Polymers, methods for preparing same, and uses thereof particularly for metal capture

Abstract

Disclosed are novel polymers that 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 polymerization, 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 having a degree of polymerization n, ranging from 2 to 10000, and containing 2 to 10000 monomer units, said monomer units being: either monomer units derived from 4-vinylpyridine, in which the carbons in position 2 and 6 are substituted by one of the substituents of the following group: carboxylic acid, or ester of 1 to 20 carbons, or monomer units derived from a co-monomer, provided that said monomer units derived from 4-vinylpyridine represent at least 20% of the degree of polymerization n, said polymer being optionally complexed with a metal, said polymer being linear or cross-linked.

2. The composition according to claim 1, comprising a linear or cross-linked polymer consisting of a monomer unit, of Formula I, ##STR00058## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer, varying from 1 to n, itself comprised from 2 to 10000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: carboxylic acid, or ester of 1 to 20 carbons, B.sub.i is a monomer unit derived from a co-monomer, whether or not forming a cross-linking bridge, M.sub.i is a metal, n.sub.i et m.sub.i, are integers equal to 0 or 1, n.sub.i+m.sub.i=1, x.sub.i is a number comprised 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 cross-linking bridge, said polymer being cross-linked when there is at least one B.sub.i forming a cross-linking bridge between two linear polymers, or comprising a non-cross-linked linear polymer consisting of monomer unit, of Formula II, ##STR00059## in which: the definitions of R.sub.i,1, R.sub.i,2, A, R.sub.4, a, r, M.sub.i, x.sub.i, n.sub.i, m.sub.i, p.sub.i and i are as described for Formula I, B.sub.i is a monomer unit derived from a co-monomer which does not form a cross-linking bridge.

3. Composition according to claim 1, comprising a polymer of Formula III, ##STR00060## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer, varying from 1 to n, itself comprised from 2 to 10000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: carboxylic acid, or ester of 1 to 20 carbons, M.sub.i is a metal, x.sub.i is a number comprised from 0 to 6, p.sub.i is the electrical charge of the metal complex ranging from −6 to +6.

4. The composition according to claim 1, comprising a homopolymer of 2,6-dicarboxyl-4-vinylpyridine of Formula V, ##STR00061## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, M is a metal, x is a number comprised from 0 to 6, p is the electrical charge of the metal complex ranging from −6 to +6, or comprising a homopolymer of 2,6-dicarboxyl-4-vinylpyridine represented by Formula VI, ##STR00062## in which: the definitions of R.sub.4, A, a and r are as described for Formula V, or comprising a homopolymer of Formula XII, ##STR00063## in which: the definitions of A, R.sub.4, r, and a are as described for Formula V, or comprising a homopolymer of 2,6-dicarboxyl-4-vinylpyridine complexed with uranium, represented by Formula XIII, ##STR00064## in which: the definitions of A, R.sub.4, r, a are as described for Formula V, xU is a number comprised from 0 to 1.

5. The composition according to claim 1, comprising a polymer with at least one monomer unit derived from a co-monomer, or comprising a polymer with at least one monomer unit derived from a co-monomer, in which the level of monomer unit derived from a co-monomer varies from a value strictly greater than 0% to a value less than 80%.

6. The composition according to claim 1, comprising a polymer with at least one monomer unit derived from a co-monomer, said monomer units being derived from styrene or acrylic acid, or comprising a polymer with at least one monomer unit derived from a co-monomer, said monomer units being derived from styrene or acrylic acid, in which the level of monomer unit derived from a co-monomer varies from a value strictly greater than 0% to a value less than 80%.

7. The composition according to claim 1, comprising a block copolymer of Formula XVIII, ##STR00065## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, 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: carboxylic acid, or ester of 1 to 20 carbons, B is a monomer unit derived from a non-forming co-monomer cross-linking bridge, d is the degree of polymerization of the block consisting of monomer units derived from 4-vinylpyridine and a is an integer, c is the degree of polymerization of the block consisting of monomer units derived from co-monomer and b is an integer, c+d=n, or comprising a two-block copolymer of Formula XIX a ##STR00066## in which: the definitions of A, R.sub.4, a, r, c and d are as described for Formula XVIII.

8. The composition according to claim 1, comprising a cross-linked copolymer, said polymer being of Formula XX, ##STR00067## in which: W is a strictly positive, indexed integer varying from 1 to the number of polymers cross-linked with the polymer of index 0, itself comprised from 1 to 1000, A.sub.0 and A.sub.w are compounds derived from polymerization initiators, R.sub.4,0 and R.sub.4,w are compounds allowing the propagation of the polymerization, whether or not originating from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, a.sub.0, r.sub.0, a.sub.w and r.sub.w are identical or different and are 0 or 1, i and j, w are integers which are strictly positive, indexed, varying respectively from 1 to n.sub.i and 1 to n.sub.j,w, n.sub.i and n.sub.j,w, being comprised from 1 to 9999, n.sub.i+n.sub.3,w=n, n being comprised from 3 to 10000, 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: carboxylic acid, or ester from 1 to 20 carbons, B.sub.i,j,w is a monomer unit derived from a co-monomer, forming a cross-linking bridge between the polymer 0 in position i and the polymer of index w in position j, C.sub.i and C.sub.j,w are monomer units derived from a co-monomer which does not form a cross-linking bridge, n.sub.i, m.sub.i, o.sub.i, n.sub.j,w, m.sub.j,w, and 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 the o.sub.i is non-zero, or comprising a cross-linked copolymer of Formula XXI: ##STR00068## in which: the definitions of w, A.sub.0, A.sub.w, a.sub.0, a.sub.w, i, j, w, n.sub.i, n.sub.j,w, m.sub.i, m.sub.j,w, o.sub.i, o.sub.j,w, R.sub.4,0, R.sub.4,w, r.sub.0 and r.sub.w are as described for Formula XX.

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

10. The composition according to claim 1, comprising a polymer soluble in aqueous solution or in sea water, or comprising a polymer complexed with a soluble or insoluble metal in aqueous solution, or comprising a polymer soluble in aqueous solution not complexed with a metal and insoluble in solution complexed with a metal, or with uranium.

11. The composition according to claim 1, comprising a polymer soluble in organic solvents, or in acetonitrile, or dimethylsulfoxide (DMSO).

12. The composition according to claim 1, comprising a polymer in which A, Ao and Aw are derived from a polymerization initiator chosen from 4-(chloromethyl)-benzoyl chloride, benzyl chloride, AIBN, methyl-2-bromo-2-methylpropanoate, said polymer being of Formula I, ##STR00069## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer, varying from 1 to n, itself comprised from 2 to 10000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: carboxylic acid, or ester of 1 to 20 carbons, B.sub.i is a monomer unit derived from a co-monomer, whether or not forming a cross-linking bridge, M.sub.i is a metal, n.sub.i et m.sub.i, are integers equal to 0 or 1, n.sub.i+m.sub.i=1, x.sub.i is a number comprised 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 cross-linking bridge, said polymer being cross-linked when there is at least one B.sub.i forming a cross-linking bridge between two linear polymers, or said polymer being of Formula II ##STR00070## in which: the definitions of R.sub.i,1, R.sub.i,2, R.sub.4, a, r, M.sub.i, x.sub.i, n.sub.i, m.sub.i, p.sub.i and i are as described for Formula I, B.sub.i is a monomer unit derived from a co-monomer which does not form a cross-linking bridge, or said polymer being of Formula III ##STR00071## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer, varying from 1 to n, itself comprised from 2 to 10000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: carboxylic acid, or ester of 1 to 20 carbons, M.sub.i is a metal, x.sub.i is a number comprised from 0 to 6, p.sub.i is the electrical charge of the metal complex ranging from −6 to +6, or said polymer being of Formula XVIII, ##STR00072## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, 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: carboxylic acid, or ester of 1 to 20 carbons, B is a monomer unit derived from a non-forming co-monomer cross-linking bridge, d is the degree of polymerization of the block consisting of monomer units derived from 4-vinylpyridine and a is an integer, c is the degree of polymerization of the block consisting of monomer units derived from co-monomer and b is an integer, c+d=n, or said polymer being of Formula XX, ##STR00073## in which: W is a strictly positive, indexed integer varying from 1 to the number of polymers cross-linked with the polymer of index 0, itself comprised from 1 to 1000, R.sub.4,0 and R.sub.4,w are compounds allowing the propagation of the polymerization, whether or not originating from said polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, a.sub.0, r.sub.0, a.sub.w and r.sub.w are identical or different and are 0 or 1, i and j, w are integers which are strictly positive, indexed, varying respectively from 1 to n.sub.i and 1 to n.sub.j,w, n.sub.i and n.sub.j,w, being comprised from 1 to 9999, n.sub.i+n.sub.j,w=n, n being comprised from 3 to 10000, 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: carboxylic acid, or ester from 1 to 20 carbons, B.sub.i,j,w is a monomer unit derived from a co-monomer, forming a cross-linking bridge between the polymer 0 in position i and the polymer of index w in position j, C.sub.i and C.sub.j,w are monomer units derived from a co-monomer which does not form a cross-linking bridge, n.sub.i, m.sub.i, o.sub.i, n.sub.j,w, m.sub.j,w, and 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 the o.sub.i is non-zero.

13. The composition according to claim 1, comprising a polymer in which R4, R4,0 et R4,w are chosen from a chlorine atom, or the compounds of Formula XXII, ##STR00074## or comprising a polymer of Formula XXIII, ##STR00075## said polymer being of Formula I, ##STR00076## in which: A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer, varying from 1 to n, itself comprised from 2 to 10000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: carboxylic acid, or ester of 1 to 20 carbons, B.sub.i is a monomer unit derived from a co-monomer, whether or not forming a cross-linking bridge, M.sub.i is a metal, n.sub.i et m.sub.i, are integers equal to 0 or 1, n.sub.i+m.sub.i=1, x.sub.i is a number comprised 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 cross-linking bridge, said polymer being cross-linked when there is at least one B.sub.i forming a cross-linking bridge between two linear polymers, or said polymer being of Formula II ##STR00077## in which: the definitions of R.sub.i,1, R.sub.i,2, A, a, r, M.sub.i, x.sub.i, n.sub.i, m.sub.i, p.sub.i and i are as described for Formula I, B.sub.i is a monomer unit derived from a co-monomer which does not form a cross-linking bridge, or said polymer being of Formula III ##STR00078## in which: A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer, varying from 1 to n, itself comprised from 2 to 10000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: carboxylic acid, or ester of 1 to 20 carbons, M.sub.i is a metal, x.sub.i is a number comprised from 0 to 6, p.sub.i is the electrical charge of the metal complex ranging from −6 to +6, or said polymer being of Formula XVIII, ##STR00079## in which: A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, 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: carboxylic acid, or ester of 1 to 20 carbons, B is a monomer unit derived from a non-forming co-monomer cross-linking bridge, d is the degree of polymerization of the block consisting of monomer units derived from 4-vinylpyridine and a is an integer, c is the degree of polymerization of the block consisting of monomer units derived from co-monomer and b is an integer, c+d=n, or said polymer being of Formula XX, ##STR00080## in which: W is a strictly positive, indexed integer varying from 1 to the number of polymers cross-linked with the polymer of index 0, itself comprised from 1 to 1000, A.sub.0 and A.sub.w are compounds derived from polymerization initiators, a.sub.0, r.sub.0, a.sub.w and r.sub.w are identical or different and are 0 or 1, i and j, w are integers which are strictly positive, indexed, varying respectively from 1 to n.sub.i and 1 to n.sub.j,w, n.sub.i and n.sub.j,w, being comprised from 1 to 9999, n.sub.i+n.sub.j,w=n, n being comprised from 3 to 10000, 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: carboxylic acid, or ester from 1 to 20 carbons, B.sub.i,j,w is a monomer unit derived from a co-monomer, forming a cross-linking bridge between the polymer 0 in position i and the polymer of index w in position j, C.sub.i and C.sub.j,w are monomer units derived from a co-monomer which does not form a cross-linking bridge, n.sub.i, m.sub.i, o.sub.i, n.sub.j,w, m.sub.j,w, and 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 the o.sub.i is non-zero.

14. A method for the preparation of a polymer having a degree of polymerization n, ranging from 2 to 10000, and containing 2 to 10000 monomer units, said monomer units being: either monomer units derived from 4-vinylpyridine, in which the carbons in position 2 and 6 are substituted by one of the substituents of the following group: carboxylic acid, or ester of 1 to 20 carbons, or monomer units derived from a co-monomer, provided that said monomer units derived from 4-vinylpyridine represent at least 20% of the degree of polymerization n, said polymer being optionally complexed with a metal, said polymer being linear or cross-linked, said method comprising the following steps: A radical polymerization step starting with the initiation of a polymerization initiator to obtain an initiated polymerization initiator followed by the contacting of said initiated polymerization initiator with, at least one monomer derived from 4-vinylpyridine in which the carbons in position 2 and 6 are substituted by ester of 1 to 20 carbons, and optionally with at least a co-monomer, with or without cross-linking, to obtain a polymer, optionally a modification step by bringing said polymer into contact with a reagent to modify at least one of the above substituents in position 2 and/or 6, in order to obtain a optionally modified polymer, optionally a complexation step by bringing said optionally modified polymer into contact with a metal to obtain an optionally modified and optionally complexed polymer.

15. The method of preparation according to claim 14, wherein the polymer is a polymer of Formula I: ##STR00081## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer, varying from 1 to n, itself comprised from 2 to 10000, and for each i: R.sub.i,1 and R.sub.i,2 are substituents chosen from the following group: carboxylic acid, or ester of 1 to 20 carbons, B.sub.i is a monomer unit derived from a co-monomer, whether or not forming a cross-linking bridge, M.sub.i is a metal, n.sub.i et m.sub.i, are integers equal to 0 or 1, n.sub.i+m.sub.i=1, x.sub.i is a number comprised 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 cross-linking bridge, said method comprising: a step of radical polymerization starting with the initiation of a polymerization initiator then continuing with the contacting of said initiated polymerization initiator with a 4-vinylpyridine derivative of Formula XXIV, ##STR00082## in which: Z.sub.i,1 et Z.sub.i,2 are ester from 1 to 20 carbons, with optionally at least one co-monomer, with or without cross-linking bridge, to obtain the polymer of Formula XXV, ##STR00083## optionally 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 of Formula XXV with a reagent containing a hydroxide anion, carbonate or phosphate, to obtain the polymer of Formula XXVI, ##STR00084## optionally a step of complexing said polymer of Formula XXVI with at least one metallic compound to obtain the polymer of Formula I.

16. The method of preparation according to claim 14, wherein the polymer is a polymer of Formula IV: ##STR00085## in which R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, i is a strictly positive, indexed integer, varying from 1 to n, itself comprised from 2 to 10000, and for each i: M.sub.i is a metal, x.sub.i is a number comprised from 0 to 6, p.sub.i is the electrical charge of the metal complex ranging from −6 to +6, R.sub.1 et R.sub.2 are substituents chosen from the following group: carboxylic acid, or ester of 1 to 20 carbons, said method comprising: a radical polymerization step starting with the initiation of a polymerization initiator then continuing by bringing said initiated polymerization initiator into contact with a monomer derived from 4-vinylpyridine of Formula XXXI, ##STR00086## in which Z.sub.1 and Z.sub.2 are ester of 1 to 20 carbons, to obtain a polymer of Formula XXXII, ##STR00087## in which: the definitions of A, R.sub.4, i, r, and a are as described for Formula IV, 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 of Formula XXXII with a reagent containing a hydroxide, carbonate or phosphate anion, to obtain the polymer of Formula XXXIII, ##STR00088## optionally a complexing step of said polymer of Formula XXXIII with at least one metal to obtain the polymer of Formula IV, or wherein the polymer is a polymer of Formula V: ##STR00089## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, M is a metal, x is a number comprised from 0 to 6, p is the electrical charge of the metal complex ranging from −6 to +6, said method comprising: a radical polymerization step starting with the initiation of a polymerization initiator and then continuing with the contacting of said initiated polymerization initiator with 4-vinylpyridine derivative of Formula XL, ##STR00090## to obtain a polymer of Formula XII, a step of modifying said polymer of Formula XII with a base to obtain a polymer of Formula VI, a step of complexing said polymer of Formula VI with a metal to obtain a polymer of Formula V.

17. The method of preparation according to claim 14, wherein the polymer is a polymer of Formula XVIII: ##STR00091## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, 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: carboxylic acid, or ester of 1 to 20 carbons, B is a monomer unit derived from a non-forming co-monomer cross-linking bridge, d is the degree of polymerization of the block consisting of monomer units derived from 4-vinylpyridine and a is an integer, c is the degree of polymerization of the block consisting of monomer units derived from co-monomer and b is an integer, c+d=n, said method comprising: a step of radical polymerization starting with 1 priming of a polymerization initiator then continuing by bringing said initiated polymerization initiator into contact with a monomer derived from 4-vinylpyridine of Formula XXXI, ##STR00092## in which: Z.sub.1 and Z.sub.2 are ester of 1 to 20 carbons, with a polymer of Formula XXXIV, ##STR00093## in which: the definitions of A, R.sub.4, a, and r are as described for Formula XVIII, B is a monomer unit derived from a co-monomer which does not form a cross-linking bridge, c is the degree of polymerization of the polymer and c is an integer strictly lower than 0.8 n, to obtain the polymer of Formula XXXV, ##STR00094## in which: d is an integer, c+d=n, 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 of Formula XXXV with a reagent containing an anion hydroxide, carbonate or phosphate, to obtain the polymer of Formula XVIII, said method optionally comprising before the radical polymerization step by bringing a monomer derived from 4-vinylpyridine of Formula XXXI into contact with a polymer of Formula XXXIV, a radical polymerization step of a co-monomer of Formula XXXVI to obtain said polymer of Formula XXXIV, ##STR00095## wherein the definition of B is a monomer unit derived from a co-monomer which does not form a cross-linking bridge.

18. The method of preparation according to claim 14, wherein the polymer is a copolymer of Formula XIX: ##STR00096## in which: R.sub.4 is a compound allowing the propagation of the polymerization, whether or not originating from a polymerization initiator, or allowing the termination of the polymerization, or a transfer agent, A is a compound derived from said polymerization initiator or a fragment derived from the polymerization method, a and r are identical or different and are 0 or 1, d is the degree of polymerization of the block consisting of monomer units, c is the degree of polymerization of the block consisting of monomer units derived from co-monomer, said method comprising: a step of radical polymerization by bringing a polymer of Formula XLI into contact, ##STR00097## with 4-vinylpyridine derivative of Formula XL, to obtain the polymer of Formula XIX, said method optionally comprising, before the radical polymerization step by bringing a monomer derived from 4-vinylpyridine of Formula XL into contact with a polymer of Formula XLI, a step of radical polymerization of styrene, to obtain said polymer of Formula XIX.

19. The method for the preparation of a polymer, according to claim 14, in which the said radical polymerization step is a polymerization of the MP, RAFT, ATRP, SARA ATRP type or a conventional radical polymerization.

20. The method of fighting counterfeiting, comprising a step of labeling of organic and/or inorganic surfaces or luxury products with a composition comprising a polymer having a degree of polymerization n, ranging from 2 to 10000, and containing 2 to 10000 monomer units, said monomer units being: either monomer units derived from 4-vinylpyridine, in which the carbons in position 2 and 6 are substituted by one of the substituents of the following group: carboxylic acid, or ester of 1 to 20 carbons, or monomer units derived from a co-monomer, provided that said monomer units derived from 4-vinylpyridine represent at least 20% of the degree of polymerization n, said polymer being optionally complexed with a metal, said polymer being linear or cross-linked.

Description

FIGURES

(1) FIG. 1 A represents a solution of uranyl nitrate at neutral pH with UO.sub.2(NO.sub.3).sub.2 alone. (C.sub.uranyl=0.1M, λ.sub.light=254 nm, room temperature).

(2) FIG. 1B 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 poly(4-vinylpyridine-2,6-dicarboxylic acid). (C.sub.uranyl=0.1 M, C.sub.polymer=0.2 M, λ.sub.light=254 nm, room temperature). The uptake of uranyl ions is total, within the detection limit (>98%).

EXAMPLES

Example 1: Synthesis of the dimethyl 4-vinylpyridine-2,6-dicarboxylate monomer

a. Synthesis of 4-hydroxypyridine-2,6-dicarboxylic acid

(3) ##STR00049##

(4) 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

(5) ##STR00050##

(6) 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

(7) ##STR00051##

(8) 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

(9) ##STR00052##

(10) 2-Dimethyl 4-iodopyridine-2,6-dicarboxylate (6.2 mmol) is added to a flask with 1 mmol of triphenylphosphine, and 0.33 mmol of Palladium(II) acetate. These compounds are dissolved in 20 mL of a THF/water solution (Ratio 9/1). Cesium(III) carbonate (19 mmol) and potassium vinyl trifluoroborate (7.5 mmol) are added to the mixture. The medium is heated at 85° C. for 8 h with stirring, then cooled and finally filtered. The white residue obtained is washed with ethyl acetate and then concentrated. The concentrate obtained is purified on silica gel. Elution with a mixture of petroleum ether and ethyl acetate (Ratio 3/1) makes it possible to obtain the 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 (Ratio 1/10).

Example 2: Synthesis of Linear poly(4-vinylpyridine-2,6-dicarboxylic acid)

a. Synthesis of Linear poly(4-vinylpyridine-2,6-dimethyl ester)

(11) ##STR00053##

(12) 4-vinylpyridine-2,6-dimethyl ester (0.5 mmol) is dissolved in 1 ml of acetonitrile solvent. Copper(Π) chloride (0.05 μmol) is added to the solution, as well as 0.2 μmol of tri-(2-picolyl) amine and 1 cm of copper wire (D 1 mm). Benzyl chloride (halogenated initiator) is added up to 5 μmol. The reactor is heated at 25° C. for 1 h with stirring. The polymer obtained is then precipitated from a mixture of THF and methanol of molar ratio (1/1). The precipitate obtained is filtered. The radical polymerization is of SARA ATRP type. The reaction was also carried out at a temperature of 30 and 50° C.

b. Synthesis of Linear poly(4-vinylpyridine-2,6-dicarboxylic acid)

(13) ##STR00054##

(14) The precipitate obtained previously and containing the linear poly(4-vinylpyridine-2,6-dimethyl ester) is re-solubilized in 1 ml of acetonitrile then hydrolyzed with 1 ml of a 1 M NaOH solution. 2 M hydrochloric acid is added until a pH of 2 is reached. The poly(4-vinylpyridine-2,6-dicarboxylic acid) precipitates and is recovered (molar yield of 80%).

Example 3: Synthesis of Block Poly [(4-vinylpyridine-2,6-dimethyl ester)-styrene]

a. Preparation of the First Block of Polystyrene

(15) ##STR00055##

(16) 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). Benzyl chloride (halogenated initiator) is added up to 10 μL. The reactor is heated at 60° C. for 10 h with stirring. The polymer obtained is then precipitated in methanol. The precipitate is filtered. The radical polymerization is of SARA ATRP type.

b. Polymerization of the Block of 4-vinylpyridine Derivatives

(17) ##STR00056##

(18) 4-vinylpyridine-2,6-dimethyl ester (0.5 mmol) is dissolved in 1 ml of dimethylsulfoxide/sulfolane solvent (Ratio 1/1). Copper(II) chloride (0.05 μmol) is added to the solution, as well as 0.2 μmol of tri-(2-picolyl) amine and 1 cm of copper wire (D 1 mm). The precipitate from step 1 is added. The reactor is heated at 50° C. for 1 h with stirring. The polymer obtained is then precipitated in methanol. The precipitate obtained is filtered. The radical polymerization is of SARA ATRP type.

Example 4: Synthesis of the Cross-Linked poly(4-vinylpyridine-2,6-dicarboxylic acid)-1,4-divinylbenzene

(19) ##STR00057##

(20) 4-vinylpyridine-2,6-dimethyl ester (0.5 mmol) is dissolved in 1 ml of dimethylsulfoxide solvent with 0.01 mmol of 1,4-divinylbenzene. Copper(II) chloride (0.05 μmol) is added to the solution, as well as 0.2 μmol of tri-(2-picolyl) amine and 1 cm of copper wire (D 1 mm). Benzyl chloride (halogenated initiator) is added up to 5 μmol. The reactor is heated to a temperature between 60 and 80° C. with stirring until the medium gels. The gel obtained is then filtered, washed using dimethylsulfoxide and dried. The radical polymerization is of SARA ATRP type.

Example 5: Uranium Capture in Fresh Water

(21) A solution of linear poly(4-vinylpyridine-2,6-dicarboxylic acid of 80 μl to 5 M is added to a solution of distilled water of 1920 μl containing 200 μmol of uranyl nitrate UO.sub.2(NO.sub.3).sub.2. The solution has a neutral pH. After 5 minutes at room temperature, the complex of poly(2,6 dicarboxylic acid-4-vinylpyridine) and uranium precipitates. More than 98% (detection limit) of the uranium is precipitated with the polymer.

Example 6: Uranium Capture in Simulated Seawater

(22) A linear solution of poly(4-vinylpyridine-2,6-dicarboxylic acid) of 80 μl to 5 M is added to a simulated aqueous solution of seawater of 1920 μl containing 200 μmol of uranyl nitrate UO.sub.2(NO.sub.3).sub.2. The simulated seawater solution at a pH of 8 and an ionic strength of 0.44. After 5 minutes at room temperature, the complex of poly(4-vinylpyridine-2,6-dicarboxylic acid) and uranium precipitates. More than 98% (detection limit) of the uranium is precipitated with the polymer.