(METH)ACRYLIC COMPOSITION, COMPOSITE MATERIAL OBTAINED FROM SUCH A COMPOSITION, PROCESS FOR THE PRODUCTION OF SAID COMPOSITION AND CORRESPONDING USES

Abstract

(Meth)acrylic composition, composite material obtained from such a composition, process for producing said composition, and corresponding uses. The present invention relates to a (meth)acrylic composition and also to a composite material obtained by polymerization of such a (meth)acrylic composition. In particular, the present invention relates to a (meth)acrylic composition also comprising a block copolymer, preferably a (meth)acrylic block copolymer, and also to a composite material obtained by polymerization of such a (meth)acrylic composition comprising a block copolymer, preferably a (meth)acrylic block copolymer.More particularly, the present invention relates to a (meth)acrylic composition comprising a (meth)acrylic block copolymer and a mineral filler, as well as a composite material obtained by polymerizing such a (meth)acrylic composition comprising a (meth)acrylic block copolymer and a mineral filler. The invention also relates to a method for manufacturing a (meth)acrylic composition comprising a (meth)acrylic block copolymer and a mineral filler, a method for manufacturing a composite material obtained by polymerizing such a (meth)acrylic composition, and also the uses of such a (meth)acrylic composition and such a composite material obtained.

Description

Title of the invention: (Meth)acrylic composition, composite material obtained from such a composition, process for the production of SAID COMPOSITION and corresponding uses Technical field

[0001] The present invention relates to a (meth)acrylic composition and also to a composite material obtained by polymerization of such a (meth)acrylic composition.

[0002] In particular, the present invention relates to a (meth)acrylic composition also comprising a block copolymer, preferably a (meth)acrylic block copolymer and also to a composite material obtained by polymerization of such a (meth)acrylic composition comprising a block copolymer, preferably a (meth)acrylic block copolymer.

[0003] More particularly, the present invention relates to a (meth)acrylic composition also comprising a (meth)acrylic block copolymer and a mineral filler as well as a composite material obtained by polymerization of such a (meth)acrylic composition comprising a (meth)acrylic block copolymer and a mineral filler.

[0004] The invention also relates to a method for manufacturing a (meth)acrylic composition comprising a (meth)acrylic block copolymer and a mineral filler, a method for manufacturing a composite material obtained by polymerization of such a (meth)acrylic composition and also the uses of such a (meth)acrylic composition and of such a composite material obtained. [Technical problem]

[0005] A composite material is a macroscopic combination of two or more immiscible materials. The composite material consists of at least one matrix material that forms a continuous phase for the cohesion of the structure and a reinforcing material having various architectures for mechanical properties.

[0006] The objective when using composite materials is to obtain from the composite material performances which are not available from its separate constituents if used alone. Therefore, composite materials are widely used in several industrial sectors such as for example construction, automotive, aerospace, transport, leisure, electronics and sports, in particular due to their better mechanical performances (higher tensile strength, higher tensile modulus, higher fracture toughness) compared to homogeneous materials and their low density.

[0007] The largest class in terms of volume on a commercial industrial scale is that of organic matrix composites, in which the matrix material is generally a polymer. The main matrix or continuous phase of a polymer composite material is either a thermoplastic polymer or a thermosetting polymer.

[0008] One way of preparing a polymer composite material based on thermoplastic polymers is to use a liquid polymer composition comprising a monomer, commonly referred to as a "syrup". Such a syrup is used for mixing with a mineral filler or impregnating the reinforcing material, for example, or a fibrous substrate.

[0009] The polymerization of the liquid polymer composition filled with a mineral filler usually takes place in a mold.

[0010] There is a need for a polymeric composition which provides a (meth)acrylic composition comprising a monomer which can be readily mixed with mineral fillers or fillers.

[0011] There is also a need to regulate the heat generated during the polymerization of a (meth)acrylic composition comprising a monomer. By "regulating the heat" is meant reducing the heat generated during the exothermic polymerization reaction, to avoid excessively high temperatures in the mold, for faster cooling and faster demolding, producing a faster process.

[0012] There is also a need to reduce the gloss of polymer composites comprising a mineral filler, in order to obtain a matte surface appearance like that of natural stones.

[0013] Another object of the present invention is to provide a method for manufacturing such a composite material, this method being easy to carry out and making it possible to obtain the material in a limited number of steps with the equipment and tools of the industrial installations currently used for the manufacture of composite materials. [CONTEXT OF THE INVENTION]Prior art

[0014] (Meth)acrylic compositions and composite materials based on com (meth)acrylic or resin positions also with mineral fillers have been described in a number of documents.

[0015] Document WO 2013 / 056845 relates to a composite material comprising a thermoplastic (meth)acrylic matrix and a reinforcing material formed by a fibrous material which may have various shapes and sizes and may be of natural or synthetic origin. The thermoplastic (meth)acrylic matrix may in particular be obtained from a viscous liquid composition, called “syrup (meth)acrylic liquid”, which comprises (meth)acrylic monomers, or mixtures of (meth)acrylic monomers, and oligomers or polymers dissolved in these monomers.

[0016] Document US2008 / 0132607 discloses a molded plastic body and a method for producing the same. A molded plastic body is produced from a cured reaction mixture. The reaction mixture in the uncured state is castable and comprises an inorganic particle-like filler in an amount of 50 to 90 percent by weight relative to the reaction mixture, a crosslinking agent, and a binder solution in an amount of 10 to 50 percent by weight relative to the reaction mixture. The binder solution has a monomer and a polymer dissolved therein.

[0017] WO2014 / 105936 relates to an improved mineral acrylic composite and a method. The document describes a composition for the manufacture of a molding, a thermoformable sheet or a plate. Said composition comprises: a.) 25 to 100 percent of a syrup, comprising: 0 to 50% by weight or 35 to 99% by weight of a prepolymerized monomer; 50 to 100% by weight or 35 to 99% by weight of at least one monomer; 0 to 20% by weight of at least one crosslinking agent; and 0 to 5% by weight of at least one chain transfer agent; and b.) solid particulate materials, comprising: 0 to 70% by weight of aluminum trihydrate; and 0 to 5% by weight of at least one dispersant.

[0018] Document EP2791075A1 discloses a synthetic marble having high hardness and a method for manufacturing the synthetic marble. The raw materials for the synthetic marble consist of 200 to 500 parts by weight of an inorganic filler, 0.2 to 5 parts by weight of a crosslinking agent, and 0.2 to 3 parts by weight of a crosslinking promoter relative to 100 parts by weight of an acrylic-based resin syrup consisting of 10 to 50 percent by weight of acrylic-based resin and 50 to 90 percent by weight of acrylic-based monomer.

[0019] Document US2021 / 0087383 discloses a thermosetting biologically based molding composition. The composition comprises (a) one or more monofunctional acrylic and / or methacrylic biomonomers and one or more polyfunctional acrylic and / or methacrylic biomonomers of plant or animal origin, (b) one or more polymers or copolymers selected from polyacrylates, polymethacrylates, polyols, polyesters derived from recycled materials or of plant or animal origin, and (c) inorganic filler particles of natural origin, wherein the proportion of the monofunctional and polyfunctional acrylic and methacrylic biomonomer(s) is 10 to 40 percent by weight, the proportion of the polymer(s) or copolymer(s) is 1 to 16 percent by weight and the proportion of the inorganic filler particles is 44 to 89 percent by weight. weight.

[0020] None of the prior art documents disclose a block copolymer in the composition. [Brief description of the invention]

[0021] Surprisingly it was found that a (meth)acrylic MCI composition comprising:

[0022] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0023] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0024] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0025] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0026] (c) optionally from 20 parts by weight to 300 parts by weight of a filler mineral C,

[0027] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and

[0028] (e) optionally from 0.01 part by weight to 5 parts by weight of a poly initiator merization;

[0029] makes it possible to provide a composition for the preparation of (meth)acrylic polymers or composites which have a lower energy release during polymerization compared to a composition not comprising component b). By "lower energy release during polymerization" is meant that the heat generated during the exothermic polymerization process is lower, which means a lower increase in temperature.

[0030] Surprisingly it was also found that a (meth)acrylic MCI composition comprising:

[0031] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0032] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0033] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0034] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0035] (c) optionally from 20 parts by weight to 300 parts by weight of a filler mineral C,

[0036] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, the

[0037] (e) optionally from 0.01 part by weight to 5 parts by weight of a poly initiator merization;

[0038] makes it possible to provide a polymeric (meth)acrylic composite after polymerization of said MCI (meth)acrylic composition which has a lower gloss compared to a composition not comprising component b).

[0039] Surprisingly it was also found that a (meth)acrylic MCI composition comprising:

[0040] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0041] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0042] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0043] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0044] (c) optionally from 20 parts by weight to 300 parts by weight of a filler mineral C,

[0045] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and

[0046] (e) optionally from 0.01 part by weight to 5 parts by weight of a poly initiator merization;

[0047] can be used to reduce the cycle time for the polymerization of said (meth)acrylic MCI composition compared to a composition not comprising component b).

[0048] Surprisingly, it has been found that a process for the preparation of a polymeric composite material from a (meth)acrylic MCI composition, said process comprising the following steps:

[0049] i) the provision of the following components

[0050] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0051] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0052] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0053] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0054] (c) from 20 parts by weight to 300 parts by weight of a mineral filler C,

[0055] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and

[0056] (e) optionally from 0.01 part by weight to 5 parts by weight of a poly initiator merization;

[0057] ii) the mixture of components a) to e).

[0058] iii) the polymerization of the (meth)acrylic composition MCI;

[0059] leads to a process for the preparation of polymeric (meth)acrylic composites which have a lower energy release during polymerization compared to a process comprising a composition not comprising component b). Description of the embodiments

[0060] According to a first aspect, the present invention relates to a (meth)acrylic MCI composition, said composition comprising:

[0061] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0062] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0063] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0064] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0065] (c) optionally from 20 parts by weight to 300 parts by weight of a filler mineral C,

[0066] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer.

[0067] According to a second aspect, the present invention relates to a (meth)acrylic MCI composition, said composition comprising:

[0068] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0069] (ai) from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0070] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0071] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0072] (c) from 20 parts by weight to 300 parts by weight of a mineral filler C,

[0073] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and

[0074] (e) from 0.01 part by weight to 5 parts by weight of a polymerization initiator.

[0075] According to a third aspect, the present invention relates to a method for the pre preparation of a (meth)acrylic MCI composition comprising the following steps:

[0076] i) the supply of the following components:

[0077] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0078] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0079] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0080] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0081] (c) optionally from 20 parts by weight to 300 parts by weight of a filler mineral C, and

[0082] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer; and

[0083] ii) the mixture of components a) to d).

[0084] According to a fourth aspect, the present invention relates to a process for the preparation of a (meth)acrylic MCI composition, the process comprising the following steps:

[0085] i) the supply of the following components:

[0086] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0087] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0088] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0089] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0090] (c) from 20 parts by weight to 300 parts by weight of a mineral filler C,

[0091] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, the

[0092] (e) from 0.01 part by weight to 5 parts by weight of a polymerization initiator; and

[0093] ii) the mixture of components a) to e).

[0094] According to a fifth aspect, the present invention relates to the use of a (meth)acrylic MCI composition for preparing a polymeric composite material, said (meth)acrylic MCI composition comprising:

[0095] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0096] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0097] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0098] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0099] (c) from 20 parts by weight to 300 parts by weight of a mineral filler C,

[0100] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer.

[0101] According to a sixth aspect, the present invention relates to the use of a (meth)acrylic MCI composition for preparing a polymeric composite material, said (meth)acrylic MCI composition comprising:

[0102] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0103] (ai) from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0104] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0105] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0106] (c) from 20 parts by weight to 300 parts by weight of a mineral filler C,

[0107] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and

[0108] (e) from 0.01 part by weight to 5 parts by weight of a polymerization initiator.

[0109] According to a seventh aspect, the present invention relates to a method for the fa manufacturing a polymer composite material from a (meth)acrylic MCI composition, said method comprising the following steps:

[0110] i) the provision of the following components

[0111] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0112] (aO from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0113] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0114] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0115] (c) from 20 parts by weight to 300 parts by weight of a mineral filler C,

[0116] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and

[0117] (e) optionally from 0.01 part by weight to 5 parts by weight of a poly initiator merization;

[0118] ii) the mixture of components a) to e).

[0119] iii) the polymerization of the (meth)acrylic composition MCI.

[0120] According to an eighth aspect, the present invention relates to a method for reducing the cycle time for the preparation of a polymeric composite material from a (meth)acrylic MCI composition, said method comprising the following steps:

[0121] i) the provision of the following components

[0122] (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising:

[0123] (ai) from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and

[0124] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0125] (b) from 0.5 parts by weight to 15 parts by weight of a BC1 block copolymer,

[0126] (c) from 20 parts by weight to 300 parts by weight of a mineral filler C,

[0127] (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and

[0128] (e) from 0.01 part by weight to 5 parts by weight of a polymerization initiator;

[0129] ii) the mixture of components a) to e).

[0130] iii) the polymerization of the (meth)acrylic composition MCI.

[0131] The term "(meth)acrylic monomer" covers both an acrylic monomer and a methacrylic monomer. Similarly, the term "(meth)acrylic polymer" covers not only an acrylic homopolymer but also a methacrylic homopolymer, an acrylic copolymer and a methacrylic copolymer.

[0132] The term "PMMA" in the present context refers to homopolymers and copolymers of methyl methacrylate (MMA), for the MMA copolymer the weight ratio of MMA within PMMA is at least 50% by weight.

[0133] The term "initiator", in the present context, refers to a chemical species that forms a compound or an intermediate compound that starts the polymerization of a monomer, which is capable of successively linking a large number of other monomers into a polymeric compound.

[0134] The term "polymer composite" as used herein refers to a multi-component material comprising a plurality of different phase domains in which at least one type of phase domain is a continuous phase and in which at least one component is a polymer.

[0135] The term "lower energy release during polymerization", in the present context, means that the heat generated during the exothermic polymerization process is lower, meaning a lower temperature increase, for the composition of the invention.

[0136] The term "thermoplastic" in the present context means a polymer that becomes liquid or becomes more liquid or less viscous when heated and that can take new shapes by the application of heat and possibly pressure. This also applies to slightly crosslinked thermoplastic polymers that can be thermoformed when heated above the softening temperature.

[0137] By specifying that a range is from x to y in the present invention, this means that the upper and lower limits of this range are included, which is equivalent to at least x and up to y.

[0138] By specifying that a range is between x and y in the present invention, this means that the upper and lower limits of this range are excluded, which is equivalent to more than x and less than y.

[0139] The liquid (meth)acrylic syrup (a) according to the invention comprises (aj) a (meth)acrylic polymer PI and (a2) a (meth)acrylic monomer ML

[0140] The liquid (meth)acrylic syrup (a) according to the (meth)acrylic composition MCI of the invention comprises between 1% by weight and 50% by weight of a (meth)acrylic polymer PI and between 50% by weight and 99% by weight of a (meth)acrylic monomer ML. Preferably, the liquid (meth)acrylic syrup comprises between 2% by weight and 50% by weight of a (meth)acrylic polymer PI and between 50% by weight and 98% by weight of a (meth)acrylic monomer Ml, more preferably between 2% by weight and 40% by weight of a (meth)acrylic polymer PI and between 60% by weight and 98% by weight of a (meth)acrylic monomer Ml, even more preferably between 3% by weight and 40% by weight of a (meth)acrylic polymer PI and between 60% by weight and 98% by weight of a (meth)acrylic monomer Ml, even more preferably between 3% by weight and 40% by weight of a (meth)acrylic polymer PI and between 60% by weight and 98% by weight of a (meth)acrylic monomer Ml. by weight and 97% by weight of a (meth)acrylic monomer Ml,advantageously between 3% by weight and 35% by weight of a (meth)acrylic polymer PI and between 65% by weight and 97% by weight of a (meth)acrylic monomer Ml and more advantageously between 3% by weight and 30% by weight of a (meth)acrylic polymer PI and between 70% by weight and 97% by weight of a (meth)acrylic monomer ML,

[0141] The dynamic viscosity of the liquid (meth)acrylic syrup is in a range of 10 mPa*s to 10,000 mPa*s, preferably 20 mPa*s to 7,000 mPa*s and advantageously preferably from 20 mPa*s to 5,000 mPa*s and more preferably from 20 mPa*s to 2,000 mPa*s and even more preferably between 20 mPa*s and 1,000 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, meaning that it does not exhibit shear thinning, the dynamic viscosity is independent of the shear in a rheometer or the speed of the spindle in a viscometer. If the liquid composition has non-Newtonian behavior, meaning that it exhibits shear thinning, the dynamic viscosity is measured at a shear rate of 1s 1 at 25 °C.

[0142] As regards the liquid (meth)acrylic syrup (a), it comprises (a,) the (meth)acrylic monomer M1 and (a2) the (meth)acrylic polymer PL. Once the (meth)acrylic composition MCI has been polymerized, the (meth)acrylic monomer M1 copolymerizes with the (meth)acrylic monomer M2 and is transformed into a (meth)acrylic polymer P2 comprising the monomeric units of the (meth)acrylic monomer M1 and the (meth)acrylic monomer M2 and other possible comonomers.

[0143] The liquid (meth)acrylic syrup of the (meth)acrylic composition MCI according to the invention may comprise only one (meth)acrylic polymer PI, but may also comprise a mixture of two, three, or even more (meth)acrylic polymers PL. If there is a mixture of different (meth)acrylic polymers PI, the difference is the composition of the respective (meth)acrylic polymer PI or the molecular weight of the respective (meth)acrylic polymer PI or both.

[0144] The (meth)acrylic polymer PI or each (meth)acrylic polymer PI included in the liquid (meth)acrylic syrup may in particular be chosen from:

[0145] . poly(alkyl acrylate)s which comprise homopolymers of alkyl acrylate and alkyl acrylate copolymers, and

[0146] . poly(alkyl methacrylate)s which comprise homopolymers of me alkyl acrylate and alkyl methacrylate copolymers.

[0147] According to a preferred embodiment, the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is a poly(methyl methacrylate) (PMMA), it being understood that, as indicated above, the poly(methyl methacrylate) (PMMA) can denote a homopolymer of methyl methacrylate (MMA) or a copolymer of MMA.

[0148] In particular, in the case where the liquid (meth)acrylic syrup comprises a mixture of two or more poly(methyl methacrylate) PI, this mixture can be formed by mixing at least two homopolymers of MMA having a different molecular weight, by mixing at least two copolymers of MMA having a com identical monomer position and different molecular weight, by mixing at least two MMA copolymers having different monomer composition or by mixing at least one MMA homopolymer and at least one MMA copolymer.

[0149] According to a first preferred embodiment, the (meth)acrylic polymer PI is chosen from a homopolymer of methyl methacrylate and a copolymer of methyl methacrylate or a corresponding mixture, the methyl methacrylate advantageously representing at least 50% by weight of the (meth)acrylic polymer PI or of each (meth)acrylic polymer PI.

[0150] According to one embodiment of the invention, methyl methacrylate represents at least 55% by weight of the (meth)acrylic polymer PI or of each (meth)acrylic polymer PI.

[0151] According to another particular embodiment, the (meth)acrylic polymer PI or each (meth)acrylic polymer PI comprises at least 70%, advantageously at least 80%, preferably at least 90% and more preferably at least 95% by weight of methyl methacrylate.

[0152] When the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is a methyl methacrylate (MMA) copolymer, it may comprise at least one comonomer containing at least one ethylenic unsaturation and which is capable of copolymerizing with methyl methacrylate. Among these monomers, mention may in particular be made of acrylic and methacrylic acids and alkyl (meth)acrylates in which the alkyl group contains from 1 to 12 carbon atoms. The term "alkyl (meth)acrylates" means an alkyl ester of acrylic acid or methacrylic acid. As examples of comonomers, mention may be made of methyl acrylate and an ethyl, butyl or 2-ethylhexyl (meth)acrylate.

[0153] Advantageously, the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and an alkyl acrylate or an alkyl methacrylate in which the alkyl group contains from 1 to 12 carbon atoms, advantageously from 1 to 6 carbon atoms and preferentially from 1 to 4 carbon atoms.

[0154] According to a first preferred embodiment, when the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is a methyl methacrylate (MMA) copolymer, this methyl methacrylate (MMA) copolymer comprises from 70% to 99.9%, advantageously from 80% to 99.9%, preferentially from 90% to 99.9% and more preferentially from 95% to 99.9% by weight of methyl methacrylate and from 0.1% to 30%, advantageously from 0.1% to 20%, preferentially from 0.1% to 10% and more preferentially from 0.1% to 5% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate. Preferably the comonomer or each comonomer is chosen from methyl acrylate and ethyl acrylate.

[0155] In an advantageous variant of the first preferred embodiment, when the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is a copolymer of methyl methacrylate (MMA), the (meth)acrylic polymer PI is a copolymer of methyl methacrylate and alkyl acrylate.

[0156] In a preferred variant of the first preferred embodiment, when the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is a copolymer of methyl methacrylate (MMA), the (meth)acrylic polymer PI is a copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate.

[0157] According to a second preferred embodiment, when the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is a methyl methacrylate (MMA) copolymer, this methyl methacrylate (MMA) copolymer comprises from 50% to 99.9%, advantageously from 52% to 99.9%, preferably from 53% to 99.9% and more preferably from 55% to 99.9% by weight of methyl methacrylate and from 0.1% to 50%, advantageously from 0.1% to 48%, preferably from 0.1% to 47% and more preferably from 0.1% to 45% by weight of at least one comonomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate. Preferably, the or each comonomer is selected from methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate.

[0158] The weight-average molecular weight, denoted Mw, of the (meth)acrylic polymer PI or of each (meth)acrylic polymer PI is generally high and may therefore be greater than 40,000 g / mol, advantageously greater than 45,000 g / mol and preferably greater than 50,000 g / mol. The weight average molecular weight can be measured by size exclusion chromatography (SEC).

[0159] The (meth)acrylic polymer PI, if not crosslinked, usually has a melt flow rate (MFR) according to ISO 1133-2:2011 (230 °C / 3.8 kg) of between 0.1 g / 10 min and 20 g / 10 min or the melt flow rate is between 0.2 g / 10 min and 18 g / 10 min, or between 0.3 g / 10 min and 16 g / 10 min or between 0.4 g / 10 min and 13 g / 10 min.

[0160] The liquid (meth)acrylic syrup of the (meth)acrylic composition MCI according to the invention may comprise only one (meth)acrylic monomer M1, but may also comprise a mixture of two, three, or even more, (meth)acrylic monomers ML. This would be a (meth)acrylic monomer M1 a, a monomer (meth)acrylic Mlb, (meth)acrylic monomers Mlc etc.

[0161] If the liquid (meth)acrylic syrup comprises one or more (meth)acrylic monomers Ml, the (meth)acrylic monomer Ml or each (meth)acrylic monomer Ml comprises only one (meth)acrylic function per monomer.

[0162] With respect to the (meth)acrylic monomer (Ml), the monomer is selected from alkylacrylic monomers, alkylmethacrylic monomers, hydroxyalkylacrylic monomers and hydroxyalkylmethacrylic monomers, and mixtures thereof. The term "alkyl acrylic monomer" or "alkyl methacrylic monomer" means an alkyl ester of acrylic acid or methacrylic acid.

[0163] Preferably, the (meth)acrylic monomer (Ml) is chosen from hydroxyalkylacrylic monomers, hydroxyalkylmethacrylic monomers, alkylacrylic monomers, alkylmethacrylic monomers and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbon atoms; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbon atoms.

[0164] Advantageously, the (meth)acrylic monomer (Ml) 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.

[0165] According to a preferred embodiment, at least 50% by weight and preferably at least 60% by weight of the (meth)acrylic monomer (Ml) is methyl methacrylate.

[0166] 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 90% by weight of the monomer (Ml) is a mixture of methyl methacrylate with optionally at least one other monomer.

[0167] In a first variant of the invention, the liquid (meth)acrylic syrup comprises

[0168] (aO from 3% by weight to 27% by weight and preferably from 3% by weight to 24% by weight of the (meth)acrylic polymer(s) PI, and

[0169] (a2) from 77% by weight to 97% by weight and preferably from 76% by weight to 97% by weight of the (meth)acrylic monomer(s) Ml.

[0170] In a second variant of the invention, the liquid (meth)acrylic syrup comprises:

[0171] (ai) from 3% by weight to 25% by weight and preferably from 4% by weight to 25% by weight and more preferably from 5% by weight to 25% by weight and even more preferably from 5% by weight to 24% by weight of the (meth)acrylic polymer(s) PI, and

[0172] (a2) from 75% by weight to 97% by weight and preferably from 75% by weight to 96% by weight and more preferably from 75% by weight to 95% by weight and even more preferably from 76% by weight to 95% by weight of the (meth)acrylic monomer(s) Ml.

[0173] In an advantageous variant, the (meth)acrylic polymer PI or each (meth)acrylic polymer PI and the (meth)acrylic monomer Ml or each (meth)acrylic monomer Ml of the liquid (meth)acrylic syrup comprises at least one same (meth)acrylic unit, such a variant making it possible to optimize the solubility of the (meth)acrylic polymer(s) PI in the (meth)acrylic monomer(s) Ml.

[0174] Preferably, the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is chosen from a homopolymer of methyl methacrylate or copolymer of methyl methacrylate and methyl acrylate and a copolymer of methyl methacrylate and ethyl acrylate or a copolymer of methyl methacrylate and butyl acrylate or a copolymer of methyl methacrylate and butyl methacrylate, the respective comonomer being present at a rate of at most 45% by weight in the copolymer.

[0175] Preferably, the (meth)acrylic monomer Ml is methyl methacrylate.

[0176] In a first advantageous variant, the liquid (meth)acrylic syrup comprises a (meth)acrylic polymer PI, rather than a mixture of (meth)acrylic polymers PI.

[0177] In a second advantageous variant, the liquid (meth)acrylic syrup comprises a mixture of two (meth)acrylic polymers PI.

[0178] In another advantageous variant, the liquid (meth)acrylic syrup comprises a (meth)acrylic monomer M1, rather than a mixture of (meth)acrylic monomers M1.

[0179] Stabilizers, or reaction inhibitors, may also be present in the liquid (meth)acrylic syrup to prevent spontaneous polymerization of the (meth)acrylic monomer(s) Ml.

[0180] These stabilizers may in particular be chosen from hydroquinone (HQ), hydroquinone monomethyl ether (HQME), 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butyl-4-methoxyphenol (Topanol O) and 2,4-dimethyl-6-tert-butylphenol (Topanol A).

[0181] These stabilizers may be present, in the liquid (meth)acrylic syrup, in a proportion not greater than 5 parts by weight, advantageously not greater than 4 parts by weight and preferably in a proportion of between 0.3 and 3 parts by weight, per 100 parts by weight of the (meth)acrylic polymer(s) PI and the (meth)acrylic monomer(s) Ml.

[0182] With regard to the (meth)acrylic monomer (M2), the monomer is multifunctional. Preferably the (meth)acrylic monomer (M2) is chosen from a compound comprising at least two (meth)acrylic functions. The (meth)acrylic monomer (M2) may also be chosen from a mixture of at least two compounds (M2a) and (M2b) each comprising at least two (meth)acrylic functions.

[0183] The (meth)acrylic monomer (M2) may be chosen 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 bisphenol A diacrylate (10); ethoxylated bisphenol A dimethacrylate (2); ethoxylated bisphenol A diacrylate (3); ethoxylated bisphenol A dimethacrylate (3); ethoxylated bisphenol A diacrylate (4); ethoxylated bisphenol A dimethacrylate (4); ethoxylated bisphenol A dimethacrylate; ethoxylated bisphenol dimethacrylate (10); ethylene glycol dimethacrylate; polyethylene glycol diacrylate (200); polyethylene glycol diacrylate (400); polyethylene glycol dimethacrylate (400); polyethylene glycol dimethacrylate (400); polyethylene glycol diacrylate (600); polyethylene glycol dimethacrylate (600);polyethylene glycol diacrylate 400; propoxylated neopentyl glycol diacrylate (2); tetraethylene glycol diacrylate; tetraethylene glycol dimethacrylate; tricyclodecanedimethanol diacrylate; tricyclodecanedimethanol dimethacrylate; triethylene glycol diacrylate; triethylene glycol dimethacrylate; tripropylene glycol diacrylate; ethoxylated trimethylolpropane triacrylate (15); ethoxylated trimethylolpropane triacrylate (3); ethoxylated trimethylolpropane triacrylate (6); ethoxylated trimethylolpropane triacrylate (9); ethoxylated pentaerythritol triacrylate 5; ethoxylated trimethylolpropane triacrylate (20); propoxylated glyceryl triacrylate (3); trimethylolpropane triacrylate; propoxylated glyceryl triacrylate (5,5); pentaerythritol triacrylate; propoxylated glyceryl triacrylate (3); propoxylated trimethylolpropane triacrylate (3); trimethylolpropane triacrylate;trimethylolpropane trimethacrylate; tris(2-hydroxyethyl) isocyanurate triacrylate; ditrimethylolpropane tetraacrylate; dipentaerythritol pentaacrylate; ethoxylated pentaerythritol tetraacrylate (4); 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; diacrylate; 2-butyl-2-ethyl-1,3-propanediol; 2-methyl-1,3-propanediol diacrylate; 2-methyl-1,3-propanediyl ethoxyacrylate; 3-methyl-1,5-pentanediol diacrylate; alkoxylated cyclohexanedimethanol diacrylate; alkoxylated hexanediol diacrylate; cyclohexanedimethanol diacrylate; ethoxylated cyclohexanedimethanol diacrylate; diethylene glycol diacrylate; dioxane glycol diacrylate; ethoxylated dipentaerythritol hexaacrylate; ethoxylated glycerol triacrylate; ethoxylated neopentyl glycol diacrylate; hydroxypivalyl hydroxypivalate diacrylate; neopentyl glycol diacrylate; poly(tetramethylene glycol) diacrylate; polypropylene glycol diacrylate 400; polypropylene glycol diacrylate 700; propoxylated ethoxylated bisphenol A diacrylate (6); propoxylated ethylene glycol diacrylate; propoxylated pentaerythritol tetraacrylate (5); and propoxylated trimethylolpropane triacrylate; or mixtures thereof.

[0184] The (meth)acrylic monomer (M2) may be present in the (meth)acrylic composition MCI between 0.01 and 5 phr by weight, per 100 parts of a liquid (meth)acrylic syrup, more preferably between 0.1 and 4.5 phr, even more preferably between 0.1 and 4 phr and advantageously between 0.1 and 3 phr.

[0185] In a first preferred embodiment, the (meth)acrylic monomer (M2) is present in the (meth)acrylic composition MCI between 0.1 and 5 phr and is chosen from a compound comprising two (meth)acrylic functions.

[0186] In a second preferred embodiment, the (meth)acrylic monomer (M2) is present in the (meth)acrylic composition MCI between 0.1 and 5 phr and is chosen from a mixture of compounds comprising two (meth)acrylic functions.

[0187] In a third preferred embodiment, the (meth)acrylic monomer (M2) is present in the (meth)acrylic composition MCI between 0.1 and 4 phr and is chosen from a mixture of compounds comprising at least two (meth)acrylic functions.

[0188] In a fourth preferred embodiment, the (meth)acrylic monomer (M2) is present in the (meth)acrylic MCI composition between 0.1 and 3 phr and is chosen from a mixture of compounds comprising at least two (meth)acrylic functions. At least one compound of the mixture comprises only two (meth)acrylic functions and presents at least 50% by weight of the (meth)acrylic monomer (M2) mixture, preferably at least 60% by weight.

[0189] The (meth)acrylic composition MCI according to the invention may also comprise a mineral filler C.

[0190] The mineral filler C may in particular comprise a filler Cl chosen from quartz, granite, marble, feldspar, clay, glass, ceramics, mica, graphite, silicates, carbonates, carbides, sulfates, silicates, hydroxides, metal oxides, metals and corresponding mixtures.

[0191] According to a particular embodiment, the charge Cl is in powder form.

[0192] Such a powder may be formed, for example, from particles, among which at least 50% by number have an average particle size, denoted D50, less than or equal to 50 pm, advantageously less than or equal to 20 pm and preferably less than or equal to 5 pm.

[0193] When the Cl filler is chosen from sulfates, this sulfate or these sulfates may be chosen from alkali metal and alkaline earth metal sulfates, preferably magnesium sulfate, calcium sulfate, strontium sulfate and barium sulfate.

[0194] When the filler Cl is chosen from metal oxides, this metal oxide or these metal oxides can be chosen from alumina A12O3, hydrated or not, barium oxide BaO, silica SiO2, magnesium oxide MgO and calcium oxide CaO.

[0195] According to a first preferred embodiment, the metal oxide is silica SiO2. This silica may in particular be a ground crystalline silica or an amorphous silica.

[0196] When the filler Cl is chosen from carbonates, this or these carbonates can be chosen from calcium carbonate (chalk), magnesium carbonate, sodium carbonate and potassium carbonate.

[0197] When the filler Cl is chosen from silicates, this or these silicates may be chosen from calcium silicate, sodium silicate, potassium silicate and magnesium silicate.

[0198] In a variant of the invention, the mineral filler C may also further comprise aluminum trihydrate A1(OH)3, noted C2, and / or reinforcing agents, noted C3.

[0199] The presence of aluminum trihydrate C2 makes it possible in particular to improve the machining of the composite material obtained from the (meth)acrylic composition MCI according to the invention MCI and also the fire resistance properties of this material.

[0200] According to a particular embodiment, the aluminum trihydrate C2 is in the form of particles, among which at least 50% by number have an average particle size, noted D50, less than or equal to 50 pm, advantageously less than or equal to 20 pm and preferably less than or equal to 5 pm.

[0201] The C3 reinforcing agents may in particular be in the form of fibers or beads. These fibers may be natural or synthetic, and short or long.

[0202] In an advantageous variant of the invention, the reinforcing agents C3 can be chosen from glass fabrics, glass fibers and glass beads.

[0203] The (meth)acrylic composition MCI according to the invention comprises from 20 parts by weight to 300 parts by weight of mineral filler C per 100 parts by weight of the syrup Liquid (meth)acrylic.

[0204] According to a particular embodiment, the (meth)acrylic composition MCI according to the invention comprises from 30 parts by weight to 280 parts by weight, advantageously from 50 parts by weight to 250 parts by weight, preferably from 60 parts by weight to 230 parts by weight, more preferably from 80 parts by weight to 200 parts by weight and even more preferably from 100 parts by weight to 200 parts by weight of mineral filler C.

[0205] The (meth)acrylic composition MCI according to the invention can also be used for the impregnation of a fibrous substrate or for being mixed with short fibers.

[0206] As regards the block copolymer BC1, it may be chosen from a thermoplastic block copolymer.

[0207] Advantageously, the block copolymer is amorphous. More advantageously, the block copolymer does not comprise any semi-crystalline or crystalline blocks.

[0208] The block copolymer BC1 comprises at least one block having a glass transition temperature Tv of less than 20°C, preferably less than 10°C, and more preferably less than 0°C.

[0209] Preferably one of the at least other blocks has a glass transition temperature Tv greater than 20°C, preferably greater than 30°C, more preferably greater than 40°C and even more preferably greater than 50°C.

[0210] Most preferably, the thermoplastic block copolymer is a thermoplastic acrylic block copolymer. This means that at least 30% by weight, preferably 40% by weight and more preferably 50% by weight of the monomers within the thermoplastic acrylic block copolymer are alkyl (meth)acrylate monomers.

[0211] Preferably, the thermoplastic acrylic block copolymer has a general formula (A)nB in which: • n is an integer greater than or equal to 1, • A is: an acrylic or methacrylic or styrene homopolymer or copolymer having a Tg greater than 50°C, preferably greater than 80°C, or a polystyrene, or an acrylic / styrene or methacrylic / styrene copolymer; • B is an acrylic or methacrylic homopolymer or copolymer having a Tg of less than 20°C, preferably less than 10°C and more preferably less than 0°C.

[0212] Preferably, in block A, the monomer is chosen from methyl methacrylate (MMA), phenyl methacrylate, benzyl methacrylate, isobutyl methacrylate, styrene (Sty) and alpha-methylstyrene and mixtures thereof. respondent. More preferably, block A is PMMA or PMMA copolymerized with acrylic or methacrylic comonomers or polystyrene (PS) or PS modified with styrenic comonomers.

[0213] Preferably, block B comprises monomers chosen from methyl acrylate, ethyl acrylate, butyl acrylate (BuA), ethylhexyl acrylate and butyl methacrylate and corresponding mixtures, more preferably butyl acrylate, said monomers representing at least 50% by weight, preferably 70% by weight of block B.

[0214] In addition, blocks A and / or B may comprise other acrylic or methacrylic comonomers bearing various chemical functional groups known to a person skilled in the art, for example acid, amide, amine, hydroxyl, epoxy or alkoxy functional groups. Block A may also incorporate groups, such as acrylic acid (AA) or methacrylic acid (MAA), in order to increase the thermal resistance thereof.

[0215] Comonomers such as styrene may also be incorporated into the B block to shift the refractive index relative to the A block.

[0216] Preferably, said thermoplastic acrylic block copolymer has a structure chosen from: AB A, AB, A3B and A4B.

[0217] The thermoplastic acrylic block copolymer, for example, may be one of the following triblock copolymers: pMMA-pBuA-pMMA, p(MMAcoMAA)-pBuA-p(MMAcoMAA), pMMA-p(BuAcoSty)-pMMA, p(MMAcoMAA)-p(BuAcoSty)-p(MMAcoMAA) and pMMA-p(BuAcoAA)-pMMA. In a first preferred embodiment, the block copolymer is of the MMA (PMMAcoMAA)-p(BuAcoSty)-P(MMAcoMAA) type.

[0218] It is also known to a person skilled in the art that PMMA-type polymers may comprise small amounts of acrylate comonomers in order to improve the thermal stability thereof. The term "small" means less than 9% by weight, preferably less than 7% by weight and more preferably less than 6% by weight.

[0219] Block B represents from 10% by weight to 85% by weight of the total weight of the block copolymer BC1, preferably from 25% by weight to 75% by weight and more preferably from 35% by weight to 65% by weight.

[0220] The block copolymer BC1 has a weight average molar mass of between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 g / mol and 300,000 g / mol and more preferably between 20,000 g / mol and 200,000 g / mol.

[0221] The block copolymers participating in the composition of the invention can be obtained by controlled radical polymerization (CRP) or by anionic polymerization; the most suitable process depending on the type of copolymer to be manufactured will be chosen.

[0222] If the process is CRP, it can be in particular in the presence of nitroxides, for block copolymers of type (A)nB and anionic or nitroxide type radical polymerization, for ABA type structures, such as the triblock copolymer.

[0223] The (meth)acrylic composition MCI according to the invention also comprises a polymerization initiator, the function of which is to ensure the start of the polymerization of the (meth)acrylic monomers M1 and M2.

[0224] The polymerization initiator may be selected from organic peroxides, peroxyesters, peroxyacetals and azo-type compounds.

[0225] The polymerization initiator may in particular comprise from 2 to 30 carbon atoms and may be chosen, for example, from tert-amyl peroxyneodecanoate, di(sec-butyl) peroxydicarbonate, diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, bis(2-ethylhexyl) peroxydicarbonate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, bis(3,5,5-trimethylhexanoyl)-peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, peroxydiethylacetate tert-butyl, tert-butyl peroxyisobutyrate, tert-amylperoxy-l-methoxycyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, l,l-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, l,l-di(tert-butylperoxy)cyclohexane, tert-amyl peroxy-2-ethylhexylcarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxy-3,5,5-trimethylhexanoate, peroxy-3,5,tert-butyl 5-trimethylhexanoate, tert-amyl peroxyacetate, tert-butyl peroxyacetate, 2,2-di(tert-butylperoxy)butane, 2,2-di(tert-amylperoxy)butane, tert-amyl peroxybenzoate, tert-butyl peroxybenzoate, butyl 4,4-di(tert-butylperoxy)valerate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 3,5-diisopropylbenzene hydroperoxide, cumene hydroperoxide and mixtures thereof.

[0226] The (meth)acrylic composition according to the invention may comprise from 0.01 part by weight to 5 parts by weight of polymerization initiator.

[0227] According to a particular embodiment, the (meth)acrylic composition according to the invention comprises from 0.02 parts by weight to 4 parts by weight and advantageously 0.03 parts by weight to 3 parts by weight of polymerization initiator per 100 parts by weight of the liquid (meth)acrylic syrup.

[0228] What has just been described for a polymerization initiator is entirely transposable to an initiator system, such a system being made up of a polymerization initiator and a polymerization activator or accelerator.

[0229] The (meth)acrylic composition according to the invention may also effectively further comprise a polymerization activator or accelerator.

[0230] According to a particular embodiment, the (meth)acrylic composition according to the invention comprises from 0.01 part by weight to 1 part by weight, advantageously from 0.02 part by weight to 0.9 part by weight and preferably from 0.03 part by weight to 0.7 part by weight of polymerization activator or accelerator per 100 parts by weight of the (meth)acrylic syrup.

[0231] The present invention relates to a process for the manufacture of a (meth)acrylic MCI composition.

[0232] According to the invention, this method comprises the steps: i) providing components a) to d) or a) to e) and ii) mixing components a) to d) or a) to e).

[0233] Step ii) of the manufacturing process according to the invention is carried out by mixing all the compounds included in the (meth)acrylic composition MCI, taking care to prepare, first, the liquid (meth)acrylic syrup and then to introduce, into this (meth)acrylic syrup, the (meth)acrylic monomers M2 and the block copolymer BC1 and, where appropriate, the polymerization activator or accelerator, and also the mineral filler C, the polymerization initiator being introduced last.

[0234] In one embodiment, the block copolymer BC1 is in the form of particles in order to have easier dispersion and dissolution. The particles preferably have a weight average particle size smaller than 800 pm. More preferably, the weight average particle size is between 40 pm and 500 pm and even more preferably between 50 pm and 300 pm.

[0235] This mixing can be done manually or can be done using a mixer.

[0236] Optionally, the mixing is carried out under a light vacuum so as to eliminate the reaction gases, typically between 80 mbar and 1 bar, advantageously between 100 mbar and 1 bar, more advantageously between 500 mbar and 900 mbar, and for a duration of between 1 minute and 6 hours, advantageously between 2 minutes and 2 hours, more advantageously between 3 minutes and 1 hour and preferably between 4 minutes and 1 hour.

[0237] Other degassing methods are possible.

[0238] The manufacturing process according to the invention is thus a process which is particularly simple to carry out and which can be easily carried out in current installations dedicated to the manufacture of a (meth)acrylic composition.

[0239] The (meth)acrylic MCI composition comprising compounds a) to d) or a) to e) has a viscosity between 50 mPa*s and 10,000 Pa*s at 23°C.

[0240] Preferably, the viscosity of the (meth)acrylic MCI composition comprising compounds a) to d) or a) to e) at 23°C is in a range of 50 mPa*s to 7,000 Pa*s, more preferably 50 mPa*s to 5,000 Pa*s, even more preferably 50 mPa*s to 2 500 Pa*s, even more preferably from 50 mPa*s to 1,000 mPa*s, even more preferably between 50 mPa*s and 500 Pa*s, advantageously between 50 mPa*s and 20,000 mPa*s and more advantageously between 50 mPa*s and 15,000 mPa*s.

[0241] The present invention relates, in a further aspect, to a composite material.

[0242] According to the invention, this composite material is obtained by polymerization of a (meth)acrylic MCI composition as defined above comprising compounds a) to e).

[0243] According to the invention, the composite material is as defined above, that is to say that it is obtained by polymerization of a (meth)acrylic MCI composition in accordance with what has been described, in particular with regard to the characteristics linked to the (meth)acrylic MCI composition, the advantageous characteristics of this (meth)acrylic MCI composition being able to be taken alone or in combination.

[0244] The invention also relates to the uses of the (meth)acrylic composition MCI and of the composite material as defined above, the advantageous characteristics of this (meth)acrylic composition and of these composite materials being able to be taken alone or in combination.

[0245] The (meth)acrylic composition MCI according to the invention can be used for the manufacture of composite parts, in particular with a thermoplastic matrix.

[0246] The (meth)acrylic composition MCI and the composite materials according to the invention can be used in many sectors and in particular in the housing, motor vehicles, railways, sports, aeronautical, aerospace, photovoltaic or wind industry sectors, and in marine applications and medical applications.

[0247] The (meth)acrylic composition MCI can be used to prepare a (meth)acrylic mineral composite and the composite material in one embodiment is a (meth)acrylic mineral composite.

[0248] For example, in the housing sector, these materials can be used for the manufacture of bathroom and / or kitchen equipment, such as worktops, kitchen sinks, bathroom basins, shower trays, bathtubs or shower screens. [Processes]

[0249] The weight average molecular weight can be measured by size exclusion chromatography (SEC). The chromatography column is calibrated with PMMA references having a molecular weight between 402 g / mol and 1,900,000 g / mol. The average molecular weight is expressed in g / mol for the number and average molecular weight Mn and Mw respectively. For the measurement the concentration is 1 g / L.

[0250] The viscosity of (meth)acrylic compositions comprising at least components a), b), c) and d) is measured with a Brookfield viscometer at 23°C, according to ISO 2555:2018 “Plastics - Resins in liquid state or in emulsions or dispersions - Determination of apparent viscosity by the single-cylinder rotary viscometer method”.

[0251] Gloss is measured according to ASTM D523 “Standard Test Method for Specular Gloss”. The measurement is made on samples that have been kept for 24 hours at a humidity of 50% ± 10% at a temperature of 23°C ± 2°C. The measurement is made in front of a black background. Examples

[0252] The compounds used for the preparation of the various (meth)acrylic compositions are as follows:

[0253] - as (meth)acrylic polymer PI: a PMMA formed by a copolymer of methyl methacrylate and ethyl acrylate, from the company Altuglas under the name Altuglas® BS 520B,

[0254] - as (meth)acrylic monomers Ml: a stabilized methyl methacrylate with hydroquinone monomethyl ether,

[0255] - as mineral filler C: aluminum trihydroxide - A1(OH)3,

[0256] - as (meth)acrylic monomer M2: an ethylene glycol dimethacrylate (EGDMA) from Sartomer under the name SR 206,

[0257] - as polymerization initiator: tert-Butyl peroxymaleate of Pergan company under the name Peroxan PM-25 S,

[0258] - as a BC1 block copolymer: a triblock copolymer comprising a block central block of poly(butyl acrylate-co-styrene) and two side blocks of poly(methyl methacrylate) prepared according to the process described for example in documents EP1468029 and EP1526138. Such copolymers are available from Arkema under the name Nanostrength®.

[0259] An SI syrup is prepared first by dissolving 25 parts by weight of PMMA (BS520, a copolymer of MMA comprising ethyl acrylate as a comonomer) as PI in 75 parts by weight of methyl methacrylate as MI, which is stabilized with MEHQ (hydroquinone monomethyl ether).

[0260] Syrup SI is used to prepare the composition of the examples of the invention and the comparative examples by adding additional compounds.

[0261] To 100 parts of syrup SI then 0.6 parts by weight of SR206 are added as M2. Different amounts of block copolymer BC1 are added as BC1 and are dissolved with stirring for 15 min at 25 °C in syrup SL

[0262] Also 400 ppm pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) are added.

[0263] Then 173.7 phr of ATH as mineral filler C is added. 1 phr of BYK 969 is also added.

[0264] Finally, 0.76 phr of anhydrous CaOH as accelerator and 1.34 of Peroxan PM-25 S as initiator are added.

[0265] Table 1 - compositions prepared in phr unless otherwise indicated [Tables 1] Methacrylic composition (comparative) 1 (according to the invention) 2 (according to the invention) Ml +P1 100 100 100 BC1 0 2 5 EGDMA (M2) 0.6 0.6 0.6 PETMP 400 ppm 400 ppm 400 ppm ATH 173.7 173.7 173.7 Initiator 1.34 1.34 1.34 Accelerator 0.76 0.76 0.76 BYK969 1 1 1

[0266] The mixtures of Table 1 are polymerized in two ways.

[0267] In a first manner, 250 g of each composition are prepared in a container and the temperature is measured using a thermal sensor in order to measure the temperature as a function of time to follow the kinetics and the heat generated by the exothermic polymerization reaction.

[0268] In a second way, a composite is prepared in the form of a plate. The reaction mixtures are poured between two glass plates with dimensions of 27 cm x 27 cm separated by a joint. The final plate has a thickness of 4 mm. The gloss of each plate is measured at 85°.

[0269] The temperature as a function of time during polymerization is shown in Figures 1 and 2. Figures 1 and 2 represent the same result, but for better visibility of the respective points, Figure 2 shows only a part of the overall [Fig.l]. Figures 1 and 2 show the temperature for Example 1 (diamond), Example 2 (triangle) according to the invention and the comparative example (square). The peak temperature for Examples 1 and 2 is much lower than the comparative example. The temperature for Examples 1 and 2 is reduced to a lower temperature level much faster than in the comparative example. This means a better control of the exothermic polymerization reaction, faster kinetics and a process involving reduced cycle times.

[0270] The brightness of the plates is measured.

[0271] Table 2 - Gloss measurements on plates obtained from the respective compositions [Tables2] Me-thacrylic composition (comparative) 1 (according to the invention) 2 (according to the invention) Gloss at 85° 37.7 12 6.6

[0272] Table 2 shows a much lower gloss for the composites obtained with the (meth)acrylic composition according to the invention. Thus, the composite obtained with a mineral filler has a surface appearance like a natural material.

Claims

Claims

1. (Meth)acrylic composition MCI comprising: (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising: (ai) from 3% by weight to 50% by weight of one or more (meth)acrylic polymers PI comprising at least 80% by weight of methyl methacrylate, and (a2) from 50% by weight to 97% by weight of one or more (meth)acrylic monomers Ml, each monomer Ml comprising only one (meth)acrylic function per monomer at least 80% by weight of the monomer (Ml) is methyl methacrylate, (b) from 0.5 parts by weight to 15 parts by weight of a block copolymer BC1 which is a thermoplastic acrylic block copolymer with at least 30% by weight of the alkyl (meth)acrylate monomers, (c) optionally from 20 parts by weight weight to 300 parts by weight of a mineral filler C, (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer,and (e) optionally from 0.01 part by weight to 5 parts by weight of a polymerization initiator.,

2. (Meth)acrylic MCI composition according to claim 1, characterized in that it further comprises (c) from 20 parts by weight to 300 parts by weight of a mineral filler c

3. V- (Meth)acrylic MCI composition according to claim 1 or 2, characterized in that it further comprises (e) from 0.01 part by weight to 5 parts by weight of a polymerization initiator.

4. Composition according to any one of claims 1 to 3, characterized in that the (meth)acrylic polymer PI or each (meth)acrylic polymer PI is chosen from a homopolymer of methyl methacrylate and a copolymer of methyl methacrylate or a corresponding mixture, the methyl methacrylate advantageously representing at least 50% by weight of the (meth)acrylic polymer PI or of each (meth)acrylic polymer PI.

5. Composition according to any one of claims 1 to 3, characterized in that the block copolymer BC1 comprises at least one

6.

7.

8. block having a glass transition temperature Tv less than 20°C and at least one other block having a glass transition temperature Tv greater than 20°C. Composition according to any one of claims 1 to 4, characterized in that the block copolymer BC1 with at least 40% by weight of alkyl (meth)acrylate monomers. Composition according to any one of claims 1 to 3, characterized in that the filler C comprises a filler Cl chosen from quartz, granite, marble, feldspar, clay, glass, ceramics, mica, graphite, silicates, carbonates, carbides, sulfates, silicates, hydroxides, metal oxides, metals and corresponding mixtures. Composition according to any one of claims 1 to 3, characterized in that the monomer M2 comprising at least two (meth)acrylic functions per monomer is chosen 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 bisphenol A diacrylate (10); ethoxylated bisphenol A dimethacrylate (2); ethoxylated bisphenol A diacrylate (3); ethoxylated bisphenol A dimethacrylate (3); ethoxylated bisphenol A diacrylate (4); ethoxylated bisphenol A dimethacrylate (4); ethoxylated bisphenol A dimethacrylate; ethoxylated bisphenol dimethacrylate (10); ethylene glycol dimethacrylate; polyethylene glycol diacrylate (200); polyethylene glycol diacrylate (400); polyethylene glycol dimethacrylate (400); polyethylene glycol dimethacrylate (400);polyethylene glycol diacrylate (600); polyethylene glycol dimethacrylate (600); polyethylene glycol diacrylate 400; propoxylated neopentyl glycol diacrylate (2); tetraethylene glycol diacrylate; tetraethylene glycol dimethacrylate; tricyclodecanedimethanol diacrylate; tricyclodecanedimethanol dimethacrylate; triethylene glycol diacrylate; triethylene glycol dimethacrylate; tripropylene glycol diacrylate; ethoxylated trimethylolpropane triacrylate (15); ethoxylated tri-methylolpropane triacrylate (3); ethoxylated trimethylolpropane triacrylate (6); ethoxylated trimethylolpropane triacrylate (9); ethoxylated pentaerythritol triacrylate 5; ethoxylated trimethylolpropane triacrylate (20); propoxylated glyceryl triacrylate (3); the;

9. trimethylolpropane triacrylate; propoxylated glyceryl triacrylate (5,5); pentaerythritol triacrylate; propoxylated glyceryl triacrylate (3); propoxylated trimethylolpropane triacrylate (3); trimethylolpropane triacrylate; trimethylolpropane trimethacrylate; tris(2-hydroxyethyl) isocyanurate triacrylate; ditrimethylolpropane tetraacrylate; dipentaerythritol pentaacrylate; ethoxylated pentaerythritol tetraacrylate (4); 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 ethoxyacrylate; 3-methyl-1,5-pentanediol diacrylate; alkoxylated cyclohexanedimethanol diacrylate;alkoxylated hexanediol diacrylate; cyclohexanedimethanol diacrylate; ethoxylated cyclohexanedimethanol diacrylate; diethylene glycol diacrylate; dioxane glycol diacrylate; ethoxylated dipentaerythritol hexaacrylate; ethoxylated glycerol triacrylate; ethoxylated neopentyl glycol diacrylate; hydroxypivalyl hydroxypivalate diacrylate; neopentyl glycol diacrylate; poly(tetramethylene glycol) diacrylate; polypropylene glycol 400 diacrylate; polypropylene glycol 700 diacrylate; propoxylated ethoxylated bisphenol A diacrylate (6); propoxylated ethylene glycol diacrylate; propoxylated pentaerythritol tetraacrylate (5); and propoxylated trimethylolpropane triacrylate; and mixtures thereof.; Process for the preparation of the (meth)acrylic MCI composition according to any one of claims 1 to 8, said process comprising the following steps: (i) the supply of the following components: (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising: (aO from 3% by weight to 50% by weight of one or more (meth)acrylic polymers PI comprising at least 80% by weight of methyl methacrylate, and (a2) from 50% by weight to 97% by weight of one or more (meth)acrylic monomers Ml, each monomer Ml comprising only one (meth)acrylic function per monomer, (b) from 0.5 parts by weight to 15 parts by weight of a block copolymer BC1 which is a thermoplastic acrylic block copolymer with at least 30% by weight of alkyl (meth)acrylate monomers, (c) optionally from 20 parts by weight to 300 parts by weight of a mineral filler C, (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and (e) optionally from 0.01 part by weight to 5 parts by weight of a polymerization initiator; and ii) the mixture of components a), b) and d) or a) to d) or a) to e).

10. A method according to claim 9, characterized in that it further comprises (c) from 20 parts by weight to 300 parts by weight of a mineral filler c

11. V-. Process according to claim 9 or 10, characterized in that it further comprises (e) from 0.01 part by weight to 5 parts by weight of a polymerization initiator.

12. Use of a (meth)acrylic MCI composition, according to any one of claims 1 to 8 or prepared according to the process according to any one of claims 9 to 11, for preparing a polymeric composite material.

13. Use of a (meth)acrylic MCI composition, according to any one of claims 1 to 8 or prepared according to the process according to any one of claims 9 to 11, for impregnating a fibrous substrate.

14. Use of a (meth)acrylic MCI composition, according to any one of claims 1 to 8 or prepared according to the process according to any one of claims 9 to 11, for reducing the cycle time for the preparation of a polymeric composite material.

15. Composite material obtained by polymerization of a (meth)acrylic MCI composition according to any one of claims 1 to 8.

16. Use of said composite material according to claim 15, for the manufacture of bathroom and / or kitchen equipment, such as worktops, kitchen sinks, bathroom basins, shower trays, bathtubs or shower screens.

17. A method for manufacturing a composite material, said method comprising: (i) the supply of the following components (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising: (aO from 3% by weight to 50% by weight of one or more (meth)acrylic polymers PI comprising at least 80% by weight of methyl methacrylate, and (a2) from 50% by weight to 97% by weight of one or more (meth)acrylic monomers Ml, each monomer Ml comprising only one (meth)acrylic function per monomer, (b) from 0.5 parts by weight to 15 parts by weight of a block copolymer BC1 which is a thermoplastic acrylic block copolymer with at least 30% by weight of alkyl (meth)acrylate monomers, (c) from 20 parts by weight to 300 parts by weight of a mineral filler C, (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and (e) from 0.01 part by weight to 5 parts by weight of a polymerization initiator; ii) the mixture of components a) to e). iii) the polymerization of the (meth)acrylic composition MCI.

18. A method for reducing the cycle time for the preparation of a polymeric composite material from a (meth)acrylic MCI composition, said method comprising: i) providing the following components (a) 100 parts by weight of a liquid (meth)acrylic syrup comprising: (aO from 3% by weight to 50% by weight of one or more (meth)acrylic polymers PI comprising at least 80% by weight of methyl methacrylate, and (a2) from 50% by weight to 97% by weight of one or more (meth)acrylic monomers Ml, each monomer Ml comprising only one (meth)acrylic function per monomer, (b) from 0.5 parts by weight to 15 parts by weight of a block copolymer BC1 which is a thermoplastic acrylic block copolymer with at least 30% by weight of alkyl (meth)acrylate monomers, (c) from 20 parts by weight to 300 parts by weight of a mineral filler C, (d) from 0.01 part by weight to 5 parts by weight of a (meth)acrylic monomer M2, the monomer M2 comprising at least two (meth)acrylic functions per monomer, and (e) from 0.01 part by weight to 5 parts by weight of a polymerization initiator; ii) the mixture of components a) to e), iii) the polymerization of the (meth)acrylic composition MCI.

Images