Composition of cross-linked polymers comprising pending exchangeable bonds and exchangeable cross-links, via aldehyde-imine and/or imine-imine exchange reactions, preparation processes and use

Patent metadata

Field	Value
Publication number	US-9994651-B2
Application number	US-201615238969-A
Country	US
Kind code	B2
Filing date	Aug 17, 2016
Priority date	Aug 17, 2015
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

The object of the invention is a composition comprising (a) cross-linked polymers containing pending links and cross-links that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions, obtained by cross-linking of linear or branched polymers; and (b) free monofunctional aldehydes and/or free monofunctional
Another object of the invention is preparation processes of such a composition and the uses of the composition.
Another object of the invention is compositions for cross-linking linear or branched polymers and their use to form a composition comprising cross-linked polymers containing pending links and cross-links that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions.
Finally, an object of the invention is the use of aldehyde to catalyze imine-imine metathesis reactions and imine-aldehyde exchange reactions.

First claim

The invention claimed is:

1. A composition comprising:
(a) cross-linked polymers containing pending links and cross-links exchangeable by aldehyde-imine exchange reactions, imine-imine exchange reactions or aldehyde-imine and imine-imine exchange reactions, wherein the polymers, before cross-linking, are linear or branched polymers with side groups carrying:
aldehyde functional groups; or
imine functional groups linked to the polymer by the carbon atom; or
imine functional groups linked to the polymer by the nitrogen atom; or
aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom; and
(b) free monofunctional aldehydes, free monofunctional imines, or both.

2. The composition according to claim 1 , wherein the linear or branched polymers contain less than 0.5 mmol of primary amine and primary ammonium functions per gram of polymer before cross-linking.

3. The composition according to claim 1 , wherein it comprises aldehydes and that a molar fraction of at least 1% of the aldehyde functions are aromatic aldehydes.

4. A composition according to claim 1 , that arises from the mixture, in the molten state or in solution, of:
of at least one linear or branched polymer P1 with side-groups carrying:
aldehyde functional groups; or
imine functional groups linked to the polymer by the carbon atom; or
imine functional groups linked to the polymer by the nitrogen atom; or
aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom; and

of at least one additive carrying at least two functional groups, chosen from imine, aldehyde or both, that are capable of reacting with the side-groups of the polymer P1 to form a cross-linked polymer composition with links and cross-links exchangeable by aldehyde-imine exchange reactions, imine-imine exchange reactions or aldehyde-imine and imine-imine exchange reactions.

5. The composition according to claim 4 , wherein free monofunctional aldehyde is also added in the mixture.

6. The composition according to claim 4 in which the additive is chosen from
a compound of formula (I) below:

in which
n is a whole number between 1 and 6;
i is a whole number between 1 and n;
the dashed bond is present or absent, depending on the valence of Y, Z, W 1 and W 2 ;
Y and Z are different, and each represents either C or N; or Y is O and Z is C;
when Y represents C, Z represents N and R 1 represents a hydrocarbon group, R 2 represents H and R 3 is absent;
when Y represents N, Z represents C and R 1 represents H or a hydrocarbon group, R 2 is absent and R 3 represents H;
when Y represents O, Z represents C and R 1 and R 2 are absent and R 3 represents H;
R 4 represents a hydrocarbon group linked to the imine and/or aldehyde functions by a covalent bond through a carbon atom;
in each block W 1 (R′)═W 2i (R″ i )(R′″),
W 1 and W 2i are different, and each represents either C or N; or W 2i is O and W 1 is C;
when W 2i represents C, W 1 represents N and R′ is absent, R″ i represents a hydrocarbon group and R′″ represents H;
when W 2i represents N, W 1 represents C and R′ represents H, R″, represents H or a hydrocarbon group and R′″ is absent;
when W 2i represents O, W 1 represents C and R″ i and R′″ are absent and R′ represents H;

when Z represents C, W 1 represents C;
when Y represents C, W 2i represents
a linear or branched polymer P2 carrying:
aldehyde functional groups; or
imine functional groups linked to the polymer by the carbon atom; or
imine functional groups linked to the polymer by the nitrogen atom; or
aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom; and
mixtures thereof.

7. The composition according to claim 6 , in which the imine functions in polymer P1 are linked to the main chain through their carbon atoms and the additive is chosen from among: a polymer P2 in which the imine functions are linked to the main chain through their nitrogen atoms, or a compound of formula (I) in which the atoms Z and W 1 represent N.

8. The composition according to claim 6 , in which the imine functions in polymer P1 are linked to the main chain through their nitrogen atoms and the additive is chosen from among: a polymer P2 in which the imine functions are linked to the main chain through their carbon atoms, a polymer P2 in which the side groups carry aldehyde functions, a polymer P2 comprising aldehyde functional groups and imine functional groups linked to the main chain through the carbon atom, or a compound of formula (I) in which the atoms Z and W 1 represent C.

9. The composition according to claim 1 that arises from the mixture, in the molten state or in solution, of:
of at least one linear or branched polymer P1′ containing functions enabling grafting,
a combination of molecules of which the molecules comprise at one end a functional group enabling covalent binding of the molecule to the polymer P1′ and at the other end a functional group chosen from among an imine function linked by its carbon atom, an imine function linked by its nitrogen atom, or an aldehyde function, and/or molecules comprising at two of their extremities functional groups enabling covalent binding of the molecule to the polymer P1′ and between these two extremities an imine function, the combination enabling grafting and the creation of pending links and cross-links exchangeable by aldehyde-imine exchange reactions, imine-imine exchange reactions or aldehyde-imine and imine-imine exchange reactions.

10. The composition according to claim 9 , wherein free monofunctional aldehyde is also added in the mixture.

11. The composition according to claim 1 , wherein the aldehyde is a molecule in which the aldehyde function is carried by an aryl or heteroaryl group or the alkene function of a terpenoid.

12. The composition according to claim 1 , in which the polymer is chosen from vinyl polymers, polyolefins, polyamides, and polysaccharides.

13. A process for preparing a cross-linked polymer composition, said process including the following steps:
choosing a linear or branched polymer P1 with side-groups carrying:
aldehyde functional groups; or
imine functional groups linked to the polymer by the carbon atom; or
imine functional groups linked to the polymer by the carbon atom; or
aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom;

choosing at least one additive carrying at least two functional groups, chosen from imine, aldehyde or both, that are capable of reacting with the side groups of the polymer P1 to form a cross-linked polymer composition containing links and cross-links exchangeable by aldehyde-imine exchange reactions, imine-imine exchange reactions or aldehyde-imine and imine-imine exchange reactions;
mixing, in the molten state or in solution, said polymer P1, said additive to obtain the said composition.

14. The process of claim 13 , wherein a free monofunctional aldehyde is further added at the mixing step.

15. A process for preparing a cross-linked polymer composition, said process including the following steps:
choosing a linear or branched polymer P1′ containing functions enabling grafting;
choosing a combination of molecules of which the molecules comprise at one end a functional group enabling covalent binding of the mole

Assignees

• Ecole Superieure Physique & Chimie Ind Ville De Paris

Inventors

• Leibler Ludwik
• Nicolay Renaud
• Rottger Max

Classifications

• C08F220/14

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title

• C08F2438/03

  Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] · CPC title

• C09D133/062

  Copolymers with monomers not covered by C09D133/06 · CPC title

• C08K5/07

  Aldehydes; Ketones · CPC title

• C09D133/12

  Homopolymers or copolymers of methyl methacrylate · CPC title