Additive composition for controlling rheology

Abstract

The present invention relates to an additive composition for controlling rheology and mechanical properties, which can be used in polymerizable compositions, putty, paints or adhesives. These compositions provide improved rheology control and they exhibit, in particular, adjustable viscosity and yield stress. Due to the properties of their components, they enhance the mechanical properties of the formulations containing them.

Description

Technical Field

[0001] The present invention relates to additive compositions for controlling rheology and mechanical properties, which can be used in polymerizable compositions, sealants, paints or adhesives. These compositions provide improvements in rheology control; they have in particular adjustable viscosities and yield stresses. They also provide enhancement of the mechanical properties of formulations containing them.

[0002] They can be used in the formulation of polymerizable monomers, adhesives, sealants or paints and more generally in all formulations when an increase in viscosity and yield stress is required.

[0003] The formulations of the compositions of the invention provide a solution for manufacturing objects by three-dimensional (3D) printing methods, and more particularly large objects that may have a size of several meters and a thickness of several centimeters. In addition, the compositions of the invention allow the exotherm generated during the polymerization of the polymerizable formulations containing them to be effectively dissipated. Due to the properties of the compositions of the invention, the mechanical properties of the formulations containing these polymerized compositions are improved, and the products obtained from the polymerized formulations containing the compositions of the invention show low shrinkage. The compositions of the invention also allow the rheology of sealant, lacquer or adhesive formulations to be effectively controlled with small amounts of these compositions. Background Art

[0004] Due to the need to control the rheology of polymerizable monomer formulations, sealants, lacquers or adhesives, there is a constant need to improve the behavior of these formulations. Therefore, the use of rheological additives or mixtures of rheological additives is common in these technical fields. In particular, these formulations often require viscous behavior and sometimes there is no flow during application.

[0005] For example, monomers used for polymerization in various fields of application usually have very low viscosities, since they are usually low molecular weight compounds. Their yield stress is close to zero. The use of functional oligomers or the addition of polymers makes it possible to increase the viscosity, but can be a source of other disadvantages, and the yield stress is still insufficient.

[0006] In formulations such as sealants and adhesives, lacquers or in 3D printing, it is often necessary to increase the viscosity and yield stress of these formulations with or without monomers for application reasons and in particular to avoid material flow before the polymerization process is complete or during the application of non-polymerizable formulations. Often, compositions are desired in which the flow is limited, or even absent, or controlled depending on the field of use. The exotherm generated during the polymerization of the monomers must also be managed to avoid potential defects. Finally, polymerized monomer compositions often exhibit insufficient mechanical properties.

[0007] 3D printing is a technology field widely used in industry and leisure. This technology allows the preparation of a single object from a definition of the object in the form of a computer file giving the dimensional parameters of the object to be printed.

[0008] It thus allows the additive manufacturing (AM) of real objects from virtual objects. It is based on slicing the virtual 3D object into thin 2D layers. These thin layers are deposited one by one by fixing them on the previous layer, thus making it possible to manufacture a real object. In the case of 3D printing using a polymerization process, the fixing of the layers on each other is possible when, for example, the constituent material of the object is a monomer composition extruded through a nozzle directed for manufacturing the object, which polymerizes once deposited on the previous thin layer.

[0009] Until now, this method of manufacturing objects has been reserved for the manufacture of small objects, most of the time being able to escape to some extent the limitations of perfect control of viscosity and yield stress.

[0010] When it comes to manufacturing large objects, new problems arise that are negligible for small objects.

[0011] For example, in 3D printing of large-sized objects, the rheological requirements that enable good stability of the material at the nozzle outlet are much higher, exothermic phenomena are more present because the heat is difficult to remove, and poor control of shrinkage after polymerization leads to poor quality objects. For the manufacture of large objects, instead of superimposing thin layers, layers several centimeters thick are used. Flow and shrinkage phenomena during polymerization are intensified and are currently difficult to solve. When manufacturing large objects, users also seek good mechanical strength of these objects.

[0012] In the currently known prior art, it is difficult to obtain polymerizable formulations that allow the manufacture of large objects with good mechanical strength while maintaining effective control of shrinkage, limiting exothermicity and effectively controlling the dimensional definition of the different overlapping lamellae resulting from the rheology of the process for manufacturing these lamellae. The flow of the formulation to be polymerized is carried out through a nozzle and must maintain dimensional stability, characterized by sufficient viscosity and yield stress. This set of technical problems is currently difficult to solve.

[0013] Due to the low viscosity provided by the monomers, formulations containing oligomers are used in the prior art, which complicates the formulation, increases the cost, and does not always allow for a clear composition when desired. EP0802455 is an example which has oligomers, which are difficult to manufacture and therefore expensive.

[0014] In the extrusion of polymerizable compositions, WO21029945 uses a similar approach, in which reactive oligomers in the form of acrylates are used. An alternative is described in WO21183396, but it assumes an additional step of prepolymerization, which increases the viscosity during use in the 3D printing process by the technique of extrusion through a nozzle, but this adds an additional step. In these examples, despite the increase in viscosity, the yield stress remains low and flow of the material is still observed.

[0015] The applicant has sought to improve the formulation, one example of which consists of monomers and initiators, because the combination of these components alone does not allow the correct construction of objects by radiation or thermal polymerization due to too low viscosity and yield stress. The shrinkage during polymerization is also too great and the objects have many defects in appearance.

[0016] The addition of block copolymers to these formulations makes it possible to improve the mechanical properties, as is known to the person skilled in the art. Furthermore, the presence of block copolymers contributes positively to the rheological properties, as is also known to the person skilled in the art.

[0017] However, the rheological behavior of these formulations is still insufficient or requires the use of large amounts of block copolymers without addressing the flow phenomena because the yield stress is still insufficient.

[0018] Diamides, and in particular fatty acid diamides, are widely used in the formulation field as rheology control agents. Mention may be made, for example, of EP 3613728.

[0019] These diamides are sometimes combined with castor oil. Thus, in EP 3919546, a combination of diamides, hydrogenated castor oil and specific polyamides (in pairs or all three together) is disclosed as a rheological additive.

[0020] In EP 3 131 996, a combination of polyamide and hydrogenated castor oil is also described.

[0021] It was observed that the changes in rheology associated with the use of these diamides and hydrogenated castor oil, in combination or not, were insufficient, considering the demands that may arise from formulations in sealants, lacquers or adhesives, whether polymerizable or not. In the case of polymerizable formulations, the specific case of applications in 3D printing is a good example of the need to manage the rheology of the formulation.

[0022] When these compounds are used, in combination with one or more monomers, large amounts of them must be used to have a significant effect. This may have the result that the polymerized monomer formulation has certain properties that deteriorate.

[0023] The combination of block copolymers, diamides and / or triamides and hydrogenated castor oil in polymerizable monomer formulations, i.e. in the presence of a polymerization initiator, is an example of a solution to the technical problems associated with rheological control, mechanical properties and polymerization management. In particular, even when a small amount of the composition of the present invention is used, a very significant effect of viscosity and yield stress increase is observed. The combination of block copolymers, diamides and / or triamides and castor oil provides a surprising effect and allows limiting the amount of these additives while providing an improvement in the mechanical properties of the obtained product, and compared to the absence of the combination of these three compounds, exothermicity is better managed during polymerization. Therefore, the combined use of block copolymers, amides and castor oil provides an unexpected sum of technical effects (improved rheology, improved mechanical properties and restricted exothermicity and shrinkage).

[0024] Thus, the Applicant has found that in addition to one or more monomer components, a combination of small amounts of castor oil, diamides and / or triamides and block copolymers provides a viscosity and yield stress that meets the requirements of sealants and adhesives, formulations of lacquers or produced in 3D printing. The combined presence of block copolymers, amides and hydrogenated castor oil is necessary to maximize the impact on the rheology of formulations containing them, and the technical effects obtained are far superior to the combination of only two of these compounds.

[0025] In the case of 3D printing, the compositions of the invention formulated with monomers show good stability of the beads of the formulation before polymerization and allow them to be placed without defects on previously polymerized thin layers. The objects obtained using these compositions also show good mechanical properties. The combination of castor oil, diamides and / or triamides and block copolymers in a composition comprising one or more monomers makes it possible to obtain significant effects that can solve the problems of the prior art in applications requiring high viscosities or alternatively regulating these viscosities, with sufficient yield stress, and achieve this with small amounts of these compounds.

[0026] The amounts of castor oil, diamide and / or triamide and block copolymer can be variable and allow fine tuning of rheological constraints associated with the formulation of sealants, adhesives, lacquers and during the manufacture of objects by 3D printing while providing benefits in shrinkage, exothermic energy management and mechanical properties. Fillers can be added to the compositions of the invention formulated with the monomers while retaining the advantages of the combination of castor oil, diamide and / or triamide and block copolymer.

[0027] The composition of the invention may also be used with ingredients derived from natural materials such as vegetable oils or fibers, whether monomers, block copolymers, diamides and / or triamides, castor oil or fillers. When fillers are present in the composition of the invention, fillers (filled or unfilled) derived from recycling of polymeric materials may be included therein, such as composite materials, which give the composition of the invention a favorable carbon balance and recyclability of the material at the end of its life. Summary of the invention

[0028] The present invention relates to a composition of matter comprising the following mixture C:

[0029] - at least one block copolymer in a proportion between 50% and 99%;

[0030] - hydrogenated castor oil in a proportion between 0.5% and 25%;

[0031] - at least one fatty acid diamide and / or at least one fatty acid triamide in a proportion between 0.5% and 25%;

[0032] % is expressed as mass of the total mass of C. DETAILED DESCRIPTION

[0033] The present invention is a composition comprising three classes of compounds, the three classes of compounds consisting of block copolymers, hydrogenated castor oil and polyamide. They can be in the form of a mixture of the three classes of compounds prepared by a dry process (a mixture of powders and / or granules of the compounds) or melt prepared by using a suitable mixing device. The present invention also relates to the use of the composition of the present invention as an organogelator in a formulation containing them.

[0034] An organogelator is understood to mean a composition which makes it possible to modify the rheology of a liquid preparation.

[0035] The block copolymers useful in the context of the present invention are multiblock copolymers, preferably free of butadiene. They consist of an A block (called hard block) having a glass transition temperature Tg greater than 25°C, preferably greater than 50°C, more preferably greater than 70°C, and a B block (called soft block) having a Tg less than 0°C, preferably less than -25°C, having the formula (AB) m , wherein m is 2-1000, preferably 4-500, or preferably linear or star-shaped, and has formula (A) n B or (B) n A, and preferably (A) n B, where n takes the value of 2 or 3, these are diblock or triblock, preferably triblock, linear or star copolymers. A combination of diblock and triblock copolymers constitutes one variant of the invention.

[0036] The term "glass transition temperature" or "Tg" denotes the temperature at which a polymer material changes from a glassy state to a non-glassy state, corresponding to a certain mobility of the polymer chains relative to each other. The glass transition temperature is determined by dynamic mechanical analysis (DMA), for example according to the method specified in the "Examples" section.

[0037] The expression "block copolymer" refers to a copolymer having a plurality of different polymer segments, wherein each segment, also indicated as a "block", consists of a sequence of monomers which may be identical or different. Thus, each segment or block may be a homopolymer or a copolymer.

[0038] Preferably, the A block comprises a sequence of monomers selected from the group consisting of linear or branched, cyclic or acyclic (meth)acrylic acids C1 to C2, substituted or unsubstituted with polar and / or hydrophilic functional groups. 18 Alkyl esters, and in particular methyl methacrylate, which may be produced from recycling processes by depolymerization, styrene and substituted styrenes, isobornyl (meth)acrylate, (meth)acrylic acid and alkyl acrylamides.

[0039] Polar and / or hydrophilic groups are understood to mean groups such as groups of the carboxyl (—COOH), hydroxyl (—OH) or amide (—CONH) type, or ethylene glycol or polyethylene glycol which may or may not be substituted at their terminal functionalities by alkyl, phosphate, phosphonate or sulfonate groups.

[0040] More preferably, the A block comprises a sequence of monomers selected from methyl methacrylate (optionally produced by a recycling process by depolymerization), styrene, isobornyl acrylate, acrylic acid or methacrylic acid, dimethylacrylamide, diethylacrylamide or isopropylacrylamide, alone or in combination.

[0041] According to one variant, the following monomers may form part of the A block: hydroxylated (meth)acrylates, in particular 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, polyethylene glycols or diol (meth)acrylates substituted or unsubstituted at their terminal functional groups by alkyl, phosphate, phosphonate or sulfonate groups.

[0042] Preferably, the B block will preferably consist of a sequence selected from butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate and lauryl acrylate and mixtures thereof, optionally mixed with styrene.

[0043] More preferably, the B block consists of a sequence of butyl acrylate monomers.

[0044] Thus, mention may be made in a non-limiting manner of the following triblock, diblock and radial triblock copolymers which can be used in the context of the present invention either individually or as a mixture:

[0045] pMMA-pBuA-pMMA, p(MMAcoMAA)-pBuA-p(MMAcoMAA), p(MMAcoAA)-pBuA-p(MMAcoAA), pMMA-p(BuAcoSty)-pMMA, p(MMAcoMAA)-p(BuAcoSty)-p(MMAcoMAA), pMMA-p(BuAcoA A)-pMMA, p(MMAcoDMA)-pBuA-p(MMAcoDMA), p(MMAcoIPA)-pBuA-p(MMAcoIPA) and preferably p(MMAcoDMA)-pBuA-p(MMAcoDMA), p(MMAcoIPA)-pBuA-p(MMAcoIPA), pMMA-pBuA-pMMA.

[0046] PMMA-pBuA, p(MMAcoMAA)-pBuA, p(MMAcoAA)-pBuA, PMMA-p(BuAcoSty), p(MMAcoMAA)-p(BuAcoSty), PMMA-p(BuAcoAA), p(MMAcoDMA)-pBuA-, p(MMAcoIPA)-pBuA- and preferably p(MMAcoDMA)-pBuA, p(MMAcoIPA)-pBuA.

[0047] pBuA-(pMMA)3, pBuA-(p(MMAcoMAA))3, pBuA-(p(MMAcoAA))3, p(BuAcoSty)-(pMMA)3, p(BuAcoSty)-(p(MMAcoMAA))3, p(BuAcoAA)-(pM MA)3, pBuA-(p(MMAcoDMA))3, pBuA-(p(MMAcoIPA))3 and preferably pBuA-(p(MMAcoDMA))3, pBuA-(p(MMAcoIPA))3, p(BuAcoSty)-(p(MMAcoMAA))3.

[0048] In all these block copolymers, MMA can be completely or partially replaced by IBOA and / or IBOMA.

[0049] Where MMA: methyl methacrylate, MAA: methacrylic acid, AA: acrylic acid, BuA: butyl acrylate, Sty: styrene, DMA: dimethylacrylamide, IPA: isopropylacrylamide, IBOA: isobornyl acrylate, IBOMA: isobornyl methacrylate

[0050] The block copolymers useful in the context of the present invention generally have a weight average molecular weight measured by SEC with polystyrene calibration of between 10 000 and 200 000 g / mol and preferably between 80 000 and 180 000 g / mol, with a hardblock / softblock mass ratio of between 75 / 25 and 40 / 60.

[0051] The block copolymers available in the context of the present invention are preferably prepared by controlled radical polymerization, without excluding other preparation methods. Controlled radical polymerization makes it possible to obtain block copolymers in successive steps within the same process operation. For example, block copolymers can be prepared by RAFT (radical addition fragmentation transfer) polymerization or by nitroxide-controlled polymerization (also referred to as NMP (nitroxide-mediated polymerization)). Preferably, the block copolymer is prepared by NMP, in particular by using N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide to counteract free radicals. The synthesis of block copolymers using the counteracting free radicals is particularly described in EP1526138.

[0052] The block copolymer is present in mixture C in a mass proportion of between 50% and 99%, preferably between 60% and 95%, more preferably between 70% and 95%, endpoints included.

[0053] Hydrogenated castor oil is a commercially available compound under CAS No. 8001-78-3. Hydrogenated castor oil consists of 85% to 90% by mass of ricinoleic acid triglycerides, most of which are hydrogenated in double bonds. There are also smaller amounts of hydrogenated linolenic acid triglycerides, hydrogenated oleic acid triglycerides and hydrogenated stearic acid triglycerides, which are the main ones.

[0054] The hydrogenated castor oil is present in mixture C in a mass proportion of between 0.5% and 25%, preferably between 2.5% and 20% and preferably between 2.5% and 15%, inclusive.

[0055] The composition of the invention comprises at least one polyamide, that is to say a compound comprising at least two amide functional groups. The polyamide is preferably at least one fatty acid diamide and / or at least one fatty acid triamide.

[0056] The diamide of the composition of the invention may be a diamide derived from the condensation of at least one diamine and at least one acid or at least one diacid and at least one amine.

[0057] The triamide of the composition of the invention may be a triamide derived from the condensation of at least one triamine and at least one acid or at least one triacid and at least one amine.

[0058] According to a first preference, they are diamides derived from the condensation of at least one diamine with at least one fatty acid.

[0059] According to a second preference, they are triamides derived from the condensation of at least one triamine with at least one fatty acid.

[0060] According to a third preference, they are mixtures of diamides derived from the condensation of at least one diamine with at least one fatty acid and triamides derived from the condensation of at least one triamine with at least one fatty acid.

[0061] The diamides are characterized in that they comprise at least one reaction product obtained from a reaction mixture comprising:

[0062] a) at least one diamine,

[0063] The diamine is selected from C2 to C24 and preferably C2 to C10 aliphatic diamines, C6 to C18 and preferably C6 to C12 alicyclic diamines, C6 to C24 and preferably C6 to C12 aromatic diamines, C7 to C24 aromatic aliphatic diamines and mixtures thereof;

[0064] b) at least one carboxylic acid,

[0065] - the carboxylic acid is a C2 to C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or hydroxy-substituted C9 to C24 fatty acid, in particular valeric acid, hexanoic acid, heptanoic acid, octanoic acid,

[0066] Nonanoic acid, decanoic acid, undecanoic acid, and preferably substituted with hydroxyl groups, among which 12-hydroxystearic acid (12-HSA), 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), 14-hydroxyeicosanoic acid (14-HEA) or mixtures thereof can be mentioned. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid.

[0067] The triamides are characterized in that they comprise at least one reaction product obtained from a reaction mixture comprising:

[0068] a) at least one triamine,

[0069] The triamine is selected from C2 to C24 and preferably C2 to C10 aliphatic triamines, C6 to C18 alicyclic triamines, C6 to C24 aromatic triamines, C7 to C24 aromatic aliphatic triamines or polyether triamines and mixtures thereof;

[0070] b) at least one carboxylic acid,

[0071] - the carboxylic acid is a C2 to C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or hydroxy-substituted C9 to C24 fatty acid, in particular valeric acid, hexanoic acid, heptanoic acid, octanoic acid,

[0072] Nonanoic acid, decanoic acid, undecanoic acid, and preferably substituted with hydroxyl groups, among which 12-hydroxystearic acid (12-HSA), 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), 14-hydroxyeicosanoic acid (14-HEA) or mixtures thereof can be mentioned. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid.

[0073] At least one diamide and / or one triamide is present in mixture C in a mass proportion of between 0.5% and 25%, preferably between 2.5% and 20% and preferably between 2.5% and 15%, endpoints included.

[0074] The (hydrogenated castor oil) / (diamide and / or triamide) mass ratio is between 1 / 4 and 4 / 1, and preferably between 1 / 3 and 2 / 3.

[0075] The composition of the invention may also comprise a mixture M of monomers, the mass proportion of the mixture C being between 1% and 40% relative to the mass C+M, preferably between 1% and 20% relative to the mass C+M.

[0076] The invention thus comprises a composition according to the invention of a mixture C and at least one monomer mixture M and the use of this mixture in a polymerizable formulation. The monomers of the mixture M used in the composition according to the invention may be monofunctional or polyfunctional, in combination or not. They are preferably derived from renewable resources. Functionality is understood to mean an entity having a polymerizable double bond.

[0077] The monofunctional monomers can be styrene and substituted styrenes, linear or branched C1 to C 18 Cyclic or acyclic, substituted or unsubstituted alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, and in particular methyl methacrylate, which may result from a recycling process by depolymerization, isobornyl (meth) acrylate with or without additional functional groups, where the additional functional groups, when they are present, may be of the hydroxyl, amine, epoxy, amide or phosphorus type. When fast kinetics are required, acrylates are preferably selected.

[0078] Among the preferred monomers of the invention, mention will be made in particular of styrene and methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and isobornyl (meth)acrylate. Preferably, these are styrene, methyl methacrylate (which may be produced by a recycling process by depolymerization) or isobornyl acrylate, alone or in combination.

[0079] More preferably, they are methyl methacrylate from a recycling process by depolymerization and / or isobornyl acrylate from renewable resources.

[0080] The multifunctional monomers carry methacrylic or acrylic functional groups and preferably carry acrylic functional groups and include dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, dimethylolpropane tetraacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol triacrylate, polyalkoxylated pentaerythritol tetraacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, 1,10-decanediol di(meth)acrylate, polyethylene glycol (meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, multifunctional (meth)acrylates from renewable resources, such as vegetable oil (meth)acrylates and preferably vegetable oil acrylates. As regards monomers carrying two or more (meth)acrylate functional groups of renewable origin, mention may be made of Sarbio from the company Sartomer. Monomers of the type described herein, and more particularly those designated 6201 (polyethylene glycol dimethacrylate 200), 6202 (1,10-dodecanediol diacrylate), 7101 (epoxy acrylate), 7106 (linseed oil acrylate), 7107 (epoxidized soybean oil diacrylate) and 7205 (polyester oligomer acrylate).

[0081] Preferably, these are monomers derived from renewable resources, such as acrylic esters of vegetable oils (linseed, soy, corn, sunflower, tung).

[0082] Combinations of two or more monomers are preferred in the context of the present invention, and combinations of monofunctional monomers with acrylate functionality and polyfunctional monomers with acrylate functionality (di-, tri-, tetra-, penta- and hexaacrylates) are preferred.

[0083] Monomers of the vinyl ether type may also be present in the context of the present invention, in particular when the polymerization is initiated by a cationic process. They may be of any type, monofunctional or polyfunctional with respect to the vinyl functionality.

[0084] Preferably, the combination of monofunctional and polyfunctional monomers will be used in respective mass ratios varying from 4 / 1 to 1 / 4.

[0085] The composition C according to the invention comprising the monomer mixture M can be polymerized using free radical or cationic polymerization initiators which may or may not be activated with the aid of electromagnetic radiation, in a mass proportion of between 0.1% and 5% of the mass of the composition M. The initiators may also be thermally activated. Preferably, they are polymerization initiators sensitive to electromagnetic radiation and more particularly to ultraviolet (UV) radiation. Such initiators are known as photoinitiators.

[0086] The present invention therefore also relates to a composition according to the invention comprising at least one monomer, an initiator and more particularly a photoinitiator sensitive to ultraviolet (UV) radiation.

[0087] Photoinitiators are compounds that are capable of generating free radicals or cations when these compounds are exposed to electromagnetic radiation. Preferably, the electromagnetic radiation has a wavelength in the ultraviolet or visible range, but the use of wavelengths in the shorter wavelength range (x-rays or gamma rays) or longer wavelength range (infrared or even further) will not depart from the scope of the present invention.

[0088] The photoinitiator can be of any type. Preferably, in the case of free radical polymerization, they are selected from those that generate free radicals by homolytic reactions in the α-position relative to the carbonyl group, such as benzoin ether derivatives, hydroxyalkylphenones, such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and those that generate free radicals by homolytic reactions in the β-position, such as thione and sulfonyl ketone derivatives, and those that form free radicals by abstracting hydrogen from hydrogen donors, such as benzophenone or thioxanthone. This process involves a charge transfer complex with an amine, followed by electron and proton transfer, to ultimately form an alkyl radical for initiation and an inactive cetyl radical. Mention may be made of benzyl diacetals, hydroxyalkylphenones, α-aminoketones, acylphosphine oxides, benzophenones, thioxanthones and in particular phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0089] It does not depart from the scope of the invention to use a combination of several photoinitiators, or a combination of a photoinitiator and a free radical initiator whose free radicals are generated thermally or by oxidation-reduction reactions, such as methylenebis(diethyl malonate)-cerium IV pairs, toluidine-type aromatic amines or H2O2 / Fe 2+ pair.

[0090] Among the initiators used in combination with the photoinitiator or alone, mention may be made of diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals and azo compounds. Possibly suitable free-radical initiators are, for example, isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, hexanoyl peroxide or dicumyl peroxide, tert-butyl perbenzoate, tert-butyl per-2-ethylhexanoate, cumene peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, pentyl perpivalate and tert-butyl peroctoate.

[0091] In the case of cationic polymerization, the photoinitiator will be a compound of the photoacid generator type which, under electromagnetic radiation, releases an acidic species, for example a proton, such as an onium salt, for example a diaryliodonium or triarylsulfonium salt, and a ferrocenium salt.

[0092] The composition C comprising the monomer mixture M and the initiator may additionally comprise one or more fillers D. The invention therefore also comprises the composition C according to the invention in the presence of a monomer mixture M, an initiator and a filler D.

[0093] The fillers that can be used in the context of the present invention can be inorganic or organic fillers. Among the inorganic fillers, mention may be made, without any limitation, of glass (preferably glass in the form of beads), calcium carbonate, talc, mica, kaolin, clay, sand, barium sulfate, feldspar, calcium phosphate and silica. Preferably, these are glass beads, the size of which is from 50 to 1000 μm, preferably from 50 to 500 μm and more preferably from 80 to 200 μm by volume, and calcium carbonate, the size of which is from 50 to 1000 μm, preferably from 50 to 500 μm and more preferably from 80 to 200 μm by volume.

[0094] The organic fillers that can be used in the context of the present invention can be chosen in a non-limiting manner from wood, cork, cereals, flax, bark or fruit stones. The organic fillers can also be products obtained from textile recycling processes, but can also be products obtained from the recycling of thermosetting polymer compositions, or from the recycling of composite materials, that is to say fillers that can themselves consist of organic and inorganic materials.

[0095] It is also possible to combine fillers, whether organic or inorganic, resulting from textile recycling processes or processes for recycling thermosetting polymer compositions or processes for recycling composite materials.

[0096] Thus, the combination of an inorganic filler and a filler from recycled materials improves the carbon footprint of the composition. With the ubiquity of composite materials today, the ability to recycle them has become an important issue. Thus, one of the preferred compositions of the present invention comprises a mixture of an inorganic filler and a filler resulting from the recycling of composite materials, and more particularly a mixture of glass beads and composite materials.

[0097] Composite material means a combined substance of at least two immiscible materials.

[0098] The filler D may be present in a mass proportion of D between 1% and 80% of the mass C+M+D, preferably between 50% and 80% of the mass C+M+D.

[0099] The composition of the invention exhibits optimal rheological properties after activation. Activation is understood to mean a state in which the composition of the invention is stirred at a temperature between 25 and 80° C., preferably between 60 and 80° C., for a period of time ranging from 30 minutes to 8 hours, formulated with other components such as monomers, initiators or fillers. This step can be done in a dedicated volume or kneading tool, such as an extruder, which in the case of 3D printing can be an extrusion device upstream of the nozzle that places the material in the manufacturing process of the 3D part.

[0100] The present invention therefore also includes compositions according to the invention in the presence of monomers M, initiators or fillers in activated form.

[0101] The activation step, which is usually described as a disadvantage, has an advantage in the present invention. Thus, the composition of the invention can be easily mixed with the filler, for example, before the activation step, since the viscosity of the mixture is minimized at this stage. It is advantageous to obtain a homogeneous mixture, which can then be activated according to known methods, usually by applying a certain temperature and stirring for a given time. The activated mixture then has the desired viscosity and yield stress characteristics.

[0102] Once polymerized, the composition of the invention exhibits good mechanical properties and little shrinkage. Exotherm is controlled and objects made by 3D printing are free of any defects.

[0103] The present invention therefore also relates to a 3D printing method using the composition of the invention and also to an object obtained with the aid of this method.

[0104] The invention also relates to the use of the composition of the invention in a process of injection, extrusion, moulding or any other process for shaping thermoplastic materials, such as impregnation of the composite, and also to the objects thus obtained.

[0105] The composition of the invention may also comprise further additives, among which UV stabilizers, plasticizers and antioxidants may be mentioned in a non-limiting manner. BRIEF DESCRIPTION OF THE DRAWINGS

[0106] Figure 1 The flow of formulations comprising a composition of the invention and a comparative composition is shown.

[0107] Example

[0108] The following examples illustrate the invention in a non-limiting manner.

[0109] Starting materials used:

[0110] Methyl methacrylate (MMA) from Aldrich is used as a model for a low molecular weight monomer and therefore has a low viscosity. It is used as the monomer in the examples to show the viscosity and yield stress with and without the composition of the invention.

[0111] Isobornyl acrylate (IBOA) and The combination of 7107, which is a monomer from Sartomer and has two acrylate functional groups and is derived from a vegetable oil (epoxidized soybean oil diacrylate), is used in an example that is more representative of the composition of the present invention.

[0112] Hydrogenated castor oil (HCO) used was from Aldrich.

[0113] The diamides which can be used in the context of the present invention are prepared as follows:

[0114] 25.8 g of ethylenediamine (0.43 mol, 0.86 amine equivalent), 135.52 g of 12-hydroxystearic acid (0.43 mol, 0.43 acid equivalent) from Aldrich and 49.94 g of hexanoic acid (0.43 mol, 0.43 acid equivalent) from Aldrich were introduced into a 1 liter round bottom flask equipped with a thermometer, Dean-Stark apparatus, condenser and stirrer under a nitrogen stream. The mixture was heated to 200° C. still under a nitrogen stream. The removed water began to accumulate in the Dean-Stark from 150° C. The reaction was checked by acid and amine index. When the acid and amine values ​​were 5 and 3.5 mg KOH / g, respectively, the reaction mixture was cooled to 150° C. and 0.65 g of sulfuric acid was added. The amine index checked after 30 minutes was less than 0.01 mg KOH / g. The reaction mixture was then discharged into a silicone mold. Once cooled to room temperature, the product was micronized in an air jet mill.

[0115] This diamide was used in Examples 1-4.

[0116] The block copolymers used are of two types:

[0117] -PMMA-pBuA-PMMA, denoted as BCP 1.

[0118] -P(MMA co IPA)-pBuA-P(MMA co IPA), denoted as BCP 2.

[0119] The block copolymers are prepared according to the protocol described in, for example, EP1526138.

[0120] The filler used was glass beads. 90-150, purchased from Weissker GmbH.

[0121] The photoinitiator used was purchased from Aldrich 819.

[0122] Measurement method:

[0123] Glass transition temperature measurement by DMA:

[0124] DMA was measured using a Rheometric Scientific ARES rheometer under the following conditions:

[0125] - Rectangular twisted geometry;

[0126] - Shear deformation at a frequency of 1 Hz;

[0127] -The temperature range varies from -125 to 150°C.

[0128] Viscosity was measured using an Anton Paar MCR301 instrument at 25 °C and 0.1 to 100 s -1 Measured under shear gradient with Couette geometry and CC27-SN13118 mobile.

[0129] - Yield stress was measured at 25°C with an Anton Paar MCR301 instrument with Couette geometry and CC27-SN13118 mobile. The measurements were carried out at a stress gradient from 1 to 100 Pa.

[0130] - Shrinkage was measured by the difference in density of the formulation before and after photopolymerization. The density of the formulation was measured using a 10 mL pycnometer. The density of the solid (product obtained from the formulation) was obtained by measuring the mass in water and in air.

[0131] Exothermity: The exothermity is determined by calculating the difference between the temperature measured using a temperature probe and the temperature in the oven during polymerization.

[0132] Impact strength: ISO 179-1:20 10.

[0133] The formulation comprising the composition of the invention was activated at 60° C. under stirring (3000 rpm) for 6 hours.

[0134] Embodiment 1:

[0135] In this example, the viscosity and yield stress of the inventive and comparative compositions were measured after activation, wherein the monomer was methyl methacrylate (MMA).

[0136] Table 1 summarizes the properties measured for these compositions: [Table 1]

[0137] Table 1 MMA % BCP1% Diamide% HCO% <![CDATA[1s -1 Viscosity under (Pa.s)]]> Yield stress (Pa) 1 Comparison 100 0 0 0 <1 none 2. Comparison 98.6 0 0.7 0.7 1 none 3. Comparison 70 30 0 0 0.8 none 4. Comparison 70 29 1 0 0.9 none 5. Comparison 70 29 0 1 0.8 none 6 Invention 70 29 0.5 0.5 19.2 8

[0138] Note in Table 1 that only the compositions of the present invention exhibit high levels of viscosity and measurable yield stress.

[0139] Embodiment 2:

[0140] In this example, the viscosity and yield stress of the compositions of the present invention and comparative compositions were measured after activation, wherein the monomers were isobornyl acrylate (IBOA) and 7107.

[0141] Table 2 summarizes the properties measured for these compositions: [Table 2]

[0142]

[0143]

[0144] In Table 2, it is observed that the compositions of the present invention provide the best viscosity and yield stress properties. Comparative Example 12, which has a very high proportion of block copolymer, exhibits acceptable viscosity levels but no measurable yield stress.

[0145] Embodiment 3:

[0146] In this example, the yield stress of the compositions of the present invention and comparative compositions were measured in the presence of fillers (glass beads) after activation, wherein the monomers are isobornyl acrylate (IBOA) and 7107.

[0147] Table 3 summarizes the properties measured for these compositions: [Table 3]

[0148]

[0149] In Table 3, for the composition of the present invention in the presence of filler (glass beads), the yield stress of the composition of the present invention is the largest.

[0150] The flow test was performed on an aluminum plate arranged at an angle of 15° to the vertical. 5 g of sample was placed on top of the plate and the flow of the material was measured after 5 minutes. Comparative sample 21 showed a flow of 5.5 cm.

[0151] Comparative Sample 22 showed a flow of 3 cm.

[0152] Sample 23 of the present invention showed no flow.

[0153] Figure 1 is a photograph of the plate 1 minute after sample deposition.

[0154] Embodiment 4:

[0155] In this example, the characteristics of heat release, impact resistance, and shrinkage were evaluated.

[0156] The formulations were cast in Teflon molds to a thickness of approximately 2 mm.

[0157] The system was placed under a Delolux 03S UV lamp (Delo) at 8 cm from the source. The lamp had an emission spectrum from 320 to 600 nm and a power of 400 W. The system was irradiated for 1 minute and 30 seconds.

[0158] Table 4 summarizes the properties of these compositions measured after activation and polymerization: [Table 4]

[0159]

[0160] The inventive examples exhibit significantly controlled exotherms, less than the exotherm of Comparative Example 25 in the presence of glass beads known to dissipate the exotherm.

[0161] The examples in the presence of the block copolymer show a reduction in shrinkage, and in a more pronounced manner in the case of inventive examples 28 and 31.

Claims

1. A composition of matter comprising the following mixture C: - at least one block copolymer in a proportion between 50% and 99%; - hydrogenated castor oil in a proportion between 0.5% and 25%; - at least one fatty acid diamide and / or at least one fatty acid triamide in a proportion between 0.5% and 25%; The % is expressed as mass of the total mass C.

2. The composition according to claim 1, further comprising at least one mixture of monomers M, C in a mass proportion relative to the mass M+C of between 1% and 40%.

3. The composition according to claim 2, further comprising an initiator in a mass proportion of between 0.1% and 5% of the mass M.

4. The composition of claim 3, wherein the initiator is a free radical initiator.

5. The composition according to claim 4, wherein the initiator is a free radical initiator of the photoinitiator type.

6. The composition according to claim 3, wherein the initiator is a cationic initiator of the photoinitiator type.

7. The composition according to claim 2 or 3, further comprising one or more fillers D, the proportion of D by mass being between 5% and 80% of the material C+M+D.

8. The composition of claim 7, wherein the filler is inorganic.

9. The composition of claim 7, wherein the filler is organic.

10. The composition according to claim 7, wherein the filler is a combination of an inorganic filler and a filler obtained from a process of recycling textile materials or recycling thermosetting polymeric compositions or recycling composite materials.

11. The composition of claim 7, wherein the filler is glass beads.

12. The composition according to any one of claims 2 to 11, wherein M consists of a combination of monofunctional and polyfunctional monomers in respective mass ratios varying from 4 / 1 to 1 / 4.

13. The composition of claims 2 to 12, wherein the monofunctional monomer is selected from styrene, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and isobornyl (meth)acrylate and vinyl ethers, and the multifunctional monomer is selected from dipentaerythritol hexaacrylate, trimethylpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, 1,10 decanediol di(meth)acrylate, polyethylene glycol (meth)acrylate, multifunctional (meth)acrylates from renewable resources, such as vegetable oil (meth)acrylates, and vinyl ethers.

14. The composition according to any one of claims 1 to 13, wherein the one or more block copolymers are selected from diblocks or triblocks, alone or in combination, consisting of an A block having a Tg greater than 25°C and a B block having a Tg less than 0°C, which are linear or star-shaped and have the formula (A) n B or (B) n A, where n takes the value of 2 or 3.

15. A composition according to any one of claims 1 to 14, wherein: - said diamides are characterized in that they comprise at least one reaction product obtained from a reaction mixture comprising: a) at least one diamine, The diamine is selected from C2 to C24 and preferably C2 to C10 aliphatic diamines, C6 to C18 and preferably C6 to C12 alicyclic diamines, C6 to C24 and preferably C6 to C12 aromatic diamines, C7 to C24 aromatic aliphatic diamines and mixtures thereof; b) at least one carboxylic acid, The carboxylic acid is a C2 to C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or hydroxy-substituted C9 to C24 fatty acid, in particular valeric acid, hexanoic acid, heptanoic acid, octanoic acid, Nonanoic acid, decanoic acid, undecanoic acid, and preferably substituted with hydroxyl groups, among which 12-hydroxystearic acid (12-HSA), 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), 14-hydroxyeicosanoic acid (14-HEA) or mixtures thereof can be mentioned. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid, - said triamides are characterized in that they comprise at least one reaction product obtained from a reaction mixture comprising: a) at least one triamine, The triamine is selected from C2 to C24 and preferably C2 to C10 aliphatic triamines, C6 to C18 alicyclic triamines, C6 to C24 aromatic triamines, C7 to C24 aromatic aliphatic triamines or polyether triamines and mixtures thereof; b) at least one carboxylic acid, The carboxylic acid is a C2 to C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or hydroxy-substituted C9 to C24 fatty acid, in particular valeric acid, hexanoic acid, heptanoic acid, octanoic acid, Nonanoic acid, decanoic acid, undecanoic acid, and preferably substituted with hydroxyl groups, among which 12-hydroxystearic acid (12-HSA), 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), 14-hydroxyeicosanoic acid (14-HEA) or mixtures thereof can be mentioned. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid.

16. A composition according to any one of claims 2 to 15 in activated form.

17. Use of the composition according to claim 1 as an organic gelator in the formulation of monomers, sealants, adhesives or paints.

18. Use of the composition according to claims 3 to 16 in a method of impregnation, 3D printing, injection, extrusion, or molding of a composite.

19. A 3D printing method using the composition according to any one of claims 3 to 16.

20. Object obtained by means of the use according to claim 18.

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