Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
  • C08G77/52—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

• the present invention relates to modified polymers of the poly (ethynylene phenylene ethynylene silylene) type.
• the invention further relates to compositions containing these modified polymers.
• the invention also relates to processes for the preparation of these modified polymers.
• the invention also relates to new self-poisoned poly (ethynylene-phenylene-ethynylene-silylene) type polymers.
• the invention relates to hardened products capable of being obtained by heat treatment of said modified or self-poisoned polymers.
• the technical field of the present invention can be defined as that of thermostable plastics, that is to say polymers which can withstand high temperatures which can reach for example up to 600 ° C.
• thermostable plastics have increased enormously in recent decades, particularly in the electronics, aeronautics and aerospace fields.
• metals such as iron, titanium and steel are thermally very resistant, but they are heavy.
• Aluminum is light but not very resistant to heat, ie up to around 300 ° C.
• Ceramics such as Sic, Si 3 N and silica are lighter than metals and very heat resistant, but they are not moldable. This is the reason why many plastics have been synthesized which are light, moldable and have good mechanical properties; these plastics are mainly carbon-based polymers.
• Polyids have the highest heat resistance of all plastics with a thermal deformation temperature of 460 ° C, however these compounds which are listed as being the most stable known at present are very difficult to use.
• Other polymers such as polybenzimidazoles, polybenzothiazoles and polybenzooxazoles have an even higher heat resistance than polyimides, but they are not moldable and are flammable.
• Polymers based on silicon such as silicones or carbosilanes have also been widely studied. The latter, such as poly (silylene ethynylene) compounds, are generally used as ceramic precursors of the carbide type. silicon SiC, resist compounds and conductive materials.
• This process essentially allows the synthesis of the compounds of formula (A) above in which the silicon carries a hydrogen atom.
• the process according to [4] is a polycondensation by dehydrogenation of a hydrosilane functionalized with a compound of diethynyl type in the presence of a metal oxide such as MgO according to the following reaction scheme (B):
• process (C) makes it possible to obtain polymers without structural defects with good yields and a low mass distribution.
• the compounds obtained by this process are perfectly pure and have perfectly characterized thermal properties. They are thermosetting polymers.
• This document also discloses the preparation of the above-mentioned polymers reinforced with glass, carbon or Sic fibers.
• thermostable composite materials The excellent thermal stability of the polymers prepared in particular in document EP-B1-0 617 073 makes them capable of constituting the resin forming the organic matrix of thermostable composite materials.
• Prepregs are semi-finished products, of low thickness, made of fibers impregnated with resin.
• Prepregs which are intended for the production of tall composite structures performance contain at least 50% fiber by volume. Also, during processing, the matrix must have a low viscosity to penetrate the reinforcing ply and properly impregnate the fiber in order to avoid its distortion and to preserve its integrity.
• the reinforcing fibers are impregnated either with a resin solution in an appropriate solvent, or with pure resin in the molten state, this is the so-called "hot melt” technique.
• the technology for manufacturing prepregs with a thermoplastic matrix is largely governed by the morphology and rheological properties of polymers.
• Injection molding is a process which consists in injecting the liquid resin into the textile reinforcement previously positioned in the impression formed by the mold and the counter-mold.
• the most important parameter is the viscosity, which must be between 100 and 1000 mPa.s at the injection temperature, which is generally 50 to 250 ° C. For these two techniques, viscosity is therefore the critical parameter which conditions the ability of the polymer to be used.
• amorphous polymers correspond to macromolecules whose skeletal structure is completely disordered. They are characterized by their glass transition temperature (Tg) corresponding to the transition from the glassy state to the rubbery state. Beyond Tg, thermoplastics are however characterized by a high creep resistance.
• Tg glass transition temperature
• the polymers prepared in document EP-B1-0 617 073 are compounds which are in powder form. The inventors were able to show, by reproducing the syntheses described in this document, that the polymers prepared would produce glass transition temperatures close to 50 ° C. Before this temperature, the viscosity of the polymer is infinite and beyond this temperature, the viscosity decreases as the temperature is increased.
• polymers can be defined as being polymers of low mass containing as unit, basic unit a functionalized silane coupled to a diethynylbenzene and carrying at the end of the chain in particular phenylacetylene functions.
• thermostable polymers of FR-A-2 798 622 have perfectly defined and modular rheological properties, which allows their use as matrices for thermostable composites. All of the properties of these polymers are described in FR-A-2 798 622, to which reference may be made. Document FR-A-2 798 622 also describes a process for the synthesis of these thermostable polymers. The developed technique allows the viscosity of the polymer to be adjusted at will, as a function of the technological constraints of processing the composite. This property is intimately linked to the molecular weight of the polymer. Low viscosities are observed on polymers with low molecular weights.
• Control of the masses is obtained by adding a reactive species to the reaction medium which blocks the polymerization reaction without affecting the overall yield of the reaction.
• This species is an analogue of one of the two reagents, used for the synthesis of the polymer but carrying a single function allowing coupling. When this species is introduced into the polymer chain, growth is stopped. The length of the polymer is then easily controlled by metered additions of chain limiter.
• the prepolymers prepared both in document EP-B1-0 617 073 from ITOH and in document FR-A-2 798 622 from BUVAT, being thermosets, the crosslinking of these materials is thermally activated.
• the reactions involved in this phenomenon mainly involve two mechanisms, which are described in an article published by ITOH [5].
• the first mechanism is a Diels Aider reaction, involving an acetylenic bond coupled to an aromatic nucleus, on the one hand, and another aromatic bond, on the other. This reaction can be illustrated as follows:
• This reaction generates a naphthalene motif. It is likely to occur regardless of the nature of Ri, R 2 , R 3 or R.
• the structures obtained by this mechanism are therefore highly aromatic and contain numerous unsaturated bonds. These characteristics are at the origin of the excellent thermal properties observed on these polymers.
• the second mechanism, involved in the crosslinking reaction of poly (ethynylene phenylene ethynylene silylene) prepolymers, is a hydrosilylation reaction, involving the SiH bond and an acetylenic triple bond. This reaction can be illustrated as follows:
• crosslinking involves the triple acetylenic bonds, simply separated by an aromatic ring. Consequently, the crosslinking density is very strong and the internode links very short.
• the hardened materials based on pol (ethynylene phenylene ethynylene silylene) are therefore part of the polymer matrices having a low deformation capacity.
• the crosslinking density can be controlled during the processing of the polymer by suitable heat treatments. Indeed, the crosslinking of the polymer stops, when the mobility of the macromolecular chains is no longer sufficient. It is assumed that this mobility is sufficient, as soon as the processing temperature is higher than the glass transition temperature of the network.
• the glass transition temperature cannot exceed that of processing and the crosslinking density is therefore controlled by the polymer curing temperature.
• sub-crosslinked materials are unstable materials whose use, at temperatures higher than that of implementation, will cause an evolution of the structure.
• the mechanical properties of poly (ethynylene phenylene ethynylene silylene) are therefore difficult to modulate by heat treatment.
• the nature of the chemical groups carried by the silicon is however capable of modulating these properties. Long chains can, in fact, play the role of plasticizer and reduce the rigidity of the associated materials.
• this principle finds limits in terms of thermal stability of the polymer because it is then affected.
• the document FR-A-2 816 624 describes polymers of poly (ethynylene phenylene ethynylene silylene) s, comprising as repeating unit, inter alia, two acetylenic bonds, at least one silicon atom and one inert spacer not involved in the crosslinking process.
• the role of the spacer is to increase the length of the cross-linking cross-links to contribute to greater mobility within the network and thus to greater flexibility of the resulting hardened materials.
• the nature of the spacer also makes it possible to modulate the mechanical properties without significantly modifying thermal properties.
• the polymers as defined in this document may optionally comprise acetylenic functions at the end of the chain in accordance with document FR-A-2 798 662.
• Document FR-A-2 816 624 describes a composition comprising the mixture of at least one poly (ethynylene phenylene ethynylene silylene) polymer and at least one compound capable of exerting a plasticizing effect in the mixture, once this last hardened.
• compositions according to document FR-A-2 836 922 are more flexible, more flexible, less brittle than the cured products prepared by heat treatment of the compositions containing a poly (ethynylene phenylene ethynylene silylene ), and which do not include a compound capable of exerting a plasticizing effect.
• the fundamental compound included in the mixture of the composition of this document is defined as a compound capable of exerting a plasticizing effect in the mixture, once it has hardened.
• the term “compound capable of exerting a plasticizing effect in the mixture”, once it has hardened, means any compound which causes an increase (even minimal) in the “plastic” character of the hardened product - it that is to say an increase in the deformability of the material constituted by the hardened product under stress - compared to a hardened product not containing said compound.
• the compound exerts an effect of decreasing the rigidity, of the hardness and, conversely, of increasing the flexibility of the flexibility of the cured product by comparison to a cured product including the same polymer, but not containing said compound capable of exerting a plasticizing effect.
• the compound “capable of exerting a plasticizing effect” is not necessarily a compound, known as plasticizer, as it is commonly defined, in particular in the field of plastics and plastics. Indeed, this compound can be chosen from many compounds which are not, generally, commonly defined as being plasticizers, but which, within the framework of the compositions of this document, are suitable compounds, in the sense that they exert a plasticizing effect in the hardened product. However, the plasticizers known as such can also be used as said compound.
• the hardened products prepared from poly (ethynylene phenylene ethynylene silylene) being extremely hard, rigid, and brittle, the inclusion in such a product of a relatively more flexible compound.
• the polymer although not conventionally listed as “plasticizer”, is sufficient to cause an increase in the mobility of the polymer network and therefore to exert a plasticizing effect.
• the compound included in the mixture although not intrinsically a "plasticizer”, plays well, then, in the final hardened material the role of a "plasticizer”.
• the compound likely to exert a plasticizing effect in this document is generally chosen among organic and inorganic polymers and resins.
• the organic polymers are generally chosen from thermoplastic polymers and thermosetting polymers.
• the thermoplastic polymers can be chosen, for example, from fluorinated polymers.
• the thermosetting polymers can be chosen, for example, from epoxy resins, polyimides (poly (bismaleimides)), polyisocyanates, formophenolic resins, silicones or polysiloxanes and all other aromatic and / or heterocyclic polymers.
• the compound capable of exerting a plasticizing effect such as a polymer is a reactive compound, that is to say capable of reacting with itself or with another compound capable of exerting a plasticizing effect or with poly (ethynylene phenylene ethynylene silylene).
• Such reactive compounds such as polymers, generally comprise at least one reactive function, chosen from acetylenic functions and hydrogenated silane functions.
• the reactive compound is chosen from hydrogenated silicone polymers and resins and / or comprising at least one acetylenic function. Silicones are known for their high thermal resistance and their high capacity for deformation under mechanical stress. Reference will be made to the description of document FR-A-2 836 922 for a detailed definition of these polymers and silicone resins.
• composition of this document that is to say the composition comprising the mixture of at least one poly (ethynylene phenylene ethynylene silylene) polymer and at least one compound capable of exerting a plasticizing effect in the mixture a once the latter has hardened
• the “plasticized” poly (ethynylene phenylene ethynylene silylene) resin can also be hardened at temperatures below the crosslinking (thermal) temperatures, under the action of a catalyst for the reactions of Helping diels and hydrosilylation.
• platinum-based catalysts such as H 2 PtCl s , Pt (DVDS), Pt (DVDS), Pt (dba), where DVDS represents divinyldisiloxane, TVTS represents trivinyltrisiloxane and dba, dibenzilidene acetone; and transition metal complexes, such as Rh 6 (CO) i6 or Rh 4 (CO) i2 , ClRh (PPh 3 ), Ir 4 (CO) ⁇ 2 and Pd (dba) can be used for the catalysis of reactions hydrosilylation.
• transition metal complexes such as Rh 6 (CO) i6 or Rh 4 (CO) i2 , ClRh (PPh 3 ), Ir 4 (CO) ⁇ 2 and Pd (dba) can be used for the catalysis of reactions hydrosilylation.
• the catalysts based on transition metal pentachloride such as TaCl 5 , NbCls or M0CI5 will in turn be advantageously used to catalyze reactions of the Diels Aider type.
• the catalysis of these reactions makes it possible to use "plasticizing" compounds of low molecular mass and therefore of low boiling point. These compounds are easily chosen by a person skilled in the art from the compounds capable of exerting a plasticizing effect mentioned above. These “plasticizers” are advantageously used to lower the viscosity of the mixture before processing.
• the materials obtained by curing the compositions of this document FR-A-2 836 922 have improved mechanical properties compared to the products obtained by curing unmodified pol (ethynylene phenylene ethynylene silylene).
• the deformation capacities of the networks thus hardened are in particular significantly improved.
• the mechanical properties of the hardened materials obtained in this document are still insufficient, in particular as regards their capacity for deformation, and they also undergo weakening, degradation, when these materials are subjected to high temperatures.
• the polymer and the composition containing it must have a sufficiently low viscosity so that they can be used, which can be handled, at these temperatures, for example from 100 to 120 ° C., which are the temperatures commonly used. used in injection and impregnation techniques.
• the object of the invention is to provide modified polymers of the poly (ethynylene phenylene ethynylene silylene) type, compositions of these polymers and cured products prepared from these polymers, which meet, inter alia, the needs listed above, which satisfy the requirements indicated above, and which do not have the drawbacks, defects, limitations and disadvantages of polymers, compositions and cured products of the prior art as shown in particular by documents EP-B1-0 617 073; FR-A-2 798 622; FR-A-2 816 624; FR-A-2 816 623 and FR-A-2 836 922.
• the object of the invention is also to provide polymers, compositions and cured products which solve the problems of the prior art.
• the polymer according to the invention can be defined as a poly (ethynylene-phenylene-ethynylene-silylene (“PEPES”) or modified or “poisoned” polymer.
• PEPES ethynylene-phenylene-ethynylene-silylene
• the polymers according to the invention meet all of the needs listed above. , meet the requirements and criteria defined above and solve the problems posed by polymers of
• the polymers modified according to the invention, as well as the cured products obtained from these modified polymers, have improved mechanical properties, increased, compared to the unmodified polymers of the prior art, as represented for example by documents EP-B1-0 617 073, FR-A-2 798 622, FR-A-2 816 624, FR-A-2 816 623, and FR-A-2 836 922, while their thermal properties are maintained .
• the improvement of the mechanical properties relates in particular to the capacity for deformation of hardened, crosslinked materials, which is considerably increased.
• Modified polymers of poly (ethynylene-phenylene-ethynylene-silylene) according to the invention which are capable of being obtained by selective addition of a specific compound with a single reactive function to the acetylenic bonds of a polymer of poly (ethynylene-phenylene-ethynylene-silylene) are not described in the prior art.
• This addition occurs on a PEPES polymer already prepared and not during the preparation process of the latter, that is to say during the polymerization reactions leading to the polymer.
• the compound with a single reactive function reacts a posteriori with the PEPES polymer (unmodified) and does not intervene in any way in the polymerization process leading to it.
• the inventors have demonstrated that the plasticization of PEPES polymers (unmodified), in particular with functionalized Si-H oligomers, as described in document FR-A-2 836 922, if it makes it possible to consume a part of the acetylenic bonds, however does not prevent the reactions of Diels Aider. These reactions take place at high temperatures, for example greater than or equal to 300 ° C., and contribute to weakening the properties of the cured networks obtained from the polymers.
• the polymer according to the invention is prepared by adding a reactive monofunctional species.
• this reactive species poisons, makes it possible to selectively block all or part of the active sites constituted by acetylenic bonds, these active acetylenic sites are the active sites which are necessary for one of the crosslinking mechanism of polymers, namely the Diels-Alder mechanism.
• the polymer according to the invention is prepared using compounds monofunctional which it has been observed, surprisingly, that they poison specifically, only, the acetylenic bonds by selective addition. This poisoning can be total or partial depending on the amount of monofunctional compound used.
• the addition of the compound with a single reactive function to a PEPES polymer surprisingly brings about, via the consumption of acetylenic bonds, an inhibition of the Diels-Alder mechanisms which intervene during crosslinking, this type of reaction does not was not prevented for example by plasticizing the PEPES polymer. It turns out that the inhibition of these reactions brings about a control of the crosslinking density.
• the concentration of reactive sites and therefore the final density of crosslinking of the hardened networks is thus reduced, which surprisingly increases all of the mechanical properties and in particular the ability to deformation and the tensile strength of crosslinked materials.
• the crosslinking density being reduced, the macromolecular mobility of the modified networks of the hardened and increased material and the systems reach their maximum conversion more quickly, which limits the evolution, the subsequent degradation of the properties, in particular mechanical, of these networks. , at high temperatures, for example above 300 ° C.
• This degradation constituted one of the essential drawbacks of the polymers, possibly with the addition of plasticizer, of the prior art.
• the invention is based on controlling the crosslinking density of the networks, as well as on the promotion / inhibition of certain reactions leading to a favorable architecture of the network associated with improved mechanical properties.
• the compound with a single reactive function is advantageously chosen from compounds whose sole reactive function is hydrogen, preferably this compound is chosen from monohydrogenated silicon compounds.
• These monohydrogenated silicon compounds can be chosen from monohydrogenated silanes which correspond to the following formula:
• R a , R b and R c which are identical or different, each independently represent an al yl radical of 1 to 20C such as a methyl radical, an alkenyl radical of 2 to 20C, or an aryl radical of 6 to 20C such as a phenyl radical.
• the behavior of the cured polymers and products according to the invention is very different from that observed in document FR-A-2 636 922 where the modulus is significantly reduced when the elongation at break increases under the effect plasticization, which leads to a small increase in the breaking stress.
• the silicon / monohydrogenated compounds can also be chosen from monohydrogenated siloxanes which correspond to the following formula:
• R a , R b , R c , R d , R e / R f and R g identical or different, each independently represent an alkyl radical of 1 to 20C such as a methyl radical, an alkenyl radical of 2 to 2OC, or an aryl radical of 6 to 20C such as a phenyl radical, and n 0 and m 0 represent an integer from 0 to 1000.
• the monohydrogenated silicon compounds can also be chosen from monohydrogenated silsesquioxanes which correspond to the following formula:
• R a , Rb Rc r Rd / Re / Rf / and R g each independently represent an alkyl radical of 1 to 20C, such as a methyl radical, an alkenyl radical of 2 to 2OC, or a aryl radical from 6 to 20C such as a phenyl radical.
• the addition is carried out in the presence of a catalyst.
• This catalyst is generally a catalyst for ydrosilylation reactions preferably chosen from platinum-based catalysts, such as H 2 PtCl 5 , Pt (DVDS), Pt (TVTS), Pt (dba), where DVDS represents divinyldisiloxane, TVTS, trivinyltrisiloxane and dba, dibenzilidene acetone; and transition metal complexes, such as Rh s (CO) ⁇ or Rh 4 (CO) ⁇ 2 , ClRh (PPh 3 ), Ir 4 (CO) i2 and Pd (dba).
• platinum-based catalysts such as H 2 PtCl 5 , Pt (DVDS), Pt (TVTS), Pt (dba), where DVDS represents divinyldisiloxane, TVTS, trivinyltrisiloxane and dba, dibenzilidene acetone
• transition metal complexes such as Rh s (CO) ⁇ or Rh 4 (CO
• the addition is generally carried out at a temperature of -20 ° C to 200 ° C, preferably from 30 to 150 ° C, depending on the viscosity and the reactivity of the polymers to be modified.
• the structure and the quantity of the single-function compound (compound, poisoning agent) used make it possible to modulate the nature and in particular the mechanical properties of the hardened networks obtained from the polymers modified according to the invention.
• the examples given in the following, in particular example 3 demonstrate the improvements in the mechanical properties obtained, for example in 3-point bending, on materials crosslinked for 2 hours at 300 ° C.
• the compound generally represents from 0.1 to 75%, preferably from 1 to 50%, more preferably from 10 to 40% by mass, of the mass of the modified polymer, that is to say that the level of poisoning is generally between 0.1 and 100%, and preferably between 10 and 50%, depending on the nature of the polymers and the poisoning agents.
• the addition is carried out under an atmosphere of inert gas such as argon.
• the poly (ethynylene phenylene ethynylene silylene) polymer which is subjected to the addition, that is to say the polymer before addition, the unmodified polymer, is not particularly limited, it can s act of any polymer of this known type, in particular it may be the poly (ethynylene phenylene ethynylene silylene) described in documents EP-B1-0 617 073, FR-A-2 798 662, FR-A-2 816 624, FR-A-2 816 623 and FR-A-2 836 922, the relevant parts of which are related to these polymers are included herein.
• the polymer may thus, according to a first embodiment of the invention, correspond to the following formula (I):
• R represents a halogen atom (such as F, Cl, Br and I), an alkyl group (linear, or branched) having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, cyclohexyl), an alkoxy group having from 1 to 20 carbon atoms (such as methoxy, ethoxy, propoxy), an aryl group having from 6 to 20 carbon atoms (such as a group phenyl), an aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyl group (linear, or branched) having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 atoms carbon (such as vinyl, allyl, cyclohexenyl
• R represents a halogen atom (such as F, Cl, Br and I), an alkyl group
• R 'and R'' represent a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an alkoxy group having from 1 to 20 atoms carbon, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms , an alkynyl group having 2 to 20 carbon atoms, one or
• the polymers according to this embodiment of the invention which are the polymers described in document FR-A-2 798 662, have a structure substantially similar to that of the polymers of document EP-B1-0 617 073 with the exception fundamental, however, the presence at the chain end of the Y groups derived from a chain limiting agent. This structural difference has very little influence on the advantageous properties of these polymers, in particular the thermal stability properties of the polymer, which are hardly affected.
• the presence at the end of the chain of this group has precisely the effect that the polymer of formula (I) or (la) has a determined length and therefore a molecular mass, perfectly defined. Consequently, this polymer (I) or (la) also has perfectly defined and modular rheological properties.
• the nature of the group Y depends on the nature of the chain-limiting agent from which it is derived, Y may, in the case of polymers of formula (I), represent a group of formula (III):
• R "' has the same meaning as R and can be the same or different from the latter
• n' has the same meaning as n and can be the same or different from the latter.
• Y may, in the case of polymers of formula (la), represent a group of formula (IV):
• q is an integer from 1 to 1000, for example from
• polymers which can be used in the invention are polymers of determined molecular mass, capable of being obtained by hydrolysis of the polymers of formula (la) and corresponding to the following formula (Ib):
• the molecular mass of the polymers (I), (la) and (Ib) according to this embodiment of the invention is perfectly defined and the length of the polymer and therefore its molecular mass can be easily controlled by metered additions of chain limiter in the mix reaction reflected by variable proportions of group Y in the polymer.
• the molar ratio of the end-of-chain groups Y to the repeating units ethynylene phenylene ethynylene silylene is generally 0.002 to 2.
• this ratio is from 0.1 to 1.
• the number-average molecular mass of the polymers (I), (la) and (Ib) according to this first embodiment of the invention, which is perfectly defined, is generally from 400 to 10,000, preferably from 400 to 5000 and the weight-average molecular mass is from 600 to 20,000, - preferably from
• the poly (ethynylene phenylene ethynylene silylene) polymer before modification can be a polymer comprising at least one repeating unit, said repeating unit comprising two acetylenic bonds, at least one silicon atom, and at least one inert spacer group.
• said polymer also comprises, at the end of the chain, groups (Y) originating from a chain limiting agent.
• the term inert spacer group generally means a group which does not intervene, which does not react during crosslinking.
• the repeating unit of this polymer can be repeated n 3 times with n 3 being an integer, for example from 2 to 1000 or even from 2 to 100.
• the polymer in this embodiment of the invention, comprises at least one repeating unit comprising at least one spacer group which does not intervene in a crosslinking process, to which the polymer can be subjected subsequently.
• the role of the spacer is in particular to constitute a crosslinking internode link sufficiently large to allow movement within the network.
• the spacer group (s) has (have) the function of spatially removing the triple bonds of the polymer, whether these triple bonds belong to the same repeating unit or to two different repeating units, consecutive.
• the spacing between two triple bonds or acetylenic functions, provided by the spacer group is generally made up of linear molecules and / or of several linked aromatic nuclei, possibly separated by single bonds.
• the spacer group can be easily chosen by a person skilled in the art.
• the choice of the nature of the spacer group also makes it possible to modulate the mechanical properties of the polymers, without significantly modifying the thermal properties.
• the spacer group or groups may, for example, be chosen from the groups comprising several aromatic rings linked by at least one covalent bond and / or at least one group divalent, polysiloxane groups, polysilane groups, etc.
• they are preferably two in number and they can be identical, or chosen from all possible combinations of two or more of the groups mentioned above.
• the repeating pattern of the polymer, according to the second embodiment of the composition of the invention may thus correspond to several formulas.
• the polymer, according to this second embodiment of the invention may be a polymer comprising a repeating unit of formula (V):
• R represents a halogen atom (such as F, Cl, Br and I), an alkyl group (linear, or branched) having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, cyclohexyl), an alkoxy group having from 1 to 20 carbon atoms (such as methoxy, ethoxy, propoxy), an aryl group having from 6 to 20 carbon atoms (such as a group phenyl), an aryloxy group having 6 to 20 carbon atoms (such as a group phenoxy), an alkenyl group (linear, or branched) having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms (such as vinyl, allyl, cyclohexenyl
• R represents a halogen atom (such as F, Cl, Br and I), an alkyl group
• the polymer in which the phenylene group can be in the form o, m or p and R, R, R ⁇ and n have the meaning already given above and n 2 is an integer from 2 to 10.
• This repeating unit is generally repeated n 3 times, with n being an integer, for example from 2 to 1000.
• the polymer, according to this second embodiment of the composition of the invention may be a polymer comprising a repeating unit of formula:
• the polymer may be a polymer comprising a repeating unit of formula:
• R 4 , R e , R 8 and n 2 have the meaning already given above, this motif being able to be repeated n 3 times.
• Rs represents a group comprising at least two aromatic rings separated by at least one covalent bond and / or a divalent group.
• the group R 8 can, for example, be chosen from the following groups:
• the polymer according to this second embodiment of the invention may comprise several different repeating units, comprising at least one inert spacer group. Said repeating units are preferably chosen from the repeating units of formulas (V), (Va), (Vb), (Vc) and (Vd), already described above.
• Said repeating patterns are repeated xi, x 2 / X3, x and X5 times respectively, where x i ⁇ x 2 , x 3 / x 4 and x 5 generally represent whole numbers from 0 to 100,000, provided that at least two among Xi, x 2 , x 3 , x and x 5 are different from 0.
• This polymer with several different repeating units can optionally comprise, in addition, one or more repeating units not comprising an inert spacer group, such as a unit of formula (Ve):
• This motif is generally repeated x ⁇ times, with x ⁇ representing an integer from 0 to 100,000.
• a preferred polymer corresponds, for example, to the formula: (Vf) where xi, x 2 , X3 / X6 are as defined above, on condition that two of xi, x 2 and X3 are different from 0.
• the initial polymers, unmodified according to this second embodiment of the invention advantageously comprises at the end of the chain groups (terminals) (Y) originating from a chain limiting agent, which makes it possible to control, to modulate their length, their molecular mass, and therefore their viscosity.
• Y depends on the nature of the chain-limiting agent from which it is derived, Y may correspond to the formula (III) or (IV) given above.
• the molecular weight of the polymers according to the invention is - because they have a chain limiter group - perfectly defined, and the length of the polymer and therefore its molecular weight can be easily controlled by metered additions of chain limiter in the reaction mixture reflected by varying proportions of the Y chain limiting group in the polymer.
• the molar ratio of the Y groups, chain limiters, at the end of the chain to repeating units of the ethynylene phenylene ethynylene silylene type is generally 0.002 to 2.
• this ratio is 0.1 to 1.
• the number average molecular weight of the polymers used in this second embodiment of the invention is generally from 400 to 100,000, and the weight average molecular weight is 500 to 1,000,000.
• the number average molecular weight polymers, in this embodiment, is advantageously due to the fact that they preferably comprise a perfectly defined chain limiting group and is generally from 400 to 10,000 and the weight-average molecular weight is from 600 to 20,000 These masses are determined by gel permeation chromatography (GPC) from a polystyrene calibration.
• GPC gel permeation chromatography
• the unmodified polymer in this second embodiment, advantageously has chain-limiting groups
• the control of the molecular weight of the polymers which generally lies in the aforementioned range makes it possible to perfectly control the viscosity polymers.
• the viscosities of the modified polymers used in this second mode of the invention are in a range of values from 0.1 to 1000 mPa.s, for temperatures ranging from 20 to 160 ° C, at l within the range of masses mentioned above.
• the viscosity also depends on the nature of the groups carried by the aromatic rings and the silicon. These viscosities are fully compatible with conventional techniques for preparing composites. It is thus possible to modify at will according to the technological constraints of implementation of the composite, the viscosity of the polymer.
• the viscosity is also linked to the glass transition temperature (Tg).
• Tg glass transition temperature
• the glass transition temperature of the polymers according to the invention will therefore generally be from -150 to + 100 ° C and more advantageously between -100 and +20 ° C.
• the poly (ethynylene phenylene ethynylene silylene) used as starting materials, in the invention can be prepared by any known process for the preparation of these polymers, for example the processes described in the documents
• polymers (I) and (la) can be prepared by the process of the document
• FR-A-2 798 662 and polymers with an inert spacer group can be prepared by processes analogous to those of documents EP-B1-0 617 073, and FR-A-2 798 662 if they contain chain-limiting groups . Reference may be made to these documents and to the other documents of the prior art cited above for a detailed description of these methods.
• the invention further relates to a process for the preparation of a modified PEPES polymer as described above, in which the following successive steps are carried out: a) - a polymer of poly (ethynylene phenylene ethynylene) is introduced silylene) (PEPES) in a reactor; b) - a compound with a single reactive function is added to said PEPES; c) - mixing said PEPES and said compound homogeneously; a catalyst which can optionally be added to the reactor either during step b), in the form of a mixture of the catalyst and of the compound with a single reactive function, (it is then clear that in step c), a mixture of homogeneously said PEPES and said mixture of compound and catalyst); either at the end of step c); d) - the compound, the PEPES, and optionally the catalyst are left in contact until the selective addition of the compound with a single reactive function to the acetylenic bonds of the PEPES polymer is complete;
• a catalyst is added to the reactor, either during step b) in the form of a mixture of the catalyst and of the compound with a single reactive function, or to the mixture of PEPES and of the compound, at the end of the 'step c).
• a catalyst it is preferable to introduce it into the reactor during step b) in admixture with the compound with a single reactive function, because, by doing so, it is ensured that the reaction is more homogeneous, more progressive, and that no "hot spots" occur, therefore the quality of the final material obtained is much better than by introducing the catalyst alone at the end of step c), not mixed with the compound.
• This catalyst is generally chosen from the compounds already listed above.
• the poly (ethynylene-phenylene-ethynylene-silylene) polymer (PEPES) from step a) (unmodified polymer, before addition) is generally chosen from the polymers already mentioned in the above.
• Steps b) to c) and d) of the process are generally carried out with stirring.
• the process is generally carried out at a temperature of -20 to 200 ° C.
• the reactor such as a flask can be heated to a temperature of 30 to 140 ° C to lower the viscosity of the polymer to be modified.
• the mixing and homogenization step can be carried out at room temperature, but if it proves difficult, it can be heated to a temperature of 30 to 140 ° C. to facilitate mixing. It is then generally expected that the system returns to room temperature before adding the catalyst.
• Step c) of contacting is generally carried out with heating, for example at a temperature of 30 to 140 ° C.
• the process preferably the whole process, is generally carried out under an atmosphere of an inert gas such as argon, in particular step d).
• the duration of the contacting of the PEPES, of the monofunctional compound and of the optional catalyst in step d) is generally from 0.1 to 24 hours, preferably from 0.5 to 8 hours, more preferably from 2 to 6 hours, this contacting being preferably carried out under an inert atmosphere, with heating and with stirring.
• the modified polymer is recovered by separation from the reaction medium by any suitable separation process, for example by filtration.
• the invention also relates to a composition
• a composition comprising a poly (ethynylene phenylene ethynylene silylene) polymer, a compound with a single reactive function and optionally a catalyst.
• the compound with a single reactive function, the polymer and the catalyst optionally included in this composition are as defined above.
• the composition generally comprises by mass: from 1 to 99% of PEPES polymer, from 1 to 50% by mass of compound with a single reactive function, and optionally from 0 to 1% by mass of catalyst.
• modified polymers according to the invention have a structure which it is not always possible to define without ambiguity by a formula, this is the reason why they have been defined above, as “being capable of being prepared” by selective addition of a monofunctional compound on a polymer of PEPES.
• modified polymers, "poisoned” according to the invention can be represented by the following formula:
• Ri 'and R 2 ' represent a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, an aryloxy group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms, a cycloalkenyl group having from 3 with 20 carbon atoms, an alkynyl group having from 2 to 20 carbon atoms, one or more of the hydrogen atoms linked to the carbon atoms of R'i and R ' 2 may be replaced by halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, disubstituted amino groups or silanyl groups; R3 represents an alkyl radical of 1 to 2 OC such as a methyl radical
• phenylene group can be in the form 0, m or p and where R 5 'represents a halogen atom (such as F, Cl, Br and I), an alkyl group (linear, or branched) having from 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, cyclohexyl), an alkoxy group having 1 to 20 carbon atoms (such as methoxy, ethoxy, propoxy) , an aryl group having 6 to 20 carbon atoms (such as a phenyl group), an aryloxy group having 6 to 20 carbon atoms (such as a phenoxy group), an alkenyl group (linear, or branched) having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms (such as vinyl, allyl, cyclohexenyl), an alky
• the invention also relates to new poly (ethylene-phenylene-ethynylene-silylene) polymers which intrinsically allow, by their macromolecular structure, to control the contribution. from the Diels-Alder mechanism to the formation of the final network of the product, hardened material, and therefore the crosslinking density of said product, material, hardened and consequently the properties and in particular of the mechanical properties of the material.
• These new polymers are called “self-poisoned” polymers to differentiate them from the modified “poisoned” polymers described above.
• These new “self-poisoned” polymers derived from PEPES are designed not to allow, due to their very structure, the Diels-Alder reaction.
• Diels-Alder reactions can be prohibited by the selective addition of monofunctional compounds to PEPES as in the case of the modified polymers according to the invention described above, but it can also be carried out by means of units structural already present in the polymer, which are inherently part of its initial structure, its basic structure; these structural units resulting directly from the polymerization reaction, and not being derived from structural modifications subsequent to the polymerization and from the action, for example, of a monofunctional reactive agent on an already synthesized polymer.
• - r and s are whole numbers from 1 to 1000; - X 0 and Z 0 identical or different each independently represent a group 0C ⁇ , a group 2 or a combination of these groups:
• R 10 R 12 2 represents
• mi and ni are integers generally between 1 and 1000, preferably between 1 and 10;
• W 0 and Y 0 identical or different each independently represent a group Bi, a group B, a group B3, or a combination of these groups Bi, B and B 3 . So
• R i4 , Ris, Ri6 identical or different have the same meaning as Rg and each independently represent a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, an alkenyl group having from 2 to 20 carbon atoms , an alkynyl group having from 2 to 20 carbon atoms or an aryl group having from 6 to 20 carbon atoms, the hydrogen atoms linked to the carbon atoms of R ⁇ 4 , Ris and Ri6 may be partially or totally replaced by halogen atoms, alkoxy groups, phenoxy groups, disubstituted amino groups or silanyl groups; - or W 0 and Y 0 can represent a group B 2 ; if we opt for the strategy of inhibiting the Diels-Alder mechanism by functionalization of the aromatic cycle, B 2 represents:
• R17, Ri r R19 and R20 which are identical or different, each independently represent a halogen atom, an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, a phenoxy group having from 6 with 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, a substituted amino group having from 2 to 20 carbon atoms or a silanyl group having from 1 to 10 carbon atoms, the hydrogen atoms bound to carbon atoms of the substituents R i , Ris, Ri9 and R20 which can be totally or partially replaced by halogen atoms, alkoxy groups, groups phenoxy, disubstituted amino groups or silanyl groups; - Or W 0 and Y 0 can represent a group B 3 chosen from divalent heterocycles.
• These self-poisoned polymers can be prepared by known preparation methods for the polymers of this type described in the documents of the prior art described above, by appropriately choosing the starting compounds to obtain the groups W 0 , X 0 , Y 0 / Z 0 specific to the structure of these hardened polymers. It should however be noted that, generally, these “self-poisoned” polymers are prepared without using a catalyst, which allows control of their structure.
• the invention also relates to the hardened product capable of being obtained by treatment. thermal at a temperature generally of 50 to 500 ° C.
• the “self-poisoned” polymers according to the invention can advantageously be hardened without a catalyst. It is one of the advantages of the self-poisoned polymers according to the invention to generally use a non-catalyzed system for their hardening. The absence of catalyst ensures greater ease of implementation and easier storage before hardening; it is possible for the user to better control the curing reaction, thanks to the absence of catalyst.
• the “self-poisoned” polymers according to the invention have several notable advantages in the context of both their synthesis and their hardening, compared to the modified polymers according to the invention; indeed, their synthesis without catalyst is better controlled, their structure ensures better control of the rate of poisoning and the absence of catalyst during hardening also allows better control of the latter and easy implementation by the user .
• the invention also relates to a composite matrix comprising the modified polymer or the new self-poisoned polymer described above.
• the cured products prepared by heat treatment of the modified, poisoned polymers or of the new self-poisoned polymers, according to the invention are for example produced by melting the polymer by generally bringing it to a temperature of 30 to 200 ° C.
• the molten polymer is put into the desired form, for example by pouring the molten polymer into a mold with the desired shape.
• the polymer cast in the mold is then degassed under vacuum, for example at 0.1 to 10 mbar for a period of time, for example 10 min. at 6 a.m. and at a temperature of 30 to 200 ° C. After degassing, it returns to atmospheric pressure generally keeping the same temperature and the actual crosslinking is carried out by heating the mold and the polymer in a gaseous atmosphere, for example in a gaseous atmosphere of air, nitrogen or an inert gas such as argon or helium.
• a gaseous atmosphere for example in a gaseous atmosphere of air, nitrogen or an inert gas such as argon or helium.
• the treatment temperature generally ranges from 50 to 500 ° C, preferably from 100 to 400 ° C and more preferably from 150 to 350 ° C, and the heating is generally carried out for a period of one minute to 100 hours, preferably 2 to 12 hours. Due to the similar structure of the polymers according to the invention and of the polymers of document EP-B1-0 617 073, their hardening process is substantially identical and reference may be made to this document on page 17, as well as in document FR-A-2 798 622, for more details. The nature and structure of the materials or cured products obtained depend on the polymer or poly (phenylene ethynylene silylene ethynylene) modified ( "poisoned”) or self-poisoned used.
• the crosslinking treatment can comprise a certain number of stages consisting of a succession of temperature rises from a starting temperature which is generally the temperature at which the degassing is carried out to a final temperature which is the crosslinking temperature . Temperature bearings are 'observed after each temperature increase and a final level is measured at crosslinking temperature which is for example 250 to 450 ° C and is maintained for 1 (or 2) to 12 hours. After the final plateau, the temperature is generally gradually lowered to room temperature, for example at 0.1 to 5 ° C / minute.
• a typical crosslinking cycle can be, for example, the following: - the temperature rises from room temperature to 180 ° C, and a 2 hour isotherm or level is observed at 180 ° C; - We go up from 180 ° C to 240 ° C, and we observe a plateau or isotherm of 2 hours at 240 ° C; - We show from 240 ° C to 300 ° C, and we observe a plateau or isotherm of 2 hours at 300 ° C; - it goes down from 300 ° C to room temperature. All temperature ramps up and down are done at the speed of 1 ° C / minute.
• These advantages are inherently linked to the modified or self-poisoned polymers according to the invention from which these hardened products are derived.
• These cured products have excellent thermal properties which are at least equivalent to those of cured products obtained under the same conditions from unpoised, unpoisoned, non-self-poisoned polymers of the prior art, for example, and mechanical properties, which are significantly improved compared to the mechanical properties of the cured products obtained from the polymers (for example unmodified) of the prior art.
• the properties of these hardened products can moreover be perfectly and precisely modulated thanks to the control of the crosslinking density provided by the modification, the poisoning of the polymer or by the specific structure of the latter in the case of “self-poisoned” polymers. ".
• the improved mechanical properties are in particular highlighted by the much higher values of the modulus of elasticity, the stress at break and the strain at break.
• the preparation of organic matrix composites comprising the polymer of the invention can be done by numerous techniques. Each user adapts it to their constraints. The principle is generally always the same: namely, impregnation of a textile reinforcement by the resin, then crosslinking by heat treatment comprising a temperature rise rate of a few degrees / minute, then a plateau close to the crosslinking temperature.
• 100 g of poly (dimethylsilylene-ethynylene-phenylene-ethynylene) are introduced into a 1 liter three-necked flask placed under argon.
• the flask is heated to 100 ° C to lower the viscosity of the polymer.
• 25 g of dimethylphenylsilane are then introduced into the flask.
• 0.5 ml of 0.1 M Pt-TVTS in THF is added dropwise.
• the system is maintained at temperature and under argon for 2 hours.
• the modified polymer is then passed through a rotary evaporator to ensure that no free poisoning agent remains (90 ° C, 0.1 mbar).
• Example 2 Preparation of poly (methylhydrosilylene-ethynylene-phenylene-ethynylene) poisoned by 20% by mass of dimethylphenylsilane
• 100 g of poly (methylhydrosilylene-ethynylene-phenylene-ethynylene) are introduced.
• 25 g of dimethylphenylsilane are then introduced into the flask. If the viscosity of the polymer allows, homogenization is carried out at room temperature. If this is difficult, the temperature of the flask is brought to 50 ° C.
• Example 3 Crosslinking of poly (dimethylsilylene-ethynylene-phenylene-ethynylene) poisoned with 20% by weight of dimethylphenylsilane
• the poisoned polymer obtained in Example 2 is brought to 40-50 ° C and poured into the cavities of a metal or silicone mold and then degassed under 40 mbar at 50 ° C for 10 min. After returning to atmospheric pressure, the following crosslinking cycle is initiated in air: from 50 to 100 ° C in 50 min., Then 1 h at 100 ° C, then from 100 to 150 ° C in 50 min., Then 1 h at 150 ° C, then 150 to 200 ° C in 25 min., then 1 h at 200 ° C, then from 200 to 250 ° C in 25 min., Then 1 h at 250 ° C, then from 250 to 300 ° C in 25 min., Then 2 h at 300 ° C, then from 300 ° C to 25 ° C in 3 h.
• Such a material exhibits in bending and at 20 ° C. a modulus of elasticity of the order of 2.8 GPa, a stress at break of the order of 50 MPa and a deformation at break of approximately 1.8 %.
• the conditions of the bending tests are detailed above (example 3).
• the material obtained from the same unmodified, unpoisoned polymer, crosslinked under the same conditions exhibits in bending and at 20 ° C. an elastic modulus of the order of 2.8 GPa, a constraint at rupture of the order of 22 MPa and a deformation at rupture of approximately 0.9%.
• Example 5 Preparation of poly (ethynylene-mesilylene-ethynylene-silylene); "self-poisoned” polymer according to the invention.
• the polymer is obtained according to the method described for example in document FR-A-2 798 662 by substituting diethynylbenzene with diethynylmesitylene. The latter is obtained by deprotection of 1,3-bis-

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