COMPOSITION OF RETICULATED POLYMERS CONTAINING EXCHANGEABLE PENDING LINKS AND EXCHANGEABLE CROSSLINK

专利摘要:
The subject of the invention is a composition comprising (a) crosslinked polymers containing exchangeable pendant bonds and exchangeable crosslinking points, by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions, obtained by crosslinking linear or branched polymers and (b) monofunctional free aldehydes and / or monofunctional free imines. The invention also relates to processes for preparing such a composition and the uses of the composition. The invention also relates to combinations for cross-linking linear or branched polymers, and their use for forming a composition comprising crosslinked polymers containing exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions. The invention finally relates to the use of aldehyde to catalyze imine-imine metathesis reactions and imine-aldehyde exchange reactions.
公开号:FR3040170A1
申请号:FR1557767
申请日:2015-08-17
公开日:2017-02-24
发明作者:Ludwik Leibler；Renaud Nicolay；Max Rottger
申请人:Ecole Superieure de Physique et Chimie Industrielles de Ville Paris ；
IPC主号:

专利说明:

Cross-linked polymer composition containing exchangeable pendant bonds and exchangeable crosslinking points, aldehyde-imine exchange reactions and / or imine-imine exchange reactions, methods of preparation and use. The invention relates to polymer compositions comprising crosslinked polymers comprising imine functions, and optionally aldehyde functions, allowing exchange reactions, as well as monofunctional free aldehydes and / or monofunctional free imines.
According to the invention, these compositions are advantageously derived from the modification of a polymer with an imine functionalized additive and / or aldehyde. This polymer may be prefunctionalized imine and / or aldehyde, depending on the case, or functionalized during the addition of said additive.
In particular, the invention provides a method for modifying the behavior of a polymer by adding a functional additive for forming a crosslinked network containing imine-imine and / or imine-aldehyde exchangeable bonds.
According to the invention, the metathesis reaction of the imines allows an exchange reaction between the substituents borne by the imines:
Rx-ON-Ry + Rx'-C = N-Ry '-> Rx-ON-Ry + Rx'-ON-Ry' + Rx-C = N-Ry '+ Rx'-C = N-Ry the invention, the imine-aldehyde exchange reaction allows an exchange between the substituents carried by the imines and the aldehydes:
Rx-C = N-Ry + Rx'-C = O Rx-C = N-Ry + Rx'-ON-Ry + Rx-C = O + Rx'-OO By "exchange reaction" is meant that Organic molecules, oligomers, polymers or polymer networks containing imine and / or aldehyde functions can exchange their substituents by metathesis reaction of the imines or by imine-aldehyde exchange reaction. These substituents can be hydrocarbon groups, oligomeric chains or polymer chains. These groups are linked to the imine and aldehyde functions via covalent bonds via a carbon atom before and after the exchange reaction. The metathesis reaction of the imines and the imine-aldehyde exchange reaction do not release a water molecule and do not require the presence of water to take place. In particular, by "exchange reaction" is meant that the polymers of the invention can exchange between them the substituents of the imine and / or aldehyde functional groups that they carry by imine metathesis reaction or by imine-aldehyde exchange reaction. . According to the invention, these functions can be pendent or part of the polymer chain, especially when they are part of a crosslinking point. Advantageously, these functions are pendent or part of a crosslinking point. Thus, the polymers are capable of exchanging chemical bonds with each other.
The metathesis reaction can proceed in the absence of catalyst or in the presence of a new, stable, readily available, inexpensive and nontoxic catalyst for the imine metathesis reaction.
Various transition metals, eg Zr (RG Bergman et al., J. Am Chem Soc., 1994, 116, 2669, RG Bergman et al., J. Am Chem Soc., 2000, 122, 751 Mo (TY Meyer et al., Organometallics, 1997, 16, 5381, TY Meyer et al., J. Am Chem Soc 1998, 120, 8035), Ti (Mountford, P. et al., Chem. Commun., 1998, 1669), Re (JH Espenson et al., Organometallics 1999, 18, 5170), Nb (JW Bruno et al., Organometallics 2000, 19, 4672) and lanthanide salts (Sc, Tb, Sm, La) (J.-M. Lehn, J. Am Chem Soc., 2005, 127, 5528) with triflate ions have been studied to catalyze the metathesis of imines. However, in addition to being generally toxic and expensive, these catalysts require several synthesis steps to be obtained. The development of non-toxic organic catalysts, readily available and inexpensive is therefore particularly interesting.
In this context, the possibility of using primary amines to catalyze the metathesis of imines in solution via trans-amination reactions has been studied. However, the inventors have found that the use of primary amines to catalyze the metathesis of imines has many disadvantages, particularly if it is desired to implement these reactions in organic polymeric materials. Indeed, by their reactivity and their nucleophilic nature, primary amines are at the origin of many parasitic reactions such as amidification reactions in polymer materials containing ester or carboxylic acid groups. Primary amines are also likely to react with other functions of interest. Non-exhaustively, in addition to the above-mentioned carboxylic acid and ester functions, the epoxide, isocyanate, anhydride or halogenated functional groups may be mentioned in a non-exhaustive manner. In addition, the parasitic reactions induced by the presence of primary amines in the organic polymer formulations are all the more so that the formulations are subjected to a rise in temperature, which is very often the case during the crosslinking process. , during implementation and / or in shape or during recycling. In addition, many vinyl monomers of interest, such as acrylates, methacrylates, acrylamides and methacrylic anhydride, are not stable in the presence of primary amines, because of parasitic reactions such as the addition of Michael and the amidification reactions. By way of example, the publication "Direct Synthesis of Controlled-Primary Structure Amine-Based Methacrylic Polymers by Living Radical Polymerization" (authors: Lihong He, Elizabeth S. Read, Steven P. Armes, and Dave J. Adams, Macromolecules 2007 , 40, 4429-4438; doi: 10.1021 / ma070670q) describes the great instability of a methacrylate monomer carrying a primary amine function and the need to protect the primary amine function in the form of ammonium salt in order to be able to polymerize the monomer. This article also discusses the degradation reactions of methacrylic polymers carrying primary amine functions by intramolecular and intermolecular amidation reactions. The review article "Michael adds reactions in macromolecular design for emerging technologies" (authors: Mather, B, Viswanathan, K., KM Miller, Long, TE, Prog Polym, Sci 31 (2006) 487- 531, doi: 10.1016 / j.progpolymsci.2006.03.001) provides examples of Michael's reaction between primary amines and different vinyl compounds. Thus, the presence of pendant primary amines on the organic polymers may cause spurious reactions, limit the functional groups that can be incorporated into the formulations as well as the nature of the monomers that can be used to prepare the polymers.
In this regard, the inventors have developed crosslinked polymer compositions in which the crosslinking reactions and the exchange reactions do not involve primary amines and can take place in the absence of catalyst or in the presence of new metathesis catalysts for imines: aldehydes.
Surprisingly, aldehyde-imine exchange reactions can also take place. These exchange reactions make it possible to obtain exchangeable polymers.
The term "exchangeable polymers" means polymers that can exchange chemical bonds, hydrocarbon groups, oligomeric chains or polymer chains by metathesis reaction of imines or by imine-aldehyde exchange reaction.
These exchange reactions also make it possible to obtain polymer compositions which may have properties of thermosetting polymers and thermoplastic polymers and which may be insoluble and heat-malleable.
By definition, a thermosetting is a polymer that hardens as a result of energy input, especially under the action of heat. Thermosets are classically divided into two families according to the glass transition temperature (Tg) of the polymer matrix constituting them. Thermosets whose matrix has a Tg greater than the operating temperature are called rigid thermosetting and thermosets whose matrix has a Tg lower than the operating temperature are called elastomers. For the purposes of the present invention, thermosetting is understood to mean both rigid thermosets and elastomers. Materials made from thermosetting polymers have the advantage that they can be cured to give them high mechanical, thermal and chemical resistance and for this reason they can replace metals in some applications. They have the advantage of being lighter than metals. They can also be used as matrices in composite materials. Conventional thermosets must be manufactured, in particular they must be molded, with the right form for their end use. Indeed, no transformation is no longer possible once they are polymerized, except machining that remains delicate because of their fragility. Flexible or hard parts and composites based on thermosetting resins are not transformable, can not be shaped, they can not be recycled. Thermoplastics belong to another class of polymeric materials. Thermoplastics can be shaped at high temperature by molding or injection but have less interesting mechanical and thermal and chemical properties than thermosets. In addition, the shaping of thermoplastics can often be carried out only in very narrow temperature ranges. Indeed, the thermoplastics when heated become liquids whose fluidity varies abruptly in the vicinity of melting / glass transition temperatures which does not allow them to apply a variety of transformation methods that exist for glass and for metals for example.
The novel polymer compositions, including crosslinked polymers, can combine the mechanical properties and insolubility of a thermoset and be implemented as a thermoplastic. It has thus been possible to develop polymer compositions which have the mechanical properties and the insolubility of a thermosetting but which can be heat-converted after hardening. In particular, materials capable of being heated to such temperatures as to become liquid without undergoing destruction or degradation of their structure have been developed. In addition, for environmental reasons, the polymer composition is advantageously recyclable.
It has been possible to develop a method for modifying the behavior of a polymer, in particular thermoplastic, by crosslinking and creating exchangeable bonds. Interestingly, these modifications can be made to the polymer during forming operations of said polymer, for example extrusion, injection or compression.
Thus, the object of the invention is to provide polymer compositions which can combine the properties of thermosets and thermoplastics, which can be prepared by mixing with a polymer one or more additives (s) making it possible to form a polymer composition. crosslinked, advantageously a crosslinked network, containing exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions or imine-imine and without the need to resort to the crosslinking step in polymers or additives containing primary amine functions. The polymer may be functionalized imine and / or aldehyde before the addition of said additive or the addition of said additive may allow the imine and / or aldehyde functionalization of the polymer and the crosslinking.
Furthermore, the invention aims at a method for modifying the behavior, for example the rheology, of a polymer by adding to the composition comprising such a polymer one or more additive (s). This (these) additive (s) is (are) functionalized (s) imine and / or aldehyde and allows (tent) to form a crosslinked polymer composition, preferably a crosslinked network containing exchangeable bonds, by aldehyde exchange reaction. imine and / or imine-imine exchange reaction. The polymer may be functionalized imine and / or aldehyde before the addition of said additive or the addition of said additive may allow the imine and / or aldehyde functionalization of the polymer and the crosslinking.
To do this, the inventors have devised and developed compositions for obtaining crosslinked polymer compositions, advantageously polymer networks, containing crosslinking points and exchangeable pendant functions.
The presence of pendant exchangeable functions and exchangeable functions in the crosslinking points makes it possible to easily control the macroscopic behavior of the polymer networks formed, independently of the degree of crosslinking. Thus, for a given crosslinking rate, a given temperature and a given deformation, a polymer network of the invention will relax the stresses faster if it contains more exchangeable pendant functions. Similarly, for a given crosslinking rate, a given temperature and a given constraint, a network of the invention will flow faster if it contains more exchangeable pendant functions.
The inventors have tried, unsuccessfully, to prepare networks of methacrylic and styrenic polymers containing pendant alcohol functions and crosslinking points incorporating ester functions in order to obtain thermosetting systems which, although insoluble even when hot, can be used. flow and be malleable.
For this purpose, polymer networks prepared from monomers carrying alcohol functions, such as, inter alia, 2-hydroxyethyl methacrylate or 4-vinylbenzyl alcohol, and crosslinking agents containing ester functions, such as, inter alia, ethylene glycol dimethacrylate 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, bisphenol A dimethacrylate, were prepared in the presence of various transesterification catalysts, such as, inter alia, zinc acetate, titanium (IV) ethoxide, , titanium (IV) isopropoxide, triphenylphosphine or triazabicyclodecene. The various formulations tested did not make it possible to prepare polymer compositions which have the mechanical properties of a thermosetting compound while being heat-transformable after hardening, without undergoing degradation of their structure, or which can be recycled without significant loss of their mechanical properties.
The inventors have also tried, unsuccessfully, to prepare from monomers or polymers containing pendant primary amine functions networks of methacrylic polymers containing crosslinking points incorporating imine functions in order to obtain thermosetting systems which, although insoluble even hot, can flow and be malleable.
To do this, methacrylic polymer networks containing crosslinking points incorporating imine functions have been prepared from methyl methacrylate, monomers bearing primary amine functions, such as 2-aminoethyl methacrylate, 2-aminoethyl methacrylamide or 4-vinylbenzylamine and crosslinking agent containing imine functions, such as the compound of formula (I) CFI, and / or terephthalaldehyde. The various formulations tested did not make it possible to prepare polymer compositions which have the mechanical properties of a thermosetting compound while being heat-transformable after hardening, without undergoing degradation of their structure, or which can be recycled without significant loss of their mechanical properties.
Similarly, the inventors have tried, unsuccessfully, to prepare networks of methacrylic and styrenic polymers containing pendant functions primary ketimines or secondary ketimines and crosslinking points incorporating secondary ketimines in order to obtain thermosetting systems which, although insoluble even hot, can flow and be malleable. The various formulations tested did not make it possible to prepare polymer compositions which have the mechanical properties of a thermosetting agent while being heat-transformable after curing or which can be recycled without significant loss of their mechanical properties.
where Rx, Ry and Rw are hydrocarbon groups, identical or different, as defined below.
Surprisingly, the inventors have been able to successfully prepare polymer networks containing pendant aldimine or secondary aldimine pendant functions and / or aldehyde functions and crosslinking points incorporating secondary aldimines. The inventors have thus been able to successfully prepare thermosetting systems which, although insoluble even when hot, can flow and be malleable.
where Rx and Ry are hydrocarbon groups, identical or different, as defined below.
It has thus been possible to prepare polymer compositions which exhibit the mechanical properties and the insolubility of a thermosetting material but which are convertible after hardening at a temperature above the glass transition temperature (Tg) or the melting temperature (Tf). the polymer, preferably greater than Tg or Tf + 10 ° C, more preferably greater than Tg or Tf + 20 ° C, still more preferably greater than Tg or Tf + 40 ° C, still more preferably greater than Tg or Tf + 80 ° C, if the glass transition temperature or the melting temperature is below 25 ° C, without undergoing destruction or degradation of their structure, and which can be recycled without significant loss of their mechanical properties.
PRESENTATION OF THE INVENTION The subject of the invention is a composition comprising (a) crosslinked polymers containing exchangeable pendant bonds and exchangeable crosslinking points, by aldehydeimine exchange reactions and / or by imine exchange reactions. imine, obtained by crosslinking linear or branched polymers and (b) monofunctional free aldehydes and / or monofunctional free imines.
The linear or branched polymers advantageously contain less than 0.5 mmol of primary amine and primary ammonium functions per gram of polymers before crosslinking and less than 0.1 mmol of primary primary amine and primary ammonium functions per gram of polymers after crosslinking
Advantageously, these compositions comprise aldehydes and at least 1 mol% of the aldehyde functions are aromatic aldehyde functions. This molar percentage is calculated with respect to the total number of moles of aldehyde functional groups bound to the polymers or molecules.
Advantageously, the polymers, before crosslinking, are linear or branched polymers having side groups bearing: aldehyde functional groups, or imine functional groups linked to the polymer by the carbon atom, or imine functional groups linked to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom.
In a variant, the composition results from mixing, in the molten state or in solution: of at least one linear or branched polymer PI having side groups carrying: aldehyde functional groups, or imine functional groups linked to the polymer by carbon atom, or imine functional groups linked to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom D'at least one additive bearing at least two imine and / or aldehyde functional groups capable of reacting with the side groups of the polymer PI to form a crosslinked network with exchangeable bonds by aldehyde-imine exchange reactions or by imine-imine exchange reactions; advantageously, monofunctional free aldehydes. The additive is advantageously a compound of formula (I) below:
wherein n, i, the dotted bond, Y and Z, R2, R3, Wa, W2i, R ', R ", and R'" are as defined below. R4 represents a hydrocarbon group linked to the imine and / or aldehyde functions by a covalent bond via a carbon atom. The additive may also be a linear or branched polymer P2 carrying aldehyde functional groups, or imine functional groups linked to the polymer by the carbon atom, or imine functional groups linked to the polymer by the atom. nitrogen, or - aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom.
In a variant, the composition results from the mixing, in the molten state or in solution: of at least one linear or branched polymer PI 'comprising functions allowing a grafting,
A combination of molecules including molecules comprising at one end a functional group for covalently linking the molecule to the polymer ΡΓ and at the other end a functional group selected from an imine function connected by its carbon atom, a linked imine function by its nitrogen atom, or an aldehyde function, and / or molecules comprising at two of their ends functional groups for covalently linking the molecule to the polymer ΡΓ and between its two ends an imine function, the combination to allow grafting and the creation of exchangeable pendant bonds and exchange points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions; advantageously, monofunctional free aldehydes.
Advantageously, the aldehyde is a molecule for which the aldehyde function is carried by an aryl group, heteroaryl or the alkene function of a terpenoid.
The linear or branched polymer, advantageously PI, PI 'or P2, is advantageously a polymer chosen from vinyls, polyolefins, polyamides and polysaccharides. The invention also relates to a process for preparing a crosslinked polymer composition, said process comprising the following steps:
Choose a linear or branched polymer PI having side groups carrying: aldehyde functional groups, or imine functional groups connected to the polymer by the carbon atom, or imine functional groups linked to the polymer by the carbon atom, or aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom;
Choose at least one additive bearing at least two imine and / or aldehyde functional groups capable of reacting with the side groups of the polymer P1 to form a crosslinked polymer composition containing exchangeable pendant bonds and exchange points exchangeable by aldehyde exchange reactions -imine and / or imine-imine exchange reactions; - Mix, in the molten state or in solution, said polymer PI, said additive and optionally a monofunctional free aldehyde, to obtain said composition. The invention also relates to a process for preparing a crosslinked polymer composition, said process comprising the following steps:
Choose a linear or connected polymer ΡΓ including functions allowing a grafting,
Choose a combination of molecules including molecules comprising at one end a functional group for covalently bonding the molecule to the polymer ΡΓ and at the other end a functional group selected from an imine function connected by its carbon atom, an imine function connected by its nitrogen atom, or an aldehyde function, and / or molecules comprising at two of their ends functional groups for covalently linking the molecule to the polymer ΡΓ and between these two ends an imine function, the combination in front of allow the grafting and the creation of exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions; Mix, in the molten state or in solution, said polymer PI ', said combination and optionally a monofunctional free aldehyde, to obtain said composition. The subject of the invention is also the use of aldehyde to catalyze the imine-imine metathesis reactions and the imine-aldehyde exchange reactions carried out in the compositions defined above. The subject of the invention is also a material obtained from the composition according to the invention. The invention also relates to a formulation comprising a composition according to the invention. The subject of the invention is also the use of an additive as defined in the invention, or of a combination as defined in the invention, in the presence of a linear or connected polymer PI or ΡΓ for the formation a composition comprising crosslinked polymers, advantageously a crosslinked network, containing exchangeable pendant bonds and exchange points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions and monofunctional free aldehydes and / or monofunctional free imines. The invention also relates to combinations for cross-linking linear or branched polymers, said combinations being chosen from combinations comprising:
A monofunctional free aldehyde + compound of formula (I), according to the invention; A monofunctional free aldehyde + polymer P2, according to the invention; A and / or B + C, and optionally a monofunctional free aldehyde according to the invention; A and / or B and / or C + D, and optionally a monofunctional free aldehyde according to the invention; A and / or B + compound of formula (I) for which Z and Wj. are N, and optionally a monofunctional free aldehyde according to the invention; or C + compound of formula (I) for which Z and Wx are a carbon atom, and optionally a monofunctional free aldehyde according to the invention A, B, C, D corresponding to the following formulas: (A) GrRx-CH = N R1, (B) G2-R'x-CI-NO, (C) G3-R "yN = CH-R" x and (D) G4-R "'x-CH = N-R'" y- G5 where the letters G1, G2, G3, G4 and G5 represent a functional group for covalently linking the molecules to the polymer chains to be functionalized, Rx, R'x, R "x, R '" x and Ry, R " Y, R "'are hydrocarbon groups. The subject of the invention is also the use of a combination according to the invention, in the presence of a linear or connected polymer PI or PI 'for the formation of a composition comprising crosslinked polymers, advantageously of a crosslinked network , containing exchangeable pendant bonds and exchange points exchangeable by aldehyde-imine exchange reactions and / or imine-imine exchange reactions and monofunctional free aldehydes and / or monofunctional free imines, in particular for modifying the rheology a composition, such as an oil or a paint, comprising said PI or PI 'polymer by adding to the composition of the combination according to the invention; the rheology is modified by choosing the concentration in said combination. Definitions: Polymer definition, linear polymer, connected polymer:
A polymer consists of a set of polymer chains of different molecular sizes, in particular of different molar masses. A polymer chain according to this invention is a chain of atoms bound only by covalent bonds CC, C = C, CX or C = X, where X is a chemical element other than carbon, advantageously with the exception of the double C = N link for the main chain. The polymer chains are derived from the covalent assembly of a large number of repeating units called monomer units. The polymer chains thus defined have molecular dimensions (characterized by their molar mass) much greater than those of single molecules and are derived from the covalent assembly of more than 5 monomer units, advantageously more than 20 monomeric units, more advantageously of more than 50 monomer units.
Polymeric chains consisting of a single type of monomer unit are called homopolymers. Polymeric chains consisting of several types of monomer unit are called copolymers. According to this invention, polymer and polymer chain are understood to mean both homopolymers and copolymers.
The constituent monomeric units of the polymer chain may be linked to a variable number of other monomer units. The number of other monomer units to which a monomer unit is attached is called valence. A monomer unit which is linked to a single other monomer unit has a valence of 1 and corresponds to a polymer chain end. A monomer unit that is linked to two other monomeric units has a valence of 2 and corresponds to a linear sequence of a polymer chain. A monomer unit that is linked to more than two other monomeric units has a valence greater than 2 and corresponds to a branch point. A polymer chain that has two ends is a linear polymer chain. A linear polymer chain is thus composed of monomer units having a valency of 2 and of two monomer units having a valence of 1. A polymer chain having more than two ends and whose molecular weight has a finite value is a branched polymer chain or connected. A branched or branched polymer chain is thus composed of monomer units having a valency of 2, monomer units having a valence greater than 2 and more than two monomer units having a valence of 1.
According to this invention, polymer and polymer chain are understood to mean both polymers and linear polymer chains as well as polymer and branched polymer chains. Definition of a pending function:
A function is pendent if it is bound by a covalent bond by one and only one of its hydrocarbon substituents (Rx or Ry aldimines or aldehyde, see definition below) to a monomer unit having a valence greater than 1. In other words a function is pendent if it is linked by a covalent bond to a polymer chain by one and only one of its hydrocarbon substituents (Rx or Ry of the aldimines or aldehyde, see definition below) and if it does not constitute an end of the chain polymer.
A function is terminal, or constitutes a chain end, if it is bound by a covalent bond by one and only one of its hydrocarbon substituents (Rx or Ry, aldimines or aldehyde, see following definition) to a monomer unit having a valence equal to 1.
An imine function is part of a crosslinking point if it is bound by its hydrocarbon substituent Rx, via a covalent bond, to a monomeric unit covalently connected to at least two other monomeric units not including said imine function, and if it is bound by its hydrocarbon substituent Ry, via a covalent bond, to a monomeric unit covalently connected to at least two other monomeric units not including said imine function.
Thus, by the term "pendant group" is meant, in the sense of the present invention, a lateral group of the polymer chain. For the purposes of the present invention, the term "side group" refers to a substituent which is not an oligomer or a polymer. A lateral group is not integrated in the main chain of the polymer. By the term "group during imine" is meant, in the sense of the present invention, a side group comprising a primary aldimine or secondary aldimine function. In the presence of a secondary aldimine, Rx-ONH-Ry, one of these two substituents is not bound to a polymer chain, except via the imine function. The imine may be attached to the side group by its carbon or nitrogen atom. By the term "group during aldehyde" is meant, in the sense of the present invention, a side group comprising an aldehyde. Definition of a free molecule:
According to this invention, a molecule is said to be "free" if it is not bound by a covalent bond to a polymer of the composition.
According to this invention, a "monofunctional free aldehyde" is a free molecule containing one and only one aldehyde function. A "monofunctional free aldehyde" may or may not contain one or more other functions as long as these are not imine, aldehyde or primary amine functions.
According to this invention, a "monofunctional free imine" is a free molecule containing one and only one imine function. A "monofunctional free imine" may or may not contain one or more other functions as long as these are not imine, aldehyde or primary amine functions. Definition crosslinking:
Crosslinking, or crosslinking of polymer chains, consists in creating covalent chemical bonds between polymer chains initially not bonded to one another by covalent bonds. The crosslinking is accompanied by an increase in connectivity, via covalent bonds, between the different polymer chains constituting the polymer. The crosslinking of linear or branched polymer chains is accompanied by an increase in the molecular dimensions of the chains, especially molar masses, and may lead to the production of a network of crosslinked polymers. The crosslinking of a network of crosslinked polymers is accompanied by an increase in the insoluble mass fraction in a good non-reactive solvent as defined below.
In the context of the invention, the crosslinking results, inter alia, from metathesis reactions between the imine functions and / or from exchange reactions between the imine and aldehyde functions carried by the pendant groups of the polymers and / or borne by the pendant groups. polymers and by the compounds of formula (I). Advantageously, the crosslinking results exclusively from metathesis reactions between the imine functions and / or exchange reactions between the imine and aldehyde functions carried by the pendant groups of the polymers and / or borne by the pendant groups of the polymers and by the compounds of formula (I). Thus, for any crosslinking reaction by metathesis reaction between imine functions, respectively for any crosslinking reaction by exchange reaction between imine and aldehyde functions, one equivalent of monofunctional free imine, respectively one equivalent of free monofunctional aldehyde, is generated, as illustrated in FIG. 3 in the case of crosslinking by metathesis reaction of linear polymers functionalized by complementary pendant imine functions.
By the term "network of crosslinked polymers" is meant, within the meaning of the present invention, a set of polymer and / or oligomeric chains connected to each other by covalent bonds and which is immersed at a mass dilution of 10 in a good solvent. The reagent of the polymer and / or oligomeric chains constituting it will have an insoluble mass fraction greater than 0.1%, advantageously greater than 0.5%, 1%, 2%, 5%, 10%, 20%, 30%, 40%. , 50%, 70% after 48 hours immersion at atmospheric pressure and for a temperature between the melting point and the boiling point of the solvent. A good non-reactive solvent is a good solvent which will not degrade the polymer chains, the imine or aldehyde functions, and which will not participate in imine-imine or aldehyde-imine exchange reactions. The insolubility can be evaluated with the naked eye or by passing the formulation on a filter having a porosity of 0.2 micrometer, advantageously 0.4 micrometer, even more preferably 1 micrometer.
The crosslinking is accompanied by the creation of crosslinking points interconnecting at least two polymer chains. These crosslinking points advantageously comprise imine functions. Thus, after crosslinking, the composition comprises imine functions at the crosslinking points and advantageously polymers comprising pendant imine and / or aldehyde functions.
Advantageously, the crosslinking results from metathesis reactions between the imine functions and / or exchange reactions between imine and aldehyde functions carried by the pendant groups of the polymers and / or borne by the pendant groups of the polymers and the compounds of formula (I ). Thus, for any crosslinking reaction by metathesis reaction between imine functions, respectively for any crosslinking reaction by exchange reaction between imine and aldehyde functions, one equivalent of monofunctional free imine, respectively one equivalent of free monofunctional aldehyde, is generated. This is illustrated by FIG. 3 in the case of cross-linking by metathesis reaction of linear polymers functionalized by complementary pendant imine functions. Definition of the glass transition:
The glass transition temperature, Tg, is defined as the temperature at which the value of the damping factor, or loss factor, tan δ is maximum by dynamic mechanical analysis at 1 Hz. The damping or loss factor, tan δ is defined as the ratio of the loss module E "on the conservation module E '(Mechanical Properties of Solid Polymers, Author (s): IM Ward, J. Sweeney; Editor: Wiley-Blackwell; Edition: 3rd Edition; Print ISBN: 9781444319507; DOI: 10.1002 / 9781119967125) Definition composition of polymers:
A polymer composition is defined as a homogeneous or non-homogeneous mixture of linear or branched polymers, capable of being bound by crosslinking points, containing exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions with potentially various fillers, additives or solvents, as defined below.
Thus, by the formula "polymer composition" is meant both solid formulations containing no or little solvent (s), as liquid formulations, containing a mass fraction of solvent (s) more important.
Thus, the term "formulation" is understood to mean both solid formulations and liquid formulations.
According to the invention, a solid formulation contains less than 30% by weight of solvent (s), more preferably less than 25% by weight of solvent (s), still more advantageously less than 20% by weight of solvent (s), even more advantageously less than 15% by mass of solvent (s), still more advantageously less than 10% by mass of solvent (s), still more advantageously less than 5% by mass of solvent (s), still more advantageously less than 2.5% by mass of solvent (s), still more preferably less than 1% by weight of solvent (s), still more preferably less than 0.5% by weight of solvent (s).
According to the invention, a solid formulation is a material.
According to the invention, a liquid formulation contains more than 30% by weight of solvent (s), more preferably more than 50% by weight of solvent (s), more advantageously more than 60% by weight of solvent (s), even more advantageously more than 70% by weight of solvent (s), more advantageously more than 75% by weight of solvent (s).
According to the invention, a liquid formulation can be a material.
A solvent is defined as a molecule, or a mixture of molecules, which is liquid at room temperature and which has the property, at room temperature, of dissolving and / or diluting other substances without modifying them chemically and without itself being modified. . Among the solvents, there are good solvents which have the property of dissolving at room temperature the substances without modifying them chemically and without itself modifying themselves, and the bad solvents which have the property of diluting without dissolving or modifying the substances chemically. at room temperature and without itself changing.
A solvent can therefore be a good solvent for one compound and a bad solvent for another compound. By way of non-limiting examples, mention may be made, as a solvent, of ethyl acetate, butyl acetate, acetone, acetonitrile, benzyl alcohol, acetic anhydride, anisole, benzene, butanol, butanone, chlorobenzene, chloroform, cyclohexane, dichloroethane, dichloromethane, dimethylformamide, dimethylsulfoxide, dioxane, water, ethanol, glycol ether, diethyl ether , ethylene glycol, heptane, hexane, mineral oils, natural oils, synthetic oils, hydrocarbons, methanol, pentane, propanol, propoxypropane, pyridine, tetrachloroethane, tetrachloromethane, tetrahydrofuran, toluene, trichlorobenzene, xylene, and mixtures thereof. Definition of radicals:
For the purposes of the present invention, the term "hydrocarbon group" is intended to mean a group comprising carbon and hydrogen atoms. This group may also include heteroatoms and / or be substituted by halogens. The hydrocarbon group advantageously comprises from 1 to 50, preferably 1 to 18, preferably 1 to 12, carbon atoms.
For the purposes of the present invention, the term "heteroatom" means atoms of sulfur, nitrogen, oxygen, boron, phosphorus and silicon.
By "halogen" is meant, in the sense of the present invention, the fluorine, chlorine, bromine and iodine atoms.
The hydrocarbon groups may be aliphatic or aromatic.
For the purposes of the present invention, the term "aliphatic" means an "alkyl", "alkenyl", "alkanediyl", "alkenediyl" or "cycloalkyl" group. The valence of the grouping will be Valued by the grouping of the grouping of the group.
The aliphatic group may include heteroatoms. In particular, it may be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide or anhydride functions. Where appropriate, the aliphatic group may be substituted in particular by a halogen, a group -R.sub.z, -OH, -NHR.sub.2, -NR.sub.zR'.sub.z, -C (O) -OH, -C (O) -NR.sub.Zrz, - C (O) -O-Rz, -O-C (O) -Rz, -O-C (O) -O-Rz, -O-C (O) -N (H) -Rz, -N (H) ) -C (O) -O-Rz, -O-Rz, -S-Rz, -C (O) -N (H) -Rz, -N (H) -C (O) -Rz with Rz, R z, identical or different, representing an alkyl radical C 50 C, or by a functional group selected from functional groups polymerizable by radical polymerization, aldehyde and / or imine functions.
By "alkyl" group is meant, in the sense of the present invention, a linear or branched, saturated or unsaturated hydrocarbon-based chain, advantageously comprising 1 to 50, preferably 1 to 18, preferably 1 to 12, carbon atoms, and which may include one or more heteroatoms. Thus, by language abuse, within the meaning of the invention the term "alkyl" also includes: - "alkenyls", that is to say, hydrocarbon chains having at least one double bond; "heteroalkyl", that is to say the alkyl groups as defined above comprising at least one heteroatom.
By "alkanediyl" group is meant, in the sense of the present invention, a divalent, saturated or unsaturated hydrocarbon chain, linear or branched, advantageously comprising from 1 to 50, preferably 1 to 18, preferably 1 to 12, carbon atoms. carbon and which may comprise one or more heteroatoms. Thus, for abuse of language, within the meaning of the invention the term "alkanediyl" also encompasses "alkenediyls", that is to say hydrocarbon chains comprising at least one double bond, such as, for example, a vinylene group ( ethenylene) or propenylene and the "heteroalkanediyl", that is to say the alkanediyl groups as defined above comprising at least one heteroatom.
By "terpenoid" is meant according to the invention any group comprising a skeleton close to a terpene. A "terpene" refers to a derivative of isoprene which is obtained by connecting C5H8 units, leading for example to monoterpenes, sesquiterpenes. By "near" is meant that the backbone is similar to a terpene or different in that at least one alkyl substituent, normally present, may be absent or carried by another atom. The backbone can be further substituted by various radicals such as aliphatic radicals, oxy, aldehydes, esters, alcohols, ethers and their sulfur or nitrogen equivalents. On a case by case basis, this "terpenoid" group will be monovalent or divalent.
By "cycloalkyl" group is meant, in the sense of the present invention, a cyclic alkyl chain, saturated or partially unsaturated, but not aromatic, advantageously comprising from 3 to 10 ring carbon atoms. The alkyl chain may comprise one or more heteroatoms, specifically referred to as "heterocycloalkyl". The grouping may comprise more than one cycle and thus comprise fused, linked or spiro rings. By way of example, mention may be made of cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, pyrrolidinyl, piperidinyl, piperazinyl or morpholinyl groups. Where appropriate, the cycloalkyl group may be substituted in particular by a halogen, a group -R.sub.z, -OH, -NHR.sub.2, -NR.sub.zR'.sub.z, -C (O) -OH, -C (O) -NR.sub.Zrz, - C (O) -O-Rz, -O-C (O) -Rz, -O-C (O) -O-Rz, -O-C (O) -N (H) -Rz, -N (H) ) -C (O) -O-Rz, -O-Rz, -S-Rz, -C (O) -N (H) -Rz, -N (H) -C (O) -Rz with Rz, R z, identical or different, representing a C 1 -C 50 alkyl radical, or by a functional group chosen from radical-polymerizable functional groups, aldehyde and / or imine functions. If appropriate, the cycloalkyl group may be divalent, it will then speak advantageously of "cycloaliphatic" radical.
By "aromatic" is meant, in the sense of the present invention, a monovalent or multivalent group comprising an aromatic hydrocarbon group. The valence of the grouping will be determined on a case by case basis.
The aromatic group may comprise heteroatoms, which will then be referred to specifically as "heteroaromatic" radical. In particular, it may be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide or anhydride functions. The aromatic group may comprise one or more contiguous or covalently linked rings. Where appropriate, the aromatic group may be substituted in particular by a halogen, a group -R.sub.z, -OH, -NHR.sub.2, -NR.sub.zR'.sub.z, -C (O) -OH, -C (O) -NR.sub.Zrz, - C (O) -O-Rz, -O-C (O) -Rz, -O-C (O) -O-Rz, -O-C (O) -N (H) -Rz, -N (H) ) -C (O) -O-Rz, -O-Rz, -S-Rz, -C (O) -N (H) -Rz, -N (H) -C (O) -Rz with Rz, R z, identical or different, representing a C 1 -C 5 alkyl radical, or by a functional group chosen from radical-polymerizable functional groups, aldehyde and / or imine functions.
The term "aromatic" includes "arylaliphatic" groups, that is to say a group comprising at least one aromatic group and at least one aliphatic group, as defined. The aliphatic group may be attached to one part of the molecule and the aromatic group may be linked to another part of the molecule. The group may comprise two aromatic groups, each connected to a part of the molecule, and connected to each other by an aliphatic chain.
By "aryl" is meant in the sense of the present invention, an aromatic hydrocarbon group. The term "aryl" embraces aralkyl and alkylaryl groups. The aromatic hydrocarbon group may be substituted one or more times, in particular with a halogen, a group -R 2, -OH, -NHR 2, -NR 2 R'z, -C (O) -OH, -C (O) -NR 2 R'z, -C (O) -O-Rz, -O-C (O) -Rz, -OC (O) -O-Rz, -O-C (O) -N (H) -Rz, -N (H) -C (O) -O-Rz, -O-Rz, -S-Rz, -C (O) -N (H) -Rz, -N (H) -C (O) -Rz with Rz, R ' z, identical or different, representing a C1-C50 alkyl radical, or by a functional group chosen from radical-polymerizable functional groups, aldehyde and / or imine functions.
By "alkyl-aryl" is meant, in the sense of the present invention, an alkyl group ti! as defined above, linked to the rest of the molecule through an aromatic group as defined above.
For the purposes of the present invention, the term "aralkyl" means an aryl group as defined above, linked to the remainder of the molecule via an aliphatic group as defined above.
For the purposes of the present invention, the term "heteroaryl" means an aryl group for which at least one of the atoms of the aromatic ring is a heteroatom. By "heteroalkyl-aryl" is meant in the sense of the present invention, an alkyl-aryl group as defined substituted by at least one heteroatom. By "heteroaralkyl" is meant in the sense of the present invention, an aralkyl group as defined substituted by at least one heteroatom.
By the term "imine" is meant in the sense of the present invention, a group comprising the function C = N. For the purposes of the invention, the imine is a primary or secondary aldimine:
where Rx and Ry are different from H and may be the same or different. Rx and Ry are hydrocarbon radicals as defined above. Advantageously, the imine is a secondary aldimine. Within the meaning of the invention, the radicals Rx and Ry are linked to the imine function by a covalent bond via a carbon atom. The imine and aldehyde groups of the invention have the following structures:
where Rx and Ry are hydrocarbon groups and wherein the atom of the groups Rx and Ry bonded to the imine or aldehyde function is a carbon atom.
In particular, independently for each group, R 1 represents an alkyl, aryl, aralkyl, alkyl-aryl or cycloalkyl radical. This radical may contain heteroatoms, in particular chosen from O, N, S or Si, and / or may be substituted. R 1 is advantageously an aryl, heteroaryl or terpenoid group. Advantageously, when the aldehyde function is carried by a terpenoid group, the aldehyde function is directly linked to an alkene function of the terpenoid.
In particular, this radical Rx 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, -NRzR'z, -C (O) -OH, -C (O) -NRzR'z, -C (O) group. -O-Rz, -O-C (O) -Rz, -O-C (O) -O-Rz, -OC (O) -N (H) -Rz, -N (H) -C (O) -O-Rz, -O-Rz, -S-Rz, -C (O) -N (H) -Rz, -N (H) -C (O) -Rz with Rz, R'z, same or different , representing a C1-C50 alkyl radical. In particular, this radical Rx may be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide or anhydride functions.
In particular, independently for each group, Ry represents an alkyl, aryl, aralkyl, alkyl-aryl or cycloalkyl radical. This radical may contain heteroatoms, in particular chosen from O, N, S or Si, and / or may be substituted. In particular, this radical Ry may be substituted with functional groups, such as ester or amide functions. In particular, this radical is substituted by a halogen, a -Rz, -OH, -NHRz, -NRzR'z, -C (O) -OH, -C (O) -NRzR'z, -C (O) group. -O-Rz, -O-C (O) -Rz, O-C (O) -O-Rz, -O-C (O) -N (H) -Rz, -N (H) -C (O) ) -O-Rz, -O-Rz, -S-Rz, -C (O) -N (H) -Rz, -N (H) -C (O) -Rz with Rz, R'z, identical or different, representing a C 50 alkyl radical. In particular, this radical Ry can be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide, anhydride functions.
These imine and aldehyde groups are advantageously linked, by Rx and / or Ry, to a polymer chain or to a functional group G allowing the molecules to be covalently bonded to the polymer chains to be functionalized, as defined hereinafter.
Description of the figures:
Figure 1. Representation of the molecules that can be used for functionalization and crosslinking in one step of the polymers.
Figure 2. Schematic representation of the functionalization of linear polymers 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 allowing the grafting of the molecules A (left), respectively the molecule C (right), can be part of the main chain (top) or the lateral / pendant groups (bottom) of the linear polymer to be functionalized.
Figure 3. Schematic representation of the crosslinking by metathesis reaction of functionalized linear polymers with complementary pendant imine functions.
Figure 4. Evolution of the elastic modulus (ordinates, MPa) as a function of temperature (abscissae, ° C) for the non-recycled N7 crosslinked polymer network (first generation, triangle), the network of cross-linked polymers N7 recycled twice (third generation; round) and the network of crosslinked polymers N7 recycled 3 times (4th generation, square).
Figure 5. Breaking stress (ordinate, MPa) for non-recycled N7 crosslinked polymer network samples (abscissa, 0), for samples of the N7 crosslinked polymer network recycled once (sbscisses, 1), for samples of the network of crosslinked polymers N7 recycled twice (abscissa, 2) and for the samples of the network of crosslinked polymers N7 recycled 3 times (abscissa, 3).
Figure 6. Elongation at Break (Ordered,%) of Non-Recycled N7 Cross-linked Polymer Network Samples (abscissa, 0), for samples of the network of N7 cross-linked polymers recycled once (x-axis, 1), for samples of network of N7 crosslinked polymers recycled twice (abscissa, 2) and for the samples of the network of crosslinked polymers N7 recycled 3 times (abscissa, 3).
Figure 7. Deformation (ordinates,%) as a function of time (abscissa, min) of non-recycled N7 crosslinked polymer network samples (1st generation, solid line), N7 network of cross-linked polymers recycled 2 times (3rd generation, line long line) and the network of N7 cross-linked polymers recycled 3 times (4th generation, short dotted line).
Figure 8. Shear relaxation modulus normalized by the initial modulus at t = 0 (ordinates, without unit) as a function of time (abscissa, seconds) of crosslinked polymer network samples NI (square), network of crosslinked polymers N4 (triangle), network of crosslinked polymers N5 (round) and crosslinked polymer network N6 (star).
The invention relates to a composition comprising (a) crosslinked polymers containing exchangeable pendant bonds and exchange points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions, obtained by crosslinking linear or branched polymers, (b) monofunctional free aldehydes and / or monofunctional free imines. Advantageously, the crosslinking step does not require the use of polymers or additives containing primary amine functions. The crosslinking results, in part or completely, from metathesis reactions between the imine functions and / or exchange reactions between the imine and aldehyde functions borne by the pendant groups of the polymers and / or carried by the pendant groups of the polymers and the compounds of formula (I). Thus, for any crosslinking reaction by metathesis reaction between imine functions, respectively for any crosslinking reaction by exchange reaction between imine and aldehyde functions, one equivalent of monofunctional free imine, respectively one equivalent of free monofunctional aldehyde, is generated, as illustrated in FIG. 3 in the case of crosslinking by metathesis reaction of linear polymers functionalized by complementary pendant imine functions. Such a composition advantageously forms a network of crosslinked linear or branched polymers containing exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions. Such a composition advantageously contains less than 1 mmol, more advantageously less than 0.8 mmol, even more advantageously less than 0.6 mmol, even more advantageously less than 0.4 mmol, still more advantageously less than 0.2 mmol, still more preferably less than 0.1 mmol, still more preferably less than 0.05 mmol, still more preferably less than 0.025 mmol, still more preferably less than 0.02 mmol, still more preferably less than 0.01 mmol, still more advantageously less than 0.005 mmol of primary amine and primary ammonium functions per gram of polymers after crosslinking.
The polymers, before crosslinking, are advantageously linear or branched polymers having side groups bearing: aldehyde functional groups, or imine pendant functional groups linked to the polymers by their carbon atom, or pendant imine functional groups linked to the polymers by their nitrogen atom, or aldehyde functional groups and imine pendant functional groups linked to the polymers by their carbon atom.
These polymers may be functionalized before and / or during the crosslinking, advantageously leading to the formation of a network of crosslinked polymers containing exchangeable crosslinking points and pendant bonds exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions.
The side groups exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions of the linear or branched polymers are advantageously distributed over the entire chain. Thus, preferably, the linear or branched polymers do not have a diblock structure, with a block containing the side groups and a block containing no exchangeable side groups by aldehyde-imine exchange reactions and / or by exchange reactions. imine imine. Preferably, the side groups exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions are distributed randomly over the entire polymer chain. Preferably, if the side groups exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions are distributed in block, then the polymer has a multiblock structure with blocks containing the exchangeable side groups distributed all along the polymer chain.
The polymers before crosslinking preferably contain less than 2 mmol, still more preferably less than 1.5 mmol, still more preferably less than 1 mmol, still more preferably less than 0.8 mmol, still more preferably less than 0.6 mmol, still more more preferably less than 0.5 mmol, still more preferably less than 0.4 mmol, still more preferably less than 0.25 mmol, still more preferably less than 0.2 mmol, still more preferably less than 0.1 mmol, still more more preferably less than 0.05 mmol of primary amine and / or primary ammonium functions per gram of polymers.
When the polymers before crosslinking are branched polymers, these polymers are advantageously not dendrimers. When the polymers connected before crosslinking are dendrimers, these dendrimers are advantageously generation three dendrimers or generation two dendrimers.
In a first variant, the polymer is functionalized before crosslinking. In particular, the composition results from mixing, in the molten state or in solution: of at least one linear or branched polymer PI having side groups carrying: aldehyde functional groups, or imine functional groups linked to the polymer by their atom of carbon, or imine functional groups linked to the polymer by their nitrogen atom, or aldehyde functional groups and imine functional groups linked to the polymer by their carbon atom D'at least one additive bearing at least two pendent imine functional groups and / or aldehyde capable of reacting with the pendant groups of the polymer P1 to form the crosslinked polymer composition, advantageously a crosslinked network, containing crosslinking points and pendant bonds exchangeable by aldehyde-imine and / or imine-exchange reactions. imine Advantageously, monofunctional free aldehydes.
To allow the formation of a crosslinked polymer composition, advantageously a network of crosslinked polymers with exchangeable bonds, it is advantageous to use as additive a crosslinking means which, used alone, will not react on itself and lose its features. Thus, the crosslinking means carries: aldehyde functions, or imine functions connected by means of their carbon atom, or imine functions connected by means of their nitrogen atom, or aldehyde functions and imine functions connected to the means by their carbon atom. The additive, crosslinking means, may be a molecule and / or a polymer. Where appropriate, combinations of molecules and / or polymers are possible.
In a first variant, the additive is a molecule comprising at least two imine and / or aldehyde functions. This additive is also referred to as "bi- or multifunctional crosslinking means". This additive can comprise only imine functions, all connected to the rest of the molecule by the carbon atom of the imine bond, or only imine functions, all connected to the rest of the molecule by the nitrogen atom of the bond imine, or only aldehyde functions. It can also include both aldehyde functions and imine functions, all related to the rest of the molecule by the carbon atom of the imine bond.
This additive is advantageously a compound of formula (I) below:
wherein n is an integer ranging from 1 to 6; i is an integer ranging from 1 to n
the dotted bond is present or absent, depending on the valence of Y, Z, W2i Y and Z are different and each represents either C or N, where Y is O and then Z is C • when Y is C, then Z is N, and R 1 is a hydrocarbon group, R 2 is H and R 3 is absent, • when Y is N, then Z is C, and R 1 is H or a hydrocarbon group, R 2 is absent and R 3 is H,
When Y is O, then Z is C and R1, R2 are absent and R3 is H R4 represents a hydrocarbon group linked to the imine and / or aldehyde functions by a covalent bond via a carbon atom in each block Wi (R ' ) = W2i (R "i) (R '"),
Wi and W2i are different and each represents either C or N, where W2i is O and then Wi is C when W2i represents C, then Wx represents N and R 'is absent, R "i represents a hydrocarbon group and R'" represents H when W2i represents N, then Wi represents C and R 'represents H, R ", represents H or a hydrocarbon group, and R'" is absent,
when W2i is O, then W3 is C and R ", R '" are absent and R' is H when Z is C, then Wi is C, when Y is C, then W2i is C. R4 can in particular represent a ring thus allowing the presence of several blocks [W1 (R ') = W2i (R "i) (R"')], possibly on each carbon atom of the ring.
The block [Wi (R ') = W2i (R "i) (R"')] is present n times as a function of the number of possible substitutions on the radical R4. The compound (I) can therefore be a compound called "star". n is an integer ranging from 1 to 6, preferably from 1 to 4. i is an integer ranging from 1 to n. From one block to another (and thus for different values of i), the definition of W2i or R "can vary, which means that the blocks are not necessarily identical to each other. W2 can not vary from one block to another, always C or always N. Similarly, the definition of R 'can not vary from one block to another, always H, or always absent Similarly, the definition of R '' can not vary from one block to the other, either always H or still absent R4 can be linked to the carbon atom or to the nitrogen atom of the functions imine and / or aldehyde. R4 is linked to imine and / or aldehyde functions by a covalent bond via a carbon atom. R4 is advantageously an aliphatic, aromatic, arylaliphatic or cycloaliphatic group which may also include heteroatoms such as O, N, S, or Si. In an advantageous variant, R4 represents an aromatic or heteroaromatic group. Advantageously, R 4 represents a C 1 -C 12 alkanediyl group, a benzene ring, a naphthalenic ring, an arylaliphatic group composed of two benzene rings connected by a C 1 -C 6 alkanediyl group, a pyrimidine ring or a triazine ring.
Advantageously, when Y represents O, then Z represents C, W2 represents C, W2i represents O, R1; R2i R "" R '"are absent and R3 and R' represent H.
Advantageously, when Y represents N or O, then Z represents C, W2 represents C, W2i represents N or O, R2 and R '"are absent, R3 and R' represent H, and, depending on the valence of Y, W2i , R2 and R ", represent a hydrocarbon group or are absent when Y and W2i represent O.
Advantageously, when Y represents C, then Z represents N, W2 represents IM, W2i represents C, R3 and R 'are absent, R2 and R "' represent H, R2 and R" represent a hydrocarbon group.
When present, preferably R2 is hydrogen, alkyl, alkenyl, aryl, cycloalkyl, heteroaryl, heteroalkyl, heterocycloalkyl, each of these groups may be substituted. R2 represents H or is absent. R3 represents H or is absent. Preferably, R 1 represents an alkyl, alkenyl, aryl, heteroaryl, alkyl-aryl, heteroalkyl-aryl, aralkyl, heteroaralkyl, cycloalkyl or heterocycloalkyl group; each of these groups can be substituted.
When 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. "" represents H or is absent. Preferably, R "is alkyl, alkenyl, aryl, heteroaryl, alkyl-aryl, heteroalkyl-aryl, aralkyl, heteroaralkyl, cycloalkyl or heterocycloalkyl, each of which groups may be substituted.
The choice of the nature of the functional groups present on the compound of formula (I) will depend on the nature of the functional groups present on the polymer PI.
Thus, when the pendant groups of the polymer PI carry aldehyde functional groups, a compound of formula (I) in which Z and Wi represent N.sub.2 is chosen as additive.
Thus, when the pendant groups of the polymer PI carry imine functional groups connected to the main chain by the carbon atom, a compound of formula (I) in which Z and Wi represent N.sub.3 is chosen as additive.
Thus, when the pendant groups of the polymer PI carry aldehyde functional groups, a compound of formula (I) in which Z and Wi represent N.sub.2 is chosen as additive.
Thus, when the pendant groups of the polymer PI carry aldehyde functional groups and imine functional groups connected to the main chain by the carbon atom, one selects as additive a compound of formula (I) in which Z and W ! represent N. Thus, when the pendant groups of the polymer PI carry imine functional groups connected to the main chain by the nitrogen atom, a compound of formula (I) in which Z and Wx represent C, Y and W2i represent, each independently of one another, N or O.
In a second variant, the additive is a polymer P2 bearing aldehyde functional groups, or imine pendant functional groups linked to the polymer by the carbon atom, or pendant imine functional groups linked to the polymer via the nitrogen atom. , or aldehyde functional groups and imine pendant functional groups linked to the polymer by the carbon atom.
The choice of the nature of the functional groups present on the polymer P2 will depend on the nature of the functional groups present on the polymer PI.
Thus, when the pendant groups of the polymer PI carry aldehyde functional groups, the polymer P2 is chosen as a polymer comprising imine functional pendant groups, where the imine is connected to the main chain via its nitrogen atom.
Thus, when the pendant groups of the polymer PI carry imine functional groups connected to the main chain by the carbon atom, the polymer P2 is chosen as a polymer comprising functional imine pendant groups, where the imine is connected to the main chain by its nitrogen atom. Δΐηςϊ Inrcmip lp <: nnlwmèrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrr In the case of the imine functional groups and the imine functional groups connected to the main chain by the carbon atom, a polymer is chosen as polymer P2. comprising imine functional pendant groups, wherein the imine is connected to the main chain via its nitrogen atom.
Thus, when the pendant groups of the polymer PI carry imine functional groups connected to the main chain by the nitrogen atom, the polymer P2 is chosen as a polymer comprising aldehyde functional groups and / or imine functional pendant groups, where the imine is connected to the main chain by its carbon atom. The invention thus makes it possible to assemble, by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions, two linear or branched polymers, even if the chemical natures of the polymers are different. The invention thus makes it possible to assemble two thermosetting polymers. It is also conceivable to assemble a polymer composition according to the invention with a linear or connected polymer P2 according to the same principle. This principle can even be extended to two compositions according to the invention that can be assembled.
In a second variant, functionalization and crosslinking are conducted simultaneously.
In particular, the composition results from the mixing, in the molten state or in solution: of at least one linear or connected polymer comprising functions enabling grafting,
A combination of molecules including molecules comprising at one end a functional group for covalently linking the molecule to the polymer ΡΓ and at another end a functional group selected from an imine function connected by its carbon atom (A), a function imine linked by its nitrogen atom (C), or an aldehyde function (B), and / or molecules comprising at two of their ends functional groups for covalently linking the molecule to the polymer PI 'and between its two extremes an imine function (D), the combination to allow the grafting and the creation of exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions; advantageously, monofunctional free aldehydes.
Thus, the polymer ΡΓ can be functionalized and crosslinked during the addition of the additive. For this, the polymer comprises functions allowing grafting, for example in its main chain or on its lateral / pendant groups.
Figure 1 shows the molecules that can be used for the one-step functionalization and crosslinking of polymers. The letters G1 G2, G3, G4 and G5 represent a functional group for covalently linking the molecules to the polymer chains to be functionalized. The functional groups Gi, G2, G3, G4 and G5 are chosen as a function of the polymers to be functionalized, functions allowing the grafting on these polymers and grafting conditions (temperature, reaction medium (in fade or in solution), kinetics, use a catalyst, etc.). Advantageously, the groups G1; G2, G3, G4 and G5 are identical. By way of non-limiting examples, the functions G can be thiol functions allowing the functionalization of the alkene bonds of polydienes, such as polybutadiene, polyisoprene and their copolymers, vinyl copolymers having pendant alkenyl functions, or polyolefins obtained by polymerization. by Ring-Opening Metathesis Polymerization (ROMP) or by metathesis polymerization of Acyclic Diene Metathesis (ADMET) (Charles E. Hoyle, Christopher N. Bowman, Angew Chem. Int.Ed. 2010, 49, 1540-1573, Kemal Arda Günay, Patrick Theato, Harm-Anton Klok, Journal of Polymer Science Part A: Polymer Chemistry 2013, 51,1-28). The G functions can also be maleimide, methacrylic, acrylic, styrenic or maleic ester functions in order to allow radical grafting on polyethylene and polypropylene for example (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 can be isocyanate functions which will thus react with the alcohol, amine or thiol pendant groups present on the polymers to be functionalized (Kemal Arda Günay, 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 G functions may also be electrophilic olefins that can give Michael additions to nucleophiles, such as thiols, amines, primary and secondary, or phosphines (Brian D. Mather, Kalpana Viswanathan, Kevin M. Miller, Timothy E. Long, Polym Polym., 2006, 31, 487-531). Among the electrophilic olefins, mention may be made, by way of non-limiting examples, of vinyl acrylates, acrylamides, maleimides, methacrylates or sulphones. The G functions can also be nucleophilic functions, such as alcohols, thiols, amines or carboxylic acids, which can give nucleophilic substitution or ring opening reactions (Kemal Arda Günay, Patrick Theato, Harm-Anton Klok, Journal of Polymer Science Part A: Polymer Chemistry 2013, 51, 1-28). These functional groups can for example open epoxide functions present in the main chain of the polymers, as found in epoxidized natural rubber, or pendant epoxide functions as found in vinyl copolymers prepared with glycidyl methacrylate. The functions G can also be alcohol, thiol or amine functions that can react with ester or activated pendant pendant functions to give new ester, thioester or amide functions. This approach can in particular be used to functionalize vinyl polymers having pendant ester functions, for example poly (methyl methacrylate). The functional groups that make it possible to bind the molecule containing the imine or aldehyde function covalently to the polymer PI 'are therefore numerous and varied and the person skilled in the art knows how to select the functional group of choice as a function of the functions present on the polymer ΡΓ and of the grafting conditions (temperature, reaction medium (melt or in solution), kinetics, use of a catalyst, etc.).
Figure 1 defines molecules (A) GrRx-CH = N-Ry, (B) G2-R'x-CH = O, (C) G3-R "yN = CH-R" x and (D) G4- Wherein G, G2, G3, G4 and G5 represent a functional group for covalently linking the molecules to the polymer chains to be functionalized, Rx, R'x, R "x, R" 'x and Ry, R "y, R"' are hydrocarbon groups. The denominations "Rx" and "Ry" are repeated by homology, without necessarily being identical, to the definition of imine and aldehyde pendant functional groups according to the invention.
In particular, R 1, R'x, R "x, R '" x are each, independently of each other, an aliphatic, terpenoic, aromatic, arylaliphatic or cycloaliphatic radical. This radical may contain heteroatoms, in particular chosen from O, N, S or Si, and / or may be substituted. Rx, R'x, R "x, R '" x are advantageously an aromatic, heteroaromatic or terpenoid group. Advantageously, when the aldehyde function is carried by a terpenoid group, the aldehyde function is directly linked to an alkene function of the terpenoid.
In particular, Rx, R'x, R''x, R '"x, each independently of one another, can be substituted by functional groups, such as ester or amide functions, in particular this radical is substituted. by a halogen, a group -Rz, -OH, -NHRz, -NRzR'z, -C (O) -OH, -C (O) -NRzR'z, -C (O) -O-Rz, -0 -C (O) -Rz, -O-C (O) -O-Rz, -O-C (O) -N (H) -Rz, -N (H) -C (O) -O-Rz, -O-Rz, -S-Rz, -C (O) -N (H) -Rz, -N (H) -C (O) -Rz with Rz, R'z, identical or different, representing an alkyl radical In particular, this radical Rx, R'x, R''x, R '"x may be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide or anhydride functions.
In particular, R y, R "y, R" "each represent, independently of one another, an aliphatic, aromatic, arylaliphatic or cycloaliphatic radical. This radical may contain heteroatoms, in particular chosen from O, N, S or Si, and / or may be substituted. In particular, this radical Ry, R "y, R '" y 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, -NRzR'z, -C (O) -OH, -C (O) -NRzR'z, -C (O) group. -O-Rz, -O-C (O) -Rz, -O-C (O) -O-Rz, -O-C (O) -N (H) -Rz, -N (H) -C ( 0) -O-Rz, -O-Rz, -S-Rz, -C (O) -N (H) -Rz, -N (H) -C (O) -Rz with Rz, R'z, identical or different, representing a C1-C50 alkyl radical. In particular, this radical Ry, R "y, R '" y may be interrupted by ester, amide, ether, thioether, secondary or tertiary amine, carbonate, urethane, carbamide or anhydride functions.
Figure 2 schematically shows the functionalization of linear polymers by the molecule A, respectively C, via the creation of covalent bonds between the molecules A, respectively C, and the polymer chains.
The combinations allowing one-step crosslinking and functionalization of polymers are: - A + C: Functionalized polymers with pendent imine functions hooked by carbon (A) + functionalized polymers with pendant imine functions suspended by nitrogen (C) and crosslinking by metathesis imine-imine reaction (Figure 3). Imine-imine metathesis reactions can take place between A and C before these functions are grafted onto the polymers (which amounts to generating a molecule equivalent to the molecule D). - B + C: Functionalized polymers with pendant aldehyde functional groups (B) + functionalized polymers with pendant imine functions suspended by nitrogen (C) and crosslinking by aldehyde-imine exchange reaction. Aldehyde-imine exchange reactions can take place between B and C before these functions are grafted onto the polymers (which amounts to generating a molecule equivalent to molecule D). - A + D: Polymers crosslinked by the molecule D + functionalized polymers with pendent imine functions hooked by the carbon (A). Imine-imine metathesis reactions can 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
In summary, any combination for which on average at least two imine and / or aldehyde functions will be grafted by polymer chain and connected to the main chain by the carbon atom and two imine functions will be grafted by polymer chain and connected to the main chain. by the nitrogen atom.
Free monofunctional aldehydes may be added additionally in each case. Other combinations are still possible when using a compound of formula (I), defined above: - A + compound (I) for which Z and Wi are N. Thus, functionalized polymers with imine pendant functions connected to the main chain by the carbon atom (A) and the crosslinking is carried out by imine-imine metathesis reaction between the pendant functions and the compound (I). Imine-imine metathesis reactions can take place between A and the compound (I) before these functions are grafted onto the polymers.
- B + compound (I) for which Z and N1 are N
- A + B + compound (I) for which Z and Wi are N
C + compound (I) for which Z and Wx are C
Again, there must be on average at least two exchangeable pendant functions grafted by polymer chain (via A, B or C). The amount of compound (I) will vary depending on its functionality. However, it can be said that the compounds (!) Must also provide on average at least two imine or aldehyde functions per polymer chain. These functions should be complementary to the functions grafted onto the polymers (via A, B or C).
Free monofunctional aldehydes may be added additionally in each case.
In the compositions according to the invention, the polymers comprise pendant imine and / or aldehyde functions. They also include imine functions in their side chains forming crosslinking points. This allows exchange between imines and improves the crosslinking of the polymers. The inventors believe that the exchange reactions between the imines and between the imines and aldehydes allow a circulation of the crosslinking points and can explain the thermoplastic behavior while the composition, in itself, is insoluble as a thermosetting.
The compositions also comprise monofunctional free aldehydes and / or monofunctional free imines, formed during the creation of the crosslinking points. To one or the other of these compositions described above, it is also possible to add a compound having a single imine or aldehyde function. This additional compound can make it possible to modulate the properties, in particular the viscosity, of polymer compositions. This compound may comprise an aryl group, or heteroaryl, or terpenoid bonded to the carbon of the aldehyde or imine. Advantageously, when the aldehyde function is carried by a terpenoid group, the aldehyde function is directly linked to an alkene function of the terpenoid.
In addition, the compositions according to the invention advantageously comprise monofunctional free aldehydes. Surprisingly, the inventors have discovered that the exchange reactions between imines can be catalyzed by an aldehyde, which may be present in the polymer (pendant CHO group) or as a molecule not bound to polymers, called "free" . The monofunctional free aldehyde may be added before, during or after the addition of the additive.
The aldehyde function can be provided 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 functionalized aldehyde molecule used to catalyze metathesis of imines is an aromatic aldehyde, namely a molecule for which the aldehyde function is carried by an aryl or heteroaryl group, preferably a benzene ring. Mention may in particular be made of benzaldehyde and its derivatives. Advantageously, the functionalized aldehyde molecule used to catalyze metathesis of imines is a molecule in which the carbon of the aldehyde function is connected by a covalent bond to an alkene function of a terpenoid. Mention may be made in particular of citral, its two isomers, geranial and neral, and their derivatives.
Surprisingly, the inventors have discovered that the imine and aldehyde functions can exchange their substituents according to the following reaction:
Rx-ON-Ry + Rx'-OO Rx-C = N-Ry + Rx'-C = N-Ry + Rx-OO + Rx'-OO
Advantageously, the carbon atom imine functions and the carbon atom aldehyde functions are directly connected to a carbon atom of an aryl group, heteroaryl or alkene function of a terpenoid. The use of functionalized aldehyde molecules, and more particularly aromatic aldehydes, such as benzaldehyde and its derivatives, including vanillin, and terpenoid aldehydes, such as cinnamaldehyde, as catalysts for the metathesis of imines has many advantages. These molecules are compatible with many polymers, these molecules are unlikely to introduce parasite reactions in polymer matrices / materials, these molecules are commercially available, can be bio-sourced or of natural origin and many aromatic aldehydes and terpenoid aldehydes are little or no toxic as evidenced by their use in the food and cosmetic industry.
As illustrated in the examples below the presence of a pendant or free aldehyde will catalyze imine-imine and imine-aldehyde metathesis exchange reactions.
The polymer PI, or ΡΓ, and optionally the polymer P2, is advantageously a thermoplastic polymer or a thermosetting polymer.
By the process according to the invention, polymeric compositions having properties of thermosets and thermoplastics can be prepared from any thermoplastic polymer.
The polymer may be chosen from: vinyls, in particular polystyrenes, poly (metha) acrylates, poly (meth) acrylamides, polydienes such as polyisoprenes and polybutadienes, polyvinyl chlorides, polyfluoro compounds, poly ( vinyl acetate), polyvinylpyrrolidone, polyvinylcarbazole, polyolefins, in particular polyethylene and polypropylene, unsaturated polyolefins, polyamides, polysaccharides.
These polymers may be functionalized to introduce imine or aldehyde functional pendant pendent groups or to introduce patterns or functions permitting grafting. The introduction of these imine or aldehyde functionalized pendant side groups can be carried out by various methods known to those skilled in the art: copolymerization of precursor monomers of the polymer with imine functionalized monomers or aldehyde (the imine or aldehyde functions not integrating to the main chain of the polymer being formed but found on a pendant side group, grafting on a reactive function of the polymer, copolymerization of precursor monomers of the polymer with monomers containing one or more functions which will serve after formation of the polymer to be grafted imine pendant functions and / or aldehyde. These functions that will be used to graft imine and / or aldehyde pendant functions may be functions that are not involved in the polymerization reaction or may be functions that are involved in the polymerization reaction but remain unreacted at the end of polymerization. either because of the stoichiometry / functionality of the monomer mixture, or because of a cessation of the polymerization before the complete conversion of all the polymerizable functions. Such processes are known to those skilled in the art and are particularly used in the synthesis of polymers by polycondensation and polyaddition. For example, the polymer PI is obtained by copolymerization, by radical route or by polycondensation, by coordination polymerization, or by polyaddition or by ring opening of a precursor monomer of the thermoplastic polymer and of a monomer bearing the imine functionalized lateral group. or aldehyde. For example, the polymer P1 'is obtained by copolymerization, by radical route or by polycondensation, by coordination polymerization, or by polyaddition or by ring opening of a precursor monomer of the thermoplastic polymer and of a monomer bearing the lateral group allowing the grafting of the molecule containing the imine or aldehyde function. Similarly, the introduction of the motifs or functions allowing grafting can be carried out by various methods known to those skilled in the art (Charles E. Hoyle, Christopher N. Bowman, Angew Chem Int Ed 2010, 49, 1540 -1573, Kemal Arda Günay, 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, Polym Prog., 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, Polym Prog., Sci 2006, 31, 487-531, TC Chung, Polym Prog 2002, 27, 39- 85. Chulsung Bae, John F. Hartwig, Hoyong Chung, Nicole K. Harris, Karen A. Switek, Marc A. Hillmyer, Angew Chem International Ed 2005, 44, 6410-6413).
As previously described, the polymers may be functionalized and crosslinked upon addition of the additive.
The number-average molecular weight, Mn, of the linear or branched polymers PI, PI 'or P2, that is to say before crosslinking, advantageously varies from 2000 g / mol to 2500000 g / mol, more preferably from 5000 to 750000 g / mol and even more preferably from 10000 g / mol to 400000 g / mol.
The dispersity, D = MW / Mn, of linear or branched polymers PI, PI ', or P2, that is to say before crosslinking, advantageously varies from 1.01 to 15, more advantageously from 1.03 to 10 and still more preferably from 1.05 to 7.5.
In the invention, the molar ratio [repeating unit of the polymer PI or PI 'not containing pendant imine or aldehyde functions]: [repeating unit of the polymer PI or PI' containing an imine pendant function + polymer repeating unit PI or PI 'containing a pendant aldehyde function] advantageously varies from 0.01 to 1000, more advantageously from 0.1 to 250 and even more advantageously from 1 to 100. Here, the term "pendant imine or aldehyde functions" is a function imine or aldehyde is a function allowing the grafting of such an imine or adéhyde function.
The molar ratio [compound of formula (I)]: [PI polymer repeating unit or PI1 containing an imine pendant function + PI polymer repeating unit or PI 'containing a pendant aldehyde function] advantageously varies from 5 to 0.001 more advantageously from 1 to 0.005 and still more preferably from 0.5 to 0.01. Here, the term "imine or pendant aldehyde functions" is an imine or aldehyde function or a function allowing the grafting of such an imine or adheyde function.
In the invention, the molar ratio [repeating unit of the polymer P2 not containing imine functions or pendant aldehyde]: [repeating unit of the polymer P2 containing an imine pendant function + repeating unit of the polymer P2 containing a pendant aldehyde function preferably varies from 0.01 to 1000, more preferably from 0.1 to 250 and even more preferably from 1 to 100.
The molar ratio [repeating unit of the polymer P2 containing an imine pendant function + repeating unit of the polymer P2 containing a pendant aldehyde function]: [repeating unit of the PI or PI 'polymer containing an imine pendant function + polymer repeating unit PI or PI 'containing a pendant aldehyde function] advantageously varies from 2500 to 0.0004, more preferably from 250 to 0.004 and still more preferably from 100 to 0.01. Here, the term "imine or pendant aldehyde functions" is an imine or aldehyde function or a function allowing the grafting of such an imine or adheyde function.
The chemical / physical properties of the polymers of the invention strongly depend on the compounds used, in particular polymers PI, ΡΓ, and if appropriate P2.
However, starting from a PI or thermoplastic polymer, the compositions according to the invention combine the properties of a thermoplastic polymer and a thermosetting polymer. In particular, the compositions according to the invention are insoluble as a thermosetting but can be recycled and / or reformed at a temperature above the glass transition temperature (Tg) or melting point (Tf) of the polymer PI, PI ', where appropriate and P2, advantageously greater than Tg or Tf + 10 ° C, more preferably greater than Tg or Tf + 20 ° C, still more preferably greater than Tg or Tf + 40 ° C, still more preferably greater than Tg or Tf + 80 ° C, if the glass transition temperature or the melting point is below 25 ° C. I r r r r r 5 5 ς ς ς ς ς ς ς ς ς ς ς ς ς ς ς ς <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<. iii ", iik u ^ ··; | J | u | Jl lUiC J U k. thermosetting and thermoplastic. In particular, the compositions according to the invention have at least one, more advantageously several, still more advantageously all, of the following properties: thermal stability three-dimensional network and therefore the polymer can be insoluble as a thermosetting polymer drops can be reused
reshaping at a temperature above the glass transition temperature (Tg) or melting temperature (Tf), preferably greater than Tg or Tf + 10 ° C, more preferably greater than Tg or Tf + 20 ° C, still more advantageously higher at Tg or Tf + 40 ° C, still more preferably greater than Tg or Tf + 80 ° C, if the glass transition temperature or the melting temperature is less than 25 ° C when cooled, it does not flow more than the reference polymer increase of the malleable hot chemical resistance it is possible to give new forms to the polymer of the invention ability to relax all or part of the stresses present in the material of the objects can be made by injection from these compositions of the objects can be made by extrusion from these compositions objects can be made by die-casting from these compositions objects can be f Thermoformed sheltering from these compositions objects can be made by depositing a solution (in English: "solvent casting") from these compositions the objects made with these compositions can be repaired the objects made with these compositions can be Welded objects manufactured with these compositions can be recycled degradable: by degradation of the polymer, linear or branched polymer chains are obtained which can be reused.
When they are in the form of liquid formulations, the crosslinked polymer compositions according to the invention, advantageously the compositions forming a crosslinked linear or branched polymer network, advantageously have the remarkable property of being able to be injected, in particular via a syringe. Depending on the degree of crosslinking of the crosslinked linear or branched polymer networks, the crosslinked polymer compositions according to the invention are injectable, in particular via a syringe, while forming a network of crosslinked polymers which is swollen with solvent (s), advantageously water, will support its weight and will flow at the scale of 30 seconds, preferably 1 minute, preferably 2 minutes, preferably 5 minutes, preferably 10 minutes, preferably 30 minutes, preferably 1 hour, preferably 2 hours, preferably 4 minutes hours, advantageously 6 hours, advantageously 8 hours, advantageously 12 hours, advantageously 1 day, without the application of a constraint.
When they are in the form of liquid formulations, the crosslinked linear or branched polymer networks according to the invention advantageously have the property of agglomerating together when they are left in contact.
The degree of crosslinking of the crosslinked polymer compositions according to the invention, advantageously the compositions in the form of liquid formulations forming crosslinked linear or branched polymer networks, can be modulated by adding to the composition of monofunctional free aldehydes, and / or monofunctional free imines, and / or compounds of formulas (I) and / or linear or branched polymers P2. Such modulation of the degree of crosslinking can make it possible to release molecules and / or polymers in the formulations containing the crosslinked polymer compositions according to the invention. Non-limiting examples of molecules or polymers that may be salted out include active principles, proteins, nucleic acids, amino acids, vitamins, flavors, catalysts, chemical reagents, pigments or the like. additives.
The composition of the invention may further comprise fillers and / or additives. The fillers and / or additives are in particular those usually used by those skilled in the art.
The composition may further comprise, in the mixture or in the network, other compatible polymer (s). The skilled person knows how to choose such a polymer.
Polymer network compositions comprising at least one polymer network whose composition has been described above may also comprise: one or more polymers, pigments, dyes, brighteners, "filler", plasticizers, impact modifiers, fibers, retarders flame, antioxidants, lubricants, wood, glass, metals.
Among the polymers that can be used in admixture with the polymer compositions or networks of the invention, mention may be made of elastomers, thermosets, thermoplastic elastomers and impact-resistant polymers.
The term "pigments" means insoluble colored particles in the composition or the polymer network. Among the pigments that can be used in the invention, mention may be made of titanium oxide, carbon black, carbon nanotubes, metal particles, silica, metal oxides, metal sulfites or any other pigment. mineral. Mention may also be made, as pigments, of phthalocyanines, anthraquinones, quinacridones, dioxazines, azo pigments or any other organic pigment, natural pigments (madder, inidigo, madder, carmine, etc.) and pigment mixtures. The pigments may represent between 0.05% and 70% by weight of the composition of the formulation.
The term "dyes" means molecules which are soluble in the composition or the polymer network and which have the capacity to absorb all or part of the visible light radiation.
The term "brightener" means a molecule that absorbs ultraviolet light radiation and then re-emits this energy by fluorescence in the visible. The brighteners are used in particular to impart a certain whiteness.
Among the "fillers" that can be used in the polymer compositions or networks of the invention include silica, clays, calcium carbonate, carbon black, kaolin.
Among the fibers that can be used in the polymer compositions or networks of the invention, mention may be made of glass fibers, carbon fibers, polyester fibers, polyamide fibers, aramid fibers, polyethylene fibers, cellulose and nano-cellulose. Vegetable fibers (flax, hemp, sisal, bamboo, etc.) can also be considered.
The presence in the compositions or polymer networks of the invention of pigments, dyes or thermally conductive fibers may be used to facilitate the heating of an article obtained from the compositions or polymer networks of the invention and thus allow the manufacture, transformation or recycling of an article obtained from the polymer compositions or networks of the invention as described below. As nonlimiting examples of thermally conductive pigments, fibers or "fillers", mention may be made of aluminum nitride (AIN), boron nitride (BN), MgSiN 2, silicon carbide (SiC), graphite , graphene, carbon nanotubes, carbon fibers, metal powders and their combinations.
The presence in the compositions or polymer networks of the invention of pigments, dyes or fibers 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 compositions or polymer networks of the invention of electroconductive pigments, fibers or "fillers" such as carbon black, carbon nanotubes, carbon fibers, metal powders, magnetic particles can be used for heating an article obtained from the compositions or polymer networks of the invention by Joule effect, by induction or by microwaves. Such heating methods may allow the manufacture, processing or recycling of an article obtained from the polymer compositions or networks of the invention as described below. Electro-conductive charges can also be used to evacuate electrostatic charges from the material or to allow electrostatic painting.
It has been found that aldehyde-catalyzed imine-imine metathesis reactions are the fastest. To the knowledge of the inventors, the use of aldehyde to catalyze imine-imine metathesis reactions has hitherto never been described.
It has also been discovered that the imine and aldehyde functions can exchange their substituents according to the following reaction:
Rx-C = N-Ry + Rx'-C = 0 Rx-C = N-Ry + Rx'-C = N-Ry + Rx-C = 0 + Rx'-C = 0 To the inventors' knowledge, the imine-aldehyde exchange reaction had heretofore never been described.
Advantageously, the aldehyde used to catalyze the metathesis of imines is an aromatic aldehyde, namely a molecule for which the aldehyde function is carried by an aryl or heteroaryl group.
Advantageously, the carbon atom of the imine functions and the carbon atom of the aldehyde functions are connected directly to an aryl or heteroaryl group.
Advantageously, the carbon atom of the imine functions and the carbon atom of the aldehyde functions are directly connected to the alkene function of a terpenoid group. The invention therefore also relates to the use of aldehyde to catalyze imine-imine metathesis reactions and imine-aldehyde exchange reactions. The aldehyde may be a monofunctional free aldehyde, a polyaldehyde or a pendant aldehyde functional group of a polymer of the composition. The invention also relates to a process for preparing the compositions according to the invention. This process advantageously comprises the following steps:
Choose a linear or branched polymer PI having side groups carrying: aldehyde functional groups, or imine functional groups connected to the polymer by the carbon atom, or imine functional groups linked to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom; - Choosing at least one additive bearing at least two imine and / or aldehyde functional groups capable of reacting with the side groups of the polymer PI to form a crosslinked polymer composition, advantageously a crosslinked network, containing exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions; - Mixing, in the molten state or in solution, said polymer PI, said additive and optionally a monofunctional free aldehyde to obtain said composition.
The choice of substitutions and additive is made according to the description given above for the compositions. A monofunctional free aldehyde or a monofunctional free imine, as described above, may be added.
The process may comprise a prior step of preparing a polymer PI, comprising copolymerization, for example by radical route, by coordination polymerization, ring-opening polymerization, polyaddition or polycondensation, of an IP precursor monomer. and a monomer bearing an imine functionalized group or aldehyde.
The method may include an earlier step of preparing a PI polymer, comprising grafting pendant aldehyde and / or imine functions onto a linear or plugged polymer.
Another method according to the invention advantageously comprises the following steps: choosing at least one linear or branched polymer P1 'comprising functions allowing a grafting, to choose a combination of molecules including molecules comprising at one end a functional group making it possible to bind in a covalently the molecule to the polymer ΡΓ and at another end a functional group selected from an imine function connected by its carbon atom to the rest of the molecule (A), an imine function connected by its nitrogen atom to the rest of the molecule ( C), or an aldehyde function (B), and / or molecules comprising at two of their ends functional groups for covalently linking the molecule to the polymer PI 'and between its two ends an imine function (D), the combination to allow the grafting and the creation of exchangeable pendant bonds and crosslinking points exchangeable by reaction reactions. aldehyde-imine exchange and / or imine-imine exchange reactions; mixing, in the molten state or in solution, said polymer PI ', said combination and optionally a monofunctional free aldehyde, to obtain said composition.
The choice of the substitutions and the combination is made according to the description given above for the compositions. A monofunctional free aldehyde or a monofunctional free imine, as described above, may be added.
The method may comprise an earlier step of preparing a polymer PI ', comprising the copolymerization, for example by a radical route, by coordination polymerization, by ring opening polymerization, by polyaddition or by polycondensation, of a precursor monomer of PI 'and a monomer carrying a functional group which subsequently makes it possible to graft pendant aldehyde and / or imine functions.
The method may comprise an earlier step of preparing a polymer PI ', comprising the grafting of pendant functions allowing the grafting of aldehyde and / or imine functions on a linear or connected polymer. The subject of the invention is also a material obtained from the composition according to the invention. The invention also relates to a method for preparing a material according to the invention, comprising the following steps:
Preparation of a composition according to the invention
Shaping of the composition thus obtained.
The notion of shaping includes both the compounding of the composition in the form of granules or powder, for example, the preparation of finished products. The shaping can be carried out by methods known to those skilled in the art for shaping thermoplastic or thermosetting polymers. In particular, mention may be made of molding, compression, injection, extrusion and thermoforming processes. Before giving it the shape of the desired object, the material will most often be in the form of granules or powder. In an interesting way, in the method according to the invention, the preparation and shaping steps can be concomitant. In particular, by the methods described above, it is possible to functionalize and crosslink a polymer, for example by extrusion or injection during its shaping or a compounding step. The invention also relates to a process for recycling a material obtained according to the invention comprising the following successive steps: a) reduction of the powdered material by mechanical grinding, b) transformation of the particles of step a) by the application to the particles of a mechanical stress at a temperature (T) greater than the glass transition temperature (Tg) or melting point (Tf) of the polymer PI, PI ', where appropriate and P2, advantageously greater than Tg or Tf + 10 ° C, more preferably greater than Tg or Tf + 20 ° C, still more preferably greater than Tg or Tf + 40 ° C, still more preferably greater than Tg or Tf + 80 ° C, if the glass transition temperature or temperature melting point is less than 25 ° C. The invention also relates to a formulation comprising a composition according to the invention. The subject of the invention is also the use of an additive as defined above or of a combination as defined above, in the presence of a linear or branched polymer PI or PI 'for the formation of a polymer composition crosslinked, preferably a crosslinked network, containing exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions. The nature of the additive or combination is chosen according to the polymer PI or PI ', in particular its functionalization, according to the criteria explained above.
In addition, a monofunctional free aldehyde or a monofunctional free imine can be added to the composition. Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly connected to an aryl or heteroaryl group.
Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly connected to the alkene function of a terpenoid group. The invention also relates to a method for modifying the rheology of a composition, such as an oil or a paint, comprising said polymer PI or PI 'by adding 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.
The nature of the additive or combination is chosen according to the polymer PI or PI ', in particular its functionalization, according to the criteria explained above.
It is also possible to add a free monofunctional aldehyde to the composition. or a free monofunctional imine. Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly connected to an aryl or heteroaryl group.
Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly connected to the alkene function of a terpenoid group. The invention also relates to combinations for cross-linking linear or branched polymers, advantageously PI, ΡΓ, said combinations being chosen from combinations comprising:
A monofunctional free aldehyde + compound of formula (I), as defined above;
A monofunctional free aldehyde + polymer P2, as defined above; A and / or B + C; A, B, C being as defined above, and optionally a monofunctional free aldehyde as defined above; A and / or B and / or C + D; A, B, C, D being as defined above, and optionally monofunctional free aldehyde as defined above; A and / or B + compound of formula (I) for which Z and Wx are N, and optionally monofunctional free aldehyde, as defined above; or C + compound of formula (I) for which Z and Wi are a carbon atom, and optionally monofunctional free aldehyde, as defined above. In the first two cases, it is necessary that the linear or branched polymers have imine exchangeable pendant functions and / or aldehyde. A, B, C, D are as previously described.
These combinations may also include a monofunctional free aldehyde or a monofunctional free imine. Advantageously, the carbon atom of the imine function and the carbon atom of the aldehyde function is directly connected to a terpenoid, aryl or heteroaryl group. Advantageously, when the aldehyde function is carried by a terpenoid group, the aldehyde function is directly linked to an alkene function of the terpenoid.
The following examples illustrate the invention and are not limiting. A. Syntheses of Monomers, Functionalisers and Compound of Formula (I) A.I. Aldehyde compound: Ml
P-Chloromethylstyrene (6.63 g, 43.4 mmol), 4-hydroxybenzaldehyde (6.25 g, 51.1 mmol) and potassium carbonate (K 2 CO 3) (17.7 g, 127.9 mmol) are introduced into a 250 ml flask containing 75 ml of dimethylformamide (DMF). The mixture is stirred under a nitrogen atmosphere for 3 hours at 70 ° C. The solution is then 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 sodium hydroxide solution and then dried over magnesium sulfate (MgSO 4). The solvent is then 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. with vigorous stirring. The solid is then filtered and dried to give the aldehyde C monomer as a white solid (8.7 g, 36.3 mmol, 84%). NMR (CDCl3, 400 MHz) δ: 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). MS MS: 97%, () m / z: [M] Calcd for C16H14O2: 238.0944; Found: 238.20 A.2. Imine compound: M2
The aldehyde compound M1 (5 g, 21 mmol) and n-butylamine (7.67 g, 105 mmol) are dissolved in 40 mL of tetrahydrofuran (THF). Anhydrous magnesium sulphate (MgSO4) is added and the reaction mixture is stirred for 48 hours at room temperature (RT). The mixture is then filtered and concentrated under reduced pressure to give the imine B monomer as a white solid (5.85 g, 19.9 mmol, 95%). * H NMR (CDCl3, 400 MHz) δ: 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). 13C NMR (CDCl3, 400 MHz) δ: 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 GC MS: 96%, ( m / z: [M] Calcd for C20H30 NO 293.4027; Found 293.25
A3. Compound of formula (I): CFI
The aldehyde compound M1 (12.0 g, 50.34 mmol) and hexane-l, 6-diamine (5.83 g, 50.34 mmol) are dissolved in 150 ml of toluene and the reaction mixture is left 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 then filtered, rinsed three times with 150 ml of methanol and dried to give the compound of formula (I) and / or compound Di in the form of a white solid (9.5 g, 17.1 mmol, 70%). 2H NMR (CDCl3, 400 MHz) δ: 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). 13C NMR (CDCl3, 400 MHz) δ: 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. A.4. Compound of formula (I): CF2
Benzaldehyde (2.05 equivalents) and hexane-l, 6-diamine (1 equivalent) are introduced into dichloromethane (2 mL per mole of hexane-1,6-diamine) and magnesium sulfate is added (3 equivalents). The reaction mixture is left stirring at ambient temperature for 24 hours, filtered and then evaporated under reduced pressure to give the compound of formula (I) D2 in the form of a yellow oil (98%, in the presence of 7 mol% of benzaldehyde). ). * H NMR (CDCl3, 400 MHz) δ: 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). 13C NMR (CDCl3, 400 MHz) δ: 161.2, 136.2, 130.4, 128.6, 128.1, 62.0, 30.8, 27.2. AT 5. Imine compound: M3
Benzaldehyde (0.9 mL, 8.8 mmol) and 4-vinylaniline (1 g, 8.4 mmol) are added to 20 mL of tetrahydrofuran and magnesium sulfate (1 g) is added. The reaction mixture is stirred at room temperature for 24 hours, filtered and then evaporated under reduced pressure to give the imine compound M3 (90%, in the presence of 5 mol% of benzaldehyde). * H NMR (CDCl3, 400 MHz) δ: 8.48 (s, 1H), 7.93-7.90 (m, 2H), 7.50-7.45 (m, 5H), 7.23-7.20 (m, 2H), 6.75 (d, J) = 17.6 Hz, 10.8 Hz, 1H), 5.76 (d, J = 17.6 Hz, 1H), 5.25 (d, J = 10.8 Hz, 1H). A.6. Imine compound: M4
Benzaldehyde (0.24 mL, 2.4 mmol) and 4-vinylbenzylamine (0.3 g, 2.25 mmol) are introduced into 10 mL of tetrahydrofuran and magnesium sulfate (0.5 g) is added. The reaction mixture is left stirring at room temperature for 24 hours, filtered and then evaporated under reduced pressure to give the imine M4 compound (90%, in the presence of 5 mol% of benzaldehyde). * H NMR (CDCl3, 400 MHz) δ: 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). B. Kinetic studies of exchange reactions
These experiments are aimed at evaluating the conditions (time, temperature, catalyst) for observing the imin-imine, irine-siline endimine ~ 3-dehyde resection.
Kinetic studies:
Stoichiometric amounts of the imine, amine or aldehyde compounds are mixed in CDCl3 and 1H NMR spectra are recorded regularly. The compounds are mixed from stock solutions and the overall concentration of the two exchangeable starting reagents is set at 0.071 mol / L (0.05 mmol / 0.7 mL).
General mixing procedure: CDCl3 is introduced into the NMR tube and the reagents are added by means of a microsyringe from stock solutions. The tube is sealed and gently stirred before starting the NMR analysis. The time elapsed between the end of introduction of all the reagents and the acquisition of the first NMR spectrum is about 3:30 minutes. For high temperature analyzes, the NMR spectrometer is pre-equilibrated at the analysis temperature. The ambient temperature for these analyzes was between 22.0 and 23.6 ° C. The following exchange reactions have been studied:
Reaction scheme of imine imine metathesis reactions B.l, B.2, B.3, B.4, B.5
B.l. Non-catalyzed imine imine metathesis at room temperature (RT)
B.2. Non-catalyzed imine-imine metathesis at 45 ° C
B.3. Imine-imine metathesis in the presence of 10 mol% of amine (butylamine) at RT
B.4. Imine-imine metathesis in the presence of 10 mol% of aldehyde (benzaldehyde) at RT B.5. Imine-imine metathesis in the presence of 10 mol% aldehyde (benzaldehyde) at 45 ° C B.6. Imine-aldehyde exchange reaction at RT
General observations: At thermodynamic equilibrium, each compound must represent 25 mol% of all the products (in the case of uncatalysed reactions). The time required to form 15% of the two new compounds resulting from the metathesis or exchange reactions of the six reactions studied are shown in the table below. This arbitrary threshold conversion, which corresponds to a conversion of 60% with respect to the thermodynamic equilibrium, was chosen in order to be able to compare the different exchange rates.
Table 1
The uncatalyzed imine-imine metathesis is the slowest exchange reaction among the reactions studied slower. The addition of free aldehyde during the metathesis imine-imine makes it possible to accelerate the reaction very substantially, almost by a factor of 7 at RT and by a factor of 30 at 45 ° C. To our knowledge, the use of aldehyde to catalyze the metathesis of imines has not yet been described.
The imine-aldehyde exchange reaction was also found to be faster than the non-catalyzed imine-imine metathesis reaction by a factor of about 3.5.
C. Synthesis of PI C.l. Polymers Example of Procedure for the Synthesis of a Polyaldehyde PI Polymer by Conventional Radical Polymerization: Pial
N-butyl methacrylate (BMA) (11.4 g, 80.0 mmol), the aldehyde compound M1 (5.0 g, 21.0 mmol) and the azoisobutyronitrile (AIBN) (27.6 mg, 0.168 mmol) are introduced into a Schlenk tube containing 3.8 mL of anisole. The reaction mixture thus obtained is bubbled at room temperature with nitrogen for 30 minutes before being stirred and heated at 65 ° C for 7.5 hours. Polymerization is stopped by placing the Schlenk tube in an ice bath at 0-2 ° C. The conversion to monomers was 55% at the end of the reaction. 3 ml of anhydrous THF are then added and the polymer is isolated by two successive precipitations in diethyl ether. The colorless solid thus obtained is dried under vacuum at 100 ° C overnight. Analysis by steric exclusion chromatography (THF eluent, PMMA calibration) of the polymer gives an apparent molecular weight Mn of 430,000 g / mol and a dispersity D of 2.55.
C.2. Example of Procedure for the Synthesis of a Polyaldehyde PI Polymer by RAFT (Reversible Addition-Fragmentation Chain Transfer) Polymerization: PlaO
Methyl methacrylate (MMA) (3.36 g, 33.6 mmol), the aldehyde compound M1 (2.0 g, 8.39 mmol), 2-phenyl-2-propyl benzodithioate (PPDT) (47.8 mg, 0.176 mmol) and ΓΑΙΒΝ (11.0 mg 0.068 mmol) are introduced into a Schlenk tube containing 3.6 ml of anisole. The reaction mixture thus obtained is bubbled at room temperature with nitrogen for 30 min before being stirred and heated at 65 ° C for 24 hours. Polymerization is stopped by placing the Schlenk tube in an ice bath at 0-2 ° C. The conversion to methyl methacrylate and monomer aldehyde C was respectively 84.4% and 92.3% at the end of the reaction. The polymer is isolated by two successive precipitations in diethyl ether. The slightly pink solid thus obtained is dried under vacuum at 100 ° C. overnight. Analysis by steric exclusion chromatography (THF eluent, PMMA calibration) of the polymer gives an apparent molar mass Mn of 23,200 g / mol and a dispersity D of 1.25. C.3. Example of Procedure for the Synthesis of a Polymer PI Polymer by RAFT (Reversible Addition-Fragmentation Chain Transfer) Polymerization: Fold
Methyl methacrylate (MMA) (4.09 g, 40.9 mmol), imine compound M2 (3 g, 10.2 mmol), 2-phenyl 2-propyl benzodithioate (PPDT) (55.7 mg, 0.2 mmol) and azobisisobutyronitrile ( AIBN) (13.4 mg, 0.08 mmol) are introduced into a Schlenk tube containing 1.5 ml of anisole. The reaction mixture thus obtained is bubbled at room temperature with nitrogen for 30 min before being stirred and heated at 65 ° C for 24 hours. Polymerization is stopped by placing the Schlenk tube in an ice bath at 0-2 ° C. The conversion to methyl methacrylate and imine B monomer was 84.3% and 99.4%, respectively.
The polymer is isolated by two successive precipitations in diethyl ether. The slightly pink solid thus obtained is dried under vacuum at 100 ° C. overnight. Analysis by steric exclusion chromatography (THF eluent, PMMA calibration) of the polymer gives an apparent molecular weight Mn of 53,900 g / mol and a dispersity D of 1.52. C.4. Polyaldehyde polymers prepared by conventional polymerization or by RAFT polymerization according to procedures C.l and C.2
The following table summarizes the synthesis of polyaldehyde polymers PI according to the procedures described in C.I and C.2. The polymerization temperature and the initial monomer / anisole volume ratio are kept constant. With the exception of Pial, for which the comonomer M is butyl methacrylate (BMA), the comonomer M is always methyl methacrylate (MMA). The polymerization times, the initial ratios [M] 0 / [M1] 0 and [M + M1] o / [PPBDT] 0 / [AIBN] 0 can vary and are reported in the table.
by conventional radical polymerization; b by radical polymerization per RAFT with an initial ratio [M + M1] O / [PPBDT] 0 of; c by radical polymerization per RAFT with an initial ratio [M + M1] O / [PPBDT] 0 of;
Table 2 D. Formation and characterization of networks of crosslinked polymers containing pendant bonds exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions. D.L. Example of liquid formulation, solubility and "degradability" tests of a crosslinked polymer network The following example shows an example of a liquid formulation and illustrates the solution formation of a crosslinked polymer network according to the invention and the possibility of to degrade the network of crosslinked polymers. 0.5 g of Pla3 polymer is dissolved in 2.5 ml of anhydrous THF and then 0.01 ml (0.03 mmol) of the compound of formula (I) CF 2 is added. After 8 hours at room temperature a network of crosslinked polymers swollen with THF is obtained. This polymer network stored at room temperature in THF for 3 days remains insoluble. The gel is then cut into two equal parts which are each placed in 5 mL of anhydrous THF. In a solution, lmL (9.9 mmol) of benzaldehyde is added, while nothing is added in the other. After 24 hours, the crosslinked polymer network in the pure anhydrous THF solution is still insoluble while the network of crosslinked polymers in the anhydrous THF solution containing 1 ml of benzaldehyde is completely dissolved. D.2. Example of a solid formulation, compression forming and solubility tests of a network of crosslinked polymers The following example presents an example of a solid formulation and illustrates the formation of a network of crosslinked polymers according to the invention, its implementation. compression form and its insolubility in a good non-reactive solvent of the polymer constituting the network of crosslinked polymers. Formation and Compression Shaping of a Network of Crosslinked Polymers 10.0 g of Pial polymer are dissolved in 40 ml of anhydrous THF and then 73 mg of the compound of formula (I) CF 2 are added. The reaction mixture is stirred at room temperature for 30 minutes before being concentrated in vacuo at 100 ° C overnight. The powder thus obtained is compression molded for 1 hour at 150 ° C. under a pressure of between 3 and 5 tons. The network of crosslinked polymers thus obtained is called NI.
Room-temperature solubility test in the THF of the network of cross-linked polymers NI A sample of the network of crosslinked polymers NI having a mass of about 75 mg is introduced into 10 ml of anhydrous THF and allowed to swell for 16 hours at room temperature. The swelling rate (SR) and the soluble fraction (SF) of the network of crosslinked polymers NI are then calculated. This test is performed on two samples.
Swelling rate = (Mass of the swollen sample-Mass of the dry sample after swelling) / (Mass of the dry sample after swelling)
Soluble fraction = (Mass of the dry sample before swelling-Mass of the dry sample after swelling) / (Mass of the dry sample after swelling)
Table 3
Solubility test at 120 ° C in the anisole of the network of crosslinked polymers NI
A sample of the network of crosslinked polymers N1 (600 mg) is placed in 100 ml of anisole and the medium is then brought to a temperature of 120 ° C. for 16 hours. After 16 h, the sample inflated strongly (its dimensions were multiplied by a factor of 2.5) while keeping the same shape. D.3. Formation and formatting by compression of crosslinked polymer networks
The following table summarizes the networks of crosslinked polymers obtained from polyaldehyde polymers prepared by conventional polymerization or by RAFT polymerization according to the procedures C.l and C.2.
The crosslinked polymer networks are prepared according to the procedure described for NI in D.2 by varying only the amount of compound of formula (I) CF2 used with 10 g of PlaX polymer.
Table 4 D.4. Example of a solid formulation, formatting by compression of crosslinked polymer networks, solubility tests and recycling of a network of crosslinked polymers The following example shows an example of a solid formulation and illustrates the formation of a network of crosslinked polymers according to the invention, its compression forming, its insolubility in a good non-reactive solvent of the polymer constituting the network of crosslinked polymers and its ability to be recycled.
Formation and Compression Shaping of a Network of Crosslinked Polymers 10.0 g of Pla6 polymer are dissolved in 40 ml of anhydrous THF and then 48 mg of the compound of formula (I) CF 2 are added. The reaction mixture is stirred at room temperature for 30 minutes before being concentrated in vacuo at 100 ° C overnight. The powder thus obtained is compression molded for 1 hour at 150 ° C. under a pressure of between 3 and 5 tons. The network of crosslinked polymers thus obtained is called N7.
Room temperature solubility test in THF of the network of crosslinked polymers N7 A sample of the network of crosslinked polymers N7 having a mass of between 30 and 140 mg is introduced into 10 ml of anhydrous THF and allowed to swell for 48 hours at room temperature. The swelling rate (SR) and the soluble fraction (SF) of the network of crosslinked polymers N7 are then calculated. This test is performed on three or four samples each time.
Swelling rate = (Mass of the swollen sample-Mass of the dry sample after swelling) / (Mass of the dry sample after swelling)
Soluble fraction = (Mass of the dry sample before swelling-Mass of the dry sample after swelling) / (Mass of the dry sample after swelling).
Recycling of the network of N7 crosslinked polymers
After the swelling tests, the samples are dried under vacuum at 110 ° C for 30 hours. The samples are then reduced to powder and then compression molded for 1 hour at 150 ° C. under a pressure of between 3 and 5 tons. The network of crosslinked polymers thus obtained.
The samples thus obtained were again subjected to a solubility test before being recycled a second time and then a third time.
The results of the solubility tests are reported in the following table.
Table 5 D.5. Physico-chemical and mechanical characterization of crosslinked polymer networks before and after recycling (s)
The following examples illustrate the ability of the crosslinked polymer networks according to the invention to be recycled without suffering significant losses of their physicochemical and mechanical properties. Characterization by dynamic mechanical analysis (DMA) of the network of N7 cross-linked polymers before and after recycling
The samples were analyzed in film tension geometry with a TA Q800 dynamic mechanical analysis device. Rectangular or dumbbell samples were used. The samples were equilibrated at the set temperature for 5 min before the start of the analysis. A precharge force of 0.01 N and a temperature ramp of 3 ° C / min were applied.
FIG. 4 shows the evolution of the elastic modulus (ordinates, MPa) as a function of temperature (abscissa, ° C) for the non-recycled N7 crosslinked polymer network (first generation, triangle), the network of recycled N7 crosslinked polymers 2 times (3rd generation, round) and the network of crosslinked polymers N7 recycled 3 times (4th generation, square).
These analyzes indicate that the elastic modulus of the network of N7 crosslinked polymers varies very little between even after three cycles of recycling and undergoes no losses both below and above the glass transition temperature.
Mechanical characterization by tensile tests of the network of N7 cross-linked polymers before and after recycling
Samples obtained from the dumbbell-shaped crosslinked polymer network N7 were tensile tested using an Instron 5064 pulling machine. The samples were stretched to rupture at a speed of 1.5 mm. min, then reduced to powder before being reformed by compression under a pressure of between 3 and 5 tons for 1 hour at 150 ° C. This procedure was repeated 3 times out of 4 to 6 samples.
FIG. 5 represents the breaking stress (ordinates, MPa) for the samples of the network of non-recycled N7 crosslinked polymers (abscissae, 0), for the samples of the network of crossed polymers IM7 recycled once (abscissae, 1), for the samples of the network of crosslinked polymers N7 recycled twice (abscissa, 2) and for the samples of the network of crosslinked polymers N7 recycled 3 times (abscissa, 3).
These analyzes indicate that the breaking stress of the network of N7 crosslinked polymers does not significantly decrease after several cycles of recycling.
FIG. 6 represents the elongation at break (ordinates,%) of non-recycled N7 crosslinked polymer network samples (abscissa, 0), for the samples of the N7 cross-linked polymer network recycled once (abscissa, 1), for the samples of the network of crosslinked polymers N7 recycled twice (abscissa, 2) and for the samples of the network of crosslinked polymers N7 recycled 3 times (abscissa, 3).
These analyzes indicate that the elongation at break of the network of N7 crosslinked polymers does not significantly decrease after several cycles of recycling.
"Degradability" tests of the network of N7 cross-linked polymers after compression shaping and after 4 cycles of compression shaping / mechanical tests / powder reduction The following example illustrates the suitability of a network of cross-linked polymers according to the invention to be degraded even after 4 compression forming cycles / mechanical tests / powder reduction.
The samples of the network of crosslinked polymer N7 1st and 4th generation were "degraded" according to the procedure described in D.l.
The samples of the N7 1st and 4th generation crosslinked polymer network could be completely dissolved and the polymers obtained after "degradation" were characterized by size exclusion chromatography (THF eluent, PMMA calibration).
The polymer obtained after degradation of the first generation N7 crosslinked polymer network (compression formed once) had an apparent molecular weight Mn of 95,000 g / mol and a dispersity D of 1.47.
The polymer obtained after degradation of the N7 4th generation cross-linked polymer network (shaping by 4-fold compression) had an apparent molar mass Mn of 91,000 g / mol and a dispersity D of 1.58.
These results indicate that the network of crosslinked polymers N7 can be fully degraded even after 4 cycles of compression shaping / mechanical tests. In addition, the characterization of the polymers after degradation indicates that the polymer chains constituting the material have not undergone during the different shaping, recycling and mechanical stray reaction tests significantly affecting their molar mass and their dispersity.
Creep tests of the network of N7 crosslinked polymers after compression shaping, after 2 cycles and 3 cycles of recycling The following example illustrates the possibility of giving new shapes to the networks of crosslinked polymers of the invention after shaping by compression, after 2 cycles and after 3 cycles of recycling.
Samples of the network of crosslinked polymers N7 1st, 3rd and 4th generation (respectively shaped once, recycled twice and recycled 3 times) were subjected to a creep experiment using a dynamic mechanical analysis apparatus TA Q800. Rectangular geometry samples were subjected to a constant stress of 0.013 MPa at 160 ° C for 200 or 300 min. After 200, respectively 300 minutes, the stress was removed and the samples were maintained at 160 ° C for 200 min, respectively 100 min. Figure 7 shows the strain (ordinates,%) as a function of time (abscissa, min) of non-recycled N7 crosslinked polymer network samples (1st generation, solid line), the network of N7 cross-linked polymers recycled 2 times (3rd generation long line) and the network of cross-linked polymers N7 recycled 3 times (4th generation, short dotted line).
These experiments indicate that N7 crosslinked polymer networks flow at 160 ° C and that the rate of deformation is not significantly changed by several shaping and recycling cycles. These experiments also indicate that after removal of the stress the samples have a permanent deformation of several% which corresponds to their new form of equilibrium. It is thus possible to give new forms to the network of non-recycled N7 crosslinked polymers, recycled 2 or 3 times.
Stress relaxation tests of crosslinked polymer networks
The following examples illustrate the capacity of the crosslinked polymer networks of the invention to relax all or part of the stresses present in the material at a temperature greater than the glass transition temperature (Tg) or melting temperature (Tf), advantageously greater than Tg. or Tf + 10 ° C, more preferably greater than Tg or Tf + 20 ° C, still more preferably greater than Tg or Tf + 40 ° C, still more preferably greater than Tg or Tf + 80 ° C, if the transition temperature vitreous or the melting temperature is below 25 ° C.
The stress relaxation experiments were performed on a TA Ares G2 rheometer using a parallel plate geometry with diameters of 25 mm. The rheometer is preheated to 150 ° C and equilibrated for 5 minutes. The samples are then placed between the two trays, equilibrated in temperature for 5 minutes before a normal force of 10-15 N is applied. After 5 minutes, a deformation of 3% is applied and the evolution of the stress as a function of time is followed.
FIG. 8 represents the shear relaxation modulus normalized by the initial modulus at t = 0 (ordinates, without unit) as a function of time (abscissa, seconds) of the crosslinked polymer network samples NI (square), of polymer network crosslinked N4 (triangle), network of crosslinked polymers N5 (round) and crosslinked polymer network N6 (star).
These experiments indicate that the crosslinked polymer networks of the invention can relax all or part of the stresses present in the material at a temperature above the glass transition temperature. E. Extrusion shaping of cross-linked polymer networks containing pendant bonds exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions. The following example illustrates the possibility of extrusion shaping the crosslinked polymer networks of the invention. 3.2 g of network of crosslinked polymers N8 are introduced into a twin DSM 5cc twin screw extruder. The extrusion is carried out at 200 ° C. with a screw rotation speed of 60 rpm, an injection time of 4 minutes and a circulation time of 11 minutes. After injection of the entire network of cross-linked polymers, the force measured by the screws reached a plateau of 3200 N. A total of 2.5 g of polymer network was extruded. F. Cross-linked poly (methyl methacrylate) network shaping test containing pendant aldehyde functions but no imine exchangeable functions The experiment presented below demonstrates that cross-linked poly (methyl methacrylate) networks containing pendant aldehyde functions which do not contain imine functions exchangeable in their crosslinking points can not be shaped by compression molding, such as the crosslinked polymer networks of the invention.
A crosslinked PMMA network containing pendant aldehyde functions was synthesized according to the procedure described below.
The methyl methacrylate (MMA) (4.0 g, 40.0 mmol), the aldehyde compound M1 (2.38 g, 10.0 mmol) and the hexanediol dimethacrylate (81.4 mg, 0.32 mmol) are introduced into a glass flask equipped with a septum. The reaction mixture thus obtained is bubbled at 65 ° C. with nitrogen for 10 min before a degassed solution of AIBN (13.1 mg, 0.08 mmol) in anisole (1.2 mL) and a degassed solution of 2- phenyl 2-propyl benzodithioate (PPBDT) (54.5 mg, 0.2 mmol) in anisole (1.2 mL) is added to the reaction mixture. The solution thus obtained is then stirred at 65 ° C. for 24 hours. The polymerization is stopped by placing the polymer in 150 mL of anhydrous tetrahydrofuran for 16 h before being filtered. This swelling / filtration operation is repeated a second time (9 hours) then the polymer is dried under vacuum at 100 ° C for 18 hours.
The network of crosslinked polymers thus obtained is reduced to powder to be shaped by compression molding. To do this, the powder is placed in a mold for 3 hours at 150 ° C. under a pressure of between 3 and 6 tons. This gives a very fragile and brittle material that breaks when handled. This material is non-transparent and the powder grains are always visible initially introduced into the mold are always visible.

权利要求:
Claims (20)
[1" id="c-fr-0001]
1. Composition comprising (a) crosslinked polymers containing exchangeable pendant bonds and exchangeable crosslinking points, by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions, obtained by crosslinking of linear or branched polymers and (b) monofunctional free aldehydes and / or monofunctional free imines.
[2" id="c-fr-0002]
2. Composition according to Claim 1, characterized in that the linear or branched polymers contain less than 0.5 mmol of primary amine and primary ammonium functions per gram of polymers before crosslinking and less than 0.1 mmol of primary amine and ammonium functions. primary per gram of polymers after crosslinking.
[3" id="c-fr-0003]
3. Composition according to any one of the preceding claims, characterized in that it comprises aldehydes and at least 1 mol% of the aldehyde functions are aromatic aldehyde functions.
[4" id="c-fr-0004]
4. Composition according to any one of the preceding claims, characterized in that the polymers, before crosslinking, are linear or branched polymers having side groups bearing: - aldehyde functional groups, or - imine functional groups linked to the polymer by the carbon atom, or - imine functional groups linked to the polymer by the nitrogen atom, or - aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom.
[5" id="c-fr-0005]
5. Composition according to any one of the preceding claims, characterized in that it results from the mixture, in the molten state or in solution: of at least one linear or branched polymer PI having side groups carrying: functional groups aldehyde, or imine functional groups linked to the polymer by the carbon atom, or imine functional groups linked to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups linked to the polymer by the atom of carbon of at least one additive bearing at least two imine and / or aldehyde functional groups capable of reacting with the lateral groups of the polymer PI to form a crosslinked polymer composition, advantageously a crosslinked network, exchangeable bonds and exchangeable crosslinking points by aldehyde-imine exchange reactions or by imine-imine exchange reactions; advantageously, monofunctional free aldehydes.
[6" id="c-fr-0006]
6. Composition according to claim 5, characterized in that the additive is a compound of formula (I) below:

wherein n is an integer ranging from 1 to 6; i is an integer ranging from 1 to n the dotted link is present or absent, depending on the valence of Y, Z, W1; W2i Y and Z are different and each represents either C or N, or Y is O and then Z is C • when Y is C, then Z is N, and Rx is a hydrocarbon group, R2 is H and R3 is absent, • when Y is N, then Z is C, and R2 is H or a hydrocarbon group, R2 is absent and R3 is H, • when Y is O, then Z is C and, R1, R2 are absent and R3 is H R4 is a hydrocarbon group linked to the imine and / or aldehyde functions by a covalent bond via a carbon atom in each block W1 (R ') = W2i (R "i) (R'"), Wi and W2i are different and each represents either C is N, where W2i is O and then W! is C when W2i is C, then Wx is N and R 'is absent, R "is a hydrocarbon group and R'" is H when W2i is N, then W2 is C and R 'is H, R "is H or a hydrocarbon group, and R '"is absent, when W2i is O, then W2 is C and R" ,, R' "are absent and R 'is H when Z is C, then Wi is C, when Y is C, then W2i represents C.
[7" id="c-fr-0007]
7. Composition according to Claim 5 or 6, characterized in that the additive is a linear or branched polymer P2 carrying: aldehyde functional groups, or imine functional groups linked to the polymer by the carbon atom, or functional groups imine linked to the polymer by the nitrogen atom, or aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom.
[8" id="c-fr-0008]
8. Composition according to any one of claims 5 to 7, characterized in that in the polymer PI imine functions are connected to the main chain by their carbon atoms and the additive is selected from: a polymer P2 in which the imine functions are connected to the main chain by their nitrogen atoms, or a compound of formula (I) in which the Z and Wx atoms represent N.
[9" id="c-fr-0009]
9. Composition according to any one of claims 5 to 7, characterized in that in the polymer PI the imine functions are connected to the main chain by their nitrogen atoms and the additive is selected from: a polymer P2 in which the imine functions are connected to the main chain by their carbon atoms, a polymer P2 whose side groups carry aldehyde functions, a polymer P2 comprising aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom, or a compound of formula (I) in which the Z and Wx atoms represent C.
[10" id="c-fr-0010]
10. Composition according to any one of claims 1 to 4, characterized in that it results from the mixture, in the molten state or in solution: Of at least one linear or connected polymer comprising functions enabling grafting, A combination of molecules including molecules comprising at one end a functional group for covalently linking the molecule to the polymer PI 'and at the other end a functional group selected from an imine function connected by its carbon atom, an imine function linked by its nitrogen atom, or an aldehyde function, and / or molecules comprising at two of their ends functional groups for covalently linking the molecule to the polymer ΡΓ and between its two ends an imine function, the combination in front of allow the grafting and the creation of exchangeable pendant bonds and exchangeable crosslinking points by aldehyde exchange reactions -imine and / or imine-imine exchange reactions; advantageously, monofunctional free aldehydes.
[11" id="c-fr-0011]
11. Composition according to any one of the preceding claims, characterized in that the aldehyde is a molecule for which the aldehyde function is carried by an aryl group, heteroaryl or the alkene function of a terpenoid.
[12" id="c-fr-0012]
12. Composition according to any one of the preceding claims, characterized in that the linear or branched polymer, advantageously PI, PI 'or P2, is a polymer selected from vinyls, polyolefins, polyamides and polysaccharides.
[13" id="c-fr-0013]
13. Process for preparing a crosslinked polymer composition, said process comprises the following steps: Choosing a linear or branched polymer PI having side groups carrying: aldehyde functional groups, or imine functional groups linked to the polymer by the carbon atom , or imine functional groups linked to the polymer by the carbon atom, or aldehyde functional groups and imine functional groups linked to the polymer by the carbon atom; Choose at least one additive bearing at least two imine and / or aldehyde functional groups capable of reacting with the side groups of the polymer PI to form a crosslinked polymer composition, advantageously a crosslinked network, containing exchangeable pendant bonds and exchangeable crosslinking points by aldehydeimine exchange reactions and / or by imine-imine exchange reactions; - Mix, in the molten state or in solution, said polymer PI, said additive and optionally a monofunctional free aldehyde, to obtain said composition.
[14" id="c-fr-0014]
14. Process for preparing a crosslinked polymer composition, said method comprises the following steps: Choosing a linear or connected polymer comprising functions enabling a grafting, Choosing a combination of molecules including molecules comprising at one end a functional group allowing to bind covalently the molecule to the polymer ΡΓ and at the other end a functional group selected from an imine function connected by its carbon atom, an imine function connected by its nitrogen atom, or an aldehyde function, and / or molecules comprising, at two of their ends, functional groups which make it possible to bind the molecule covalently to the polymer ΡΓ and between these two ends an imine function, the combination being capable of allowing the grafting and the creation of exchangeable pendant bonds and crosslinking points that can be exchanged by reactions exchange aldehyde-imine and / or by reacti exchange imine-imine; Mix, in the molten state or in solution, said polymer PI ', said combination and optionally a monofunctional free aldehyde, to obtain said composition.
[15" id="c-fr-0015]
15. Use of aldehyde to catalyze imine-imine metathesis reactions and imine-aldehyde exchange reactions performed in the compositions defined in claims 1 to 12.
[16" id="c-fr-0016]
16. Material obtained from the composition according to any one of claims 1 to 12.
[17" id="c-fr-0017]
17. Formulation comprising a composition according to any one of claims 1 to 12.
[18" id="c-fr-0018]
18. Use of an additive as defined in any one of claims 5 to 7, or a combination as defined in claim 10, in the presence of a linear or connected polymer PI or PI 'for training a composition comprising crosslinked polymers, advantageously a crosslinked network, containing exchangeable pendant bonds and crosslinking points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions, monofunctional free aldehydes and / or monofunctional free imines.
[19" id="c-fr-0019]
Combinations for cross-linking linear or branched polymers, advantageously PI, PI ', said combinations being chosen from combinations comprising: A monofunctional free aldehyde + compound of formula (I), as defined in one of the preceding claims; A monofunctional free aldehyde + polymer P2, as defined in one of the preceding claims; A and / or B + C, and optionally a monofunctional free aldehyde as defined in one of the preceding claims; A and / or B and / or C + D, and optionally a monofunctional free aldehyde as defined in one of the preceding claims; A and / or B + compound of formula (I) for which Z and Wx are N, and optionally a monofunctional free aldehyde, as defined in one of the preceding claims; or C + compound of formula (I) for which Z and Wx are a carbon atom, and optionally a monofunctional free aldehyde, as defined in one of the preceding claims A, B, C, D corresponding to the following formulas: A) R1-Rx-CH = N-Ry, (B) G2-R'x-CH = O, (C) G3-R "yN = CH-R" x and (D) G4-R '"x- CH = N-R '"y-G5 where the letters Gx, G2, G3, G4 and G5 represent a functional group allowing the molecules to be covalently bonded to the polymer chains to be functionalized, Rx, R'x, R" x, R '"x and Ry, R''y, R'" are hydrocarbon groups.
[20" id="c-fr-0020]
20. Use of a combination as defined in claim 19, in the presence of a linear or connected polymer PI or PI 'for the formation of a composition comprising crosslinked polymers, advantageously a crosslinked network, containing bonds. exchangeable pendants and exchange points exchangeable by aldehyde-imine exchange reactions and / or by imine-imine exchange reactions and monofunctional free aldehydes and / or monofunctional free imines, in particular for modifying the rheology of a composition , such as an oil or a paint, comprising said polymer PI or ΡΓ by adding to the composition of the combination according to the invention; the rheology is modified by choosing the concentration in said combination.

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同族专利:

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公开号 | 公开日

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JP2018523743A|2018-08-23|

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FR3040170B1|2019-02-01|

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CA3031551A1|2017-02-23|

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US9994651B2|2018-06-12|

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US20170051082A1|2017-02-23|

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EP3337835A1|2018-06-27|

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CN108431057B|2021-06-18|

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JP6908956B2|2021-07-28|

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EP3337835B1|2021-12-01|

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WO2017029311A1|2017-02-23|

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法律状态:
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2017-02-24| PLSC| Publication of the preliminary search report|Effective date: 20170224 |

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2018-08-13| PLFP| Fee payment|Year of fee payment: 4 |

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2020-08-10| PLFP| Fee payment|Year of fee payment: 6 |

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2021-07-09| PLFP| Fee payment|Year of fee payment: 7 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1557767A|FR3040170B1|2015-08-17|2015-08-17|COMPOSITION OF RETICULATED POLYMERS CONTAINING EXCHANGEABLE PENDING LINKS AND EXCHANGEABLE CROSSLINKING POINTS, BY ALDEHYDE-IMINE EXCHANGE REACTIONS AND / OR IMINE-IMINE EXCHANGE REACTIONS, PROCESSES OF PREPARATION AND USE|

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FR1557767|2015-08-17|FR1557767A| FR3040170B1|2015-08-17|2015-08-17|COMPOSITION OF RETICULATED POLYMERS CONTAINING EXCHANGEABLE PENDING LINKS AND EXCHANGEABLE CROSSLINKING POINTS, BY ALDEHYDE-IMINE EXCHANGE REACTIONS AND / OR IMINE-IMINE EXCHANGE REACTIONS, PROCESSES OF PREPARATION AND USE|

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EP16759992.7A| EP3337835B1|2015-08-17|2016-08-17|Composition of cross-linked polymers comprising pending exchangeable bonds and exchangeable cross-links, via aldehyde-imine and/or imine-imine exchange reactions, preparation processes and use|

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US15/238,969| US9994651B2|2015-08-17|2016-08-17|Composition of cross-linked polymers comprising pending exchangeable bonds and exchangeable cross-links, via aldehyde-imine and/or imine-imine exchange reactions, preparation processes and use|

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PCT/EP2016/069483| WO2017029311A1|2015-08-17|2016-08-17|Composition of cross-linked polymers comprising pending exchangeable bonds and exchangeable cross-links, via aldehyde-imine and/or imine-imine exchange reactions, preparation processes and use|

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JP2018508727A| JP6908956B2|2015-08-17|2016-08-17|Compositions, preparation methods, and uses of crosslinked polymers, including pendant bonds and interchangeable crosslinks that can be exchanged by aldehyde-imine and / or imine-imine exchange reactions.|

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CA3031551A| CA3031551A1|2015-08-17|2016-08-17|Composition of cross-linked polymers comprising pending exchangeable bonds and exchangeable cross-links, via aldehyde-imine and/or imine-imine exchange reactions, preparation processes and use|

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CN201680060814.1A| CN108431057B|2015-08-17|2016-08-17|Compositions comprising pendant linkages and exchangeable cross-linked polymers exchangeable by aldehyde-imine and/or imine-imine exchange reactions, methods of preparation and uses|