• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a curable resin which is an excellent substitute for phenolic resins and is therefore capable of replacing phenolic resins in all applications in which they are used. This resin is characterized in that it comprises: (1) at least one prepolymer resulting from the prepolymerization of a compound A comprising one or more aromatic or heteroaromatic rings, at least one -O-CH2-C≡CH group and at least one group selected from the groups -O-CH2-C≡CH and -CH2-CH = CH2, these groups being borne by the aromatic ring or heteroaromatic ring (s); and (2) a compound B comprising at least two thiol groups (-SH). The invention also relates to a material which is obtained by curing this curable resin and, in particular, to a composite ablative material. The invention also relates to a material obtained by curing this curable resin.
    公开号:FR3047243A1
    申请号:FR1650755
    申请日:2016-01-29
    公开日:2017-08-04
    发明作者:Bastien RIVIERE；Brigitte Defoort；Cécile LESAMBER；Xavier Coqueret
    申请人:Centre National de la Recherche Scientifique CNRS；Airbus Defence and Space SAS；Universite de Reims Champagne Ardenne URCA；
    IPC主号:
    专利说明:

    CURABLE RESIN RESIN WITH PHENOLIC RESINS AND APPLICATIONS THEREOF
    DESCRIPTION
    TECHNICAL FIELD The invention relates to the field of curable resins and materials obtained from these resins.
    More specifically, it relates to a curable resin which is an excellent substitute for phenolic resins and is therefore capable of replacing phenolic resins in all applications in which they are used and, especially but not only, in the manufacture of so-called "ablative" composite materials such as those that come into the constitution: thermal shields that protect vehicles sent into space (shuttles, artificial satellites, rockets, probes, etc.) kinetic heating they undergo when they enter at high speed in the atmosphere of a planet of the solar system (Earth, Mars, Venus, Jupiter, etc.) or a satellite of a planet (moon for example); or nozzle walls of propulsion engines, for example, for space launchers. The invention also relates to a material which is obtained by curing this curable resin and, in particular, to a composite ablative material. The invention furthermore relates to the use of said curable resin for the manufacture of an ablative composite material and, more specifically, to a ablative thermal protection composite material, in particular for the aerospace industry.
    STATE OF THE PRIOR ART
    An ablative material is defined as a material that is capable of being ablated, i.e. a loss of substance by chemical decomposition, state change, or mechanical erosion under the effect of a flow of material or material. radiation (Official Journal of the French Republic of 22 September 2000).
    Typically, in the case of an ablative material of the type of those mentioned above, the outer layer of the ablative material which is directly in contact with the environment, for example the atmosphere during a reentry phase in the atmosphere, undergoes under the effect of the heat a chemical transformation as well as a recession which is linked to this transformation but also to other phenomena such as mechanical or aerodynamic shears.
    This outer layer radiates outwards and its chemical conversion consumes energy, the two effects contributing to a lower transmission of heat to the inner layers of the material and, therefore, thermal insulation of the underlying structure.
    A good ablative material must be such that: its chemical transformation under the effect of heat is (very) endothermic; its thermal conductivity is low, steady state and / or transient (diffusivity in this case); and its chemical transformation is not accompanied by a recession too fast.
    This last point is acquired when the chemical transformation of the ablative material is accompanied by the formation of a "crust" which, on the one hand, limits or even eliminates the recession of purely chemical origin and, on the other hand, is able to withstand the mechanical recession associated with shearing.
    For applications of atmospheric re-entry or propulsion, the expected "crusts" are based on carbon or silica and come from the pyrolysis of polymers, organic or silicone, respectively.
    It is considered that the organic polymers best suited to the manufacture of ablative materials must be capable of giving a large amount of carbon, which is expressed by the fact that their "coke rate" must be high. This coke content is defined as the mass of the residue which is obtained when a sample of an organic polymer is decomposed by pyrolysis, at a temperature greater than or equal to 900 ° C. and under a neutral gas (nitrogen or argon), referred to the initial mass of this sample. The coke content is greater than 50% and can even exceed 60% for the best organic polymers with ablative potential. This is the case of the coke content of certain phenolic resins, which are, to date, the curable resins most frequently used for the manufacture of ablative materials. The high coke content of these resins is also used for the development of certain radiative thermal protective composite materials, namely ceramic matrix composites.
    Phenolic resins are obtained by polycondensation of monomers from petrochemicals: phenol and formaldehyde, which is why they are also called phenol-formaldehyde resins or formophenolic resins. The widespread use of phenolic resins in the plastics industry is explained by their thermal resistance (they only start to decompose at around 300 ° C), their electrical resistance, their fire resistance and by the low smoke they generate when exposed to flames. Since 1908, phenolic resins have been associated with various reinforcing materials to make parts for electronics. In aeronautics, they can act as binders in composite materials reinforced with fiberglass or aramid for interior design parts (aircraft floors for example), radomes and sails. Large volumes of phenolic resins are, moreover, used as varnish or for the manufacture of wood panels (agglomerates, plywood, oriented chipboard, etc.).
    However, it turns out that phenol is toxic and highly corrosive to unprotected living tissue, while formaldehyde is known to be carcinogenic (it is believed to cause nasopharyngeal cancers) and the vapors it emits are extremely irritating to humans. eyes and the respiratory tract. These two compounds are therefore under the supervision of Regulation (EC) No 1907/2006 of the European Parliament and the Council called "REACh", whose main objective is to better protect human health and the environment against the risks that may present the chemicals, and the materials obtained from phenol and formaldehyde are, therefore, threatened with obsolescence.
    Given the place currently occupied by phenolic resins in the plastics industry and the disadvantages that their precursors exhibit in terms of toxicity, it would be desirable to have new curable resins which, while having similar properties to those of phenolic resins can be obtained from non-toxic precursors or, at least, less toxic than phenol and formaldehyde.
    It turns out, moreover, that the polycondensation of phenol and formaldehyde is never complete, hence the presence of volatile compounds and water molecules which are very difficult to eliminate if a well-defined thermal cycle does not occur. is not followed during this polycondensation and which can lead to porous materials in their native state as well as degassing during the life of materials made from phenolic resins. However, these degassing can have very harmful consequences in certain applications such as, for example, aerospace applications.
    The inventors have therefore set themselves the general goal of developing curable resins suitable for replacing phenolic resins in all their applications and, in particular, in their use as ablative materials, and the preparation of which is free from the disadvantages presented by that of phenolic resins, both in terms of the toxicity of the precursors used and in terms of porosity and degassing of the materials obtained from these resins.
    In this context, they have more specifically set the goal that these resins: (1) have properties similar to those of a commercial phenolic resin commonly used in aerospace for the production of ablative composite materials, Ablaphene RA 101, namely: a coke level greater than 50%, a glass transition temperature above 250 ° C (ideally the highest possible) and a sufficiently low viscosity at temperatures below 80 ° C .; C (typically less than 2 Pa.s) to allow their use in reinforcement fiber impregnation processes without having to use organic solvent; and (2) can be obtained from precursors which, besides not being toxic or only very slightly toxic, are derived from biomass so as to overcome the volatility of the prices of fossil raw materials, to anticipate their rarefaction, to reduce the release of greenhouse gases from fossil fuels, to preserve the environment and to give resins and materials obtained from them a renewable character.
    STATEMENT OF THE INVENTION
    These and other objects are achieved by the invention which provides, in the first place, a curable resin, which is characterized in that it comprises: (1) at least one prepolymer which results from the prepolymerization of a compound A comprising one or more aromatic or heteroaromatic rings, at least one -O-CH 2 -C = CH group and at least one group selected from -O-CH 2 -C = CH and -CH 2 -CH = CH 2, these groups being carried by the aromatic or heteroaromatic ring (s); and (2) a compound B comprising at least two thiol groups (-SH).
    In what precedes and what follows, the term "prepolymer" is taken in its usual acceptance, namely that it designates an oligomer or a polymer having at least two reactive groups which allow it to participate in a subsequent polymerization, and this , whether under the effect of heat, light (visible light, ultraviolet or infrared), ionizing radiation (electron beam, β or γ radiation, X-rays, ...) or any other way.
    In the context of the invention, the reactive groups of the prepolymer are represented by the groups -O-CH2-C = CH and / or -CH2-CH = CH2 free that includes this prepolymer, that is to say among those -O-CH2-C = CH and / or -CH2-CH = CH2 groups of the molecules of the compound A which did not participate in the polymerization of this compound.
    In what precedes and what follows, the term "aromatic cycle" is also taken in its usual acceptance, namely that it designates a unicycle or a polycycle which satisfies Hückel's rule and which therefore has a number of electrons delocalized π equal to An + 2, while the term "heteroaromatic ring" means an aromatic ring as just defined, but at least one carbon atom is replaced by a nitrogen atom, of oxygen or sulfur.
    Thus, the aromatic ring (s) can in particular be benzene or naphthalenic rings, while the heteroaromatic ring (s) can be, in particular, furanic, pyrrolic, thiophenic, pyridine, quinolinic, isoquinoline, pyrazine, pyrimidine rings, etc.
    According to the invention, compound A is the product of a propargylation of a compound A 'which comprises one or more aromatic or heteroaromatic rings, at least one hydroxyl (-OH) or carboxyl (-COOH) group and at least one a group chosen from hydroxyl, carboxyl and -CH 2 -CH = CH 2 groups, these groups being borne by the aromatic ring or heteroaromatic ring (s).
    This propargylation, which consists in substituting the hydrogen atom of the hydroxyl and / or carboxyl group or groups that the compound A 'comprises by a group -CH 2 -C = CH, can in particular be carried out as described by M. C. Joshi et al. in Bioorg. Med. Chem. Lett. 2007,17 (11), 3226-3230 (reference [1]), that is to say by reacting the compound A 'with a propargyl halide, typically propargyl bromide, in a strongly basic medium such as a medium comprising potassium carbonate in N, N-dimethylformamide, sodium hydride in tetrahydrofuran, or aqueous sodium hydroxide solution.
    Typically, the compound A 'and hence the compound A derived therefrom are such that: they comprise only one aromatic or heteroaromatic ring, in which case the two groups which must comprise at least the compounds A' and A are carried by the same heteroaromatic aromatic ring; or they comprise two or more aromatic or heteroaromatic rings, in which case the two groups which the compounds A 'and A must bear at least may be carried by the same aromatic or heteroaromatic ring or by two different aromatic or heteroaromatic rings.
    In the foregoing and the following, it is considered that a group is carried by an aromatic or heteroaromatic ring when this group is attached to an atom of this ring, and this, whether directly, that is to say ie by a covalent bond, or indirectly, that is to say by means of an acyclic spacer group such as, for example, a divalent, saturated or unsaturated C 1 to C 4 hydrocarbon group.
    However, in the context of the invention, it is preferred that the groups carried by the aromatic or heteroaromatic ring or rings are attached to an atom of this or these rings by a covalent bond or by a divalent methylene group (-CH 2 -).
    On the other hand, when the compound A 'and hence the compound A derived therefrom comprise two or more aromatic rings, then it is preferred that these rings be connected to each other either directly, i.e. a covalent bond, either by a divalent acyclic group comprising not more than 4 carbon atoms.
    Thus, the compound A 'can in particular be chosen from: allylated monophenols, that is to say compounds which comprise a phenolic group and a -CH 2 -CH = CH 2 group such as, for example, 2-allylphenol, chavicol (or 4-allylphenol), eugenol (or 2-methoxy-4- (2-propenyl) phenol), 4-allyl-2,6-dimethylphenol, etc .; polyphenols, ie compounds which comprise at least two phenolic groups such as, for example, resorcinol (or 1,3-benzenediol) and its two isomers: hydroquinone (or benzene-l, 4- diol) and pyrocathecol (or benzene-1,2-diol), phloroglucinol (or benzene-1,3,5-triol) and its two isomers: pyrogallol (or benzene-1,2,3-triol) and hydroxyquinol (or benzene-1,2,4-triol), resveratrol (or 5- [2- (4-hydroxyphenyl) ethenyl] -1,3-benzenediol), dimers of allylated monophenols such as dimers of eugenol (2-methoxy-4- (2-propenyl) phenol), etc .; phenolic acids, also known as phenolic acids, which comprise at least one phenolic group and at least one carboxylic acid group such as, for example, parahydroxybenzoic acid (or 4-hydroxybenzoic acid), gallic acid (or acid 3, 4,5-trihydroxybenzoic acid) and its five isomers including phloroglucinic acid (or 2,4,6-trihydroxybenzoic acid) and pyrogalolcarboxylic acid (or 2,3,4-trihydroxybenzoic acid), vanillic acid (or acid 4-hydroxy-3-methoxybenzoic acid), salicylic acid (or 2-hydroxybenzoic acid) and its two isomers: 3-hydroxybenzoic acid and 4-hydroxybenzoic acid, protocatechic acid (or 3,4-hydroxybenzoic acid), dihydroxybenzoic acid) and its five isomers including gentisic acid (or 2,5-dihydroxybenzoic acid) and α-, β- and γ-resorcylic acids, etc .; and polycarboxylic acids having one or more aromatic or heteroaromatic rings such as, for example, phthalic acid (or benzene-1,2-dicarboxylic acid), isophthalic acid (or benzene-1,3-dicarboxylic acid), terephthalic acid (or benzene-1,4-dicarboxylic acid), trimilletic acid (or 1,2,3-benzene tricarboxylic acid), trimesic acid (or 1,3,5-benzene tricarboxylic acid), 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-carbonyldiphthalic acid, dehydromucic acid (or 2,5-furandicarboxylic acid), and the like.
    According to the invention, the compound A 'can be derived from the petrochemical as well as be derived from the biomass, or directly, that is to say that it is itself extracted from the biomass or produced by the biomass. this biomass (production by a bacterial or fungal culture for example), or indirectly, that is to say by transformation of a precursor which itself is extracted from biomass or produced by biomass.
    However, in the context of the invention, it is preferred that the compound A and therefore the compound A 'from which it is obtained be derived from the biomass. In this respect, it is recalled that biomass is represented by any organic matter of plant origin (including algae), animal, bacterial or fungal. This is why it is preferred to choose the compound A 'from those of the abovementioned compounds which can be obtained from biomass, that is to say the chavicol, eugenol, resorcinol, hydroquinone, pyrocathecol, phloroglucinol, pyrogallol, hydroxyquinol, resveratrol, monophenol dimers allyl, parahydroxybenzoic acid, gallic acid and its five isomers, vanillic acid, salicylic acid, acid 3 hydroxybenzoic acid, 4-hydroxybenzoic acid, protocatechic acid and its five isomers, and more, among: eugenol which can be obtained in particular by extracting essential oils of clove; phloroglucinol which can in particular be obtained by bioconversion of glucose, xylose or arabinose as described in PCT International Application WO 2006/044290 (reference [2]); resorcinol which can in particular be obtained by hydrogenation of phloroglucinol as also described in reference [2]; gallic acid which can be obtained in particular by hydrolysis of gallic tannins present in many plants or by glucose bioconversion as described in PCT International Application WO 01/071020 (reference [3]); pyrogallol which may in particular be obtained by decarboxylation of gallic acid, for example by heat or by biocatalysis as also described in reference [3] above; and eugenol dimers, such as the dimer of formula (I) below:
    (I) which can be obtained from eugenol by a metathesis reaction of the type described by H. E. Blackwell et al. in J. Am. Chem. Soc. 2000, 122, 58-71 (reference [4]).
    The prepolymerization of compound A can be carried out thermally, for example by subjecting this compound to a series of steps of 2 hours each at 180 ° C. (with a return to ambient temperature between each stage) and this, under an inert atmosphere ( nitrogen or argon), so as to obtain a substance called stage B (or "B-stage" in English), comprising a mixture of prepolymers and residual monomers. The prepolymerization can be stopped from the moment when the heat generated during the polymerization of the material in stage B is lower than the heat released during the polymerization of the monomer alone, which can easily be
    determined by differential scanning calorimetry (DSC). Typically, the number of steps is between 10 and 15.
    According to the invention, the compound B, whose role is to allow a control of the polymerization / crosslinking profile of the prepolymer (s) during the curing of the resin (in particular with a reduction of the energy released during this curing) as demonstrated in the examples which follow, can be any thiolated compound provided that it comprises at least two thiol functions.
    Thus, compound B may also be derived from petrochemicals such as ethane-1,2-thiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, bis (3 -sulfanylpropanoate) 1,2-ethanediyl, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) or dipentaerythritol hexa (3-mercaptopropionate), than be derived from biomass.
    However, here again, it is preferred that the compound B be obtained from the biomass. This is the reason why compound B is preferably the product of a thiolation of a compound B '(that is to say a grafting of at least two thiol functions on this compound B which is itself derived from biomass and which comprises two or more groups selected from hydroxyl and carboxyl groups.
    Also, the compound B 'is it, preferably, chosen from: the same polyphenols and phenolic acids derived from biomass as those mentioned above for the compound A', namely resorcinol, hydroquinone, pyrocathecol, phloroglucinol, pyrogallol, hydroxyquinol, resveratrol, dimers of allylated monophenols, parahydroxybenzoic acid, gallic acid and its five isomers, vanillic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, protocatechic acid and its five isomers, and polyphenol macromolecules derived from biomass such as, for example, lignins and tannins.
    In the context of the invention, the term "lignin" covers any lignin derived from biomass, whatever the mode in which it was extracted from this biomass, as well as any macromolecular extract obtained by fractionation of a lignin.
    Moreover, compound B 'is chosen from phloroglucinol, resorcinol, gallic acid, pyrogallol, lignins and the eugenol dimer of formula (I) above.
    The thiolation of the compound B 'can in particular consist in replacing the hydrogen atom of each hydroxyl or carboxyl group carried by the compound B' by a group - (ChhhSH, in which case it can be carried out according to a protocol similar to that described by S. Chatani et al., In Macromol, 2014, 47 (15), 4894-4900 (reference [5]), that is to say by subjecting the compound B 'to an allylation reaction with a halogenide. allyl, typically allyl bromide, in a strongly basic medium, and then subjecting the thus allylated compound B 'to a radical addition reaction with thioacetic acid in the presence of a free radical generating agent such as azobisiso-butyronitrile (or AIBN), then subjecting the resulting product to a reaction to turn the thioesters groups it carries into thiol groups.
    According to a particularly preferred arrangement of the invention, the compounds A and B are both derived from biomass, in which case the resin may be described as a totally biosourced resin.
    This biosourced resin may, for example, comprise: at least one propargylated resorcinol prepolymer, propargylated gallic acid or a propargylated eugenol dimer; and a thiolated resorcinol, a thiolated gallic acid, a thiolated lignin or a thiolated eugenol dimer.
    In this resin, the respective proportions of the prepolymer (s) and of the compound B may vary over a wide range depending on the destination of the resin and, therefore, on the properties that it is desired to confer on it, but also on the properties that are wishes to confer on the materials it will use to manufacture.
    Thus, for example, when the resin is intended for the manufacture of a thermal protective ablative composite material and a coke content greater than 50% is desired, then this resin typically comprises from 80 to 95 parts by weight of prepolymer (s) for 5 to 20 parts by weight of compound B.
    In accordance with the invention, the resin may further comprise a compound C which is the product of a propargylation of a polyphenol macromolecule derived from biomass such as, for example, a lignin or a tannin, in which case the resin may, for example, for example, comprising: at least one propargylated resorcinol prepolymer, propargylated gallic acid or a propargylated eugenol dimer; a thiolated resorcinol, a thiolated gallic acid, a thiolated lignin or a thiolated eugenol dimer; and a propargylated lignin. Here again, the respective proportions of the prepolymer (s), the compound B and the compound C can vary over a wide range depending on the destination of the resin. However, when this resin is intended for the manufacture of a thermal protective ablative composite material and a coke content greater than 50% is desired, then it typically comprises from 30 to 94 parts by weight of prepolymer (s), from 5 to 20 parts by weight of compound B and from 1 to 50 parts by weight of compound C, the proportion of compound C being more preferably between 1 and 30 parts by weight in the case where this compound is a lignin.
    The resin may also comprise one or more adjuvants which, again, are chosen according to the destination of this resin as well as its mode of implementation and, in particular, the manner in which it is desired to achieve its hardening.
    Thus, for example, this or these adjuvants may be chosen from latent initiators (or initiators) for polymerization / crosslinking in the case where the curing of the resin is intended to be carried out thermally or partially by photochemical means, the accelerators of polymerization / crosslinking, polymerization / crosslinking inhibitors, antioxidants, flexibilizers, plasticizers, anti-UV agents, flame retardants, compatibilizers, anti-shrinkage agents and fillers, all of these adjuvants and conditions in which they can be used being well known to those skilled in the art. On this point, the reader can refer to reference works such as the "ENGINEERING TECHNIQUES", "Plastics and Composites" volumes.
    According to the invention, the curing of the resin can be carried out by any means capable of inducing the polymerization / crosslinking of the prepolymer (s) and, in particular, by the application of a heat treatment, a light treatment (visible light, UV or IR) or ionizing radiation (electron beam, β or γ radiation, X-rays, etc.).
    Although the resin according to the invention has a composition very different from that of the phenolic resins and can be, if desired, completely biobased, it has been found to have properties similar to those of phenolic resins and, in particular, to those Ablaphene RA 101 phenolic resin which is commonly used in aerospace for the preparation of ablative composite materials, in terms of coke rate, glass transition temperature and viscosity.
    The resin according to the invention is therefore likely to be used in all applications of phenolic resins and, more specifically, in the manufacture of ablative composite materials.
    Also, the invention also relates to a material which is characterized in that it is obtained by curing a curable resin as defined above, this curing being optionally followed by a heat treatment to further improve the thermomechanical stability of this material.
    According to the invention, this material is preferably a material forming the matrix of a composite material of the type comprising a matrix in which there is a reinforcement.
    The reinforcement present in the composite material can be of different types.
    Thus, it may especially be a reinforcement consisting of fibers such as glass fibers, quartz fibers, carbon fibers, graphite fibers, silica fibers, metal fibers such as steel or aluminum fibers, boron fibers, ceramic fibers such as silicon carbide or boron carbide fibers, synthetic organic fibers such as aramid fibers, polyethylene fibers, polyester fibers or poly (p-phenylene benzobisoxazole) fibers, better known by the acronym PBO, natural organic fibers such as hemp fibers, flax fibers or silk fibers, or mixtures of such fibers, in which case this Depending on the nature of the constituent fibers, reinforcement may be in the form of chopped yarns, crushed fibers, continuous filament mats, chopped filament mats, rovings in English, fabrics, knitwear, women's others, etc., or in the form of complexes made by association of different types of planar materials.
    It can also be a reinforcement consisting of particles such as cork particles or refractory fillers of the tungsten type, magnesium oxide, calcium oxide, alumina, silica, zirconium dioxide, titanium dioxide, beryllium oxide. etc.
    Furthermore, the manufacture of the composite material can be carried out by any of the techniques known to those skilled in the art of composite materials such as, for example, by impregnation, by simultaneous injection molding, by autoclaved lay-up molding, by vacuum molding, by Resin Transfer Molding (RTM), by low pressure wet process molding, by BMC (Bulk Molding Compound), by compression molding of pre-impregnated mats (or SMCs for Sheet Molding Compound), by filament winding, by centrifugation or by pultrusion, the impregnation being preferred in the case where the reinforcement consists of fibers.
    Preferably, the composite material is an ablative composite material and, more specifically, a composite ablative thermal protection material, especially for aerospace. Another subject of the invention is the use of a curable resin as defined above for the manufacture of an ablative composite material and, more specifically, of ablative thermal protection material, in particular for aerospace purposes. . Other features and advantages of the invention will appear on reading the additional description which follows, which relates to examples of the preparation of resins according to the invention and of their characteristics and which is given with reference to the appended figures. .
    Of course, this additional description is only given as an illustration of the subject of the invention and does not constitute a limitation of this object.
    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1 illustrates the methods of the heat treatment having been applied to the resins according to the invention for their hardening in the experiments which are reported in Examples 1 to 4 which follow; the temperature, denoted Θ and expressed in ° C, is indicated on the ordinate axis while the time, denoted t and expressed in hours, is indicated on the abscissa axis.
    FIG. 2 illustrates the thermogravimetric analysis curve (or ATG curve) obtained for a sample of a first resin according to the invention - hereinafter called resin R4 - after hardening; the residual mass of the sample, denoted Mr and expressed in% of the initial mass, is indicated on the ordinate axis while the temperature, denoted Θ and expressed in ° C, is indicated on the abscissa axis.
    Figure 3 illustrates the differential scanning calorimetry (or DSC curve) curve obtained during curing of a sample of the R4 resin (dashed line); for comparison, is also shown the DSC curve obtained, under the same conditions, during the curing of a control sample, differing from the sample of the resin R4 only in that it does not include compound B (full line curve); the heat flux, denoted Φ and expressed in W / g, is indicated on the ordinate axis, while the temperature, denoted Θ and expressed in ° C, is indicated on the abscissa axis.
    FIG. 4 illustrates the conservation module curve, denoted E 'and expressed in MPa (solid line curve), and the curve of the loss factor or tan δ (dashed curve) as obtained by dynamic mechanical analysis (or DMA) for a sample of the R4 resin after curing; the conservation modulus and the tan δ are indicated on the ordinates of ordinate, respectively of left and right, while the temperature, noted Θ and expressed in ° C, is indicated on the abscissa axis.
    FIG. 5 illustrates the evolution of the dynamic viscosity, denoted μ and expressed in Pa.s (solid line curve), of the resin R4, as a function of the temperature, denoted Θ and expressed in ° C (dashed curve) .
    FIG. 6 illustrates the evolution of the dynamic viscosity, denoted μ and expressed in Pa.s, of the resin R4, as measured at the temperature of 55 ° C., as a function of the shear rate, denoted D and expressed in s. -1, which has been applied to it during a charge cycle (x) and a discharge cycle (o).
    FIG. 7 illustrates the evolution of the dynamic viscosity, denoted μ and expressed in Pa.s, of the resin R4, as determined at the temperature of 55 ° C. and for a shear rate of 10 s -1, depending on the of time, noted t and expressed in hours.
    FIG. 8 illustrates the reaction scheme that has been followed for the preparation of a thiolated resorcinol which is reported in Example 2 below.
    FIG. 9 illustrates the ATG curve obtained for a sample of a second resin according to the invention - hereinafter called resin R6 - after hardening; the residual mass of the sample, denoted Mr and expressed in% of the initial mass, is indicated on the ordinate axis while the temperature, denoted Θ and expressed in ° C, is indicated on the abscissa axis.
    Figure 10 illustrates the DSC curve obtained during curing of a sample of resin R6 (dotted line); for comparison, is also shown the DSC curve obtained, under the same conditions, during the curing of a control sample, differing from the sample of the resin R6 only in that it does not include compound B (full line curve); the heat flux, denoted Φ and expressed in W / g, is indicated on the ordinate axis while the temperature, denoted Θ and expressed in ° C, is indicated on the abscissa axis.
    FIG. 11 illustrates the conservation module curve, denoted E 'and expressed in MPa (solid line curve), and the curve of the loss factor or tan δ (dashed curve) as obtained by DMA for a sample of the resin R6 after hardening; the conservation modulus and the tan δ are indicated on the ordinates of ordinate, respectively of left and right, while the temperature, noted Θ and expressed in ° C, is indicated on the abscissa axis.
    FIG. 12 illustrates the evolution of the dynamic viscosity, denoted μ and expressed in Pa.s (solid curve), of the resin R6, as a function of the temperature, denoted by Θ and expressed in ° C (dashed curve) .
    FIG. 13 illustrates the evolution of the dynamic viscosity, denoted μ and expressed in Pa.s, of the resin R 6, as measured at the temperature of 65 ° C., as a function of the shear rate, denoted D and expressed in s. "1, which has been applied to it during a charge cycle (x) and a discharge cycle (o).
    FIG. 14 illustrates the evolution of the dynamic viscosity, denoted μ and expressed in Pa.s, of the resin R 6, as determined at the temperature of 65 ° C. and for a shear rate of 10 s -1, depending on the of time, noted t and expressed in hours.
    FIG. 15 illustrates the chemical structures of resorcinol propargylated, denoted 5, of a phenylpropanoid unit, denoted 6, of a propargylated lignin (the remainder of the propargylated lignin being symbolized by the letter L inscribed in a circle), of a propargylated eugenol dimer, noted 7, and propargylated gallic acid, noted 8.
    DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS OF THE INVENTION EXAMPLE 1 Preparation and Characteristics of a First Type of Curable Resins According to the Invention
    The present example relates to a first type of resins according to the invention which comprise: a mixture of prepolymers obtained by prepolymerization of resorcinol propargylated (compound A); and pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) as compound B. 1.1 - Preparation of resins: * Preparation of propargylated resorcinol:
    Resorcinol propargylated is prepared according to a protocol inspired by that described in reference [1] above.
    To this end, 100 g of resorcinol (SIGMA-ALDRICH) are solubilized in 1.7 L of β-dimethylformamide (DMF) to which 1.27 kg of potassium carbonate (K 2 CO 3) are added with mechanical stirring. Then, 115 mL of propargyl bromide in 80% solution in toluene is added to the solution. Mechanical agitation is maintained for 12 hours. After filtration and dilution in ethyl acetate, the medium is washed 3 times with brine and 2 times with deionized water. The organic phase is dried over anhydrous magnesium sulfate (MgSO 4), filtered and concentrated under reduced pressure. 156 g of resorcinol propargylated, denoted 5 in FIG. 15 (Yield: 92%) are thus obtained. * Prepolymerization of resorcinol propargylated: 50 g of the resorcinol propargylé obtained above are introduced into a 250 ml two-neck flask containing a magnetic bar. The balloon is surmounted by a water cooler. The medium is subjected to a heat treatment comprising steps of 2 hours at 180 ° C separated from each other by a return to ambient temperature under a stream of nitrogen. After 10 steps at 180 ° C., a viscous material which is fluidized by raising the temperature is obtained, which corresponds to a mixture of propargylated resorcinol prepolymers (yield: 100%). * Mixture of resorcinol propargylated prepolymers and PETMP:
    Five resins, hereinafter referred to as R1, R2, R3, R4 and R5 resins, are prepared by adding the mixture of pre-polymers of resorcinol propargylated above to PETMP (available from SIGMA-ALDRICH), with simple manual stirring and prepolymer ratios of resorcinol propargylated / PETMP of 95/5, 90/10, 85/15, 80/20 and 75/25 respectively. 1.2 - Hardening of the resins:
    For their hardening, samples of the resins R1 to R5 are placed in an oven previously heated to 100 ° C. and subjected to the heat treatment whose modalities are illustrated in FIG.
    As visible in this figure, this heat treatment comprises 7 stages located respectively at 100 ° C., 120 ° C., 140 ° C., 160 ° C., 180 ° C., 200 ° C. and 220 ° C., each of 2 hours and separated by each other a rise in temperature of 1 ° C / minute. 1.3 - Coke rate after hardening:
    The coke levels of the resins R1 to R5 after curing are determined by an ATG which is carried out using a TA Instruments Q500 thermogravimetric analyzer and by applying to samples of these cured resins a rise in temperature between room temperature. and 900 ° C, at 5 ° C per minute and under nitrogen flow.
    For each resin, the coke rate corresponds to the residual mass presented by the sample of this resin at the end of the ATG, expressed as a percentage of the mass initially presented by this sample.
    The coke levels thus obtained for the resins R1 to R5 after curing are shown in Table I below while the ATG curve obtained for the resin sample R4 is illustrated in FIG. 2.
    Table I
    This table shows that the presence of PETMP up to 20% by mass or less in a resin comprising a mixture of prepolymers of resorcinol propargylé allows to confer on this resin, after curing, a coke rate greater than 50%. 1.4 - Calorimetric monitoring of the hardening: The influence of the presence of PETMP in the resin R4 on the reactivity of the mixture of resorcinol propargylated prepolymers is assessed by a DSC analysis which is carried out using a Q100 calorimeter of TA Instruments and subjecting a sample of uncured resin R4 to a temperature rise between 0 ° C and 300 ° C at 3 ° C / min and under nitrogen flow.
    The DSC curve obtained for this sample is illustrated in FIG. 3 (dashed curve). By way of comparison, this figure also shows the DSC curve obtained, under the same conditions, for a control sample, comprising the same mixture of resorcinol propargylated prepolymers as the R4 resin but free of PETMP.
    This figure shows that the presence of PETMP at a level of 20% by mass in the resin R4 allows the polymerization / crosslinking of the mixture of resorcinol propargylated prepolymers: (1) to start at a lower temperature: 110 ° C. versus 160 ° C .; (2) to take place in a wider temperature range: 110-270 ° C versus 160 ° C-280 ° C; and (3) to have a lower enthalpy: 770 J / g versus 880 J / g.
    The presence of PETMP at a level of 20% by mass in the resin R4 thus allows a better control of the reactivity of the mixture of resorcinol propargylated prepolymers and a less violent course of the polymerization / crosslinking of this mixture of prepolymers. 1.5 - No runaway during hardening:
    No runaway was observed during the hardening of resins R1 to R5.
    On the other hand, the curing of resins comprising the same mixture of resorcinol propargylated prepolymers as the resins R1 to R5 but PETMP free has resulted in runaway, in which case the material carbonizes with a strong smoke release. 1.6 - Loss of mass during hardening:
    The mass lost by the resin R4 during its curing is determined by subjecting a sample of this resin to a rise in temperature between 100 and 220 ° C and comparing the weight of this sample before and after this heat treatment.
    The mass loss is 10%. 1.7 - Glass transition temperature:
    The glass transition temperature of the resin R4 after hardening is determined by a DMA which is carried out by means of a TA Instruments Q800 dynamic mechanical analyzer (single lever mode, frequency of 1 Hz, amplitude of 30 μιτι) and in FIG. subjecting a parallelepipedic sample (17.5 mm x 2 mm x 10 mm) of the cured resin R4 to a temperature rise between 0 ° C and 350 ° C at a rate of 3 ° C / minute.
    The results of this analysis are illustrated in Figure 4 which shows the curve of the conservation module (curve in solid line) and the curve of the loss factor or tan δ (dashed curve) obtained for this sample as a function of temperature.
    As shown in this figure, the drop of the storage module of the cured resin R4 occurs at 315 ° C. The glass transition temperature of this resin is therefore 315 ° C. 1.8 - Rheological characteristics before hardening:
    Samples of the uncured resin R4 are subjected to rheological measurements which are carried out by means of an ARES rheometer of TA Instruments (cone / plane geometry 0 = 50 mm, air gap = 50 μιτι) equipped with a calibration system. Peltier temperature regulation (APS from TA Instruments).
    The results of these measurements are illustrated in FIGS. 5 to 7 which represent: FIG. 5: the evolution of the dynamic viscosity of the resin R4 (curve in solid lines) as a function of the temperature (dashed curve); FIG. 6 shows the evolution of the dynamic viscosity of resin R4 at constant temperature (55 ° C.) as a function of the shear rate, during a charge cycle (x) and a discharge cycle ( o); Figure 7: the evolution of the dynamic viscosity of the resin R4 at constant temperature (55 ° C) and constant shear rate (10 s'1) as a function of time.
    These figures show: on the one hand, that the dynamic viscosity of the resin R4 is less than 2 Pa.s beyond 39 ° C (Figure 5); on the other hand, that the resin R4 has a Newtonian behavior, that is to say that its dynamic viscosity is independent of the shear rate (FIG. 6); and finally, that the dynamic viscosity of the resin R4 is very stable over time and can be maintained at less than 2 Pa.s for at least 4 hours at a temperature which is below 80 ° C (Fig. 7) , which makes it possible to envisage a use of this resin in processes for manufacturing composite materials by impregnation without the use of organic solvents. EXAMPLE 2 Preparation and Characteristics of a Second Kind of Curable Resin According to the Invention
    The present example relates to a second type of resin according to the invention, which comprises: a mixture of prepolymers obtained by prepolymerization of resorcinol propargylated (compound A); and resorcinol thiolated as compound B. 2.1 - Preparation of the resin:
    The mixture of propargylated resorcinol prepolymers is prepared as described in point 1.1 of Example 1 above while the thiolated resorcinol is prepared according to the reaction scheme illustrated in FIG. 8, which is inspired by that described in reference [ 5] above. * Preparation of resorcinol thiolated:
    As can be seen in FIG. 8, the first step of this preparation consists in subjecting resorcinol, noted 1, to an allylation reaction.
    To this end, 11.61 g of resorcinol are solubilized in 465 ml of DMF in a 2.5 L reactor whose contents are stirred mechanically. Then, 150 g of K2CO3 and 19 ml of allyl bromide are added successively to the medium. The reaction is carried out for 12 hours at room temperature. The reaction medium is then diluted in ethyl acetate and filtered. The washing is carried out by extraction with brine and permutated water. The organic phase is dried over anhydrous MgSO4 and concentrated under reduced pressure. 13.18 g of the compound noted in FIG. 8 are thus obtained (yield: 66%).
    The second step is to subject the compound 2 to a radical addition reaction with thioacetic acid to replace the allyl groups with thioester groups.
    To this end, 13.06 g of compound 2 and 5.56 g of azobisisobutyronitrile (AIBN) are solubilized in 59 ml of 1,4-dioxane. The medium is degassed for 40 minutes by bubbling argon in the medium. Excess thioacetic acid (18 mL) is added to the medium left under argon. The temperature is raised to 63 ° C. After 24 hours of stirring and return to ambient temperature, the medium is diluted in diethyl ether. The organic phase is washed with saturated sodium bicarbonate solution (NaHCO 3), with brine and finally with deionized water. After evaporation of the diethyl ether, 15.52 g of the compound denoted 3 in FIG. 8 are obtained in the form of white crystals (yield: 66%).
    The third step consists in subjecting the compound 3 to solvolysis in an aqueous-alcoholic medium to transform the two thioester groups into thiol groups.
    To do this, 15.50 g of compound 3 are introduced into a 250 ml two-neck flask surmounted by a water cooler. Then, 150 ml of methanol and 18 ml of concentrated hydrochloric acid (HCl) are added to the flask. The medium is placed under magnetic stirring and the temperature is raised to 70 ° C. for 3 hours. After returning to ambient temperature, 200 mL of chloroform and 200 mL of deionized water are added to the medium. The aqueous phase is extracted 4 times with 200 mL of chloroform. The organic phase fractions are combined and concentrated under reduced pressure.
    Thus obtained 8.19 g of a product (yield: 70%) including the infrared spectrum (which shows the absence of the absorption band resorcinol -OH groups and the appearance of a signal at 2565 cm 1 indicating the presence of -SH groups), elemental analysis (calculated: 55.8% C, 7.02% H, 24.8% S, found: 55.6% C, 7.21% H, 24, 8% S) and the 13C and XH NMR spectra confirm that it is indeed resorcinol thiolated, denoted 4 in FIG. 8. * Mixture of prepolymers of proparpylated resorcinol and resorcinol thiole:
    A resin, hereinafter referred to as R6 resin, is prepared by adding the mixture of resorcinol propiolated resorcinol prepolymers to resorcinol thiole, with simple manual stirring and in a mass ratio allowing the introduction of a quantity of thiol groups identical to that present in the resin R4 of Example 1 above, which gives a weight ratio prepolymers resorcinol propargylated / resorcinol thiole 79/21. 2.2 - Hardening of the resin:
    The hardening of the resin R6 is carried out under conditions identical to those described in point 1.2 of Example 1 above. 2.3 - Coke rate after hardening:
    The coke level of the resin R6 after curing is determined by subjecting a sample of this cured resin to ATG which is carried out under conditions identical to those described in point 1.3 of Example 1 above.
    The ATG curve obtained for the resin sample R6 is illustrated in FIG. 9.
    This figure shows that the coke content of the resin R6 is 54%. 2.4 - Calorimetric monitoring of the hardening: The influence of the presence of thiol resorcinol in the resin R6 on the reactivity of the mixture of resorcinol propargylated prepolymers is appreciated by subjecting a sample of uncured resin R6 to a DSC analysis which is carried out under conditions identical to those described in point 1.4 of Example 1 above.
    The DSC curve obtained for this sample is illustrated in FIG. 10 (dashed curve). By way of comparison, this figure also shows the DSC curve obtained, under the same conditions, for a control sample comprising the same mixture of resorcinol propargylated prepolymers as the R6 resin but free of resorcinol thiolated.
    This figure shows that the presence of resorcinol thiole at 21% by weight in the resin R6 produces the same effects as those produced by the presence of PETMP in the resin R4.
    The presence of resorcinol thiolated to 21% by weight in the resin R6 thus allows better control of the reactivity of the mixture of resorcinol propargylated prepolymers and a less violent course of the polymerization / crosslinking of this mixture of prepolymers. 2.5 - No runaway during hardening:
    No racing was observed during the hardening of the R6 resin. 2.6 - Loss of mass during hardening:
    The mass lost by the resin R6 during its curing is determined under the same conditions as those previously described in point 1.6 of Example 1 above.
    The mass loss is 12%. 2.7 - Glass transition temperature:
    The glass transition temperature of the resin R6 after curing is determined by subjecting a sample of this cured resin to a DMA which is carried out under the same conditions as those previously described in point 1.7 of Example 1 above.
    The results of this analysis are illustrated in Figure 11 which shows the conservation modulus curve (solid curve) and the curve of the loss factor or tan δ (dashed curve) obtained for this sample as a function of temperature.
    This figure shows that the drop of the storage module of the cured R6 resin occurs at 312 ° C. The glass transition temperature of this resin is therefore 312 ° C. 2.8 - Rheological characteristics before hardening:
    Samples of the uncured resin R6 are subjected to rheological measurements which are carried out using the same apparatus as that described in point 1.8 of Example 1 above.
    The results of these measurements are illustrated in FIGS. 12 to 14 which represent: FIG. 12: the evolution of the dynamic viscosity of the resin R6 (solid line curve) as a function of the temperature (dashed curve); FIG. 13: the evolution of the dynamic viscosity of the resin R6 at constant temperature (65 ° C.) as a function of the shear rate, during a charge cycle (x) and a discharge cycle ( o); Figure 14: the evolution of the dynamic viscosity of the resin R6 at constant temperature (65 ° C) and constant shear rate (10 s-1) as a function of time.
    These figures show: first, that the dynamic viscosity of the resin R6 is less than 2 Pa.s beyond 51 ° C (Figure 12); on the other hand, that the resin R6 has a Newtonian behavior (FIG. 13); and finally, that the dynamic viscosity of the resin R6 is very stable over time and can be maintained at less than 2 Pa.s for at least 4 hours at a temperature which is below 80 ° C. (FIG. 14). ). EXAMPLE 3 Preparation and characteristics of a third type of curable resin according to the invention
    The present example relates to a third type of resin according to the invention, which comprises: a mixture of prepolymers obtained by prepolymerization of resorcinol propargylated (compound A); and a thiolated lignin as compound B. 3.1 - Preparation of the resin:
    The mixture of propargylated resorcinol prepolymers is prepared as described in point 1.1 of Example 1 above while the thiolated lignin is prepared following a protocol inspired by that described in reference [5] above. * Preparation of thiolated lignin:
    The first step of this preparation is to subject a lignin to an allylation reaction.
    To do this, 40 g of a lignin (lignin Kraft Indulin AT) are solubilized in 800 ml of a solution of sodium hydroxide (NaOH) at 0.5 mol / L in a reactor equipped with a lid allowing the passage of a stirring blade and the installation of a water cooler. Then 62 ml of allyl bromide are added and the temperature of the medium is raised to 60 ° C for 4 hours. After stopping the agitation, the majority of the allylated lignin sediment while the allylated lignin still dispersed can be recovered by centrifugation. The allylated lignin thus obtained is then washed with osmosis water until neutrality of the washing water. It is then lyophilized.
    The infrared spectrum of this lignin shows a decrease in the signal associated with the -OH groups at 3450 cm.sup.1 and the appearance of a new absorption band at 3078 cm.sup.1 corresponding to the functionalization of part of the -OH groups of the lignin by allyl groups (-CH2-CH = CH2).
    31P NMR analysis after derivatization of the lignin with 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP) indicates that the aromatic -OH groups of the lignin were functionally functionalized. Quasi-quantitative: 3.7 mmol of aromatic -OH groups / g of lignin before allylation versus 0.4 mmol of remaining aromatic-OH groups / g of lignin after allylation.
    The second step is to subject the allylated lignin to a radical addition reaction with thioacetic acid to replace the allyl groups in thioester groups.
    To this end, 10 g of dried allylated lignin are solubilized in 50 ml of 1,4-dioxane using a vortex mixer. Then, 2 g of AIBN are solubilized in 21 ml of 1,4-dioxane and added to the allylated lignin solution. Oxygen is removed from the reaction chamber by bubbling argon in the solution for 40 minutes. After adding 20 ml of thioacetic acid, the medium is heated at 70 ° C. for 24 hours under an inert atmosphere. The product is then recovered by precipitation in a large volume of diethyl ether, filtered and immediately dispersed in saturated NaHCO 3 solution. The thioesterified lignin thus obtained is washed to neutrality of the washing water and freeze-dried.
    The infrared spectrum of this lignin shows the disappearance of the signal at 3078 cm 1 and the appearance of a very intense aborption band at 1689 cm -1 corresponding to the presence of the thioester groups.
    The third step is to subject the thioesterified lignin to deprotection to turn the thioester groups into thiol groups.
    To do this, 8.16 g of this lignin are solubilized in 75 ml of DMF with vortex stirring. The solution is degassed by bubbling argon in the medium. Then, 3.3 mL of acetic acid and 2.8 mL of hydrazine monohydrate are introduced successively and dropwise. After stirring for 1 hour, the thiolated lignin can be precipitated in a large volume of water and washed with osmosis water.
    The infrared spectrum of this lignin shows the disappearance of the signal centered at 1689 cm 1 as well as the appearance of an absorption band at 2564 cm 1 attributed to the presence of thiol groups. Elemental analysis indicates that the mass percentage of sulfur is 11% versus 1.5% for raw lignin before any modification. * Mixture of resorcinol propargylated prepolymers and thiolated lignin:
    A resin, hereinafter referred to as R7 resin, is prepared by adding the mixture of resorcinol propargylated prepolymers to the thiolated lignin, with simple manual stirring and in a mass ratio of prepolymers of resorcinol propargylated / thiolated lignin of 86/14. 3.2 - Hardening of the resin:
    The hardening of the resin R7 is carried out under conditions identical to those described in point 1.2 of Example 1 above. 3.3 - Characteristics of the resin:
    The resin R7 is subjected to analyzes to determine its coke level after hardening, its mass loss during hardening and its glass transition temperature, which is carried out in the same way as described in points 1.3, 1.6 and 1.7. of Example 1 above.
    The results are shown in Table II below.
    Table II
    EXAMPLE 4 Preparation and characteristics of a fourth type of curable resin according to the invention
    The present example relates to a fourth type of resin according to the invention, which comprises: a mixture of prepolymers obtained by prepolymerization of resorcinol propargylated (compound A); PETMP as compound B; and a propargylated lignin as compound C. 4.1 - Preparation of the resin:
    The mixture of propargylated resorcinol prepolymers is prepared as described in point 1.1 of Example 1 above while the propargylated lignin is prepared as described below. * Preparation of the propargylated lignin: 20.1 g of lignin (lignin Kraft Indulin AT) are solubilized in 400 ml of a solution of NaOH at 0.5 mol / l. Then 22 ml of propargyl bromide in 80% solution in toluene are added to the solution and the temperature of the medium is raised and maintained at 75 ° C for 4 hours. The propargylated lignin is then recovered by centrifugation and washed with osmosis water until neutrality of the washing water. It is then lyophilized.
    The infrared spectrum of this lignin, denoted 6 in FIG. 15, shows the appearance of the characteristic signals of the alkyne function at 3283 cm 1 and 2120 cm -1. A 31P NMR analysis after derivatisation by the TMDP shows that the aromatic groups of the lignin have been modified in a quasi-quantitative manner: 3.7 mmol of aromatic -OH groups / g of lignin before propargylation versus 0.5 mmol of -OH groups remaining aromatic / g of propargylated lignin. * Mixture of propargylated resorcinol prepolymers, propargylated lignin and PETMP:
    A resin, hereinafter referred to as R8 resin, is prepared by adding the mixture of propargylated resorcinol prepolymers and propargylated lignin to PETMP after fine grinding of the propargylated lignin to ensure homogeneous dispersion thereof, with simple manual stirring. in a weight ratio prepolymers of resorcinol propargylé / PETMP / lignin propargylée 75/10/15. 4.2 - Hardening of the resin:
    The hardening of the resin R8 is carried out under conditions identical to those described in point 1.2 of Example 1 above. 4.3 - Characteristics of the resin:
    The resin R8 is subjected to analyzes to determine its coke level after hardening, its loss of mass during curing and its glass transition temperature, which is carried out in the same way as described in points 1.3, 1.6 and 1.7. of Example 1 above.
    The results are shown in Table III below.
    Table III
    EXAMPLE 5 Preparation of a propargylated eugenol dimer useful as compound A according to the invention * Preparation of the eugenol dimer of formula (!) Above:
    The eugenol dimer is prepared by metathesis of eugenol according to a protocol inspired by that described in reference [4] above.
    To do this, 24 ml of eugenol (SIGMA-ALDRICH) are placed in the presence of 0.530 g of Grubbs first-generation catalyst, under an inert atmosphere and magnetic stirring, at room temperature. Once the medium becomes thicker and frozen, the system is placed under reduced pressure (100 kPa) for 48 hours. The solid obtained is solubilized in 1 L of a 1 mol / l aqueous NaOH solution and filtered on celite to remove the catalyst. The filtrate is acidified by adding concentrated HCl until precipitation of a pale gray solid. The solid is collected by filtration on a Buchner funnel and washed with deionized water until neutrality of the washing water. The product is
    then dispersed in a minimum volume of a water-ethanol mixture (50:50 v / v), solubilized by raising the temperature (40 ° C) and then placed at 5 ° C until precipitation. The solid obtained is filtered on a Buchner funnel and washed with water-ethanol solution. The recovered compound is solubilized in dichloromethane and washed with water. The organic phase is concentrated under reduced pressure to obtain 3.0 g of eugenol dimer (Yield: 13%). * Proparqylation of the eugenol dimer: 1.5 g of the eugenol dimer are solubilized in 24 ml of DMF in which 7.5 g of K2CO3 are introduced with magnetic stirring. Then 1.2 ml of propargyl bromide in 80% solution in toluene are then introduced. Magnetic stirring is maintained for 12 hours. After filtration and dilution in ethyl acetate, the medium is washed 3 times with brine and 2 times with deionized water. The organic phase is dried over MgSO 4, filtered and concentrated under reduced pressure.
    There is thus obtained 1.62 g of propargylated eugenol dimer, denoted 7 in FIG. 15 (Yield: 86%). EXAMPLE 6 Preparation of propargylated gallic acid useful as compound A according to the invention 5.0 g of gallic acid (SIGMA-ALDRICH) are solubilized in 317 ml of DMF in which 101 g of K2CO3 are introduced with magnetic stirring. Then, 32.7 mL of propargyl bromide in 80% solution in toluene is added to the solution. Magnetic stirring is maintained for 12 hours. After filtration and dilution in ethyl acetate, the medium is washed 3 times with brine and 2 times with deionized water. The organic phase is dried over MgSO 4, filtered and concentrated under reduced pressure.
    There are thus obtained 7.4 g of propargylated gallic acid, denoted 8 in FIG. 15 (yield: 78%).
    REFERENCES CITED
    [1] M. C. Joshi et al., Bioorg. Med. Chem. Lett. 2007,17 (11), 3226-3230 [2] WO-A-2006/044290 [3] WO-A-01/071020 [4] H. E. Blackwell et al., J. Am. Chem. Soc. 2000, 122, 58-71 [5] S. Chatani et al., Macromol. 2014, 47 (15), 4894-4900
    权利要求:
    Claims (22)
    [1" id="c-fr-0001]
    A curable resin, characterized in that it comprises: (1) at least one prepolymer which results from the polymerization of a compound A comprising one or more aromatic or heteroaromatic rings, at least one -O-Chh-C ^ group CH and at least one group selected from -O-CH2-C = CH and -CH2-CH = CH2, which groups are supported by the aromatic or heteroaromatic ring (s); and (2) a compound B comprising at least two thiol groups (-SH).
    [2" id="c-fr-0002]
    2. Curable resin according to claim 1, characterized in that the compound A is the product of a propargylation of a compound A 'which comprises one or more aromatic or heteroaromatic rings, at least one hydroxyl (-OH) or carboxyl group (-COOH) and at least one group selected from hydroxyl, carboxyl and -CH2-CH = CH2, these groups being borne by the aromatic ring or heteroaromatic.
    [3" id="c-fr-0003]
    3. Curable resin according to claim 2, characterized in that compound A 'is chosen from allylated monophenols, polyphenols, phenolic acids and polycarboxylic acids with one or more aromatic or heteroaromatic rings.
    [4" id="c-fr-0004]
    4. Curable resin according to claim 2 or claim 3, characterized in that the compound A is derived from biomass.
    [5" id="c-fr-0005]
    5. curable resin according to claim 4, characterized in that the compound A 'is selected from chavicol, eugenol, resorcinol, hydroquinone, pyrocathecol, phloroglucinol, pyrogallol, hydroxyquinol, resveratrol, allyl monophenol dimers, parahydroxybenzoic acid, gallic acid and its five isomers, vanillic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, protocatechic acid and its five isomers.
    [6" id="c-fr-0006]
    6. Curable resin according to claim 5, characterized in that the compound A 'is chosen from resorcinol, phloroglucinol, gallic acid, pyrogallol and eugenol dimer of formula (I) below:

    (L)
    [7" id="c-fr-0007]
    7. curable resin according to any one of claims 1 to 6, characterized in that the compound B is derived from biomass.
    [8" id="c-fr-0008]
    The curable resin according to claim 7, characterized in that compound B is the product of a thiolation of a compound B 'which is obtained from biomass and which comprises two or more groups selected from the groups hydroxyl and carboxyl.
    [9" id="c-fr-0009]
    9. curable resin according to claim 8, characterized in that the compound B 'is selected from resorcinol, hydroquinone, pyrocathecol, phloroglucinol, pyrogallol, hydroxyquinol, resveratrol, allyl monophenol dimers, l parahydroxybenzoic acid, gallic acid and its five isomers, vanillic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, protocatechic acid and its five isomers, lignins and tannins.
    [10" id="c-fr-0010]
    10. curable resin according to claim 9, characterized in that the compound B 'is selected from resorcinol, phloroglucinol, gallic acid, pyrogallol, lignins and eugenol dimer of formula (I) below :



    (I)
    [11" id="c-fr-0011]
    11. curable resin according to any one of claims 1 to 10, characterized in that the compounds A and B are both derived from biomass.
    [12" id="c-fr-0012]
    12. Curable resin according to claim 11, characterized in that it comprises: at least one propargylated resorcinol prepolymer, propargylated gallic acid, a propargylated lignin or a propargylated eugenol dimer; and a thiolated resorcinol, a thiolated gallic acid, a thiolated lignin or a thiolated eugenol dimer as compound B.
    [13" id="c-fr-0013]
    13. curable resin according to any one of claims 1 to 12, characterized in that it comprises from 80 to 95 parts by weight of prepolymer (s) for 5 to 20 parts by weight of compound B.
    [14" id="c-fr-0014]
    14. curable resin according to any one of claims 1 to 12, characterized in that it comprises more a compound C which is the product of a propargylation of a polyphenol macromolecule derived from biomass.
    [15" id="c-fr-0015]
    15. curable resin according to claim 14, characterized in that the polyphenol macromolecule is a lignin or a tannin.
    [16" id="c-fr-0016]
    16. Phenolic resin according to claim 14 or claim 15, characterized in that it comprises: at least one propargylated resorcinol prepolymer, propargylated gallic acid or a propargylated eugenol dimer;

    a thiolated resorcinol, a thiolated gallic acid, a thiolated lignin or a eugenol dimer thiolated as compound B; and a propargylated lignin as compound C.
    [17" id="c-fr-0017]
    17. Curable resin according to any one of claims 14 to 16, characterized in that it comprises from 30 to 94 parts by weight of prepolymer (s), from 5 to 20 parts by weight of compound B and from 1 to 50 parts by mass of compound C.
    [18" id="c-fr-0018]
    18. Material, characterized in that it is obtained by curing a curable resin according to any one of claims 1 to 17.
    [19" id="c-fr-0019]
    19. Material according to claim 18, characterized in that it is a material forming the matrix of a composite material of the type comprising a matrix in which there is a reinforcement.
    [20" id="c-fr-0020]
    20. Material according to claim 19, characterized in that the composite material is a composite ablative material.
    [21" id="c-fr-0021]
    21. Use of a curable resin according to any one of claims 1 to 17 for the manufacture of an ablative composite material.
    [22" id="c-fr-0022]
    22. Use according to claim 21, wherein the ablative composite material is a ablative thermal protection composite material.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3408179B1|2020-09-16|Curable resin as a substitute for phenolic resins and the applications thereof
    Wang et al.2019|Facile in situ preparation of high-performance epoxy vitrimer from renewable resources and its application in nondestructive recyclable carbon fiber composite
    Maiorana et al.2016|Structure property relationships of biobased n-alkyl bisferulate epoxy resins
    Brodin et al.2010|The behavior of kraft lignin during thermal treatment
    Oliveira et al.2008|Phenol–furfural resins to elaborate composites reinforced with sisal fibers—Molecular analysis of resin and properties of composites
    Fan et al.2011|Comparative studies of products obtained from solvolysis liquefaction of oil palm empty fruit bunch fibres using different solvents
    Li et al.2017|Preparation of bio-based phenol formaldehyde foams using depolymerized hydrolysis lignin
    Hu et al.2013|Synthesis of foaming resol resin modified with oxidatively degraded lignosulfonate
    Trindade et al.2004|Phenolic thermoset matrix reinforced with sugar cane bagasse fibers: attempt to develop a new fiber surface chemical modification involving formation of quinones followed by reaction with furfuryl alcohol
    US20140171379A1|2014-06-19|Lignin compositions, methods of producing the compositions, methods of using lignin compositions, and products produced thereby
    Hao et al.2019|A high‐lignin‐content, removable, and glycol‐assisted repairable coating based on dynamic covalent bonds
    Xie et al.2015|Physicochemical characterization of lignin recovered from microwave‐assisted delignified lignocellulosic biomass for use in biobased materials
    Rodrigues et al.2014|Recycling of carbon fibers inserted in composite of DGEBA epoxy matrix by thermal degradation
    Maafi et al.2010|Elaboration and characterization of composites of castor oil‐based polyurethane and fibers from alfa stems
    Liu et al.2018|Development of acrylated soybean oil‐based UV‐curable coatings with high impact strength from low viscosity oligomer
    Yang et al.2020|Strong interface construction of carbon fiber–reinforced PEEK composites: An efficient method for modifying carbon fiber with crystalline PEEK
    Hassouma et al.2016|Design of new cardanol derivative: synthesis and application as potential biobased plasticizer for poly |
    Tejeda-Ricardez et al.2003|Design of a batch solvolytic liquefaction reactor for the valorization of residues from the agricultural foodstuff
    Liang et al.2018|Lignin-based grinding wheels with aluminum oxide: Synthesis and characterization
    Da Silva et al.2012|Composites from a forest biorefinery byproduct and agrofibers: Lignosulfonate-phenolic type matrices reinforced with sisal fibers
    Rana et al.2021|Synergistic effect of water-ethanol-formic acid for the depolymerization of industrial waste | lignin to phenolic monomers
    Imman et al.2021|Fractionation and characterization of lignin from sugarcane bagasse using a sulfuric acid catalyzed solvothermal process
    Gopalakrishnan et al.2011|Studies on Bio-Based Polyurethanes-Thermal and Mechanical Properties
    Kormin et al.2017|Thermal properties of biopolyol from oil palm fruit fibre | using solvolysis liquefaction technique
    Zhou2013|Understanding lignin pyrolysis reactions on the formation of mono-phenols and pyrolytic lignin from lignocellulosic materials
    同族专利:
    公开号 | 公开日
    WO2017129661A1|2017-08-03|
    FR3047243B1|2019-11-01|
    EP3408179B1|2020-09-16|
    EP3408179A1|2018-12-05|
    US10829581B2|2020-11-10|
    US20190040178A1|2019-02-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2011131691A1|2010-04-22|2011-10-27|Astrium Sas|Thermal protection material|
    US6472190B1|2000-03-16|2002-10-29|Board Of Trustees Operating Michigan State Univerisity|Biocatalytic synthesis of galloid organics|
    KR101340580B1|2004-10-12|2013-12-11|보드 오브 트러스티즈 오브 미시건 스테이트 유니버시티|Biosynthesis of phloroglucinol and preparation of 1,3-dihydroxybenzene therefrom|
    US20120286435A1|2011-03-04|2012-11-15|Ppg Industries Ohio, Inc.|Process for preparing molded optical articles|FR3099157A1|2019-07-23|2021-01-29|Arianegroup Sas|PROCESS FOR MANUFACTURING CHROMENES BY GOLD CATALYSIS INTENDED FOR THE PREPARATION OF THERMOSETTING RESINS|
    FR3099158B1|2019-07-23|2021-07-30|Arianegroup Sas|PROCESS FOR MANUFACTURING CHROMENES BY CATALYSIS WITH COPPER SALTS INTENDED FOR THE PREPARATION OF THERMOSETTING RESINS|
    FR3099159B1|2019-07-23|2021-07-30|Arianegroup Sas|PROCESS FOR MANUFACTURING CHROMENES BY THERMOLYSIS INTENDED FOR THE PREPARATION OF THERMOSETTING RESINS|
    FR3112782A1|2020-07-24|2022-01-28|Arianegroup Sas|PROCESS FOR THE POLYMERIZATION OF CHROMINES BY CATIONIC WAY|
    法律状态:
    2017-01-31| PLFP| Fee payment|Year of fee payment: 2 |
    2017-08-04| PLSC| Publication of the preliminary search report|Effective date: 20170804 |
    2018-01-31| PLFP| Fee payment|Year of fee payment: 3 |
    2018-06-01| CD| Change of name or company name|Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, FR Effective date: 20180424 Owner name: UNIVERSITE DE REIMS CHAMPAGNE-ARDENNE, FR Effective date: 20180424 Owner name: ARIANEGROUP SAS, FR Effective date: 20180424 |
    2018-06-01| CA| Change of address|Effective date: 20180424 |
    2018-06-08| TQ| Partial transmission of property|Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, FR Effective date: 20180425 Owner name: ARIANEGROUP SAS, FR Effective date: 20180425 Owner name: UNIVERSITE DE REIMS CHAMPAGNE-ARDENNE, FR Effective date: 20180425 |
    2019-01-30| PLFP| Fee payment|Year of fee payment: 4 |
    2020-01-21| PLFP| Fee payment|Year of fee payment: 5 |
    2021-01-21| PLFP| Fee payment|Year of fee payment: 6 |
    2022-01-19| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1650755A|FR3047243B1|2016-01-29|2016-01-29|CURABLE RESIN RESIN WITH PHENOLIC RESINS AND APPLICATIONS THEREOF|
    FR1650755|2016-01-29|FR1650755A| FR3047243B1|2016-01-29|2016-01-29|CURABLE RESIN RESIN WITH PHENOLIC RESINS AND APPLICATIONS THEREOF|
    US16/073,719| US10829581B2|2016-01-29|2017-01-26|Curable resin as a substitute for phenolic resins and the applications thereof|
    EP17701859.5A| EP3408179B1|2016-01-29|2017-01-26|Curable resin as a substitute for phenolic resins and the applications thereof|
    PCT/EP2017/051619| WO2017129661A1|2016-01-29|2017-01-26|Curable resin as a substitute for phenolic resins and the applications thereof|
    [返回顶部]