Novel graft polymer, method for producing the same, and use thereof, particularly for metal capture

Abstract

To provide novel polymers that are grafted onto a substrate, and a use of the polymer for metal capture in aqueous media, particularly uranium capture in seawater or in final nuclear waste from nuclear power plants.SOLUTION: There is provided a composition comprising a polymer grafted onto a support, in particular grafted covalently, the polymer having a degree of polymerization n, ranging from 1 to 10,000, and containing n monomer units. The monomer units are either a) monomer units derived from 4-vinylpyridine, in which the carbons in positions 2 and 6 can be substituted by one of the substituents of the following group: carboxylic acid, ester of 1 to 20 carbons, or b) the monomer units derived from 4-vinylpyridine and monomer units derived from a co-monomer. The polymer may be complexed with a metal, and may be linear or crosslinked.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to novel graft polymers, methods for their production and use, in particular for use in metal capture.

Background Art

[0002] The uranium identified by the current method (mining) is a non-renewable resource that will be consumed in about a century. There are two possibilities as ways to overcome the uranium shortage · Collect from dissolved uranium in seawater · Recycling of spent fuel to reduce the loss of fissile materials due to final waste. The estimated amount of nuclear fuel in the sea is 45 trillion tons (about 10 times the amount on land), which is a consumption amount for more than a thousand years and is an interesting resource. In recent years, research has accelerated and a simple method for recovering uranium from 3.3 ppb of seawater has been discovered.

[0003] Generally, polymers are developed for capturing seawater uranium as new materials. When this polymer is immersed in seawater, it forms a uranium-polymer complex, enabling the extraction of uranium from seawater. By reprocessing this polymer, uranium can be recovered by dissociating the complex from water. However, the presence of poisons in the polymer reduces the effectiveness of such a method. In addition to the competition between vanadium and uranium in seawater, the recovery ability of the polymer is limited by complexation with the current polymer instead of uranium. The reprocessing of spent fuel from nuclear power plants is already incorporated into the round life cycle. Current uranium reprocessing is based on liquid-liquid extraction methods in the presence of complex-forming compounds, such as the DIAMEX or PUREX methods. This method uses toxic compounds and is costly.

Summary of the Invention

Means for Solving the Problems

[0004] One aspect of the present invention relates to a novel support-grafted polymer (a polymer grafted onto a support), which can be solvated or not solvated depending on the state of the medium in which it is found and can easily transition from one state to another. Another aspect of the present invention relates to a novel support-grafted polymer that can complex with metals, especially metals present in trace amounts in the medium in which they are found. Another aspect of the present invention relates to a method for capturing metals, especially uranium, especially uranium in seawater. Another aspect of the present invention relates to a method for selectively capturing uranium in seawater in high yield. Another aspect of the present invention relates to a method for reprocessing used nuclear fuel for the purpose of recovering unreacted fissionable materials. Another aspect of the present invention relates to the use of a novel support-grafted polymer complexed with a metal as a catalyst in a heterogeneous catalytic reaction. Another aspect of the present invention relates to the use of a novel support-grafted polymer for cell labeling in the biomedical field or for labeling counterfeits in the field of countering counterfeits.

Brief Description of the Drawings

[0005]

Figure 1

Figure 2

Figure 3

DETAILED DESCRIPTION OF THE INVENTION

[0006] The present invention relates to a composition comprising a polymer grafted onto a support, specifically a polymer covalently grafted onto a support, or consisting of said polymer, wherein the polymer has a degree of polymerization n of 1 to 10,000, contains n monomer units, and the monomer units are · Monomer units derived from 4-vinylpyridine in which the carbons at positions 2 and 6 are substituted by substituents from the following group: hydrogen, an alkyl group having 1 to 20 carbons, an alkene group having 1 to 20 carbons, an aryl group having 1 to 20 carbons, a carboxylic acid having 1 to 20 carbons, an alcohol having 1 to 20 carbons, an ether having 1 to 20 carbons, an ester having 1 to 20 carbons, an amine having 1 to 20 carbons, a heterocyclic ring having 1 to 5 rings in which the heteroatom is nitrogen, oxygen, sulfur or phosphorus, an amide having 1 to 20 carbons, a thiol having 1 to 20 carbons, a phosphine having 1 to 20 carbons, and the substituents may together form a ring and may contain a sulfur or phosphorus atom, or · Monomer units derived from a comonomer, provided that the two substituents are not hydrogen simultaneously, provided that the monomer units derived from 4-vinylpyridine represent at least 20% of the degree of polymerization n, the polymer may be complexed with a metal, the polymer is linear or crosslinked, the polymer is irreversibly linked to the support.

[0007] The polymer used in the present invention has the advantage of having different solvation characteristics depending on the substituents of the monomer units derived from 4-vinylpyridine and the composition of the component monomer units of the polymer. For example, when the substituents at the 2- and 6-positions of all monomer units are carboxylic acid groups, the solvation of the resulting polymer (without a support) changes with the pH of the solution. In a neutral or basic medium, the polymer is solvated in an aqueous medium. In a very acidic aqueous medium, the polymer can no longer be solvated. Due to this property, the solvation of the obtained polymer can be easily changed, and the behavior of the polymer can be modified for metal capture. The polymer of the present invention is grafted onto a support, and thus has the advantage that the polymer can be easily immobilized. Therefore, the recovery of the polymer in solution or its storage in a reactor is facilitated, especially in the case of heterogeneous catalytic reactions, compared to free polymers. The polymer of the present invention contains monomer units derived from 4-vinylpyridine in excess of 20%, especially in excess of 30%, especially in excess of 40%, especially in excess of 50%, especially in excess of 60%, especially in excess of 70%, especially in excess of 80%, especially in excess of 90%, especially 100%. The polymer of the present invention is adaptable and can be optimized to meet the difficulties encountered. For example, when the substituents at the 2- and 6-positions are very bulky, spacer comonomers can be added in a significant proportion (>50%) to limit the steric hindrance around the monomer units derived from 4-vinylpyridine.

[0008] The polymer of the present invention can include any of the following a) A single type of monomer unit derived from 4-vinylpyridine without including monomer units derived from comonomers. In this case, the polymer is a homopolymer b) A single type of monomer unit derived from 4-vinylpyridine and a single type of monomer unit derived from a comonomer. In this case, the polymer is a copolymer c) Monomeric units derived from a single type of 4-vinylpyridine and multiple types of monomeric units derived from different comonomers, in which case the polymer is a copolymer d) Multiple different types of monomeric units derived from 4-vinylpyridine and not containing monomeric units derived from comonomers e) Multiple different types of monomeric units derived from 4-vinylpyridine and monomeric units derived from a single type of comonomer, in which case the polymer is a copolymer f) Multiple types of monomeric units derived from different 4-vinylpyridines and multiple types of monomeric units derived from different comonomers, in which case the polymer is a copolymer.

[0009] The polymers of the present invention are either complexed with a metal or not, for example, complexes

Chemical formula

[0010] According to the present invention, the term "polymer" means a chain of monomeric units. The number of monomeric units forming the polymer of the present invention can be 1. Thus, a monomer grafted onto a support constitutes part of the present invention. In the following, the term polymer does not include the support. According to the present invention, the term "support" means a substance to which a polymer is directly or indirectly bonded and which enables immobilization of the polymer. The support can be used directly in the synthesis of the polymer or can be converted so as to be graftable with the polymer of the present invention or usable in the synthesis of the polymer. The support is stable and insoluble under storage conditions and under polymer use conditions. According to the present invention, the term "polymer grafted onto a support" means an assembly formed by a polymer, the support to which the polymer is bonded, and, when the bond is indirect, a linker of any component between the polymer and the support.

[0011] According to the present invention, the term "homopolymer" means a polymer in which all the component monomer units of the polymer have the same formula, in other words, all the monomer units are monomer units derived from 4-vinylpyridine, and all the monomer units derived from 4-vinylpyridine have the same substituents at the 2- and 6-positions. The metal that may be complexed with the monomer unit can vary within the same homopolymer. The bonding forms of the same acid-base couple are considered the same with respect to the concept of the homopolymer. For example, a polymer having a COOH group in the first monomer unit and a COO - group in the second monomer unit is still considered a homopolymer. According to the present invention, the term "copolymer" means a polymer in which at least one monomer unit is derived from a comonomer and at least one monomer unit is derived from 4-vinylpyridine.

[0012] According to the present invention, the term "4-vinylpyridine derivative" refers to a compound of the formula

Chemical formula

[0013] According to the present invention, the term "monomer derived from 4-vinylpyridine" refers to a compound of the formula

Chemical formula

[0014] According to the present invention, the term "comonomer" refers to a compound of the formula [Chemical formula] (wherein B i is different from a 4-vinylpyridine derivative) is meant to mean a compound of

[0015] According to the present invention, the term "monomer unit derived from 4-vinylpyridine" refers to the basic constituent elements that make up the polymer [Chemical formula] (R i,1 and R i,2 are as defined above) is meant to mean

[0016] According to the present invention, the term "monomer unit derived from a comonomer" refers to the formula that makes up the polymer [Chemical formula] (wherein B i is different from a 4-vinylpyridine derivative) is meant to mean the basic constituent elements of

[0017] According to the present invention, the term "irreversibly bonded to the support" means that the polymer cannot be detached from the support under the conditions of use According to the present invention, the term "linear polymer" means a polymer in which all monomer units are linked in one direction to form a chain without branches or crosslinks According to the present invention, the term "crosslinked polymer" means a polymer in which at least one linear polymer is linked by at least one crosslinking bridge, the crosslinking bridge being formed by monomer units derived from a comonomer belonging to at least one of the two linear polymers, and the monomer units derived from the comonomer being covalently bonded to the carbon chain of another linear polymer.

[0018] According to the present invention, the term "carbon chain" means a linear carbon sequence formed during the polymerization of the monomers constituting the polymer by carbon-carbon double bonds. According to the present invention, the term "alkyl group having 1 to 20 carbons" means a linear or branched acyclic saturated carbon chain containing 1 to 20 carbons. Examples of alkyl groups having 1 to 20 carbons include a methyl group, an ethyl group, a propyl group, a butyl group and the like. Within the alkyl group, one or more hydrogens may be substituted by a group selected from a halogen, hydroxy, alkoxy, amino, nitro, cyano, trifluoro, carboxylic acid, carboxylic acid ester, phosphine, thiol and the like. According to the present invention, the term "alkene group having 2 to 20 carbons" means a linear or branched acyclic carbon chain containing 2 to 20 carbon atoms and containing at least one carbon-carbon double bond. Examples of alkene groups having 2 to 20 carbons include an ethenyl group, a propenyl group, a butenyl group and the like. Within the alkene group, one or more hydrogens may be substituted by a group selected from a halogen, hydroxy, alkoxy, amino, nitro, cyano, trifluoro, carboxylic acid, carboxylic acid ester, phosphine, thiol and the like.

[0019] According to the present invention, the term "aryl group having 2 to 20 carbons" means a carbon chain containing at least one saturated ring or partially saturated ring and containing 2 to 20 carbon atoms, in which no heteroatom is present in the ring. Examples of aryl groups having 2 to 20 carbons include a phenyl group, a benzyl group and the like. Within the aryl group, one or more hydrogens may be substituted by a group selected from a halogen, hydroxy, alkoxy, amino, nitro, cyano, trifluoro, carboxylic acid, carboxylic acid ester, phosphine, thiol and the like. According to the present invention, the term "1- to 5-membered heterocyclic ring" means at least one ring containing a saturated or partially saturated ring of 1 to 5 members, containing ring-forming atoms different from carbon, and having a carbon chain containing 2 to 20 carbon atoms. Examples of the heterocyclic ring containing 2 to 20 carbon atoms include pyrrolidinyl, piperidinyl, etc. In the heterocyclic ring, one or more hydrogens may be substituted by a group selected from halogen, hydroxy, alkoxy, amino, nitro, cyano, trifluoro, carboxylic acid, carboxylic acid ester, phosphine, thiol, etc. According to the present invention, the term "thiol of 1 to 20 carbons" refers to SR 2 and means a carbon chain containing 1 to 20 carbon atoms. According to the present invention, the term "phosphine of 1 to 20 carbons" refers to PR 3 and means a carbon chain containing 1 to 20 carbon atoms.

[0020] According to a specific embodiment, the present invention, as described above, comprises or consists of a polymer having a degree of polymerization n of 1 to 10,000, containing n monomer units, and grafted onto a support, specifically covalently grafted, wherein the monomer units are · A monomer unit derived from 4-vinylpyridine in which the carbons at the 2- and 6-positions are substituted by one of the following substituents: hydrogen, an alkyl group of 1 to 20 carbons, an alkene group of 1 to 20 carbons, an aryl group of 1 to 20 carbons, a carboxylic acid of 1 to 20 carbons, an alcohol of 1 to 20 carbons, an ether of 1 to 20 carbons, an ester of 1 to 20 carbons, an amine of 1 to 20 carbons, a 1- to 5-membered heterocyclic ring in which the heteroatom is nitrogen, oxygen, sulfur or phosphorus, an amide of 1 to 20 carbons, a thiol of 1 to 20 carbons, a phosphine of 1 to 20 carbons (wherein the substituents may together form a ring and may contain a sulfur or phosphorus atom), or · A monomer unit derived from a comonomer, provided that when one of the selected substituents represents hydrogen, an alkyl group of 1 to 4 carbons, an aryl group of 1 to 4 carbons or an alkene group of 1 to 4 carbons, the other substituent is different from any of hydrogen, an alkyl group of 1 to 4 carbons, an aryl group of 1 to 4 carbons and an alkene group of 1 to 4 carbons, However, the monomer unit derived from 4-vinylpyridine represents a degree of polymerization n of at least 20%, the polymer may be complexed with a metal, the polymer is linear or crosslinked, the polymer is irreversibly bound to the support.

[0021] According to a particular embodiment, the composition of the invention is, as described above, grafted onto a support and comprises or consists of a polymer having one or more types of monomer units derived from 4-vinylpyridine and one or more types of monomer units derived from comonomers, which polymer may or may not be complexed with one or more metals.

[0022] The composition of the invention has the formula I

Chemical formula

[0023] In this embodiment, the polymer grafted onto the support of formula I can be, for example, as described below: ·A polymer containing at least one type of monomer unit derived from 4-vinylpyridine and at least one type of monomer unit derived from a comonomer · A polymer containing at least two types of monomer units derived from 4-vinylpyridine and not containing monomer units derived from comonomers · A homopolymer containing a single type of monomer unit derived from 4-vinylpyridine, These polymers are either complexed with a metal or not. In this embodiment, the polymer grafted onto the support of formula I can adopt any configurational form of the copolymer, specifically a random polymer, block copolymer, periodic copolymer or random copolymer. These polymers can themselves be linear or crosslinked and may or may not be complexed with a metal. In this embodiment, each monomer unit forming the polymer grafted onto the support of formula I can be positively or negatively charged depending on the presence or absence of the monomer unit and the complexing metal which is itself charged.

[0024] In this embodiment, the support is covalently bonded to the polymer · directly, or · by a single compound T that links between the support and the polymer, or · by a single compound A derived from the polymerization initiator that links between the support and the polymer, or · by a compound T that binds to the compound A acting as a linker between the support and the polymer and derived from the polymerization initiator and the end of the polymer is · the last carbon of the polymer chain (meaning r = 0 in formula I), or · a compound that propagates polymerization, such as a chlorine atom Cl, or · a compound that terminates polymerization, or · a transfer agent, such as benzyl benzodithioate. In this embodiment, the compound T is · a compound of the support, and / or · a compound that modifies the support surface to create surface binding sites and can be.

[0025] In this embodiment, for example, when the support is silica SiO 2 the surface of the support is pretreated with a mixture of H 2 SO4 / H 2 O 2 to enable the formation of SiOH sites on the support surface. In this case, the compound T (here SiOH) is a compound derived from the support. In this embodiment, for example, when the support is polyethylene terephthalate (PET), the support surface is pretreated with polyethyleneimine. This compound cleaves the bonds on the support surface and binds to the support, thereby creating many NH 2 and NH bonding sites on the pretreated support surface. In this case, the compound T consists of a compound that modifies the surface and a compound derived from the support.

[0026] According to the present invention, the term "bonding site" means a site located on the support surface to which a compound, particularly a polymerization initiator or a monomer unit or the polymer of the present invention, binds. According to the present invention, the term "polymerization initiator" means a compound capable of initiating polymerization. After initiation, the monomers constituting the final polymer react with this compound. According to the present invention, the term "compound for propagating polymerization" means a compound capable of reacting with one monomer to increase the degree of polymerization of the formed polymer by 1. According to the present invention, the term "compound for terminating polymerization" means a compound that cannot react with monomers to continue polymerization and is not re-stimulated. According to the present invention, the term "transfer agent" means a compound that alone cannot react with monomers to continue polymerization but can be stimulated by a radical compound in the reaction medium to become a compound capable of propagating polymerization. As a RAFT "transfer agent", for example, a compound of the formula R-S-C(=S)-Z (such as benzyl benzodithioate) can be mentioned.

[0027] According to a specific embodiment, the composition of the present invention is a polymer having one or more types of monomer units derived from 4-vinylpyridine and one or more monomer units derived from a comonomer, and is a non-crosslinked linear polymer grafted on a support and complexed with one or more metals or not, or consists of or comprises such a polymer.

[0028] The composition of the present invention has the formula II

Chemical formula

[0029] According to a specific embodiment, the composition of the present invention is a polymer having one or more types of monomer units derived from 4-vinylpyridine and no monomer units derived from a comonomer, and is a non-crosslinked linear polymer grafted on a support and complexed with one or more metals or not, or consists of or comprises such a polymer.

[0030] The composition of the present invention has the formula III

Chemical formula

[0031] In this embodiment, the absence of the copolymer can increase the ability of the polymer grafted on the support to capture metals. When 100% of the monomer units are monomer units derived from 4-vinylpyridine in which two substituents at the 2-position and 6-position are carboxylic acid groups, the complexing ability with metals is doubled compared to the complexing ability of a polymer containing 50% of monomer units derived from the copolymer. In this embodiment, if it is possible to have a plurality of monomer units derived from different 4-vinylpyridines, it is possible to complex with different metals according to the monomer units, or to complex with the same metal in various ways according to the monomer units. Due to this difference, different catalytic sites can be obtained on the same polymer, and a catalytic reaction that requires a plurality of different catalytic sites with a single catalyst can be carried out.

[0032] According to a specific embodiment, the composition of the present invention is a polymer having a single type of monomer unit derived from 4-vinylpyridine and no monomer unit derived from a comonomer, grafted onto a support, comprising or consisting of a non-crosslinked linear polymer that is complexed or not complexed with one or more metals.

[0033] The composition of the present invention has the formula IV

Chemical formula

[0034] In this embodiment, the polymer grafted onto the support of Formula IV is a homopolymer. In this embodiment, the polymer grafted onto the support can be optimized for a single action. For example, a polymer containing only monomer units derived from 4-vinylpyridine in which two substituents at the 2- and 6-positions are carboxylic acid groups exhibits optimal activity for capturing uranyl ions in an aqueous solution.

[0035] According to a particular embodiment, the composition of the present invention is a polymer having a single type of monomer unit derived from 4-vinylpyridine in which two substituents at the 2- and 6-positions are carboxylic acid groups as described above, having no monomer units derived from comonomers, and being a non-crosslinked linear polymer grafted onto a support and complexed or not complexed with a single metal, or consists of such a polymer.

[0036] The composition of the present invention has the formula V

Chemical formula

[0037] In this embodiment, the polymer grafted onto the support of Formula V is a homopolymer having monomer units derived from a single type of 4-vinylpyridine in which two substituents at the 2-position and 6-position are carboxylic acid groups. In this embodiment, all the component monomer units of the polymer grafted onto the support of Formula V are complexed with the same metal or not complexed at all. In this embodiment, all the component monomer units of the polymer grafted onto the support of Formula V have the same charge. In this embodiment, the component polymer of Formula V has the advantage of being able to be easily solvated in an aqueous medium, having solubility dependent on the pH conditions of the aqueous medium and the ability to complex with a metal that may optionally be present in the solution.

[0038] According to a particular embodiment, the composition of the present invention is a polymer as described above, having monomer units derived from a single type of 4-vinylpyridine in which two substituents at the 2-position and 6-position are carboxylic acid groups and having no monomer units derived from comonomers, comprising or consisting of an uncrosslinked linear polymer grafted onto a support and not complexed with a metal.

[0039] The composition of the present invention has the formula VI

Chemical formula

[0040] In this embodiment, the polymer grafted onto the support of Formula VI contains monomer units derived from a single type of 4-vinylpyridine in which the two substituents at the 2- and 6-positions are carboxylic acid groups, and is a homopolymer that is not complexed with a metal. In this embodiment, the polymer grafted onto the support of Formula VI varies depending on the pH of the solution in which the polymer is found. Thus, the polymer grafted onto the support of Formula VI is one of the following formulas: ·In a very acidic medium: the polymer grafted onto the support of Formula VII ·When the pH is slightly increased: the polymer grafted onto the support of Formula VIII ·When the pH continues to increase: the polymer grafted onto the support of Formula IX ·When the pH continues to increase further: the polymer grafted onto the support of Formula X ·In neutral and basic media: the polymer grafted onto the support of Formula XI. In this embodiment, the ratio n of the polymer grafted to the support of formula VIII 1 / n 2 and the ratio n of the polymer grafted to the support of formula IX 1 / n 2 and n 1 / n 3 as well as the ratio n of the polymer grafted to the support of formula X 2 / n 3 are dependent on the pH of the solution. The variations in the ratios between n 1 , n 2 and n 3 in the polymers of formula VIII, formula IX and formula X affect the overall charge of the polymer, the solvation ability of the polymer and the ability of the polymer to complex with metals.

[0041] According to a specific embodiment, the composition of the present invention is a polymer grafted to a support, having a single type of monomer unit derived from 4-vinylpyridine in which two substituents at the 2-position and 6-position are methyl ester groups and having no monomer unit derived from a comonomer, and comprises or consists of a non-crosslinked linear polymer that is not complexed with a metal.

[0042] The composition of the present invention comprises or consists of a homopolymer grafted to a support of formula XII

Chemical formula

[0043] In this embodiment, the homopolymer grafted to the support of formula XII is a homopolymer having a single type of monomer unit derived from 4-vinylpyridine in which two substituents at the 2-position and 6-position are methyl ester groups. In this embodiment, none of the monomer units forming the polymer grafted to the support of formula XII are complexed with a metal. In this embodiment, the resulting polymer is solvated in an organic solution, such as DMSO and acetonitrile. This property enables the easy polymerization of a monomer derived from 4-vinylpyridine in which two substituents at the 2- and 6-positions are methyl ester groups.

[0044] According to a specific embodiment, the composition of the present invention is a polymer grafted onto a support having a single type of monomer unit derived from 4-vinylpyridine in which two substituents at the 2- and 6-positions are carboxylic acid groups and having no monomer unit derived from a comonomer, and comprises or consists of a non-crosslinked linear polymer complexed with uranium.

[0045] The composition of the present invention has the formula XIII [Chemical formula] (wherein, ·Su, T, A, R 4 , t, a and r are as defined in formula I, ·xU is a number from 0 to 1) of a ceridamic acid homopolymer complexed with uranium and grafted onto a support, specifically formulas VII, XIV, XV, XVI and XVII [Chemical formula] [Chemical formula] (wherein, ·Su, T, A, R 4 , t, a and r are as defined in formula I, ·n 1 , n 2 and n 3 are non-zero integers, ·In formula XIV, n 1 + n 2 = n, ·In formula XV, n 1 + n 2 + n 3 = n, ·In formula XVI, n2 +n 3 =n) comprises a polymer grafted to a support or consists of the homopolymer thereof.

[0046] In this embodiment, the polymer grafted to the support of formula XIII comprises monomer units derived from a single type of 4-vinylpyridine where the two substituents at the 2- and 6-positions are carboxylic acid groups, and each monomer unit is a homopolymer grafted to a support that may or may not form a complex with a uranyl cation. In this embodiment, the polymer grafted to the support of formula XIII varies depending on the pH of the solution in which the polymer is found. Thus, the polymer grafted to the support of formula XIII has one of the following formulas: · In a very acidic medium: the polymer grafted to the support of formula VII · When the pH is slightly increased: the polymer grafted to the support of formula XIV · As the pH continues to increase: the polymer grafted to the support of formula XV · As the pH continues to increase further: the polymer grafted to the support of formula XVI · In neutral and basic media: the polymer grafted to the support of formula XVII.

[0047] In this embodiment, the ratio n 1 / n 2 of the polymer grafted to the support of formula XIV 1 / n 2 and n 1 / n 3 as well as the ratio n 2 / n 3 of the polymer grafted to the support of formula XVI 1 n 2 n 3 and n In this embodiment, for example, in a neutral pH solution containing uranyl ions, the component polymer of formula V solvates to become the component polymer of formula XI. This polymer complexes with uranyl ions to become the precipitated polymer of formula XVII. Next, the component polymer of formula XVII is placed in an aqueous solution of strong acidic pH. This polymer reacts to release uranyl ions while becoming the component polymer of formula VII. The component polymer of formula VII no longer solvates and precipitates.

[0048] According to a specific embodiment, the composition of the present invention comprises or consists of a polymer grafted onto a support having monomer units derived from at least one comonomer, specifically monomer units derived from styrene, acrylic acid or tert-butyl acrylate, as described above. In this embodiment, the polymer contains monomer units derived from at least one comonomer, specifically this comonomer is styrene, acrylic acid or tert-butyl acrylate. In this embodiment, the comonomer acts as a spacer by reducing the steric hindrance around the monomer unit derived from 4-vinylpyridine that enables easier access of the metal to the complexation site, or as an agent that modifies the properties of the polymer, particularly radiation resistance or heat resistance. acts.

[0049] According to a specific embodiment, the composition of the present invention comprises or consists of a copolymer grafted onto a support in which the proportion of monomer units derived from the comonomer is more than 0% and 80% or less, as described above. In this embodiment, the polymer contains monomer units derived from at least one comonomer, but the proportion of monomer units derived from the comonomer can take all values more than 0% and 80% or less, particularly more than 0% and 10% or less, more than 0% and 20% or less, more than 0% and 30% or less, more than 0% and 40% or less, more than 0% and 50% or less, more than 0% and 60% or less, more than 0% and 70% or less, more than 0% and 80% or less.

[0050] According to certain embodiments, the composition of the present invention has, as described above, monomer units derived from a single type of 4-vinylpyridine and monomer units derived from a single type of comonomer, and comprises or consists of a non-crosslinked linear block polymer that is grafted to a support and not complexed with a metal.

[0051] The composition of the present invention is of formula XVIII

Chemical formula

[0052] According to the present invention, the term "block copolymer" means a polymer in which at least one monomer unit is derived from a comonomer and monomer units of the same formula are linked to each other. In this embodiment, the polymer is polymerized in block form where the first block contains only monomer units derived from the copolymer and the second block contains only monomer units derived from 4-vinylpyridine. In this embodiment, the polymer has the characteristics and properties of each block. If the support is not stable in water but the grafted polymer has to be used in an aqueous medium, the hydrophobic block near the support can protect the support from the action of water, while the outer block can be active in the aqueous medium. According to certain embodiments, the composition of the present invention comprises or consists of any of the polymers grafted to the following supports, as described above: ·A non-crosslinked linear block polymer having monomer units derived from a single type of 4-vinylpyridine in which two substituents at the 2- and 6-positions are methyl ester groups and monomer units derived from a single type of comonomer (styrene), and not complexed with a metal, or ·A non-crosslinked linear block polymer having monomer units derived from a single type of 4-vinylpyridine in which two substituents at the 2- and 6-positions are carboxylic acid groups and monomer units derived from a single type of comonomer (styrene), and not complexed with a metal.

[0053] The composition of the present invention is a 2-block copolymer grafted onto a support of formula XIXa and XIXb

Chemical formula

[0054] In this embodiment, the polymer is polymerized in a block form in which the first block contains only monomer units derived from styrene and the second block contains all monomer units derived from 4-vinylpyridine. In this embodiment, the polymer grafted onto the support of formula XIXb is not solvated in an aqueous medium. The block consisting of monomer units derived from styrene is hydrophobic. The block consisting of monomer units derived from 4-vinylpyridine in which two substituents at the 2- and 6-positions are carboxylic acid groups is hydrophilic. Thus, when the support is not stable in water, the polystyrene block limits the contact between the support and water, while the block of monomer units derived from 4-vinylpyridine can be active in an aqueous medium.

[0055] According to certain embodiments, the composition of the present invention is a copolymer grafted to a support having one or more types of monomer units derived from 4-vinylpyridine and one or more comonomer-derived monomer units, which is non-linear and cross-linked to at least one other polymer, with or without complexing with one or more metals, and comprises or consists of such a copolymer.

[0056] The composition of the present invention has the formula XX

Chemical formula

[0057] In this embodiment, the polymer grafted onto the support of formula XX is a crosslinked copolymer grafted onto a support, in which the crosslinked bridge is formed only of monomer units derived from a comonomer. In this embodiment, the polymer grafted onto the support of formula XX may contain monomer units derived from a comonomer that do not form a crosslinked bridge. In this embodiment, the polymer can form a hydrogel. The hydrogel on the support surface can improve the mechanical stability of the polymer assembly and the support.

[0058] According to a particular embodiment, the composition of the present invention is a copolymer having monomer units derived from one or more types of 4-vinylpyridine and monomer units derived from one or more types of comonomers, as described above, which is non-linear and crosslinked to at least one other polymer, and which comprises or consists of a copolymer grafted onto a support and complexed or not complexed with one or more metals.

[0059] The composition of the present invention has the formula XX

Chemical formula

[0060] According to certain embodiments, the composition of the present invention is a copolymer grafted onto a support having a single type of monomer unit derived from 4-vinylpyridine and a single type of comonomer (1,4-divinylbenzene) monomer unit, wherein the two substituents at the 2- and 6-positions are carboxylic acid groups, which is not complexed with a metal, is non-linear, and is cross-linked to at least one other polymer, or consists of said copolymer.

[0061] The composition of the present invention has the formula XXI

Chemical formula

[0062] In this embodiment, the polymer grafted onto the support of formula XXI is a cross-linked copolymer containing a single type of monomer unit derived from 4-vinylpyridine and a single type of comonomer (1,4-divinylbenzene) monomer unit, wherein the two substituents at the 2- and 6-positions are carboxylic acid groups. In this embodiment, the 1,4-divinylbenzene-derived monomer units of the polymer grafted onto the support of formula XXI may or may not form a cross-linking bridge. At least one cross-linking bridge is formed in the polymer grafted onto the support of formula XXI.

[0063] According to certain embodiments, the composition of the present invention comprises or consists of a polymer grafted to a support complexed with a metal, as described above. In this embodiment, the polymer is complexed with at least one metal atom, particularly for use as a chelating agent or catalyst. According to certain embodiments, the composition of the present invention comprises or consists of a polymer grafted to a support complexed with a metal selected from actinides, lanthanides or transition metals, as described above. In this embodiment, the polymer complexes with a particular family of metals.

[0064] According to certain embodiments, the composition of the present invention comprises or consists of a polymer grafted to a support complexed with uranium, as described above. In this embodiment, the polymer grafted to the support complexes only with uranium. This polymer is useful for recovering uranium from seawater or spent nuclear fuel. This polymer also enables the production of uranium-based catalysts that catalyze reactions, such as the decomposition of volatile organic compounds in the gas phase or the oxidation of methane to methanol.

[0065] According to certain embodiments, the composition of the present invention comprises or consists of a polymer grafted to a support solvated in an aqueous solution, particularly seawater, as described above. In this embodiment, the polymer without a support is solvated in an aqueous solution, particularly seawater. This is particularly true for homopolymers having monomer units derived from 4-vinylpyridine where the two substituents at the 2- and 6-positions are carboxylic acid groups. The carboxylic acid groups facilitate the solvation of the polymer under neutral or basic pH conditions, such as in seawater.

[0066] According to certain embodiments, the composition of the present invention comprises or consists of a polymer grafted to a support, complexed with a metal, which is solvated or non-solvated in an aqueous solution as described above. In this embodiment, when the polymer is complexed with a metal, it is solvated or non-solvated depending on the state in which the polymer is found.

[0067] According to certain embodiments, the composition of the present invention comprises or consists of a polymer grafted to a support, which is solvated when not complexed with a metal and non-solvated when complexed with a metal, particularly uranium, as described above. In this embodiment, the polymer is solvated in an aqueous solution and when the polymer complexes with a metal, the polymer precipitates with the metal. This is particularly true for the polymer grafted to the support of formula VI, which polymer is solvated in water at neutral pH and forms formula XIII and precipitates at neutral pH when complexed with uranium.

[0068] According to certain embodiments, the composition of the present invention comprises or consists of a polymer grafted to a support, which is solvated particularly in organic solvents such as acetonitrile and dimethyl sulfoxide (DMSO) as described above. In this embodiment, the polymer is solvated in an organic solvent such as acetonitrile, which is particularly true for a homopolymer containing monomer units derived from 4-vinylpyridine in which the two substituents at the 2- and 6-positions are methyl ester groups.

[0069] According to certain embodiments, the composition of the present invention comprises or consists of a polymer grafted to a support, wherein the support Su of formula I is selected from polyvinyl chloride-polyvinylidene chloride (PVC-co-PVDC) copolymer, polyvinyl chloride (PVC), PET or SiO 2 and comprises or consists of the polymer grafted to the support. In this embodiment, the polymer of the present invention can be grafted onto various supports based on polymers such as PVC or substrates such as silica.

[0070] According to a particular embodiment, the composition of the present invention, as described above, comprises or consists of a polymer grafted onto a support, wherein the compound T of formula I is SiOH or a compound of formula XXII

Chemical formula

[0071] In this embodiment, the linkage between the polymer and the support comprises or consists of a compound T derived from the support or a compound that modifies the support surface, and the compound serves as a linker between the support and an optional component polymerization initiator or the polymer. In this embodiment, the linker between the support and the polymer consists of only the compound T or consists of the compound T linked to the compound A.

[0072] According to a particular embodiment, the composition of the present invention, as described above, comprises or consists of a polymer grafted onto a support, wherein A of formula I is 4-(chloromethyl)benzoyl chloride, benzyl chloride, AIBN, methyl-2-bromo-2-methylpropanoate or a compound of formula XXIII

Chemical formula

[0073] In this embodiment, a portion of the polymerization initiator binds the polymer to the compound T or binds directly to the support. This does not cover all cases and includes polymerization initiators that can be used in radical polymerization.

[0074] According to a particular embodiment, the composition of the present invention, as described above, the compound R of formula I 4 is a chlorine atom or a compound of formula XXIV [Chemical formula] Comprising or consisting of a polymer grafted onto a support, selected from the compounds of

[0075] In this embodiment, the ends of the polymer cannot be the last carbon in the polymer chain. The above list is not complete and includes chain transfer agents that can be used in so-called controlled radical polymerization.

[0076] According to certain embodiments, the compositions of the invention are, as described above, of formula XXV, formula XXVI, formula XXVII, formula XXVIII, formula XXIX or formula XXX [Chemical formula] [Chemical formula] [Chemical formula] Comprising or consisting of a polymer grafted onto a support of

[0077] In this embodiment, the polymers of formulas XXV - XXXIX are · Homopolymers consisting of monomer units substituted with two carboxylic acid groups for polymers grafted onto supports of formulas XXVI, XXVIII and XXX, derived from 4-vinylpyridine; · Homopolymers consisting of monomer units substituted with two methyl ester groups for polymers grafted onto supports of formulas XXV, XXVII and XXIX, derived from 4-vinylpyridine. The polymers grafted onto the supports of formulas XXV and XXVI are supported on a silica support. The polymers grafted onto the supports of formulas XXVII and XXVIII are supported on a PET fiber. The polymers grafted onto the supports of formulas XXIX and XXX are supported on a PVC-co-PDVC fiber.

[0078] The present invention relates to a method for producing a polymer grafted onto a support, in particular covalently grafted onto a support, which is carried out by a grafting method (the “grafted to” or “grafted from” technique). According to the present invention, the term “grafting onto” means a polymerization method in which the polymer at the end of the polymerization step is not grafted onto the support and is in a free state. The step of grafting onto the support is after the polymerization. According to the present invention, the term “grafting from” means a polymerization method in which the stimulus (initiation) of the polymerization is made on a compound covalently bonded to the support or directly on the support. Then, the monomer reacts with the support to form a polymer chain. The polymer grafted onto the support grows from the support according to this technique.

[0079] The present invention further includes the following production steps: a. A step of pretreating the support by contacting the support with a pretreatment agent and / or physical pretreatment, which is an optional additional step for obtaining a support that may be pretreated. b. A preliminary grafting step on the support that may be pretreated by contacting the support that may be pretreated with a polymerization initiator, which is an optional additional step for obtaining a support that may be pretreated and optionally preliminarily grafted. c. Initiated by stimulation of the support that is optionally pretreated and optionally preliminarily grafted, and the support that is optionally pretreated and optionally preliminarily grafted is · At least one monomer derived from 4-vinylpyridine in which the carbon atoms at positions 2 and 6 are substituted by one of the following groups: hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkene group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a carboxylic acid having 1 to 20 carbon atoms, an alcohol having 1 to 20 carbon atoms, an ether having 1 to 20 carbon atoms, an ester having 1 to 20 carbon atoms, an amine having 1 to 20 carbon atoms, a 1- to 5-membered heterocyclic ring in which the heteroatom is nitrogen, oxygen, sulfur or phosphorus, an amide having 1 to 20 carbon atoms, a thiol having 1 to 20 carbon atoms, a phosphine having 1 to 20 carbon atoms (wherein the substituents may together form a ring and may contain a sulfur or phosphorus atom), and · Optionally, contacting with at least one comonomer, while crosslinking or without crosslinking, to obtain a polymer grafted onto a support by a radical polymerization step, d. Optionally, an additional modification step of contacting the polymer grafted onto the support with an agent that modifies at least one of the substituents to obtain a polymer grafted onto the support, which may be modified e. Optionally, an additional complexation step of contacting the polymer grafted onto the support, which may be modified, with a metal cation to obtain a polymer grafted onto the support, which may be modified and may be complexed Relates to a method for producing a polymer grafted onto the above support, in particular a polymer covalently grafted onto a support, comprising:

[0080] The method for producing a polymer grafted onto a support according to the present invention is a "grafting from" method. The polymer synthesis method of the present invention has the advantage that the polymerization step can be easily controlled. The presence of the modification step allows monomers having groups different from the final groups at the 2- and 6-positions to be polymerized. For example, a monomer derived from 4-vinylpyridine having two carboxylic acid groups at the 2- and 6-positions is not solvated in an organic solution. Therefore, it is very difficult to polymerize this monomer in an organic solution. On the other hand, a monomer derived from 4-vinylpyridine having two methyl ester groups at the 2- and 6-positions is solvated in an organic medium. As a result, polymerization of a monomer derived from 4-vinylpyridine having two methyl ester groups at the 2- and 6-positions is possible, and the ester functional group can be hydrolyzed to an acid functional group by a subsequent modification step. The polymer thus obtained having an acid functional group is not solvated in an organic medium.

[0081] The polymer synthesis method of the present invention has the advantage that the polymerization step can be easily controlled. The modification step can protect two groups of the monomer derived from 4-vinylpyridine. In fact, when the groups at the 2- and 6-positions are very reactive (COOH, NH2 etc.), these groups are likely to react during the polymerization step. This can lead to uncontrolled branching formation and / or loss of specific groups. By using a post-polymerization modification step, polymerization can be initiated using a protecting group that will be removed in a later modification step. The use of a controlled radical polymerization method such as RAFT or ATRP polymerization improves the control over the polymerization. The polymer synthesis method of the present invention further includes a step of producing a monomer derived from 4-vinylpyridine. According to the present invention, the term "radical polymerization" means a polymerization technique capable of polymerizing a monomer, and the propagation of the polymerization is ensured by the presence of radicals. Examples of radical polymerization include so-called classical radical polymerization, reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP). According to the present invention, the term "stimulating a support that has been optionally pretreated and optionally pre-grafted" means a step capable of initiating polymerization. For example, in the case of radical polymerization, this step can generate radicals on a support that may have been pretreated and optionally pre-grafted by physical or chemical means, and monomer units react with the support.

[0082] According to a particular embodiment, formula I

Chemical formula

Chemical formula

Chemical formula

[0083] In this embodiment, the method for synthesizing a polymer grafted onto a support of formula I is · If the surface of the support has no binding sites, a step of pretreating the support, or · If the surface of the support has binding sites but these binding sites cannot be stimulated to initiate radical polymerization, a step of pre-grafting the support, or · If the surface of the support has binding sites and these binding sites can be stimulated to initiate radical polymerization, a radical polymerization step starting from. In this embodiment, the synthesis method of the polymer grafted onto the support of formula I is a polymerization following the "grafting from" technique.

[0084] The synthesis method of the polymer grafted onto the support of formula I is as follows: · If the support is pretreated and the pretreated support cannot be stimulated to initiate radical polymerization, a step of pre-grafting the support (in this case, the synthesis is continued by a radical polymerization step using the pretreated and pre-grafted support as a polymerization initiator), or · If the support is pretreated and the pretreated support can be stimulated to initiate radical polymerization, a radical polymerization step using the pretreated support as a polymerization initiator, or · If the support is not pretreated but pre-grafted, a radical polymerization step using the pre-grafted support as a polymerization initiator is continued. After polymerizing to obtain a polymer grafted onto the support of formula XXXIV, if the substituents of the monomer units derived from 4-vinylpyridine are different in formula I and formula XXXIV, a modification step is performed to react the substituents of formula XXXIV different from those of formula I to obtain a polymer grafted onto the support of formula XXXV. If the polymer grafted onto the support of formula I is complexed with a metal, in order to obtain the polymer grafted onto the support of formula I, a step of complexing the polymer grafted onto the support of formula XXXV is required. In this embodiment, by the polymerization step of this synthesis method, comonomers and different types of monomers derived from 4-vinylpyridine can also be polymerized. During the polymerization step, a crosslinking bridge can be formed.

[0085] According to a specific embodiment, R i,1 and R i,2 The above manufacturing method for the polymer of the present invention grafted onto the support of formula II, wherein the definitions are as described in formula II, includes the following steps: a. A step of pretreating the support by contacting the support with a pretreatment agent and / or the action of physical pretreatment on the support to obtain a pretreated support of formula XXXI. b. A step of pre-grafting a pretreated support of formula XXXI by contacting the pretreated support of formula XXXI with a polymerization initiator, and an optional additional step for obtaining a pretreated and optionally pre-grafted support of formula XXXII c. Initiated by stimulation of a support of formula XXXII which is optionally pretreated and optionally pre-grafted, contacting the support of formula XXXII which is optionally pretreated and optionally pre-grafted with a 4-vinylpyridine derivative of formula XXXIII and, optionally, at least one comonomer, with or without crosslinking, to obtain a polymer grafted onto a support of formula XXXIV

Chemical formula

Chemical formula

[0086] In this embodiment, the method for synthesizing the polymer grafted onto the support of formula II is a polymerization according to the "grafting from" technique. In this embodiment, the method for synthesizing the polymer grafted onto the support of formula II starts from the radical polymerization of monomers that form the polymer grafted onto the support of formula XXXVI. These monomers consist of a 4-vinylpyridine-derived monomer that may not have the same substituents as the 4-vinylpyridine-derived monomer present in formula II and a comonomer that is an optional additional component. The comonomer is selected so as not to form a crosslinking bridge or is absent. After polymerizing to obtain the polymer grafted onto the support of formula XXXVI, if the substituents of the 4-vinylpyridine-derived monomer units are different in formula II and formula XXXVI, a modification step is performed to react the substituents of formula XXXVI different from those of formula II to obtain the polymer grafted onto the support of formula XXXVII. When the polymer grafted onto the support of formula II is complexed with a metal, a step of complexing the polymer grafted onto the support of formula XXXVII is carried out to obtain the polymer grafted onto the support of formula II.

[0087] According to a specific embodiment, t = 1, and R i,1 and R i,2 The above manufacturing method for the polymer grafted onto the support of formula II of the present invention, where the definitions of are as described in formula II, includes the following steps: a. Pretreating the support by contacting the support with a pretreatment agent and / or the action of physical pretreatment to obtain formula XXXVIII

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0088] In this embodiment, the method for synthesizing a polymer grafted onto a support of Formula II where t = 1 is a polymerization according to the "grafting from" technique. In this embodiment, the method for synthesizing a polymer grafted onto a support of Formula II where t = 1 starts with a step of pretreating the support to obtain a pretreated polymer. The synthesis method of the polymer grafted onto a support of Formula II where t = 1 is · If the surface binding sites of the pretreated support cannot be stimulated to initiate radical polymerization, a pre-grafting step of obtaining a pretreated and pre-grafted support, followed by a radical polymerization step using the pretreated and pre-grafted support as an initiator, or · If the surface binding sites of the pretreated support can be stimulated to initiate radical polymerization, a polymerization step using the pretreated support as a polymerization initiator and is continued thereby. After polymerizing to obtain a polymer grafted onto a support of Formula XL, if the substituents of the 4-vinylpyridine-derived monomer units are different in Formulas II and XL, a modification step is performed to react substituents of Formula XL different from those of Formula II to obtain a polymer grafted onto a support of Formula XLI. If the polymer grafted onto a support of Formula II is complexed with a metal, a complexing step of the polymer grafted onto a support of Formula XLI is performed to obtain a polymer grafted onto a support of Formula II where t = 1.

[0089] According to a particular embodiment, R i,1 and R i,2The definition of is as described in Formula II, and the method for producing the polymer of the present invention grafted onto the support of Formula II with t = 1 and a = 1 includes the following steps: a. Pretreating the support by contacting the support with a pretreatment agent and / or by the action of physical pretreatment on the support to obtain a pretreated support of Formula XXXVIII

Chemical formula

Chemical formula

Chemical formula

[0090] In this embodiment, the method of synthesizing a polymer grafted onto a support of formula II where t = 1 and a = 1 is a polymerization following the "grafting from" technique In this embodiment, the synthesis method of the polymer grafted onto a support of formula II where t = 1 and a = 1 includes the following steps · Step of pretreating the support to obtain a pretreated polymer · Step of pre-grafting to obtain a pretreated and pre-grafted support · Radical polymerization step using the pretreated and pre-grafted support as an initiator After polymerizing to obtain a polymer grafted onto a support of formula XLIII, if the substituents of the monomer units derived from 4-vinylpyridine are different in formulas II and XLIII, a modification step is performed to react the substituents of formula XLIII different from those of formula II to obtain a polymer grafted onto a support of formula XLIV If the polymer grafted onto the support of formula II is complexed with a metal, a step of complexing the polymer grafted onto the support of formula XLIV is performed to obtain a polymer grafted onto a support of formula II where t = 1 and a = 3

[0091] According to a particular embodiment, t = 0 and a = 0, and Ri,1 and R i,2 The above manufacturing method for a polymer grafted onto a support of the present invention of Formula II, where the definitions of and R are as described in Formula II, does not include a pretreatment step or a stimulation step, and includes the following steps: a. Starting with the stimulation of the support, and then contacting the support with a 4-vinylpyridine derivative of Formula XXXIII and optionally at least one comonomer, with or without crosslinking, to obtain a polymer grafted onto a support of Formula XLV

Chemical formula

Chemical formula

[0092] In this embodiment, the method for synthesizing a polymer grafted onto a support of Formula II where t = 0 and a = 0 is a polymerization following the "grafting from" technique. In this embodiment, the method for synthesizing a polymer grafted onto a support of Formula II where t = 0 and a = 0 does not include a pretreatment step or a pre-grafting step. The surface of the support has binding sites capable of initiating radical polymerization upon stimulation. This method is carried out by radical polymerization using the support as a polymerization initiator. After polymerizing to obtain a polymer grafted onto a support of Formula XLV, if the substituents of the 4-vinylpyridine-derived monomer units are different in Formulas II and XLV, a modification step is performed to react the substituents of Formula XLV different from those of Formula II to obtain a polymer grafted onto a support of Formula XLVI. If the polymer grafted onto a support of Formula II is complexed with a metal, a step of complexing the polymer grafted onto a support of Formula XLVI is carried out to obtain a polymer grafted onto a support of Formula II where t = 0 and a = 0.

[0093] According to a specific embodiment, t = 1 and a = 1, and the above manufacturing method for a polymer grafted onto a support of the present invention of Formula III where the definitions of R i,1 and R i,2 are as described in Formula III includes the following steps: a. A step of pretreating the support by contacting the support with a pretreatment agent and / or the action of physical pretreatment on the support to obtain a pretreated support of Formula XXXVIII b. A step of pre-grafting the pretreated support of Formula XXXVIII by contacting the pretreated support of Formula XXXVIII with a polymerization initiator to obtain a pretreated and pre-grafted support of Formula XLII c. Starting from the stimulation of the pretreated and pre-grafted support of Formula XLII, contacting the pretreated and pre-grafted support with a 4-vinylpyridine derivative of Formula XXXIII to obtain Formula XLVII

Chemical formula

Chemical formula

[0094] In this embodiment, the method for synthesizing a polymer grafted onto a support of Formula III where t = 1 and a = 1 is a polymerization following the "grafting from" technique. In this embodiment, the synthesis method of the polymer grafted onto a support of Formula III where t = 1 and a = 1 includes the following steps: · A step of pretreating the support to obtain a pretreated polymer · A step of pre-grafting to obtain a pretreated and pre-grafted support · A radical polymerization step using the pretreated and pre-grafted support as an initiator. After obtaining a polymer grafted to a support of formula XLVII by coincidence, when the substituents of the monomer units derived from 4-vinylpyridine are different in formula III and formula XLVII, a modification step is performed to react the substituents of formula XLVII different from those of formula III to obtain a polymer grafted to a support of formula XLVIII. When the polymer grafted to the support of formula III is complexed with a metal, a step of complexing the polymer grafted to the support of formula XLVIII is carried out to obtain a polymer grafted to a support of formula III where t = 1 and a = 1.

[0095] According to a particular embodiment, t = 1 and a = 1 and R 1 and R 2 The above manufacturing method for a polymer grafted to a support of the present invention of formula IV, where the definitions of are as described in formula IV, includes the following steps: a. A step of pretreating the support by contact of the support with a pretreatment agent and / or the action of physical pretreatment on the support to obtain a pretreated support of formula XXXVIII b. A step of pre-grafting the pretreated support of formula XXXVIII by contact of the pretreated support of formula XXXVIII with a polymerization initiator to obtain a pretreated and pre-grafted support of formula XLII c. Starting from the stimulation of the pretreated and pre-grafted support of formula XLII, the pretreated and pre-grafted support is converted to formula XLIX

Chemical formula

[0096] In this embodiment, the method for synthesizing a polymer grafted onto a support of formula IV where t = 1 and a = 1 is a polymerization following the "grafting from" technique. In this embodiment, the method for synthesizing a polymer grafted onto a support of Formula IV where t = 1 and a = 1 includes the following steps: · A step of pretreating the support to obtain a pretreated polymer · A step of pre-grafting to obtain a pretreated and pre-grafted support · A radical polymerization step using the pretreated and pre-grafted support as an initiator After polymerizing to obtain a polymer grafted onto a support of Formula L, if the substituents of the 4-vinylpyridine-derived monomer units are different in Formulas IV and L, a modification step is performed to react a substituent of Formula L different from that of Formula IV to obtain a polymer grafted onto a support of Formula LI If the polymer grafted onto a support of Formula IV is complexed with a metal, a step of complexing the polymer grafted onto a support of Formula LI is performed to obtain a polymer grafted onto a support of Formula IV where t = 1 and a = 1

[0097] According to a specific embodiment, for a polymer grafted onto a support of the present invention of Formula XX where the definitions of R j,w,1 、R j,w,2 、R i,1 and R i,2 are as described in Formula XX, the above manufacturing method includes the following steps: a. Pretreating the support by contacting the support with a pretreatment agent to obtain a pretreated support of Formula LII

Chemical formula

[0098] In this embodiment, the method of synthesizing the polymer grafted onto the support of formula XX is a polymerization following the "grafting from" technique. In this embodiment, the synthesis method of the polymer grafted onto the support of formula XX starts with the following steps: · If the surface of the support has no binding sites, a step of pretreating the support, or · When the surface of the support has binding sites but these binding sites cannot be stimulated to initiate radical polymerization, the step of pre-grafting the support, or · When the surface of the support has binding sites and these binding sites can be stimulated to initiate radical polymerization, the radical polymerization step.

[0099] The method for synthesizing the polymer grafted onto the support of formula XX is continued by the following steps: · When the support has been pretreated and the pretreated support cannot be stimulated to initiate radical polymerization, the step of pre-grafting the support (in this case, the synthesis is continued by a radical polymerization step using the pretreated and pre-grafted support as a polymerization initiator), or · When the support has been pretreated and the pretreated support can be stimulated to initiate radical polymerization, the radical polymerization step using the pretreated support as a polymerization initiator, or · When the support has not been pretreated and is pre-grafted, the radical polymerization step using the pre-grafted support as a polymerization initiator. The polymerization step involves contacting the support with a comonomer capable of forming a crosslinking bridge, a comonomer incapable of forming a crosslinking bridge, and a monomer derived from 4-vinylpyridine to polymerize all the crosslinked polymers simultaneously. After polymerizing to obtain the polymer grafted onto the support of formula LV, if the substituents of the monomer units derived from 4-vinylpyridine are different in formulas XX and LV, a modification step is performed to react the substituents of formula LV different from those of formula XX to obtain the polymer grafted onto the support of formula LVL. When the polymer grafted onto the support of formula XX is complexed with a metal, in order to obtain the polymer grafted onto the support of formula XX, a step of complexing the polymer grafted onto the support of formula LVI is required.

[0100] The present invention further relates to a method for producing a polymer grafted onto a support, specifically a polymer covalently grafted onto a support, the method comprising the following production steps: a. A step of pretreating the support by contacting the support with a pretreatment agent and / or the action of physical pretreatment on the support, which is an optional additional step of obtaining a pretreated support if applicable, b. · contacting a stimulated polymerization initiator with · a monomer derived from at least one 4-vinylpyridine in which the carbon atoms at positions 2 and 6 are substituted by one of the following groups: hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkene group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a carboxylic acid having 1 to 20 carbon atoms, an alcohol having 1 to 20 carbon atoms, an ether having 1 to 20 carbon atoms, an ester having 1 to 20 carbon atoms, an amine having 1 to 20 carbon atoms, a 1- to 5-membered heterocycle in which the heteroatom is nitrogen, oxygen, sulfur or phosphorus, an amide having 1 to 20 carbon atoms, a thiol having 1 to 20 carbon atoms, a phosphine having 1 to 20 carbon atoms (wherein the substituents may together form a ring and may contain a sulfur or phosphorus atom), and · optionally, at least one comonomer and contacting them to obtain a free polymer by radical polymerization, c. Optionally, by contacting the optionally pretreated support with the free polymer, the optionally pretreated support is pre-grafted to obtain a polymer grafted onto the support, d. An optional additional step of obtaining a polymer grafted onto the support and optionally modified by contacting the polymer grafted onto the support with at least one agent for modifying the substituents Z i,1 and Z i,2 e. An optional additional complexation step of obtaining a polymer grafted onto the support, optionally modified and optionally complexed by contacting the polymer grafted onto the support and optionally modified with a metal cation. The steps of the method can be in any order, provided that ​- Step a is before step c, - Step b is before step c, - Step b is before step d, - Step d is before step e, Specifically, the order is as follows: abcde, abdce, abdec, bacde, badce, badec, bdace, bdaec, deac.

[0101] The method for synthesizing the polymer grafted onto the support of the present invention can be a "grafting onto" method. The polymer synthesis method of the present invention has the advantage of being flexible. The steps of this method can be in a different order. The constraints to be respected are as follows: · Any optional pretreatment step is before the grafting step, · The polymerization step is before the grafting step, · The polymerization step is before the modification step, · The modification step is before the complexation step. The desired step order is as follows: · Pretreatment, polymerization, grafting, modification, complexation · Pretreatment, polymerization, modification, grafting, complexation · Pretreatment, polymerization, modification, complexation, grafting · Polymerization, pretreatment, grafting, modification, complexation · Polymerization, pretreatment, modification, grafting, complexation · Polymerization, pretreatment, modification, complexation, grafting · Polymerization, modification, pretreatment, grafting, complexation · Polymerization, modification, pretreatment, complexation, grafting · Polymerization, modification, complexation, pretreatment, grafting. The polymer synthesis method of the present invention may include an additional step of producing a monomer derived from 4-vinylpyridine.

[0102] According to the present invention, the term "stimulated polymerization initiator" means a polymerization initiator that can bind to a monomer through a stimulation phase to form the first monomer unit. According to a particular embodiment, R 1 and R 2 The above production method for a polymer grafted to a support of the present invention of formula II, wherein the definitions are as described in formula II, includes the following steps: a. Contacting a stimulated polymerization initiator with a 4-vinylpyridine derivative of formula XXXIII

Chemical formula

Chemical formula

[0103] In this embodiment, the method for synthesizing a polymer grafted to a support of formula II includes the following steps: polymerization, modification, complexation, pretreatment, grafting. In this embodiment, the synthesis method of the polymer grafted to a support of formula II is a polymerization according to the "grafting to" technique.

[0104] According to a particular embodiment, the above manufacturing method for a polymer grafted to a support of formula II, wherein the definitions of R i,1 and R i,2 are as described in formula II, includes the following steps: a. Contacting the activated polymerization initiator with a 4-vinylpyridine derivative of formula XXXIII and optionally at least one comonomer to obtain a free polymer of formula LVII

Chemical formula

Chemical formula

Chemical formula

[0105] In this embodiment, the method for synthesizing the polymer grafted onto the support of formula II is in the form of polymerization, modification, complexation, pretreatment, and grafting. In this embodiment, the method for synthesizing the polymer grafted onto the support of formula II is a polymerization according to the "grafting onto" technique.

[0106] According to a specific embodiment, the polymerization step of the above production method for the polymer grafted onto the support of the present invention is of formula XLIX [Chemical formula] (wherein, ·Z 1 and Z 2 are the following group: hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkene group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a carboxylic acid having 1 to 20 carbon atoms, an alcohol having 1 to 20 carbon atoms, an ether having 1 to 20 carbon atoms, an ester having 1 to 20 carbon atoms, an amine having 1 to 20 carbon atoms, a 1- to 5-membered heterocyclic ring in which the heteroatom is nitrogen, oxygen, sulfur, or phosphorus, an amide having 1 to 20 carbon atoms, a thiol having 1 to 20 carbon atoms, a phosphine having 1 to 20 carbon atoms, a substituent selected therefrom (wherein the substituents may together form a ring and may contain a sulfur or phosphorus atom)) of 4-vinylpyridine derivative with a compound of formula LX [Chemical formula] (wherein ·Su, A, T, B, R 4 , and the definitions of r, a, t and c are as described in formula XVIII) Contact with a polymer grafted onto a support of to obtain a polymer of formula LXI

Chemical formula

[0107] In this embodiment, the polymerization step of the method for synthesizing the polymer grafted onto the support of formula XVIII is a block polymerization initiated by the stimulation of the polymer grafted onto the support of formula LX. By this stimulation, the radical polymerization step of the monomer derived from 4-vinylpyridine can be initiated. By this polymerization, a block following the first block pre-existing in the polymerization initiator used can be formed. In this embodiment, the polymerization step of the method for synthesizing the polymer grafted onto the support of formula XVIII is a "grafting from" technique.

[0108] According to a specific embodiment, the above method for producing the polymer of the present invention includes the following steps: a. Pretreating the support by contacting the support with a pretreatment agent and / or the action of physical pretreatment on the support to obtain a pretreated support of formula XXXI, b. Pre-grafting the pretreated support of formula XXXI by contacting the pretreated support of formula XXXI with a polymerization initiator to obtain a pretreated and pre-grafted support of formula XXXII, c. The pretreated and pre-grafted support of formula XXXII and formula LXII

Chemical formula

[0109] In this embodiment, the method for synthesizing a polymer grafted onto a support of formula XVIII starts with the polymerization of a comonomer that enables the synthesis of a polymer grafted onto a support of formula LX. Then, the polymer grafted onto this support is used as a polymerization initiator.

[0110] According to a particular embodiment, the polymerization step of the above manufacturing method for a polymer grafted onto a support of the present invention comprises contacting a stimulated polymerization initiator with a 4-vinylpyridine derivative of formula XXXIII to obtain a free polymer of formula LXIII

Chemical formula

[0111] In this embodiment, by the polymerization step of the method for synthesizing a polymer grafted onto a support of formula III, only the monomer derived from 4-vinylpyridine can be polymerized to obtain a free polymer containing only monomer units derived from 4-vinylpyridine. In this embodiment, only the polymerization step of the method for synthesizing a polymer grafted onto a support of formula III can be incorporated into the "grafting onto" technique.

[0112] According to a specific embodiment, the polymerization step of the above manufacturing method for the polymer grafted onto the support of the present invention involves contacting a stimulated polymerization initiator with a 4-vinylpyridine derivative of formula XLIX to obtain a free polymer of formula LXIV [Chemical formula] (wherein ·A", Z 1 , Z 2 , R 4 , r, a and i are defined as described in formula IV) and starting from obtaining the free polymer.

[0113] In this embodiment, by the polymerization step of the method for synthesizing the polymer grafted onto the support of formula IV, a single type of monomer unit derived from 4-vinylpyridine can be polymerized to obtain a free homopolymer containing only monomer units derived from 4-vinylpyridine. In this embodiment, only the polymerization step of the method for synthesizing the polymer grafted onto the support of formula IV can be incorporated into the "grafting onto" technique.

[0114] According to a specific embodiment, for the polymer grafted onto the support of the present invention where the polymer is of formula XXVIII and the support is made of PET, the above manufacturing method includes the following steps: a. Pretreating the PET support by contacting it with polyethyleneimine to obtain a pretreated support of formula LXV [Chemical formula] (wherein T' represents a compound of formula LXVI [Chemical formula] ), and b. Pre-grafting the pretreated support of formula LXV by contacting it with 4-(chloromethyl)benzoyl chloride to obtain a pretreated support of formula LXVII [Chemical formula] (wherein T represents a compound of formula XXII, and X' represents a compound of formula LXVIII [Chemical formula] )( Step of obtaining a pretreated and pre-grafted support of c. Reacting the pretreated and pre-grafted support of formula LXVII with a 4-vinylpyridine derivative of formula LXIX [Chemical formula] and CuCl 2 , TPMA and metallic copper to obtain a polymer grafted onto a support of formula XXVII where X represents a compound of formula LXX [Chemical formula] and R 4 represents a chlorine atom, the radical polymerization step of the 4-vinylpyridine derivative onto the support to obtain a polymer grafted onto a support of formula XXVII d. Step of modifying the polymer grafted onto a support of formula XXVII with a base to obtain a polymer grafted onto a support of formula XXVIII.

[0115] In this embodiment, the method for synthesizing a polymer grafted onto a support of formula XXVIII is a polymerization according to the "grafting from" technique. In this embodiment, the synthesis method of the polymer grafted onto a support of formula XXVIII includes the following steps: · Step of pretreating the support to obtain a pretreated support of formula LXV · Pre-grafting step of obtaining a pretreated and pre-grafted support of formula LXVII · Radical polymerization step of using the pretreated and pre-grafted support as an initiator to obtain a polymer grafted onto a support of formula XXVII ·Modifying the support of formula XXVII with a grafted polymer to obtain a polymer grafted on the support of formula XXVIII. In this embodiment, the support on which the polymer is grafted is made of PET.

[0116] According to a specific embodiment, the above manufacturing method for a polymer grafted on a support of the present invention, wherein the polymer is of formula XXXV and the support is silica, includes the following steps: a. Pretreating the support by contacting the silica support with an acid to obtain a pretreated support of formula LXXI

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0117] In this embodiment, the method for synthesizing the polymer grafted to the support of Formula XXVI is a polymerization using the "grafting from" technique. In this embodiment, the method for synthesizing the polymer grafted to the support of Formula XXVI includes the following steps: · Pretreating the support to obtain a pretreated support of Formula LXXI · Pre-grafting to obtain a pretreated and pre-grafted support of Formula LXVII · Using the pretreated and pre-grafted support as an initiator to perform a radical polymerization step to obtain a polymer grafted to the support of Formula XXV · Modifying using the polymer grafted to the support of Formula XXV to obtain a polymer grafted to the support of Formula XXVI. In this embodiment, the support grafted with the polymer is SiO 2 is.

[0118] According to a specific embodiment, when the polymer is of Formula XXX and the support is the support of the present invention containing PVC and PVDC, the above manufacturing method for the polymer grafted to the support includes the following steps: a. Reacting the support with a 4-vinylpyridine derivative of Formula LXIX and CuCl 2 , TPMA and metallic copper to obtain a polymer grafted to the support of Formula XXIX where R 4 represents a chlorine atom, the polymerization step of the 4-vinylpyridine derivative onto the support b. Modifying the polymer of Formula XXIX with a base to obtain a polymer grafted to the support of Formula XXX. In this embodiment, the method for synthesizing the polymer grafted to the support of Formula XXX is a polymerization according to the "grafting from" technique. In this embodiment, the synthesis method of the polymer grafted onto the support of Formula XXVI includes the following steps: · A radical polymerization step of obtaining a polymer grafted onto the support of Formula XXIX by directly using the support as an initiator · A step of modifying using the polymer grafted onto the support of Formula XXV to obtain a polymer grafted onto the support of Formula XXX.

[0119] In this embodiment, the support onto which the polymer is grafted is PVC-co-PDVC.

[0120] According to a specific embodiment, the radical polymerization step of the above manufacturing method is NMP, RAFT, ATRP type polymerization or conventional radical polymerization.

[0121] According to a specific embodiment, the manufacturing method of the polymer of the present invention of Formula XXX includes the following steps: a. Contacting the compound of Formula LXXV

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0122] The present invention further relates to the use of the composition of the present invention selected from the group comprising the capture and recovery of metals, homogeneous or heterogeneous catalysts, labeling of organic and / or inorganic surfaces, and fluorescent labeling of biomolecules. According to a particular embodiment, the composition of the present invention can be used as an adsorbent for metals in seawater, specifically as an adsorbent for actinides and lanthanides, more specifically as an adsorbent for uranium, and even more specifically as a selective adsorbent for uranium over vanadium. According to a particular embodiment, the composition of the present invention can be used as a treatment agent for metal-contaminated effluents, specifically radioactive effluents, particularly nuclear waste from nuclear power plants.

Examples

[0123] Examples Example 1: Synthesis of monomer dimethyl 4-vinylpyridine-2,6-dicarboxylate a. Synthesis of 4-hydroxypyridine-2,6-carboxylic acid

Chemical formula

[0124] b. Synthesis of dimethyl 4-chloropyridine-2,6-dicarboxylate

Chemical formula

[0125] c. Synthesis of dimethyl 4 - iodopyridine - 2,6 - dicarboxylate

Chem.

[0126] d. Synthesis of dimethyl 4 - vinylpyridine - 2,6 - dicarboxylate

Chem.

[0127] Example 2: Preparation of the support a. Preparation of a pre - poly(ethylene terephthalate) (PET) support

Chem.

[0128] b. Preparation of pre-grafted silica support

Chemical formula

Chemical formula

[0129] Example 3: Synthesis of poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted onto a PET support by the "grafting from" technique

Chemical formula

[0130] Example 4: Preparation of poly(4-vinylpyridine-2,6-dicarboxylic acid) grafted onto a PET support by the "grafting from" technique The poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted onto the previously obtained PET support plate was immersed in 3 mL of 1 M NaOH. The plate was washed with 2 M hydrochloric acid and then with distilled water. Thereafter, the poly(4-vinylpyridine-2,6-dicarboxylic acid) on the PET support was recovered.

[0131] Example 5: Preparation of poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted onto a silica support by the "grafting from" technique Dimethyl 4-vinylpyridine-2,6-dicarboxylate (1.5 mmol) was dissolved in 3 mL of an organic solvent (acetonitrile). To this solution, CuCl 2 (0.15 μmol) was added together with 0.6 μmol of TPMA and 3 cm of copper wire (1 mm in diameter). To this solution, a 2 cm × 1 cm plate of the pre-grafted silica support was added. The reactor was left at room temperature for a time (several hours to several days) proportional to the desired thickness of the polymer layer. Then, the plate was washed with acetonitrile and dried.

[0132] Example 6: Preparation of poly(4-vinylpyridine-2,6-dicarboxylic acid) grafted onto a silica support by the "grafting from" technique The poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted onto the previously obtained silica support plate was immersed in 3 mL of 1 M NaOH. The plate was washed with 2 M hydrochloric acid and then with distilled water. Thereafter, poly(4-vinylpyridine-2,6-dicarboxylic acid) on the silica support was recovered.

[0133] Example 7: Preparation of poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted onto a PVC-co-PVDC support by the "grafting from" technique Dimethyl 4-vinylpyridine-2,6-dicarboxylate (1.5 mmol) was dissolved in 3 mL of an organic solvent (acetonitrile). To this solution, CuCl 2 (0.15 μmol) was added together with 0.6 μmol of TPMA and a 3 cm copper wire (1 mm in diameter). To this solution, a PVC-co-PVDC fiber (50 mg) was added. The reactor was left at room temperature for a time (several hours to several days) proportional to the desired thickness of the polymer layer. The fiber was then washed with acetonitrile and dried.

[0134] Example 8: Preparation of poly(4-vinylpyridine-2,6-dicarboxylic acid) grafted onto a PVC-co-PVDC support by the "grafting from" technique The poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted onto the previously obtained PVC-co-PVDC support was immersed in 3 mL of 1 M NaOH. The plate was washed with 2 M hydrochloric acid and then with distilled water. Thereafter, poly(4-vinylpyridine-2,6-dicarboxylic acid) on the PVC-co-PVDC support was recovered.

[0135] Example 9: Preparation of crosslinked poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted onto a PET support Dimethyl 4-vinylpyridine-2,6-dicarboxylate (1.5 mmol) was dissolved in 3 mL of an organic solvent (acetonitrile) together with 15 μmonl of 1,3-divinylbenzene. To this solution, CuCl 2(0.15 μmol) is added together with 0.6 μmol of TPMA and a 3 cm copper wire (1 mm in diameter). To this solution, a 2 cm × 1 cm plate of the pre-grafted PET support is added. The reactor is left at room temperature for a time (several hours to several days) proportional to the desired thickness of the polymer layer. Then, the plate is washed with acetonitrile and dried.

[0136] Example 10: Preparation of Block-containing Poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) Grafted onto a PET Support Styrene (1 mL) is dissolved in 1 mL of sulfolane solvent. To this solution, copper(II) chloride (0.25 mg) is added together with 5 mg of tri-(2-picolyl)amine and a 1 cm copper wire (1 mm in diameter) per milliliter of solution. The pre-grafted PET plate is immersed. The reactor is closed and heated at 60 °C for 10 hours with stirring. Then, the PET plate on which styrene has polymerized is washed with sulfolane, then with water, and further with acetone, and then dried. Dimethyl 4-vinylpyridine-2,6-dicarboxylate (1.5 mmol) is dissolved in 3 mL of an organic solvent (acetonitrile). To this solution, CuCl 2 (0.15 μmol) is added together with 0.6 μmol of TPMA and a 3 cm copper wire (1 mm in diameter). To this solution, the PET plate on which styrene has polymerized is added. The reactor is left at room temperature for a time (several hours to several days) proportional to the desired thickness of the polymer layer. Then, the plate is washed with acetonitrile and dried.

[0137] Example 11: Uranium Capture in Pure Water Poly(4-vinylpyridine-2,6-dicarboxylic acid) grafted onto a PET support is placed in a 1 mM uranyl nitrate UO 2 (NO 3 ) 2 solution at neutral pH. After 5 minutes at room temperature, the modified support is taken out, washed with water, and the fluorescence is examined under a UV lamp (254 nm).

[0138] Example 12: Uranium Capture in Simulated Seawater Poly(4-vinylpyridine-2,6-dicarboxylic acid) (15 mg) grafted onto a PVC-co-PVDC support up to a grafting degree of 40% was placed in a solution of 1 mM uranyl nitrate UO 2 (NO 3 ) 2 in simulated seawater (initial pH 8, initial ionic strength: 0.44). After 5 minutes at room temperature, the modified support was taken out, washed with water, and fluorescence was examined under a UV lamp (254 nm). Uranium uptake was also confirmed by the disappearance of uranium in the solution, which was observed by fluorescence. The uranium uptake is 98% (detection limit) or more. Also, the uranium uptake is, the total when the polymer grafted onto the support has a grafting degree of 175% (introduced mass 3 mg). The grafting degree is the ratio of the increased fiber mass during grafting to the mass of the ungrafted fiber.

Claims

1. A composition comprising a polymer having a degree of polymerization n of 1 to 10,000, containing n monomer units, and grafted onto a support, specifically covalently grafted, wherein the monomer units are - monomer units derived from 4-vinylpyridine in which the carbons at the 2- and 6-positions are substituted by a carboxylic acid having 1 to 20 carbons or an ester having 1 to 20 carbons, or - monomer units derived from the 4-vinylpyridine and comonomer, provided that the monomer units derived from 4-vinylpyridine represent at least 20% of the degree of polymerization n, the polymer may be complexed with a metal, the polymer is linear or crosslinked, the polymer is irreversibly bonded to the support, a composition.

2. The polymer of formula I 【Chemical 1】 (wherein, - Su is the support onto which the polymer is grafted, - A is a group derived from a polymerization initiator, - T is a group derived from a compound that links between the support and the compound derived from the polymer initiator or between the support and the first monomer unit, ・R 4 is a group derived from a compound that propagates polymerization with or without being derived from a polymerization initiator, a compound that terminates polymerization, or a chain transfer agent, - t, a, and r are the same or different and are 0 or 1, - i is a subscript that is a positive integer varying between 1 and n (n = 1 to 10,000), for each i ・R i,1 and R i,2 are substituents selected from the following group: carboxylic acids having 1 to 20 carbon atoms, esters having 1 to 20 carbon atoms, ・B i is a monomer unit derived from a comonomer that forms or does not form a cross-linking bridge, ・M i is a metal cation, ・n i is a positive number greater than 0 and less than or equal to 1, and m i is a positive number greater than or equal to 0 and less than 1, ・n i +m i =1、 ・x i is a number from 0 to 6, and ・p i is the charge of a metal complex that is from -6 to +6, B that forms a crosslinked bridge i When there is none, the polymer is linear, and B that forms a crosslinked bridge between two linear polymers i When at least one exists, the polymer is crosslinked) ), a composition according to claim 1 comprising a polymer grafted onto a support.

3. Formula II 【Chemical 2】 (wherein, ・Su, R i,1 , R i,2 , T, A, n i , m i , R 4 , M i , t, a, r, x i , p i and the definitions of i are as described in claim 2, ・B i is a monomer unit derived from a comonomer that does not form a cross-linking bridge) ), a composition according to claim 2 comprising a polymer grafted onto a support.

4. Formula III [Chemical Formula 3] (wherein, ・Su, R i,1 , R i,2 , T, A, R 4 , M i , t, a, r, x i , p i and the definitions of i are as described in claim 2) ), a composition according to claim 2 comprising a polymer grafted onto a support.

5. Formula IV 【Chemical Formula 4】 (wherein, ・Su, T, A, R 4 , M i , t, a, r, x i , p i and the definitions of i are as described in claim 2, ・R 1 and R 2 are substituents selected from the following group: carboxylic acids having 1 to 20 carbon atoms, esters having 1 to 20 carbon atoms) ), a composition according to claim 2 comprising a polymer grafted onto a support.

6. Formula V [Chemical Formula 5] (wherein, ・Su, T, A, R 4 , and the definitions of t, a, and r are as described in claim 2, - n is as defined in claim 1, - M is a metal cation, - x is a number from 0 to 6, - p is the charge of the metal complex which is from -6 to +6) ), a composition according to claim 2 comprising a homopolymer grafted onto a support.

7. Formula VI 【Chemical Formula 6】 (wherein, Su, T, A, R 4 The definitions of t, a, and r are as described in claim 2, n is as defined in claim 1) ), a composition according to claim 2 comprising a homopolymer grafted onto a support.

8. Formula XII 【Chemical Formula 7】 (wherein, ・Su, T, A, R 4 , the definitions of t, a, and r are as described in claim 2, and n is as defined in claim 1) ), a composition according to claim 2 comprising a homopolymer grafted onto a support.

9. Formula XIII 【Chemical Formula 8】 (wherein, ・Su, T, A, R 4 , the definitions of t, a and r are as described in claim 2, - n is as defined in claim 1, ・xU is a number from 0 to 6) The composition according to claim 2, which is grafted onto a support and comprises a homopolymer complexed with uranium and grafted onto a support.

10. The composition according to claim 2, comprising a polymer grafted onto a support and having at least one monomer unit derived from a comonomer.

11. The composition according to claim 10, comprising a copolymer grafted onto a support, wherein the proportion of monomer units derived from the comonomer is more than 0% and 80% or less.

12. Formula XVIII 【Chemical Formula 9】 (In the formula, ・The definitions of Su, T, A, R4, t, a and r are as described in claim 2, ・R 1 and R 2 are substituents selected from the following group: carboxylic acids having 1 to 20 carbon atoms, esters having 1 to 20 carbon atoms, ・B is a monomer unit derived from a comonomer, ・d is the degree of polymerization of a block consisting of monomer units derived from 4-vinylpyridine, and d is an integer, ・c is the degree of polymerization of a block consisting of monomer units derived from a comonomer, and c is an integer, ・d + c = n, and n is the degree of polymerization described in claim 1) The composition according to claim 10, which is grafted onto a support and comprises a diblock copolymer.

13. Formula XIX 【Chemical Formula 10】 (In the formula, - Su, T, A, R 4 , and the definitions of t, a, and r are as described in claim 2, ・The definitions of c and d are as described in claim 12) The composition according to claim 12, which is grafted onto a support and comprises a diblock copolymer.

14. The composition according to claim 1, comprising a polymer grafted onto a support and complexed with a metal.

15. The composition according to claim 10, comprising a polymer grafted onto a support and complexed with a metal.

16. The composition according to claim 14, comprising a polymer grafted onto a support and complexed with a metal selected from actinides, lanthanides or transition metals.

17. The composition according to claim 14, comprising a polymer grafted onto a support and complexed with uranium.

18. The composition according to claim 1, comprising a polymer grafted onto a support and solvated in an aqueous solution or seawater.

19. The composition according to any one of claims 14 to 17, comprising a polymer grafted onto a support, complexed with a metal, and solvated or not solvated in an aqueous solution.

20. The composition according to claim 1 or 18, comprising a polymer grafted onto a support, which is solvated in an aqueous solution when not complexed with a metal and not solvated in a solution when complexed with a metal.

21. The composition according to claim 1, comprising a polymer grafted onto a support and solvated in an organic solvent.

22. The support Su is a polyvinyl chloride-polyvinylidene chloride (PVC-co-PVDC) copolymer, polyvinyl chloride (PVC), PET, or SiO 2 The composition according to claim 1, comprising a polymer grafted onto a support selected from

23. The composition according to claim 2, comprising a polymer grafted onto a support, wherein A is derived from a polymerization initiator selected from 4-(chloromethyl)benzoyl chloride, benzyl chloride, AIBN, methyl-2-bromo-2-methylpropanoate, or a compound of formula XXIII 【Chemical Formula 14】

24. R 4 is a chlorine atom or formula XXIV 【Chemical Formula 15】 The composition according to claim 2, comprising a polymer grafted onto a support, selected from the groups of

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