Rheology control additive composition

Abstract

The present invention relates to an additive composition for controlling rheology and mechanical properties, which can be used in polymerizable compositions, sealants, paints or adhesives. These compositions bring about an improvement in the control of rheology and have, in particular, a viscosity and a yield stress that can be adjusted. The present composition brings about a strengthening of the mechanical properties of the formulations containing them, depending on the nature of the components therein.

Description

Technical Field

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

[0002] They are useful in all formulations in which an increase in viscosity and yield stress is desired, more generally in formulations of polymerizable monomers, adhesives, sealants or paints.

[0003] The formulations of the compositions of the present invention provide a solution for manufacturing objects by three-dimensional (3D) printing methods, more particularly large objects that can have dimensions of several meters and a thickness of several centimeters. Furthermore, the compositions of the present invention enable the effective dissipation of the heat generated during the polymerization of the polymerizable formulations containing them. Due to the properties of the compositions of the present invention, the mechanical properties of the formulations containing these polymer compositions are improved and the products obtained from the polymer formulations containing the compositions of the present invention exhibit low shrinkage. The compositions of the present invention also make it possible to effectively control the rheology of sealants, paints or adhesive formulations with small amounts of these compositions.

Background Art

[0004] The need to control the rheology of polymerizable monomer formulations, sealants, paints or adhesives has led to a continuous need to improve the behavior of these formulations. Thus, the use of rheology additives or mixtures of rheology additives is common in these technical fields. In particular, these formulations often desire a viscous behavior and sometimes no flow during application.

[0005] For example, monomers used in polymerization in various application fields are usually low molecular weight compounds and thus usually have a very low viscosity. Their yield stress is close to 0. The use of functional oligomers or the addition of polymers can increase the viscosity but can cause other drawbacks and the yield stress remains insufficient.

[0006] In formulations such as sealants and adhesives, paints, or 3D printing, for application reasons, it is often necessary to increase the viscosity and yield stress of these formulations regardless of the presence or absence of monomers, especially to avoid the flow of materials before the polymerization process is completed or during the application of non-polymerizable formulations. Generally, compositions in which the flow is restricted or even non-existent or otherwise controlled depending on the field of use are desirable. The exothermicity generated during the polymerization of monomers also has to be managed to avoid potential defects that may occur. Finally, polymerizable monomer compositions generally exhibit insufficient mechanical properties.

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

[0008] Thus, additive manufacturing (AM) of real objects from virtual objects becomes possible. 3D printing is based on slicing a virtual 3D object into thin 2D layers. These thin layers are deposited one by one by fixing them on top of the preceding layer, and as a result, it becomes possible to manufacture a real object. In the case of 3D printing using a polymerization process, fixing the layers to each other can be done, for example, when the constituent material of the object is a monomer composition extruded through a nozzle induced for the manufacture of the object and polymerizes after being deposited on the previous thin layer.

[0009] So far, this approach for manufacturing objects has mostly remained limited to the manufacture of small objects where it is possible to some extent to be less restricted by the constraint of complete control of viscosity and yield stress.

[0010] When it comes to manufacturing large objects, new problems that can be ignored in small objects arise.

[0011] For example, in the 3D printing of large objects, the rheology requirements to enable good stability of the material at the nozzle outlet are much more stringent, heat dissipation is difficult so there is more heat generation, and insufficient control of shrinkage after polymerization leads to poor-quality objects. In the case of manufacturing large objects, instead of thin layers being stacked, the layers are several centimeters thick. The phenomena of flow and shrinkage during polymerization deteriorate and are not fully resolved at present. When manufacturing large objects, users also require good mechanical strength for these objects.

[0012] At the currently known state of the art, it is difficult to have a polymerizable formulation that enables the manufacture of large objects with good mechanical strength while effectively controlling the shrinkage effect, limiting exothermicity, and effectively controlling the dimensional definition of these different overlapping thin layers resulting from the rheology during the process of manufacturing thin layers. The flow of the formulation to be polymerized occurs through the nozzle and must maintain dimensional stability characterized by sufficient viscosity and yield stress. This series of technical challenges is not fully resolved at present.

[0013] Since the viscosity provided by monomers is low, formulations containing oligomers have been used in the prior art, but this complicates the formulation, increases costs, and does not necessarily enable obtaining it when a transparent composition is desired. European Patent No. 0802455 is an example of this using oligomers that are difficult to manufacture and thus expensive.

[0014] In the extrusion molding of the coincidence composition, WO 2021 / 029945 uses a similar method by using a reactive oligomer in the form of acrylate. An alternative is described in WO 2021 / 183396, which envisages an additional step of performing prepolymerization, which increases the viscosity during use in a 3D printing method by an extrusion molding technique through a nozzle, but this adds an additional step. In these examples, despite the increase in viscosity, the yield stress remains low and material flow is still observed.

[0015] The applicant of the present application is trying to improve a formulation consisting of a monomer and an initiator. This is because the combination of these components alone does not allow for proper construction of an object by irradiation polymerization or thermal polymerization due to too low viscosity and yield stress. The shrinkage during polymerization is also too large and the object has many defects in appearance.

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

[0017] However, the rheological behavior of these formulations remains insufficient or the yield stress remains insufficient, so it does not solve the flow phenomenon but requires the use of a large amount of block copolymer.

[0018] Diamides, especially fatty acid diamides, are widely used in the compounding field as agents for rheology control. For example, European Patent No. 3613728 can be cited.

[0019] These diamides may be combined with castor oil. Thus, European Patent No. 3919546 discloses a composition combining all two or three of diamide, hydrogenated castor oil and a specific polyamide as a rheology additive.

[0020] EP 3131996 also describes a combination of polyamide and hydrogenated castor oil.

[0021] Whether used in combination or not, the rheological changes associated with the use of these diamides and hydrogenated castor oil are observed to be insufficient considering the needs that may arise from the formulation, whether polymerizable or not, in sealants, paints or otherwise adhesives. In the case of polymerizable formulations, in particular in the case of applications in 3D printing, it 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, they need to be used in large amounts in order to obtain a significant effect. This can have the result of degrading certain properties of the polymerizable monomer formulation.

[0023] The combination of block copolymers, 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 related to rheology 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 is observed on the increase in viscosity and yield stress. The combination of block copolymers, diamides and / or triamides, and castor oil provides a surprising effect, allowing the amount of these additives to be limited while improving the mechanical properties of the resulting product and providing an exothermicity during polymerization that is better controlled than in the absence of the combination of these three compounds. Thus, the combined use of block copolymers, amides and castor oil results in an unexpected addition of technical effects (improvement of rheology, improvement of mechanical properties, and limitation of exothermicity and shrinkage).

[0024] Accordingly, the Applicant has found that, in addition to one or more monomer components, by combining small amounts of castor oil, diamide and / or triamide, and block copolymers, it is possible to provide viscosities and yield stresses that meet the requirements arising in sealants and adhesives, paint formulations, or 3D printing. The presence of the combination of block copolymer, amide and hydrogenated castor oil is necessary to maximize the effect on the rheology of the formulations containing them, and the resulting technical effect is far superior to that of 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 for placement without defects on previously polymerized thin layers. The objects obtained using these compositions also exhibit good mechanical properties. The combination of castor oil, diamide and / or triamide, and block copolymer in a composition containing one or more monomers makes it possible to obtain a remarkable effect that can solve the existing technical problems in applications that require sufficient yield stress and high viscosity or alternatively the adjustment of these viscosities, and to achieve this effect with small amounts of these compounds.

[0026] The amounts of castor oil, diamide and / or triamide, and block copolymer can be variable and can finely tune the rheological constraints associated with the formulation of sealants, adhesives, paints, and during the manufacture of objects by 3D printing, while providing the advantages of shrinkage, heat generation energy management, and mechanical properties. Fillers can be added into the compositions of the invention formulated with monomers while retaining the advantages of the combination of castor oil, diamide and / or triamide, and block copolymer.

[0027] The composition of the present invention can also be used together with components derived from natural materials such as vegetable oils or fibers, regardless of whether it contains monomers, block copolymers, diamides and / or triamides, castor oil, or fillers. When a filler is present in the composition of the present invention, a filler derived from the recycling of polymer materials, such as a composite material, may be included therein, whether filled or not, thereby imparting to the composition of the present invention a favorable carbon balance of the materials and recyclability at the end of their life.

Summary of the Invention

[0028] The present invention relates to the following mixture C: - At least one block copolymer in a proportion of 50% to 99%, - Hydrogenated castor oil in a proportion of 0.5% to 25%, - At least one fatty acid diamide and / or at least one fatty acid triamide in a proportion of 0.5% to 25% comprising, % being represented in mass form relative to the total mass of C, relates to a mass composition.

Brief Description of the Drawings

[0029]

Figure 1

Embodiments for Carrying Out the Invention

[0030] The present invention is a composition comprising three classes of compounds: a block copolymer, hydrogenated castor oil, and a polyamide. They can be in the form of a mixture of these three classes of compounds, which are prepared by drying (a mixture of powders and / or granules of the compounds) or by melting using a suitable mixing device. The present invention also relates to the use of the composition of the present invention as an organic gelling agent in a formulation containing the composition of the present invention.

[0031] Organogelators are understood to mean compositions that make it possible to modify the rheology of liquid formulations.

[0032] The block copolymers useful in the context of the present invention are multiblock copolymers, preferably butadiene-free, consisting of A blocks (called hard blocks) with a glass transition temperature Tg above 25°C, preferably above 50°C, more preferably above 70°C, and B blocks (called soft blocks) with a Tg below 0°C, preferably below -25°C, with m ranging from 2 to 1000, preferably from 4 to 500, and preferably linear or star-shaped, of the formula (AB) m and n is 2 or 3, and is a diblock or triblock, preferably triblock, linear or star copolymer of formula (A) n B or (B) n A, preferably (A) n B. The combination of a diblock copolymer with a triblock copolymer constitutes one variant of the invention.

[0033] The term "glass transition temperature" or "Tg" refers to the temperature at which a polymeric material changes from a glassy to a non-glassy state and corresponds to a specific mobility between polymer chains. The glass transition temperature is determined by dynamic mechanical analysis (DMA), for example, according to the method specified in the "Examples" section.

[0034] The term "block copolymer" refers to a copolymer having multiple different polymer segments, each of which may be referred to as a "block," and which is made up of a sequence of monomers that may be the same or different. Thus, each segment or block may be a homopolymer or a copolymer.

[0035] Preferably, the A block is a linear or branched, cyclic or acyclic C1-C6 block, whether or not substituted with polar and / or hydrophilic functional groups. 18It contains a sequence of monomers selected from alkyl (meth)acrylates, in particular methyl methacrylate, styrene and substituted styrenes, isobornyl (meth)acrylate, (meth)acrylic acid, and alkyl acrylamides, which may in some cases result from a recycling process by depolymerization.

[0036] Polar groups and / or hydrophilic groups are understood to mean groups of the carboxylic acid (-COOH), hydroxyl (-OH) or amide (-CONH) type, or alternatively, ethylene glycol or polyethylene glycol groups, which are either unsubstituted or have terminal functional groups substituted by alkyl, phosphate, phosphonate or sulfonate groups.

[0037] More preferably, the A block contains a sequence of monomers selected from methyl methacrylate, styrene, isobornyl acrylate, acrylic acid or methacrylic acid, dimethylacrylamide, diethylacrylamide, or isopropylacrylamide, which may optionally be obtained from a recycling process by depolymerization, either alone or in combination.

[0038] According to one variant form, 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 glycol or glycol (meth)acrylates, which are either unsubstituted or have terminal functional groups substituted by alkyl, phosphate, phosphonate or sulfonate groups.

[0039] Preferably, the B block consists of a sequence of monomers preferentially selected from butyl acrylate, 2-ethylhexyl acrylate, octyl, nonyl and lauryl acrylate, and their mixtures, optionally mixed with styrene.

[0040] More preferably, the B block consists of a sequence of butyl acrylate monomers.

[0041] Thus, the following triblock copolymers, diblock copolymers and star triblock copolymers, which can be used alone or as a mixture in the context of the present invention, can be mentioned non - limitatively. 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(BuAcoAA) - 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. 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. 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(MMAcoDMA))3, pBuA - (p(MMAcoIPA))3, and preferably pBuA - (p(MMAcoDMA))3, pBuA - (p(MMAcoIPA))3, p(BuAcoSty) - (p(MMAcoMAA))3.

[0042] In all of these block copolymers, MMA may be wholly or partly replaced by IBOA and / or IBOMA.

[0043] MMA: methyl methacrylate, MAA: methacrylic acid, AA: acrylic acid, BuA: butyl acrylate, Sty: styrene, DMA: dimethylacrylamide, IPA: isopropylacrylamide, IBOA: isobornyl acrylate, IBOMA: isobornyl methacrylate.

[0044] Block copolymers useful in the context of the present invention typically have a weight average molecular weight of 10,000 to 200,000 g / mol, preferably 80,000 to 180,000 g / mol, as measured by SEC using polystyrene calibration, and a hard block / soft block mass ratio of 75 / 25 to 40 / 60.

[0045] Block copolymers useful in the context of the present invention are not excluded by other preparation methods, but are preferably prepared by controlled radical polymerization. Controlled radical polymerization enables the block copolymer to be obtained in sequential steps within the same process operation. For example, the block copolymer can be prepared by RAFT (radical addition fragmentation chain transfer) polymerization or by nitroxide-mediated polymerization, also known as NMP (nitroxide-mediated polymerization). Preferably, the block copolymer is prepared by NMP, particularly NMP using N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide as the radical. The synthesis of block copolymers using this radical is described in particular in European Patent No. 1526138.

[0046] The block copolymer is present in mixture C in a mass fraction of 50% to 99%, preferably 60% to 95%, more preferably 70% to 95%, including the end points.

[0047] Hydrogenated castor oil is a commercially available compound with the CAS number 8001-78-3. Hydrogenated castor oil consists of 85% to 90% by mass of ricinoleic acid triglyceride, and most of its double bonds are hydrogenated. A small amount of hydrogenated linolenic acid triglyceride, hydrogenated oleic acid triglyceride, and hydrogenated stearic acid triglyceride are also present therein, but these are the main ones.

[0048] Hydrogenated castor oil is present in mixture C in a mass ratio of 0.5% to 25%, preferably 2.5% to 20%, preferably 2.5% to 15%, including the endpoints.

[0049] The composition of the present invention contains at least one polyamide, that is, a compound containing at least two amide functional groups. This polyamide is preferably at least one fatty acid diamide and / or at least one fatty acid triamide.

[0050] The diamide of the composition of the present invention may be a diamide derived from the condensation of at least one diamine and at least one acid, or the condensation of at least one diacid and at least one amine.

[0051] The triamide of the composition of the present invention may be a triamide derived from the condensation of at least one triamine and at least one acid, or the condensation of at least one triacid and at least one amine.

[0052] According to a first preference, they are diamides derived from the condensation of at least one diamine and at least one fatty acid.

[0053] According to a second preference, they are triamides derived from the condensation of at least one triamine and at least one fatty acid.

[0054] According to a third preference, they are a mixture of a diamide derived from the condensation of at least one diamine and at least one fatty acid, and a triamide derived from the condensation of at least one triamine and at least one fatty acid.

[0055] The diamide is a) at least one diamine selected from C2-C24, preferably C2-C10 aliphatic diamines, C6-C18, preferably C6-C12 cycloaliphatic diamines, C6-C24, preferably C6-C12 aromatic diamines, C7-C24 arylaliphatic diamines, and mixtures thereof, and b) at least one carboxylic acid selected from C2-C36 carboxylic acids, preferably linear or branched, saturated or unsaturated, unsubstituted or hydroxyl group-substituted C9-C24 fatty acids, especially pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, preferably substituted with a hydroxyl group, among which 12-hydroxystearic acid (12-HSA), 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), 14-hydroxyicosanoic acid (14-HEA) or mixtures thereof, and is obtained from a reaction mixture containing a carboxylic acid, and is characterized by containing at least one reaction product. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid.

[0056] The triamide is a) at least one triamine selected from C2-C24, preferably C2-C10 aliphatic triamines, C6-C18 cycloaliphatic triamines, C6-C24 aromatic triamines, C7-C24 arylaliphatic triamines, or polyether triamines, and mixtures thereof, and b) at least one carboxylic acid selected from C2 - C36 carboxylic acids, preferably linear or branched, saturated or unsaturated, unsubstituted or hydroxyl group - substituted C9 - C24 fatty acids, especially pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, preferably substituted with a hydroxyl group, among which 12 - hydroxystearic acid (12 - HSA), 9 - or 10 - hydroxystearic acid (9 - HSA or 10 - HSA), 14 - hydroxy eicosanoic acid (14 - HEA) or mixtures thereof are mentioned, carboxylic acids, and characterized by comprising at least one reaction product obtained from a reaction mixture containing . The most preferred hydroxylated carboxylic acid is 12 - hydroxystearic acid.

[0057] At least one diamide and / or at least one triamide is present in mixture C in a mass ratio of 0.5% - 25%, preferably 2.5% - 20%, preferably 2.5% - 15%, including the endpoints.

[0058] The mass ratio of (hydrogenated castor oil) / (diamide and / or triamide) is 1 / 4 - 4 / 1, preferably 1 / 3 - 2 / 3.

[0059] The composition of the present invention may also contain a monomer mixture M in a mass ratio of 1% - 40%, preferably 1% - 20% of mixture C with respect to mass C + M.

[0060] Accordingly, the present invention includes the composition of the present invention of mixture C and at least one mixture M of monomers, and the use of this mixture in a polymerizable formulation. The monomers of mixture M used in the composition of the present invention may be monofunctional or polyfunctional, and may or may not be in combination. They preferably originate from renewable resources. The functionality is understood to mean an entity having a polymerizable double bond.

[0061] Monofunctional monomers are styrene and substituted styrenes, linear or branched C1 - C 18Cyclic or acyclic, substituted or unsubstituted alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, and in particular methyl methacrylate obtained from a recycling process by depolymerization, isobornyl (meth)acrylate which may or may not have additional functional groups, and when present, the additional functional groups may be of the hydroxyl, amine, epoxy, amide or phosphorus-containing type. When rapid kinetics are desired, acrylates are preferably selected.

[0062] Among the preferred monomers of the present invention, in particular styrene, and methyl, ethyl, butyl and isobornyl (meth)acrylate are mentioned. Preferably, these are styrene, methyl methacrylate obtained in some cases from a recycling process by depolymerization, or isobornyl acrylate, either alone or in combination.

[0063] More preferably, they are methyl methacrylate from a recycling process by depolymerization, and / or isobornyl acrylate from renewable resources.

[0064] The polyfunctional monomers have methacrylic or acrylic functionality, preferably acrylic functionality, 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, polyfunctional (meth)acrylates from renewable resources, such as vegetable oil (meth)acrylates, preferably vegetable oil acrylates. Regarding monomers having two or more (meth)acrylate functional groups of renewable origin, monomers of Sartomer's Sarbio range (registered trademark) can be mentioned, more specifically, reference numbers 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).

[0065] Preferably, these are monomers derived from renewable resources such as acrylates of vegetable oils (linseed, soybean, corn, sunflower, castor).

[0066] Combinations of two or more monomers are preferred in the context of the present invention, preferably combinations of monofunctional monomers having an acrylate functional group and polyfunctional monomers having an acrylate functional group (di -, tri -, tetra -, penta - and hexaacrylates).

[0067] Vinyl ether type monomers may also be present in the context of the present invention, particularly when the polymerization is initiated by a cationic process. They can be mono - functional or multi - functional of any kind with respect to the vinyl functional group.

[0068] Preferably, a combination of a mono - functional monomer and a multi - functional monomer is used, where the respective mass ratios vary from 4 / 1 to 1 / 4.

[0069] The composition C of the present invention containing the monomer mixture M may be polymerized using a radical or cationic polymerization initiator, which may or may not be activated with the assistance of electromagnetic irradiation, in a mass ratio of 0.1% to 5% of the mass of the composition M. The initiators may also be thermally activated. Preferably, they are polymerization initiators sensitive to electromagnetic irradiation, more particularly ultraviolet (UV) irradiation. Such initiators are called photoinitiators.

[0070] Accordingly, the present invention also relates to a composition of the present invention comprising at least one monomer and an initiator, more particularly a photoinitiator sensitive to ultraviolet (UV) irradiation.

[0071] A photoinitiator is a compound that can generate free radicals or cations when these compounds are exposed to electromagnetic irradiation. Preferably, the electromagnetic irradiation has wavelengths in the ultraviolet or visible range, although using wavelengths in a shorter wavelength range (X - rays or gamma rays) or a longer wavelength range (infrared or even beyond) does not depart from the scope of the present invention.

[0072] The photoinitiator can be of any kind. Preferably, they are those that generate free radicals by a homolytic cleavage reaction at the α-position relative to the carbonyl group in the context of radical polymerization, such as benzoin ether derivatives, hydroxyalkylphenones, such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and those that generate free radicals by a homolytic cleavage reaction at the β-position, such as sulfide ketones and sulfonyl ketone derivatives, and those that form free radicals by abstraction of hydrogen from a hydrogen donor, such as benzophenone or thioxanthone. This process involves a charge transfer complex with an amine, followed by electron and proton transfer, ultimately forming the alkyl radical of the initiator and an inert cetyl radical. Benzyl diacetal, hydroxyalkylphenone, alpha-aminoketone, acylphosphine oxide, benzophenone, thioxanthone, particularly phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide may be mentioned.

[0073] The use of combinations of some photoinitiators, or combinations of a photoinitiator with a radical initiator that generates radicals thermally or by a redox reaction, such as methylenebis(diethylmalonate)cerium(IV) pair, a toluidine-type aromatic amine, or H2O2 / Fe 2+ pair is not outside the scope of the present invention.

[0074] Among the initiators that are combined with or used alone with a photoinitiator, examples include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxyacetals, and azo compounds. Suitable radical initiators are, for example, isopropyl carbonate, benzoyl, lauroyl, caproyl, or dicumyl peroxide, tert-butyl perbenzoate, tert-butyl per-2-ethylhexanoate, cumyl hydroperoxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, amyl perpivalate, and tert-butyl peroctoate.

[0075] In the case of cationic polymerization, the photoinitiator is a photoacid generator-type compound that releases acid species such as protons under electromagnetic irradiation, such as onium salts, for example diaryliodonium or triarylsulfonium salts, and ferrocenium salts.

[0076] The composition C containing the monomer mixture M and the initiator may further contain one or more fillers D. Accordingly, the present invention also includes the composition C of the present invention in the presence of the monomer mixture M, the initiator, and the filler D.

[0077] The fillers that can be used in the context of the present invention can be inorganic fillers or organic fillers. Among the inorganic fillers, examples include glass, preferably glass in the form of beads, calcium carbonate, talc, mica, kaolin, clay, sand, barium sulfate, feldspar, calcium phosphate, and silica, but are not limited thereto. Preferably, these are glass beads with a size varying in volume from 50 to 1000 μm, preferably 50 to 500 μm, more preferably 80 to 200 μm, and calcium carbonate with a size varying in volume from 50 to 1000 μm, preferably 50 to 500 μm, more preferably 80 to 200 μm.

[0078] The organic fillers that can be used in the context of the present invention can be selected without limitation from wood, cork, cereals, linen, bark or fruit stones. The organic fillers can also be products obtained from the textile recycling process, as well as products obtained from the recycling of thermosetting polymer compositions, or alternatively products obtained from the recycling of composite materials, i.e., fillers that can themselves be composed of organic and inorganic materials.

[0079] It is also possible to combine fillers, whether organic or inorganic, obtained from the textile recycling process or from the process of recycling thermosetting polymer compositions, or alternatively from the process of recycling composite materials.

[0080] Thus, the combination of inorganic fillers and fillers from recycled materials improves the carbon footprint of the composition. With the spread of today's composite materials, 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, more particularly a mixture of glass beads and composite materials.

[0081] A composite material means an aggregate of at least two immiscible materials.

[0082] Filler D may be present in a proportion of 1% to 80% by weight of C + M + D, preferably 50% to 80% by weight of C + M + D.

[0083] The compositions of the present invention exhibit the best rheological properties after activation. Activation is understood to mean a residence with stirring of the composition of the present invention incorporated into other components such as monomers, initiators or fillers, at a temperature of 25 to 80 °C, preferably 60 to 80 °C, for a period of 30 minutes to 8 hours. This step can be completed with dedicated equipment or with a kneading tool such as an extruder, which can be an extrusion device upstream of the nozzle that places the material within the process of manufacturing the part in 3D in the case of 3D printing.

[0084] Accordingly, the present invention also includes the composition of the present invention in the presence of an activated monomer M, an initiator or a filler.

[0085] The activation step, often described as a drawback, has advantages in the present invention. Thus, the composition of the present invention can be easily mixed with, for example, a filler before the activation step, because the viscosity of the mixture is minimized at this stage. Obtaining a homogeneous mixture is facilitated, and then the mixture can be activated by applying temperature and stirring for a given time according to known means. At this time, the activated mixture has the desired properties of viscosity and yield stress.

[0086] Once polymerized, the composition of the present invention exhibits good mechanical properties and hardly shrinks. The exothermic property is controlled, and the objects produced by 3D printing show no defects.

[0087] Accordingly, the present invention also relates to a 3D printing method using the composition of the present invention, and also to an object obtained by this method.

[0088] The present invention also relates to the use of the composition of the present invention in injection molding, extrusion molding, molding methods or any other method for molding thermoplastic materials, such as in the impregnation of composite materials, and also to the objects thus obtained.

[0089] The composition of the present invention may also contain additional additives, including but not limited to UV stabilizers, plasticizers and antioxidants.

Examples

[0090] The following examples illustrate the present invention without limitation.

[0091] Starting materials used: Methyl methacrylate (MMA) manufactured by Aldrich is used as a model of a low molecular weight, and thus low viscosity, monomer. This is used as a monomer in examples showing viscosity and yield stress with or without using the composition of the present invention.

[0092] In a more representative example of the composition of the present invention, isobornyl acrylate (IBOA), a monomer manufactured by Sartomer and having two acrylate functional groups, is used in combination with Sarbio® 7107 derived from vegetable oil (epoxidized soybean oil diacrylate).

[0093] The hydrogenated castor oil (HCO) used is manufactured by Aldrich.

[0094] The diamide that can be used in the context of the present invention is prepared as follows.

[0095] Into a 1-liter round-bottom flask equipped with a thermometer, Dean Stark apparatus, condenser and stirrer, 25.8 grams of ethylenediamine (0.43 mol, 0.86 amine equivalent), 135.52 grams of 12-hydroxystearic acid (0.43 mol, 0.43 acid equivalent) manufactured by Aldrich, and 49.94 grams of hexanoic acid (0.43 mol, 0.43 acid equivalent) manufactured by Aldrich are introduced under a nitrogen stream. The mixture is heated to 200 °C still under a nitrogen stream. The water removed accumulates in the Dean Stark from 150 °C. The reaction is confirmed by the acid and amine indices. When the acid value and amine value are 5 mg KOH / g 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 index confirmed after 30 minutes is less than 0.01 mg KOH / g. Then, the reaction mixture is discharged into a silicone mold. After cooling to room temperature, the product is micronized with an air jet mill.

[0096] This diamide is used in Examples 1 to 4.

[0097] There are two types of block copolymers used. - PMMA-pBuA-PMMA, denoted as BCP1 - P(MMA co IPA)-pBuA-p(MMA co IPA), denoted as BCP2

[0098] The block copolymers are prepared according to the protocol described, for example, in European Patent No. 1526138.

[0099] The filler used is glass beads. TechBeads® 90 - 150 available from Weissker GmbH.

[0100] The photoinitiator used is Irgacure® 819 available from Aldrich.

[0101] Measurement method: Glass transition temperature measurement by DMA: DMA is determined using a Rheometric Scientific ARES rheometer under the following conditions: - Rectangular torsion geometry, - Shear deformation at a frequency of 1 Hz, - Temperature range varying from 125 to 150 °C.

[0102] Viscosity is measured using a Anton Paar MCR301 instrument at 25 °C with a shear gradient of 0.1 - 100 s -1 using a Couette geometry and CC27 - SN13118 mobile.

[0103] - Yield stress is measured using a Anton Paar MCR301 instrument at 25 °C using a Couette geometry and CC27 - SN13118 mobile. The measurement is carried out with a stress gradient of 1 - 100 Pa.

[0104] -Shrinkage is measured by the difference in density of the formulation before and after photopolymerization. The density of the formulation is measured using a 10 mL hydrometer. The density of the solid (the product obtained from the formulation) is obtained by measuring the mass in water and in air.

[0105] Exothermic property: The exothermic property is determined by calculating the difference between the temperature measured during polymerization using a temperature probe and the temperature in the oven. Impact: ISO179-1:2010.

[0106] The formulation containing the composition of the present invention is activated at 60 °C for 6 hours while stirring (at 3000 rpm).

[0107] Example 1: In this example, monomer methyl methacrylate (MMA) is used to measure the viscosity and yield stress of the composition of the present invention and the comparative composition after activation.

[0108] Table 1 summarizes the properties measured for these compositions. [Table 1] TIFF2025524402000001.tif51170

[0109] Note that in Table 1, only the composition of the present invention shows a high level of viscosity and measurable yield stress.

[0110] Example 2: In this example, monomer isobornyl acrylate (IBOA) and Sarbio® 7107 are used to measure the viscosity and yield stress of the composition of the present invention and the comparative composition after activation.

[0111] Table 2 summarizes the properties measured for these compositions. [Table 2] TIFF2025524402000002.tif69170

[0112] In Table 2, it is observed that the best viscosity and yield stress characteristics are provided by the compositions of the present invention. Comparative Example 12, which has a very high proportion of block copolymer, exhibits an acceptable viscosity level but has no measurable yield stress.

[0113] Example 3: In this example, monomer isobornyl acrylate (IBOA) and Sarbio® 7107 are used, and the yield stress of the activated compositions of the present invention and comparative compositions is measured in the presence of a filler (glass beads).

[0114] Table 3 summarizes the characteristics measured for these compositions. [Table 3] TIFF2025524402000003.tif40170

[0115] In Table 3, using the composition of the present invention in the presence of a filler (glass beads), the yield stress is maximized with the composition of the present invention.

[0116] A flow test was conducted on an aluminum plate arranged at an angle of 15° from the vertical. A 5 g 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.

[0117] Comparative Sample 22 showed a flow of 3 cm.

[0118] Sample 23 of the present invention did not show flow.

[0119] Figure 1 is a photograph of the plate 1 minute after sample adhesion.

[0120] Example 4: In this example, the characteristics of exothermicity, impact resistance, and shrinkage are evaluated.

[0121] The formulation is cast into a Teflon mold to a thickness of approximately 2 mm.

[0122] Place the system 8 cm from the light source under a Delolux 03S UV lamp (Delo). The lamp has an emission spectrum of 320 - 600 nm and an output of 400 W. Irradiate the system for 1 minute and 30 seconds.

[0123] Table 4 summarizes the properties measured for these compositions after activation and polymerization. [Table 4] TIFF2025524402000004.tif63170

[0124] Examples of the present invention exhibit a well - controlled exothermicity that is lower than the exothermicity of Comparative Example 25 in the presence of glass beads known to dissipate heat.

[0125] Examples in the presence of block copolymers show a decrease in shrinkage, more notably in the case of Examples 28 and 31 of the present invention.

Claims

1. The following mixture C: - At least one block copolymer in a proportion of 50% to 99%, - Hydrogenated castor oil in a proportion of 0.5% to 25%, - At least one fatty acid diamide and / or at least one fatty acid triamide in a proportion of 0.5% to 25% comprising, % being expressed in the form of mass relative to the total mass of C, a mass composition.

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

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

4. The composition according to claim 3, wherein the initiator is a radical initiator.

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

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

7. The composition according to claim 2 or 3, further comprising one or more fillers D in a mass proportion of filler D of 5% to 80% of the insert C + M + D.

8. The composition according to claim 7, wherein the filler is an inorganic substance.

9. The composition according to claim 7, wherein the filler is an organic substance.

10. The composition according to claim 7, wherein the filler is a combination of an inorganic filler and a filler resulting from a process of recycling a textile material, or a process of recycling a thermosetting polymer composition, or a process of recycling a composite material.

11. The composition according to 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 a monofunctional monomer and a polyfunctional monomer, the respective mass ratios of which vary from 4 / 1 to 1 / 4.

13. The monofunctional monomer is selected from styrene, methyl, ethyl, butyl and isobornyl (meth)acrylate, and vinyl ether, and the polyfunctional 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, polyfunctional (meth)acrylate from renewable resources, such as vegetable oil (meth)acrylate and vinyl ether, the composition according to any one of claims 2 to 12.

14. One or more block copolymers are linear or star-shaped and have the formula (A) ｎ B or (B) ｎ Selected individually or in combination from di-block or tri-blocks consisting of an A block having a Tg above 25 °C and a B block having a Tg below 0 °C of A, wherein n takes a value of 2 or 3, the composition according to any one of claims 1 to 13.

15. A composition according to any one of claims 1 to 14, comprising the following: - comprising at least one reaction product obtained from a reaction mixture containing the following diamide: a) at least one diamine The diamine is selected from C2-C24, preferably C2-C10 aliphatic diamines, C6-C18, preferably C6-C12 cycloaliphatic diamines, C6-C24, preferably C6-C12 aromatic diamines, C7-C24 arylaliphatic diamines, and mixtures thereof; b) at least one carboxylic acid The carboxylic acid is a C2-C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or hydroxyl group-substituted C9-C24 fatty acid, especially pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, preferably substituted with a hydroxyl group, among which 12-hydroxystearic acid (12-HSA), 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), 14-hydroxyicosanoic acid (14-HEA) or mixtures thereof may be mentioned. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid. - characterized by comprising at least one reaction product obtained from a reaction mixture containing the following triamide: a) at least one triamine Triamine is selected from C2-C24, preferably C2-C10 aliphatic triamines, C6-C18 cycloaliphatic triamines, C6-C24 aromatic triamines, C7-C24 arylaliphatic triamines or polyether triamines, and mixtures thereof; b) at least one carboxylic acid The carboxylic acid is a C2-C36 carboxylic acid, preferably a linear or branched, saturated or unsaturated, unsubstituted or hydroxyl group-substituted C9-C24 fatty acid, especially pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, preferably substituted with a hydroxyl group, among which 12-hydroxystearic acid (12-HSA), 9- or 10-hydroxystearic acid (9-HSA or 10-HSA), 14-hydroxyicosanoic acid (14-HEA) or mixtures thereof are mentioned. The most preferred hydroxylated carboxylic acid is 12-hydroxystearic acid.

16. The composition according to any one of claims 2 to 15, which is in an activated form.

17. Use of the composition according to claim 1 as an organic gelling agent in a formulation of a monomer, sealant, adhesive or paint.

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

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

20. An object obtained by the use according to claim 18.

Images