(Meth)acrylic compositions for composites, methods for preparing and using same

Abstract

The present invention relates to a (meth)acrylic composition suitable for (meth)acrylic polymer compositions and (meth)acrylic polymer composites, its preparation method, its use, and the resulting (meth)acrylic polymer compositions and (meth)acrylic polymer composites. In particular, the present invention relates to a (meth)acrylic composition that is crosslinked upon polymerization and is suitable for (meth)acrylic composites, more specifically for reinforcing elements or fiber-reinforced polymer (FRP) rebars. More particularly, the present invention relates to a (meth)acrylic composition suitable for producing reinforcing elements or FRP rebars, preparing such a (meth)acrylic composition, composite reinforcing elements or rebars comprising it after polymerization, and a method for preparing such composite reinforcing elements or FRP rebars. The present invention also relates to the use of such a (meth)acrylic composition, and the use of reinforcing elements or FRP rebars for concrete.

Description

[Technical field]

[0001] The present invention relates to a (meth)acrylic composition suitable for (meth)acrylic polymer compositions and (meth)acrylic polymer composites, a process for preparing the same, its use, and the resulting (meth)acrylic polymer compositions and (meth)acrylic polymer composites.

[0002] In particular, the present invention relates to (meth)acrylic compositions which, upon polymerization, are crosslinked and are suitable for use in (meth)acrylic composites, more particularly reinforcing elements or fiber reinforced polymer (FRP) rebars.

[0003] More particularly, the present invention relates to (meth)acrylic compositions suitable for producing reinforcing elements or FRP rebars, to preparing such (meth)acrylic compositions, to composite reinforcing elements or rebars comprising same after polymerization, and to a method for preparing such composite reinforcing elements or FRP rebars.

[0004] The invention also relates to the use of such (meth)acrylic compositions and to the use of such compositions in reinforcing elements for concrete or FRP rebars. [Background technology]

[0005] Document WO2013 / 056845 discloses composites by in situ polymerization of thermoplastic (meth)acrylic resins. Polymer composites obtained by in situ polymerization of thermoplastic (meth)acrylic resins with fibrous materials containing long fibers and their uses, a method for producing such composites, and manufactured mechanical or structured parts or articles comprising this polymer composite. The polymerization uses a radical initiator selected from diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy acetals or azo compounds. This document does not disclose anything about crosslinking after polymerization of the polymers, the resulting polymer composite compositions, and their heat resistance, especially at high temperatures.

[0006] Document WO2014 / 013028 discloses an impregnation process for fibrous substrates, a liquid (meth)acrylic syrup for the impregnation process, a polymerization method thereof, and a structured article obtained therefrom. The liquid (meth)acrylic syrup comprises a (meth)acrylic polymer, a (meth)acrylic monomer, and at least one initiator or initiator system for initiating the polymerization of the (meth)acrylic monomer. The initiator or initiator system is activated by heat. This document does not disclose anything about crosslinking after polymerization of the polymer, the resulting polymer composite composition, and its heat resistance, especially at high temperatures.

[0007] Document CA2839915 discloses a bendable FRP rebar comprising thermoplastic materials, which may include PE, PS, PMMA, POM, PC, PSLU, PAI, PET, PEEK, PEK, PEI, PES PA6 and PA12. The rebar is made of flexible polyester.

[0008] Document WO2020 / 079015 discloses a (meth)acrylic composition for composites. The composition comprises a liquid (meth)acrylic syrup containing a (meth)acrylic polymer and a (meth)acrylic monomer, and a (meth)acrylic comonomer (M2) containing at least two (meth)acrylic functional groups. When polymerized, the resulting polymer composition exhibits better heat resistance, but lacks sufficient chemical resistance, especially alkali resistance.

[0009] All the prior art documents do not disclose (meth)acrylic compositions suitable for the preparation of polymer compositions or composites with improved heat and chemical resistance. Summary of the Invention

[0010] A composite material is a macroscopic combination of two or more immiscible materials. A composite material is composed of at least a matrix material that forms the continuous phase for the cohesion of the structure, and a reinforcing material with different structures for the mechanical characteristics.

[0011] The purpose of using composite materials is to achieve performance from the composite material that is not available from its separate components when used alone.

[0012] As a result, composite materials are widely used in several industrial sectors, such as construction, automotive, aerospace, transportation, leisure, electronics, and sports, especially due to their better mechanical performance (higher tensile strength, higher tensile modulus, higher fracture toughness) compared to homogeneous materials and their low density.

[0013] Thermosetting polymers consist of cross-linked three-dimensional structures. The cross-linking is obtained by curing reactive groups inside so-called prepolymers. Curing can be obtained, for example, by heating the polymer chains to permanently cross-link and harden the material.

[0014] To prepare a polymer composite, the prepolymer is mixed with other components (e.g., glass beads in a particulate composite, or short fibers in a fibrous composite) or is wetted or impregnated with other components (e.g., a woven net) and then cured.

[0015] The disadvantage of a thermosetting polymer matrix is ​​its very high cross-linking: the matrix cannot be molded in other forms: once the polymer is cured, the form is fixed.

[0016] Thermoplastic polymers consist of eclectic linear or branched polymer chains. They are heated to mix the two components necessary for the production of composites and cooled for hardening. The limitation in using thermoplastic polymers for the production of composites is their high viscosity in the molten state. Wetting or precise impregnation of the fibers with the thermoplastic polymer can be achieved only if the thermoplastic is sufficiently fluid. To have a low viscosity or sufficient fluidity of the thermoplastic polymer, the chain length (molecular mass) can be reduced. However, too low a molecular weight has a negative effect on the performance of the composite, especially the mechanical characteristics. On the other hand, to reduce the viscosity, the temperature of the thermoplastic polymer could be increased in a significant way. As a result, the continuous working temperature is relatively high, exceeding 200 ° C, which directly affects the economics (cost) of the composite due to the impact of high energy costs. Furthermore, thermoplastic polymers tend to decompose when the temperature is too high, this is especially true for semi-crystalline thermoplastic polymers with high melting points such as polyamides (e.g. PA6.6), polyethersulfones (PES), polyetherimides (PEI), polyetheretherketones (PEEK) or polyphenylene sulfide (PPS). This heat-induced degradation leads to a reduction in the molecular weight of the polymer matrix, which is important for the cohesion of the composite.

[0017] Another method for impregnating fibrous substrates is to dissolve the thermoplastic polymer in an organic solvent. However, this method requires a lot of solvent that must be evaporated. Using large amounts of solvent is environmentally problematic from an energy and pollution standpoint.

[0018] To prepare polymer composites based on thermoplastic polymers, thermoplastic polymer resins, commonly known as "syrups", are used to blend or impregnate reinforcing materials, such as fillers or fibrous substrates. Once polymerized, the thermoplastic polymer syrup constitutes the matrix of the composite. During impregnation, when preparing a polymer composite, the viscosity of the impregnation syrup must be controlled and adapted so as not to be too fluid or too viscous, in order to accurately impregnate each fiber of the fibrous substrate. If the wetting is partial, depending on whether the syrup is too fluid or too viscous, "bare" zones appear, i.e. non-impregnated zones, and zones where droplets of polymer form on the fibers, which are responsible for the generation of air bubbles, respectively. These "bare" zones and these air bubbles give rise to the appearance of defects in the final composite, which are particularly responsible for the loss of mechanical strength of the final composite. However, the viscosity range useful for impregnation is low for stocking such materials.

[0019] It is preferred to use thermoplastic polymers in the composites as well, to allow for thermoforming and recycling.

[0020] However, one drawback of thermoplastic composites, especially those with fibrous reinforcement, is thermal stability: when thermoplastic composites are thermoformed or exposed to higher temperatures for longer periods of time, several important properties change in an undesirable manner, such as a decrease in flexural strength retention and delamination in the polymer at the fiber interfaces.

[0021] Another drawback of certain thermoplastic composites is their limited resistance to chemical environments, particularly alkaline resistance.

[0022] There is a need for composite compositions that are thermoformable and provide high heat resistance.

[0023] There is a need for composite compositions that also have sufficient chemical resistance, particularly alkali resistance.

[0024] There is a need for composite compositions that can be thermoformed and provide high heat and alkali resistance.

[0025] It is an object of the present invention to have a composition for preparing a thermoplastic (meth)acrylic composition having high heat and chemical resistance at high temperatures.

[0026] It is also an object of the present invention to have a composition for preparing a thermoformable thermoplastic composite composition having high heat and chemical resistance at high temperatures.

[0027] Chemical resistance in the present invention means in particular alkaline resistance, which means a high pH, ​​preferably greater than 10, more preferably greater than 11, even more preferably greater than 12, advantageously up to 13. This resistance should be achieved at 60° C. for 3 months.

[0028] A further object of the present invention is to have a composition for preparing a thermoformable polymer composite having high heat and chemical resistance. High heat resistance in the present invention also means that delamination in the composite is at least strongly reduced.

[0029] Another object of the present invention is to provide a method for preparing a (meth)acrylic composition for a (meth)acrylic polymer composition, or for preparing a (meth)acrylic composite composition having high heat and chemical resistance.

[0030] Yet another object of the present invention is to have a method for preparing a (meth)acrylic hybrid composition having high heat and chemical resistance.

[0031] Surprisingly, a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) optionally between 0.1 and 5 phr of an initiator (INI) to initiate the polymerization of the (meth)acrylic monomers (M1) with the polymerizable groups (PG1) and (PG2); The (meth)acrylic composition MC1 comprises: It has been found that it is possible to provide a composition for preparing a (meth)acrylic polymer or composite having improved heat and chemical resistance compared to a composition not comprising component b).

[0032] Surprisingly, a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) optionally between 0.1 and 5 phr of an initiator (INI) to initiate the polymerization of the (meth)acrylic monomers (M1) with the polymerizable groups (PG1) and (PG2); The (meth)acrylic composition MC1 comprises: It has also been found that component b) can be used to increase the heat and chemical resistance of a polymer or polymer composite made from composition MC1, compared to a composition not containing the component b).

[0033] Surprisingly, a process for preparing a (meth)acrylic polymer composition MCP1 or a process for preparing a (meth)acrylic polymer composite composition PC1, comprising the steps of: i) providing a (meth)acrylic composition MC1, a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) optionally between 0.1 and 5 phr of an initiator (INI) to initiate the polymerization of the (meth)acrylic monomers (M1) with the polymerizable groups (PG1) and (PG2); Providing a (meth)acrylic composition MC1 comprising: ii) polymerizing the (meth)acrylic composition MC1; The method includes: It has also been found to provide (meth)acrylic polymer or composite compositions with better heat and chemical resistance compared to compositions not containing component b).

[0034] Surprisingly, i) providing a polymer composite PC1 or a part made of a polymerized (meth)acrylic composition MC1, ii) heating the polymer composite PC1 or the part, iii) deforming the polymer composite PC1 or the part; The method includes: It has also been discovered that this provides a method for deforming not only the polymer composite PC1 or polymer composite part, but also any mechanical or structured part or product, which does not change its mechanical characteristics in a significant way once bent.

[0035] Surprisingly, there is provided a method for preparing a polymer composite PC1 from a (meth)acrylic composition MC1, comprising the steps of: i) a fiber or fibrous substrate, a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) optionally impregnating with a (meth)acrylic composition MC1, comprising between 0.1 and 5 phr of an initiator (INI) for initiating the polymerization of the (meth)acrylic monomer (M1) and the polymerizable groups (PG1) and (PG2); ii) polymerizing the (meth)acrylic composition MC1; The method includes: It has also been found that this results in a polymer composite PC1 having better heat and chemical resistance compared to a polymer composite made from a composition that does not contain component b). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] According to a first aspect, the present invention relates to a (meth)acrylic composition MC1, which comprises a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) optionally, between 0.1 and 5 phr of an initiator (INI) for initiating the polymerization of the (meth)acrylic monomers (M1) with the polymerizable groups (PG1) and (PG2); Includes.

[0037] According to a second aspect, the present invention relates to a (meth)acrylic composition (MC1), a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) optionally, between 0.1 and 5 phr of an initiator (INI) for initiating the polymerization of the (meth)acrylic monomers (M1) with the polymerizable groups (PG1) and (PG2); Includes.

[0038] According to a third aspect, the present invention relates to a method for preparing a (meth)acrylic composition MC1, comprising: i) the following components: a) 100 parts of a liquid (meth)acrylic syrup comprising: a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1); and a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) optionally, between 0.1 and 5 phr of an initiator (INI) for initiating the polymerization of the (meth)acrylic monomers (M1) with the polymerizable groups (PG1) and (PG2); Providing ii) mixing components a) to b or a) to c); The present invention relates to a method comprising the steps of:

[0039] According to a fourth aspect, the present invention relates to the use of a (meth)acrylic composition MC1 for impregnating a fiber or a fibrous substrate, said (meth)acrylic composition MC1 comprising a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) Between 0.1 and 5 phr of an initiator (INI) for initiating the polymerization of the (meth)acrylic monomers (M1) with the polymerizable groups (PG1) and (PG2). Includes.

[0040] According to a fifth aspect, the present invention relates to a method for preparing a polymer conjugate PC1 from a (meth)acrylic composition MC1, said method comprising the steps of: i) providing a (meth)acrylic composition MC1, a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) Between 0.1 and 5 phr of an initiator (INI) for initiating the polymerization of the (meth)acrylic monomers (M1) with the polymerizable groups (PG1) and (PG2). Providing a (meth)acrylic composition MC1 comprising: ii) polymerizing the (meth)acrylic composition MC1, optionally with the impregnated fibers or fibrous substrate; Includes.

[0041] According to a sixth aspect, the present invention relates to a method for preparing a (meth)acrylic polymer composite composition PC1 from a (meth)acrylic composition MC1, comprising: i) a fiber or fibrous substrate, a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) impregnation with a (meth)acrylic composition MC1 comprising between 0.1 and 5 phr of an initiator (Ini) for initiating the polymerization of the (meth)acrylic monomer (M1) and the polymerizable groups (PG1) and (PG2); ii) polymerizing the (meth)acrylic composition MC1 impregnated in the fiber or fibrous substrate; The present invention relates to a method comprising the steps of:

[0042] According to a seventh aspect, the present invention relates to a method for modifying a (meth)acrylic polymer composite composition PC1 or a polymer composite part, as well as a mechanical or structured part or product, said method comprising the steps of: i) providing a (meth)acrylic polymer composite composition PC1 or part made by polymerizing a (meth)acrylic composition MC1 having pre-impregnated fibers or fibrous substrates, said composition MC1 comprising: a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) containing between 0.1 and 5 phr of an initiator (INI) for initiating the polymerization of the (meth)acrylic monomer (M1) with the polymerizable groups (PG1) and (PG2), Providing a (meth)acrylic polymer composite composition PC1 or a part; ii) heating the (meth)acrylic polymer composite composition PC1 or part; iii) deforming the (meth)acrylic polymer composite composition PC1 or the part; Includes.

[0043] The term "(meth)acrylic" as used refers to any type of acrylic and methacrylic monomer or polymer.

[0044] The term "PMMA" as used refers to homopolymers and copolymers of methyl methacrylate (MMA), where the weight ratio of MMA within the PMMA is at least 70% by weight.

[0045] The term "monomer" as used refers to a molecule that can undergo polymerization.

[0046] The term "polymerization" as used refers to the process of converting a monomer or mixture of monomers into a polymer.

[0047] The term "thermoplastic polymer" as used refers to a polymer that becomes liquid or more liquid or less viscous when heated and can assume new shapes through the application of heat and pressure. This also applies to crosslinked thermoplastic polymers that can be thermoformed when heated above their softening temperature.

[0048] The term "thermoset polymer" as used refers to a prepolymer in a soft, solid or viscous state that is irreversibly transformed by curing into an infusible, insoluble polymer network.

[0049] The term "polymer composite" as used refers to a multi-component material that includes multiple distinct phase domains, at least one of which is a continuous phase, and at least one of which is a component polymer.

[0050] The term "rebar" as used refers to reinforcing bars used as tensioning devices in reinforced concrete and reinforced masonry structures to strengthen and assist concrete under tension. Rebar significantly increases the tensile strength of the concrete or structure.

[0051] The term "initiator" as used refers to a chemical species that forms a compound that initiates the polymerization of a monomer or an intermediate compound that can be sequentially linked with multiple other monomers into a polymeric compound.

[0052] The abbreviation "phr" means parts by weight per 100 parts of composition. For example, 1 phr of initiator in a composition means adding 1 kg of initiator to 100 kg of composition.

[0053] The abbreviation "ppm" means parts by weight per million parts by weight of a composition. For example, 1000 ppm of a compound in a composition means that 0.1 kg of the compound is present in 100 kg of the composition.

[0054] In the present invention, a range from x to y is meant to include the upper and lower limits of the range, corresponding to at least x to at most y.

[0055] In the present invention, when a range is stated to be between x and y, it is meant that the upper and lower limits of the range are excluded, and is equivalent to being greater than x and less than y.

[0056] The (meth)acrylic syrup a) of the (meth)acrylic composition MC1 according to the invention comprises a (meth)acrylic polymer (P1) and a (meth)acrylic monomer (M1).

[0057] The liquid (meth)acrylic syrup a) of the (meth)acrylic composition MC1 according to the invention comprises between 10% and 50% by weight of the (meth)acrylic polymer (P1) and between 50% and 90% by weight of the (meth)acrylic monomer (M1). Preferably, the liquid (meth)acrylic syrup a) comprises between 10% and 40% by weight of the (meth)acrylic polymer (P1) and between 60% and 90% by weight of the (meth)acrylic monomer (M1); more preferably between 10% and 30% by weight of the (meth)acrylic polymer (P1) and between 70% and 90% by weight of the (meth)acrylic monomer (M1).

[0058] The dynamic viscosity of the liquid (meth)acrylic syrup a) ranges from 10 mPa*s to 10000 mPa*s, preferably from 20 mPa*s to 7000 mPa*s, advantageously from 20 mPa*s to 5000 mPa*s, more advantageously from 20 mPa*s to 2000 mPa*s, and even more advantageously between 20 mPa*s and 1000 mPa*s. The viscosity of the syrup can be easily measured with a rheometer or viscometer. The dynamic viscosity is measured at 25°C. If the liquid (meth)acrylic syrup has Newtonian behavior, i.e. no shear thinning, the dynamic viscosity is independent of the shear in the rheometer or the speed of the moving body in the viscometer. If the liquid composition LC1 has non-Newtonian behavior, i.e. shear thinning, the dynamic viscosity is independent of the shear in the rheometer or the speed of the moving body in the viscometer. -1 The shear rate is measured at .

[0059] Regarding the (meth)acrylic composition MC1 of the present invention, it comprises a (meth)acrylic monomer (M1) and a (meth)acrylic polymer (P1). Upon polymerization, the (meth)acrylic monomer (M1) is transformed into a (meth)acrylic polymer (P2) comprising monomer units of the (meth)acrylic monomer (M1) and possible other monomers.

[0060] Preferably, the kinematic viscosity of the (meth)acrylic composition MC1 also ranges from 10 mPa*s to 20000 mPa*s, preferably from 20 mPa*s to 15000 mPa*s, advantageously from 20 mPa*s to 10000 mPa*s, more advantageously from 20 mPa*s to 5000 mPa*s, and even more advantageously between 20 mPa*s and 2000 mPa*s. The kinematic viscosity is measured similarly.

[0061] The (meth)acrylic polymer (P1) may be a polyalkyl methacrylate or a polyalkyl acrylate. By polyalkyl methacrylate or polyalkyl acrylate is meant a polymer comprising at least 50% by weight of monomers selected from alkyl esters of acrylic acid or alkyl esters of methacrylic acid. According to a preferred embodiment, the (meth)acrylic polymer (P1) is polymethyl methacrylate (PMMA).

[0062] The term "PMMA" refers to methyl methacrylate (MMA) homopolymer or copolymer, or mixtures thereof.

[0063] According to one embodiment, the methyl methacrylate (MMA) homopolymer or copolymer comprises at least 70% by weight methyl methacrylate, preferably at least 80%, advantageously at least 90%, more advantageously at least 95%.

[0064] According to another embodiment, the (meth)acrylic polymer (P1) is a mixture of at least one homopolymer and at least one copolymer of MMA, or a mixture of at least two homopolymers or two copolymers of MMA having different average molecular weights, or a mixture of at least two copolymers of MMA with different monomer compositions.

[0065] Copolymers of methyl methacrylate (MMA) contain from 70% to 99.9% by weight of methyl methacrylate and from 0.1% to 30% by weight of at least one monomer containing at least one ethylenic unsaturation capable of copolymerizing with methyl methacrylate.

[0066] These monomers are well known and may in particular be mentioned: acrylic acid and methacrylic acid and alkyl (meth)acrylates, the alkyl group of which contains from 1 to 12 carbon atoms. By way of example, mention may be made of methyl acrylate and ethyl, butyl or 2-ethylhexyl (meth)acrylate. Preferably, the comonomer is an alkyl acrylate, the alkyl group of which contains from 1 to 4 carbon atoms.

[0067] According to a first preferred embodiment, the copolymer of methyl methacrylate (MMA) comprises from 80% to 99.9% by weight, advantageously from 85% to 99.9%, more advantageously from 90% to 99.9%, of methyl methacrylate and from 0.1% to 20% by weight, advantageously from 0.1% to 15%, more advantageously from 0.1% to 10%, of at least one monomer containing at least one ethylenic unsaturation capable of being copolymerized with methyl methacrylate. Preferably, the comonomer is selected from methyl acrylate and ethyl acrylate, and mixtures thereof.

[0068] The weight average molecular mass of the (meth)acrylic polymer (P1) must be high, meaning more than 50 000 g / mol, preferably more than 70 000 g / mol, more preferably more than 90 000 g / mol, most preferably more than 100 000 g / mol.

[0069] The weight average molecular mass can be determined by size exclusion chromatography (SEC).

[0070] The (meth)acrylic polymer (P1) is completely soluble in the (meth)acrylic monomer (M1) or in the mixture of (meth)acrylic monomers. This allows the viscosity of the (meth)acrylic monomer (M1) or in the mixture of (meth)acrylic monomers to be increased. The resulting solution is a liquid composition, commonly called a "syrup" or a "prepolymer". As mentioned above, the dynamic viscosity value of the liquid (meth)acrylic syrup a) is between 10 mPa.s and 10000 mPa.s. The viscosity of the syrup can be easily measured with a rheometer or viscometer. The dynamic viscosity is measured at 25°C.

[0071] Advantageously, the liquid (meth)acrylic composition or syrup does not contain additional voluntarily added solvents.

[0072] Concerning the (meth)acrylic monomer (M1), the monomer is selected from alkylacrylic monomers, alkylmethacrylic monomers, hydroxyalkylacrylic monomers and hydroxyalkylmethacrylic monomers, and mixtures thereof, where alkylacrylic monomers and alkylmethacrylic monomers refer to alkyl esters of acrylic acid or methacrylic acid.

[0073] Preferably, the (meth)acrylic monomer (M1) is selected from hydroxyalkyl acrylic monomers, hydroxyalkyl methacrylic monomers, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbons.

[0074] More preferably, the (meth)acrylic monomer (M1) is selected from alkylacrylic or alkylmethacrylic monomers and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbons.

[0075] Advantageously, the (meth)acrylic monomer (M1) is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate, and mixtures thereof.

[0076] More preferably, the (meth)acrylic monomer (M1) is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.

[0077] According to a preferred embodiment, at least 50% by weight, preferably at least 60% by weight, of the (meth)acrylic monomers (M1) is methyl methacrylate.

[0078] According to a first more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, advantageously at least 80% by weight and even more advantageously at least 90% by weight of the monomer (M1) is a mixture of methyl methacrylate and optionally at least one other monomer.

[0079] According to a second more preferred embodiment, at least 95% by weight, more preferably at least 98% by weight of the monomers (M1) are methyl methacrylate.

[0080] According to a third more preferred embodiment, 100% by weight of the monomer (M1) is methyl methacrylate.

[0081] Concerning component (LC1) of composition (PC1), it is preferred that it is liquid. By liquid, it is meant that component (LC1) is liquid in the temperature interval between -20°C and 40°C, preferably between 0°C and 40°C, more preferably between 10°C and 40°C. It may still be liquid outside these limits, but is liquid at least between these limits.

[0082] The viscosity of component (LC1) is between 0.5 mPa*s and 30 Pa*s at 25°C. Preferably, the viscosity is between 1 mPa*s and 25 Pa*s, more preferably between 10 mPa*s and 20 Pa*s, even more preferably between 50 mPa*s and 18 Pa*s, advantageously between 100 mPa*s and 18 Pa*s. The viscosity of component (LC1) is a dynamic viscosity. In the presence of shear thinning, the value of the dynamic viscosity is taken at a shear rate of 1 1 / s. The viscosity is measured with a rheometer.

[0083] Component (LC1) is present in the (meth)acrylic composition MC1 in an amount by weight between 0.01 and 30 phr, preferably between 0.1 and 25 phr, more preferably between 0.5 and 20 phr, even more preferably between 1 and 20 phr, advantageously between 1 and 18 phr, relative to 100 parts of the liquid (meth)acrylic syrup.

[0084] In a first more advantageous embodiment, compound (C1) is present in the (meth)acrylic composition MC1 in an amount between 1 and 20 phr by weight, more advantageously between 2 and 20 phr by weight.

[0085] In a second more advantageous embodiment, compound (C1) is present in the (meth)acrylic composition MC1 in an amount between 1 and 15 phr by weight, more advantageously between 2 and 15 phr by weight.

[0086] In a third more advantageous embodiment, compound (C1) is present in the (meth)acrylic composition MC1 in an amount between 1 and 11 phr by weight, more advantageously between 2 and 11 phr by weight.

[0087] The compound (C1) having at least two polymerizable groups (PG1) and (PG2) and at least two hydroxyl groups represents at least 30% by weight of component (LC1), more preferably at least 40% by weight of component (LC1).

[0088] In one embodiment, the compound (C1) having at least two polymerizable groups (PG1) and (PG2) and at least two hydroxyl groups represents 100% by weight of component (LC1).

[0089] In another embodiment, component (LC1) can also be a mixture of several compounds, one of which is a compound (C1) having at least two polymerizable groups (PG1) and (PG2) and at least two hydroxyl groups.

[0090] The component (LC1) or the liquid component (LC1) may further comprise a monomer (M2) or a mixture of monomers (M2x), each monomer of the monomer (M2) or the mixture of monomers (M2x) comprising at least one carbon double bond. The monomer (M2) or the mixture of monomers (M2x) is different from the monomer (M1).

[0091] Monomer (M2) may be selected from (meth)acrylic, allylic or styrenic monomers for (Mx) or mixtures thereof.

[0092] In a variation, the monomer (M2) may be selected from (meth)acrylic monomers, allylic monomers or mixtures thereof for (Mx).

[0093] Preferably, the monomer (M2) is selected from styrene, α-methylstyrene, vinyltoluene, divinylbenzene, alkyl(meth)acrylates having an alkyl group containing 1 to 10 carbon atoms, and hydroxyethyl(meth)acrylate, as well as difunctional (meth)acrylates such as butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and di(meth)acrylates having a glycol structure, and polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate.

[0094] In a first more preferred embodiment, the monomer (M2) is selected from alkyl (meth)acrylates having an alkyl group containing 1 to 10 carbon atoms, and hydroxyethyl (meth)acrylate, as well as difunctional (meth)acrylates such as butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and di(meth)acrylates having a glycol structure, and polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate.

[0095] In a second more preferred embodiment, the monomer (M2) for (Mx) or the mixture thereof does not comprise styrene.

[0096] In a third more preferred embodiment, the monomer (M2) or the mixture thereof for (Mx) does not comprise a styrenic monomer.

[0097] In a fifth more preferred embodiment, the monomer (M2) for (Mx) or the mixture thereof comprises a styrene-based monomer.

[0098] In a fifth more preferred embodiment, the monomer (M2) is selected from compounds containing at least two (meth)acrylic functional groups. The (meth)acrylic monomer (M2) can also be selected from a mixture of at least two compounds (M2a) and (M2b), each containing at least two (meth)acrylic functional groups.

[0099] The (meth)acrylic monomer (M2) selected from compounds containing at least two (meth)acrylic functional groups is selected from 1,3-butylene glycol dimethacrylate; 1,4-butanediol dimethacrylate; 1,6 hexanediol diacrylate; 1,6 hexanediol dimethacrylate; diethylene glycol dimethacrylate; dipropylene glycol diacrylate; ethoxylated (10) bisphenol a diacrylate; ethoxylated (2) bisphenol a dimethacrylate; ethoxylated (3) bisphenol a diacrylate;ethoxylated(3) bisphenol a dimethacrylate;ethoxylated(4) bisphenol a diacrylate;ethoxylated(4) bisphenol a dimethacrylate;ethoxylated bisphenol a dimethacrylate;ethoxylated(10) bisphenol dimethacrylate;ethylene glycol dimethacrylate;polyethylene glycol(200) diacrylate;polyethylene glycol(400) diacrylate;polyethylene glycol(400) dimethacrylate;polyethylene glycol(400) dimethacrylate;polyethylene glycol(600) diacrylate;polyethylene glycol(600) dimethacrylate;polyethylene glycol 400 diacrylate;propoxylated(2) neopentyl glycol diacrylate;tetraethylene glycol diacrylate;tetraethylene glycol dimethacrylate;tricyclodecane dimethanol diacrylate;tricyclodecane dimethanol dimethacrylate;triethylene glycol diacrylate;triethylene glycol dimethacrylate;tri ...methacrylate;triethylene glycol diacrylate;triethylene glycol dimethacrylate;tripropoxylated(2) neopentyl glycol diacrylate;tetraethylene glycol diacrylate;tetraethylene glycol dimethacrylate;tricyclodecane dimethanol diacrylate;tricyclodecane dimethacrylate;triethylene glycol diacrylate;triethylene glycol dimethacrylate;tripropoxylated(2) neopentyl glycol diacrylate;tetraethylene glycol diacrylate;tetraethylene glycol dimethacrylate;tricyclodecane dimethanol diacrylate;tricyclodecane dimethacrylate;triethylene glycol dimethacrylate;tripropoxylated(2 Ethoxylated (15) Trimethylolpropane triacrylate;ethoxylated (3) Trimethylolpropane triacrylate;ethoxylated (6) Trimethylolpropane triacrylate;ethoxylated (9) Trimethylolpropane triacrylate;ethoxylated 5 Pentaerythritol triacrylate;ethoxylated (20) Trimethylolpropane triacrylate;propoxylated (3) Glyceryl triacrylate;trimethylolpropane triacrylate;propoxylated (5.5) Glyceryl triacrylate; Pentaerythritol triacrylate; Propoxylated (3) Glyceryl triacrylate; Propoxylated (3) Trimethylolpropane triacrylate; Trimethylolpropane triacrylate; Trimethylolpropane trimethacrylate; Tris(2-hydroxyethyl)isocyanurate triacrylate; Ditrimethylolpropane tetraacrylate; Dipentaerythritol pentaacrylate; Ethoxylated (4) Pentaerythritol tetraacrylate; Pen Pentaerythritol tetraacrylate;Dipentaerythritol hexaacrylate;1,10-Decanediol diacrylate;1,3-Butylene glycol diacrylate;1,4-Butanediol diacrylate;1,9-Nonanediol diacrylate;2-(2-Vinyloxyethoxy)ethyl acrylate;2-Butyl-2-ethyl-1,3-propanediol diacrylate;2-Methyl-1,3-propanediol diacrylate;2-Methyl-1,3-propanediyl ethoxy acrylate;3-Methyl The alkoxylated 1,5-pentanediol diacrylate may be selected from alkoxylated cyclohexane dimethanol diacrylate, alkoxylated hexanediol diacrylate, cyclohexane dimethanol diacrylate, ethoxylated cyclohexane dimethanol diacrylate, diethylene glycol diacrylate, dioxane glycol diacrylate, ethoxylated dipentaerythritol hexaacrylate, ethoxylated glycerol triacrylate, ethoxylated neopentyl glycol diacrylate, hydroxypivalyl hydroxypivalic acid diacrylate, neopentyl glycol diacrylate, poly(tetramethylene glycol) diacrylate, polypropylene glycol 400 diacrylate, polypropylene glycol 700 diacrylate, propoxylated (6) ethoxylated bisphenol A diacrylate, propoxylated ethylene glycol diacrylate, propoxylated (5) pentaerythritol tetraacrylate, and propoxylated trimethylolpropane triacrylate.

[0100] Preferably, the (meth)acrylic monomer (M2) is selected from ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, triethylene glycol dimethacrylate and triethylene glycol diacrylate or mixtures thereof.

[0101] The monomer (M2) can be present in the (meth)acrylic composition MC1 in an amount by weight between 0.01 and 15 phr, preferably between 0.1 and 10 phr, more preferably between 0.1 and 9 phr, even more preferably between 0.1 and 8.5 phr and advantageously between 0.1 and 8 phr, relative to 100 parts of the liquid (meth)acrylic syrup.

[0102] The at least two polymerizable groups (PG1) and (PG2) of compound (C1) are preferably carbon double bonds.

[0103] The at least two polymerizable groups (PG1) and (PG2) of the compound (C1) are more preferably α,β-unsaturated carbonyl groups.

[0104] The at least two polymerizable groups (PG1) and (PG2) of compound (C1) can be chosen from acrylate groups, methacrylate groups or condensation products containing maleic acid or itaconic acid or fumaric acid.

[0105] Preferably, compound (C1) is a vinyl ester or an unsaturated polyester.

[0106] In a first more preferred embodiment, the compound (C1) is a vinyl ester. A vinyl ester is typically a reaction product obtainable by reacting a polyepoxide (such as an epoxy resin) with an ethylenically unsaturated double bond-containing monocarboxylic acid, for example (meth)acrylic acid, and has the same backbone as the polyepoxide in the main chain and is curable due to the presence of an unsaturated double bond in the molecule. The backbone may be one or more types of backbone selected from the group consisting of bisphenol A, bisphenol F, phenol novolac, cresol novolac, hydrogenated bisphenol A, hydrogenated bisphenol F, aliphatic ester, aliphatic ether, and aromatic ester type backbone.

[0107] In a second more preferred embodiment, compound (C1) is an unsaturated polyester. The unsaturated polyester is the reaction product of at least one dibasic organic acid or anhydride thereof with at least one polyhydric alcohol.

[0108] In one embodiment of the first more preferred embodiment, compound (C1) comprises the following structure (1): TIFF2025500286000001.tif19170

[0109] In another embodiment of the first more preferred embodiment, compound (C1) comprises the following structure (2): TIFF2025500286000002.tif27170

[0110] In yet another embodiment of the first more preferred embodiment, compound (C1) comprises the following structure (3): TIFF2025500286000003.tif27170In the formula, R1 is H or CH3.

[0111] In yet another embodiment of the first more preferred embodiment, compound (C1) comprises the following structure (4): TIFF2025500286000004.tif27170In the formula, R1 is H or CH3.

[0112] The structures (1) to (4) may be present more than once in compound (C1).

[0113] More preferably, compound (C1) contains any of structures (1) to (4) at least twice.

[0114] As regards the initiator (INI) for initiating the polymerization of the (meth)acrylic monomer (M1) and optionally (M2), it is selected from radical initiators.

[0115] Preferably, the initiator (INI) is activated by heat.

[0116] The radical initiator (INI) may be selected from peroxy group-containing compounds or azo group-containing compounds, preferably from peroxy group-containing compounds.

[0117] Preferably, the peroxy group-containing compound contains from 2 to 30 carbon atoms.

[0118] Preferably, the peroxy group-containing compound is selected from diacyl peroxides, peroxy esters, peroxy dicarbonates, dialkyl peroxides, peroxy acetals, hydroperoxides or peroxy ketals.

[0119] The initiators (INI) were diisobutyryl peroxide, cumyl peroxyneodecanoate, di(3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, di-(2-ethylhexyl)-pentanoate, and di-n-propyl peroxydicarbonate. peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, dibenzoylperoxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydiethylacetate, tert-butylperoxyisobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy) tert-butylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexyl carbonate, tert-amylperoxyacetate, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amylperoxybenzoate, tert-butylperoxyacetate, butyl 4,4-Di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di-(2-tert-butyl-peroxyisopropyl)-benzene, 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert t-butyl peroxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, 2,2'-azobis-isobutyronitrile (AIBN), 2,2'-azodi-(2-methylbutyronitrile), azobisisobutyramide, 2,2'-azo-bis(2,4-dimethylvaleronitrile), 1,1'-azodi(hexahydrobenzonitrile), or 4,4'-azobis(4-cyanopentanoic acid).

[0120] Preferably, the initiator (Ini) is diisobutyryl peroxide, cumyl peroxyneodecanoate, di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert-butylsilyl) peroxydicarbonate, cyclohexyl) peroxydicarbonate, di-(2-ethylhexyl)-peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, ter t-Butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butyl Peroxydiethyl acetate, tert-butylperoxyisobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexyl carbonate, tert-amylperoxyacetate, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butylperoxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di-(2-tert-butyl-peroxyisopropyl)-benzene, 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, and mixtures thereof.

[0121] With regard to the fibrous substrate, there may be mentioned several fibers, which may be in the form of strips, wraps, braids, locks or pieces, unidirectional rovings or continuous filament mats, fabrics, felts or nonwovens. The fibrous materials may have various forms and dimensions, either one-dimensional, two-dimensional or three-dimensional. The fibrous substrate comprises an assembly of one or more fibers. When the fibers are continuous, the assembly forms a fabric.

[0122] The one-dimensional form corresponds to linear long fibers. The fibers may be discontinuous or continuous. The fibers may be in the form of continuous filaments, arranged randomly or parallel to each other. The fibers are defined by their aspect ratio, which is the ratio between the length and diameter of the fiber. The fibers used in the present invention are long or continuous fibers. The fibers have an aspect ratio of at least 1000, preferably at least 1500, more preferably at least 2000, advantageously at least 3000, more advantageously at least 5000, even more advantageously at least 6000, even more advantageously at least 7500, and most advantageously at least 10000.

[0123] Two-dimensional forms correspond to nonwoven or woven fibrous mats or reinforcements or fiber bundles, which may also be braided. Even if a two-dimensional form has a certain thickness and therefore in principle has three dimensions, it is considered according to the invention to be two-dimensional.

[0124] Three-dimensional forms correspond, for example, to nonwoven fibrous mats or reinforcements, or stacked or folded bundles of fibers or mixtures thereof, an assembly of two-dimensional forms in three dimensions.

[0125] The fibrous materials may be of natural or synthetic origin. Natural materials may include vegetable, wood, animal or mineral fibres.

[0126] Natural fibres are for example sisal, jute, hemp, flax, cotton, coconut fibre and banana fibre. Animal fibres are for example wool or hair.

[0127] The synthetic material may include polymeric fibers selected from fibers of thermoset polymers, thermoplastic polymers, or mixtures thereof.

[0128] The polymeric fibers may be comprised of polyamides (aliphatic or aromatic), polyesters, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins and vinyl esters.

[0129] The mineral fibres may also be chosen from glass fibres, in particular glass fibres of type E, R or S2, basalt fibres, boron fibres or silica fibres.

[0130] The fibrous substrate of the present invention is selected from vegetable fibers, wood fibers, animal fibers, mineral fibers, synthetic polymeric fibers, glass fibers and carbon fibers, and mixtures thereof.

[0131] Preferably, the fibrous substrate is selected from mineral fibers, more preferably from glass fibers or carbon fibers.

[0132] The fibres of the fibrous substrate have a diameter between 0.005 μm and 100 μm, preferably between 1 μm and 50 μm, more preferably between 5 μm and 30 μm, advantageously between 10 μm and 25 μm.

[0133] Preferably, the fibers of the fibrous substrate of the present invention are selected from continuous fibers (meaning that the aspect ratio does not necessarily apply in relation to long fibers) for a one-dimensional morphology of the fibrous substrate, or from long or continuous fibers for a two-dimensional or three-dimensional morphology.

[0134] According to a third aspect, the present invention relates to a method for preparing a (meth)acrylic composition MC1, said method comprising the steps of providing components a) and b).

[0135] In a process variation, the compound (C1) of component c) can also be generated in situ by providing certain compounds which react to generate compound (C1). As an example, a diepoxy compound is blended with (meth)acrylic acid.

[0136] The present invention further provides a method for preparing a polymer composite PC1 from a (meth)acrylic composition MC1, comprising the steps of: i) a fiber or fibrous substrate, a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10% and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising at least two polymerizable groups (PG1) and (PG2) and a compound (C1) having at least two hydroxyl groups, c) impregnation with a (meth)acrylic composition MC1 comprising between 0.1 and 5 phr of an initiator (INI) for initiating the polymerization of the (meth)acrylic monomer (M1) and the polymerizable groups (PG1) and (PG2); ii) polymerizing the (meth)acrylic composition MC1 impregnated in the fiber or fibrous substrate; The present invention relates to a method comprising the steps of:

[0137] Components a) to c) in the method for preparing the polymer composite are the same as those defined above and their respective weight ratios. The preferred ranges and preferred properties of each compound can be varied in any combination.

[0138] The weight ratio of the fibers or fibrous substrate to the (meth)acrylic composition MC1 can be between 1:10 and 10:1. Preferably, this ratio is between 1:10 and 9:1.

[0139] The polymerization step is typically carried out at a temperature below 160°C, preferably below 150°C, even more preferably below 140°C.

[0140] Preferably, the polymerization step is carried out at a temperature between 40°C and 160°C, preferably between 80°C and 140°C, even more preferably between 100°C and 130°C.

[0141] According to another preferred embodiment, the polymerization step is carried out at a temperature between 60°C and 125°C, preferably between 80°C and 125°C, even more preferably between 100°C and 125°C.

[0142] The polymer composite PC1 is preferably a (meth)acrylic polymer composite, meaning that at least 50% by weight of the polymer matrix of the composite is a (meth)acrylic polymer.

[0143] More preferably, at least 75% by weight of the polymer matrix of the composite is a (meth)acrylic polymer or a mixture of (meth)acrylic polymers.

[0144] The (meth)acrylic polymer of the polymer matrix of the composite is a polymer that contains at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, and even more preferably at least 75% by weight of monomer units in the (meth)acrylic polymer that are derived from (meth)acrylic monomers.

[0145] The polymer composite PC1 is preferably a fiber-reinforced polymer composite.

[0146] The present invention further relates to a method for producing a polymer composite part, as well as a mechanical or structured part or product, from the (meth)acrylic composition MC1. The method for producing a polymer composite part comprises a method for preparing a polymer composite PC1 from the (meth)acrylic composition MC1.

[0147] Concerning the method for manufacturing mechanical or structured parts or products as well as polymer composite parts or for preparing the polymer composite PC1 from the (meth)acrylic composition MC1; various methods can be used to prepare these parts. Reaction injection molding (RIM), reinforced reaction injection molding (R-RIM) and their variants, press molding, compression molding, liquid compression molding (LCM) or sheet molding compounds (SMC) or bulk molding compounds (BMC), as vacuum-assisted resin infusion (VARI), pultrusion, vacuum bag molding, pressure bag molding, autoclave molding, resin transfer molding (RTM) and their variants, (HP-RTM, C-RTM, I-RTM), can be mentioned. All these methods are known to those in the field of preparing composites, without going into too much detail.

[0148] A first preferred manufacturing method for producing a composite part or for preparing a polymer composite PC1 from a (meth)acrylic composition MC1 is the transfer of the liquid composition to a fibrous substrate by impregnating the latter with a mould. The methods requiring a mould are listed above and include the expression moulding.

[0149] A second preferred manufacturing method for producing composite parts or for preparing polymer composites PC1 from (meth)acrylic composition MC1 is a method in which a liquid composition is used in a pultrusion process. The fibers are led through a resin batch containing the composition according to the invention. The fibers as fibrous substrate are, for example, in the form of unidirectional rovings or continuous filament mats. After impregnation in a resin bath, the wet fibers are pulled through a heated die where polymerization takes place.

[0150] A third preferred manufacturing method or process for preparing polymer composite PC1 from (meth)acrylic composition MC1 is vacuum assisted resin infusion (VARI).

[0151] The process for manufacturing composite parts, as well as mechanical or structured parts or products, or the process for preparing the (meth)acrylic polymer composite PC1 from the (meth)acrylic composition MC1 can further comprise a step of post-forming or deformation. Post-forming includes bending to change the shape of the composite part.

[0152] The methods for manufacturing composite parts, as well as mechanical or structured parts or products, may further comprise welding or bonding or lamination steps.

[0153] The thermoplastic composite parts obtained from the process or method according to the invention can be post-molded after polymerization of the liquid composition of the invention. Molding includes bending to change the morphology of the composite.

[0154] After polymerization of the inventive (meth)acrylic composition MC1 and / or the thermoplastic parts obtained from the process according to the invention or the composite parts produced can be welded, glued or laminated.

[0155] The invention further relates to a method for deforming a polymer composite PC1 or a polymer composite part, as well as a mechanical or structured part or product, said method comprising the steps of: i) providing a polymer composite PC1 or part; ii) heating the polymer composite PC1 or the part; iii) deforming the polymer composite PC1 or the part; Includes.

[0156] It is understood that during deformation, the polymer composite PC1 changes its morphology during the deformation process. After the deformation process, the morphology of the polymer composite PC1 differs from that of the polymer composite PC1 provided before the heating process.

[0157] The deformation can be, for example, twisting, bending, curving or folding.

[0158] The temperature of the heating step is at least 120°C, preferably 140°C, more preferably at least 160°C.

[0159] The temperature in the heating step is 230°C or less, preferably 200°C or less.

[0160] Preferably, the temperature of the heating step is between 160°C and 200°C, advantageously between 160°C and 180°C.

[0161] In an exemplary embodiment of the method for transforming the polymer composite PC1 or polymer composite part, as well as mechanical or structured parts or products, the method comprises: i) providing a polymer composite PC1 in the form of an FRP rebar; ii) heating the FRP rebar; iii) bending the FRP rebar; Includes.

[0162] A twisting step may also be included between steps ii) and iii).

[0163] The bending can be performed, for example, by the methods and apparatus disclosed in WO2021 / 008896.

[0164] Uses of mechanical parts made from the composite materials thus produced include automotive applications, transportation applications such as buses or trucks, marine applications, rail applications, sports, aerospace applications, photovoltaic applications, computer related applications, construction and building applications, telecommunications applications and wind energy applications.

[0165] Mechanical parts made of composite materials are in particular car parts, boat parts, bus parts, train parts, sports equipment, airplane or helicopter parts, spacecraft or rocket parts, photovoltaic module parts, materials for construction or building, such as composite rebars, dowels and stirrups for civil engineering and high-rise construction, wind turbine parts, such as spar caps for the girders of wind turbine blades, furniture parts, construction or building parts, telephone or mobile phone parts, computer or television parts or printer or copier parts.

[0166] In a first preferred embodiment, the mechanical parts made of composite material are in particular construction or building materials, such as composite rebars, dowels and stirrups for civil engineering and high-rise construction.

[0167] In a second preferred embodiment, the mechanical part made of composite material is in particular a wind turbine part, for example a spar cap of a girder of a wind turbine blade.

[0168] In one particular embodiment, the composite part produced is a bendable FRP rebar for use in concrete.

[0169] The present invention further relates to a reinforced concrete comprising as reinforcing elements a composite bar made according to the method for preparing the (meth)acrylic polymer composite composition PC1, said composite bar comprising the polymerized (meth)acrylic composition MC1 as a polymer matrix.

[0170] [method] Alkaline resistance is evaluated in accordance with ASTM D7705 / D7705M-12 (Reapproved 2019) Standard Test Method for Alkaline Resistance of Fiber-Reinforced Polymer (FRP) Matrix Composite Bars Used in Concrete Construction.

[0171] According to the method and apparatus disclosed in WO2021 / 008896, a fiber reinforced polymer (FRP) matrix composite bar is heated to a maximum of 170°C and then bent. EXAMPLES

[0172] A liquid (meth)acrylic syrup S0 is prepared by dissolving 25 parts by weight of PMMA (BS520, a copolymer of MMA with ethyl acrylate as comonomer) in 75 parts by weight of methyl methacrylate stabilized with MEHQ (hydroquinone monomethyl ether). Syrup S0 is used to prepare the compositions of the examples of the invention by adding additional compounds. Syrup S0 has a dynamic viscosity of 475 mPa*s at 25°C.

[0173] Comparative Example 1: Syrup S2 is prepared from syrup S0 by adding 2 parts by weight of ethylene glycol dimethacrylate to 100 parts by weight of syrup S0.

[0174] Example 1 Syrup S1 is prepared from syrup S0 by adding 10 parts by weight of bisphenol A epoxy dimethacrylate (CN159 from SARTOMER), 7.44 parts of styrene and 0.23 parts of methacrylic acid to 100 parts by weight of syrup S0.

[0175] Each of the syrups S1 and S2 is blended with 1 phr of initiator di(4-tert-butylcyclohexyl) peroxydicarbonate (P16 - Perkadox® 16 from Akzo Nobel), 1 phr of Luperox LP and 1 phr of Trigonox 21S (from AKZO) per part of the syrup, which are added as polymerization initiators. Each composition is mixed to obtain a homogeneous composition. Each composition is placed under vacuum and degassed at 21°C.

[0176] The syrup is used in the pultrusion method to prepare straight FRP rebars with a diameter of 13 mm. The polymerization is carried out at a temperature between 100°C and 130°C, and the length of the pultrusion die is 1 m.

[0177] Comparative Example 2: Using Schock vinylester-based FRP rebar: Straight Schock Combar® with a core diameter of 12 mm

[0178] The resulting FRP rebars are tested for alkali resistance and bendability.

[0179] Table 1 results TIFF2025500286000005.tif31170

[0180] The rebar samples according to the invention are much better, they are alkali resistant and can be bent.

Claims

1. a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10 and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, and b) between 0.01 and 30 phr by weight of a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2) and at least two hydroxyl groups, c) optionally, between 0.1 phr and 5 phr of initiator (Ini) for initiating the polymerization of the (meth)acrylic monomer (M1) with the polymerizable groups (PG1) and (PG2); The (meth)acrylic composition MC1 comprises:

2. The (meth)acrylic composition MC1 according to claim 1, characterized in that the two polymerizable groups (PG1) and (PG2) of the compound (C1) are carbon double bonds.

3. The (meth)acrylic composition MC1 according to claim 1, wherein the two polymerizable groups (PG1) and (PG2) of the compound (C1) are α,β-unsaturated carbonyl groups.

4. 2. The (meth)acrylic composition MC1 according to claim 1, characterized in that the two polymerizable groups (PG1) and (PG2) of compound (C1) are selected from acrylate groups, methacrylate groups, or condensation products comprising maleic acid, itaconic acid, or fumaric acid.

5. 2. The (meth)acrylic composition MC1 according to claim 1, wherein the compound (C1) is a vinyl ester or an unsaturated polyester.

6. 2. The (meth)acrylic composition MC1 according to claim 1, characterized in that the (meth)acrylic monomer (M1) is selected from alkylacrylic or alkylmethacrylic monomers and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbons.

7. 2. (Meth)acrylic composition MC1 according to claim 1, characterized in that it comprises between 0.1 phr and 5 phr of an initiator (Ini) for initiating the polymerization of the (meth)acrylic monomer (M1) with the polymerizable groups (PG1) and (PG2).

8. A method for preparing the (meth)acrylic composition MC1 according to claim 1, comprising: i) the following ingredients: a) 100 parts of a liquid (meth)acrylic syrup, a1) between 10 and 50% by weight of a (meth)acrylic polymer (P1), a2) between 50% and 90% by weight of a (meth)acrylic monomer (M1) containing only one (meth)acrylic functional group, b) between 0.01 and 30 phr by weight of a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2) and at least two hydroxyl groups, c) optionally, between 0.1 phr and 5 phr of an initiator (INI) to initiate the polymerization of the (meth)acrylic monomer (M1) with the polymerizable groups (PG1) and (PG2); providing ii) mixing components a)-b or a)-c); A method comprising:

9. A method for preparing a (meth)acrylic polymer composition or for preparing a (meth)acrylic polymer composite PC1, comprising: i) providing a (meth)acrylic composition MC1 according to claim 1 or a (meth)acrylic composition MC1 prepared by the method according to claim 8; ii) polymerizing the (meth)acrylic composition MC1; A method comprising:

10. A method for preparing polymer conjugate PC1, comprising: i) impregnating a fiber or a fibrous substrate with the (meth)acrylic composition MC1 according to claim 1 or the (meth)acrylic composition MC1 prepared by the method according to claim 8; ii) polymerizing the (meth)acrylic composition MC1 impregnated into the fiber or fibrous substrate; A method comprising:

11. 1. A method for deforming a polymer composite PC1 or a polymer composite part, as well as a mechanical or structured part or product, comprising: i) providing a polymer composite PC1 or part made by polymerizing a (meth)acrylic composition MC1 according to claim 1 or prepared by the method according to claim 8; ii) heating the polymer composite PC1 or the part; iii) deforming the polymer composite PC1 or the part; A method comprising:

12. 12. The method of claim 11, wherein the deformation is a twist, a bend, a curve, or a folding.

13. 12. The method according to claim 11, characterized in that the polymer composite PC1 is in the form of an FRP rebar.

14. i) providing a polymer composite PC1 in the form of an FRP rebar; ii) heating the FRP rebar; iii) bending the FRP rebar; The method of claim 11 , comprising:

15. 1. A method for preparing FRP rebar, comprising: i) providing a (meth)acrylic composition MC1 according to claim 1 or a (meth)acrylic composition MC1 prepared by the method according to claim 8; ii) impregnating a fiber or fibrous substrate with the (meth)acrylic composition MC1; iii) polymerizing the (meth)acrylic composition MC1 impregnated into the fiber or fibrous substrate; A method comprising:

16. 10. Use of the (meth)acrylic composition MC1 according to claim 1 or prepared by the method according to claim 8 for impregnating fibers or fibrous substrates.

17. 10. Use of the (meth)acrylic composition MC1 according to claim 1 or the (meth)acrylic composition MC1 prepared by the method according to claim 8 for preparing FRP rebars.

18. 16. Use of FRP rebar made by the method of claim 15 in concrete.