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    • 专利摘要:
    The present invention relates to a composition containing, in addition to an epoxy-type thermosetting resin and / or an anhydride-type hardener, at least one organic vitrimer-effect catalyst. 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:FR3020366A1
    申请号:FR1453676
    申请日:2014-04-24
    公开日:2015-10-30
    发明作者:Christophe Duquenne；Michel Melas；Philippe Gentilhomme；Jean-Pierre Disson
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a composition containing, in addition to a thermosetting resin of the epoxy type and / or an anhydride type hardener, at least one epoxy-type resins and / or an anhydride-type hardener. organic vitrimer effect catalyst. This composition allows the manufacture of vitrimeric resins, that is to say deformable resins in the thermoset state.
    [0002] BACKGROUND ART Thermoset resins have the advantage of having high mechanical, thermal and chemical resistance and for this reason can replace metals in certain 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 thermoset polymers, there may be mentioned unsaturated polyesters, phenoplasts, polyepoxides, polyurethanes, 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, or thermoset, except machining that often remains delicate. Flexible or hard parts and composites based on thermosetting resins are not transformable 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 melting and glass transition temperatures, which does not allow them to apply a variety of processing methods that exist for glass and for metals, for example. However, melted thermoplastic resins generally have viscosities that are generally too high to lend themselves to the impregnation of fabrics in order to obtain composite materials. 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 able to pass indefinitely from a solid state to a viscoelastic liquid, such as glass, have been referred to as "vitrimers". Unlike thermoplastics, the viscosity of the vitrimers varies slowly with temperature, which allows them to be used for the production of objects having particular shapes incompatible with a molding process, without using a mold or precisely controlling the shaping temperature . The particular properties of vitrimers are related to the ability of their network to reorganize beyond a certain temperature, without modifying the number of intramolecular bonds or depolymerizing, under the effect of internal exchange reactions. These reactions cause stress relaxation 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, obtained from an epoxy-type thermosetting resin and an anhydride-type hardener, it has been suggested to use as a catalyst a metal salt of zinc, of tin, magnesium, cobalt, calcium, titanium or zirconium, preferably zinc acetylacetonate (WO 2012/101078). Similarly, various catalysts have been suggested for use in thermoset / 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 organic or inorganic in nature and may especially be triazabicyclodecene (TBD), although zinc acetylacetonate is, again, preferred. It has further been proposed to use TBD as a catalyst in epoxy resin and acid curative systems (M. CAPELOT et al., ACS Macro Lett., 2012, 1, 789-792). In this application, the TBD is used at a level of 5 mol% relative to the number of moles of epoxy functional groups in the thermosetting resin. There was no reason to believe that this catalyst could be used in a system based on epoxy resin and anhydride and non-acid type hardener, since the reactions in these two systems are very different and lead in particular to a network. diester and hydroxy monoesters, respectively. In addition, it was not foreseeable that this catalyst could be used in anhydride type hardener systems in a much smaller amount than in acidic hardener based systems. In addition, the TBD has a boiling point of 125-130 ° C., and it would have been expected that its incorporation into an epoxy-anhydride system would be accompanied by limitations in the temperature of use, lest cracks should appear, bubbles, or deformities.
    [0003] However, the inventors have demonstrated that the use of TBD as a catalyst in epoxy-anhydride systems made it possible to obtain materials having improved vitrimeric properties compared to materials obtained from zinc acetylacetonate, in that the constraints developed within the materials were relaxed more completely and faster and at lower catalyst levels. The materials obtained using the TBD thus have better deformation properties, which are more compatible with an industrial thermoforming process, which requires very rapid deformation and stress relaxation at the industrial rates used. In addition, this ability to deform is not obtained at the expense of the crosslinking density, and therefore the mechanical properties of the material, which can also be modulated by adjusting the rate of TBD. 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 mass loss measured in particular by thermogravimetric analysis (ATG). It has been observed that TBD has better thermal stability than zinc acetylacetonate. 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 "thermoset" is meant a thermosetting resin chemically crosslinked so that its gel point is reached or exceeded. By "gel point" is meant 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, it is possible to carry out the test described in patent application WO 97/23516, page 20. A resin is considered to be thermoset in the sense of the invention since its gel level, that is to say the percentage of its residual mass after solventization relative to its initial mass before solvent setting, is equal to or greater than 75%.
    [0004] The term "hardener" refers to a crosslinking agent capable of crosslinking a thermosetting resin. This is a generally polyfunctional compound bearing reactive anhydride functions capable of reacting with reactive functions carried by the resin. When referring to intervals, expressions of the type "from ... a" include the bounds of the interval. Expressions of the type "between ... and ..." exclude the bounds of the interval. SUMMARY OF THE INVENTION The invention firstly relates to a composition comprising at least: a catalyst comprising, and preferably consisting of, a compound of formula (I): ## STR2 ## in which: X denotes a nitrogen atom or a group -CH-, R1 denotes a hydrogen atom, a C1-C6 alkyl group or a phenyl group which may be substituted by a C1-C4 alkyl group, R2, R3 and R4 denote independently a hydrogen atom, a C1-C6 alkyl group, or a phenyl group which may be substituted by a C1-C4 alkyl group, or an acetyl group, or R1 and R2 together with the atoms to which they are attached form saturated or unsaturated heterocycle and / or R3 and R4 form together with the atoms to which they are bonded a saturated or unsaturated heterocycle, - a thermosetting resin comprising at least one and advantageously several epoxide functions and optionally at least one and advantageously several hy free hydroxyl and / or ester, and / or a thermosetting resin hardener selected from carboxylic acid anhydrides. The above catalyst will be referred to hereinafter as "organic vitrimer catalyst" or "vitrimer catalyst". The vitrimer effect catalyst facilitates the internal exchange reactions within a thermoset resin so as to render it deformable. It is understood that this catalyst is present, in the composition of the invention, in addition to the catalysts that may already be intrinsically present in the thermosetting resin and / or in the hardener, because of their preparation which can be carried out in presence of low-grade catalysts.
    [0005] 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 hardener; - 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.
    [0006] The invention also relates to a method of deformation of an object as defined above, such as a method of assembly, welding, repair or recycling, including the application to this object of a mechanical stress at a temperature (T) greater than the glass transition temperature Tg of the thermoset resin. Finally, it relates to the use of one or more objects as described above in the fields of the automobile, aeronautics, boating, aerospace, sports, building, electrical, lighting and lighting industries. electrical insulation, electronics, wind, packaging or printing. DETAILED DESCRIPTION As indicated above, the composition according to the invention contains a vitrimer-forming catalyst of formula (I): ## STR2 ## in which: X denotes a nitrogen atom or a group - CH-, R1 denotes a hydrogen atom, a C1-C6 alkyl group or a phenyl group which may be substituted by a C1-C4 alkyl group, R2, R3 and R4 independently denote a hydrogen atom, an alkyl group C1-C6 or a phenyl group which may be substituted by a C1-C4 alkyl group, or an acetyl group, or R1 and R2 together with the atoms to which they are bonded form a saturated or unsaturated heterocycle and / or R3 and R4 form together with the atoms to which they are bound a saturated or unsaturated heterocycle. It is preferred that R 1 and R 2 together with the atoms to which they are bonded form a saturated or unsaturated heterocycle, preferably saturated, and that R 3 and R 4 form together and with the atoms that they are bound a saturated or unsaturated heterocycle, preferably saturated. It is preferred that the C1-C6 alkyl or phenyl groups are unsubstituted.
    [0007] Examples of vitrimer effect catalysts which can be used in the present invention are the following: These catalysts may also be designated as guanidine catalysts. Preferably, the vitrimer effect catalyst is triazabicyclodecene (TBD). According to one embodiment of the invention, the catalyst represents from 0.1 to less than 5 mol%, preferably from 0.1 to 4 mol%, more preferably from 0.5 to 2 mol%, relatively the molar amount of epoxy functions contained in said thermosetting resin.
    [0008] The composition according to the invention may further comprise at least one hardener of carboxylic acid anhydride type (comprising at least one -C (O) -O-C (O) -) function. Examples of anhydride hardeners which may be mentioned include cyclic anhydrides, for example phthalic anhydride, nadic or methyladiene anhydride, dodecenylsuccinic anhydride (DD SA), glutaric anhydride; partially or fully hydrogenated aromatic anhydrides such as tetrahydrophthalic anhydride, or methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride; and their mixtures. Mention may also be made, as anhydride hardeners, of succinic anhydride, maleic anhydride, trimellitic anhydride, trimellitic anhydride and ethylene glycol adduct, chlorendic anhydride, tetrachlorophthalic anhydride and dianhydride. pyromellitic (PMDA), 1,2,3,4 cyclopentanetetracarboxylic acid dianhydride, aliphatic acid polyanhydrides such as polyazelaic polyanhydride, polysebacic polyanhydride and mixtures thereof. In particular, it is possible to use the anhydrides of the following formulas and their mixtures: and more preferably MTHPA. Anhydrous hardener may also be the commercial hardener HY905 sold by Huntsman, which is a liquid mixture of several anhydrides. Advantageously, the amount of hardener is such that the number of moles of epoxy functional groups of the resin can 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 according to the invention may also comprise at least one thermosetting resin comprising at least one and advantageously several epoxide functions and optionally at least one and advantageously several free hydroxyl functions and / or ester functions. Such a resin will be referred to as an "epoxy resin". Preferably, the epoxy resin represents at least 10% by weight, at least 20% by weight, at least 40% by weight, at least 60% by weight, at least 60% by weight, at least 60% by weight, at least 60% by weight, at least 60% by weight. weight, or even 100% by weight, of the total weight of thermosetting resin present in the composition. There are two major categories of epoxy resins: glycidyl epoxy resins, and non-glycidyl epoxy resins. The glycidyl epoxy resins are themselves classified as glycidyl ether, glycidyl 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 diol, diacid or diamine with epichlorohydrin. The non-glycidyl epoxy resin is 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. o C H2 DGEBA-based resins have excellent electrical properties, low shrinkage, good adhesion to many metals and good resistance to moisture, mechanical shock and good thermal 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. As a general rule, n varies from 0 to 25.
    [0009] Novolac epoxy resins (the formula is shown below) are glycidyl ethers of phenolic novolac resins. They are obtained by reacting phenol with formaldehyde in the presence of an acid catalyst to produce a novolac phenolic resin, followed by reaction with epichlorohydrin in the presence of sodium hydroxide as a catalyst. Novolac epoxy resins generally contain several epoxy groups. The multiple epoxide groups make it possible to produce thermoset resins of high crosslinking density. 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 properties. , resistance to heat and moisture. 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), bisphenol A diglycidyl ether hydrogenated, bisphenol F diglycidyl ether, tetraglycidyl methylene dianiline, pentaelythritol tetraglycidyl ether, trimethylol triglycidyl ether (TMPTGE), tetrabromo bisphenol A diglycidyl ether, or hydroquinone 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, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glyco diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, terephthalic acid diglycidyl ester, poly (glycidyl acrylate), poly (glycidyl methacrylate), epoxidized polyunsaturated fatty acids, epoxidized vegetable oils, especially epoxidized soybeans, epoxidized fish oils, and epoxidized limonene; glycidyl esters of versatic acid such as those sold under the name CARDURA® E8, E10 or E12 by the company Momentive (CARDURA® E 10 of CAS 26761-45-5); the epoxidized cycloaliphatic resins sold under the name ARALDITE® CY179, CY184, MY0510 and MY720 by the company Huntsman, the CY179 and CY184 resins corresponding respectively to the following formulas: ## STR2 ## Triglycidyl isocyanurate (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-nonylphenyl glycidyl ether, pt-butyl phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ester of acid dimer, cyclohexane dimethanol diglycidyl ether, polyglycidyl ether of ricin oil; 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 vitrimer effect catalyst, the hardener, and optionally an epoxy thermosetting resin, as defined above. According to this embodiment, the number of moles of catalyst can range from 0.1 to 10%, preferably from 0.5 to 5%, preferably from 0.5 to 2%, relative to the number of moles of anhydride functions. . 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 that result from the invention. 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 polymers which can be used in admixture with the composition of the invention, mention may be made of: elastomers, thermoplastics, thermoplastic elastomers, impact additives.
    [0010] By pigments is meant insoluble colored particles in the composition of the invention. As pigments that may be used according to the invention, mention may be made of titanium oxide, carbon black, carbon nanotubes, metal particles, silica, metal oxides, metal sulfides or any other mineral pigment. mention phthalocyanines, anthraquinones, quinacridones, dioxazines, azo pigments or any other organic pigment, natural pigments (madder, indigo, purple, cochineal, etc.) and mixtures of pigments. By dyes is meant soluble molecules in the composition of the invention and having the ability to absorb a portion of the 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. It may be mentioned without limitation: 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 mixtures thereof, can serve to ensure the heating of a material or an object made from such a composition, by means of a radiation source such as a laser. The presence, in the composition of the invention, of pigments, fibers or electrically conductive 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 microwaves. Such heating may allow the implementation of a method of manufacturing, processing or recycling a material or an object according to a method which will be described later. The additional compounds may also be chosen from one or more other catalysts and / or hardeners, of any type known to those skilled in the art, playing these roles insofar as they do not alter the advantageous properties resulting from the invention. They will be referred to as "additional catalyst" and "additional hardener". 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: tertiary amines, optionally blocked, 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. imidazoles, such as 2-methylimidazole (2-MI), 2-phenylimidazole (2-PI), 2-ethyl-4-methylimidazole (EMI), 1-propylimidazole, 1-ethyl-3-methylimidazolium chloride; 1- (2-hydroxypropyl) imidazole. phosphoniums: tetraalkyl and alkyltriphenylphosphonium halides. amine salts of polyacids, aniline-formaldehyde condensates, N, N-alkanolamines, trialkanolamines borates, fluoroborates such as boron trifluoride monoethylamine (BF3-MEA), organosubstituted phosphines, monoimidazoline salts quaternary, 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 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. 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. The additional catalyst for vitrimer effect may for example be present in the composition of the invention in a proportion of 0.1 to 10% by weight and preferably from 0.1 to 5% by weight relative to the total weight of the composition. Furthermore, 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 (for example control of the glass transition temperature and / or the modulus of a thermoset 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, polymercaptans, dicyandiamides and mixtures thereof. 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 triamine, triethylene tetramine, tetraethylene pentamine, dihexylene triamine, cadaverine, putrescine, hexanediamine, spermine, isophorone diamine, and the like. aromatic amines such as phenylene diamine, diamino diphenylmethane, diamino diphenylsulfone, methylenebischlorodiethylaniline, meta-xylylene diamine (MXDA) and its hydrogenated derivatives such as 1,3-bis (aminomethylcyclohexane) (1,3-BAC ); and their mixtures.
    [0011] An additional amine hardener may be further selected from polyetheramines, for example Huntsman's JEFFAMINES, optionally in admixture with other additional hardeners. Preferred additional hardeners include diethylenetriamine, triethylenetetramine, hexanediamine, and mixtures thereof. 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 functions, in particular a linear or branched polyhydroxyalkane, such as glycerol, trimethylolpropane or pentaelythritol. It has indeed been observed that the addition of this compound to the reaction mixture further improves the vitrimeric properties of the material, that is to say to obtain a material capable of relaxing more completely and faster constraints after application of 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 vitrimer-forming 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. Kits The composition according to the invention may be prepared from a kit 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.
    [0012] 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 different compositions can be stored together or separately. It is also possible to store some of the compositions together while keeping them separate from the other compositions.
    [0013] 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.
    [0014] The packaging may consist of a container having two or even three internal compartments for the separate storage of each of the compositions. According to one variant, the kit may consist of a single container containing a mixture of the two or three compositions in appropriate quantities. In the latter case, the intervention of the operator is advantageously limited to heating.
    [0015] 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 dosing. Uses The composition described above can be used for the manufacture of a hot deformable thermoset resin object. The thermoset resin obtained from the composition according to the invention is heat deformable. Deformable "hot" means at a temperature (T) greater than the glass transition temperature Tg of the thermoset resin.
    [0016] 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 normalized stress 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, - a percentage of stresses G 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 storage module (G ') at the rubber 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 greater than or equal to 15 MPa, these quantities being measured according to the protocols indicated in the examples below.
    [0017] 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 paint or an adhesive film. Also included are powders, granules, etc. The object according to the invention may be manufactured according to a manufacturing process comprising - a) the preparation or the provision of a composition according to the invention, b) the shaping of the composition resulting from step a) c) the application an energy allowing the hardening of the resin, d) the cooling of the thermoset resin.
    [0018] The steps a) b) c) of the process can be successive or simultaneous. The preparation of the composition can be carried out 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. The shaping can be carried out by any technique known to those skilled in the field of thermosetting resins, especially by molding. 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 molding"), reaction-injection-molding (or RIM) or any other methods known to those skilled in the art, as described in the books "Epoxy Polymer", edited by JP
    [0019] 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 form of powder or grains by any known technique of the skilled person. Mechanical grinding can also be performed at the end of step d).
    [0020] 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.
    [0021] 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. 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 "applying an energy for the hardening of the resin" is generally meant a rise in temperature. 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.
    [0022] 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.
    [0023] This is for example a laminated material, comprising an alternating superposition of layers of thermoset resin obtained from at least one composition according to the invention, with layers of wood, metal, or glass. 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). Deformation Process The thermoset resins obtained as described herein have the advantage of exhibiting a slow variation of viscosity over a wide range of temperatures, which makes the behavior of an object of the invention comparable to that of inorganic glasses and makes it possible to apply deformation procedures that are not generally applicable to conventional thermosets. It can thus be shaped by applying stresses of the order of 1 to 10 MPa without sinking under its own weight.
    [0024] 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. However, large objects, which are more likely to sag, can be maintained by a frame as for glass work. 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" is meant in the sense of the present invention, the application of a mechanical force, locally or on all or part of the object, the mechanical force tending to a shaping or deformation of the object. Among the mechanical stresses that may be employed are: pressure, molding, kneading, extrusion, blowing, injection, stamping, twisting, bending, pulling and shearing. This 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 kneading, 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 distinct constraints, of the same nature or not, applied simultaneously or sequentially to all or 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 causing a rise in temperature for carrying out the processes of the invention include: an oven, a microwave oven, a heating resistor, a flame, an exothermic chemical reaction, a laser beam, an iron ironing, a hot air gun, an ultrasonic tank, a heating punch ... The temperature rise can be made to compensate or not and its duration is adapted to the expected result. Although the resin does not flow during deformation, thanks to the exchange reactions, 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 reheated later, it will not return to its original form. In fact, the exchange reactions that occur at high temperatures favor a reorganization of the crosslinking points of the network of the thermoset 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 that are stable, difficult or even impossible to obtain by molding, from simpler elementary shapes. In particular, it is very difficult to obtain by molding forms resulting from a twist. In a complementary manner, the choice of appropriate temperature conditions, heating duration under stress and cooling makes it possible to transform an object of the invention while controlling the persistence of certain internal mechanical stresses within this object, and then, if object thus transformed is subsequently reheated, a new controlled deformation of this object by controlled release of the constraints can be operated. Recycling processes 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 applying a mechanical grinding, and the particles thus obtained are then used in a method of manufacturing an object according to the invention. In particular, according to this method, the particles are simultaneously subjected to a rise in temperature and to a mechanical stress allowing their transformation into an object according to the invention. The mechanical stress allowing the transformation of the particles into an object may for example comprise compression in a mold, kneading, and / or extrusion. This method makes it possible in particular, by applying a sufficient temperature and an appropriate mechanical stress, to mold new objects from the objects of the invention.
    [0025] Another advantage of the invention is that it makes it possible to manufacture objects based on thermoset resin 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.
    [0026] "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.
    [0027] Any method known to those skilled in the art can be used for this purpose. These elementary parts are then convertible, under the joint action of heat and mechanical stress, into objects of the desired shape: for example, ribbons can by stamping be cut into smaller pieces of selected shape, 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 transformation step of the elementary parts according to the invention can be performed by the end user without chemistry equipment (non-toxicity, no expiry date, no VOC, no weighing reagents). A particular case of the deformation process already described thus comprises: a) the use as raw material of an object of the invention in the form of an elementary unit or a set of elementary units, b) the application simultaneous mechanical stress and elevation of temperature to shape the object to form a new object, c) cooling of the object resulting from step b).
    [0028] 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 recycling method of an object of the invention may comprise: a) the use of an object of the invention as raw material, b) the application of a mechanical stress and possibly a temperature rise simultaneous to transform this object into a set of elementary units, c) the cooling of this set of elementary units. Applications The fields of application of the present invention are mainly those of thermosetting resins, in particular those of epoxy resins, in particular the automobile (which includes any type of motorized vehicle including heavy goods vehicles), aeronautics, boating, aerospace, sports, building, electrical, electrical insulation, electronics, wind, packaging and printing. The compositions, materials and objects of the invention may for example be incorporated in formulations, 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.
    [0029] The compositions of the invention can also be used to manufacture adhesives, advantageously thermally crosslinkable or photo-crosslinkable, to encapsulate connectors (the composition of the invention can be applied by potting or injection), to produce electrical insulator parts or even to make prototypes.
    [0030] EXAMPLES The following examples illustrate the invention without limiting it. Characterization methods Mechanical analysis: the samples of examples 1 to 4 were subjected to a dynamic mechanical analysis (DMA) Precisely, a bar of dimensions 10x30x3mm was fixed between two clamps and stressed in rectangular torsion (imposed deformation of 0.05% ) in a RHE3 device of RHEOMETRIC SCIENTIFIC, 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 the peak of the peak of the tan curve, and is hereinafter considered as the Tg of the sample, while the conservation modulus G 'was determined on the rubber plateau at 200 ° C. . EXAMPLE 1 Synthesis of an Epoxy-Anhydride Network in the Presence of 1% Organic Catalyst Four samples of vitrimer material (Ia, Ib, Ic and 1d respectively) were prepared in the presence of 1% of TBD by the following method. In a beaker were added a DGEBA-type epoxy resin (DOW DER332, Equivalent Epoxy Weight: 174 g / eq) in the form of a viscous liquid, as well as TBD (ALDRICH) in a proportion of 1 mol% of catalyst per mole of functions. epoxide. The beaker was placed in an oil bath thermostated at 100-120 ° C until the catalyst dissolved in the resin to obtain a homogeneous and transparent mixture. To this mixture, out of the bath, methyl tetrahydrophthalic anhydride (MTHPA) (MW = 166.18 g / mol) was then added to the mixture, then the whole was homogenized for a few minutes in the bath before being poured into a mold. hollow metal of 70x140x3mm slightly silicone. The mold was secured by a silicone seal to a metal plate covered with a Teflon coating, then the assembly was introduced into a heating press previously set at a temperature of 140 ° C. and placed at the beginning of cooking at a temperature of 140.degree. pressure of 10 bar. The cooking was carried out for 17 hours.
    [0031] To make these samples, a molar ratio of the epoxide functions of the resin to anhydride functions of the hardener respectively equal to 1 / 0.5 was used; 1 / 0.8; 1/1; and 1 / 0.8 for samples 1a, 1b, 1c and 1d.
    [0032] The Tg and the conservation modulus of the materials thus obtained were measured. These materials each had a Tg of 130 ° C, 148 ° C, 148 ° C and 114 ° C and a storage modulus at 200 ° C of 15 MPa, 14 MPa, 15 MPa and 7.5 MPa. Two samples of vitrimer material were prepared identically, replacing the TDB with DBU (1,8-DiazaBicyclo [5.4.01Undec-7-ene], or DOTG (DiOrthoToluidineGuanidine), for a molar ratio of the epoxide functions of the resin with anhydride functions of the hardener equal to 1/1. These materials had a Tg of 132 ° C and 125 ° C, respectively, and a storage modulus at 200 ° C of 14 MPa and 10 MPa.
    [0033] Comparative Example 2 Synthesis of an Epoxy-Anhydride Network in the Presence of 10% of Zinc Acetylacetonate Three samples of material (respectively 2a, 2b and 2c) were prepared in an identical manner to Example 1, except that the catalyst was replaced by zinc acetylacetonate or Zn (acac) 2 at a content of 10 mol% Zn with respect to the epoxy functions.
    [0034] These materials had, respectively, a Tg of 124 ° C, 142 ° C and 130 ° C and a storage modulus at 200 ° C of 14.3 MPa, 14.5 MPa and 13.5 MPa. Comparative Example 3 Synthesis of an Epoxy-Anhydride Network in the Presence of Nitrogen Catalys Five samples 3a-3e of material were prepared in the same manner as in Example 1, using varying amounts of different nitrogen-opening catalysts. epoxide not corresponding to formula (I) described herein, namely: methyl imidazolidone (or 2-MIA), 2,4,6-tri (dimethylaminomethyl) phenol (hereinafter "Anc" for Ancamine K54 d AIR PRODUCTS) and 1,4-diazabicyclooctane (or DABCO). The molar ratio of the epoxide functions of the resin to the anhydride functions of the hardener was set at 1: 0.8. The characteristics of these materials are summarized in the following Table 1.
    [0035] Table 1 3a 3b 3c 3d 3rd Catalyst 2-MIA Anc DABCO DABCO DABCO Catalyst / Epoxide (% mol) 2.5 2 1 5 10 G '(MPa) 15 10 7 11 10 Tg (° C) 144 130 110 130 130 Example 4: Synthesis of an epoxy-anhydride network in the presence of TBD and polyol Three samples were prepared identically to the sample Ib of Example 1, except that a polyol was added in liquid form to the hardener to ambient temperature. The Tg and the conservation modulus G 'of the materials thus obtained were measured, which are collated in Table 2 below. Table 2 Ech. 4a 4b 4c Polyol Glycerol Glycerol TMP *% mol orvepoxy 10 20 10 Tg (° C) 146 144 144 G '(MPa) 15 16.7 * trimethylol propane Example 5: Study of the vitrimeric properties of different materials The samples of Examples 1 to 4 were subjected to an experiment consisting in imposing on a specimen of material of 40x20x2mm a deformation under a flow of nitrogen, in 3-point bending, using a Metravib apparatus of the DMA50N type, after the sample had was brought to a temperature equal to Tg + 100 ° C or 200 ° 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 given a force equal to zero and the deformation (recovery) of the sample 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 (G / Go) is then plotted as a function of time, and for each test, 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 hereinafter referred to as000s The results obtained are collated in Table 3 below. Table 3 Ech. lb Id 2a comp 2b comp 2nd comp T (s) 345 1015 1655 1555 1600 2400 1565 as000s 96 100 100 93 100 87 84 (0/0) Ech. 3a (comp) 3b 3c (comp) 3d comp 3rd (comp I (comp) T (s)> 5000> 5000> 5000> 5000 2350 as000s 0 0 28 54 82 (%) Sample 4a 4b 4c T (s) 385 315 670 as000s 100 100 93 (%) As can be seen from this table, the catalysts according to the invention (samples 1a-1d) make it possible to obtain materials capable of relaxing their stresses more completely, and generally faster, than the materials obtained from 10% zinc acetylacetonate catalyst (samples 2a to 2c) These vitrimeric properties can be further improved by adding a polyol to the reagent mixture (Examples 4a to 4c). Moreover, they are not obtained to the detriment of the mechanical properties of the material, which has a storage modulus (G ') to the rubber plateau greater than or equal to 5 MPa (see Example 1).
    [0036] In contrast, the materials of Examples 3a to 3e do not exhibit vitrimeric properties, except to use a very high catalyst content (Example 3e). Even in this case, the properties obtained remain poor. Example 6: Study of the thermal stability of different vitrimeric materials The thermal stability of a material identical to that of Example 1b was evaluated, except that it was obtained using a catalyst amount equal to 0.5 mol% relative to the number of moles of epoxide functions in the resin (hereinafter, Example 1d). The results were compared with those obtained with the material of Comparative Example 2b. The measurement was carried out by ATG on a Perkin Elmer TGA7 type apparatus, performing a temperature sweep of 25 ° C. to 500 ° C. in 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 2b and 305 ° C in the case of the material of Example 1d. In addition, the loss of material after 1 h at 250 ° C amounted to 8.4% in the case of the material of Comparative Example 2b and only 1.5% in the case of the material of Example 1d. These results confirm the better heat resistance of the materials according to the invention at the temperatures of fitness and recycling. Tests carried out on the materials obtained in Example 1 with DBU and DOTG showed that the temperature leading to a loss of material of 1% was respectively 315 ° C. and 295 ° C., and the loss of material after 1 h. at 250 ° C was 4.1% for the DBU.
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. A composition comprising: a catalyst comprising, and preferably consisting of, a compound of formula (I): ## STR1 ## wherein X denotes a nitrogen atom or a group -CH-, R1 denotes an atom hydrogen, a C1-C6 alkyl group or a phenyl group which may be substituted by a C1-C12 alkyl group; R2, R3 and R4 independently denote a hydrogen atom, a C1-C6 alkyl group, or a group phenyl which may be substituted by a C1-C4 alkyl group, or an acetyl group, or R1 and R2 together with the atoms to which they are attached form a saturated or unsaturated heterocycle and / or R3 and R4 together with the atoms to which they are bound to a saturated or unsaturated heterocycle, 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 the selected one from carboxylic acid anhydrides.
    [0002]
    2. Composition according to claim 1, characterized in that R1 and R2 together with the atoms to which they are bonded form a saturated or unsaturated heterocycle, preferably unsaturated, and that R3 and R4 form together with the atoms to which they are attached. are bound a saturated or unsaturated heterocycle, preferably saturated.
    [0003]
    3. Composition according to claim 1 or 2, characterized in that the catalyst is triazabicyclodecene (TBD).
    [0004]
    4. Composition according to any one of claims 1 to 3, characterized in that the catalyst represents from 0.1 to less than 5 mol%, preferably from 0.1 to 4 mol%, more preferably from 0, 5 to 2 mol%, relative to the molar amount of epoxy functions contained in said thermosetting resin.
    [0005]
    5. Composition according to any one of claims 1 to 4, characterized in that the thermosetting resin is a diglycidyl ether of bisphenol A (DGEBA).
    [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 the resin can 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.
    [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 complement to 100% being provided by the catalyst and optionally by additional compounds chosen from: polymers, pigments, dyes, fillers, plasticizers, long fibers or short, woven or not, flame retardants, antioxidants, lubricants, wood, glass, metals and mixtures thereof.
    [0008]
    8. Composition according to any one of the preceding claims, further comprising at least one polyol.
    [0009]
    9. Composition according to claim 8 characterized in that the polyol is glycerol, trimethylolpropane or pentaerythritol.
    [0010]
    10. 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 thermosetting resin.
    [0011]
    11. Use of the composition according to any one of claims 1 to 9 for the manufacture of a hot deformable thermoset resin object.
    [0012]
    12. Object comprising a thermoset resin obtained from a composition as defined in any one of claims 1 to 9.
    [0013]
    A method of deforming an object, such as a method of assembling, welding, repairing or recycling, comprising applying to an object according to claim 12 a mechanical stress at a temperature (T ) greater than the glass transition temperature Tg of the thermoset resin.
    [0014]
    14. Use of one or more objects according to claim 12 in the fields of automobiles, aeronautics, boating, aerospace, sports, building, electrical, electrical insulation, electronics, wind power, packaging or printing.15
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    同族专利:
    公开号 | 公开日
    US20170044305A1|2017-02-16|
    FR3020366B1|2017-10-27|
    CN106459376A|2017-02-22|
    EP3134454B1|2019-11-20|
    ES2771873T3|2020-07-07|
    EP3134454A1|2017-03-01|
    WO2015162352A1|2015-10-29|
    CN106459376B|2018-12-18|
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    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|
    CN112961463A|2021-02-07|2021-06-15|四川大学|Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof|
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    法律状态:
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    2015-10-30| PLSC| Publication of the preliminary search report|Effective date: 20151030 |
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    2022-01-07| ST| Notification of lapse|Effective date: 20211205 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1453676A|FR3020366B1|2014-04-24|2014-04-24|COMPOSITION FOR THE PRODUCTION OF EPOXY / ANHYRIDE TYPE VITRIMER RESINS COMPRISING AN ORGANIC CATALYST|FR1453676A| FR3020366B1|2014-04-24|2014-04-24|COMPOSITION FOR THE PRODUCTION OF EPOXY / ANHYRIDE TYPE VITRIMER RESINS COMPRISING AN ORGANIC CATALYST|
    US15/305,995| US20170044305A1|2014-04-24|2015-04-09|Composition for manufacturing epoxy/anhydride vitrimer resins including an organic catalyst|
    EP15718553.9A| EP3134454B1|2014-04-24|2015-04-09|Composition for manufacturing epoxy/anhydride vitrimer resins including an organic catalyst|
    CN201580033900.9A| CN106459376B|2014-04-24|2015-04-09|For manufacturing the composition including organic catalyst of epoxy/acid acid anhydride glass shape body resin|
    ES15718553T| ES2771873T3|2014-04-24|2015-04-09|Composition for the manufacture of epoxy / anhydride type vitrimer resins comprising an organic catalyst|
    PCT/FR2015/050951| WO2015162352A1|2014-04-24|2015-04-09|Composition for manufacturing epoxy/anhydride vitrimer resins including an organic catalyst|
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