Rheology control additive compositions

Abstract

The present invention relates to compositions of additives for controlling rheology and mechanical properties, which can be used in polymerizable compounds, sealants, paints, or adhesives. These compositions improve rheological control; in particular, they offer adjustable viscosity and yield stress. Due to the nature of their constituents, they enhance the mechanical properties of the formulations containing them.

Description

Title of the invention: Rheology control additive compositions Technical field

[0001] The present invention relates to compositions of additives for controlling rheology and mechanical properties, which can be used in polymerizable compositions, sealants, paints or adhesives. These compositions provide an improvement in the control of rheology; in particular, they have a viscosity and a threshold stress which can be adjusted. They also provide a reinforcement of the mechanical properties of the formulations containing them.

[0002] They are useful in formulations of polymerizable monomers, adhesives, mastics, or even paints and more generally in all formulations when an increase in viscosity and threshold stress are sought.

[0003] The formulation of the compositions of the invention provides solutions for manufacturing objects by a three-dimensional (3D) printing process, and more particularly large objects that can have dimensions of several meters and thicknesses of several centimeters. In addition, the compositions of the invention allow good dissipation of the exotherms generated during the polymerization of polymerizable formulations containing them. Due to the nature of the compositions of the invention, the mechanical properties of the formulations comprising these polymerized compositions are improved and the products obtained from polymerized formulations comprising the compositions of the invention exhibit low shrinkage. The compositions of the invention also allow good control of the rheology of the formulations of sealants, paint or even adhesives, with small quantities of these compositions. CONTEXT :

[0004] With the need to control the rheology of formulations of polymerizable monomers, mastics, paints or even adhesives, the need has arisen to constantly improve the behavior of these formulations. The use of rheology additives or mixtures of rheology additives is therefore common in these technical fields. In particular, viscous behavior is often sought for these formulations and sometimes the absence of flow during application.

[0005] For example, the monomers that are used in polymerization in different application fields most often have a very low viscosity because they are most often low molecular weight compounds. Their threshold 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 threshold constraint remains insufficient.

[0006] In formulations such as sealants and adhesives, paints, or in 3D printing, it is often necessary to increase the viscosity and the threshold stress of these formulations with or without monomer for application reasons and in particular to avoid material flow before the polymerization process is completed or when applying non-polymerizable formulations. Generally, compositions are sought whose flow is limited, or even non-existent, or even controlled depending on the areas of use. The exothermicity generated during the polymerization of the monomers must also be controlled to avoid potentially generated defects. Finally, polymerized monomer compositions generally have insufficient mechanical properties.

[0007] 3D printing is a technical field widely used in industry and leisure. This technology allows the preparation of individual objects 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 therefore allows additive manufacturing (AM) of a real object from a virtual object. It is based on cutting the 3D virtual object into thin 2D lamellae. These thin lamellae are deposited one by one, fixing them on the previous ones, which allows the real object to be manufactured. In the case of 3D printing using polymerization processes, fixing the lamellae on each other is possible when, for example, the material constituting the object is a composition of monomers extruded through a guided nozzle for the manufacture of the object which is polymerized once deposited on the previous layer.

[0009] Until now this approach to manufacturing objects was reserved for the manufacturing of small objects, most of the time being able to do away to a certain extent with perfect control of viscosity and threshold stress.

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

[0011] For example, in 3D printing of large objects, the rheology allowing good holding of the material at the nozzle outlet is much more demanding, exothermic phenomena are more present because the heat is difficult to eliminate and poorly controlled shrinkage after polymerization leads to poor quality objects. For the manufacture of large objects, thin lamellae are no longer superimposed but lamellae a few centimeters thick. The phenomena of flow and shrinkage during polymerization are exacerbated and are currently poorly resolved. When fa When building large objects, the user also seeks good mechanical resistance for these objects.

[0012] In the currently known state of the art, it is difficult to have a polymerizable formulation which allows the manufacture of large objects with good mechanical strength, while maintaining good control of shrinkage, limiting exothermicity and with good control of the dimensional definition of the different layers superimposed resulting from the rheology during the manufacturing process of these layers. The flow of the formulation to be polymerized is done through a nozzle and must maintain a dimensional strength characterized by sufficient viscosity and threshold stress. This set of technical problems is poorly resolved today.

[0013] Due to the low viscosity provided by the monomers, formulations comprising oligomers are used in the prior art, which complicates the formulations, increases costs, and does not always make it possible to obtain transparent compositions when desired. EP0802455 is an example with oligomers that are difficult to manufacture and therefore expensive.

[0014] In the extrusion of polymerizable compositions, WO21029945 uses a similar approach with the use of reactive oligomers in the form of acrylates. An alternative is described in WO21183396 but assumes an additional step of carrying out a pre-polymerization, this to increase the viscosity when used in a 3D printing process by the extrusion technique through a nozzle, but this adds an additional step. In these examples, despite the increases in viscosity, the threshold stresses remain low and a flow of the material is still observed.

[0015] The applicant sought to improve the formulations, one example of which is made up of monomers and initiator, because the sole combination of these components does not allow the correct construction of an object by polymerization under irradiation or thermally due to a viscosity and a threshold stress that are too low. The shrinkage during polymerization is also too great and the objects have many appearance defects.

[0016] The addition of block copolymers within these formulations makes it possible to improve the mechanical properties, which is known to those skilled in the art. The presence of block copolymers also makes a positive contribution to the rheology, which is also known to those skilled in the art.

[0017] However, the rheological behavior of these formulations remains insufficient or requires the use of large quantities of block copolymers without resolving the flow phenomena because the threshold stress remains insufficient.

[0018] Diamides and in particular fatty acid diamides are widely used in the field of formulation as agents allowing the control of rheology. For example, EP3613728 can be cited.

[0019] These diamides are sometimes associated with castor oil. Thus in EP3919546, compositions of diamides, hydrogenated castor oil and a particular polyamide, either two by two or all three together, are disclosed as rheology additives.

[0020] In EP3131996 the combination of polyamide and hydrogenated castor oil is also described.

[0021] It is found that the changes in rheology associated with the use of these diamides and hydrogenated castor oil, in combination or not, are insufficient with regard to the needs that can be generated by formulations whether they are polymerizable or not, in mastics, paints or even in adhesives. In the case of polymerizable formulations, the particular case of 3D printing applications is a good example of the need to control the rheology of the formulations.

[0022] When using these compounds, combined with one or more monomers, it is necessary to use large quantities to have a significant effect. This can have the consequence of degrading certain properties of the polymerized monomer formulations.

[0023] The combination of block copolymer, diamides and / or triamides and hydrogenated castor oil in a polymerizable monomer formulation, i.e. in the presence of a polymerization initiator, is an example of a solution to the technical problems relating to control of rheology, mechanical properties and control of polymerizations. In particular, very significant effects of increasing viscosity and yield stress are observed even when using small amounts of the compositions of the invention. The combination of block copolymer, diamides and / or triamides and castor oil provides a surprising effect and makes it possible to limit the amount of these additives while providing improvements in the mechanical properties of the products obtained and with exothermicity during polymerizations that is better controlled than in the absence of the combination of these three compounds.The combined use of block copolymers, amides and castor oil therefore provides a number of unexpected technical effects (improved rheology, improved mechanical properties, limited exotherms and shrinkage).

[0024] Thus, in addition to the monomer component(s), the applicant has found that the combination of small amounts of castor oil, diamide and / or triamide, and block copolymers provides a viscosity and a threshold stress in line with the needs generated in formulations of sealants and adhesives, paints, or in 3D printing. The combined presence of block copolymer, amide and hydrogenated castor oil is necessary to maximize the effects on the rheology of the formulations containing them, and the technical effect obtained is much greater than the combination of only two of these compounds.

[0025] In the case of 3D printing, the compositions of the invention formulated with monomers exhibit good bead strength of the formulation before polymerization and allow their placement on the previously polymerized layer without defect. The objects obtained using these compositions also exhibit good mechanical properties. The combination of castor oil, diamide and / or triamide, and block copolymers within a composition comprising one or more monomers makes it possible to obtain a significant effect making it possible to solve existing technical problems in applications requiring high viscosities or adjustment of these viscosities, with sufficient threshold constraints, and this with small quantities of these compounds.

[0026] The amounts of castor oil, diamide and / or triamide, and block copolymers can be variable and make it possible to finely adjust the rheological constraints linked to the formulation of mastics, adhesives, paints and during the manufacture of objects by 3D printing, while providing advantages in terms of shrinkage, exothermic control and mechanical properties. Fillers can be added to the compositions of the invention formulated with monomers while retaining the advantage of the combination of castor oil, diamide and / or triamide, and block copolymers.

[0027] The compositions of the invention can 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 compositions of the invention, fillers derived from the recycling of polymer materials, whether filled or not, such as composite materials, can be included, which provides the compositions of the invention with a favorable carbon footprint and recyclability of the materials at the end of their life. Summary of the invention

[0028] The invention relates to a mass composition comprising the following mixture C:

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

[0030] - hydrogenated castor oil in proportions of between 0.5 and 25%;

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

[0032] The % being expressed in mass form for the total mass of C. Description of the embodiments

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

[0034] By organogelator is meant compositions making it possible to modify the rheology of liquid formulations.

[0035] The block copolymers useful in the context of the present invention are multi-block copolymers, preferably not containing butadiene. They consist of blocks A (called hard blocks) having a glass transition temperature Tg greater than 25°C, preferably greater than 50°C and more preferably greater than 70°C, and blocks B (called soft blocks) having a Tg less than 0°C, preferably less than -25°C, of ​​formula (AB)m with m taking the values ​​between 2 and 1000 and preferably between 4 and 500, or preferably linear or star-shaped copolymers of formula (A)nB or (B)nA, and preferably (A)nB, with n taking the values ​​of 2 or 3, that is to say di-block or tri-block copolymers and preferably tri-block, linear or star-shaped. A combination of di-block and tri-block copolymers constitutes a variant of the invention.

[0036] The term "glass transition temperature" or "Tg" designates the temperature at which the polymer material passes from the glassy state to a non-glassy state corresponding to a certain mobility of the polymer chains between them. 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" designates a copolymer having a plurality of different polymer segments, each segment, also referred to as a "block", being made up of a chain of monomers which may be identical or different. Thus, each segment or block may be a homopolymer or a copolymer.

[0038] Preferably, the blocks A comprise the chain of monomers chosen from linear or branched alkyl (meth)acrylates from C 1 to C 12, encyclic or not, substituted or not by polar and / or hydrophilic functions, and in particular methyl methacrylate, optionally resulting from a recycling process by depolymerization, styrene and substituted styrenes, isobornyl (meth)acrylates, (meth)acrylic acids as well as alkyl acrylamides.

[0039] By polar and / or hydrophilic, we mean groups such as carboxylic (-COOH), hydroxyl (-OH), amide (-CONH) groups, or even ethylene glycol or polyethylene glycol substituted or not on their terminal function by alkyl, phosphate, phosphonate or sulfonate groups.

[0040] More preferably, the blocks A comprise the chain of monomers alone or in combination chosen from methyl methacrylate, optionally derived from a depolymerization recycling process, styrene, isobutyl acrylate, acrylic acid or methacrylic acid, dimethyl acrylamide, diethyl acrylamide or isopropyl acrylamide.

[0041] According to a variant, the following monomers may be part of block A: hydroxylated (meth)acrylates, in particular 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, polyethylene glycol or glycol (meth)acrylates substituted or not on their terminal function by alkyl, phosphate, phosphonate or sulfonate groups.

[0042] Preferably, the blocks B will preferably consist of the chain of monomers chosen from butyl acrylate, acrylate of 2- ethylhexyl, octyl, nonyl, lauryl acrylate and mixtures thereof, optionally mixed with styrene. More preferably, the B-blocks consist of a chain of butyl acrylate monomers.

[0043] The following non-limiting tri-block ,di-block and star triblock copolymers usable within the scope of the invention, alone or in mixture, can thus be cited:

[0044] pMMA-pBuA-pMMA, p(MMAcoMAA)-pBuA-p(MMAcoMAA), p(MMAcoAA)-pBuA-p(MMAcoAA), pMMA-p(BuAcoSty)-pMMA, p(MMAcoMAA)-p(BuAcoSty)-p(MMAco-AMA), pMMAco-AA p(MMAco DMA)-pBuA- p(MMAco DMA), p(MMAco IPA)-pBuA- p(MMAco IPA) and preferably p(MMAco DMA)-pBuA- p(MMAco DMA), p(MMAco IPA)-pBuA- p(MMAco IPA), pMMAco-pBuA-p.

[0045] pMMA-pBuA, p(MMAcoMAA)-pBuA, p(MMAcoAA)-pBuA, pMMA-p(BuAcoSty), p(MMAcoMAA)-p(BuAcoSty), pMMA-p(BuAcoAA), p(MMAco DMA)-pBuA-, p(MMAco IPA)-pBuA- p(MMAco DMA)-pBuA, p(MMAco IPA)-pBuA.

[0046] pBuA-(pMMA)3, pBuA-(p(MMAcoMAA))3, pBuA-(p(MMAcoAA))3, p(BuAcoSty)-(pMMA)3, p(BuAcoSty)-(p(MMAcoMAA))3, p(BuAcoAA)-(pMMA)3, pBuA- (p(MMAco DMA))3, pBuA- (p(MMAco IPA))3 and preferably pBuA-(p(MMAco DMA))3, pBuA- (p(MMAco IPA))3, p(BuAcoSty)-(p(MMAcoMAA))3.

[0047] In all these block copolymers, MMA may be substituted in whole or in part by IBOA and / or IBOMA.

[0048] With MMA: methyl methacrylate, MAA: methacrylic acid, AA: acrylic acid, BuA: butyl acrylate, Sty: styrene, DMA: dimethylacrylamide, IPA: isopropylacrylamide, IBOA: isobornyl acrylate, IBOMA: isobornyl methacrylate

[0049] The block copolymers useful in the context of the present invention typically have a molecular weight by weight measured by SEC with a calibration po lystyrene between 10,000 and 200,000 g / mol and preferably between 80,000 and 180,000 g / mol, with a hard block / soft block mass ratio between 75 / 25 and 40 / 60.

[0050] The block copolymers useful in the context of the present invention are preferably prepared by controlled radical polymerization, without excluding other methods of preparation. Controlled radical polymerizations make it possible to obtain the block copolymers in sequential steps within the same process operation. For example, the block copolymers can be prepared by "RAFT" (Radical Addition Fragmentation Transfer) polymerization or by nitroxide-controlled polymerization, also called "NMP" (Nitroxide Mediated Polymerization). Preferably, the block copolymers are prepared by NMP, in particular by NMP using the counter radical N-tert-Butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide. The synthesis of block copolymers using this counter radical is described in particular in EP1526138.

[0051] The block copolymers are present within the mixture C in mass proportions of between 50 and 99%, preferably between 60 and 95% and more preferably between 70 and 95%, limits included.

[0052] Hydrogenated castor oil is a compound found commercially under CAS No. 8001-78-3. Hydrogenated castor oil consists of 85 to 90% by mass of ricinolic acid triglyceride, a large part of the double bond of which is hydrogenated. It also contains, in smaller quantities, hydrogenated linolenic acid triglycerides, hydrogenated oleic acid triglycerides, and hydrogenated stearic acid triglycerides, the main ones.

[0053] The hydrogenated castor oil is present in the mixture C in mass proportions of between 0.5 and 25%, preferably between 2.5 and 20% and more preferably between 2.5 and 15%, limits included.

[0054] The compositions of the invention comprise at least one polyamide, that is to say compounds comprising at least two amide functions. Preferably, it is at least one fatty acid diamide and / or at least one fatty acid triamide.

[0055] The diamides of the compositions of the invention may be diamides resulting from the condensation of at least one diamine on at least one acid or of at least one diacid on at least one amine.

[0056] The triamides of the compositions of the invention may be triamides resulting from the condensation of at least one triamine on at least one acid or of at least one triacid on at least one amine.

[0057] According to a first preference, these are diamides resulting from the condensation of at least one diamine on at least one fatty acid.

[0058] According to a second preference, these are triamides resulting from the condensation of at least one triamine on at least one fatty acid.

[0059] According to a third preference, it is a mixture of diamides resulting from the condensation of at least one diamine on at least one fatty acid and triamides resulting from the condensation of at least one triamine on at least one fatty acid.

[0060] The diamides are characterized in that they comprise at least one reaction product obtained from a reaction mixture comprising:

[0061] a) at least one diamine

[0062] The diamine being chosen from a C2 to C24 aliphatic diamine, and preferably a C2 to C10 aliphatic diamine, a C6 to C18 cycloaliphatic diamine, and preferably a C6 to C12 aliphatic diamine, a C6 to C24 aromatic diamine, and preferably a C6 to C12 aliphatic aryl diamine, and mixtures thereof;

[0063] b) at least one carboxylic acid

[0064] The carboxylic acid being a C2 to C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or substituted by a hydroxyl group, C9 to C24 fatty acid, in particular pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid,

[0065] nonanoic acid, decanoic acid, undecanoic acid and preferably substituted by a hydroxyl group among which we can cite 12-hydroxy stearic acid (12-HSA), 9- or 10-hydroxy stearic acid (9-HSA or 10-HSA), 14-hydroxy eicosanoic acid (14-HEA) or their mixtures. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid.

[0066] The triamides are characterized in that they comprise at least one reaction product obtained from a reaction mixture comprising:

[0067] a) at least one triamine

[0068] The triamine being chosen from a C2 to C24 aliphatic triamine, and preferably a C2 to C10 aliphatic triamine, a C6 to C18 cycloaliphatic triamine, a C6 to C24 aromatic triamine, a C7 to C24 aliphatic aryl triamine, or polyether triamines, and mixtures thereof;

[0069] b) at least one carboxylic acid

[0070] The carboxylic acid being a C2 to C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or substituted by a hydroxyl group, C9 to C24 fatty acid, in particular pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid,

[0071] nonanoic acid, decanoic acid, undecanoic acid and preferably substituted by a hydroxyl group among which we can cite 12-hydroxy stearic acid (12-HSA), 9- or 10-hydroxy stearic acid (9-HSA or 10-HSA), 14-hydroxy eicosanoic acid (14-HEA) or their mixtures. Carboxylic acid The most preferred hydroxylated acid is 12-hydroxystearic acid.

[0072] At least one diamide and / or one triamide is present within the mixture C in mass proportions of between 0.5 and 25%, preferably between 2.5 and 20% and more preferably between 2.5 and 15%, limits included.

[0073] The mass ratio (hydrogenated castor oil) / (diamide and / or triamide) is between 1 / 4 and 4 / 1, and preferably between 1 / 3 and 2 / 3.

[0074] The compositions of the invention may also comprise a mixture M of monomers in mass proportions of the mixture C of between 1 and 40% relative to the mass C+ M, and preferably from 1 to 20% relative to the mass C+ M.

[0075] Thus, the present invention comprises the compositions of the invention of the mixture C and at least one mixture M of monomers as well as the use of this mixture in polymerizable formulations. The monomers of the mixture M used in the compositions of the invention may be mono or multifunctional, in combination or not. They are preferably derived from renewable resources. Functional is understood to mean an entity having a polymerizable double bond.

[0076] The monofunctional monomers may be styrene and substituted styrenes, linear or branched alkyl (meth)acrylates from C 1 to C 12, cyclic or not, substituted or not, alkoxyalkyl (meth)acrylates, and in particular methyl methacrylate, optionally resulting from a recycling process by depolymerization, isobornyl (meth)acrylates with additional functionalities or not, the additional functionalities when present being able to be of the hydroxy, amine, epoxy, amide, or even phosphorus type. When rapid kinetics are desirable, acrylates will preferably be chosen.

[0077] Among the preferred monomers of the invention, mention will be made in particular of styrene, methyl, ethyl, butyl, isobornyl (meth)acrylates. Preferably, it is styrene, methyl methacrylate, optionally resulting from a recycling process by depolymerization, or isobornyl acrylate, alone or in combination.

[0078] More preferably, it is methyl methacrylate from a recycling process by depolymerization and / or isobornyl acrylate from renewable resources.

[0079] The multifunctional monomers carry methacrylic or acrylic functions and preferably acrylic functions among which we can cite di-pentaerythritol hexaacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, dimethylolpropane tetraacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol triacrylate, polyalkoxylated pentaerythritol tetra acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate 1,10 decanediol di (meth)acrylate, polyethylene (meth)acrylates glycol, dipropylene glycol diacrylate, tripropylene glycol diacrylate, multifunctional (meth)acrylates from renewable resources, such as (meth)acrylates from vegetable oils and preferably acrylates from vegetable oils. With regard to monomers carrying several (meth)acrylate functions of renewable origin, we can cite the monomers from the company Sartomer in the Sarbio ® range, and more particularly the references 6201 (polyethylene glycol 200 dimethacrylate), 6202 (1,10 dodecane diol diacrylate), 7101 (epoxy acrylate), 7106 (linseed oil acrylate), 7107 (epoxidized soybean oil diacrylate), 7205 (polyester oligomer acrylate).

[0080] Preferably, these are monomers derived from renewable resources such as acrylates of vegetable oils (linseed, soybean, corn, sunflower, tung).

[0081] A combination of several monomers is preferred within the scope of the invention and preferably a combination of monofunctional monomers in acrylate functions and multifunctional monomers in acrylate functions (di, tri, tetra, penta and hexa acrylate).

[0082] Monomers of the vinyl ether type may also be present within the scope of the invention, in particular when the polymerization is initiated by a cationic process. They may be of any type, monofunctional or multifunctional in vinyl functions.

[0083] Preferably, a combination of monofunctional and multifunctional monomers will be used in respective mass ratios varying from 4 / 1 to 1 / 4.

[0084] The compositions C of the invention comprising a mixture M of monomers can be polymerized using a radical or cationic polymerization initiator which may or may not be activated with the aid of electromagnetic radiation in mass proportions of between 0.1 and 5% of the mass of the composition M. The activation of the initiators can also be carried out thermally. Preferably, these are polymerization initiators sensitive to electromagnetic radiation and more particularly to ultraviolet (UV) radiation. Such initiators are called photoinitiators.

[0085] Thus, the invention also relates to the compositions of the invention comprising at least one monomer, an initiator, and more particularly a photoinitiator sensitive to Ultraviolet (UV) radiation.

[0086] Photoinitiators are compounds capable of generating free radicals or cations when these compounds are exposed to electromagnetic radiation. Preferably, the electromagnetic radiation has wavelengths in the ultraviolet or visible range, but it would not be outside the scope of the invention to use wavelengths in shorter (X-rays or gamma rays) or longer (infrared or beyond) wavelength ranges.

[0087] The photoinitiators can be of any type. Preferably, they are chosen in the context of a radical polymerization from those which generate free radicals by a homolytic cleavage reaction in the a position relative to the carbonyl group, such as benzoin ether derivatives, hydroxyalkylphenones, such as Phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and in the [3] position such as ketone sulfides and sulfonyl ketone derivatives, those which form free radicals by abstraction of hydrogen from a hydrogen donor, such as benzophenones or thioxanthones. The process involves a charge transfer complex with an amine, then an electron and proton transfer to lead to the formation of an initiating alkyl radical and an inactive ketyl radical.Examples include benzyl diacetals, hydroxyalkyl phenones, alpha amino ketones, acyl phosphine oxides, benzophenones, thioxanthones and in particular Phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide.

[0088] It would not be outside the scope of the invention to use a combination of several photoinitiators, or a combination of photoinitiators and radical initiator(s) whose radicals are generated thermally or by an oxidation-reduction reaction, for example the methylene bis (diethyl malonate)-cerium IV couple, an aromatic amine of the toluidine type or the H2O2 / Fe2+ couple.

[0089] Among the initiators combined with the photoinitiators or used alone, mention may be made of diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals, azo compounds. Suitable radical initiators are, for example, isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, 2-ethyl tert-butyl perhexanoate, cumyl hydroperoxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, amyl perpivalate, tert-butyl peroctoate.

[0090] In the case of cationic polymerization, the photoinitiators will be compounds of the photoacid generator type which release acid species such as protons under electromagnetic irradiation such as onium salts, for example diaryliodonium or triarylsulfonium salts, and ferrocenium salts.

[0091] The compositions C comprising a mixture M of monomers and initiator may additionally comprise one or more fillers D. Thus the invention also comprises the compositions of the invention C in the presence of a mixture M of monomers, initiator and fillers D.

[0092] The fillers that can be used in the context of the invention may be mineral or organic fillers. Among the mineral fillers, mention may be made, without limitation, of glass, preferably in the form of beads, calcium carbonate, talc, mica, kaolin, clays, sands, barium sulfate, feldspar, calcium phosphate, silicas. Preferably, these are glass beads whose size varies from 50 to 1000 pm in volume and preferably between 50 and 500 pm and more preferably from 80 to 200 pm and calcium carbonate whose size varies from 50 to 1000 pm in volume and preferably between 50 and 500 pm and more preferably from 80 to 200 pm

[0093] The organic fillers that can be used in the context of the invention can be chosen in a non-limiting manner from wood, cork, cereals, flax, fruit bark or pits. The organic fillers can also be products resulting from the processes of recycling textile materials but also from the recycling of thermosetting polymer compositions, or even from the recycling of composite materials, that is to say fillers themselves that can be composed of organic and mineral materials.

[0094] It is also possible to combine fillers, whether mineral or organic, from textile recycling processes or from the recycling of thermosetting polymer compositions, or from the recycling of composite materials.

[0095] Thus the combination of mineral fillers and fillers from recycled materials improves the carbon footprint of the composition. With the omnipresence of composite materials today, being able to recycle them has become an important issue. Thus, one of the preferred compositions of the invention comprises a mixture of mineral fillers and fillers from the recycling of composite materials and more particularly glass beads with composite materials.

[0096] By composite material is meant an assembly of at least two immiscible materials.

[0097] The fillers D may be present in mass proportions of D of between 1 and 80% of the mass C + M + D and preferably between 50 and 80% of the mass C + M + D.

[0098] The compositions of the invention have the best rheological characteristics after activation. Activation means a stay under agitation of the compositions of the invention at a temperature between 25 and 80°C, preferably between 60 and 80°C, for a time between 30 minutes and 8 hours, formulated with other components such as monomers, initiators or fillers. This step can be completed in a dedicated capacity or in a mixing tool such as an extruder which in the case of 3D printing can be the extrusion device upstream of the nozzle arranging the material within the manufacturing process of the 3D part.

[0099] Thus the invention also includes the compositions of the invention in the presence of monomers M, initiators or fillers in activated form.

[0100] The activation step often described as a disadvantage presents an advantage in the present invention. Thus it is possible to easily mix the compositions of the invention with fillers for example, before the activation step because at this stage the viscosity of the mixture is minimized. Obtaining a homogeneous mixture is facilitated and the mixture can then be activated according to known means, typically by applying a temperature and stirring for a given time. The activated mixture then has the desired viscosity and threshold stress characteristics.

[0101] Once polymerized, the compositions of the invention have good mechanical properties and little shrinkage. The exothermicity is controlled and the objects produced by 3D printing do not have any defects.

[0102] The invention therefore also relates to a 3D printing method using the compositions of the invention as well as the objects obtained using this method.

[0103] The invention also relates to the use of the compositions of the invention in injection, extrusion, molding or any other process for shaping thermoplastic materials such as the impregnation of composites, as well as the objects thus obtained.

[0104] The compositions of the invention may also comprise additional additives among which may be mentioned, without limitation, UV stabilizers, plasticizers, antioxidants.

[0105] Figure: [Fig.l] illustrates the flow of formulations comprising the compositions of the invention and comparative compositions. Examples

[0106] The following examples illustrate the invention in a non-limiting manner.

[0107] Raw materials used:

[0108] Methyl methacrylate (MMA) from Aldrich is used as a low molecular weight and therefore low viscosity monomer model. It is used as a monomer in the examples showing viscosity and yield stress using compositions of the invention or without the compositions of the invention.

[0109] Isobornyl acrylate (IBOA) is used in the most representative examples of the compositions of the invention, in combination with Sarbio® 7107 which is a monomer from the company Sartomer and having two acrylate functionalities and derived from vegetable oil (epoxidized soybean oil diacrylate).

[0110] The hydrogenated castor oil (HCO) used is from Aldrich.

[0111] A diamide usable in the context of the invention is prepared in the following way:

[0112] In a 1 liter flask equipped with a thermometer, a Dean Stark, a condenser and a stirrer, 25.8 grams are introduced under a stream of nitrogen of ethylenediamine (i.e. 0.43 moles, 0.86 amine equivalents), 135.52 grams of 12-hydroxystearic acid (i.e. 0.43 moles, 0.43 acid equivalents), from Aldrich, 49.94 grams of hexanoic acid (i.e. 0.43 moles, 0.43 acid equivalents) from Aldrich. The mixture is heated to 200°C still under a stream of nitrogen. The eliminated water accumulates in the Dean Stark from 150°C. The reaction is controlled by the acid and amine values. When the acid and amine values ​​are 5 and 3.5 mg KOH / g respectively, the reaction mixture is cooled to 150°C and 0.65 g of sulfuric acid is added. The amine value checked 30 minutes later is less than 0.01 mg KOH / g. The reaction mixture is then discharged into a silicone mold. Once cooled to room temperature, the product is micronized in an air jet mill.

[0113] This diamide is used in Examples 1 to 4.

[0114] The block copolymers used are of two types:

[0115] -pMMA-pBuA-pMMA denoted BCP 1.

[0116] -p(MMA co IPA)-pBuA- p(MMA co IPA) denoted BCP 2.

[0117] The block copolymers are prepared according to a protocol described for example in EP1526138.

[0118] The fillers used are glass beads. TechBeads® 90-150 available from Weissker GmbH.

[0119] The photoinitiator used is irgacure® 819 available from Aldrich.

[0120] Measurement methods:

[0121] Measurement of the glass transition temperature by DMA:

[0122] The DMA is determined using a Rheometric Scientific ARES rheometer under the following conditions:

[0123] - Rectangular torsion geometry;

[0124] - Shear deformation at a frequency of 1 Hz;

[0125] -Temperature range from -125 to 150°C.

[0126] -The viscosity is measured with an Anton Paar MCR301 device at 25°C and a shear gradient of 0.1 to 100 s1, with a duvet geometry and a CC27-SN13118 spindle.

[0127] -The threshold stress is measured with an Anton Paar MCR301 device at 25°C with a duvet geometry and a CC27-SN13118 mobile. The measurement is carried out in stress gradient from 1 to 100 Pa.

[0128] -Shrinkage is measured by a difference in density of the formulations before and after photopolymerization. The density of the formulation is measured using a 10 mL picnometer. The density of the solid (product obtained from the formulation) is obtained by measuring the mass in water and in air.

[0129] Exothermicity: Exothermicity is determined by calculating the difference between the tem temperature measured during polymerization using a temperature probe and the temperature in the oven.

[0130] Shock: ISO 179-1:2010.

[0131] The activation of the formulations comprising the compositions of the invention is carried out at 60°C with stirring (at 3000 rpm) for 6 hours.

[0132] Example 1:

[0133] In this example, the viscosities and threshold stresses are measured for compositions of the invention and comparative compositions after activation, with the methyl methacrylate monomer (MMA).

[0134] Table 1 shows the characteristics measured for these compositions:

[0135] [Tables 1] table 1 MMA% 8CP1 % diamide % HCO% Viscosity (Pa.s| at 1s'* stress at south (Pa) 1 comparative 100 0 0 0 <1 non-existent 2 comparative 98.6 0 0.7 0.7 1 non-existent 3 comparative 70 30 0. 0 0.8 non-existent 4 comparative 70 29 1 0 0.9 non-existent 5 comparative 70 29 0' 1 0.8 non-existent 6 invention 70 29 0 3 0.5 19.2 8

[0136] It is noted in Table 1 that only the composition of the invention has a high level of viscosity and a measurable threshold stress.

[0137] Example 2:

[0138] In this example, the viscosities and threshold stresses are measured for compositions of the invention and comparative compositions after activation with isobornyl acrylate (IBOA) and Sarbio® 7107 monomers.

[0139] Table 2 shows the characteristics measured for these compositions.

[0140] [Tables2] table 2}BOA % Sarbio® 7107 8CP2 % diamide % HCO % Viscosity (Pa.s) at ls-1 stress at threshold (Pa) 7 comparative 80 20 Ô OO 0.04 non-existent 8 comparative 76.,2 19 4.8 O 0 0.12 non-existent 9 comparative 75.,2 19 4.8 1 o 0.15 non-existent 10 comparative 75.2. 19 4.8 0 1 0.12 non-existent 11 invention 75.2 19 4.8 0.5 0.5 7.7 5 12 comparative 56 14 30 O 0 58 non-existent 13 comparative 63 16 21 O o 8 non-existent 14 comparative 53 16 70 1 0 7 non-existent 15 comparative 63 16 2'0 G 1 8 non-existent 16 invention 63 16 20 0.5 0.5 14.4 5 17 invention 63 16 19 1 1 38.3 26 18 invention 61 15.2 19.2 2 3 2.3 183 44

[0141] In Table 2 it can be seen that the best viscosity and threshold stress characteristics are provided by the compositions of the invention. Comparative Example 12, which has very high proportions of block copolymer, has an acceptable viscosity level but does not have a measurable threshold stress.

[0142] Example 3:

[0143] In this example, the threshold stresses are measured for compositions of the invention and comparative compositions in the presence of fillers (glass beads) after activation, with the monomers isoborole acrylate (IBOA) and Sarbio® 7107.

[0144] Table 3 shows the characteristics measured for these compositions:

[0145] [Tables 3] table 3 glass beads % IBOA% Sarbio* 7107 % BCP2 % diamide % HCD % stress at threshold' (Pa) 19 comparative 70 22.8 5.7 1.5 0 Q 5 20 invention 70 NJ in 5.7 1.5 0.15 0.2 25 21 comparative 75 19 4.75 1.25 0 o 5 22 comparative 75 19.8 4.95 0 0.125 0.1 50 23 invention 75 18.8 4.7 1.25 0.125 0.1 100'

[0146] In Table 3, with compositions of the invention in the presence of fillers (glass beads), the threshold stresses are maximum with the compositions of the invention.

[0147] A flow test was carried out on aluminum plates arranged at an angle of 15° to the vertical. 5 g of sample were placed at the top of the plates and the flow of material was measured after 5 minutes. Comparative sample 21 showed a flow of 5.5 cm.

[0148] Comparative sample 22 has a flow of 3 cm.

[0149] The sample of the invention 23 does not exhibit any flow.

[0150] [Fig.l] is a photo of the plates 1 minute after depositing the samples.

[0151] Examples 4:

[0152] In this example the exothermicity, impact resistance and shrinkage characteristics are evaluated.

[0153] The formulations are poured into a Teflon mold to a thickness of approximately 2mm.

[0154] The system is placed under a DELOLUX 03S UV lamp (DELO) 8cm from the source. The lamp has an emission spectrum of 320 to 600 nm and a power of 400W. The system is irradiated for 1 minute 30 seconds.

[0155] Table 4 shows the characteristics measured for these compositions after activation and polymerization:

[0156] [Tables4] table 4 glass beads % IBOA %' Sarbio* 7107 % BCP2 % diamide % HCO Photo- initiator shock (KJ / m2) exothermicity rq shrinkage % 24 comparative 0 98 0 0 0 0 2 74 25 comparative 75 24.5 0 0 0 0 0.5 6 26 comparative 0 93.1 0 4.9 0 0 2 37 7.4 27 comparative 0 88.2 0 9.8 0 0 2 21 6.1 28 invention 0 87.2 0 9.8 0.5 0.5 2 6 4 29 comparative 0 0 97 0 0.5 LÙ Q 2 3.2 30 comparative 0 78 19 0 0.5 0.5 2 8.6 5.8 31 invention 0 74 18 5 0.5 0.5 2 11.8 4.6 32 comparative 0 97 0 0 0.5 0.5 2 7.2

[0157] The example of the invention shows a clearly controlled exothermicity, lower than that of comparative example 25 in the presence of glass beads which are known to dissipate exothermicity.

[0158] The examples in the presence of the block copolymer show a reduction in shrinkage, and this is more pronounced in the case of examples of the invention 28 and 31.

Claims

Claims

1. Mass composition comprising the following mixture C: - at least one block copolymer in proportions of between 50 and 99%; - hydrogenated castor oil in proportions of between 0.5 and 25%; - at least one fatty acid diamide and / or at least one fatty acid triamide in proportions of between 0.5 and 25%; The % being expressed in mass form for the total mass C.

2. Composition according to claim 1 further comprising a mixture M of at least one monomer in mass proportions of C of between 1 and 40% relative to the mass M + C.

3. Composition according to claim 2 further comprising initiator in mass proportions of between 0.1 and 5% of the mass M

4. 1V1. Composition according to claim 3 in which the initiator is a radical initiator.

5. Composition according to claim 4 in which the initiator is a radical initiator of the photo-initiator type.

6. Composition according to claim 3 in which the initiator is a cationic initiator of the photoinitiator type.

7. Composition according to 2 or 3 additionally comprising one or more fillers D in mass proportions D of between 5 and 80% of the filler C+M+D.

8. Composition according to claim 7 in which the fillers are mineral.

9. Composition according to claim 7 in which the fillers are organic.

10. Composition according to claim 7 in which the fillers are a combination of mineral fillers and fillers resulting from a process of recycling textile materials or recycling thermosetting polymer compositions, or even recycling composite materials.

11. Composition according to claim 7 in which the fillers are glass beads.

12. Composition according to one of claims 2 to 11 in which M consists of a combination of monofunctional and multi-functional monomers. functional in respective mass ratios varying from 4 / 1 to 1 / 4.

13. Composition according to claim 2 to 12 in which the monofunctional monomers are chosen from styrene, methyl, ethyl, butyl, isobornyl (meth)acrylates, vinyl ethers and the multifunctional monomers are chosen from dipentaerythritol hexaacrylate, trimethylpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate 1,10 decanediol di (meth)acrylate, polyethylene glycol (meth)acrylates, multifunctional (meth)acrylates from renewable resources, such as vegetable oil (meth)acrylates, vinyl ethers.

14. Composition according to one of claims 1 to 13 in which the block copolymer(s) are chosen from di-blocks, tri-blocks, alone or in combinations, consisting of A blocks having a Tg greater than 25°C, and B blocks having a Tg less than 0°C, linear or star-shaped, of formula (A)nB or (B)nA, with n taking the values of 2 or 3.

15. Composition according to one of claims 1 to 14 in which: - the 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 being chosen from a C2 to C24 aliphatic diamine, and preferably a C2 to C10 aliphatic diamine, a C6 to C18 cycloaliphatic diamine, and preferably a C6 to C12 aliphatic diamine, a C6 to C24 aromatic diamine, and preferably a C6 to C12 aliphatic aryl diamine, and mixtures thereof;b) at least one carboxylic acid The carboxylic acid being a C2 to C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or substituted by a hydroxyl group, C9 to C24 fatty acid, in particular pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid and preferably substituted by a hydroxyl group, among which mention may be made of 12-hydroxy stearic acid (12-HSA), 9- or 10-hydroxy stearic acid (9-HSA or 10-HSA), 14-hydroxy eicosanoic acid (14-HEA) or mixtures thereof. The most hydroxylated carboxylic acid;

16.

17.

18.

19.

20. preferred is 12-hydroxystearic acid, - the 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 being chosen from a C2 to C24 aliphatic triamine, and preferably a C2 to C10 aliphatic triamine, a C6 to C18 cycloaliphatic triamine, a C6 to C24 aromatic triamine, a C7 to C24 aliphatic aryl triamine, or polyether triamines, and mixtures thereof; b) at least one carboxylic acid The carboxylic acid being a C2 to C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or substituted by a hydroxyl group, C9 to C24 fatty acid, in particular pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid and preferably substituted by a hydroxyl group among which mention may be made of 12-hydroxy stearic acid (12-HSA), 9- or 10-hydroxy stearic acid (9-HSA or 10-HSA), 14-hydroxy eicosanoic acid (14-HEA) or mixtures thereof. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid. Composition according to one of claims 2 to 15 in activated form. Use of the composition according to claim 1 as an organo-gelator in a formulation of monomers, mastics, adhesives, paints. Use of a composition according to claims 3 to 16 in a 3D printing process, by injection, extrusion, molding or impregnation of composites. 3D printing method using a composition according to one of claims 3 to 16. Object obtained using a use according to claim 18.

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