Graft polymers, methods for preparing same, and uses thereof particularly for metal capture

Abstract

Disclosed are novel polymers that are grafted onto a substrate. These polymers contain monomer units derived from 4-vinylpyridine and monomer units derived from a co-monomer. The polymers may be complexed with a metal, and linear or crosslinked. Also disclosed are methods for preparing these polymers by radical polymerisation, as well as to their use for metal capture in aqueous media, particularly uranium capture in seawater or in final nuclear waste from nuclear power plants.

Claims

1. A composition comprising a polymer grafted covalently onto a support, said polymer having a degree of polymerization n.sub.p, ranging from 2 to 10,000, and containing n.sub.p monomer units, said monomer units being: either 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: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, or monomer units derived from a co-monomer, provided that the two substituents cannot both be hydrogen, and provided that said monomer units derived from the 4-vinylpyridine represent at least 20% of the degree of polymerization n.sub.p, said polymer being optionally complexed with a metal or a metal oxide, said polymer being linear or crosslinked, said polymer being irreversibly linked to a support.

2. The composition according to claim 1, comprising a polymer grafted onto a support, said polymer being selected from the group consisting of Formula I, Formula II and Formula III, ##STR00093## in which: Su is the support on which the polymer is grafted, A is derived from a polymerization initiator, T is making the link between the support and the optional compound resulting from a polymerization initiator or between the support and the first monomer unit, R.sub.4 is H when r is 0 or when r is 1 a moiety allowing the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, t, a and r are identical or different and are 0 or 1, i is a positive, indexed integer varying from 1 to n.sub.p, n.sub.p being from 2 to 10,000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, provided that when R.sub.i,1 represents hydrogen, then R.sub.i,2 is different from hydrogen, and vice versa, B.sub.i is a part of a monomer unit derived from a co-monomer when it is forming a crosslinking bridge, or a monomer unit derived from a co-monomer when it is not forming a crosslinking bridge, M.sub.i is a metallic cation, n.sub.i and m.sub.i, are integers equal to 0 or 1, n.sub.i+m.sub.i=1, x.sub.i is a number from 1 to 6, p.sub.i is the electrical charge of the metal complex ranging from 6 to +6, said polymer being linear when there is no B.sub.i forming a crosslinking bridge, said polymer being crosslinked when there is at least one B.sub.i forming crosslinking bridge between two linear polymers ##STR00094## in which the definitions of Su, R.sub.i,1, R.sub.i,2, T, A, n.sub.i, m.sub.i, R.sub.4, M.sub.i, t, a, r, x.sub.i, p.sub.i and i are as described above, B.sub.i is a part of a monomer unit derived from a co-monomer when it is forming a crosslinking bridge, or a monomer unit derived from a co-monomer when it is not forming a crosslinking bridge, ##STR00095## in which: the definitions of Su, R.sub.i,1, R.sub.i,2, T, A, R.sub.4, M.sub.i, t, a, r, x.sub.i, p.sub.i and i are as described above.

3. The composition according to claim 1, comprising a homopolymer grafted on a support, said polymer grafted on a support being of formula selected from the group consisting of Formula IV, Formula V, Formula VI, Formula XII and Formula XIII; ##STR00096## in which: Su is the support on which the polymer is grafted, A is a compound derived from a polymerization initiator, T is a compound making the link between the support and the optional compound resulting from a polymerization initiator or between the support and the first monomer unit, R.sub.4 is H when r is 0 or when r is 1 a moiety allowing the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, t, a and r are identical or different and are 0 or 1, i is a positive, indexed integer varying from 1 to n, n being from 2 to 10,000, and for each i: M.sub.i is a metallic cation, x.sub.i is a number from 1 to 6, p.sub.i is the electrical charge of the metal complex ranging from 6 to +6, R.sub.1 and R.sub.2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, provided that when R.sub.i represents hydrogen, then R.sub.2 is different from hydrogen, and vice versa; ##STR00097## in which: the definitions of Su, T, A, R.sub.4, t, a, and r are as described above, M is a metallic cation, x is a number comprised from 1 to 6, p is the electrical charge of the metal complex ranging from 6 to +6; ##STR00098## in which: the definitions of Su, T, A, R.sub.4, t, a, and r are as described above; ##STR00099## in which: the definitions of Su, T, A, R.sub.4, t, a, and r are as described above; ##STR00100## in which: the definitions of Su, T, A, R.sub.4, t, a, and r are as described above, xU is a number comprised from 1 to 6.

4. The composition according to claim 1, comprising a polymer grafted on a support, said polymer having at least one monomer unit derived from a co-monomer, or comprising a copolymer grafted on a support, in which the level of monomer unit derived from a co-monomer varies strictly from a value greater than 0% to a value less than 80%.

5. The composition according to claim 1, comprising of a two-block copolymer, grafted on a support, said polymer grafted on a support being of Formula XVIII or Formula XIX: ##STR00101## in which: Su is the support on which the polymer is grafted, A is a compound derived from a polymerization initiator, T is a compound making the link between the support and the optional compound resulting from a polymerization initiator or between the support and the first monomer unit, R.sub.4 is H when r is 0 or when r is 1 a moiety allowing the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, t, a and r are identical or different and are 0 or 1, R.sub.1 and R.sub.2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms, provided that when R.sub.1 represents hydrogen, then R.sub.2 is different from hydrogen, and vice versa, B is a monomer unit derived from a co-monomer, d is the degree of polymerization of the block consisting of the monomer units derived from 4-vinylpyridine and d is an integer, c is the degree of polymerization of the block consisting of the monomer units derived from the co-monomer and c is an integer, d+c=n.

6. The composition according to claim 1, comprising a crosslinked copolymer grafted onto a support, said polymer grafted onto a support being of Formula XX or Formula XXI, ##STR00102## in which: Su is the support on which the polymers are fixed, w is a strictly positive, indexed whole number, varying from 1 to the number of polymers crosslinked with the polymer of index 0, and comprised from 1 to 1000, A.sub.0 and the A.sub.w are compounds originating from polymerization initiators, T.sub.0 and the T.sub.w are compounds making the link between the support and the possible compounds originating from polymerization initiators or between the support and the respective first monomer unit, R.sub.4,0 and R.sub.4,w, are H when r.sub.o or r.sub.w is zero and when r.sub.o or r.sub.w is 1 a moiety permitting the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, t.sub.0, a.sub.0, r.sub.0, t.sub.w, a.sub.w and the r.sub.w are the same or different and are 0 or 1, i and j, w are strictly positive, indexed integers, varying respectively from 1 to n.sub.i, and from 1 to n.sub.j,w, n.sub.i et n.sub.j,w being included from 1 to 9999, n.sub.i+n.sub.j,w=n, n being between 3 and 10,000, and for each i and each j, w: R.sub.i,1, R.sub.i,2, R.sub.j,w,1 and R.sub.j,w,2 are substituents chosen from the following group: hydrogen, alkene radical of 3 to 20 carbons, radical aryl of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, said substituents being able to be cyclized between them and which may contain sulfur or phosphorus atoms, provided that when R.sub.i,1, represents hydrogen, then R.sub.i,2 is different from hydrogen, and vice versa, provided that when R.sub.j,w,1 represents hydrogen, then R.sub.j,w,2 is different from hydrogen, and vice versa, B.sub.i,j,w is a monomer unit derived from a co-monomer, forming a crosslinking bridge between the polymer 0 in position i and the polymer of index w in position j, the C.sub.i and the C.sub.j,w are monomer units derived from a co-monomer which does not form a crosslinking bridge, n.sub.i, m.sub.i, o.sub.i, n.sub.j,w, m.sub.j,w, and the o.sub.j,w, are integers equal to 0 or 1, n.sub.i+m.sub.i+o.sub.i=1, n.sub.j,w+m.sub.j,w+o.sub.j,w=1 the sum of the o.sub.j,w, is non-zero, and the sum of o.sub.i is non-zero.

7. The composition according to claim 1, comprising a polymer grafted on a support in which said polymer grafted on a support is complexed with a metal chosen from actinides, lanthanides or transition metals, or with uranium.

8. The composition according to claim 1, comprising a polymer grafted on a support, said polymer grafted on a support being solvated in aqueous solution; or said polymer grafted on a support being complexed with a metal, and being solvated or not in aqueous solution; or said polymer grafted on a support being solvated in aqueous solution not complexed with a metal and non-solvated in solution complexed with a metal; or said polymer grafted on a support being solvated or in organic solvents.

9. A method for preparing a polymer grafted covalently or not covalently to a support, said polymer having a degree of polymerization n, ranging from 2 to 10,000, and containing n monomer units, said monomer units being: either 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: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, said substituents can be cyclized with each other and contain sulfur or phosphorus atoms, or monomer units derived from a co-monomer, provided that the two substituents cannot both be hydrogen, and provided that said monomer units derived from the 4-vinylpyridine represent at least 20% of the degree of polymerization n, said polymer being optionally complexed with a metal or a metal oxide, said polymer being linear or crosslinked, said polymer being irreversibly linked to a support, comprising the following preparation steps: a. optionally a step of pretreatment of the support by bringing said support into contact with a pretreatment reagent and/or a physical pretreatment, in order to obtain a support that may be pretreated, b. optionally a pre-grafting step on the support which may be pretreated by bringing said support, which may be pretreated, into contact with a polymerization initiator, in order to obtain a support which may be pretreated and optionally pre-grafted, c. a radical polymerization step starting with the initiation of the support, if necessary pretreated and optionally pre-grafted into contact with, then continuing by bringing the support optionally pretreated and optionally pre-grafted with: at least one monomer 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: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms, and optionally at least one co-monomer, with or without crosslinking, to obtain a polymer grafted onto the support, optionally said radical polymerization step is a polymerization of NMP, RAFT, ATRP or or a conventional radical polymerization, d. an optional modification step by bringing the polymer grafted onto the support into contact with a reagent to modify at least one of the above-mentioned substituents, to obtain a polymer grafted onto the support and optionally modified, e. an optional complexation step by bringing the polymer grafted onto the support and optionally modified into contact with a metal cation to obtain a polymer grafted onto the support, optionally modified and optionally complexed.

10. The method according to claim 9, for preparing a polymer grafted on a support, said polymer grafted on a support being of Formula I, ##STR00103## in which: Su is the support on which the polymer is grafted, A is a compound derived from a polymerization initiator, T is a compound making the link between the support and the optional compound resulting from a polymerization initiator or between the support and the first monomer unit, R.sub.4 is H when r is 0 or when r is 1 a moiety allowing the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, t, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer varying from 1 to n, n being from 2 to 10,000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms, provided that when R.sub.i,1 represents hydrogen, then R.sub.i,2 is different from hydrogen, and vice versa, B.sub.i is a part of a monomer unit derived from a co-monomer when it is forming a crosslinking bridge, or a monomer unit derived from a co-monomer when it is not forming a crosslinking bridge, M.sub.i is a metallic cation, n.sub.i and m.sub.i, are integers equal to 0 or 1, n.sub.i+m.sub.i=1, x.sub.i is a number from 0 to 6, p.sub.i is the electrical charge of the metal complex ranging from 6 to +6, said polymer being linear when there is no B.sub.i forming a crosslinking bridge, said polymer being crosslinked when there is at least one B.sub.i forming crosslinking bridge between two linear polymers, said method comprising: a. optionally a step of pretreatment of the support by bringing said support into contact with a pretreatment reagent and/or by the action of a physical pretreatment on said support, in order to obtain a support that may be pretreated with Formula XXXI, ##STR00104## in which T is a compound resulting from the pretreatment of the support Su, containing fragments either of the support, or of the pretreatment reagent, or of both, t is an integer equal to 0 or 1, b. optionally a step of pre-grafting onto the optionally pretreated support of Formula XXXI by bringing the support into contact with a polymerization initiator, in order to obtain a support that is optionally pretreated and optionally pre-grafted of Formula XXXII, ##STR00105## in which A is a compound resulting from the pre-grafting step on the support, containing fragments of the polymerization initiator, a is an integer equal to 0 or 1, c. a radical polymerization step starting with the priming of the optionally pretreated and optionally pre-grafted support of Formula XXXII followed by the contacting of the optionally pretreated and optionally pre-grafted support with the 4-vinylpyridine derivative of Formula XXXIII, ##STR00106## in which: Z.sub.i,1 and Z.sub.i,2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms, said polymerization step being carried out: optionally with at least one co-monomer, with or without crosslinking, to obtain a polymer grafted on a support of Formula XXXIV ##STR00107## d. a modification step, when at least one of the Z.sub.i,1 is different from R.sub.i,1 or when at least one of the Z.sub.i,2 is different from R.sub.i,2, of the said polymer Formula XXXIV with a reagent for modifying at least one of the above substituents Z.sub.i,1 and Z.sub.i,2, said reagent containing a hydroxide, carbonate or phosphate anion, in order to obtain the polymer grafted on a support of Formula XXXV ##STR00108## e. optionally a complexing step of said polymer grafted on a support of Formula XXXV with at least one metal cation to obtain the polymer grafted on a support of Formula I.

11. The method according to claim 9, for preparing a polymer grafted on a support said polymer being of Formula II with t=1 and a=1, ##STR00109## in which Su is the support on which the polymer is grafted, A is a compound derived from a polymerization initiator, T is a compound making the link between the support and the optional compound resulting from a polymerization initiator or between the support and the first monomer unit, R.sub.4 is H when r is 0 or when r is 1 a moiety allowing the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, r is 0 or 1, i is a strictly positive, indexed integer varying from 1 to n, n.sub.p being from 2 to 10,000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms, provided that when R.sub.i,1 represents hydrogen, then R.sub.i,2 is different from hydrogen, and vice versa, M.sub.i is a metallic cation, n.sub.i and m.sub.i, are integers equal to 0 or 1, n.sub.i+m.sub.i=1, x.sub.i is a number from 0 to 6, p.sub.i is the electrical charge of the metal complex ranging from 6 to +6, B.sub.i is a monomer unit derived from a co-monomer, not forming a crosslinking bridge, said method comprising: a. a step of pretreatment of the support by bringing the support into contact with a pretreatment reagent and/or by the action of a physical pretreatment on said support, in order to obtain a pretreated support of Formula XXXVIII, ##STR00110## in which: T is a compound resulting from the pretreatment of the support Su, containing fragments either of the support, or of the pretreatment reagent, or of both, b. a step of pre-grafting said pretreated support of Formula XXXVIII by bringing it into contact with a polymerization initiator, in order to obtain a pretreated and pre-grafted support of Formula XLII ##STR00111## in which: A is a compound resulting from the pre-grafting step on the support, containing fragments of the polymerization initiator, c. a radical polymerization step starting with the priming of the pretreated and pre-grafted support of Formula XLII followed by bringing the pretreated and pre-grafted support into contact with the 4-vinylpyridine derivative of Formula XXXIII and optionally with at least one co-monomer to obtain a polymer grafted on a support of Formula XLIII ##STR00112## in which: the definitions of A, R.sub.4, B.sub.i, n.sub.i, m.sub.i, r and i are as described above in Formula II, Z.sub.i,1 and Z.sub.i,2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms, d. a modification step, when at least one of the Z.sub.i,1 is different from R.sub.i,1 or when at least one of the Z.sub.i,2 is different from R.sub.i,2 of said polymer grafted on a support of Formula XLIII with a reagent for modifying at least one of Z.sub.i,1 or Z.sub.i,2 said reagent containing a hydroxide, carbonate or phosphate anion, to obtain the polymer grafted on a support of Formula XLIV ##STR00113## e. optionally a complexing step of said polymer grafted on a support of Formula XLIV with at least one metal cation to obtain the polymer grafted on a support of Formula II, in which t=1 and a=1; or said polymer grafted on a support being of Formula II with t=0 and a=0, said method comprising neither a pretreatment step nor a priming step and comprising a. a radical polymerization step starting with the priming of the support and followed by bringing the support into contact with the 4-vinylpyridine derivative of Formula XXXIII, and optionally with at least one co-monomer, with or without crosslinking, for obtain a polymer grafted onto a support of Formula XLV ##STR00114## in which: the definitions of Su, R.sub.4, B.sub.i, n.sub.i, m.sub.i, r and i are as described above, the definitions of Z.sub.i,1 and Z.sub.i,2 are as described above, b. a modification step, when at least one of Z.sub.i,1 is different from R.sub.i,1 or when at least one of Z.sub.i,2 is different from R.sub.i,2, of said polymer grafted on a support of Formula XLV with a reagent to modify at least one of Z.sub.i,1 or Z.sub.i,2 said reagent containing a hydroxide, carbonate or phosphate anion, to obtain the polymer grafted on a support of Formula XLVI, ##STR00115## c. optionally a complexing step of said polymer grafted on a support of Formula XLVI with at least one metal cation to obtain the polymer grafted on a support of Formula II with t=0 and a=0.

12. The method according to claim 9, for preparing a polymer grafted on a support, said polymer being of Formula IV with t=1 and a=1, ##STR00116## in which: Su is the support on which the polymer is grafted, A is a compound derived from a polymerization initiator, T is a compound making the link between the support and the optional compound resulting from a polymerization initiator or between the support and the first monomer unit, R.sub.4 is H when r is 0 or when r is 1 a moiety allowing the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, r is 0 or 1, i is a strictly positive, indexed integer varying from 1 to n, n being from 2 to 10,000, and for each i: M.sub.i is a metallic cation, x.sub.i is a number from 0 to 6, p.sub.i is the electrical charge of the metal complex ranging from 6 to +6, R.sub.1 and R.sub.2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms, provided that when R.sub.1 represents hydrogen, then R.sub.2 is different from hydrogen, and vice versa; said method comprising: a. a step of pretreatment of the support by bringing the support into contact with a pretreatment reagent and/or by the action of a physical pretreatment on said support, in order to obtain a pretreated support of Formula XXXVIII, ##STR00117## in which T is a compound resulting from the pretreatment of the support Su, containing fragments either of the support, or of the pretreatment reagent, or of both, b. a step of pre-grafting the pretreated support of Formula XXXVIII by bringing it into contact with a polymerization initiator, to obtain a pretreated support and pre-grafting of Formula XLII, ##STR00118## in which: A is a compound resulting from the pre-grafting step on the support, containing fragments of the polymerization initiator, c. a radical polymerization step, starting with priming the pretreated and pre-grafted support of Formula XLII, followed by bringing the pretreated and pre-grafted support into contact with the 4-vinylpyridine derivative of Formula XLIX, ##STR00119## in which: Z.sub.1 and Z.sub.2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents optionally being cyclized with one another and optionally containing sulfur or phosphorus atoms, to obtain a polymer grafted on a support of Formula L ##STR00120## in which: the definitions of T and A are as described above, R.sub.4 is H when r is 0 or when r is 1 a moiety allowing the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, r is 0 or 1, i is a positive, indexed integer varying from 1 to n, n being from 2 to 10,000; d. a modification step, when Z.sub.1 is different from R.sub.1 or when Z.sub.2 is different from R.sub.2, of said polymer grafted on a support of Formula L with a reagent to modify at least one of the above substituents Z.sub.1 and Z.sub.2, and containing a hydroxide anion, carbonate or phosphate, to obtain the polymer grafted on a support of Formula LI, ##STR00121## e. optionally a step of complexing said polymer grafted on a support of Formula LI with at least one metal cation to obtain the polymer grafted on a support of Formula IV in which t=1 and a=1.

13. The method according to claim 9, for preparing a polymer grafted on a support in which the said polymerization step bringing into contact a 4-vinylpyridine derivative of Formula XLIX ##STR00122## in which: Z.sub.1 and Z.sub.2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of I to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms with a polymer grafted on a support of Formula LX, ##STR00123## in which: Su is the support on which the polymer is grafted, A is a compound derived from a polymerization initiator, T is a compound making the link between the support and the optional compound resulting from a polymerization initiator or between the support and the first monomer unit, R.sub.4 is H when r is 0 or when r is 1 a moiety allowing the propagation of the polymerization, whether or not derived from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, t, a and r are identical or different and are 0 or 1, B is a monomer unit derived from a co-monomer, c is the degree of polymerization of the block consisting of the monomer units derived from the co-monomer and c is an integer, to obtain a polymer grafted onto a support of Formula LXI, ##STR00124## in which: d is the degree of polymerization of the block consisting of the monomer units derived from 4-vinylpyridine and d is an integer, d+c=n; or comprising: a. a step of pretreatment of the support by bringing said support into contact with a pretreatment reagent and/or by the action of a physical pretreatment on said support, in order to obtain a pretreated support of Formula XXXI, ##STR00125## in which T is a compound resulting from the pretreatment of the support Su, containing fragments either of the support, or of the pretreatment reagent, or of both, b. a step of pre-grafting said pretreated support of Formula XXXI by bringing it into contact with a polymerization initiator, in order to obtain a pretreated and pre-grafted support of Formula XXXII; ##STR00126## in which A is a compound resulting from the pre-grafting step on the support, containing fragments of the polymerization initiator, c. a radical polymerization step by bringing the pretreated and pre-grafted support of Formula XXXII into contact with a co-monomer of Formula LXII to obtain said free polymer of Formula LX ##STR00127## in which the definition of B is as described above, before the radical polymerization step by bringing a monomer derived from 4-vinylpyridine of Formula XXXIII into contact with a polymer grafted onto a support of Formula LX, ##STR00128## in which: Z.sub.i,1 and Z.sub.i,2 are substituents chosen from the following group: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, the said substituents being able to be cyclized with one another and optionally containing sulfur or phosphorus atoms.

14. A method of fighting counterfeiting, comprising a step of labeling of organic and/or inorganic surfaces or luxury products with a composition comprising a polymer grafted covalently or not covalently onto a support, said polymer having a degree of polymerization n, ranging from 2 to 10,000, and containing n monomer units, said monomer units being: either 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: hydrogen, alkene radical of 1 to 20 carbons, aryl radical of 1 to 20 carbons, carboxylic acid of 1 to 20 carbons, alcohol of 1 to 20 carbons, ether of 1 to 20 carbons, ester of 1 to 20 carbons, amine of 1 to 20 carbons other than heterocycles, amide of 1 to 20 carbons, thiols of 1 to 20 carbons, phosphine of 1 to 20 carbons, said substituents can be cyclized with each other and contain sulfur or phosphorus atoms, or monomer units derived from a co-monomer, provided that the two substituents cannot both be hydrogen, and provided that said monomer units derived from the 4-vinylpyridine represent at least 20% of the degree of polymerization n, said polymer being optionally complexed with a metal or a metal oxide, said polymer being linear or crosslinked, said polymer being irreversibly linked to a support.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the image of PVC-co-PDVC fibers (PVC/PDVC=7/3) before grafting obtained by scanning electron microscopy. The average diameter of the fibers is 12 m.

(2) FIG. 2 represents the image of PVC-co-PDVC fibers (PVC/PDVC=7/3) after grafting of poly(2,6-dicarboxylic acid-4-vinylpyridine) obtained by scanning electron microscopy. The average diameter of the fibers is 23 m.

(3) FIG. 3A shows a solution of uranyl nitrate at neutral pH with UO.sub.2(NO.sub.3).sub.2 alone. (C.sub.uranyl=1 mM, .sub.light=254 nm, room T).

(4) FIG. 3B represents a uranium uptake test in the form of uranyl nitrate in solution at neutral pH with UO.sub.2(NO.sub.3).sub.2 and grafted poly(2,6-dicarboxylic acid-4-vinylpyridine) on the PVC-co-PDVC support of FIG. 2, (C.sub.uranyl=1 mM, m.sub.polymer=15 mg, .sub.light=254 nm, room T). The fibers have a degree of grafting of 40%. (Degree of grafting=100gain in mass of fibers/mass of fibers before grafting). Uranium ions are completely captured, within the detection limit (>98%).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Example 1: Synthesis of the Monomer Dimethyl 4-vinylpyridine-2,6-dicarboxylate

a. Synthesis of 4-hydroxypyridine-2,6-carboxylic Acid

(5) ##STR00085##

(6) This reaction is known in the prior art, in particular in the reference. RSC Adv., 2014, 4, 25486.

b. Synthesis of Dimethyl 4-chloropyridine-2,6-dicarboxylate

(7) ##STR00086##

(8) This reaction is known in the prior art, in particular in the reference J. Chem. Soc, Dalton Trans., 2000, 2031-2043.

c. Synthesis of Dimethyl 4-iodopyridine-2,6-dicarboxylate

(9) ##STR00087##

(10) This reaction is known in the prior art, in particular in the reference Tetrahedron, 2008, 64, 399-411.

d. Synthesis of Dimethyl 4-vinylpyridine-2,6-dicarboxylate

(11) ##STR00088##

(12) dimethyl 4-iodopyridine-2,6-dicarboxylate (6.2 mmol) was added to a flask with 1 mmol of triphenylphosphine, and 0.33 mmol of Palladium(II) acetate. These compounds were dissolved in 20 mL of a THF/water solution (Ratio 9/1). Cesium(III) carbonate (1 mmol) and potassium vinyl trifluoroborate (7.5 mmol) were added to the mixture. The medium was heated to 85 C. for 8 h with stirring, then cooled and finally filtered. The white residue obtained was washed with ethyl acetate and then concentrated. The concentrate obtained was purified on silica gel. Elution with a mixture of petroleum ether and ethyl acetate (3/1 Ratio) made it possible to obtain dimethyl 4-vinylpyridine-2,6-dicarboxylate in the form of one gram of white solid at 78% by mass, recrystallized from a mixture of dichloromethane and petroleum ether (1/10 Ratio).

Example 2: Preparation of the Supports

(13) Preparation of the Pre-Poly(Ethylene Terephthalate) (PET) Support

(14) ##STR00089##

(15) PET fibers were aminolyzed in a solution of Polyethyleneimine between 5 and 10 mol % and dimethyl sulfoxide at 50 C. for 6 h. The fibers were then washed with water and dried, which made it possible to obtain a pretreated PET support. The pretreated support was then added in a solution of 4-(chloromethyl)benzoyl chloride in diethyl ether in the presence of ethylamine overnight. The resulting fibers were washed with dichloromethane and then dried, which made it possible to obtain a pre-grafted PET support.

(16) b. Preparation of the Pre-Grafted Silica Support

(17) ##STR00090##

(18) An initiator (APTES-CMB) was obtained by reaction between 6.2 mL of 3-aminopropyltriethoxysilane and 5.5 g of 4-(chloromethyl)benzoyl chloride under an inert atmosphere, in the presence of 4.5 mL of triethylamine, the whole being dissolved in 20 mL dichloromethane.

(19) ##STR00091##

(20) A silica surface was treated with a piranha solution (mixture of sulfuric acid and hydrogen peroxide 7/3 by volume) which made it possible to obtain a pretreated silica support. The pretreated silica was placed in a solution containing APTES-CMB in anhydrous toluene. The mixture was brought to 70 C. for one hour and then it was washed with toluene and then water. The resultant was annealed at 100 C. for 15 minutes. The solid obtained is the pre-grafted silica support.

Example 3: Synthesis of Poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) Grafted onto the PET Support in Rafted From

(21) ##STR00092##

(22) Dimethyl-4-pyrimidine-2,6-dicarboxylate (1.5 mmol) was dissolved in a volume of 3 ml of an organic solvent (acetonitrile). CuCl.sub.2 (0.15 mol) was added to the solution as well as 0.6 mol of TPMA and 3 cm of copper wire (diameter 1 mm). A 2 cm by 1 cm plate of pre-grafted PET support was added to the solution. The reactor was left at room temperature for a time proportional to the thickness of the desired polymer layer (from a few hours to a few days). The plate was then washed with acetonitrile and then dried.

Example 4: Preparation of the Poly(4-vinylpyridine-2,6-dicarboxylic Acid) Grafted on the PET Support in Grafted From

(23) The poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted on the PET support plate, obtained previously, was inserted into 3 mL of 1 M NaOH. The plate is washed with 2M hydrochloric acid, then with distilled water. The poly(4-vinylpyridine-2,6-dicarboxylic acid) on the PET support was then recovered.

Example 5: Preparation of Poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) Grafted onto the Silica Support in Grafted From

(24) Dimethyl 4-vinylpyridine-2,6-dicarboxylate (1.5 mmol) was dissolved in a volume of 3 ml of an organic solvent (Acetonitrile). CuCl.sub.2 (0.15 mol) was added to the solution as well as 0.6 mol of TPMA and 3 cm of copper wire (diameter 1 mm). A plate of 2 cm by 1 cm of pre-grafted silica support was added to the solution. The reactor was left at room temperature for a time proportional to the thickness of the desired polymer layer (from a few hours to a few days). The plate was then washed with acetonitrile and then dried.

Example 6: Preparation of poly(4-vinylpyridine-2,6-dicarboxylic Acid) Grafted onto the Silica Support in Grafted From

(25) The poly(2,6-dimethyl 4-vinylpyridine dicarboxylate) grafted onto the silica support plate, obtained previously, was inserted into 3 ml of 1 M NaOH. The plate is washed with 2M hydrochloric acid, then with distilled water. The poly(4-vinylpyridine-2,6-dicarboxylic acid) on the silica support was then recovered.

Example 7: Preparation of poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) Grafted onto the PVC-co-PVDC Support in Grafted From

(26) Dimethyl 4-vinylpyridine-2,6-dicarboxylate (1.5 mmol) was dissolved in a volume of 3 ml of an organic solvent (acetonitrile). CuCl.sub.2 (0.15 mol) was added to the solution as well as 0.6 mol of TPMA and 3 cm of copper wire (diameter 1 mm). PVC-co-PVDC fibers (50 mg) were added to the solution. The reactor was left at room temperature for a time proportional to the thickness of the desired polymer layer (from a few hours to a few days). The fibers were then washed with acetonitrile and then dried.

Example 8: Preparation of the poly(4-vinylpyridine-2,6-dicarboxylic Acid) Grafted onto the PVC-co-PVDC Support in Grafted From

(27) The poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) grafted on the PVC-Co-PVDC support fibers, obtained previously, was inserted into 3 ml of 1 M NaOH. The fibers are washed with hydrochloric acid at 2M, then with distilled water. The poly(4-vinylpyridine-2,6-dicarboxylic acid) on the PVC-co-PDVC support was then recovered.

Example 9: Preparation of the Crosslinked Poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) Grafted onto the PET Support

(28) Dimethyl 4-vinylpyridine-2,6-dicarboxylate (1.5 mmol) is dissolved in a volume of 3 mL of an organic solvent (Acetonitrile), as well as 15 mol of 1,3-divinylbenzene, CuCl.sub.2 (0.15 mol) is added to the solution along with 0.6 mol of TPMA and 3 cm of copper wire (diameter 1 mm). A 2 cm by 1 cm plate of pre-grafted PET support is added to the solution. The reactor is left at room temperature for a time proportional to the thickness of the desired polymer layer (from a few hours to a few days). The plate is then washed with acetonitrile and then dried.

Example 10: Preparation of poly(dimethyl 4-vinylpyridine-2,6-dicarboxylate) with Blocks Grafted onto the PET Support

(29) Styrene (1 mL) is dissolved in 1 ml of sulfolane solvent. Copper(II) chloride (0.25 mg) is added to the solution, as well as 5 mg of Tri-(2-picolyl) amine and 1 cm of copper wire per milliliter of solution (D 1 mm). A pre-grafted PET plate is inserted. The reactor is closed and heated at 60 C. for 10 h with stirring. The PET plate polymerized with styrene is then washed with sulfolane then water and then acetone and dried.

(30) Dimethyl 4-vinylpyridine-2,6-dicarboxylate (1.5 mmol) is dissolved in a volume of 3 ml of an organic solvent (Acetonitrile). CuCl.sub.2 (0.15 mol) is added to the solution as well as 0.6 mol of TPMA and 3 cm of copper wire (diameter 1 mm), The PET plate polymerized with styrene is added to the solution. The reactor is left at room temperature for a time proportional to the thickness of the desired polymer layer (from a few hours to a few days). The plate is then washed with acetonitrile and then dried.

Example 11: Uranium Capture in Fresh Water

(31) Poly(4-vinylpyridine-2,6-dicarboxylic acid) grafted on the PET support is put in a solution of uranyl nitrate UO.sub.2(NO.sub.3).sub.2 at 1 mM in 1 distilled water at neutral pH. After 5 minutes at room temperature, the modified support is removed, washed with water and examined under UV lamp (254 nm) for observation of fluorescence

Example 12: Uranium Capture in Simulated Seawater

(32) Poly(4-vinylpyridine-2,6-dicarboxylic acid) grafted on the PVC-co-PVDC support (15 mg) to a degree of grafting of 40% is put in a solution of uranyl nitrate UO.sub.2(NO.sub.3).sub.2 at 1 mM in simulated seawater (initial pH: 8, initial ionic strength: 0.44) and at an. After 5 minutes at room temperature, the modified support is removed, washed with water and examined under UV lamp (254 nm) for observation of fluorescence. Uranium uptake is also verified by the disappearance of uranium in the solution seen by fluorescence.

(33) Uranium uptake is more than 98% (detection limit).

(34) Uranium uptake is also total in the case where the polymer grafted on a support has a degree of grafting of 175%, with an introduced mass of 3 mg.

(35) The degree of grafting is the ratio between the mass of fibers gained during grafting, compared to the mass of non-grafted fibers.