Particles containing reversible covalent bonds which may be sequentially formed and broken multiple times

Patent metadata

Field	Value
Publication number	US-9765163-B2
Application number	US-201214437595-A
Country	US
Kind code	B2
Filing date	Oct 23, 2012
Priority date	Oct 23, 2012
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

The present invention is directed to a particle-containing entity P-(A--B-M) x wherein P is a solid particle attached to at least one polymer M through one or several reversible covalent bonds -A---B-, wherein A and B are functional groups respectively grafted to P and M thus forming the P-(A---B-M) x particle-containing entity with x being greater than or equal to 1, M has a degree of polymerization comprised between 5 and 1000, preferably ranging from 5 to 500, and wherein the reversible covalent bond -A---B- is chosen among an imine, a disulfide, a boronic ester or an acetal. The invention is also directed to a method of preparing this particle-containing entity, a method for sequentially forming and breaking the reversible covalent bond -A---B- in said particle-containing entity P-(A---B-M) x and dispersions comprising same.

First claim

The invention claimed is:

1. A method for sequentially forming and breaking a reversible covalent bond -A---B- in a particle-containing entity P-(A---B-M) x wherein P is a solid particle attached to at least one polymer M through one or several reversible covalent bonds -A---B-,
A and B are functional groups respectively grafted to P and M thus forming the P-(A---B-M) x particle-containing entity with x being greater than or equal to 1,
M has a degree of polymerization comprised between 5 and 1000 and
wherein the reversible covalent bond -A---B- is selected from the group consisting of an imine, a disulfide, a boronic ester or an acetal and wherein one of functional groups A and B comprises an amine function, a hydroxylamine function or an imine function, and the other comprises an aldehyde function, a ketone function or an imine function so that the resulting -A---B- reversible covalent bond is an imine, said method comprising the following steps:
attaching the functional group A to the surface of the solid particle P, thereby forming A-functionalized particles P or providing said A-functionalized particles P;
attaching the functional group B to a polymer M, thereby forming B-functionalized polymers M or providing said B-functionalized polymers M, and wherein the functional group B is able to form a reversible covalent bond with the functional group A;
reacting the A-functionalized particles P with at least one B-functionalized polymer M to form a reversible covalent bond between the functional groups A and B, thereby forming the P-(A---B-M)x; and,
breaking the covalent bonds -A---B- that link the A-functionalized particles and the B-functionalized particles.

2. The method according to claim 1 , wherein the imine covalent bond can be broken by acid hydrolysis or by reaction with a competitor molecule C carrying at least one of the following functional groups: primary amine, hydroxylamine, aldehyde, ketone or imine.

3. A method for sequentially forming and breaking a reversible covalent bond -A---B- in a particle-containing entity P-(A---B-M) x wherein P is a solid particle attached to at least one polymer M through one or several reversible covalent bonds -A---B-,
A and B are functional groups respectively grafted to P and M thus forming the P-(A---B-M) x particle-containing entity with x being greater than or equal to 1,
M is a linear, branched, hyperbranched, grafted, comb-like, star-like, cyclic, a homopolymer, a block copolymer, a random copolymer, a gradient copolymer, an alternating copolymer or a multiblock copolymer and has a degree of polymerization comprised between 5 and 1000 and
wherein the reversible covalent bond -A---B- is selected from the group consisting of an imine, a disulfide, a boronic ester or an acetal and wherein one of functional groups A and B comprises an amine function, a hydroxylamine function or an imine function, and the other comprises an aldehyde function, a ketone function or an imine function so that the resulting -A---B- reversible covalent bond is an imine, said method comprising the following steps:
attaching the functional group A to the surface of the solid particle P, thereby forming A-functionalized particles P or providing said A-functionalized particles P;
attaching the functional group B to a polymer M, thereby forming B-functionalized polymers M or providing said B-functionalized polymers M, and wherein the functional group B is able to form a reversible covalent bond with the functional group A;
reacting the A-functionalized particles P with at least one B-functionalized polymer M to form a reversible covalent bond between the functional groups A and B, thereby forming the P-(A---B-M)x;
breaking the covalent bonds -A---B- that link the A-functionalized particles and the B-functionalized particles; and
recovering the A-functionalized particles P after the breaking of the covalent bond(s) -A---B- by physical separation.

4. A method, for sequentially forming and breaking a reversible covalent bond -A---B- in a particle-containing entity P-(A---B-M) x wherein P is a solid particle attached to at least one polymer M through one or several reversible covalent bonds -A---B-,
A and B are functional groups respectively grafted to P and M thus forming the P-(A---B-M) x particle-containing entity with x being greater than or equal to 1,
M has a degree of polymerization comprised between 5 and 1000 and
wherein the reversible covalent bond -A---B- is selected from the group consisting of an imine, a disulfide, a boronic ester or an acetal wherein the polymer M is a stabilizing agent capable of dispersing the particle P in a medium and the particles P are pigments selected from the group consisting of TiO 2 , Cr 2 O 3 , Fe 2 O 3 ,Fe 3 O 4 anthraquinones, phthalocyanines, perylene, quinacridone or indigoid, said method comprising the following steps:
attaching the functional group A to the surface of the solid particle P, thereby forming A-functionalized particles P or providing said A-functionalized particles P;
attaching the functional group B to a polymer M, thereby forming B-functionalized polymers M or providing said B-functionalized polymers M, and wherein the functional group B is able to form a reversible covalent bond with the functional group A;
reacting the A-functionalized particles P with at least one B-functionalized polymer M to form a reversible covalent bond between the functional groups A and B, thereby forming the P-(A---B-M)x; and,
breaking the covalent bonds -A---B- that link the A-functionalized particles and the B-functionalized particles.

Assignees

• Ecole Superieure Physique & Chimie Ind Ville De Paris
• Univ Pierre Et Marie Curie Paris 6
• Centre Nat De La Rech Scientifique—Cnrs
• Ecole Superieure De Physique Et De Chimie Ind De La Ville De Paris (Espci)

Inventors

• Nicolay Renaud
• Soulie-Ziakovic Corinne
• Leibler Ludwik
• Prevoteau Alexandre
• Griffete Nebewia

Classifications

• C09D125/06

  Polystyrene · CPC title

• C08L71/00

  Compositions of polyethers obtained by reactions forming an ether link in the main chain (of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06); Compositions of derivatives of such polymers · CPC title

• C09D171/00

  Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain (based on polyacetals C09D159/00; based on epoxy resins C09D163/00; based on polythioether-ethers C09D181/02; based on polyethersulfones C09D181/06); Coating compositions based on derivatives of such polymers · CPC title

• C08F112/08 Primary

  Styrene · CPC title

• C09B68/444

  Polyether · CPC title