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    • 专利摘要:
    The present invention relates to a composition comprising, in addition to a thermosetting resin of epoxy type and / or an anhydride type hardener, at least one catalyst comprising an organometallic complex of titanium. This composition allows the manufacture of vitrimeric resins, that is to say deformable resins in the thermoset state. It also relates to a kit for the manufacture of this composition, an object obtained from this composition and a kit for the manufacture of this object.
    公开号:FR3020367A1
    申请号:FR1453677
    申请日:2014-04-24
    公开日:2015-10-30
    发明作者:Christophe Duquenne；Sebastien-Jun Mougnier；Francois-Genes Tournilhac；Ludwik Leibler
    申请人:Centre National de la Recherche Scientifique CNRS；Arkema France SA；Fonds ESPCI Georges Charpak ；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to an epoxy-type, epoxy-containing and / or an anhydride-type hardener comprising at least one epoxy type a catalyst comprising an organometallic titanium complex. This composition allows the manufacture of vitrimer resins, that is to say deformable resins in the thetmodurci state.
    [0002] TECHNICAL BACKGROUND Thermoset resins have been found to have high mechanical, thermal and chemical resistance and for this reason may replace metals in some applications. They have the advantage of being lighter than metals. They can also be used as matrices in composite materials, as adhesives, and as coatings. Among the polymeric polymers that may be mentioned are unsaturated polyesters, plienoplastcs, polyepoxides, polyurethanes and aminoplasts. The conventional thermosetting resins must be used, in particular they must be molded so as to obtain from the outset the form suitable for the end use. Indeed, no transformation is no longer possible once the resin is polymerized, except machining that often remains delicate. Flexible or hard parts and composites based on thermosetting resins are not friable or workable, they can not be recycled or welded. In addition to thermosetting resins, a class of polymer materials, thermoplastics, has been developed. Thermoplastics can be shaped at high temperature by molding or injection but have less desirable mechanical and thermal and chemical properties than thermoset resins. In addition, the shaping of the thermoplastics can be carried out only in very narrow temperature ranges. Indeed, when heated, thermoplastics become liquids whose fluidity varies abruptly in the vicinity of the melting and glass transition temperatures, which does not apply them a whole variety of transformation methods that exist for glass and for metals for example. In this context, vitrimers have been designed to combine the advantages of thermosets and thermoplastics. These materials exhibit both the mechanical and solvent-resistant properties of thermoset resins and the ability to be reshaped and / or repaired thermoplastic materials. These polymeric materials which are capable of passing indefinitely from a solid state to a viscoelastic liquid, which is used to turn the glass, have been termed "vitrimers". Unlike thermoplastics, the viscosity of vitrimers varies slowly with temperature, which makes it possible to use them for the production of objects having particular shapes incompatible with a molding process, without using a mold or to precisely control the heat setting temperature. .
    [0003] The particular properties of vitrimers are related to the ability of their network to reorganize beyond a certain temperature, without altering the number of intramolecular bonds or depolymerizing, under the effect of internal exchange reactions. These reactions entail a relaxation of the stresses within the material which becomes malleable, while maintaining its integrity and remaining insoluble in any solvent. These reactions are made possible by the presence of a catalyst. In the case of epoxy-anhydride type vitrimers, it has been suggested to use as a catalyst a metal salt of zinc, tin, magnesium, cobalt, calcium, titanium or zirconium, preferably acetylacetonate. zinc (WO2010101078). Likewise, various catalysts have been suggested for use in thermorund / supramolecular hybrid systems obtained from a thermosetting resin, an anhydride type or preferably an acid type hardener and a compound comprising an associative group and a function allowing its grafting on the thermosetting resin (WO 2012/152859). These catalysts may be based on different metals, including titanium, and may be in the form of various salts, especially alkoxides (or alcoholates) such as titanium isopropoxide, although zinc acetylacetonate is, again , prefer. However, the inventors have demonstrated that the stresses developed within the yeasts obtained from zinc acetylacetanoate were relaxed less completely and less rapidly than in materials prepared from catalysts under the control of the complex. organometallic titanium. The latter therefore have better deformation properties, which are more compatible with an industrial thermoforming process, which requires very rapid deformation and stress relaxation. In addition, unlike materials obtained from other titanium catalysts, this ability to deform is not obtained at the expense of the crosslinking density, and therefore the mechanical properties of the material.
    [0004] In addition, another disadvantage of zinc acetylacetonate is the fact that at the temperatures (250 to 350 ° C) required for the transformation, this catalyst is not sufficiently stable, which causes gaseous releases during handling. hot material, resulting in a loss of mass measured in particular by therniogravimetric analysis (ATG).
    [0005] SUMMARY OF THE INVENTION Definitions By "thermosetting" resin is meant a monomer, oligomer, prepolymer, polymer or any macromolecule capable of being chemically crosslinked. More preferred is a monomer, oligomer, prepolymer, polymer or any macromolecule capable of being chemically crosslinked when it is reacted with a hardener (also called a crosslinking agent) in the presence of a source of energy, for example heat or radiation, and possibly a catalyst. By "thermoset" resin or "thennodurci" is meant a thermosetting resin chemically crosslinked so that its gel point is reached or exceeded. By gel point means the degree of crosslinking from which the resin is almost no longer soluble in the solvents. Any method conventionally used by those skilled in the art may be implemented to verify it. For example, the test described in patent application WO 97/23516, page 20, may be copper-plated. A resin is considered to be thermochemical for the purposes of the invention, provided that its gel level, that is to say the percentage of its residual mass after solventization relative to its mass HIillL before solvent setting, is equal to or greater than 75%. The term "hardener" refers to a crosslinking agent capable of reticle thermosetting resin. This is a generally polyfunctional compound carrying reactive anhydride functions capable of reacting with reactive functions carried by the resin. By organometallic titanium complex is meant titanium alkoxides, titanium dieemics such as titanium acelyl acetonate, and titanium carboxylates derived from carboxylic acids of formula R'COOH with R 'denoting a linear or branched alkyl chain saturated or unsaturated having from 1 to 24 carbon atoms. "Titanium alkoxide" means titanium compounds comprising a titanium atom connected to four -OR groups in which: - each of the R groups independently denotes a linear or branched hydrocarbon chain containing 1 to 20 carbon atoms, saturated or unsaturated, optionally interrupted by one or more heteroatoms chosen from N, O, S and P, optionally interrupted or terminated by one or more saturated, partially unsaturated or totally unsaturated hydrocarbon-based rings, or each pair of adjacent R groups forming a saturated ring or unsaturated having from 5 to 7 members, optionally substituted with a hydrocarbon chain as defined above.
    [0006] When reference is made to intervals, eions of the type "from ... to" include the bounds of the interval. Expressions of the type "between ... and ..." exclude the bounds of the interval. The invention firstly relates to a composition comprising at least: a catalyst comprising, and prefél e: u: e consisting of an organometallic titanium complex, a thermosetting resin comprising at least one and advantageously several epoxide functions and optionally to at least one and advantageously several free hydroxyl and / or ester functions, and / or a thermosetting resin hardener selected from carboxylic acid anhydrides. The above catalyst may be designated in the following description by "catalyst vitrenerous effect". The vitrimer effect catalyst facilitates the internal exchange reactions within a thermoset resin so as to render it deformable. It is understood that the above catalyst is present in the composition of the invention in addition to the catalysts which may already be intrinsically present in the thermosetting resin and / or the hardener, because of their preparation. It can be carried out in the presence of low-grade catalysts. It is understood that the composition does not comprise a compound comprising an associative group and a function allowing its grafting on the thermosetting resin. The invention also relates to a kit for the manufacture of such a composition, comprising at least: a first composition comprising the catalyst, alone or with the hardener or the thermosetting resin; Optionally a second composition comprising the; optionally a third composition comprising the thermosetting resin. It also relates to the use of the aforementioned composition for the manufacture of a hot deformable thermoset resin object, and an object comprising a thermoset resin obtained from the composition according to the invention. The invention further relates to a method of deforming an object hereinbefore, such as a method of assembling, welding, repairing or recycling, including applying to this object a constraint mechanical at a temperature (T) higher than the glass transition temperature Tg of theiniodurcie resin. Its object is the use of one or more objects as described above in the fields of the automobile, aeronautics, boating, aerospace, sports, building, electrical, electrical insulation, electronics, wind power, packaging! printing. DETAILED DESCRlPTION As indicated previously. the composition according to the invention contains a catalyst comprising an organometallic complex of titanium, preferably a titanium alkoxide. Examples of titanium alkoxides are titanium propoxide, titanium isopropoxide, titanium butoxide and the compounds resulting from the reaction of these alkoxides with glycols, such as the compounds obtained according to the following reaction: R = H, methyl n ranging from 0 to 100, in particular titanium bis (3-phenoxy-1,2-propandioxide), referred to herein as "Ti (PPD) 2", obtained with n = 0, according to the following reaction : 3eq OH 0) 80 ° C 4 Gold without this list being exhaustive. It is preferred to use titanium isopropoxide Ti (iPr) 4 and Ti (PPD) 2 titanium Phenoxypropanediol, as illustrated in the previous reaction. The organometallic titanium complex catalyst may also be a titanium carboxylate derived from at least one carboxylic acid of formula R'COOH with R 'denoting a linear or branched, saturated or unsaturated alkyl chain containing from 1 to 24 carbon atoms. carbon.
    [0007] Examples of carboxylic acids that may be mentioned are fatty acids derived from the hydrolysis of vegetable oils, 2-ethylhexanoic acid, benzoic acid and its substituted derivatives, salicylic acid, ricinoleic acid, 12-hydroxystearic acid, lactic acid, glycolic acid, acrylic acid and methacrylic acid. Phthalic, oxalic or succinic acids may also be suitable.
    [0008] According to one embodiment of the invention, the catalyst represents from 1 to 50 mol%, preferably from 2 to 25 mol%, preferably 5 to 20 mol%, more preferably 10 to 15 mol%, relative to the molar amount of epoxy functions in said thermosetting resin. The composition according to the invention may further comprise at least one type carboxylic acid anhydride hardener (comprising at least one -C (O) -O-C (O) -) function. The number of moles of titanium atoms can range from 1 to 50%, preferably from 2 to 25%, preferably from 5 to 20%, relative to the number of moles of anhydride functions of the hardener. Particularly suitable anhydride hardeners are cyclic anhydrides, such as, for example, phthalic anhydride, dialkyl or methylnadic anhydride, dodecenylsulphonic anhydride (DDSA), glutaric anhydride; partially or fully hydrogenated anhydrides, such as anhydride tetrahydrophthalite, or methyltetrahydrophthalic anhydride, hexahydroplital anhydride or methylhexahydrophthalic anhydride; and their mixtures.
    [0009] Mention may also be made, as anhydride hardeners, of succinic anhydride, maleic anhydride, trimellitic anhydride, the adduct of trimellitic anhydride and of ethylene glycol, chlorendic anhydride, tetrachlorophthalic anhydride and pyromellitic dianhydride. (PMDA), 1,2,3,4-cyclopcioanelacarboxylic acid dianhydride, aliphatic acid polyanhydrides such as polyazelaic polyanhydride, polyanhydridc., Polysébacique and mixtures thereof. In particular, it is possible to use the anhydrides of magnesium, and their mixtures: ## STR2 ## and more preferably MTHPA. The anhydride type hardener can also be referred to as the commercial hardener HY905 sold by Hunstman, which is a liquid mixture of several anhydrides. Advantageously, the amount of hardener is such that the number of moles of epoxide functional groups of the resin may range from 50 to 300%, preferably from 100% to 200%, preferably from 125 to 150%, and may be up to the number of moles of fonctio71 .; anhydride hardener. The composition according to the invention may comprise at least one thermosetting resin comprising at least one and advantageously several epoxide functions and optionally at least one and advantageously more free hydroxyl functions and / or ester functions. Such a resin will be referred to as an "epoxy resin". Advantageously, the epoxy resin represents at least 10% by weight, at least 20% by weight, at least 40% by weight, at least 60% by weight, or even 100% by weight, of the total weight of thermosetting resin. There are two main classes of epoxy resins: glycidyl epoxy resins, and non-glycidyl epoxy resins. The glycidyl epoxy resins are themselves classified as glycidyl ether, glyc: dyl ester and glycidyl amine. The non-glycidyl epoxy resins are of the aliphatic or cycloaliphatic type. The glycidyl epoxy resins are prepared by a condensation reaction of a di, diacid or diamine with epichlorohydrin. Non-glycidyl epoxy resins are formed by peroxidation of the olefinic double bonds of a polymer. Of the epoxy glycidyl ethers, the bisphenol A diglycidyl ether (DGEBA) shown below is the most commonly used. The DGEBA-based resins have excellent electrical properties, low shrinkage, good adhesion to many metals and good resistance to humidity, mechanical shock and good heat resistance. The properties of the DGEBA resins depend on the value of the degree of polymerization n, which itself depends on the stoichiometry of the synthesis reaction. Generally, n ranges from 0 to 25. The Novolac epoxy resins (whose formula is shown below) are glycidyl ethers of novolak phenolic resins. They are obtained by reacting phenol with formaldehyde in the presence of an acid catalyst to produce a phenolic phenol resin, followed by reaction with epichlorohydrin in the presence of sodium hydroxide as a catalyst.
    [0010] CH3 O C-L- H2 Novolac epoxy resins generally contain several epoxide groups. The multiple epoxide groups make it possible to produce thermoset resins with a high density of crosslinking. Novolac epoxy resins are widely used to make materials for microelectronics because of their superior resistance to high temperature, excellent moldability, and superior mechanical, electrical, heat and heat resistance properties. 'humidity. The thermosetting resin that may be used in the present invention may for example be chosen from: Novolac epoxy resins, bisphenol A diglycidyl ether (DGEBA), hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetraglycidyl methylene dianiline, pentaerythritol tetraglycidyl ether, triethylol triglycidyl ether (TMPTGE), tetrabromo bisphenol A diglycidyl ether, or hydroquinyl diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethylol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether , neopentylglycol diglycidyl ether, bispbenol A polyethyl ethylene glycol diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, diglycidyl ester of terephthalic acid, poly (glycidyl acrylate), poly (glycidyl methacrylate), epoxidized polyunsaturated fatty acids, epoxidized vegetable oils, especially epoxidized soybean oil, epoxidized fish oils, and epoxidized limonene; glycidyl esters of versatic acid such as those sold under the name CARDURe E8, El0 or E12 by the company Momentive (CARDURAe El ° CAS 26761-45-5); the epoxidized cycloaliphatic resins sold under the name ARALDITE e CY179, CY184, MY0510 and MY720 by the company BA.SF, the CY179 resins and the CY184 respectively corresponding to the following formulas: triglyeidyl isocyanttrate (TGIC); glycidyl methacrylate, alkoxylated glycidyl (meth) acrylates; C8-C10 alkyl glycidyl ethers, C12-C14 alkyl glycidyl ethers, glycidyl ester of neodecanoic acid, butyl glycidyl ether, cresyl glycidyl ether, phenyl glycidyl ether, p-nonyphenyl glycidyl ether, p-nonylpitynyl glycidyl ether, pt-butyl phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl acid dimer ester, cyclohexane dimethanol diglycidyl ether, castor oil polyglycidyl ether; and the mixtures of the aforementioned resins. Advantageously, it is more particularly chosen from: DGEBA, bisphenol F diglycidyl ether, Novolac resins, TMPTGE, 1,4-butanediol diglycidyl ether, ARALDITE CY184 of formula (II) above, TGIC, epoxidized soybean oil and mixtures thereof. More preferably still, it is DGEBA. According to one embodiment, the composition comprises, or even consists of, the catalyst, the hardener and optionally a thermosetting epoxy resin, as defined above. According to this embodiment, the number of moles of titanium atoms can range from 1 to 50%, preferably from 2 to 25%, preferably from 5 to 20%, relative to the number of moles of anhydride functional groups. When the composition further comprises the resin, the number of moles of epoxide functional groups of the resin may range from 50 to 300%, preferably from 100% to 200%, preferably from 125 to 150%, relative to the number of moles of anhydride functions of the hardener. The composition of the invention may optionally comprise one or more additional compounds, insofar as their presence does not alter the advantageous properties which result from Vinification. Examples of such additional compounds are: polymers, pigments, dyes, fillers, plasticizers, long or short fibers, woven or not, flame retardants, antioxidants, lubricants, wood, glass, metals and their mixtures. Advantageously, the content of thermosetting resin and / or hardener ranges from 10% to 90% by weight, in particular from 20% to 80% by weight, and even from 30% to 70% by weight, relative to the total weight of the composition. 100% being provided by the catalyst and optionally by additional compounds chosen from the abovementioned compounds. Among the polyesters which may be employed in admixture with the composition of the invention, there may be mentioned: elastomers, thermoplastics, thermoplastic elastomers, impact additives. By pigments is meant insoluble colored particles in the composition of the invention. As pigments that can be used according to the invention, mention may be made of oxide of bed, carbon black, carbon nanotubes, metal particles, silica, metal oxides, metal sulphides or any other pigment n 1-al, there may also be mentioned phthaloeyanines, anthraquinones, quinacridones, dioxazines, azo pigments or any other organic pigment, natural pinn ... nk (madder, indigo, purple, cochineal, etc.) and pigment mixtures. The term "dyes" means soluble molecules having the composition of the invention and having the capacity of absorbing a pallet of visible radiation. Among the fillers that may be employed in the composition of the invention, there may be mentioned fillers conventionally used in polymer formulations. Non-limiting mention may be made of silica, clays, carbon black, kaolin, talc, calcium carbonate, whiskers and mixtures thereof. Among the fibers that can be used in the composition of the invention, mention may be made of: glass fibers, carbon fibers, polyester fibers, polyamide fibers, aramid fibers, cellulosic and nanocellulosic fibers or fibers vegetables (flax, hemp, sisal, bamboo ...) and their mixtures. The presence, in the composition of the invention, of pigments, dyes or fibers capable of absorbing radiation, or their mixtures, can ensure the heating of a material or an article made from a such composition, by means of a ray source, such as a laser, The presence, in the composition of the invention, of electrically conductive pigments, fibers or fillers such as carbon black , carbon nanotubes, carbon fibers, metal powders, magnetic particles or mixtures thereof, may be used for heating a material or an article made from such a composition, by Joule effect, by induction or by Such heating may permit the implementation of a process for the manufacture, processing or recycling of a material or an object according to the process which will be described later. to be chosen from one or more Other catalysts and / or hardeners of all kinds known to those skilled in the art as playing these roles insofar as they do not adversely affect the advantageous properties resulting from inversion. They will be referred to as "additional catalyst" and "hardener 30". According to a preferred embodiment of the invention, the composition described here also contains one or more additional catalysts which are specific for the epoxide opening, such as: - optionally blocked tertiary amines, for example: 2,4,6-tris (dimethylaminomethyl) phenol (for example sold under the name Ancamine), o- (dimethylaminomethyl) phenol, benzyldimethylamine (BDMA), 1,4-diazabicyclo (2,2,2) octane (DABCO), methyltribenzyl ammonium chloride. irnidazoles, such as 2-11: L (2-MI), 2-phenylimidazole (2-P1), 2-ethyl-4-methyl-imidazole (EMI), 1-propylimidazole, 1-ethyl-3-chloride; methylimidazolium, 1- (2-hydroxypropyl) imidazole. phosphoniums: tetraalkyl and alkyltriphenylphosphonium halides. polyacid amine salts, aniline-formaldehyde condensates, N, N-alkanolamines, trialkanolamines borates, fluoroborates such as boron trifluoride monoethylamine (BF3-MEA), organosubstituted phosphines, quaternary monoimidazoline salts , mercaptans, polysulfides. and their mixtures. Preferably, the epoxide opening catalyst is chosen from: tertiary amines, imidazoles, and mixtures thereof. (Hetero) aromatic amines such as 2-methylimidazole and tris (dimethylaminomethyl) phenol are more particularly preferred as an epoxide opening catalyst for use in this invention. This additional catalyst for opening epoxide is advantageously used in the composition in a proportion of 0.1% to 5% by mole relative to the number of moles of epoxide functional groups carried by the thermosetting resin.
    [0011] It is also possible to use one or more additional vitrimer-effect catalysts chosen from the catalysts cited in the applications WO2011 / 151584, WO2012 / 101078 and WO 2012/152859, again insofar as their presence does not alter the advantageous properties. arising from the invention. For example, the catalyst having a vitreous effect component may be present in the composition of the invention in amounts of from 0.1 to 10% by weight and preferably from 0.1 to 5% by weight relative to the total weight of the composition. Moreover, the use of an additional hardener makes it possible to obtain, for the materials manufactured in fine, a wide range of mechanical properties at ambient temperature, eg control of the glass transition temperature and / or the modulus of a thecrystoclurc resin). As examples of additional hardeners, mention may be made of epoxy resin hardeners, in particular those chosen from amines, polyamides, polycarboxylic acids, phenolic resins, anhydrides (optionally other than those described above as acid hardeners), isocyanates, polymereaptans, dicyandiamides and mixtures thereof.
    [0012] In particular, an additional amine hardener may be selected from primary or secondary amines having at least one -NH 2 function or two -NH functions and from 2 to 40 carbon atoms. These amines may, for example, be chosen from aliphatic amines such as diethylene oxide, triethylene tetramine, tetraethylene pentatine, dihexylene triamine, cadaverine, putrescine, hexane diamine, spennine and ophorone diamine, as well as aromatic amines. such as phenylene diamine, diamino diphenylmethane, diamino diphenylsulfone, methylenebischlorodiethylaniline, nylon-xylylene diamine (MXDA) and its hydrogenated derivatives such as 1,3-bis (aminomethylcyclohexane) (1, 3-BAC); and their mixtures. An additional amine hardener may be further selected from polyetheramines, for example Huntsman JEFFAMINS, optionally in admixture with other additional hardeners. Preferred additional hardeners include diethylenetriamine, triethylenetetramine, hexanedioline. and their mixtures. According to a preferred embodiment of the invention, the composition described herein also contains at least one polyol, that is to say a compound comprising at least two hydroxyl functional groups, in particular a linear or branched polyhydroxyalkane, such as glycerol, trimethylolpropane or pentaerythritol, preferably glycerol. It has indeed been observed that the addition of this compound to the reaction mixture makes it possible to further improve the vitrimeric properties of the material, that is to say to obtain a material capable of more completely and more rapidly relaxing the stresses. after applying a deformation. Process for preparing the composition The compounds of the composition according to the invention are either commercially available or easily synthesizable by those skilled in the art from commercially available raw materials. The composition of the invention can be obtained by simply bringing into contact the compounds it contains. This contacting is preferably carried out at a temperature ranging from 15 ° C. to 130 ° C., in particular from 50 ° C. to 125 ° C. The contacting can be carried out with or without homogenization means. According to a particular embodiment, the process comprises a first step in which the catalyst is pre-introduced into the resin or hardener, preferably into the hardener. The catalyst can then be in the form of a dispersion if it is a powder or a solution. This dispersion or dissolution can be carried out at room temperature or hot to obtain the desired viscosity characteristics.
    [0013] According to another particular embodiment, the method comprises a first step of forming an activated species, comprising contacting the hardener or the thermosetting resin with the catalyst, so as to complex the titanium atom of the catalyst in hardener or thermosetting resin. Kits The composition according to the invention may be prepared from a kit comprising at least the first composition comprising the catalyst, alone, or with the hardener or the curable resin; optionally a second composition comprising the hardener; optionally a third composition comprising the thermosetting resin. It is also possible to provide a kit for the manufacture of an object according to the invention, comprising at least: a first composition comprising the catalyst, alone, or with the hardener or the thermosetting resin; optionally a second composition comprising the hardener, optionally a third composition comprising the thermosetting resin. The various compositions may be stored together or separately. It is also possible to store together some of the compositions while keeping them separate from other compositions. The different compositions are stored generally at room temperature. Preferably, when the second and third compositions are both present in the kit, they are in a package adapted to prevent a crosslinking reaction between the thermosetting resin and the hardener from occurring without the intervention of an operator. The packaging may consist of a container having two or even three internal compartments for the separate storage of each of the compositions. Alternatively, the kit may consist of a single container, containing a mixture of appropriate amounts of the two or three positions, i. In the latter case, the intervention of the operator is advantageously limited to heating. It may be provided a means for bringing into contact the contents of the different compartments, advantageously so as to initiate the crosslinking in the container. It is also possible to provide a kit consisting of several separate bottles associated in the same package and each comprising the appropriate amounts of each of the compositions for the preparation of the composition of the invention, so as to prevent the user from weighing operations. and / or dosage. Uses The composition described above can be used for the manufacture of a hot deformable thermoset resin object. When the components of the present invention are mixed, it is believed, without wishing to be bound by theory, that the catalyst opens the anhydride ring of the hardener to form a carboxylic acid monoester which subsequently opens the epoxy ring of the resin. thermosetting to form a diester and a free hydroxyl group. The thermosetting resili obtained from the composition according to the invention is heat deformable. By "hot" deblockable means at a temperature (T) greater than the glass transition temperature Tg of the thermoset resin. The thermoset resin obtained from the composition according to the invention advantageously has: a glass transition temperature (Tg) of between 60 and 170 ° C., preferably between 80 and 150 ° C., more preferably between 100 and 140 ° C. . a relaxation time t necessary to obtain a control value equal to 1 / e at a temperature equal to Tg + 100 ° C and / or at 200 ° C, which is less than 5000 seconds, preferably less than 2000 seconds, more preferably less than 1000 seconds or even less than 500 seconds, - a percentage of stresses relaxed after 5000 seconds at a temperature equal to Tg + 100 ° C and / or at 200 ° C, which is at least 80%, preferably at least 90%, more preferably at least 95%, or even 100%, - a preservation module (G ') with a caoutehoutique plateau, for example at a temperature of between 150 and 200 ° C, greater than 5 MPa, preferably greater than or equal to 10 MPa, or even higher or 6r.F: 1 to 15 MPa, these quantities being measured according to the protocols indicated in the examples below.
    [0014] Objects and Methods of Manufacture The invention also relates to an object comprising a thermoset resin obtained from at least one composition according to the invention. By "object" is meant in the sense of the present invention, a piece in three dimensions. This definition includes coatings, films, sheets, ribbons, etc. The objects according to the invention may especially consist of coatings deposited on a support, such as a protective layer, a peini w-c: or an adhesive film. Also included are powders, granules, etc. The object according to the invention can be manufactured according to a manufacturing method comprising: a) preparing or providing a composition according to the invention, b) the shaping of the composition resulting from step a) c) the application of an energy allowing the hardening of the resin, d) the cooling of the thermoset resin, the steps a) b) c) the Process may be successive or simultaneous, The preparation of the composition can be done in a mixer of any type known to those skilled in the art. It can in particular be done by contacting the compositions described in connection with the kit so as to form a composition according to the invention. Shaping can be carried out by any technique known to those skilled in the art in the form of thermosetting resins, especially by molding.
    [0015] Notably, the invention makes it possible to provide also other forming modes such as casting, filament winding, continuous or interlayer molding, infusion, pultrusion, resin transfer molding or RTM. (for "resin transfer niolding"), the reaction-injection-molding (or R.1-114) or any other methods known to those skilled in the art, as described in the books "Epoxy Polymer", published by JP
    [0016] Pascault and R.J.J. Williams, Wiley-VCH, Weinheim 2010 or "Industrial Chemistry", by R. Perrin and JP Scharff, Dunod, Paris, 1999. The shaping can consist of a putting into evidence of powder or grains by any known technique of the skilled person. Mechanical grinding can also be performed at the end of step d).
    [0017] As regards the shaping of the composition in the form of a coating, it is advantageous to use any method known in the art, in particular: the application of the composition by brush or roller; dipping a support to be coated in the composition; the application of the composition in the form of a powder.
    [0018] If one tries to shape a thermoset resin composition of the prior art in the same manner as described above, the material or object obtained is no longer deformable or repairable, nor recyclable once the point of resin gel is reached or exceeded. The application of a moderate temperature to such an object according to the prior art does not lead to any observable or measurable transformation, and the application of a very high temperature leads to the degradation of this object.
    [0019] On the contrary, the objects of the invention, because they are made from a composition according to the invention, can be deformed, welded, repaired and recycled by raising their temperature. By "application of an energetic perincitane the hardening of the resin" is generally meant a rise in height. The application of an energy for the hardening of the resin may for example consist of heating at a temperature ranging from 50 to 250 ° C, for example from 50 to 120 ° C. It is also possible to carry out an activation by radiation, for example by UV radiation or electron beam, or by chemical means, in particular radical, for example by means of peroxides.
    [0020] The cooling of the thermoset resin is usually carried out by allowing the material or the object to return to ambient temperature, with or without the use of a cooling means. An object according to the invention can be composite. It can in particular result from the assembly of at least two objects, at least one of which, and advantageously both, comprises at least one thermoset resin obtained from at least one composition according to the invention. This is, for example: c a layered material, having an alternating superposition of layers of thermosetting resin obtained at. from at least one composition according to the invention, with layers of wood, metal, or glass.
    [0021] An object of the invention may also comprise one or more additional components chosen from those mentioned above and in particular: polymers, pigments, dyes, fillers, plasticizers, long or short fibers, woven or otherwise, retarding agents flame, antioxidants, lubricants, wood, glass, metals. When such an object is manufactured according to one of the manufacturing methods described above, the additional compounds can be introduced before, during or after step a). Deforming Method The hardened numbers obtained as described herein have the advantage of having a slow variation in viscosity over a wide range of temperatures, making the behavior of an object of the invention comparable to that of inorganic glasses. and allows to apply to them deformation processes which are not generally applicable to conventional Iodides. can thus be shaped by applying stresses of the order of 1 to 10 MPa without sinking under its own weight.
    [0022] In the same way, one can deform this object to a temperature higher than the temperature Tg, then in a second time eliminate the internal stresses at a higher temperature. The low viscosity of these objects at these temperatures allows in particular the injection or press molding. It should be noted that no depolymerization is observed at high temperatures and the objects of the invention retain their crosslinked structure. This property allows the repair of an object of the invention which would be fractured in at least two parts by simply welding these parts together. No mold is required to maintain the shape of the objects of the invention during the repair process at elevated temperatures. In the same way, one can transform an object of the invention by applying a mechanical stress to only part of the object without using a mold because the objects of the invention do not flow. Once, objects of large size, which are more likely to sag, may be held by a frame for working glass.
    [0023] Thus, the object as described above can be deformed according to a method comprising the application to the object of a mechanical stress at a temperature (T) greater than the temperature Tg. The assembly, welding, repair and recycling is a special case of this deformation process. Preferably, to allow the deformation in a time compatible with an industrial application, the deformation process comprises the application to the object of the invention of a mechanical stress at a temperature (T) greater than the glass transition temperature Tg of the thermoset resin that it contains. Usually, such a deformation process is followed by a step of cooling to room temperature, optionally with application of at least one mechanical stress. By "mechanical stress". for the purposes of the present invention, the application of a mechanical force, locally or on all or part of the object, said mechanical force tending to a shaping or deformation of the object. Among the mechanical stresses that may be used, there may be mentioned: pressure, molding, kneading, extrusion, blowing, injection. stamping, twisting, bending, pulling and cisaifleTnent. It may be, for example, a twist applied to the subject of the invention in the form of a ribbon. This may be a pressure applied by means of a plate or a mold on one or more faces of an object of the invention, the stamping of a pattern in a plate or a leaf. It may also be a pressure exerted in parallel on two objects of the invention in contact with each other so as to cause a welding of these objects. In the case where the object of the invention consists of granules, the mechanical stress may consist of mixing, for example in a mixer or around the screw of an extruder. It can also consist of an injection or an extrusion. The mechanical stress may also consist of blowing, which may for example be applied to an object sheet of the invention. The mechanical stress may also consist of a multiplicity of discrete contractions, of the same nature or not, applied simultaneously or successively to any part of the object of the invention, or in a localized manner. This deformation process may include a step of mixing or agglomeration of the subject of the invention with one or more additional components chosen from those mentioned above and in particular: polymers, pigments, dyes, fillers, plasticizers, long or short fibers, woven or not, flame retardants, antioxidants, lubricants. The rise in the temperature in the deformation process can be achieved by any means known as heating by conduction, convection, induction, point, infrared, microwave or radiant. The means for raising the temperature for the implementation of the processes of the invention include: an oven, a microwave oven, a heating resistor, a flamer, an exothermic chemical reaction, a laser beam, a iron, a hot air gun, an ultrasonic tank, a punch chatiffinit ... The temperature rise can be made by palliate or not and its duration is adapted to the expected result. Although the resin does not flow during deformation, thanks to the exchange reactions, by choosing a suitable temperature, heating time and cooling conditions, the new form can be free from any residual stress. The object is thus not weakened or fractured by the application of mechanical stress. And if the deformed object is subsequently reheated, it will not return to its original shape. In fact, the exchange reactions that occur at high temperatures favor a reorganization of the crosslinking points of the network of the thernioduric resin so as to cancel the mechanical stresses. A sufficient heating time makes it possible to cancel completely these mechanical stresses internal to the object which were caused by the application of the external mechanical stress. This method therefore makes it possible to obtain complex shapes which are stable, difficult or even impossible to obtain by molding. In particular, it is very difficult to obtain shapes resulting from torsion by molding, and in a complementary manner the choice of temperature conditions, of the duration of heating under stress and of Suitable cooling enables an object of the invention to be transformed by controlling the persistence of certain internal mechanical stresses within this object, and then, if the object thus transformed is subsequently reheated, a new controlled deformation of this object by controlled release. The object obtained according to the invention can also be recycled: either by direct treatment of the object: for example an object of the invention broken or damaged is repaired by a deformation process as described above and can thus recover its function of previous use or another function - or the object is reduced to particles by app mechanical crushing, and the particles thus obtained are cristiiie implemented in a method of manufacturing an object according to the invention. In particular, according to this method, the particles are subjected simultaneously to a rise in temperature and to a mechanical stress allowing their transformation into an object according to the invention. The mechanical opposite allowing the transformation of the particles into an object may for example comprise a compression in a mold, a kneading, and / or an extrusion. This method makes it possible, by applying a sufficient temperature and an appropriate mechanical stress, to mold new objects to. from the objects of Another advantage of the in. It is possible to manufacture thermoset resin articles from solid raw materials. These solid raw materials are thus objects according to the invention in the form of parts, an elementary unit or a set of elementary units. "Elementary units" means parts which have a shape and / or an aspect adapted to their subsequent transformation into an object, for example: particles, granules, balls, rods, plates, sheets, films, ribbons, rods, tubes etc. By "set of elementary units" is meant at least 2 elementary units, for example at least 3, at least 5, at least 10, or even at least 100 elementary units. Any method known to those skilled in the art can be used for this purpose. These elementary parts are then transformable, under the joint action of heat and a mechanical 701. -int, into objects of the desired form: by, .cxeropt. ,, ruhe -) by stamping be cut into smaller pieces of enoisie form, sheets can be superimposed and assembled by compression. These elementary parts based on thermoset resin are more easily storable, transportable and manipulable than the liquid formulations from which they are derived. Indeed, the stage of transformation of the elementary parts according to the invention can be carried out by the end user without chemistry equipment (non-toxicity, no expiry date, no VOC, no weighing of reactions).
    [0024] A particular case of the deformation process already described thus comprises: the use as raw material of an object of the invention in the form of an elementary unit or of a set of elementary units, b) the simultaneous application of a mechanical stress and a rise in temperature to shape the object to form a new object, the cooling of the object resulting from step b). Another advantage of this method is to allow the recycling of the new manufactured object, it can be repackaged in the form of units or elementary parts which can in turn be shaped in accordance with the invention. The method of recycling an object of the invention may comprise: a) the use of an object of the invention as a raw material, b) the application of a mechanical stress and possibly an elevation of simultaneous temperature to transform this object into a set of elementary units, c) the cooling of this set of elemental units. Applicant 1, e ,; fields of application of the present invention are mainly those of thermosetting resins, in particular those of epoxy resins, no: an-ruent automobile (which includes any type of motorized vehicle including trucks), aeronautics , 20 nautical, aerospace, sports, building, electrical, electrical insulation, electronics, wind, packaging and printing. For example, the composition, materials and objects of the invention may be incorporated by reference. especially with typical additives such as fillers, antioxidants, flame retardants, UV protectors, pigments, dyes. The formulations can for example be used for coating paper, inks, paints. The materials or objects of the invention can be used in the form of powders, granules, or else be incorporated in composite materials, in particular those comprising glass, carbon, aramid, or plant-based fibers ( flax fiber, hemp, ...). These fibers may be long fibers or short fibers, woven or not. The compositions of the invention can also be applied as coatings, for example as a metal protection varnish, pipe protection, soil protection. The compositions of the invention may furthermore be used to manufacture adhesives, advantageously thermoreversible or photocrosslinkable, to be used to connect connectors (the composition of the invention may be applied by potting or injection), to produce electrical insulator parts. or eTlcore to make prototypes.
    [0025] FIGURES FIG. 1 represents the superposition of 1H NMR spectra (CDCl3, 400MHz) of various catalysts with a liquid effect. Figure 2 shows superposition of the ATG curves of the catalyst Zn (aca and catalyst Ti (PPD) 2), Figure 3 illustrates the superposition of stress relaxations (at 260 ° C) of the vitrimers catalyzed by 5 mol% of Ti (iPr). 4, and 5 mol% Ti (PPD) 2 and 5 mol% Zn (acac) 2 The static force is plotted versus time Figure 4 illustrates the variation of the relaxation time for a DGEBA / Glutaric anhydride catalyzed by 5 mol% of Ti (PPD) 2 as a function of the inverse of the temperature Figure 5 illustrates the DMA curves of a DGEBA / Glutaric anhydride system with 5 mol% of Ti (PPD) 2. EXAMPLES The following examples illustrate the invention without limiting it: Characterization Methods Nuclear Magnetic Resonance Analysis: All Nuclear Magnetic Resonance (NMR) analyzes were performed on a resonance frequency apparatus at 400MHz, with cs. .Joroform as deuterated solvent and at concentrations of 8mg / r nL. Thermal Analysis: The Tg of the samples of Examples 2 to 4 was characterized by scanning calorimetric scanning (DSC) analysis. The following procedure was applied: first heating at 10 ° C / min from -70 ° C to 170 ° C, isothermal 5 min at 170 ° C, cooling at -10 ° C / min to -70 ° C , isothermal at -70 ° C. for 5 min then second heating up to 170 ° C. at 10 ° C./min. Inechanical analysis: the conservation modules (G ') of the samples of Examples 2 to 4 were measured by mechanical analysis The following protocol has been applied: Oscillation amplitude of 2511m, 1 Hz 1 Hz, starting temperature at -25 ° C, -1-npe. final ailage at 200 ° C., heating at 3 ° C./min The tests were carried out on 30 nm × 13 mm × 5 mm and the samples of examples 5 to 8 were also subjected to a DMA analysis, under conditions slightly different) -1): - éuTénient, a bar of dimensions 10x30x3mm was fixed between two clamps and biased in rectangular torsion (imposed deformation of 35 0.0 5%) in a RHE3 device of RHEOMETRIC SCILIN HIHIC, with a frequency of 1 Hz, performing a temperature sweep of 25 to 250 ° C with a temperature ramp of 3 ° C / min The value of Ta was determined at peak of the tan8 curve, and is considered hereinafter as the Tg of the sample, while the conservation modulus G 'was determined on the rubber plateau at 200 ° C. Example 1 Preparation of a Catalyst According to the Invention This example illustrates the synthesis of a catalyst used according to the invention. The reaction scheme is shown below: Phenoxypropanediol (10 g, 0.06 mol) was placed in a 100 ml volume monocolumn flask, and the flask was heated to room temperature. the reagent is liquid (80 ° C) and allowed to stir 15 ml. Still at 80 ° C, titanium isopropoxide (5.63 g, 0.02 mol) was added dropwise, very slowly. It was allowed to stir for 4h under an inert atmosphere and then the medium was gradually placed under dynamic vacuum at 80 ° C where it was left for 15h to remove the isopropanol. The ligand exchange reaction was almost instantaneous. During the addition of the titanium isopropoxide, the product precipitated and the reaction medium became white. In order to remove excess ligand, the product was placed at the end of the reaction (in solid form) in an Erlenmeyer flask with 100 nit of chloroform and allowed to stir overnight (phenoxypropanediol is very soluble in chloroform) . The product was recovered by filtration and then dried under dynamic vacuum at 50 ° C. for 15 h. The final product was characterized by proton NMR (see Figure 1). Thereafter, it will be named Ti (PPD) 2. EXAMPLE 2 SySTeS of an epoxy-anhydride network in the presence of 5% Ti (PPD) In a Teflon beaker were added 19 g of epoxy resin of the type DGEBA (DER332) in liquid form (DOW, Equivalent Epoxy Mass) 174 g / eq) and 2.1 g of Ti (PPD) 2 prepared in Example 1 (MW = 383.87 g / mol), which corresponded to 0.05 gram atom of titanium per epoxy function. The reagents were mixed while heating with a hot air gun (r --- 60 ° C) for 2min. The mixture became white, not translucent. 6.23 g of glutaric anhydride (CAS 108-55-4, MW = 111.1 g / mol) were then added in solid form, heating cry with the aid of a hot-air gun. 150 ° C.) until complete solubilization. The mixture was no longer white and became translucent. At that time, it was cast in a mold of dimensions 100x100x1.4mm (prh11.1.JTé at 140 ° C) between two sheets of non-stick silicone paper, then cooked in a press at 140 ° C for 8h . An infrared spectrum measurement made on the material at the end of the reaction showed the complete disappearance of the signals of the anhydride (1810cm-) and the epoxy (915cm-1). On the sample after polymerization, the characteristic band of the ester functions at 1735cm-1 and a broad absorption mass at 3200-3600cm-1, characteristic of the hydroxyl groups, were recorded. The material exhibited in DMA a Tg of the order of 70 ° C., a storage modulus of 2.2 GPa at 25 ° C. and 25 MPa at 150 ° C. Its DMA curve is shown in FIG. 5. As can be seen from this Figure, the material has a storage modulus at 25 ° C and 150 ° C of 2.2 GPa and 25 MPa, respectively. The Ta value is 74 ° C and the fineness of the tan delta peak shows that the material is homogeneous. In addition, Figure 4 shows the variation of the relaxation time of this material as a function of the inverse of the temperature. As can be seen from this Figure, the relaxation time follows an Arrhenius law of the type: ## EQU1 ## To which the normalization constant is a time (s), Ea is an activation Perm (J. R the universal constant of perfect gases (Lmol-1), and T the temperature (K). The activation energy, determined from the slope (Ea / R), is about 80 klinohl.K-1. Comparative Example 3: Synthesis of an EpahydriCe Network in the Presence of 5% Zinc Acetylacetonate A comparative sample was prepared using the same protocol as in Example 2, but using zinc acetylacetonate as catalyst at the same concentration, in other words at 0.05 gram atom of titanium per epoxy function. The material exhibited in DMA a Tg of the order of 70 ° C, a storage modulus of 2 GPa at 25 ° C and 19 MPa at 150 ° C. ExemplA: Synthesis of an epoxy-hydroxide network in the presence of 5% of titanium isopropoxide A sample was prepared using the same protocol as in Example 2, but using titanium isopropoxide (CAS 546-68 -9, MW 284.22g / mol) as a catalyst at the same concentration, that is to say 0.05 atonogram of titanium per epoxy function. The material exhibited in DMA a Tg of the order of 67 ° C, a storage modulus of 2.4 GPa at 25 ° C and 8.5 MPa at 150 ° C. EXAMPLE 5 Synthesis of an epoxy-hydride network in the presence of 10% of titanium isopropoxide Three samples of Ht Cirau vitrimer were prepared respectively 5a, 5b and 5e) according to the following method. e DGEBA (DER332) in faith: 174 g / eq), med. anhydride) 1 In a beaker was added a liquid epoxy resin (DOW, Equivalent Epoxy Weight: tetrahydrophthalic (MTHP.A)) ( MW = 166.18 g / mol) and titanium isopropoxide (supplied by DORF KETAL), at 0.1 gram atom of titanium per epoxy function The reactants were mixed and then homogenized in a bath of The oil was thermostated at 100 ° C. for about 10 minutes, then poured into a slightly siliconized hollow metal mold 70 × 140 × 3 mm, the mold was secured by a silicone seal to a metal plate covered with a Teflon coating, and then the whole was introduced into a heating press previously set at a temperature of 140 ° C. and placed at the beginning of cooking at a pressure of 10 bars, and the cooking was carried out for 17 hours. a molar ratio of epoxide functions the anhydride functional resin of the hardener respectively equal to 1 / 0.8; 1/1 and 1 / 1.2. Tg was measured by DMA and the conservation modulus of the materials thus obtained. These materials had a Tg of 118 ° C, 116 ° C and 102 ° C, respectively, and a storage modulus at 200 ° C of 17 MPa, 12.6 MPa and 11.6 MPa. Comparative Example 6: Snthe of an epoxy-anhydrous network in the presence of 10% zinc acetylacetonate Three material samples (6a, 6b and 6e, respectively) were prepared in the same manner as in Example 5, except that The catalyst was replaced by zinc acetylacetonate or Zn (acac) 2.
    [0026] These materials exhibited a Tg of 138 ° C., 130 ° C. and 112 ° C., respectively, and a storage modulus at 200 ° C. of 16 MPa, 13.5 MPa and 10.2 MPa. Example 7 Synthesis of an Epoxy-Anhydride Network in the Presence of 10% Titanium Zetoethylacetonate A sample of material was prepared in the same manner as in Example 5, using a molar ratio of the epoxide functions of the resin to the functions anhydride of the hardener equal to 1 / 0.8, except that the catalyst was replaced by titanium acetylacetonate or Ti (acae) 2.
    [0027] This matte had a Tg of 112 ° C and a storage modulus at 200 ° C of 8.0 MPa. EXAMPLE 5 Synthesis of an Epoxy-Anhydride Network in the Presence of Titanium Isopropoxide and an Additional Amine-type Analyzer Two samples of vitrimer material were prepared according to a method similar to that described in Example 5 , whose operating conditions have been modified as described in Table 1 below. Additional samples were prepared by adding a variable amount of additional amine catalyst, namely either 2-methyl imidazole (hereinafter "2-MIA") or 2,4,6-tri (dimethylaminomethyl) phenol ( hereinafter, "Anc" for Ancar, K54 AIR PRODUCTS), to the system before curing. Table 1 Sample 8a 8b 8e 8d 8e 8f foxide DER332 DLR32 DER332 DER332 DER332 I) [R332 MTHPA MTHPA MTHPA MTHPA `, / iTHPA Additive 2-MLA 2-MIA Anc A Catalyst Ti (iPr) 4 Ti (iPr) 4 Ti ( iPr) 4 Ti (iPr) 4 Ti (iPr) 4 Ti (iPr) 4% mol 0.5% 2.5% 1% 2% amine / epoxy% mol 5% 5% 5% 10% 10% catalyst / epoxy Tg (° C) 136 122 120 118 108 114 G '(MPa) 17 12 12 17 13 17 Example 9: Study of the relaxation and deformation properties of various glass materials a) The samples of Examples 2, 3 and 4 were was subjected to a stress relaxation experiment: the stress relaxation times were measured using a DMA (or DMTA for Dynamie Mechanical Thermal Analysis) in 3-point bending geometry. The following protocol was applied: heating up to test temperature, isothermal 20min then application of a deformation of%. The tests were carried out on samples of dimensions 30.mmx13mmx1,4mm.
    [0028] The results are collated in the appended FIG. 3. As shown in this FIGURE, the samples obtained from the catalysts according to the invention have similar performances and clearly superior to those of the material obtained from zinc acetylacetonate, in the as their constraints are relaxed more completely and faster. b) In parallel, each of the samples prepared according to Examples 5 to 8 was subjected to an experiment consisting in imposing on a 40x20x2mm test piece a deformation under nitrogen flow, in 3-point bending, with the aid of a Metravib device type 20 DMA5ON, after the sample has been brought to a temperature equal to Tu + 100 ° C and stabilized for 5 min at this temperature. The evolution of the stresses induced in the material to maintain the constant deformation is monitored for 5000 seconds and measured using a sensor. The sample is then imposed a force equal to zero and the deformation (recovery) of the eci-Lantillon is measured for an additional 5000 seconds. When the material retains the deformation that has been imposed on it, it is considered that all the stresses have been relaxed. The normalized stress (cilao) is then plotted as a function of time, and the relaxation time T required to obtain a normalized stress value equal to 1 / e, as well as the percentage of stresses relaxed at 5000 seconds, are recorded for each test. Hereinafter Ci5opos The results obtained are collated in Table 2 below.
    [0029] Table 2 As is apparent from this table, the catalysts according to the invention (samples 5a to 5c and 7) make it possible to obtain materials capable of relaxing their stresses more completely and more rapidly than the materials obtained from the same amount of zinc acetylacetonate catalyst (samples 6a to 6c). Moreover, these performances are not obtained at the expense of the mechanical properties of the material. In addition, these performances of the catalysts according to the invention are further improved in the presence of an additional catalyst of the amine type, such as the comparison of samples 8b and 8c with sample 8a and samples 8e and 8f with sample 8d. Example 10: Study of the thermal stability of different vitrimeric materials a) The samples of Examples 2, 3 and 4 were subjected to a gravimetric analysis (ATG). 10 mg of product (catalyst or resin) were placed in an alumina capsule. Gravimetric measurements were made from 25 ° C to 900 ° C at 10 ° C / min. The samples obtained from the catalysts according to the invention are more stable than those obtained from zinc acetylacetonate, in a temperature range suitable for their industrial processing, that is to say up to a temperature of 200. ° C approx. The Ti catalyst (PPD) 2 is even stable above this temperature and does not substantially degrade to 300 ° C. Ech, Li 6a comp 6b comp 6c comp -c 75 510 370 105 1565 3630 a 5 0 0 0 s 00 100 100 100 84 69 0 (%) Ech. In particular, it was observed that the material of Example 2 had a loss of mass of only 0.07% at 260 ° C, while the material of Comparative Example 3 exhibited a mass loss of 1.68% at the same temperature. b) The attached FIG. 2 shows that the Zn (acac) 2 catalyst is less thermally stable than the Ti (PPD) 2 since it degrades at 200 ° C. whereas the latter suffers only a slight loss of mass up to 300 ° C. c) The thermal stability of the materials of Examples 5a and 6a and of Example 2 was also evaluated by ATG on a Pork in Linier apparatus of the TGA7 type, by carrying out a temperature sweep of 25 ° C. to 500 ° C. C at a ramp of 10 ° C / min The temperature leading to a loss of material of 1% was 176 ° C in the case of the material of Comparative Example 6a and 235 ° C in the case of the material of the Example 5a, which confirms the better heat resistance of the materials according to the invention at the temperatures of fitness and recycling. The temperature leading to a material loss of 1% was 254 ° C. in the case of the material of Example 2 made with Ti (PPD) 2.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONSI. Composition comprising at least: a catalyst comprising, and preferably consisting of, an organometallic titanium complex, a thermosetting resin comprising at least one and advantageously several epoxide functional groups and optionally at least one and advantageously several free hydroxyl and / or ester functions, and or a thermosetting resin hardener selected from carboxylic acid anhydrides. 10
    [0002]
    2. Composition according to claim 1, characterized in that the organometallic complex is chosen from alkane alkoxides, titanium diketones such as cry, titanium acetonate acetonate, and titanium carboxylates derived from carboNylic acids; R'COOH with R 'denotes a linear or branched, saturated or unsaturated ilkyl chain having from 1 to 24 carbon atoms.
    [0003]
    3. Composition according to claim 1 or 2, characterized in that the organometallic complex is a titanium alkoxide selected from titanium compounds having a titanium atom connected to four -OR groups where: - each of the groups R denotes independently a hydrocarbon chain having 1 to 20 carbon atoms, linear or branched, saturated or unsaturated, optionally interrupted by one or more heteroatoms selected from N, O, S and P, optionally interrupted or terminated by one or more saturated hydrocarbon rings, partially unsaturated or fully unsaturated, or each pair of adjacent R groups form saturated or unsaturated ring having from 5 to 7 members, optionally substituted with a hydrocarbon chain as defined above.
    [0004]
    4. A composition according to any one of the preceding claims, characterized in that the organometallic complex is titanium isopropoxide or titanium bis (3-phenoxy-1,2-propandioxide) Ti (PPci) 2,
    [0005]
    5. Composition according to any one of the preceding claims, characterized in that the thermosetting resin is a diglycidyl ether of bisphenol A (DGEBA). 35
    [0006]
    6. Composition according to any one of the preceding claims, characterized in that the amount of hardener is such that the number of moles of epoxide functions of stirring can range from 50 to 300%, preferably from 100% to 200%, preferably from 125 to 150 Va, relative to the number of moles of anhydride functions of the hardener.
    [0007]
    7. Composition according to any one of the preceding claims, characterized in that the content of thermosetting resin and / or hardener ranges from 10% to 90% by weight, in particular from 20% to 80% by weight or even 30 to 70% by weight. By weight, relative to the total weight of the composition, the 100% complement being provided by the catalyst and optionally by additional compounds chosen from: polymers, pigments, dyes, fillers, plasticizers, long or short fibers, woven or not, flame retardants, antioxidants, lubricants, wood, glass, metals and mixtures thereof. 15
    [0008]
    8. Composition according to any one of the preceding claims, further comprising at least one additional catalyst for opening epoxide, preferably selected from tertiary amines such as 2,4,6-tri (dimethylaminomethyl) phenol, and imidazoles such as 2-methyl imidazole. 20
    [0009]
    9. Composition according to any one of the preceding claims, further comprising at least one polyol.
    [0010]
    10. Composition according to claim 9 characterized in that the polyol is glycerol, triethylolpropane or pentaerythritol. 25
    [0011]
    11. Kit for the manufacture of a composition according to any one of the preceding claims, comprising at least: - a first composition comprising the catalyst, alone, or with the hardener or the thermosetting resin; Optionally a second composition comprising the hardener; optionally a third composition comprising the thertitodureissable resin.
    [0012]
    12. Use of the composition according to any one of claims 1 to 10 for the manufacture of a hot deformable thermoset resin object. 35
    [0013]
    13. An object comprising a thermoset resin obtained from a composition as defined in any one of reveridicios) 1 to 10.
    [0014]
    A method of deforming an object, such as a method of assembling, welding, repairing or recycling, comprising applying to an object according to claim 13 a mechanical stress at a temperature (T ) greater than the glass transition temperature Tg of the thermoset resin.
    [0015]
    15. Use of one or more objects according to claim 13 in the 10 automotive, aeronautics, marine, aerospace, sports, building, electrical, electrical insulation, automotive and marine industries. electronics, wind power, packaging, printing.
    类似技术:
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    同族专利:
    公开号 | 公开日
    CN106661196A|2017-05-10|
    WO2015162387A3|2016-08-04|
    FR3020367B1|2017-10-27|
    EP3134457B1|2020-10-07|
    US20170044307A1|2017-02-16|
    WO2015162387A2|2015-10-29|
    US10155842B2|2018-12-18|
    EP3134457A2|2017-03-01|
    CN106661196B|2019-02-22|
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    FR2975101B1|2011-05-10|2013-04-26|Arkema France|THERMODY / SUPRAMOLECULAR HYBRID RESINS AND COMPOSITES WHICH CAN BE HOT-FILLED AND RECYCLED|CN108546336B|2018-04-25|2020-11-10|上海交通大学|Method for preparing reworkable cross-linked elastomer by utilizing transamination|
    GB201810371D0|2018-06-25|2018-08-08|Univ Manchester|Vitrimer containing a biocatalyst|
    TWI702235B|2019-11-14|2020-08-21|國立中興大學|Toughening vitrimer and preparation method thereof|
    AT523758B1|2020-04-17|2022-02-15|Polymer Competence Center Leoben Gmbh|Curable composition for producing a vitrimer and vitrimer obtainable therefrom and method for its production|
    CN111704751A|2020-06-03|2020-09-25|大连理工大学|Preparation method of Vitrimer material based on carboxyl-containing polysaccharide and dynamic ester bond|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1453677A|FR3020367B1|2014-04-24|2014-04-24|TITANIUM CATALYST FOR EPOXY / ANHYRIDE TYPE VITRIMER RESINS|FR1453677A| FR3020367B1|2014-04-24|2014-04-24|TITANIUM CATALYST FOR EPOXY / ANHYRIDE TYPE VITRIMER RESINS|
    PCT/FR2015/051109| WO2015162387A2|2014-04-24|2015-04-23|Titanium-based catalyst for vitrimer resins of expoxy/anhyride type|
    EP15725790.8A| EP3134457B1|2014-04-24|2015-04-23|Titanium-based catalyst for vitrimer resins of expoxy/anhyride type|
    US15/306,000| US10155842B2|2014-04-24|2015-04-23|Titanium-based catalyst for vitrimer resins of epoxy/anhydride type|
    CN201580034071.6A| CN106661196B|2014-04-24|2015-04-23|The catalyst based on titanium of VITRIMER resin for epoxy/acid acid anhydride type|
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