Method for sequentially synthesising poly(alkoxyamine amide)s, copolymers obtained and uses thereof

Patent metadata

Field	Value
Publication number	US-9834642-B2
Application number	US-201414916004-A
Country	US
Kind code	B2
Filing date	Aug 29, 2014
Priority date	Sep 5, 2013
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

Synthesizing poly(alkoxyamine amide)s, which have a monomer chain with at least one thermolabile bond between monomers from an acid monomer of a monohalogenated carboxylic acid X—C(R,R′)—Y—COOH and an amine monomer having a free terminal free-radical nitroxide group >N—O ∘ and a free terminal primary amine —NH 2 . The synthesis involves two separate and chemically selective chemical reactions. One reacts the —COOH and —NH 2 groups to obtain an amide bond —NH—CO—Y—C(R, R′)—, and the other reacts the —Y—C(R, R′) ∘ free-radical with the nitroxide function >N—O ∘ in order to obtain an alkoxyamine bond —Y—C(R, R′)—O—N<. The chemical reactions are performed in alternating fashion with catalysts and a novel halogenated acid monomer X—C(R,R′)—Y—COOH or a novel free-radical amine monomer having a free terminal group >N—O ∘ and a free terminal primary amine —NH 2 , until a complete copolymer chain is obtained. Also the polymers obtained and the uses thereof.

First claim

The invention claimed is:

1. Method for synthesizing poly(alkoxyamine amide) macromolecules or copolymers comprising
(A) reacting a first monohalogenated carboxylic acid monomer of the formula X—CRR′—Y—COOH with a first amine monomer having a free terminal nitroxide free radical group (N—O—) and a terminal primary amine group (—NH 2 ) where the reacting consists of two chemical reactions, the first reaction consisting of a reaction between the —COOH groups and the —NH 2 group to form an amide group (—NH—CO—Y—CRR′—) and the second reaction consisting of a reaction between the halogen X on the monohalogenated carboxylic acid monomer (—Y—CRR′—X) with a catalyst to form a radical (—Y—CRR′—) which reacts with the nitroxide free radical group (N—O—) to form an alkoxyamine group (—Y—CRR′—O—N—),
(B) repeating the reaction of step (A) with the same or a different monohalogenated carboxylic acid monomer and the same or a different amine monomer to form a poly(alkoxyamine amide) macromolecule or copolymer,
where each X is independently a halogen,
where each R is independently selected from the group consisting of H, CH 3 , an alkyl group that has 2 to 6 carbon atoms optionally substituted,
where each R′ is independently selected from the group consisting of H,CH 3 , an alkyl group that has 2 to 6 carbon atoms optionally substituted,
where each Y is independently selected from the group consisting of a covalent bond and —COO—Z— where Z is a linear, branched, or cyclic hydrocarbon chain with 1 to 15 carbon atoms which is optionally substituted by a functional group selected from the group consisting of —OH,

—NH 3 , —COOH, —CN, an alkyne group, an alkene group —N 2 , —SO 3 ,
where the poly(alkyoxyamine amide) macromolecule or copolymer has at least one thermolabile bond between the monomers where the thermolabile bond has a dissociation temperature and the dissociation temperature is greater than 30° C. and less than 150° C.,
and where the reaction of step (A) takes place in solution or on a solid substrate.

2. The method according to claim 1 , wherein the reaction of step (A) is initiated on a solid substrate equipped with a chemically reactive primer group, which reacts with either the first amine or the first monohalogenated carboxylic acid monomer to fix a monomer to the substrate.

3. The method according to claim 2 , wherein the chemically reactive primer group on the solid substrate is selected from the group consisting of —NH 2 , —Br, —Cl, —COOH, and a terminal free radical nitroxide.

4. The method according to claim 1 , wherein for the first monohalogenated carboxylic acid X—C(R,R′)—Y—COOH, X is independently selected from the group consisting of Br and Cl.

5. The method according to claim 4 , wherein prior to step (A), the first monohalogenated carboxylic acid is obtained by separating the first monohalogenated carboxylic acid from a corresponding dihalogenated symmetrical anhydride of the formula X—CRR′—Y—CO—O—CO—Y—CRR′—X.

6. The method according to claim 1 , wherein the catalyst that is used is a halogenated metal salt.

7. The method according to claim 1 , wherein the first amine monomer is selected from the group consisting of:

8. The method according to claim 1 , wherein first monohalogenated carboxylic acid monomer is Br—C(CH 3 ) 2 —COOH and first amine monomer is

and the catalyst is CuBr.

9. Poly(alkoxyamine amide) that is obtained by the method according to claim 1 .

10. The poly(alkoxyamine amide) according to claim 9 , comprising more than one different monohalogenated carboxylic acid monomer and more one than different amine monomer resulting in more than one thermolabile bond.

11. The poly(alkoxyamine amide) according to claim 10 , wherein the more than one thermolabile bonds have identical or different dissociation temperatures.

12. A method of making a coded message or data store, comprising forming an element of a code or data to be stored from the poly(alkoxyamine amide) according to claim 9 , wherein said element is selected from the group consisting of a binary code, a multinary code, a letter and a sign of the alphanumeric.

13. The method according to claim 12 , wherein the thermolabile bond(s), during a heating stage of the poly(alkoxyamine amide) above a dissociation temperature of said thermolabile bond(s), breaks said thermolabile bond(s) and thus at least alters permanently the coded message or the stored data resulting in the coded message or the stored data becoming at least partially incomprehensible and/or unusable.

14. A coded message or data store, comprising the poly(alkoxyamine amide) correspond to claim 9 , wherein different monomers of the poly(alkoxyamine amide) correspond to a predefined element of said code or data to be stored, and wherein thermolabile bond(s) of the poly(alkoxyamine amide) during a heating stage of the poly(akoxyamine amide) above a dissociation temperature of said thermolabile bond(s), breaks said thermolabile bond(s) and thus at least alters permanently the coded message or the stored data in such a way that the coded message or the stored data becomes at least partially incomprehensible and/or unusable.

Assignees

• Centre National De La Recherche Scientifique (Etablissement Public National À Caractère Scientifique
• Centre Nat Rech Scient

Inventors

• Lutz Jean-Francois
• Meszynska Anna

Classifications

• H04K1/00

  Secret communication · CPC title

• C08G69/00 Primary

  Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule (products obtained from isocyanates or isothiocyanates C08G18/00; polyamide-imides C08G73/14) · CPC title

• G09C5/00

  Ciphering apparatus or methods not provided for in the preceding groups, e.g. involving the concealment or deformation of graphic data such as designs, written or printed messages · CPC title