Polymer composition comprising crosslinked silicones with exchangeable crosslinking points, preparation method and uses

Abstract

The invention relates to a silicone composition comprising (a) crosslinked polymers comprising consecutive SiO units containing exchangeable pendant bonds and exchangeable crosslinking points, that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions, obtained by crosslinking linear or branched polymers comprising consecutive SiO units and (b) monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines.

Claims

1. A silicone composition comprising (a) crosslinked polymers comprising consecutive SiO units containing exchangeable pendant bonds and exchangeable crosslinking points, that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions, obtained by crosslinking of linear or branched polymers comprising consecutive SiO units and (b) monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines.

2. The composition according to claim 1, wherein said composition comprises aldehydes and wherein at least 1 mol % of the aldehyde functions are aromatic aldehyde functions.

3. The composition according to claim 1, wherein the crosslinked polymers, before crosslinking, are linear or branched polymers having side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by the carbon atom, or imine functional groups bound to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups bound to the polymer by the carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom.

4. The composition according to claim 1, wherein said composition results from mixing, in the molten state or in solution, of: at least one linear or branched silicone polymer, comprising consecutive SiO units P1 having side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by the carbon atom, or imine functional groups bound to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups bound to the polymer by the carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom; and at least one additive bearing at least two imine and/or aldehyde and/or primary amine functional groups able to react with the side groups of the silicone polymer P1 to form a composition of crosslinked polymers with exchangeable bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions or by imine-imine exchange reactions or by imine-primary amine exchange reactions; optionally, monofunctional free aldehydes.

5. The composition according to claim 4, wherein the additive is a compound of formula (I) or of formula (II) or a mixture of these compounds, the formulas (I) and (II) meeting the following definitions: ##STR00018## in which: n, n is an integer varying from 1 to 6; i is an integer varying from 1 to n; the bonds in dashed lines are present or absent, as a function of the valency of Y, Z, W.sub.1, W.sub.2i; Y and Z are different and each represents either C or N, or Y is O and then Z is C: when Y represents C, then Z represents N, and R.sub.1 represents a hydrocarbon group, R.sub.2 represents H and R.sub.3 is absent, when Y represents N, then Z represents C, and R.sub.1 represents H or a hydrocarbon group, R.sub.2 is absent and R.sub.3 represents H, when Y is O, then Z is C and, R.sub.1, R.sub.2 are absent and R.sub.3 represents H; R.sub.4 and R.sub.4 represent a hydrocarbon group bound to the amine and/or imine and/or aldehyde functional groups by a covalent bond via a carbon atom; in each block W.sub.1(R)W.sub.2i(R.sub.i)(R): W.sub.1 and W.sub.2i are different and each represents either C or N, or W.sub.2i is O and then W.sub.1 is C: when W.sub.2i represents C, then W.sub.1 represents N and R is absent, R.sub.i represents a hydrocarbon group and R represents H, when W.sub.2i represents N, then W.sub.1 represents C and R represents H, R.sub.i represents H or a hydrocarbon group, and R is absent, when W.sub.2i is O, then W.sub.1 is C and R.sub.i, R are absent and R represents H; when Z represents C, then W.sub.1 represents C, when Y represents C, then W.sub.2i represents C; and when the additive is a mixture of compounds of formula (I) and of formula (II) then the compound of formula (I) Z represents N and W.sub.1 represents N.

6. The composition according to claim 5, wherein: the silicone polymer P1 has side groups bearing imine functional groups bound to the main chain by their carbon atoms and the additive is selected from: a silicone polymer P2 of which the side groups bear imine functional groups bound to the main chain by their nitrogen atoms, a silicone polymer P2 of which the side groups bear primary amine functional groups, a silicone polymer P2 comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the main chain by their nitrogen atoms, a compound of formula (I) in which the atoms Z and W.sub.1 represent N, a compound of formula (II), a mixture of compounds of formula (II) and of formula (I) in which the atoms Z and W.sub.1 represent N, or a mixture of these additives; the silicone polymer P1 has side groups bearing imine functional groups bound to the main chain by their nitrogen atoms and the additive is selected from: a silicone polymer P2 of which the side groups bear imine functional groups bound to the main chain by their carbon atoms, a silicone polymer P2 of which the side groups bear aldehyde functional groups, a silicone polymer P2 comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom, a compound of formula (I) in which the atoms Z and W1 represent C or a mixture of these additives; the silicone polymer P1 has side groups bearing aldehyde functional groups and the additive is selected from: a silicone polymer P2 having side groups bearing imine functional groups bound to the main chain by their nitrogen atoms, a silicone polymer P2 comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the polymer by the nitrogen atom, a compound of formula (I) in which the atoms Z and W1 represent N or a mixture of these additives; the silicone polymer P1 has side groups bearing primary amine functional groups and the additive is a silicone polymer P2 comprising side groups bearing imine functional groups bound to the polymer by the carbon atom, a silicone polymer P2 comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom, a compound of formula (I) in which the atoms Z and W1 represent C and, Y and one W2i at least represents N, the other W2i represents, each independently of each other, N or O where appropriate or a mixture of these additives; the silicone polymer P1 has side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the main chain by their carbon atoms and the additive is a silicone polymer P2 comprising side groups bearing primary amine functional groups, a silicone polymer P2 comprising side groups bearing imine functional groups bound to the polymer by the nitrogen atom, a silicone polymer P2 comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the polymer by the nitrogen atom, a compound of formula (I) in which the atoms Z and W1 represent N, a compound of formula (II), a mixture of compounds of formula (II) and of formula (I) in which the atoms Z and W1 represent N or a mixture of these additives; or the silicone polymer P1 has side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the main chain by their nitrogen atoms and the additive is a silicone polymer P2 comprising side groups bearing aldehyde functional groups, a silicone polymer P2 comprising side groups bearing imine functional groups bound to the polymer by the carbon atom, a silicone polymer P2 comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom, a compound of formula (I) in which the atoms Z and W1 represent C or a mixture of these additives.

7. Combinations for crosslinking linear or branched silicone polymers, comprising consecutive SiO units, said combinations being selected from combinations comprising: a monofunctional free aldehyde+compound of formula (I), as defined in claim 5; compound of formula (II)+compound of formula (I) in which Z represents N and W1 represents N, as defined in claim 5; A and/or B+compound of formula (I) for which Z and W1 are N, and optionally a monofunctional free aldehyde, as defined in claim 5; A, optionally B, +compound of formula (II) and optionally a monofunctional free aldehyde, as defined in claim 5; or C and/or E+compound of formula (I) for which Z and W1 are C, and optionally a monofunctional free aldehyde, as defined in claim 5; A, B, C, D, E meeting the following formulas: (A) G.sub.1-Rx-CHN-Ry, (B) G.sub.2-Rx-CHO, (C) G.sub.3-Ry-NCHRx and (E) G.sub.6-Rw-NH.sub.2, where the letters G.sub.1, G.sub.2, G.sub.3, and G.sub.6 represent a functional group making it possible to bond in a covalent manner the molecules to the polymer chains to functionalise, Rx, Rx, Rx and Ry, Ry, Rw are hydrocarbon groups.

8. A method for forming a composition comprising crosslinked polymers containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; and monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines, comprising using a combination as defined in claim 7, in the presence of a linear or branched silicone polymer, comprising consecutive SiO units P1 or P1, wherein: the consecutive SiO units P1 have side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by the carbon atom, or imine functional groups bound to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups bound to the polymer by the carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom; and the consecutive SiO units P1 comprise functional groups enabling grafting.

9. The method according to claim 8, further comprising modifying a rheology of the composition by including an oil, a paint or a cosmetic formulation therein.

10. The composition according to claim 4, wherein the additive is a linear or branched silicone polymer P2, comprising consecutive SiO units, having side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by the carbon atom, or imine functional groups bound to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups bound to the polymer by the carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom.

11. Combinations for crosslinking linear or branched silicone polymers, comprising consecutive SiO units, said combinations comprising a monofunctional free aldehyde+silicone polymer P2, as defined in claim 10.

12. A method for forming a composition comprising crosslinked polymers containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; and monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines, comprising using a combination as defined in claim 11, in the presence of a linear or branched silicone polymer, comprising consecutive SiO units P1 or P1, wherein: the consecutive SiO units P1 have side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by the carbon atom, or imine functional groups bound to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups bound to the polymer by the carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom; and the consecutive SiO units P1 comprise functional groups enabling grafting.

13. The method according to claim 12, further comprising modifying a rheology of the composition by including an oil, a paint or a cosmetic formulation therein.

14. A method for forming a composition comprising crosslinked silicone polymers, comprising consecutive SiO units containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions, monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines comprising using an additive as defined in claim 4 in the presence of a linear or branched silicone polymer, the linear or branched silicone polymer comprising the consecutive SiO units P1 as defined in claim 4 or consecutive SiO units P1 comprising functional groups enabling grafting.

15. The composition according to claim 1, wherein said composition results from mixing, in the molten state or in solution, of: at least one linear or branched silicone polymer P1, comprising consecutive SiO units, and comprising functional groups enabling grafting; and a combination of molecules including molecules comprising at one end a functional group making it possible to bond in a covalent manner the molecule to the polymer P1 and at the other end a functional group selected from an imine function bound to the molecule by its carbon atom, an imine function bound to the molecule by its nitrogen atom, an aldehyde function or a primary amine function, and/or molecules comprising at two of their ends functional groups making it possible to bond in a covalent manner the molecule to the polymer P1 and between its two ends an imine function, the combination having to enable the grafting and the creation of exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; optionally, monofunctional free aldehydes.

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

17. A method for catalysing the imine-imine metathesis reactions and imine-aldehyde exchange reactions carried out in the compositions defined in claim 1, which comprises using aldehyde.

18. A material obtained from the composition according to claim 1.

19. A formulation comprising the composition according to claim 1.

20. Combinations for crosslinking linear or branched silicone polymers, comprising consecutive SiO units said combinations being selected from combinations comprising: A and/or B+C, and optionally a monofunctional free aldehyde as defined in claim 1; A, optionally B, +C and/or E, and optionally a monofunctional free aldehyde as defined in claim 1; or A and/or B and/or C+D and/or E, and optionally a monofunctional free aldehyde as defined in claim 1; A, B, C, D, E meeting the following formulas: (A) G.sub.1-Rx-CHN-Ry, (B) CHO, (C) G.sub.3-Ry-NCHRx, (D) G.sub.4-Rx-CHNRy-G.sub.5 and (E) G.sub.6-Rw-NH.sub.2, where the letters G.sub.1, G.sub.2, G.sub.3, G.sub.4, G.sub.5 and G.sub.6 represent a functional group making it possible to bond in a covalent manner the molecules to the polymer chains to functionalise, Rx, Rx, Rx, Rx and Ry, Ry, Ry, Rw are hydrocarbon groups.

21. A method for forming a composition comprising crosslinked polymers containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; and monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines, comprising using a combination as defined in claim 20, in the presence of a linear or branched silicone polymer, comprising consecutive SiO units P1 or P1, wherein: the consecutive SiO units P1 have side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by the carbon atom, or imine functional groups bound to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups bound to the polymer by the carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom; and the consecutive SiO units P1 comprise functional groups enabling grafting.

22. A method according to claim 21, further comprising modifying a rheology of the composition by including an oil, a paint or a cosmetic formulation therein.

23. A method for preparing a composition of crosslinked silicone polymers, comprising consecutive SiO units, said method comprising: choosing a linear or branched silicone polymer, comprising consecutive SiO units P1 having side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by the carbon atom, or imine functional groups bound to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups bound to the polymer by the carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom; choosing at least one additive bearing at least two imine and/or aldehyde and/or primary amine functional groups able to react with the side groups of the polymer P1 to form a composition of crosslinked polymers containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; and mixing, in the molten state or in solution, said polymer P1, said additive and, optionally a monofunctional free aldehyde to obtain said composition.

24. A method for preparing a composition of crosslinked polymers, said method comprising the following steps: choosing a linear or branched silicone polymer, comprising consecutive SiO units P1 comprising functional groups enabling grafting; choosing a combination of molecules including molecules comprising at one end a functional group making it possible to bond in a covalent manner the molecule to the polymer P1 and at the other end a functional group selected from an imine function bound to the molecule by its carbon atom, an imine function bound to the molecule by its nitrogen atom, an aldehyde function, or a primary amine function and/or molecules comprising at two of their ends functional groups making it possible to bond in a covalent manner the molecule to the polymer P1 and between these two ends an imine function, the combination having to enable the grafting and the creation of exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; and mixing, in the molten state or in solution, said polymer P1, said combination and optionally a monofunctional free aldehyde, to obtain said composition.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1. Representation of molecules being able to be used for the functionalisation and the crosslinking in one step of the polymers P1.

(2) FIG. 2. Schematic representation of the functionalisation of linear polymers P1 by the molecule A (left), respectively the molecule C (right), via the creation of covalent bonds between the molecules A, respectively C, and the polymer chains. The functions enabling the grafting of the molecules A (left), respectively the molecule C (right), may form part of the main chain (top) or side/pendant groups (bottom) of the linear polymer to functionalise.

(3) FIG. 3. Schematic representation of the crosslinking by metathesis reaction of linear polymers functionalised by complementary pendant imine functions.

DETAILED DESCRIPTION

(4) The object of the invention is a silicon composition comprising (a) crosslinked polymers comprising consecutive SiO units containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions, obtained by crosslinking of linear or branched polymers comprising consecutive SiO units, (b) monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines. The crosslinking results, in part or totally, from metathesis reactions between the imine functions and/or exchange reactions between the imine and aldehyde functions and/or exchange reactions between the imine and primary amine functions borne by the pendant groups of the polymers and/or borne by the pendant groups of the polymers and the compounds of formula (I) and/or (II). Thus, for any crosslinking reaction by metathesis reaction between imine functions, respectively for any crosslinking reaction by exchange reaction between imine and aldehyde functions, respectively for any crosslinking reaction by exchange reaction between imine and primary amine functions, one equivalent of monofunctional free imine, respectively one equivalent of monofunctional free aldehyde, respectively one equivalent of monofunctional free primary amine, is generated, as illustrated by FIG. 3 in the case of the crosslinking by metathesis reaction of linear polymers functionalised by complementary pendant imine functions. Such a composition advantageously forms a network of crosslinked linear or branched polymers containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions.

(5) The polymers, before crosslinking, are advantageously linear or branched polymers having side groups bearing: aldehyde functional groups, or pendant imine functional groups bound to the polymers by their carbon atom, or pendant imine functional groups bound to the polymers by their nitrogen atom, or pendant aldehyde functional groups and imine functional groups bound to the polymers by their carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom.

(6) These polymers may be functionalised prior to and/or during crosslinking advantageously leading to the formation of a network of crosslinked polymers containing exchangeable crosslinking points and exchangeable pendant bonds that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions.

(7) The side groups exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions of linear or branched polymers are advantageously spread out over the whole of the chain. Thus, preferably, the linear or branched polymers do not have a di-block structure, with one block containing side groups and one block not containing side groups exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions. Preferably, the side groups exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions are spread out in a random manner over the whole of the polymer chain. Preferably, if the side groups exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions are spread out in blocks, then the polymer has a multiblock structure with blocks containing exchangeable side groups spread out all along the polymer chain.

(8) When the polymers before crosslinking are branched polymers, these polymers are advantageously not dendrimers. When the branched polymers before crosslinking are dendrimers, these dendrimers are advantageously third generation dendrimers or second generation dendrimers.

(9) In a first alternative, the polymer is functionalised before crosslinking. In particular, the composition results from the mixing, in the molten state or in solution, of: at least one linear or branched polymer P1 having side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by their carbon atom, or imine functional groups bound to the polymer by their nitrogen atom, aldehyde functional groups and imine functional groups bound to the polymer by their carbon atom, primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom. at least one additive bearing at least two pendant imine and/or aldehyde and/or primary amine functional groups able to react with the pendant groups of the polymer P1 to form the composition of crosslinked polymers, advantageously a crosslinked network, containing crosslinking points and exchangeable pendant bonds that are exchangeable by aldehyde-imine and/or imine-imine and/or imine-primary amine exchange reactions Advantageously, monofunctional free aldehydes.

(10) To enable the formation of a composition of crosslinked polymers, advantageously a network of crosslinked polymers, with exchangeable bonds, as additive is advantageously used a crosslinking means which, used alone, is not going to react with itself and lose its functionalities. Thus, the crosslinking means bear: aldehyde functions, or imine functions bound by means of their carbon atom, or imine functions bound by means of their nitrogen atom, or aldehyde functions and imine functions bound by means of their carbon atom, or primary amine functions, or primary amine functions and imine functions bound by means of their nitrogen atom.

(11) The additive, crosslinking means, may be a molecule and/or a polymer. Where appropriate, combinations of molecules and/or polymers may be envisaged.

(12) In a first alternative, the additive is a molecule comprising at least two imine and/or aldehyde functions. This additive is also designated bi- or multifunctional crosslinking means. This additive may comprise uniquely imine functions, all bound to the remainder of the molecule by the carbon atom of the imine bond, or uniquely imine functions, all bound to the remainder of the molecule by the nitrogen atom of the imine bond, or uniquely aldehyde functions. It may also comprise both aldehyde functions and imine functions, all bound to the remainder of the molecule by the carbon atom of the imine bond.

(13) This additive is advantageously a compound of following formula (I):

(14) ##STR00005## in which n is an integer varying from 1 to 6; i is an integer varying from 1 to n the bonds in dashed lines are present or absent, as a function of the valency of Y, Z, W.sub.1, W.sub.2i Y and Z are different and each represents either C or N, or Y is O and then Z is C when Y represents C, then Z represents N, and R.sub.1 represents a hydrocarbon group, R.sub.2 represents H and R.sub.3 is absent, when Y represents N, then Z represents C, and R.sub.1 represents H or a hydrocarbon group, R.sub.2 is absent and R.sub.3 represents H, when Y is O, then Z is C and, R.sub.1, R.sub.2 are absent and R.sub.3 represents H R.sub.4 represents a hydrocarbon group bound to the imine and/or aldehyde functions by a covalent bond via a carbon atom in each block W.sub.1(R)W.sub.2i(R.sub.i)(R), W.sub.1 and W.sub.2i are different and each represents either C or N, or W.sub.2i is O and then W.sub.1 is C when W.sub.2i represents C, then W.sub.1 represents N and R is absent, R.sub.i represents a hydrocarbon group and R represents H, when W.sub.2i represents N, then W.sub.1 represents C and R represents H, R.sub.i represents H or a hydrocarbon group, and R is absent, when W.sub.2i is O, then W.sub.1 is C and R.sub.i, R are absent and R represents H

(15) when Z represents C, then W.sub.1 represents C,

(16) when Y represents C, then W.sub.2i represents C.

(17) R.sub.4 may in particular represent a ring thereby enabling the presence of several blocks [W.sub.1(R)W.sub.2i(R.sub.i)(R)], optionally on each carbon atom of the ring.

(18) The block [W.sub.1(R)W.sub.2i(R.sub.i)(R)] is present n times as a function of the number of possible substitutions on the radical R.sub.4. The compound (I) may thus be a compound called star-shaped.

(19) n is an integer varying from 1 to 6, preferably from 1 to 4.

(20) i is an integer varying from 1 to n.

(21) From one block to the other (and thus for different values of i), the definition of W.sub.2i or R.sub.i can vary, which signifies that the blocks are not necessarily identical to each other. Conversely, the definition of W.sub.1 cannot vary from one block to the other, either always C, or always N. Similarly the definition of R cannot vary from one block to the other, either always H, or always absent. Similarly, the definition of R cannot vary from one block to the other, either always H, or always absent.

(22) R.sub.4 may be bound to the carbon atom or to the nitrogen atom of the imine and/or aldehyde functions. R.sub.4 is bound to the imine and/or aldehyde functions by a covalent bond via a carbon atom. R.sub.4 is advantageously an aliphatic, aromatic, arylaliphatic or cycloaliphatic group that may also comprise heteroatoms such as O, N, S, or Si. In an advantageous alternative, R.sub.4 represents an aromatic or heteroaromatic group. Advantageously, R.sub.4 represents a C.sub.1-C.sub.12 alkanediyl group, a benzene ring, a naphthalene ring, an arylaliphatic group composed of two benzene rings bound by a C.sub.1-C.sub.6 alkanediyl group, a pyrimidine ring, a triazine ring.

(23) Advantageously, when Y represents O, then Z represents C, W.sub.1 represents C, W.sub.2i represents O, R.sub.1, R.sub.2, R.sub.i, R are absent and R.sub.3 and R represent H.

(24) Advantageously, when Y represents N or O, then Z represents C, W.sub.1 represents C, W.sub.2i represents N or O, R.sub.2 and R are absent, R.sub.3 and R represent H, and, as a function of the valency of Y, W.sub.2i, R.sub.1 and R.sub.i represent a hydrocarbon group or are absent when Y and W.sub.2i represent O.

(25) Advantageously, when Y represents C, then Z represents N, W.sub.1 represents N, W.sub.2i represents C, R.sub.3 and R are absent, R.sub.2 and R represent H, R.sub.1 and R.sub.i represents a hydrocarbon group.

(26) When it is present, advantageously R.sub.1 represents a hydrogen atom, an alkyl, alkenyl, aryl, cycloalkyl, heteroaryl, heteroalkyl, heterocycloalkyl group, each of these groups may be substituted. R.sub.2 represents H or is absent. R.sub.3 represents H or is absent. Preferably, R.sub.1 represents an alkyl, alkenyl, aryl, heteroaryl, alkyl-aryl, heteroalkyl-aryl, aralkyl, heteroarlalkyl, cycloalkyl or heterocycloalkyl group; each of these groups may be substituted.

(27) When it is present, advantageously R, represents a hydrogen atom, an alkyl, alkenyl, aryl, cycloalkyl, heteroaryl, heteroalkyl, heterocycloalkyl group, each of these groups may be substituted. R represents H or is absent. R represents H or is absent. Preferably, R.sub.i represents an alkyl, alkenyl, aryl, heteroaryl, alkyl-aryl, heteroalkyl-aryl, aralkyl, heteroarlalkyl, cycloalkyl or heterocycloalkyl group; each of these groups may be substituted.

(28) Alternatively or in addition, the additive is a molecule comprising a primary amine function. This additive is advantageously a compound of following formula (II):

(29) ##STR00006## in which n is an integer varying from 1 to 6; R.sub.4 represents a hydrocarbon group bound to the amine functions by a covalent bond via a carbon atom

(30) R.sub.4 may in particular represent a ring thereby enabling the presence of several blocks [NH.sub.2], optionally on each carbon atom of the ring.

(31) The block [NH.sub.2] is present n times as a function of the number of possible substitutions on the radical R.sub.4. The compound (II) may thus be a so-called star-shaped compound.

(32) n is an integer varying from 1 to 6, preferably from 1 to 4.

(33) R.sub.4 is bound to the primary amine functions by a covalent bond via a carbon atom. R.sub.4 is advantageously an aliphatic, aromatic, arylaliphatic or cycloaliphatic group that may also comprise heteroatoms such as O, N, S, or Si. In an advantageous alternative, R.sub.4 represents an aromatic or heteroaromatic group. Advantageously, R.sub.4 represents a C.sub.1-C.sub.12 alkanediyl group, a benzene ring, a naphthalene ring, an arylaliphatic group composed of two benzene rings bound by a C.sub.1-C.sub.6 alkanediyl group, a pyrimidine ring, a triazine ring.

(34) When the compound of formula (II) is used in a mixture with the compound of formula (I), then the compound of formula (I) is such that Z represents N and W.sub.1 represents N.

(35) The choice of the nature of the functional groups present on the compound of formula (I) and the choice of the compounds (I), (II) or mixtures thereof, is going to depend on the nature of the functional groups present on these side groups of the polymer P1.

(36) Thus, when the pendant groups of the polymer P1 bear aldehyde functional groups, as additive is chosen a compound of formula (I) in which Z and W.sub.1 represent N.

(37) Thus, when the pendant groups of the polymer P1 bear imine functional groups bound to the main chain by the carbon atom, as additive is chosen a compound of formula (I) in which Z and W.sub.1 represent N, a compound of formula (II) or a mixture of compound of formula (I) in which Z and W.sub.1 represent N and compound of formula (II).

(38) Thus, when the pendant groups of the polymer P1 bear aldehyde functional groups and imine functional groups bound to the main chain by the carbon atom, as additive is chosen a compound of formula (I) in which Z and W.sub.1 represent N, a compound of formula (II) or a mixture of compound of formula (I) in which Z and W.sub.1 represent N and compound of formula (II).

(39) Thus, when the pendant groups of the polymer P1 bear imine functional groups bound to the main chain by the nitrogen atom, as additive is chosen a compound of formula (I) in which Z and W.sub.1 represent C, Y and W.sub.2i represent, each independently of each other, N or O.

(40) Thus, when the pendant groups of the polymer P1 bear primary amine functional groups, as additive a compound is chosen of formula (I) in which Z and W.sub.1 represent C, Y and one W.sub.2i at least represents N, the other W.sub.2i represents, each independently of each other, N or O where appropriate.

(41) Thus, when the pendant groups of the polymer P1 bear primary amine functional groups and imine functional groups bound to the main chain by the nitrogen atom, as additive is chosen a compound of formula (I) in which Z and W.sub.1 represent C, Y and W.sub.2i represent, each independently of each other, N or O.

(42) In a second alternative, the additive is a polymer P2 bearing: aldehyde functional groups, or pendant imine functional groups bound to the polymer by the carbon atom, or pendant imine functional groups bound to the polymer by the nitrogen atom, or pendant aldehyde functional groups and pendant imine functional groups bound to the polymer by the carbon atom, or primary amine functions, or primary amine functions and imine functions bound by means of their nitrogen atom.

(43) The choice of the nature of the functional groups present on the polymer P2 is going to depend on the nature of the functional groups present on the polymer P1.

(44) Thus, when the pendant groups of the polymer P1 bear aldehyde functional groups, as polymer P2 is chosen a silicone having side groups bearing imine functional groups bound to the main chain by their nitrogen atoms, a silicone comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the polymer by the nitrogen atom.

(45) Thus, when the pendant groups of the polymer P1 bear imine functional groups bound to the main chain by the carbon atom, as polymer P2 is chosen a silicone of which the side groups bear imine functional groups bound to the main chain by their nitrogen atoms, a silicone of which the side groups bear primary amine functional groups, a silicone comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the main chain by their nitrogen atoms.

(46) Thus, when the pendant groups of the polymer P1 bear aldehyde functional groups and imine functional groups bound to the main chain by the carbon atom, as polymer P2 is chosen a silicone comprising side groups bearing primary amine functional groups, a silicone comprising side groups bearing imine functional groups bound to the polymer by the nitrogen atom, a silicone comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the main chain by their nitrogen atoms.

(47) Thus, when the pendant groups of the polymer P1 bear imine functional groups bound to the main chain by the nitrogen atom, as polymer P2 is chosen a silicone of which the side groups bear imine functional groups bound to the main chain by their carbon atoms, a silicone of which the side groups bear aldehyde functional groups, a silicone comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom.

(48) Thus, when the pendant groups of the polymer P1 bear primary amine functional groups, as polymer P2 is chosen a silicone comprising side groups bearing imine functional groups bound to the polymer by the carbon atom, a silicone comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom.

(49) Thus, when the pendant groups of the polymer P1 bear primary amine functional groups and imine functional groups bound to the main chain by their nitrogen atoms, as polymer P2 is chosen a silicone comprising side groups bearing aldehyde functional groups, a silicone comprising side groups bearing imine functional groups bound to the polymer by the carbon atom, a silicone comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom.

(50) The invention thus makes it possible to assemble, by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions, two linear or branched polymers, even if the chemical natures of the polymers are different. It may also be envisaged to assemble a polymer composition according to the invention with a linear or branched polymer P2 according to the same principle. This principle may be extended to two compositions according to the invention which may be assembled.

(51) The additives are advantageously selected such that: the silicone polymer P1 has side groups bearing imine functional groups bound to the main chain by their carbon atoms and the additive is selected from: a silicone polymer P2 of which the side groups bear imine functional groups bound to the main chain by their nitrogen atoms, a silicone polymer P2 of which the side groups bear primary amine functional groups, a silicone polymer P2 comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the main chain by their nitrogen atoms, a compound of formula (I) in which the atoms Z and W.sub.1 represent N, a compound of formula (II), a mixture of compounds of formula (II) and of formula (I) in which the atoms Z and W.sub.1 represent N, or a mixture of these additives; the silicone polymer P1 has side groups bearing imine functional groups bound to the main chain by their nitrogen atoms and the additive is selected from: a silicone polymer P2 of which the side groups bear imine functional groups bound to the main chain by their carbon atoms, a silicone polymer P2 of which the side groups bear aldehyde functional groups, a silicone polymer P2 comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom, a compound of formula (I) in which the atoms Z and W.sub.1 represent C, or a mixture of these additives; the silicone polymer P1 has side groups bearing aldehyde functional groups and the additive is selected from: a silicone polymer P2 having side groups bearing imine functional groups bound to the main chain by their nitrogen atoms, a silicone polymer P2 comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the polymer by the nitrogen atom, a compound of formula (I) in which the atoms Z and W.sub.1 represent N or a mixture of these additives; the silicone polymer P1 has side groups bearing primary amine functional groups and the additive is a silicone polymer P2 comprising side groups bearing imine functional groups bound to the polymer by the carbon atom, a silicone polymer P2 comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom, a compound of formula (I) in which the atoms Z and W.sub.1 represent C and, Y and one W.sub.2i at least represents N, the other W.sub.2i represents, each independently of each other, N or O where appropriate, or a mixture of these additives; the silicone polymer P1 has side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the main chain by their carbon atoms and the additive is a silicone polymer P2 comprising side groups bearing primary amine functional groups, a silicone polymer P2 comprising side groups bearing imine functional groups bound to the polymer by the nitrogen atom, a silicone polymer P2 comprising side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the polymer by the nitrogen atom, a compound of formula (I) in which the atoms Z and W.sub.1 represent N, a compound of formula II, a mixture of compounds of formula (II) and of formula (I) in which the atoms Z and W.sub.1 represent N or a mixture of these additives; the silicone polymer P1 has side groups bearing primary amine functional groups and side groups bearing imine functional groups bound to the main chain by their nitrogen atoms and the additive is a silicone polymer P2 comprising side groups bearing aldehyde functional groups, a silicone polymer P2 comprising side groups bearing imine functional groups bound to the polymer by the carbon atom, a silicone polymer P2 comprising side groups bearing aldehyde functional groups and side groups bearing imine functional groups bound to the polymer by the carbon atom, a compound of formula (I) in which the atoms Z and W.sub.1 represent C, or a mixture of these additives.

(52) In a second alternative, the functionalisation and the crosslinking are conducted simultaneously.

(53) In particular, the composition results from the mixing, in the molten state or in solution, of: At least one linear or branched silicone polymer P1, comprising consecutive SiO units, and comprising functions enabling grafting; A combination of molecules including molecules comprising at one end a functional group making it possible to bond in a covalent manner the molecule to the polymer P1 and at another end a functional group selected from an imine function bound by its carbon atom (A), an imine function bound by its nitrogen atom (C), an aldehyde function (B), or a primary amine function (E), and/or molecules comprising at two of their ends functional groups making it possible to bond in a covalent manner the molecule to the polymer P1 and between its two ends an imine function (D), the combination having to enable the grafting and the creation of exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; Advantageously, monofunctional free aldehydes.

(54) Thus, the polymer P1 may be functionalised and crosslinked during the addition of the additive. To do so, the polymer comprises functions enabling grafting, for example in its main chain or on its side/pendant groups.

(55) FIG. 1 presents the molecules being able to be used for polymer functionalisation and crosslinking in one step. The letters G.sub.1, G.sub.2, G.sub.3, G.sub.4, G.sub.5 and G.sub.6 represent a functional group making it possible to bond in a covalent manner the molecules to the polymer chains to functionalise. The functional groups G.sub.1, G.sub.2, G.sub.3, G.sub.4, G.sub.5 and G.sub.6 are chosen as a function of the polymers to functionalise, functions enabling the grafting onto these polymers and the grafting conditions (temperature, reaction medium (molten or in solution), kinetics, use of a catalyst, etc.). Advantageously, the groups G.sub.1, G.sub.2, G.sub.3, G.sub.4, G.sub.5 and G.sub.6 are identical.

(56) As non-limiting examples, the functions G may be thiol functions enabling the functionalisation of the alkene bonds present in the silicone, either in its main chain or as pendant functions, or both in its main chain and as pendant functions. The functions G may also be maleimide, methacrylic, acrylic, styrenic or maleic ester functions in order to enable radical grafting on alkyl or alkene units for example present in the silicone chain and/or as pendant functions (G. Moad, Prog. Polym. Sci. 1999, 24, 81-142; Elisa Passagliaa, Serena Coiai, Sylvain Augier, Prog. Polym. Sci. 2009, 34, 911-947). The functions G may be isocyanate functions that will thus react with the pendant alcohol, amine or thiol groups present on these polymers to functionalise (Kemal Arda Gnay, Patrick Theato, Harm-Anton Klok, Journal of Polymer Science Part A: Polymer Chemistry 2013, 51, 1-28; Charles E. Hoyle, Andrew B. Lowe, Christopher N. Bowman, Chem. Soc. Rev., 2010, 39, 1355-1387). The functions G may also be electrophilic olefins being able to give Michael additions with nucleophiles, such as thiols, primary and secondary amines, or phosphines (Brian D. Mather, Kalpana Viswanathan, Kevin M. Miller, Timothy E. Long, Prog. Polym. Sci. 2006, 31, 487-531). Among electrophilic olefins may be cited as non-limiting examples, acrylates, acrylamides, maleimides, methacrylates or vinyl sulphones. The functions G may also be nucleophilic functions, such as alcohols, thiols, amines or carboxylic acids, which can give nucleophilic substitution or ring opening reactions (Kemal Arda Gnay, Patrick Theato, Harm-Anton Klok, Journal of Polymer Science Part A: Polymer Chemistry 2013, 51, 1-28). These functional groups may for example open epoxide functions present in the main chain of the polymers, or pendant epoxide functions such as are found in copolymers prepared with glycidyl methacrylate. The functions G may also be alcohol, thiol or amine functions that can react with pendant ester or activated ester functions to give new ester, thioester or amide functions. The functional groups making it possible to bond in a covalent manner the molecule containing the imine or aldehyde or primary amine function to the polymer P1 are thus numerous and varied and those skilled in the art know how to select the functional group of choice as a function of the functions present on the polymer P1 and the grafting conditions (temperature, reaction medium (molten or in solution), kinetics, use of a catalyst, etc.).

(57) FIG. 1 defines the molecules (A) G.sub.1-Rx-CHNRy, (B) G.sub.2-Rx-CHO, (C) G.sub.3-Ry-NCHRx, (D) G.sub.4-Rx-CHNRy-G.sub.5 and (E) G.sub.6-Rw-NH.sub.2, where the letters G.sub.1, G.sub.2, G.sub.3, G.sub.4, G.sub.5 and G.sub.6 represent a functional group making it possible to bond in a covalent manner the molecules to the polymer chains to functionalise, Rx, Rx, Rx, Rx and Ry, Ry, Ry and Rw are hydrocarbon groups. The denominations Rx and Ry are reused by homology, without being necessarily identical, with the definition of the pendant imine and aldehyde functional groups according to the invention.

(58) In particular, Rx, Rx, Rx, Rx each represent, independently of each other, an aliphatic, terpenoid, aromatic, arylaliphatic or cycloaliphatic radical. This radical may contain heteroatoms, in particular selected from O, N, S or Si, and/or may be substituted. Rx, Rx, Rx, Rx are advantageously an aromatic, heteroaromatic or terpenoid group. Advantageously, when the aldehyde function is borne by a terpenoid group, the aldehyde function is directly bound to an alkene function of the terpenoid. Rx, Rx, Rx, Rx are bound to the imine or aldehyde functions by a covalent bond via a carbon atom.

(59) In particular, Rx, Rx, Rx, Rx, each, independently of each other, may be substituted by functional groups, such as ester or amide functions. In particular, this radical is substituted by a halogen, a Rz, OH, NHRz, NRzRz, C(O)OH, C(O)NRzRz, C(O)ORz, OC(O)Rz, OC(O)ORz, OC(O)N(H)Rz, N(H)C(O)ORz, ORz, SRz, C(O)N(H)Rz, N(H)C(O)Rz group with Rz, Rz, identical or different, representing a C.sub.1-C.sub.50 alkyl radical. In particular, this radical Rx, Rx, Rx, may be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide, anhydride functions.

(60) In particular, Ry, Ry, Ry each represent, independently of each other, an aliphatic, aromatic, arylaliphatic or cycloaliphatic radical. Ry, Ry, Ry are bound to the imine functions by a covalent bond via a carbon atom. This radical may contain heteroatoms, in particular selected from O, N, S or Si, and/or may be substituted. In particular, this radical Ry, Ry, Ry may be substituted by functional groups, such as ester or amide functions. In particular, this radical is substituted by a halogen, a Rz, OH, NHRz, NRzRz, C(O)OH, C(O)NRzRz, C(O)ORz, OC(O)Rz, OC(O)ORz, OC(O)N(H)Rz, N(H)C(O)ORz, ORz, SRz, C(O)N(H)Rz, N(H)C(O)Rz group with Rz, Rz, identical or different, representing a C.sub.1-C.sub.50 alkyl radical. In particular, this radical Ry, Ry, Ry may be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide, anhydride functions.

(61) In particular, Rw represents an aliphatic, aromatic, arylaliphatic or cycloaliphatic radical. Rw is bound to the amine functions by a covalent bond via a carbon atom. This radical may contain heteroatoms, in particular selected from O, N, S or Si, and/or may be substituted. In particular, this radical Rw may be substituted by functional groups, such as ester or amide functions. In particular, this radical is substituted by a halogen, a Rz, OH, NHRz, NRzRz, C(O)OH, C(O)NRzRz, C(O)ORz, OC(O)Rz, OC(O)ORz, OC(O)N(H)Rz, N(H)C(O)ORz, ORz, SRz, C(O)N(H)Rz, N(H)C(O)Rz group with Rz, Rz, identical or different, representing a C.sub.1-C.sub.50 alkyl radical. In particular, this radical Rw may be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide, anhydride functions.

(62) FIG. 2 schematically shows the functionalisation of linear polymers P1 by the molecule A, respectively C, via the creation of covalent bonds between the molecules A, respectively C, and the polymer chains.

(63) The combinations enabling crosslinking and functionalisation of polymers in one step are: A+C: Polymers functionalised with pendant imine functions coupled by the carbon (A)+polymers functionalised with pendant imine functions coupled by the nitrogen (C) and crosslinking by imine-imine metathesis reaction (FIG. 3). Imine-imine metathesis reactions may take place between A and C before these functions are grafted onto the polymers (which comes down to generating a molecule equivalent to the molecule D). B+C: Polymers functionalised with pendant aldehyde functions (B)+polymers functionalised with pendant imine functions coupled by nitrogen (C) and crosslinking by aldehyde-imine exchange reaction. Aldehyde-imine exchange reactions may take place between B and C before these functions are grafted onto the polymers (which comes down to generating a molecule equivalent to the molecule D). A+D: Polymers crosslinked by the molecule D+polymers functionalised with pendant imine functions coupled by the carbon (A). Imine-imine metathesis reactions may take place between A and D before these functions are grafted onto the polymers. B+D C+D A+B+C A+B+D B+C+D A+B+C+D E+A E+D A+E+C A+E+D A+C+D+E A+B+C+E A+B+D+E A+B+C+D+E A+C+D A+B+E B+C+E B+C+D+E

(64) To summarise, any combination for which on average at least two imine and/or aldehyde functions will be grafted per polymer chain and bound to the main chain by the carbon atom and two imine and/or primary amine functions will be grafted per polymer chain and bound to the main chain by the nitrogen atom.

(65) Monofunctional free aldehydes may be added in addition in each case.

(66) Other combinations are further possible when a compound of formula (I) or of formula (II), defined previously, is used: A+compound (I) for which Z and W.sub.1 are N. Polymers functionalised with pendant imine functions bound to the main chain by the carbon atom (A) are thus prepared then crosslinking takes place by imine-imine metathesis reaction between the pendant functions and the compound (I). Imine-imine metathesis reactions may take place between A and the compound (I) before these functions are grafted onto the polymers. B+compound (I) for which Z and W.sub.1 are N A+B+compound (I) for which Z and W.sub.1 are N C+compound (I) for which Z and W.sub.1 are C E+compound (I) for which Z and W.sub.1 are C, Y and one W.sub.2i at least are N C+E+compound (I) for which Z and W.sub.1 are C A+compound (II) A+B+compound (II)

(67) Once again, it is necessary that there are on average at least two grafted exchangeable pendant functions per polymer chain (via A, B, C or E). The quantity of compound (I) will vary depending on its functionality. However, it may be said that the compounds (I) also have to provide on average at least two imine or aldehyde functions per polymer chain. These functions have to be complementary to the functions grafted onto the polymers (via A, B, C or E).

(68) Monofunctional free aldehydes may be added in addition in each case.

(69) In the compositions according to the invention, the polymers include pendant imine and/or aldehyde and/or primary amine functions. They also include imine functions in their side chains forming crosslinking points. This enables an exchange between imines and improves the crosslinking of the polymers. The inventors think that the exchange reactions between imines and between imines and aldehydes and between imines and primary amines enable a circulation of crosslinking points.

(70) The compositions also include monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines, formed during the creation of the crosslinking points.

(71) To one or the other of these compositions described previously, it is further possible to add a compound having a single imine or aldehyde or primary amine function. This additional compound may make it possible to modulate the properties, notably the viscosity, of the polymer compositions. This compound may comprise an aryl, or heteroaryl, or terpenoid group bound to the carbon of the aldehyde or the imine or the primary amine. Advantageously, when the aldehyde function is borne by a terpenoid group, the aldehyde function is directly bound to an alkene function of the terpenoid.

(72) Moreover, the compositions according to the invention advantageously include monofunctional free aldehydes. In a surprising manner, the inventors have discovered that the exchange reactions between imines may be catalysed by an aldehyde, which may be present in the polymer (pendant CHO group) or as a molecule not bound to the polymers, designated free. The monofunctional free aldehyde may be added before, during or after the addition of the additive.

(73) The aldehyde function may be borne by a molecule comprising at least one CHO group: additive of formula (I) and/or additive P2 and/or monofunctional free aldehyde. Advantageously, in the presence of a molecule, the aldehyde functionalised molecule used to catalyse the metathesis of imines is an aromatic aldehyde, namely a molecule for which the aldehyde function is borne by an aryl or heteroaryl group, preferably a benzene ring. Benzaldehyde and derivatives thereof may notably be cited. Advantageously, the aldehyde functionalised molecule used to catalyse the metathesis of imines is a molecule in which the carbon of the aldehyde function is bound by a covalent bond to an alkene function of a terpenoid. Citral, its two isomers, geranial and neral, and derivatives thereof may notably be cited.

(74) In a surprising manner, the inventors have discovered that the imine and aldehyde functions can exchange their substituents according to the following reaction:
Rx-(H)CNRy+Rx-(H)CO.fwdarw.Rx-(H)CNRy+Rx-(H)CNRy+Rx-(H)CO+Rx-(H)CO

(75) Advantageously, the carbon atom of the imine functions and the carbon atom of the aldehyde functions are directly bound to a carbon atom of an aryl, heteroaryl group or to the alkene function of a terpenoid.

(76) The use of aldehyde functionalised molecules, and more particularly aromatic aldehydes, such as benzaldehyde and derivatives thereof, notably vanillin, and terpenoid aldehydes, such as cinnamaldehyde, as catalysts for the metathesis of imines has numerous advantages. These molecules are compatible with numerous polymers, these molecules are not very likely to introduce parasitic reactions in the polymer matrices/materials, these molecules are commercially available, may be bio-sourced or sourced from natural origins and numerous aromatic aldehydes and terpenoid aldehydes are barely or not toxic as shown by their use in the food industry and cosmetics.

(77) As illustrated in the examples below, the presence of a pendant or free aldehyde is going to catalyse the imine-imine metathesis and imine-aldehyde exchange reactions.

(78) The silicone polymers may be functionalised to introduce imine or aldehyde or primary amine functionalised pendant side groups or to introduce units or functions enabling grafting. The introduction of these imine or aldehyde or primary amine functionalised pendant side groups can be done by different methods known to those skilled in the art: copolymerisation of precursor monomers of the polymer with functionalised imine or aldehyde or primary amine monomers (the imine or aldehyde or primary amine functions not being integrated in the main chain of the polymer in the course of formation but located on a pendant side group) (M. Spinu, J. E. Mc Grath, J. Polym. Sci. Part A Polym. Chem. 1991, 29, 657), grafting on a reactive function of the polymer, copolymerisation of precursor monomers of the polymer with monomers containing one or more functions that will serve after formation of the polymer to graft pendant imine and/or aldehyde and/or primary amine functions (W. Noli, Chemistry and Technology of Silicones. Academiv Press, New York, 1968). Such methods are known to those skilled in the art and the synthesis of silicone copolymers with pendant functions is notably described in chapter 3 Side Group Modified (authors: B. Boutevin, F. Guida-Pietrasanta and A. Ratsimihety) of the book Silicon-Containing Polymers (Ed. R. G. Jones, W. Ando, J. Chojnowski, Springer, 2000). One method commonly used for the introduction of pendant functions onto silicones is the hydrosilylation reaction. This reaction corresponds to the addition of an unsaturated compound on a SiH bond. Numerous silicones containing hydrosilane functions, including polymethylhydrosiloxane (PMHS) and poly(dimethylsiloxane-co-methylhydrosiloxane) (PDMSMHS) copolymers, are commercially available (Gelest, Dow, Siltech, ShinEtsu, Wacker, etc.). The hydrosilylation reaction takes place either in the presence of radical initiators, or in the presence of catalysts. Among catalysts for the hydrosilylation reaction may be cited tertiary amines, Lewis acids and transition metal complexes, notably complexes of platinum (J. V. Crivello, J. L. Lee, J Polym. Sci., Part A, Polym. Chem., 1990, 28, 479; J. N. Lewis, J. Amer. Chem. Soc. 1991, 112, 5998; J. V. Crivelto, D. Bi, J Polym. Sci., Part A, Polym. Chem., 1993, 31, 3121). The hydrosilylation reaction notably makes it possible to prepare silicones containing pendant amine, imine functions (J. V. Crivello, G. Lohden, Macromolecules, 1995, 28, 8057), epoxy functions (L. Lecamp, C. Vaugelade, B. Youssef, C. Bunel, Eur. Polym. J., 1997, 33, 1453; J. V. Crivello, M. Fan, J Polym Sci., Part A. Polym Chem., 1991, 29, 1853; J. V. Crivello, Bo Yang, Whan-Gi Kim, J Polym. Sci., Part A. Polym. Chem., 1995, 33, 2415), acrylate and methacrylate functions (K. D. Belfield, X. Z. Lin, I. Cabasso, J Polym. Sci. Part A Polym. Chem. 1991, 29, 1073; R. Puyenbroek, J. J. Jansema, J. C. Van de Grampel, B. A. C. Rousseeuw, E. W. J. M. Van der Drift, Polymer 1996, 37, 847). Thiolene addition is another approach commonly used to functionalise silicones. It involves the addition of a thiol compound on a pendant vinyl bond of a silicone. Numerous silicones containing vinylsilane functions, notably polymethylhvinylsiloxane (PMVS) and poly(dimethylsiloxane-co-methylhvinylsiloxane) (PDMSMVS) copolymers, are commercially available (Gelest, Dow, Siltech, ShinEtsu, Wacker, etc.). Thiolene addition on silicones containing vinylsilane functions notably make it possible to prepare silicones containing pendant primary amine, imine, aldehyde functions. The introduction of units or functions enabling grafting may also be done according to other methods known to those skilled in the art (Charles E. Hoyle, Christopher N. Bowman, Angew. Chem. Int. Ed. 2010, 49, 1540-1573; Kemal Arda Gnay, Patrick Theato, Harm-Anton Klok, Journal of Polymer Science Part A: Polymer Chemistry 2013, 51, 1-28; G. Moad, Prog. Polym. Sci. 1999, 24, 81-142; Elisa Passagliaa, Serena Coiai, Sylvain Augier, Prog. Polym. Sci. 2009, 34, 911-947; Charles E. Hoyle, Andrew B. Lowe, Christopher N. Bowman, Chem. Soc. Rev., 2010, 39, 1355-1387; Brian D. Mather, Kalpana Viswanathan, Kevin M. Miller, Timothy E. Long, Prog. Polym. Sci. 2006, 31, 487-531; T. C. Chung, Prog. Polym. Sci. 2002, 27, 39-85. Chulsung Bae, John F. Hartwig, Hoyong Chung, Nicole K. Harris, Karen A. Switek, Marc A. Hillmyer, Angew. Chem. Int. Ed. 2005, 44, 6410-6413).

(79) As described previously, the polymers may be functionalised and crosslinked during the addition of the additive.

(80) The number average molar mass, M.sub.n, of the linear or branched polymers P1, P1, or P2, that is to say before crosslinking, advantageously varies from 1000 g/mol to 2500000 g/mol, more advantageously from 2000 to 750000 g/mol and even more advantageously from 7500 g/mol to 400000 g/mol.

(81) The dispersity, D=M.sub.w/M.sub.n, of the linear or branched polymers P1, P1, or P2, that is to say before crosslinking, varies advantageously from 1.01 to 15, more advantageously from 1.03 to 10 and even more advantageously from 1.05 to 7.5.

(82) In the invention, the molar ratio [repeating unit of the polymer P1 or P1 not containing pendant imine or aldehyde or primary amine functions]:[repeating unit of the polymer P1 or P1 containing a pendant imine function+repeating unit of the polymer P1 or P1 containing a pendant aldehyde function+repeating unit of the polymer P1 or P1 containing a pendant primary amine function] advantageously varies from 0.01 to 1000, more advantageously from 0.1 to 250 and even more advantageously from 1 to 100. Pendant imine or aldehyde or primary amine function here designates either an imine or aldehyde or primary amine function or a function enabling the grafting of such an imine or aldehyde or primary amine function.

(83) The molar ratio [compound of formula (I)]:[repeating unit of the polymer P1 or P1 containing a pendant imine function+repeating unit of the polymer P1 or P1 containing a pendant aldehyde function+repeating unit of the polymer P1 or P1 containing a pendant primary amine function] advantageously varies from 5 to 0.001 more advantageously from 1 to 0.005 and even more advantageously from 0.5 to 0.01. Pendant imine or aldehyde or primary amine function here designates either an imine or aldehyde or primary amine function or a function enabling the grafting of such an imine or aldehyde or primary amine function.

(84) In the invention, the molar ratio [repeating unit of the polymer P2 not containing pendant imine or aldehyde or primary amine functions]:[repeating unit of the polymer P2 containing a pendant imine function+repeating unit of the polymer P2 containing a pendant aldehyde function+repeating unit of the polymer P2 containing a pendant primary amine function] advantageously varies from 0.01 to 1000, more advantageously from 0.1 to 250 and even more advantageously from 1 to 100.

(85) The molar ratio [repeating unit of the polymer P2 containing a pendant imine function+repeating unit of the polymer P2 containing a pendant aldehyde function+repeating unit of the polymer P2 containing a pendant primary amine function]:[repeating unit of the polymer P1 or P1 containing a pendant imine function+repeating unit of the polymer P1 or P1 containing a pendant aldehyde function+repeating unit of the polymer P1 or P1 containing a pendant primary amine function] advantageously varies from 2500 to 0.0004, more advantageously from 250 to 0.004 and even more advantageously from 100 to 0.01. Pendant imine or aldehyde or primary amine function here designates either an imine or aldehyde or primary amine function or a function enabling the grafting of such an imine or aldehyde or primary amine function.

(86) When they are in the form of liquid formulations, the compositions of crosslinked polymers according to the invention, advantageously the compositions forming a network of crosslinked linear or branched polymers, advantageously have the remarkable property of being able to be injected, notably via a syringe. Depending on the level of crosslinking of the networks of crosslinked linear or branched polymers, the compositions of crosslinked polymers according to the invention are injectable, notably via a syringe, while forming a network of crosslinked polymers which, swollen by solvent(s), advantageously water, will be able to supports its own weight and will not flow at the scale of 30 seconds, advantageously 1 minute, advantageously 2 minutes, advantageously 5 minutes, advantageously 10 minutes, advantageously 30 minutes, advantageously 1 hour, advantageously 2 hours, advantageously 4 hours, advantageously 6 hours, advantageously 8 hours, advantageously 12 hours, advantageously 1 day, without the application of a stress.

(87) When they are in the form of liquid formulations, the networks of linear or branched crosslinked polymers according to the invention advantageously have the property of agglomerating together when they are left in contact.

(88) The crosslinking rate of the compositions of crosslinked polymers according to the invention, advantageously the compositions in the form of liquid formulations forming networks of linear or branched crosslinked polymers, may be modulated by addition to the composition of monofunctional free aldehydes, and/or monofunctional free imines, and/or monofunctional free primary amines and/or compounds of formulas (I) and/or (II) and/or linear or branched polymers P2. Such a modulation of the level of crosslinking can make it possible to release molecules and/or polymers into the formulations containing the compositions of crosslinked polymers according to the invention. Active ingredients, proteins, nucleic acids, amino acids, vitamins, aromas, catalysts, chemical reagents, pigments or other additives may be cited as non-restrictive examples of molecules or polymers being able to be released.

(89) The composition of the invention may further comprise fillers and/or additives. The fillers and/or the additives are in particular those normally used by those skilled in the art.

(90) The composition may further comprise, in the mixture or in the network, other compatible polymer(s). Those skilled in the art know how to choose such a polymer.

(91) Compositions of polymer networks comprising at least one polymer network of which the composition has been described above may also comprise: one or more polymers, pigments, colorants, brightening agents, fillers, plastifiers, impact modifiers, fibres, flame retarders, antioxidants, lubricants, wood, glass, metals.

(92) Among the polymers that may be used in mixture with the polymer compositions or networks of the invention may be cited elastomers, thermosettings, thermoplastic elastomers, impact resistant polymers.

(93) The term pigments signifies coloured particles insoluble in the polymer composition or the network. Among pigments that may be used in the invention may be cited titanium oxide, carbon black, carbon nanotubes, metal particles, silica, metal oxides, metal sulphites or any other mineral pigment. As pigments may also be cited phthalocyanines, anthraquinones, quinacridones, dioxazines, azoic pigments or any other organic pigment, natural pigments (madder, inidigo, garance, carmin, etc.) and mixtures of pigments. The pigments may represent between 0.05% and 70% by weight of the composition of the formulation.

(94) The term colorants signifies molecules that are soluble in the polymer composition or network and which have the capacity of absorbing all or part of visible light radiation.

(95) The term brightening agent signifies a molecule which absorbs ultraviolet light radiation and next re-emits this energy by fluorescence in the visible. Brightening agents are notably used to impart a certain whiteness.

(96) Among fillers that may be used in the polymer compositions or networks of the invention may be cited silica, clays, calcium carbonate, carbon black, kaolins.

(97) Among fibres that may be used in the polymer compositions or networks of the invention may be cited glass fibres, carbon fibres, polyester fibres, polyamide fibres, aramid fibres, polyethylene fibres, cellulose and nano-cellulose fibres. Plant fibres (linen, hemp, sisal, bamboo, etc.) may also be envisaged.

(98) The presence in the polymer compositions or networks of the invention of heat conducting pigments, colorants or fibres may be used to facilitate the heating of an article obtained from the polymer compositions or networks of the invention and thereby enable the manufacture, the transformation or the recycling of an article obtained from polymer compositions or networks of the invention as described below. As non-limiting examples of heat conducting pigments, fibres or fillers may be cited aluminium nitride (AlN), boron nitride (BN), MgSiN.sub.2, silicon carbide (SiC), graphite, graphene, carbon nanotubes, carbon fibres, metal powders and combinations thereof.

(99) The presence in the polymer compositions or networks of the invention of pigments, colorants or fibres capable of absorbing radiation may be used to ensure the heating of an article obtained from the polymer compositions or networks of the invention by means of a radiation source, such as a laser for example. The presence in the polymer compositions or networks of the invention of electro-conductive pigments, fibres or fillers such as carbon black, carbon nanotubes, carbon fibres, metal powders, magnetic particles may be used to ensure the heating of an article obtained from polymer compositions or networks of the invention by Joule effect, by induction or by microwaves. Such heating methods can enable the manufacture, the transformation or the recycling of an article obtained from polymer compositions or networks of the invention as described below. Electro-conductive fillers may also make it possible to evacuate electrostatic charges from the material or to enable electrostatic painting.

(100) The invention also relates to a method for preparing compositions according to the invention. This method advantageously comprises the following steps: Choosing a linear or branched silicone polymer, comprising consecutive SiO units P1 having side groups bearing: aldehyde functional groups, or imine functional groups bound to the polymer by the carbon atom, or imine functional groups bound to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups bound to the polymer by the carbon atom, or primary amine functional groups, or primary amine functional groups and imine functional groups bound to the polymer by the nitrogen atom; Choosing at least one additive bearing at least two imine and/or aldehyde and/or primary amine functional groups able to react with the side groups of the polymer P1 to form a composition of crosslinked polymers, advantageously a crosslinked network, containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; mixing, in the molten state or in solution, said polymer P1, said additive and where appropriate a monofunctional free aldehyde, to obtain said composition.

(101) The choice of the substitutions and the additive is made according to the description given previously for the compositions. It is possible to add a monofunctional free aldehyde or a monofunctional free imine or a monofunctional free primary amine, as described previously.

(102) The method may comprise a prior step of preparing a polymer P1, comprising the copolymerisation, by ring opening polymerisation or by polycondensation, of a precursor monomer of P1 and of a monomer bearing an imine or aldehyde or primary amine functional group.

(103) The method may comprise a prior step of preparing a polymer P1, comprising the grafting of pendant aldehyde and/or imine and/or primary amine functions onto a linear or branched polymer.

(104) Another method according to the invention advantageously comprises the following steps: choosing at least one linear or branched silicone polymer, comprising consecutive SiO units P1 comprising functions enabling grafting, choosing a combination of molecules including molecules comprising at one end a functional group making it possible to bond in a covalent manner the molecule to the polymer P1 and at another end a functional group selected from an imine function bound by its carbon atom to the remainder of the molecule (A), an imine function bound by its nitrogen atom to the remainder of the molecule (C), or an aldehyde function (B), or a primary amine function (E) and/or molecules comprising at two of their ends functional groups making it possible to bond in a covalent manner the molecule to the polymer P1 and between its two ends an imine function (D), the combination having to enable the grafting and the creation of exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions; mixing, in the molten state or in solution, said polymer P1, said combination and where appropriate a monofunctional free aldehyde, to obtain said composition.

(105) The choice of the substitutions and the combination is made according to the description given previously for the compositions. A monofunctional free aldehyde or a monofunctional free imine, or a monofunctional free primary amine may be added, as described previously.

(106) The method may comprise a prior step of preparing a polymer P1, comprising the copolymerisation, by ring opening polymerisation or by polycondensation, of a precursor monomer of P1 and a monomer bearing a functional group making it possible thereafter to graft pendant aldehyde and/or imine and/or primary amine functions.

(107) The method may comprise a prior step of preparing a polymer P1, comprising the grafting of pendant functions enabling the grafting of aldehyde and/or imine and/or primary amine functions on a linear or branched polymer.

(108) The invention also relates to a material obtained from the composition according to the invention.

(109) The invention also relates to a method for preparing a material according to the invention, comprising the following steps: Preparing a composition according to the invention; Shaping the composition thereby obtained.

(110) The notion of shaping includes not just the compounding of the composition in the form of granules or powder for example but also the preparation of finished products. The shaping may be carried out by methods known to those skilled in the art for the shaping of thermoplastic or thermosetting polymers. Moulding, compression, injection, extrusion, thermoforming methods may notably be mentioned. Before giving it the shape of the desired object, the material will be the most often in the form of granules or powder.

(111) Interestingly, in the method according to the invention, the steps of preparation and shaping may be concomitant. In particular, by the methods described previously, it is possible to functionalise and crosslink a polymer for example by extrusion or injection during its shaping or a step of compounding.

(112) The invention also relates to a formulation comprising a composition according to the invention.

(113) The invention also relates to the use of an additive as defined previously or a combination as defined previously, in the presence of a linear or branched polymer P1 or P1 for the formation of a composition of crosslinked polymers, advantageously a crosslinked network, containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions. The nature of the additive or the combination is chosen as a function of the polymer P1 or P1, in particular its functionalisation, according to the criteria explained previously.

(114) It is further possible to add to the composition a monofunctional free aldehyde or a monofunctional free imine or a monofunctional free primary amine. Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly bound to an aryl or heteroaryl group.

(115) Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly bound to the alkene function of a terpenoid group.

(116) The compositions according to the invention may serve for any use of silicones described in the introduction. In particular, the compositions according to the invention may be used to prepare patches, dressings, pressure sensitive adhesives or sensitive skin adhesives. Similarly, depending on the degree of crosslinking, it is possible to obtain compositions according to the invention which may be used in non-stick coatings.

(117) The invention also relates to a method for modifying the rheology of a composition, such as an oil or a paint or a cosmetic composition, comprising said polymer P1 or P1 by addition to the composition of the additive according to the invention or the combination according to the invention. The rheology is modified by choosing the concentration of said additive or combination.

(118) The nature of the additive or the combination is chosen as a function of the polymer P1 or P1, in particular its functionalisation, according to the criteria explained previously.

(119) It is further possible to add to the composition a monofunctional free aldehyde or a monofunctional free imine or a monofunctional free primary amine. Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly bound to an aryl or heteroaryl group.

(120) Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly bound to the alkene function of a terpenoid group.

(121) The invention also relates to combinations for crosslinking linear or branched silicone polymers, comprising consecutive SiO units, advantageously P1, P1, said combinations being selected from combinations comprising: A monofunctional free aldehyde+compound of formula (I), as defined previously; Compound of formula (II)+compound of formula (I)) in which Z represents N and W.sub.1 represents N, as defined previously; A monofunctional free aldehyde+silicone polymer P2, as defined previously; A and/or B+C; A, B, C being as defined previously, and optionally a monofunctional free aldehyde as defined previously; A, optionally B, +C and/or E, and optionally a monofunctional free aldehyde, as defined previously; A and/or B and/or C+D and/or E, and optionally a monofunctional free aldehyde as defined previously; A and/or B+compound of formula (I) for which Z and W.sub.1 are N, and optionally a monofunctional free aldehyde, as defined previously; or A, optionally B, +compound of formula (II) and optionally a monofunctional free aldehyde, as defined previously; C and/or E+compound of formula (I) for which Z and W.sub.1 are a carbon atom, and optionally a monofunctional free aldehyde, as defined previously.

(122) In the first three cases, it is necessary that the linear or branched polymers have exchangeable pendant imine and/or aldehyde and/or primary amine functions.

(123) A, B, C, D, E are as described previously.

(124) These combinations may also comprise a monofunctional free aldehyde or a monofunctional free imine or a monofunctional free primary amine. Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function are directly bound to a terpenoid, aryl or heteroaryl group. Advantageously, when the aldehyde function is borne by a terpenoid group, the aldehyde function is directly bound to an alkene function of the terpenoid.

(125) The present invention also relates to the use of a combination such as previously, in the presence of a linear or branched silicone polymer, comprising consecutive SiO units P1 or P1 for the formation of a composition comprising crosslinked polymers, advantageously a crosslinked silicone network, containing exchangeable pendant bonds and exchangeable crosslinking points that are exchangeable by aldehyde-imine exchange reactions and/or by imine-imine exchange reactions and/or by imine-primary amine exchange reactions and monofunctional free aldehydes and/or monofunctional free imines and/or monofunctional free primary amines, in particular to modify the rheology of a composition, such as an oil, a paint or a cosmetic formulation, comprising said polymer P1 or P1 by addition to the composition of the combination according to the invention; the rheology could be modified by choosing the concentration of said combination.

(126) The following examples illustrate the invention and are not limiting.

(127) A. Synthesis of Functionalising Agents A, B, C and D and of Compounds of Formula (I)

(128) A.1. Functionalising Agent B: B1

(129) ##STR00007##

(130) p-chloromethylstyrene (6.63 g, 43.4 mmol), 4-hydroxybenzaldehyde (6.25 g, 51.1 mmol) and potassium carbonate (K.sub.2CO.sub.3) (17.7 g, 127.9 mmol) are introduced into a 250 mL round bottom flask containing 75 mL of dimethylformamide (DMF). The mixture is left under stirring under nitrogen atmosphere for 3 hours at 70 C. The solution is next poured into 500 mL of water, and the mixture is extracted three times with 150 mL of ethyl acetate. The organic phases are combined, washed three times with 150 mL of 0.5 M aqueous solution of sodium hydroxide, then dried over magnesium sulphate (MgSO.sub.4). The solvent is next evaporated to give a slightly yellow solid. The solid is introduced into 100 mL of heptane and the mixture is heated for 1 hour at 50 C. under strong stirring. The solid is next filtered and dried to give the functionalising agent B B1 in the form of a white solid (8.7 g, 36.3 mmol, 84%).

(131) .sup.1H NMR (CDCl.sub.3, 400 MHz) : 9.89 (s, 1H), 7.84 (d, 2H, J=8.8 Hz), 7.42 (m, 4H), 7.07 (d, 1H, J=8.8 Hz), 6.73 (dd, 1H, J=17.6 Hz, 10.8 Hz), 5.77 (d, 1H, J=17.6 Hz), 5.28 (d, 1H, J=10.8 Hz), 5.14 (s, 2H).

(132) GC MS: 97%, ( ) [M] Calculated for C16H14O2: 238.0944; Found: 238.20

(133) A.2. Functionalising Agent A: A1

(134) ##STR00008##

(135) The functionalising agent B1 (5 g, 21 mmol) and n-butylamine (7.67 g, 105 mmol) are dissolved in 40 mL of tetrahydrofuran (THF). Anhydrous magnesium sulphate (MgSO.sub.4) is added and the reaction medium is left under stirring for 48 hours at room temperature (RT or TA). The mixture is next filtered and concentrated under reduced pressure for the functionalising agent A A1 in the form of a white solid (5.85 g, 19.9 mmol, 95%).

(136) .sup.1H NMR (CDCl.sub.3, 400 MHz) : 8.20 (s, 1H), 7.66 (d, 2H, J=8.8 Hz), 7.41 (m, 4H), 6.99 (d, 2H, J=8.8 Hz), 6.73 (dd, 1H, J=17.6 Hz, 10.8 Hz), 5.77 (d, 1H, J=17.6 Hz), 5.27 (d, 1H, J=10.8 Hz), 5.09 (s, 2H), 3.58 (t, 2H, J=7.2 Hz), 1.67 (m, 2H), 1.38 (m, 2H), 0.95 (t, 3H, J=7.2 Hz).

(137) .sup.13C NMR (CDCl.sub.3, 400 MHz) : 160.5, 160.0, 137.4, 136.4, 136.2, 129.6, 129.5, 127.8, 126.5, 114.9, 114.2, 69.8, 61.4, 32.2, 20.5, 14.0

(138) GC MS: 96%, ( ) m/z: [M] Calculated for C.sub.20H.sub.30 NO 293.4027; Found 293.25

(139) A.3. Compound of Formula (I) and/or Functionalising Agent D: CF1

(140) ##STR00009##

(141) The compound aldehyde M1 (12.0 g, 50.34 mmol) and hexane-1,6-diamine (5.83 g, 50.34 mmol) are dissolved in 150 mL of toluene and the reaction mixture is left under stirring at room temperature for 24 hours, during which a white precipitate is formed. The mixture is filtered and the precipitate is rinsed three times with 150 mL of methanol. The precipitate is next filtered, rinsed three times with 150 mL of methanol and dried to give the compound of formula (I) and/or the functionalising agent D CF1 in the form of a white solid (9.5 g, 17.1 mmol, 70%).

(142) .sup.1H NMR (CDCl.sub.3, 400 MHz) : 8.19 (s, 2H), 7.66 (d, 4H, J=8.8 Hz), 7.41 (m, 8H), 6.99 (d, 4H, J=8.8 Hz), 6.73 (dd, 2H, J=17.6 Hz, 10.8 Hz), 5.77 (d, 2H, J=17.6 Hz), 5.27 (d, 2H, J=10.8 Hz), 5.08 (s, 4H), 3.57 (t, 4H, J=7.2 Hz), 1.70 (m, 4H), 1.41 (m, 4H).

(143) .sup.13C NMR (CDCl.sub.3, 400 MHz) : 160.7, 160.1, 137.5, 136.4, 136.2, 129.6, 127.7, 126.5, 114.9, 114.3, 69.8, 61.7, 31.0, 27.2.

(144) A.4. Compound of Formula (I): CF2

(145) ##STR00010##

(146) Benzaldehyde (2.05 equivalent) and hexane-1,6-diamine (1 equivalent) are introduced into dichloromethane (2 mL per mol of hexane-1,6-diamine) and magnesium sulphate is added (3 equivalents). The reaction mixture is left under stirring at room temperature for 24 hours, filtered then evaporated under reduced pressure to give the compound of formula (I) CF2 in the form of a yellow oil (98%, in the presence of 7 mol % of benzaldehyde).

(147) .sup.1H NMR (CDCl.sub.3, 400 MHz) : 8.26 (s, 1H), 7.72 (m, 2H), 7.38 (m, 3H), 3.63 (t, J=6.8 Hz, 2H), 1.74 (m, 2H), 1.42 (m, 2H).

(148) .sup.13C NMR (CDCl.sub.3, 400 MHz) : 161.2, 136.2, 130.4, 128.6, 128.1, 62.0, 30.8, 27.2.

(149) A.5. Compound of Formula (I): CF3

(150) ##STR00011##

(151) 1.5 g of terephthaldehyde (1 eq.) and 3 g of octylamine (2.1 eq.) are solubilised in 5 mL of anhydrous THF. 8 g of anhydrous magnesium sulphate (6 eq.) are added. The mixture is placed under stirring at room temperature. After 12 h, the suspension is filtered on filter paper and the THF evaporated under reduced pressure to give the compound of formula (I) CF3 in the form of a pale yellow solid (quantitative reaction).

(152) .sup.1H NMR (CDCl.sub.3, 400 MHz) : 8.28 (s, 2H), 7.76 (s, 4H), 3.61 (t, J=7.1 Hz, 4H), 1.70 (qt, J=7.1 Hz, 4H), 1.27 (m, 20H), 0.87 (t, J=7.1 Hz, 6H).

(153) A.6. Functionalising Agent C: C1

(154) ##STR00012##

(155) Benzaldehyde (0.9 mL, 8.8 mmol) and 4-vinylaniline (1 g, 8.4 mmol), or functionalising agent E E1, are introduced into 20 mL of tetrahydrofuran and magnesium sulphate (1 g) is added. The reaction mixture is left under stirring at room temperature for 24 hours, filtered then evaporated under reduced pressure to give the functionalising agent C C1 (90%, in the presence of 5 mol % of benzaldehyde).

(156) .sup.1H NMR (CDCl.sub.3, 400 MHz) : 8.48 (s, 1H), 7.93-7.90 (m, 2H), 7.50-7.45 (m, 5H), 7.23-7.20 (m, 2H), 6.75 (dd, J=17.6 Hz, 10.8 Hz, 1H), 5.76 (d, J=17.6 Hz, 1H), 5.25 (d, J=10.8 Hz, 1H).

(157) A.7. Functionalising Agent C: C2

(158) ##STR00013##

(159) Benzaldehyde (0.24 mL, 2.4 mmol) and 4-vinylbenzylamine (0.3 g, 2.25 mmol)), or functionalising agent E E2, are introduced into 10 mL of tetrahydrofuran and magnesium sulphate (0.5 g) is added. The reaction mixture is left under stirring at room temperature for 24 hours, filtered then evaporated under reduced pressure to give the functionalising agent C C2 (90%, in the presence of 5 mol % of benzaldehyde).

(160) .sup.1H NMR (CDCl.sub.3, 400 MHz) : 8.40 (s, 1H), 7.81-7.78 (m, 2H), 7.44-7.31 (m, 7H), 6.73 (dd, J=17.6 Hz, 10.8 Hz, 1H), 5.74 (d, J=17.6 Hz, 1H), 5.25 (d, J=10.8 Hz, 1H), 4.83 (s, 2H).

(161) B. Kinetic Studies of Exchange Reactions

(162) These experiments aim to evaluate the conditions (time, temperature, catalyst) making it possible to observe the imine-imine, imine-amine and imine-aldehyde exchange reactions.

(163) Kinetic Studies:

(164) Stoichiometric quantities of the imine, amine or aldehyde compounds are mixed in CDCl.sub.3 and .sup.1H NMR spectra are recorded regularly. The compounds are mixed from mother solutions and the overall concentration of the two starting reagents that can exchange is set at 0.071 mol/L (0.05 mmol/0.7 mL).

(165) General Mixing Procedure:

(166) CDCl.sub.3 is introduced into the NMR tube and the reagents are added by means of a micro-syringe from mother solutions. The tube is hermetically sealed and gently stirred before starting the NMR analysis. The time passed between the end of introduction of all the reagents and the acquisition of the first NMR spectrum is around 3:30 minutes. For analyses at high temperatures, the NMR spectrometer is equilibrated beforehand at the analysis temperature. The room temperature for these analyses was comprised between 22.0 and 23.6 C. The following exchange reactions were studied:

(167) Reaction scheme of the imine-imine metathesis reactions B.1, B.2, B.3, B.4, B.5

(168) ##STR00014##

(169) B.1. Non-catalysed imine-imine metathesis at room temperature (AT)

(170) B.2. Non-catalysed imine-imine metathesis at 45 C.

(171) B.3. Imine-imine metathesis in the presence of 10 mol % of amine (butylamine) at AT

(172) B.4. Imine-imine metathesis in the presence of 10 mol % of aldehyde (benzaldehyde) at AT

(173) B.5. Imine-imine metathesis in the presence of 10 mol % of aldehyde (benzaldehyde) at 45 C.

(174) B.6. Imine-aldehyde exchange reaction at AT

(175) ##STR00015##

(176) General Observations:

(177) At thermodynamic equilibrium, each compound must represent 25 mol % of all of the products (in the case of non-catalysed reactions). The time required to form 15% of the two new compounds derived from metathesis or exchange reactions of the six reactions studied are presented in the table below. This arbitrary conversion threshold, which corresponds to a conversion of 60% compared to thermodynamic equilibrium, has been chosen in order to be able to compare the different exchange rates.

(178) TABLE-US-00001 TABLE 1 Reaction: 1 2 3 4 5 6 time [h] to form 32.5 23 7.5 4.75 0.75 8.75 15% of N-n- butylbenzimine time [h] to form 32.5 23 12.5 4.75 0.75 8.75 15% of N-tert- butylimine monomer

(179) The non-catalysed imine-imine metathesis is the slowest exchange reaction among the slower reactions studied. The addition of free aldehyde during imine-imine metathesis makes it possible to substantially accelerate the reaction, practically by a factor 7 at AT and a factor 30 at 45 C. To our knowledge, the use of aldehyde to catalyse the metathesis of imines has not yet been described.

(180) The imine-aldehyde exchange reaction also proved to be more rapid than the non-catalysed imine-imine metathesis reaction, by a factor of around 3.5.

(181) C. Polymers P1

(182) C.1. Polymer P1 Bearing Primary Amine Functional Groups: AMS-163

(183) ##STR00016##

(184) The siloxane copolymer bearing primary amine functions used in the following examples was purchased from the Gelest Company (CAS 99363-37-8). The characteristics of the grade AMS-163 are: Mn=50000 g/mol, 6-7 mol % of aminopropylsiloxane units, i.e. around 42 amine functions per polymer chain on average.

(185) C.2. Exemplary Operating Procedure for the Synthesis of a Polymer P1 Bearing Imine Functional Groups Bound by the Nitrogen Atom: AMS-163Benz

(186) ##STR00017##

(187) 10 g of AMS-163 are solubilised in 10 mL of anhydrous THF. After total dissolution, 0.91 g of benzaldehyde (1.05 equivalents/to the amine functions) and 3 g of anhydrous magnesium sulphate (3 eq./to the amine functions) are added. The solution is stirred with a magnetic stirrer at room temperature for 12 h. After stopping the stirring, the mixture (suspension of magnesium sulphate) is left to settle for 24 h, then centrifuged at 9000 rpm for 30 minutes. The supernatant is evaporated and AMS-163Benz is recovered in the form of a slightly viscous transparent liquid. .sup.1H NMR analysis in anhydrous CDCl.sub.3 (15 mg of polymer/0.7 mL CDCl.sub.3) shows that the conversion of the pendant primary amine functions into pendant imine functions is total: the signal of the alpha methylene protons of the amine function (=2.6 ppm) has disappeared. A new signal has appeared at 3.5 ppm for the alpha methylene protons of the imine function formed, and the signal of the imine proton at 8.3 ppm.

(188) D. Formation and Characterisation of Networks of Crosslinked Polymers containing Exchangeable Pendant Bonds that are Exchangeable by Aldehyde-Imine Exchange Reactions and/or by Iimine-Imine Exchange Reactions and/or by Imine-Primary Amine Exchange Reactions.

(189) D.1. Networks of crosslinked polymers containing pendant bonds and exchangeable crosslinking points that are exchangeable by imine-primary amine exchange reactions.

(190) The following examples present examples of liquid formulation and illustrate the formation in solution of a network of crosslinked polymers according to the invention.

(191) a/ 25.3 g of AMS-163 are solubilised in 10 g of anhydrous THF. 0.54 g (3 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 2 g of anhydrous THE and added under stirring to the solution of AMS-163. After around 2 h, a network of crosslinked polymers is obtained.

(192) b/ 25.3 g of AMS-163 are solubilised in 10 g of anhydrous THF. 0.9 g (5 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 2 g of anhydrous THF and added under stirring to the solution of AMS-163. After around 2 h, a network of crosslinked polymers is obtained.

(193) c/ 25.3 g of AMS-163 are solubilised in 10 g of anhydrous THF. 1.8 g (10 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 2 g of anhydrous THF and added under stirring to the solution of AMS-163. After around 2 h, a network of crosslinked polymers is obtained.

(194) The following examples present examples of solid formulation and illustrate the formation of networks of crosslinked polymers according to the invention as well as their shaping by compression.

(195) d/ 25.3 g of AMS-163 are solubilised in 10 g of anhydrous THF. 0.54 g (3 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 2 g of anhydrous THF and added under stirring to the solution of AMS-163. After around 2 h, a network of crosslinked polymers is obtained. The THF is evaporated under a vacuum jar for 4 h at 100 C. Drying is completed in a vacuum oven at 120 C. for 12 h to remove residual THF.

(196) The dry network of crosslinked polymers is cut into pieces then shaped under heating press at 130 C. and 3 tonnes for 1 h.

(197) e/ 25.3 g of AMS-163 are solubilised in 10 g of anhydrous THF. 0.9 g (5 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 2 g of anhydrous THF and added under stirring to the solution of AMS-163. After around 2 h, a network of crosslinked polymers is obtained. The THF is evaporated under a vacuum jar for 4 h at 100 C. Drying is completed in a vacuum oven at 120 C. for 12 h to remove residual THE.

(198) The dry network of crosslinked polymers is cut into pieces then shaped under heating press at 130 C. and 3 tonnes for 1 h.

(199) D.2. Networks of Crosslinked Polymers containing Pendant Bonds and Exchangeable Crosslinking Points that are Exchangeable by Imine-Aldehyde Exchange Reactions.

(200) The following examples present examples of liquid formulation and illustrate the formation in solution of a network of crosslinked polymers according to the invention.

(201) a/ 29.4 g of AMS-163Benz are solubilised in 20.3 g of anhydrous THF. 0.22 g (3 eq. per siloxane chain) of terephthaldehyde are dissolved in 2 g of anhydrous THF and added under stirring to the solution of AMS-163Benz. After around 2 h, a network of crosslinked polymers is obtained.

(202) b/ 24.2 g of AMS-163Benz are solubilised in 18 g of anhydrous THF. 0.31 g (5 eq. per siloxane chain) of terephthaldehyde are dissolved in 2 g of anhydrous THF and added under stirring to the solution of AMS-163Benz. After around 2 h, a network of crosslinked polymers is obtained.

(203) The following examples present examples of solid formulation and illustrate the formation of networks of crosslinked polymers according to the invention, their shaping by compression and their insolubility in a good non-reactive solvent of the polymer constituting the network of crosslinked polymers.

(204) c/ 29.4 g of AMS-163Benz are solubilised in 20.3 g of anhydrous THF. 0.22 g (3 eq. per siloxane chain) of terephthaldehyde are dissolved in 2 g of anhydrous THF and added under stirring to the solution of AMS-163Benz. After around 2 h, a network of crosslinked polymers is obtained. The THF is evaporated under a vacuum jar for 4 h at 100 C. The drying is completed in a vacuum oven at 120 C. for 12 h to remove residual THF.

(205) The dry network of crosslinked polymers is cut into pieces then shaped under heating press at 130 C. and 3 tonnes for 1 h.

(206) Solubility test at room temperature in anhydrous THF

(207) A sample (139 mg) of the network of crosslinked polymers thereby obtained is introduced into 10 mL of anhydrous THF and left to swell for 24 hours at room temperature. The swelling rate (SR) and the soluble fraction (SF) of the network of crosslinked polymers are next calculated.
Swelling rate=(Mass of the swollen sampleMass of the dry sample after swelling)/(Mass of the dry sample after swelling)
Soluble fraction=(Mass of the dry sample before swellingMass of the dry sample after swelling)/(Mass of the dry sample before swelling)
Insoluble fraction=100soluble fraction

(208) Results: swelling rate SR=15.4; soluble fraction SF=29.6%; insoluble fraction=70.4%

(209) d/ 24.2 g of AMS-163Benz are solubilised in 18 g of anhydrous THF. 0.31 g (5 eq. per siloxane chain) of terephthaldehyde are dissolved in 2 g of anhydrous THF and added under stirring to the solution of AMS-163Benz. After around 2 h, a network of crosslinked polymers is obtained. The THF is evaporated under a vacuum jar for 4 h at 100 C. The drying is completed in a vacuum oven at 120 C. for 12 h to remove residual THF.

(210) The dry network of crosslinked polymers is cut into pieces then shaped under heating press at 130 C. and 3 tonnes for 1 h.

(211) Solubility test at room temperature in anhydrous THF

(212) A sample (130 mg) of the network of crosslinked polymers thereby obtained is introduced into 10 mL of anhydrous THF and left to swell for 16 hours at room temperature. The swelling rate (SR) and the soluble fraction (SF) of the network of crosslinked polymers are next calculated. Results: swelling rate SR=6.21; soluble fraction SF=13.9%; insoluble fraction=86.1%.

(213) D.3. Networks of Crosslinked Polymers containing Pendant Bonds and Exchangeable Crosslinking Points that are Exchangeable by Imine-Imine Exchange Reactions.

(214) The following examples present examples of liquid formulation and illustrate the formation in solution of a network of crosslinked polymers according to the invention.

(215) a/ 22.3 g of AMS-163Benz are solubilised in 18 g of anhydrous THF. 0.445 g (3 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 4 g of anhydrous THF and added under stirring to the solution of AMS-163Benz. After around 2 h, a network of crosslinked polymers is obtained.

(216) b/ 22 g of AMS-163Benz are solubilised in 18 g of anhydrous THF. 0.733 g (5 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 4 g of anhydrous THF and added under stirring to the solution of AMS-163Benz. After around 2 h, a network of crosslinked polymers is obtained.

(217) The following examples present examples of solid formulation and illustrate the formation of networks of crosslinked polymers according to the invention, their shaping by compression and their insolubility in a good non-reactive solvent of the polymer constituting the network of crosslinked polymers.

(218) c/ 22.3 g of AMS-163Benz are solubilised in 18 g of anhydrous THF. 0.445 g (3 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 4 g of anhydrous THF and added under stirring to the solution of AMS-163Benz. After around 2 h, a network of crosslinked polymers is obtained. The THF is evaporated under a vacuum jar for 4 h at 100 C. The drying is completed in a vacuum oven at 120 C. for 12 h to remove residual THF.

(219) The dry network of crosslinked polymers is cut into pieces then shaped under heating press at 130 C. and 3 tonnes for 1 h.

(220) Solubility test at room temperature in anhydrous THF

(221) A sample (120 mg) of the network of crosslinked polymers thereby obtained is introduced into 10 mL of anhydrous THF and left to swell for 24 hours at room temperature. The swelling rate (SR) and the soluble fraction (SF) of the network of crosslinked polymers are next calculated. Results: swelling rate SR=23.6; soluble fraction SF=32%; insoluble fraction=68%

(222) d/ 22 g of AMS-163Benz are solubilised in 18 g of anhydrous THF. 0.733 g (5 eq. per siloxane chain) of compound of formula (I) CF3 are dissolved in 4 g of anhydrous THF and added under stirring to the solution of AMS-163Benz. After around 2 h, a network of crosslinked polymers is obtained. The THF is evaporated under a vacuum jar for 4 h at 100 C. The drying is completed in a vacuum oven at 120 C. for 12 h to remove residual THF.

(223) The dry network of crosslinked polymers is cut into pieces then shaped under heating press at 130 C. and 3 tonnes for 1 h.

(224) Solubility test at room temperature in anhydrous THF

(225) A sample (144 mg) of the network of crosslinked polymers thereby obtained is introduced into 10 mL of anhydrous THE and left to swell for 24 hours at room temperature. The swelling rate (SR) and the soluble fraction (SF) of the network of crosslinked polymers are next calculated. Results: swelling rate SR=6.47; soluble fraction SF=11.2%; insoluble fraction=88.8%.