromatic heterocycle such as a pyrrolyl, furyl, thienyl or pyridinyl group
- an aryl group or a substituted aryl group such as a tosyl or a diazonium group
- aromatic heterocycle such as a pyrrolyl, furyl, thienyl or pyridinyl group
- an aryl group or a substituted aryl group such as a tosyl or a diazonium group
- aromatic heterocycle such as a pyrrolyl, furyl, thienyl or pyridinyl group
- said structuring element, or said crosslinking element or both carry at least one coordinating group, advantageously a phosphate group.
- material with a homogeneous structure means a material in which the concentration of complexing domains is constant in the entire volume of material.
- crosslinking element being crosslinked with said structuring element a crosslinking element being covalently bonded to a structuring element and the formation of one or more three-dimensional networks by chemical bonding.
- the complexing domain is a rare earth complexing agent.
- material capable of being swollen in water or in an organic solvent means a material capable of absorbing and preserving very large quantities, even up to 1000 times their mass, of water or a solvent organic.
- the swelling property of said material is essential for the good performance of said material.
- the swelling property directly affects the accessibility of all the complexing domains of said material and therefore the property of the complex of the invention.
- This property is flexible and adjustable through the thickness of the layer of said material and the degree of crosslinking.
- structural element means a constituent of the aforesaid material forming the main structure of said material and capable of establishing physical interactions, within the structure in which it is implemented and having capacities to develop structuring properties leading to textures of semi-solid or solid appearance.
- crosslinking element means a constituent of said material connecting the different parts of the structuring element.
- the ratio of the molar proportion between the structuring element and the crosslinking element in said material can be from 90/10 to 50/50.
- the structuring element in said material determines the main physicochemical properties of said material.
- the role of the crosslinking element in a material of the invention is to form a matrix structure and to distribute the complexing domains of the strategic metals in a homogeneous three-dimensional manner in the matrix of the aforesaid material.
- Said crosslinking element may also bring additional physicochemical properties to said material of the invention.
- a complexing domain of strategic metals, especially rare earths a group capable of binding to a strategic metal, particularly a rare earth, by coordination link, or to encapsulate, thanks to its conformation space, a strategic metal, especially a rare earth.
- a complexing domain may be formed by a cage molecule or a phosphate group, known for their capacity to bind specifically to rare earths.
- carrier molecule means a molecule having a structure comprising a cavity and capable of encapsulating an atom, an ion or another molecule within said cavity.
- cage molecules that may be used in the context of the invention, mention may be made of the calix [n] arenes, in which n is an integer of 4 to 100, advantageously of between 4 and 50, even more preferably between 4 and 8, in particular the calix [4] arene, the calix [5] arena, the calix [6] arena, the calix [7] arena and the calix [8] arena, or the crown ethers, especially the 12-crown-4, 15-crown-5, 18- crown- 6 and 21-crown-7, or cyclodextrins, especially ⁇ -, ⁇ - and ⁇ -cyclodextrins.
- n is an integer of 4 to 100, advantageously of between 4 and 50, even more preferably between 4 and 8, in particular the calix [4] arene, the calix [5] arena, the calix [6] arena, the calix [7] arena and the calix [8] arena, or the crown ethers, especially the 12-crown-4, 15-c
- either the structuring element or the crosslinking element comprises a cage molecule
- either the structuring element or the crosslinking element, or the two elements carry at least one coordinating group, for example a phosphate group.
- a coordinating group for example a phosphate group.
- 12-crown-4 ether can form a specific complexing domain to separate lanthanum from europium (Ali et al., J. Chem Chem Eng 2006, Vol 25, 15).
- the calix [4] arenes functionalized with a diglycolamide can form complexing domains for separating europium from americium.
- said material may comprise complexing domains of different types, such as those formed respectively by calixarenes and crown ethers.
- said complexing domain is a combined complexing domain, formed by at least two complexing domains that bind together by nucleophilic substitution or electrophilic substitution.
- an entity capable of forming a complexing domain combined after the crosslinking mention may be made of a crown calixarene or a phosphorylated calixarene.
- a combined complexing domain can produce a synergistic effect for the extraction or separation of strategic metals from a single complexing domain.
- said material comprises several complexing domains specific to the different strategic metals respectively.
- Strategic metals means metals that are essential for the economic development of a state, but which present a risk of shortage or difficulty of supply.
- strategic metal refers to metals selected from antimony, indium, beryllium, magnesium, cobalt, niobium, platinoids, gallium, germanium, tantalum, tungsten, molybdenum, titanium, mercury, cesium, lithium, strontium and rare earths.
- rare earths refers to a group of chemical elements consisting of scandium (Se), yttrium (Y), and the fifteen lanthanides, namely lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).
- Se scandium
- Ce cerium
- Pr praseodymium
- Nd neodymium
- Pm promethium
- Sm samarium
- Eu europium
- Gd gadolinium
- Tb terbium
- Dy dysprosium
- Ho holmium
- Er erbium
- the complex of the invention comprises a solid material having a matrix and homogeneous structure, having a structuring element and a crosslinking element, said material being at least insoluble in water or in an organic solvent and capable of to be inflated by water or said organic solvent, at least one of the two elements carrying or forming a rare earth complexing domain.
- polymer consisting of monomers means a macromolecule characterized by the repetition of one or more types of monomers.
- a polymer that can be used in the context of the invention is an organic polymer.
- the polymer corresponds to formula (A) or (
- R a , R a ' identical or different, each independently represent a hydrogen atom, a fluorine atom or a C 1 -C 6 alkyl group
- R b , Rb ' which may be identical or different, each represent, independently of each other, an OH, CN, CO 2 Rd, a C 6 -C 10 aryl or 5- or 7-membered heteroaryl group, said aryl groups or heteroaryls being optionally substituted by one or more substituents selected from a group -SO 3 H and a phosphate group;
- R c is a hydrogen atom or - (CH 2 ) 2 NH 2 ,
- R d is a hydrogen atom or a C 1 -C 6 alkyl group.
- a polymer that can be used in the invention as a structuring element or a crosslinking element mention may in particular be made of polymers having based on acrylic acid (PAA), 4-vinylpyridine polymers (P4VP), fluorinated polymers such as polyvinylidene fluoride (PVDF), polyvinyl alcohcol (PVA), polymethyl methacrylate (PMMA), polyethyleneimine ( PEI), or polyacrylonitrile (PAN).
- PAA acrylic acid
- P4VP 4-vinylpyridine polymers
- PVDF polyvinylidene fluoride
- PVA polyvinyl alcohcol
- PMMA polymethyl methacrylate
- PEI polyethyleneimine
- PAN polyacrylonitrile
- the molecular weight of the polymer can vary to a large extent, especially 2,000 g. mol "1 to 1,000,000 g mol " 1 .
- the molecular weight of the polymer is between 50,000 g. mol "1 and 300 000 g. mol"
- said polymer is a polymer based on acrylic acid.
- polymer based on acrylic acid means a polymer comprising the following repeating unit: - (CH 2 -CX (COOH)) n - where X is H, or a C 1 -C 6 alkyl group, especially CH 3 or C 2 H 5 .
- the polymer forming a structuring element or a crosslinking element of a material of the invention is a homopolymer of acrylic acid, also designated PAA below, having in particular a molecular weight of 130,000 g. mol "1.
- the solution employed in step i) may further comprise a second homopolymer of acrylic acid of different molecular weight.
- the polymer forming a structuring element or a crosslinking element of a material of the invention is a polymer based on 4-vinylpyridine, especially a poly (4-vinylpyridine).
- 4-vinylpyridine-based polymers means polymers derived from poly (4-vinylpyridine) by substitution of a hydrogen
- coordinating group means a group of atoms able to bind to a metal atom by a covalent or coordination bond, or ionic said group of atoms not being included in a ring structure, in particular a cage molecule.
- (C 1 -C 15 ) alkyl refers to a linear or branched saturated chain of 1 to 15 carbons.
- Such an alkyl can be, for example, methyl, ethyl, propyl, isoprolyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, tert-pentyl, hexyl , heptyl, octyl, nonyl, decyl, undecyl, or dodecyl.
- (C 1 -C 6) alkyl refers to a linear or branched saturated chain of 1 to 6 carbons.
- Such an alkyl can be, for example, methyl, ethyl, propyl, isoprolyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, tert-pentyl, hexyl .
- (C 2 -C 5 ) alkenyl refers to a linear or branched chain of 2 to 15 carbons containing at least one double bond.
- alkenyl may be, for example, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 4-pentenyl, or 2-hexenyl.
- (C 2 -C 5 ) alkynyl refers to a linear or branched chain of 2 to 15 carbons containing at least one triple bond. By way of example, mention may be made of ethynyl or propynyl.
- (C 1 -C 5 ) alkoxy refers to a (C 1 -C 5 ) -O-alkyl radical.
- such an alkoxy can be for example a methoxy, an ethoxy, a propoxy, a butoxy or a pentoxy.
- aryl or aryl C 6 -C 0 refers to a monocyclic or polycyclic aromatic ring, optionally substituted.
- an aryl may be, for example, phenyl, benzyl, tolyl, xylyl or naphthyl.
- aromatic heterocycle or “heteroaryl” means an unsaturated monocyclic or polycyclic structure comprising atoms of at least two different elements chosen from carbon, nitrogen and sulfur atoms.
- aromatic heterocycles mention may be made of pyrrolyl, furyl, thienyl or pyridinyl.
- Aryl (Ci-Ci 5 ) alkyl is understood to mean an aryl substituted with a (C 1 -C 15 ) alkyl, in particular an aryl substituted with a methyl, an ethyl, a propyl, an isoprolyl or an n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl.
- carbonyl refers in particular to an anhydride group or a carboxylic group and its derivatives.
- said structuring element and said crosslinking element may be formed by compounds of the same chemical nature.
- said structuring element and said crosslinking element may both be formed by polymers, provided that either the polymer forming said structuring element or the polymer forming said crosslinking element, or the two polymers carry at least one coordinating group, such as a phosphate group.
- said structuring element and said crosslinking element can both be formed by cage molecules.
- the aforesaid structuring element and the aforesaid crosslinking element are formed by an entity chosen from (a) a polymer consisting of monomers and (b) a cage molecule, said structuring element being different. said crosslinking element.
- said polymer consisting of monomers is preferably chosen from a polymer based on acrylic acid, in particular a homopolymer of acrylic acid or a polymer based on 4-vinylpyridine, in particular a poly (4-vinylpyridine).
- Said cage molecule in the aforesaid embodiment is chosen from the group comprising calix [n] arenes in which n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8, crown ethers and cyclodextrins.
- a particular embodiment of the invention relates to a complex comprising a solid material having a matrix and homogeneous structure, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said solvent organic, in which:
- the aforesaid structuring element is formed by a calix [n] arene in which n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8, and
- the aforesaid crosslinking element is formed by a poly (4-vinylpyridine).
- Another particular embodiment of the invention relates to a complex comprising a solid material with a matrix and homogeneous structure, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said organic solvent, wherein:
- the aforesaid structuring element is formed by a poly (4-vinylpyridine) and
- the aforesaid crosslinking element is formed by a calix [n] arene in which n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8.
- the invention relates to a complex comprising a solid material having a matrix and homogeneous structure, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said organic solvent, wherein:
- the aforesaid structuring element is formed by a calix [n] arene in which n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8, and
- the aforesaid crosslinking element is formed by a homopolymer of acrylic acid.
- the invention relates to a complex comprising a solid material having a matrix and homogeneous structure, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said organic solvent, wherein:
- the aforesaid structuring element is formed by a homopolymer of acrylic acid and
- the aforesaid crosslinking element is formed by a calix [n] arene in which n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8.
- the aforesaid material is deposited on the surface of a solid support and bonded to the support by non-covalent bonding.
- said solid support may be an organic or inorganic support, in particular a conductor, a semiconductor or an insulator. It can be chosen in particular from metals such as copper, nickel, stainless steel, aluminum, iron, titanium, or their oxides, such as titanium dioxide (TiO 2 ), iron oxides, or aluminum oxides; mineral oxides, especially those based on silicon oxide commonly called glasses; plastics; cellulosic papers, synthetic papers such as Teslin®, carbon fibers, especially woven or non-woven fibers, and composite materials such as fiberglass-reinforced epoxy resins, carbon fibers or natural fibers.
- metals such as copper, nickel, stainless steel, aluminum, iron, titanium, or their oxides, such as titanium dioxide (TiO 2 ), iron oxides, or aluminum oxides
- mineral oxides especially those based on silicon oxide commonly called glasses
- plastics cellulosic papers, synthetic papers such as Teslin®, carbon fibers, especially woven or non-woven fibers, and composite materials such as fiberglass-reinforced
- the bond formed between the aforesaid material and the support is a non-covalent bond.
- the invention relates to a complex comprising or consisting of:
- a solid material with a matrix and homogeneous structure said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said organic solvent, wherein, the aforesaid structuring element and the aforesaid crosslinking element are formed by an entity chosen from (a) a polymer consisting of monomers and (b) a cage molecule, said structuring element being different from said crosslinking element.
- a conductive support in particular a carbon fiber support, makes it possible to electrically regenerate the aforementioned non-conducting solid material and to eliminate the use of regeneration reagents, such as an acid, a base, or an organic solvent, present in a washing solution for eluting the strategic metals captured by said material, which allows the complex of the invention to be regenerated in an environmentally friendly condition.
- regeneration reagents such as an acid, a base, or an organic solvent
- a complex of the invention comprises or consists of a carbon fiber support and a solid material with a matrix and homogeneous structure, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said organic solvent, in which:
- the aforesaid structuring element is formed by a calix [n] arene in which n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8;
- a complex of the invention comprises or consists of a support made of carbon fiber and a solid material with a matrix and homogeneous structure, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said organic solvent, wherein:
- the aforesaid structuring element is formed by a poly (4-vinylpyridine);
- a complex of invention comprises or consists of a support made of carbon fiber and a solid material with a matrix and homogeneous structure, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said solvent organic, in which: the aforesaid structuring element is formed by a calix [n] arene in which n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8;
- the aforesaid crosslinking element is formed by a homopolymer of acrylic acid.
- a complex of the invention comprises or consists of a carbon fiber support and a solid material with a matrix and homogeneous structure, said material being at least insoluble in water or in an organic solvent and capable of being swollen by water or said organic solvent, wherein:
- the aforesaid structuring element is formed by a homopolymer of acrylic acid
- the aforesaid crosslinking element is formed by a calix [n] arene in which n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8.
- Another aspect of the invention relates to crosslinking or structuring elements consisting of new phosphorylated calixarenes of formula (I)
- Xi and X 2 each independently represent each other H or a
- R 3 and R 4 each independently of one another is H or (C 1 -C 6) alkyl, provided that X 1 and X 2 are not simultaneously H,
- Li, L 2 , l 3 and L 4 are spacer groups, chosen independently of one another, from the group consisting of (C 3 -C 10) cycloalkylenyl, O, NH, - (CH 2 ) q -, q being a integer from 0 to 12, or from 1 to 12
- R 3 and R 4 are as defined above, Z 1 and Z 2 not being all the
- n is an integer from 4 to 100, advantageously from 4 to 50, preferentially from 4 to 8.
- novel phosphorylated calixarenes of the invention bearing functional groups are capable of reacting with another compound also bearing at least one compatible functional group, which allows the aforementioned new calixarenes to crosslink with said compounds carrying at least one compatible functional group.
- said calixarene is the compound of formula (Ia):
- the invention relates to a complex as described above, in which the aforesaid structuring element and the aforesaid crosslinking element are respectively formed by an entity chosen from (a) a polymer consisting of monomers and (b) ) a phosphorylated calixarene of formula (I), said structuring element being different from said crosslinking element.
- the invention relates to a complex as described above, in which the aforesaid structuring element and the aforesaid crosslinking element are respectively formed by (a) a polymer based on acrylic acid, in particular a homopolymer of acrylic acid, or a polymer based on 4-vinylpyridine, in particular a poly (4-vinylpyridine) and (b) a phosphorylated calixarene of formula (I), said structuring element being different from said crosslinking element.
- the invention relates to a complex as described above, in which the aforesaid structuring element and the aforesaid crosslinking element are respectively formed by an entity chosen from (a) a polymer consisting of monomers and ( b) the phosphorylated calixarenes of formula (Ia) and / or of formula (Ib), said structuring element being different from said crosslinking element.
- the invention relates to a complex as described above, in which the aforesaid structuring element and the aforesaid crosslinking element are respectively formed by an entity chosen from (a) a poly (4-vinylpyridine) ) and (b) the phosphorylated calixarenes of formula (Ia) and of formula (Ib), said structuring element being different from said crosslinking element.
- the invention relates to a complex comprising a support made of carbon fiber and a solid material as described above, in which the aforesaid structuring element and the aforesaid crosslinking element are formed respectively by an entity chosen from (a) a poly (4-vinylpyridine) and (b) the phosphorylated calixarenes of formula (Ia) and of formula (Ib), said structuring element being different from said crosslinking element.
- the present invention also relates to the use of a phosphorylated calixarene of formula I, in particular calixarenes phosphorylated compounds of formula (Ia) and of formula (Ib), for the preparation of a complex of the invention.
- the present invention also relates to a method for preparing a said complex of the invention.
- Said method comprises:
- a first step of contacting a liquid mixture or a solid mixture comprising an agent capable of structuring and an agent capable of crosslinking with a surface of a solid support, at least one of the two agents carrying a complexing domain or being capable of forming a complexing domain after crosslinking, for strategic metals consisting of rare earths, antimony, indium, beryllium, magnesium, cobalt, niobium, platinoids, gallium, germanium, tantalum, tungsten, molybdenum, titanium, mercury, cesium, lithium and strontium,
- said agent capable of structuring and said agent capable of crosslinking being identical or different and corresponding to the formula Ri-LR 2 , in which:
- a coordinating group advantageously a phosphate group
- halogen chosen from F, Cl, Br, I,
- Hal represents a halogen atom as defined above
- a sulphate or sulphonate group optionally protected by a protecting group of sulphate or sulphonate group
- thiol optionally protected by a protective group of thiols
- a cage molecule optionally substituted with at least one functional group chosen from:
- a halogen chosen from F, Cl, Br, I,
- Hal represents a halogen atom
- a sulphate or sulphonate group optionally protected by a protecting group of sulphate or sulphonate group
- an aryl group or a substituted aryl group such as a tosyl group, a diazonium group,
- aromatic heterocycle such as a pyrrolyl, furyl, thienyl or pyridinyl group
- a sulphate or sulphonate group optionally protected by a sulphate or sulphonate protecting group
- a halogen selected from F, Cl, Br, I,
- thiol optionally protected by a protecting group of the thiols
- an aryl group or a substituted aryl group such as a tosyl group or a diazonium group
- aromatic heterocycle such as a pyrrolyl, furyl, thienyl or pyridinyl group
- a sulphate or sulphonate group optionally protected by a sulphate or sulphonate protecting group
- thiol optionally protected by a protecting group of the thiols
- halogen chosen from F, Cl, Br, I,
- an aryl group or a substituted aryl group such as a tosyl group, a diazonium group,
- aromatic heterocycle such as a pyrrolyl, furyl, thienyl or pyridinyl group
- a sulphate or sulphonate group optionally protected by a sulphate or sulphonate protecting group
- halogen chosen from F, Cl, Br, I,
- Ri and R 2 are functional groups selected from the group consisting of:
- a halogen chosen from F, Cl, Br, I,
- a sulphate or sulphonate group optionally protected by a sulphate or sulphonate protecting group
- a thiol optionally protected by a protective group of thiols,
- the groups R 1, R 2 or L-functional groups of a crosslinkable agent being chosen such that they are capable of reacting with the groups R 1, R 2 or functional groups borne by L of a suitable agent structuring to allow crosslinking between said structuring and crosslinking agents;
- the heat treatment is carried out at a temperature of 20 ° C to 200 ° C, especially at a temperature of 60 ° C to 150 ° C, particularly at a temperature of 80 ° C to 100 ° C.
- the heat treatment may be carried out by any means known to those skilled in the art, for example by heating in an oven, or by directly applying hot and dry air to a liquid or solid mixture comprising an agent capable of structuring and a agent capable of crosslinking, or by applying it to substrates having a high thermal conductivity, such as metals, and certain heat-stable polymers such as polyimide, poly (p-phenyleneterephthalamide) (PPD-T or Kevlar®) or polytetrafluoroethylene (PTFE or Teflon®).
- PPD-T or Kevlar® polytetrafluoroethylene
- PTFE polytetrafluoroethylene
- the duration of heat treatment depends on the temperature applied during this treatment. Low temperature heat treatment may take several hours. Typically, when this treatment is performed at 80 ° C, the treatment time can be up to 72h; when the treatment temperature is increased to 200 ° C, the treatment time can be reduced to 60 minutes, typically from 2 to 30 minutes.
- an agent capable of structuring and an agent capable of crosslinking become respectively the structuring element and the crosslinking element of a material as described above.
- the crosslinking between the agent capable of structuring and the agent capable of crosslinking is carried out via the functional groups carried respectively by the agent capable of structuring and by the agent capable of crosslinking.
- a crosslinkable agent bearing a halogen atom as a functional group may react with a pyridinyl group-bearing structuring agent, for example a poly (4-vinylpyridine).
- certain functional groups such as amines, sulphates or sulphonates, thiols, may be protected by the appropriate protective groups up to before heat treatment. .
- amine protecting group of tert-butyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, carboxybenzyl, acetyl, benzoyl, benzyl or carbamates; as a sulphate or sulphonate protecting group, mention may be made of trifluoroethyl, and as a thiol protecting group an acetyl group, tert-butyl, benzyl, 2-cyanoethyl or a disulfide bridge.
- Said liquid mixture comprising an agent capable of structuring and an agent capable of crosslinking may further comprise a solvent.
- Said solvent may be an inorganic or organic solvent for solubilizing said agent capable of structuring and said agent capable of crosslinking to obtain a clear and homogeneous solution.
- a suitable solvent for solubilizing said agent capable of structuring or said agent capable of crosslinking For example, a polymer based on acrylic acid may be solubilized in an alcohol, especially ethanol, or a hydroalcoholic mixture; P4VP can be solubilized in an alcohol or tetrahydrofuran (THF); the calixarenes can be solubilized in an organic solvent, such as THF or DMSO (dimethyl sulfoxide).
- the removal of the solvent can be carried out by any conventional techniques known to those skilled in the art, such as simple air drying, in particular for the liquid mixture comprising alcoholic solvents, for example with ethanol, or evaporation under reduced pressure and / or by heating for the solvents having a higher boiling point, in particular for liquid mixtures comprising hydroalcoholic solvents.
- the thickness of the aforesaid material is adjustable, according to the general knowledge of those skilled in the art, via the respective concentrations of the agent capable of structuring and the agent capable of crosslinking and / or via the successive deposition of layers of material on another previously deposited layer.
- the method of the invention may further comprise, after the formation of said solid material as defined previously in the invention, a step of rinsing with water or with an appropriate solvent of said material obtained.
- Rinsing makes it possible to eliminate all unreacted products after the step of forming material as defined previously in the invention.
- a liquid mixture may be applied to the surface of the solid support according to various methods, in particular by dipping (immersion-emersion), centrifugation (spinning), spraying (spray), spraying (inkjet, spraying) or by transfer (brush, felt brush, pad).
- solid mixture is meant a mixture obtained from an initial liquid mixture after evaporation of the solvent in said liquid mixture.
- the agent capable of structuring and the agent capable of crosslinking are not or little crosslinked together in said solid mixture.
- Said solid mixture can be formed in situ on a solid support after solvent removal.
- Said solid mixture may also be previously formed on a support different from that contained in the complex of the invention and subsequently deposited on the support contained in the complex.
- the invention relates to a method for preparing a complex comprising a solid material as defined previously in the invention, wherein said structuring element and said crosslinking element are chosen from (a) a polymer consisting of of monomers and (b) a cage molecule, said structuring element and said crosslinking element being different, said method comprising the formation of said material by heat treatment, at a temperature between 20 ° C and 200 ° C, of a liquid mixture or solid comprising:
- a coordinating group advantageously a phosphate
- halogen chosen from F, Cl, Br, I, - -OH,
- Hal represents a halogen atom
- a sulphate or sulphonate group optionally protected by a protecting group of sulphate or sulphonate group
- thiol optionally protected by a protective group of thiols
- halogen chosen from F, Cl, Br, I,
- Hal represents a halogen atom
- a sulphate or sulphonate group optionally protected by a protecting group of sulphate or sulphonate group
- thiol optionally protected by a protective group of thiols
- said polymer and said cage molecule being capable of reacting via functional groups to allow crosslinking between said polymer and said cage molecule.
- the invention relates to a method for preparing a complex comprising a solid material as defined previously in the invention, wherein said structuring element and said crosslinking element are chosen from a poly (4- vinyipyridine) and a calix [n] arene, wherein n is an integer from 4 to 100, said structuring element and said crosslinking element being different, said method comprising forming said material by heat treatment, at a temperature between ° C and 200 ° C, a mixture liquid or solid comprising a poly (4-vinylpyridine) and a halogen-substituted calix [n] arene.
- the present invention also relates to a complex that can be obtained by implementing the method as described above.
- a complex obtained according to the aforesaid process comprises a solid support
- said material is bonded to said solid support by non-covalent bonding.
- Certain complexes of the present invention comprising a solid support can be obtained according to any technique known to those skilled in the art, in particular according to the following method:
- the gamma radiation in particular radiation at a wavelength of between 1 nm and 5 nm, may for example be produced by a cesium 137 source of 55 TBq (660 keV gamma photons) whose radiation dose may vary between 5, 5 and 50 Gy.
- An electronic radiative treatment may be implemented by an electron beam from, for example, a column of a scanning electron microscope. Typically an energy range of 0.5 and 30 keV is preferred.
- Said polymer, said solvent and said solid support implemented in step i) are respectively as previously defined.
- Said complexing agent is a compound capable of forming a complexing domain as defined previously after crosslinking with a polymer.
- Said method may further comprise a step o), prior to step i), of subjecting the solid support to a surface pretreatment of oxidative type, in particular chemical and / or radiative, so as to increase the affinity of the support solid with the solution containing the polymer and the complexing agent.
- the oxidative treatment can be done by oxygen plasma and the radiative treatment can be a UV-Ozone activation.
- complexes according to the invention when said complexes comprise a solid support with a layer of material, in which the structuring element or the crosslinking element is formed by a polymer based on acrylic acid, can be obtained according to following process:
- said solution does not comprise an adhesion primer based on aryldiazonium salts
- Said acrylic acid-based polymer, said complexing agent, said solvent and said solid support implemented in step i) are respectively as defined above.
- Said method may further comprise a step o), prior to step i), of subjecting the solid support to a surface pretreatment of oxidative type, in particular chemical and / or radiative, so as to increase the affinity of the support solid with the solution containing the polymer and the complexing agent.
- oxidative type in particular chemical and / or radiative
- Another aspect of the invention relates to the use of the complexes described in the present invention, or complexes obtained by the methods described in the present description, for extracting or separating, from an aqueous medium or a liquid medium.
- organic, strategic metals including rare earths.
- the subject of the invention is a method for extracting or separating, from an aqueous medium or an organic liquid medium, strategic metals, in particular rare earths, said method comprising a step of implementing contact of an aqueous or organic liquid medium with at least one complex described in the present invention, or complexes obtained by the methods described in the present description
- aqueous medium or "organic liquid medium” means a wastewater effluent, or any solution containing the strategic metals, in particular the rare earths, to be extracted or separated.
- said method of the invention makes it possible to specifically extract or separate one or more specific strategic metals, in an aqueous or organic liquid medium comprising several metals. including rare earths, the same group or different groups.
- a complex of the invention will be able to choose a complex of the invention according to the strategic metals to be extracted or separated and according to the properties of the medium from which the strategic metals are extracted.
- a complex of the invention comprising a material as defined above which is insoluble but capable of being swollen in the medium from which the strategic metals are extracted.
- the method of the invention may further comprise a step of recovering strategic metals, in particular rare earths, retained in the aforementioned complex.
- strategic metals in particular rare earths
- a desorption solution optionally by implementing an electrodisorption method.
- the present invention is illustrated by Figures 1 to 6 and Examples 1 to 5 which follow.
- FIG. 1 represents the matrix of a material according to the invention, in which the structuring element is formed by the molecules -cages (C).
- FIG. 2 represents the matrix of a material according to the invention, in which the complexing domain for a molecule of interest (M) is formed by the structuring element.
- FIG. 3 represents the matrix of a material described in the invention, in which the structuring element is formed by a polymer; the crosslinking element is formed by the cage molecules.
- FIG. 4 illustrates the retention of europium by the "KT103-P4VP-carbon felt” complex ((b) and (c)) or by a reference complex (a) as measured according to example 2.
- the presence of europium is detected by X-ray photoelectron spectrometry.
- FIG. 5 represents the IR transmittance as a function of the wavelength of a "PAA-calix-gold" complex obtained by heat treatment according to example 4.
- the spectrum (a) is recorded just after deposition and drying alcohol .
- Spectrum (b) is recorded after annealing at 200 ° C.
- the spectrum (c) is obtained after 10 minutes of hydrolysis at pH 10.
- the spectrum (d) is obtained after rapid rinsing of an initial film with water.
- FIGS. 6A and 6B illustrate a complex of the invention consisting of a carbon felt covered by a matrix material in three dimensions, before (FIG. 6A) and after (FIG. 6B) the contact with water, clearly highlighting the phenomenon of swelling of said material.
- Calixarene KT101 is synthesized according to the chemical reaction illustrated below:
- calixarene 49 0.248 mmol
- NaI 0.545 mmol
- the disk-shaped carbon felts (Mersen®) 2 cm in diameter are soaked in said reaction mixture containing the aforesaid N-calixpyridinium iodide in an amount of 10 -3 M-10 -4 M to extract the d-element.
- interest present in a concentration of 10 "3 M-10" 4 M in an aqueous solution used as a model effluent. They are then annealed in an oven at 100 ° C. for 8 hours in order to complete the crosslinking reaction.
- step (ii) is subjected to a competitive test to evaluate the effectiveness and specificity of said complex for the extraction of cesium.
- Aliquots of about 0.9 g from 3 carbon felt discs obtained in step (ii) are immersed for 20 minutes or 5 days, at room temperature, into a solution of 20 ml of concentrations about 10 " 4 M of cesium nitrate and about 0.1 M of sodium nitrate
- This solid phase consists of carbon felt loaded with a polymer carrying a calixarene at a concentration allows a percentage of extraction of between 10 and 90%.
- the cesium concentrations, at the beginning (C) and at the end of the treatment (C f ), are determined by atomic absorption spectrometry
- Phosphorylated calixarenes are synthesized according to the following reaction steps:
- the calixarene 5,17-dibromo-25,27-bis (4-chlorobutoxy) calix [4] arene (hereinafter referred to as KT 102) is obtained by the direct addition of bromine atoms to the KT46 calixarene according to the method described by Guillon et al. (Supramolecular Chemistry, 2004, 16, 319).
- KT 102 is then subjected to a NiBr 2 catalyzed Arbuzov reaction to give a mixture of two phosphorylated calixarenes, namely the compound Ia and the compound Ib, the set called the KT103 series is used as it is in the following reactions without further purification.
- the composition of the KT103 mixture is confirmed by MALDI-TOF spectrometry.
- the reaction medium is deposited by dipping as described in the preceding example on carbon felts (Mersen®) disk-shaped 2 cm in diameter in an amount sufficient to extract the element of interest present in a concentration of 10 "3 M-10" 4 M in an aqueous solution used as a model effluent. Then the markers The carbon is annealed in an oven at 100 ° C for 8 hours to complete the crosslinking reaction.
- carbon felts Mersen®
- the carbon felts are rinsed with deionized water for 8 h at room temperature to confirm the insolubility of the polymer "P4VP-KT103" in an aqueous medium.
- a reference complex consisting of a gold plate coated with a P4VP polymer cross-linked with diiodohexane is prepared according to the same method.
- the crosslinked polymer is deposited on a gold plate, washed with ethanol and then with deionized water and dried in an oven for 8 hours at 100 ° C.
- step (ii) About 0.9 g of carbon felts (3 discs 2 cm in diameter) obtained in step (ii) are immersed for 20 minutes at room temperature in 20 ml of a solution containing about 10 -3 M The carbon felts are then rinsed with ethanol to remove uncompacted metal ions and dried in an oven.
- the europium retained by the "KT103-P4VP-carbon felt" complex is analyzed by XPS (X-ray photoelectron spectrometry).
- the "KT103-P4VP-carbon felt" complex retains the europium ions contained in the test solution.
- a solution of polyacrylic acid (PAA) is prepared at 50 mg in 10 ml of ethanol.
- a solution of 25,27-bis (4-chlorobutoxy) calix [4] arenes-crown-6 (calixarene 49) is prepared at 11 g in 40 ml of DMSO (dimethylsulfoxide).
- the final solution is made by adding 600 ⁇ l of the calix 49 solution in 10 ml of PAA solution (ie about 5 mg of PAA per 16.5 mg of calix 49 per milliliter of solution). The mixture is stirred for 30 minutes to clarify.
- a solution of Polyethylene imine (PEI), molecular weight 25000, is prepared by dissolving 5 mg of PEI in 10 ml of deionized water.
- a first impregnation of the carbon felt discs is made with an aqueous solution of polyethylene imine (PEI) 5 mg / 10 ml.
- PEI polyethylene imine
- the felt is filled with a pasteur pipette until visual detection of complete impregnation. Then the felt is allowed to dry.
- the primary coating of PEI polymer having positive charges
- PAA negatively charged
- a second impregnation is made with the PAA and calixarene solution described above until visual detection of complete impregnation.
- the felt is allowed to dry naturally.
- the Gamma irradiation is done for 8h in a Gamma Cell 3000 Elan with photons of 662 keV (5.5 Gy / min).
- step (i) 3 felts prepared according to step (i), as well as the PAA-coated control felts, are respectively introduced into a pill-filled container and covered with 20 ml of a solution of 0.2 mM / 10 mM Cs + / Na + in tap water; they are left for 20 min at room temperature with regular stirring. The cesium molar concentrations of the samples were then measured by flame absorption spectroscopy.
- a solution of PAA (acrylic acid polymer) is prepared at 150 mg in 10 ml of ethanol.
- a solution of calixarene 49 is prepared at 11 g in 40 ml of DMSO (dimethylsulfoxide).
- the final solution is made by adding 200 ⁇ of the calix solution
- a slide-type glass slide (7.5x2.5 cm) is gilded by a vacuum metallization process.
- the application of the PAA solution on the gold plate is done by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous with a thickness of 70 to 100 nm. At this point DMSO is still present in the trace state in the film.
- the glass slides coated with the PAA are then heated to
- Figure 5 shows the results of the IR spectra recorded on the gold plates for different process steps.
- the bands corresponding to the calixarenes are slightly visible, especially at 1454, 1246, 1208, 1093 and 764 cm-1.
- Spectrum (d) is obtained with rapid rinsing of an initial film (equivalent to spectrum (a)) with water. Partial removal of PAA is achieved and it becomes easier to observe the bands of calixarene molecules that are relatively hydrophobic. This procedure increases the proportion of calixarene in PAA films. This spectrum also shows that a large proportion of calixarene is present in the film. Referring to the concentrations of the initial PAA and calixarene solutions, the proportion on spectrum (a) is 60 mg calixarene per 150 mg PAA.
- a PAA solution is prepared at 150 mg in 10 ml of ethanol.
- a solution of calixarene 49 is prepared at 11 g in 40 ml of DMSO (dimethylsulfoxide). The final solution is made by adding 200 ⁇ l of the Calix 49 solution in 10 ml of PAA solution. Stirring for 30 minutes is necessary to clarify the mixture.
- DMSO dimethylsulfoxide
- a slide-type glass slide (7.5x2.5 cm) is gilded by a vacuum metallization process.
- the application of the PAA solution and calixarene is done by soaking-withdrawal (immersion-emersion) in order to obtain, after evaporation of the ethanol, a film of PAA covering and homogeneous with a thickness of 70 to 100 nm.
- the DMSO is still present in the trace state in the film, prolonged natural drying, or even heating at 100 ° C / lh is sufficient to remove traces of the solvent DMSO.
- the glass slide coated with PAA + calix 49 is introduced into the irradiation chamber of a Cell 3000 Elan gamma with photons of 662 keV (5.5 Gy / min). The irradiation lasts 8 hours.
- the PAA film is immobilized on the surface after 8 hours of irradiation. Radical crosslinking mechanisms did occur in the volume of the film.
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Abstract
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FR1452958A FR3019547B1 (en) | 2014-04-03 | 2014-04-03 | NEW COMPLEXES FOR CATION SEPARATION |
PCT/EP2015/097016 WO2015150588A1 (en) | 2014-04-03 | 2015-04-03 | Novel complexes for the separation of cations |
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EP (1) | EP3126343A1 (en) |
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FR3072093A1 (en) * | 2017-10-11 | 2019-04-12 | Universite Paris-Sud | CRYPTANDS BASED ON CALIX [4] ARENES ASSOCIATED WITH A NITROGEN MACROCYCLE AND THEIR USE FOR THE SELECTIVE EXTRACTION OF STRATEGIC METALS |
CN114761100A (en) * | 2019-10-12 | 2022-07-15 | 阿尔特姆斯产品公司 | System and method for separating gallium-68 |
WO2022082324A1 (en) | 2020-10-19 | 2022-04-28 | Pontificia Universidad Católica | Solid-liquid extraction process for recovering ions of interest from solid materials |
CN113877551B (en) * | 2021-10-25 | 2023-12-29 | 湖北科技学院 | Heavy metal and radioactive metal ion adsorption material and preparation method thereof |
WO2024035944A1 (en) * | 2022-08-12 | 2024-02-15 | University Of Kansas | Extraction of critical minerals using polyanions |
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JPS5647406A (en) * | 1979-09-28 | 1981-04-30 | Mitsubishi Chem Ind Ltd | Production of immobilized crown compound |
JPS5915323B2 (en) * | 1981-08-28 | 1984-04-09 | 工業技術院長 | Method for producing alkali metal trap material |
JPS58189205A (en) * | 1982-04-28 | 1983-11-04 | Sugai Kagaku Kogyo Kk | Resin-bound bisazocrown ether, production thereof and selective ion extractant obtained therefrom |
US6297395B1 (en) * | 1995-11-10 | 2001-10-02 | The Secretary Of State For Defence In Her Brittanic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Calixarenes and their use for sequestration of metals |
JPH10120914A (en) * | 1996-10-18 | 1998-05-12 | Mitsubishi Chem Corp | Ionic electroconductive solid polyelectrolyte and its production |
JP2000047018A (en) * | 1998-07-28 | 2000-02-18 | Jsr Corp | Radiation-sensitive composition for color filter |
JP4761805B2 (en) * | 2005-03-29 | 2011-08-31 | 国立大学法人東京工業大学 | Zinc isotope separation method and apparatus |
JP2012091112A (en) * | 2010-10-27 | 2012-05-17 | Mitsubishi Paper Mills Ltd | Magnetic chelating agent |
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- 2015-04-03 WO PCT/EP2015/097016 patent/WO2015150588A1/en active Application Filing
- 2015-04-03 CN CN201580018332.5A patent/CN106458962A/en active Pending
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CA2944642A1 (en) | 2015-10-08 |
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US20170044142A1 (en) | 2017-02-16 |
US20180179192A2 (en) | 2018-06-28 |
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JP6657174B2 (en) | 2020-03-04 |
FR3019547B1 (en) | 2017-12-22 |
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