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

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.

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.