(Meth)acrylic composition IN MULTIPLE PARTS, process for producing SAID COMPOSITION and uses thereof

Abstract

Multipart (meth)acrylic composition, process for producing said composition, and uses thereof. The present invention relates to a multipart (meth)acrylic composition, a process for preparing the multipart (meth)acrylic composition, and uses of such a multipart (meth)acrylic composition. In particular, the present invention relates to a multipart (meth)acrylic composition, a process for preparing the multipart (meth)acrylic composition, and uses of such a multipart (meth)acrylic composition. The invention also relates to a multipart (meth)acrylic polymeric composite material, a process for preparing such a multipart (meth)acrylic composite material, and an object comprising such a multipart (meth)acrylic polymeric composite material.

Description

Title of the invention: Multi-part (meth)acrylic composition, process for producing said composition and uses thereof technical field

[0001] The present invention relates to a (meth)acrylic composition, a process for preparing the (meth)acrylic composition and uses of such a (meth)acrylic composition.

[0002] In particular, the present invention relates to a (meth)acrylic composition comprising several parts, a method for preparing the (meth)acrylic composition and uses of such a (meth)acrylic composition.

[0003] The invention also relates to a polymeric (meth)acrylic composite material, made of a (meth)acrylic composition comprising several parts, a method for preparing such a (meth)acrylic composite material made of a (meth)acrylic composition comprising several parts and an object comprising such a polymeric (meth)acrylic composite material made of a (meth)acrylic composition comprising several parts. [Technical problem]

[0004] Many materials used today are not pure materials based on a single compound but are a mixture of several components or a composite material.

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

[0006] The objective when using composite materials is to obtain from the composite material performance that cannot be obtained from its separate constituents if they are used alone. Consequently, composite materials are widely used in several industrial sectors, such as, for example, construction, automotive, boating or marine, aerospace, transport, leisure, electronics and sports, in particular because of their better mechanical performance (higher tensile strength, higher tensile modulus and better resistance to breakage) compared to homogeneous materials and their low density.

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

[0008] One way of preparing a polymeric composite material based on thermoplastic polymers is to use a liquid polymer composition comprising a monomer, commonly called a "syrup". Such a syrup is used to be mixed with a mineral filler or to impregnate the reinforcing material, for example a fibrous substrate, and then polymerized.

[0009] Before using such a liquid polymer composition, it may be necessary to store and transport it after preparation to the polymerization site. Therefore, a certain shelf life is required. Even if the composition is prepared at the polymerization site, a certain pot life is required. For example, for the preparation of large parts, such as filling large molds by injection molding or for impregnating large quantities of a reinforcing material, such as by an infusion process for preparing large wind turbine blades or large boat parts, as well as thick parts. This pot life is necessary to ensure a medium to long polymerization time to keep the liquid polymer composition liquid long enough to allow the injection or infusion of large quantities of the liquid polymer composition over a period of time.

[0010] At the end of the use of the object or article comprising the composite material, said object or article must be easily recyclable.

[0011] There is a need for (meth)acrylic compositions having a medium to long pot life.

[0012] There is a need for (meth)acrylic compositions that can be used for injection into large molds or for the preparation of large composite parts.

[0013] There is also a need to propose a manufacturing process for (meth)acrylic compositions having a medium to long pot life.

[0014] There is also a need to offer (meth)acrylic compositions with an adjustable pot life.

[0015] There is also a composition and a method for preparing a composition for the preparation of large or thick objects. By large, we mean in a dimension of at least 4 m, even 5 m or even 10 m. By thick, we mean an object which, at at least one point, has a thickness of at least 1 cm, preferably 2 cm, or even 5 cm.

[0016] There is also a need for a process for preparing (meth)acrylic composite materials of large dimensions, preferably a length in one dimension of at least 4 m, or even 5 m, or even 10 m, or of an object having at least at one point a thickness of at least 1 cm, preferably 2 cm, or even 5 cm.

[0017] Another object of the present invention is to propose a method for manufacturing a polymeric (meth)acrylic composite material having a medium to long polymerization time.

[0018] By long pot life, we mean at least 1 hour at 25 °C preferably up to at least 2 hours at 25 °C and more preferably up to at least 3 hours without significant polymerization, which means without significant increase in viscosity and / or temperature.

[0019] An adjustable pot life of the composition means that by adjusting a single component of the composition, the pot life is significantly modified. [CONTEXT OF THE INVENTION] Prior art

[0020] Document WO2013 / 056845 describes a composite material obtained by in-situ polymerization of thermoplastic (meth)acrylic resins. The polymeric composite material obtained by in-situ polymerization of a thermoplastic (meth)acrylic resin and a fibrous material containing long fibers, and its use, a method for manufacturing such a composite material, and a manufactured mechanical or structured part or article comprising this polymeric composite material are also described. The document does not disclose anything regarding pot life.

[0021] Document WO2014 / 013028 describes an impregnation process for a substrate The document describes a fibrous material, a liquid (meth)acrylic syrup for the impregnation process, its polymerization method, and a structured article thus obtained. The liquid (meth)acrylic syrup comprises a (meth)acrylic polymer, a (meth)acrylic monomer, and at least one initiator or initiation system to start the polymerization of the (meth)acrylic monomer. The document does not disclose any information regarding pot life.

[0022] Nothing in the cited prior art discloses a (meth)acrylic composition having a sufficient pot life. [Brief description of the invention]

[0023] Surprisingly, it was discovered that a (meth)acrylic (MCI) composition comprising:

[0024] a first-part composition (A) comprising:

[0025] (Aa) 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising:

[0026] (AaO of 1% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0027] (Aa2) 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.

[0028] (Ab) at least one organic aldehyde

[0029] (Ac) an inhibitor;

[0030] a second part composition (B) comprising:

[0031] (Ba) a transition metal,

[0032] (Bb) a reducing agent,

[0033] (Bc) possibly an inhibitor,

[0034] (Bd) possibly one or more (meth)acrylic monomers (M2) and / or possibly one or more (meth)acrylic polymers (P2); and

[0035] a third-part composition (C) comprising:

[0036] (Ca) from 0.01 parts by weight to 5 parts by weight of a polymerization initiator,

[0037] makes it possible to provide a composition that has a sufficient shelf life in the pot and a pot life sufficient for the preparation of large parts and for the preparation of polymeric (meth)acrylic compositions (MPC1) and composite (meth)acrylic materials (MPCM1).

[0038] Surprisingly, it was also discovered that a (meth)acrylic (MCI) composition comprising:

[0039] a first-part composition (A) comprising:

[0040] (Aa) 100-n parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising:

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

[0042] (Aa2) 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] (Ab) at least one organic aldehyde

[0044] (Ac) an inhibitor;

[0045] a second part composition (B) comprising:

[0046] (B a) a transition metal,

[0047] (Bb) a reducing agent,

[0048] (Bc) possibly an inhibitor,

[0049] (Bd) n parts by weight of a liquid (meth)acrylic syrup (LMS2) comprising:

[0050] (Bdi) of 1% by weight to 50% by weight of one or more (meth)acrylic polymers (P2), and

[0051] (Bd2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics (M2), and

[0052] a third-part composition (C) comprising:

[0053] (Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator,

[0054] n being from 0 to 100, makes it possible to provide a composition which has sufficient pot life and sufficient pot life for the preparation of large parts and for the preparation of a polymeric (meth)acrylic composition (MPC1) and a polymeric (meth)acrylic composite material (MPCM1).

[0055] Surprisingly, it was also discovered that a (meth)acrylic composition

[0056] (MCI) comprising:

[0057] a first-part composition (A) comprising:

[0058] (Aa) 100-n parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising:

[0059] (AaO from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0060] (Aa2) 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.

[0061] (Ab) at least one organic aldehyde

[0062] (Ac) an inhibitor;

[0063] a second part composition (B) comprising:

[0064] (B a) a transition metal,

[0065] (Bb) a reducing agent,

[0066] (Bc) possibly an inhibitor,

[0067] (Bd) n parts by weight of a liquid (meth)acrylic syrup (LMS2) comprising:

[0068] (Bdi) of 1% by weight to 50% by weight of one or more (meth)acrylic polymers (P2), and

[0069] (Bd2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics (M2), and

[0070] a third-part composition (C) comprising:

[0071] (Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator,

[0072] n being from 0 to 100, can be used for the preparation of large parts comprising a (meth)acrylic polymeric composition (MPC1) and a (meth)acrylic polymeric composite material (MPCM1).

[0073] Surprisingly, a process for preparing a (meth)acrylic (MCI) composition has been discovered, said process comprising the following steps:

[0074] (i) supply of a first-part composition (A) comprising:

[0075] (Aa) 100-n parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising:

[0076] (AaO of 1% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0077] (Aa2) 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.

[0078] (Ab) at least one organic aldehyde

[0079] (Ac) an inhibitor;

[0080] (ii) supply of a second part composition (B) comprising:

[0081] (Ba) a transition metal,

[0082] (Bb) a reducing agent,

[0083] (Bc) possibly an inhibitor,

[0084] (Bd) n parts by weight of a liquid (meth)acrylic syrup (LMS2) comprising:

[0085] (Bdi) of 1% by weight to 50% by weight of one or more (meth)acrylic polymers (P2), and

[0086] (Bd2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics (M2), and

[0087] iii) supply of a third-party composition (C) comprising:

[0088] (Ca) from 0.01 parts by weight to 5 parts by weight of a polymerization initiator,

[0089] iv) mixture of the three compositions provided;

[0090] n being from 0 to 100, allows to prepare a composition which has a sufficient pot life and a sufficient pot life for the preparation of large parts and for the preparation of a polymeric (meth)acrylic composition (MPC1) and a polymeric (meth)acrylic composite material (MPCM1). Description of the implementation methods

[0091] According to a first aspect, the present invention relates to a (meth)acrylic (MCI) composition, said composition comprising:

[0092] a first-part composition (A) comprising:

[0093] (Aa) 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising:

[0094] (AaO of 1% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0095] (Aa2) 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.

[0096] (Ab) at least one organic aldehyde

[0097] (Ac) an inhibitor;

[0098] a second part composition (B) comprising:

[0099] (B a) a transition metal,

[0100] (Bb) a reducing agent,

[0101] (Bc) possibly an inhibitor,

[0102] (Bd) optionally one or more (meth)acrylic monomers (M2) and / or optionally one or more (meth)acrylic polymers (P2); and

[0103] a third-part composition (C) comprising:

[0104] (Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator.

[0105] According to a second aspect, the present invention relates to a composition (meth)acrylic (MCI), said composition comprising:

[0106] a first-part composition (A) comprising:

[0107] (Aa) 100-n parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising:

[0108] (AaO from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0109] (Aa2) 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.

[0110] (Ab) at least one organic aldehyde

[0111] (Ac) an inhibitor;

[0112] a second part composition (B) comprising:

[0113] (Ba) a transition metal,

[0114] (Bb) a reducing agent,

[0115] (Bc) possibly an inhibitor,

[0116] (Bd) n parts by weight of a liquid (meth)acrylic syrup (LMS2) comprising:

[0117] (Bdi) from 1% by weight to 50% by weight of one or more (meth)acrylic polymers (P2), and

[0118] (Bd2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics (M2),

[0119] a third-part composition (C) comprising:

[0120] (Ca) from 0.01 part by weight to 5 parts by weight of a polymerization initiator;

[0121] characterized in that 0 < n < 100.

[0122] According to a third aspect, the present invention relates to a process for preparing a (meth)acrylic (MCI) composition comprising the following steps:

[0123] (i) supply of a first-part composition (A) comprising:

[0124] (Aa) 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising:

[0125] (AaO of 1 wt% to 50 wt% of one or more (meth) acrylic polymers (PI), and

[0126] (Aa2) 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.

[0127] (Ab) at least one organic aldehyde

[0128] (Ac) an inhibitor;

[0129] (ii) supply of a second part composition (B) comprising:

[0130] (B a) a transition metal,

[0131] (Bb) a reducing agent,

[0132] (Bc) possibly an inhibitor,

[0133] (Bd) optionally one or more (meth)acrylic monomers (M2) and / or optionally one or more (meth)acrylic polymers (P2); and

[0134] (iii) supply of a third-party composition (C) comprising:

[0135] (Ca) from 0.01 parts by weight to 5 parts by weight of a polymerization initiator,

[0136] (iv) mixture of the three compositions supplied.

[0137] According to a fourth aspect, the present invention relates to a process for preparing a (meth)acrylic (MCI) composition, the process comprising the following steps:

[0138] (i) supply of a first-part composition (A) comprising:

[0139] (Aa) 100-n parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising:

[0140] (AaO from 1% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0141] (Aa2) 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.

[0142] (Ab) at least one organic aldehyde

[0143] (Ac) an inhibitor;

[0144] (ii) supply of a second part composition (B) comprising:

[0145] (Ba) a transition metal,

[0146] (Bb) a reducing agent,

[0147] (Bc) possibly an inhibitor,

[0148] (Bd) n parts by weight of a liquid (meth)acrylic syrup (LMS2) comprising:

[0149] (Bdi) of 1% by weight to 50% by weight of one or more (meth)acrylic polymers (P2), and

[0150] (Bd2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylics (M2), and

[0151] (iii) supply of a third-party composition (C) comprising:

[0152] (Ca) from 0.01 parts by weight to 5 parts by weight of a polymerization initiator,

[0153] iv) mixture of the three compositions supplied;

[0154] n being from 0 to 100.

[0155] According to a fifth aspect, the present invention relates to the use of a (meth)acrylic composition (MCI) according to the first aspect or the second aspect to prepare a (meth)acrylic polymeric material (MPC1) or a (meth)acrylic polymeric composite material (MPCM1).

[0156] According to a sixth aspect, the present invention relates to a (meth)acrylic polymeric material (MPC1) or a (meth)acrylic polymeric composite material (MPCM1) prepared by polymerization of the (meth)acrylic composition (MCI) according to the first or second aspect.

[0157] According to a seventh aspect, the present invention relates to a process for preparing a (meth)acrylic polymeric material (MPC1), said process comprising the following steps:

[0158] (i) supply of a (meth)acrylic (MCI) composition according to the first or the second aspect,

[0159] (ii) polymerization of the (meth)acrylic (MCI) composition.

[0160] According to an eighth aspect, the present invention relates to a process for preparing a polymeric (meth)acrylic composite material (MPCM1), said process comprising the following steps: i. supply of a (meth)acrylic (MCI) composition according to the first or second aspect, ii. contacting the (meth)acrylic (MCI) composition with a reinforcing material, (iii) polymerization of the (meth)acrylic (MCI) composition.

[0161] 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.

[0162] The term “PMMA” refers to homo- and copolymers of methyl methacrylate (MMA), for the MMA copolymer the weight ratio of MMA inside the PMMA is at least 50% by weight.

[0163] The term "initiator" refers to a chemical species that forms a compound or an intermediate compound that initiates the polymerization of a monomer, one that is capable of successively bonding with a large number of other monomers in a polymeric compound.

[0164] The term “polymer composite” refers to a multicomponent material comprising several 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.

[0165] The term "thermoplastic" refers to a polymer that transforms into a liquid or becomes more liquid or less viscous when heated and that can take on new shapes by the application of heat and possibly pressure. This also applies to slightly cross-linked thermoplastic polymers that can be thermoformed when heated above their softening temperature.

[0166] By specifying that a range goes 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.

[0167] 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.

[0168] The (meth)acrylic (MCI) composition comprises a first-part composition (A), a second-part composition (B), and a third-part composition (C). Each partial composition and its respective components are detailed below. The quantity of each respective component of the respective compositions is given in parts by weight relative to the weight of the liquid (meth)acrylic syrup (LMS1) or to the sum of the liquid (meth)acrylic syrups (LMS1) and (LSM2), which is 100 parts by weight.

[0169] The first part composition (A) according to the invention comprises the components (Aa) a liquid (meth)acrylic syrup, (Ab) at least one organic aldehyde and (Ac) optionally an inhibitor. The liquid (meth)acrylic syrup (LSM1) of composition (Aa) comprises (AaO) a (meth)acrylic polymer (PI) and (Aa2) a (meth)acrylic monomer (Ml).

[0170] The liquid (meth)acrylic syrup (LSM1) of the first part composition (A) according to the (meth)acrylic (MCI) composition of the invention comprises between 1% by weight and 50% by weight of at least one (meth)acrylic polymer (PI) and between 50% by weight and 99% by weight of at least one (meth)acrylic monomer (Ml).

[0171] Preferably, the liquid (meth)acrylic syrup (LSM1) 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 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 of a (meth)acrylic monomer (Ml). 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).

[0172] The dynamic viscosity of the liquid (meth)acrylic syrup (LSM1) is in the range of 10 mPa*s to 10,000 mPa*s, preferably from 20 mPa*s to 7,000 mPa*s, and advantageously from 20 mPa*s to 5,000 mPa*s, and more advantageously from 20 mPa*s to 2,000 mPa*s, and even more advantageously between 20 mPa*s and 1,000 mPa*s. The viscosity of the syrup can easily be measured with a rheometer or a viscometer. The dynamic viscosity is measured at 23 °C. If the liquid (meth)acrylic syrup exhibits Newtonian behavior, meaning that it does not thin under shear, the dynamic viscosity is independent of shear in a rheometer or of the velocity of the moving part in a viscometer. If the liquid composition has non-Newtonian behavior, meaning that it exhibits fluidization under shear, the dynamic viscosity is measured at a shear rate of 1 s⁻¹ at 23 °C.

[0173] With regard to the liquid (meth)acrylic syrup (LSM1), it comprises (Aa2) the (meth)acrylic monomer (Ml) and (AaJ) the (meth)acrylic polymer (PI). After polymerization of the (meth)acrylic composition (MCI), the (meth)acrylic monomer (Ml) finally polymerizes with other (meth)acrylic monomers and is transformed into a (meth)acrylic polymer (P2) comprising the monomeric units of the (meth)acrylic monomer (Ml) and other possible comonomers.

[0174] The liquid (meth)acrylic syrup (LSM1) of the first part composition (A) of the (meth)acrylic (MCI) composition according to the invention may comprise a single (meth)acrylic (PI) polymer, but may also comprise a mixture of two, three (meth)acrylic (PI) polymers, or even more. If there is a mixture of different (meth)acrylic (PI) polymers, the difference is the composition of the respective (meth)acrylic (PI) polymer, or the molecular weight of the respective (meth)acrylic (PI) polymer, or both.

[0175] The (meth)acrylic PI polymer or polymers included in the liquid (meth)acrylic syrup may in particular be selected from:

[0176] . poly(alkyl acrylate) comprising alkyl acrylate homopolymers and alkyl acrylate copolymers, and

[0177] . poly(alkyl methacrylate) comprising homopolymers of alkyl methacrylate and alkyl methacrylate copolymers.

[0178] According to a preferred embodiment, the (meth)acrylic polymer or polymers (PI) is a poly(methyl methacrylate) (PMMA), it being understood that, as indicated below- Above, poly(methyl methacrylate) (PMMA) can refer to a homopolymer of methyl methacrylate (MMA) or a copolymer of MMA.

[0179] In particular, in the case where the liquid (meth)acrylic syrup (LMS1) comprises a mixture of two or more poly(methyl methacrylate) (PI), this mixture can be formed by mixing at least two homopolymers of MMA of different molecular weight, by mixing at least two copolymers of MMA having an identical monomer composition and a different molecular weight, by mixing at least two copolymers of MMA having a different monomer composition or by mixing at least one homopolymer of MMA and at least one copolymer of MMA.

[0180] According to a first preferred embodiment, the (meth)acrylic (PI) polymer is chosen from a methyl methacrylate homopolymer or a methyl methacrylate copolymer or a mixture of these, the methyl methacrylate advantageously representing at least 50% by weight of the or each (meth)acrylic (PI) polymer.

[0181] According to one embodiment of the invention, methyl methacrylate represents at least 55% by weight of the or each (meth)acrylic polymer (PI).

[0182] According to another particular embodiment, the (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.

[0183] When the (meth)acrylic (PI) polymer or polymers are copolymers of methyl methacrylate (MMA), they may comprise at least one comonomer containing at least one ethylenic unsaturation and capable of copolymerizing with methyl methacrylate. Examples of such comonomers include acrylic and methacrylic acids and alkyl (meth)acrylates in which the alkyl group contains from 1 to 12 carbon atoms. Alkyl (meth)acrylates are defined as alkyl esters of acrylic acid or methacrylic acid. Examples of such comonomers include methyl acrylate and an ethyl, butyl, or 2-ethylhexyl (meth)acrylate.

[0184] Advantageously, the (meth)acrylic polymer (PI) or each polymer is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and an alkyl acrylate or an alkyl methacrylate having an alkyl group containing from 1 to 12 carbon atoms, advantageously from 1 to 6 carbon atoms and preferably from 1 to 4 carbon atoms.

[0185] According to a first preferred embodiment, when the (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%, preferably from 90% to 99.9%, and more preferably from 95% to 99.9% by weight of methyl methacrylate and from 0.1% to 30%, advantageously from 0.1% to 20%, preferably from 0.1% to 10%, and more preferably from 0.1% to 5% by weight of at least one comonomer containing at least one ethylenic unsaturation copolymerizable with methyl methacrylate. Preferably, the comonomer(s) is / are selected from methyl acrylate and ethyl acrylate.

[0186] In an advantageous variant of the first preferred embodiment, when the (meth)acrylic (PI) polymer or each polymer is a methyl methacrylate (MMA) copolymer, the (meth)acrylic (PI) polymer is a methyl methacrylate and alkyl acrylate copolymer.

[0187] In a preferred embodiment of the first preferred embodiment, when the (meth)acrylic (PI) polymer or each polymer is a methyl methacrylate (MMA) copolymer, the (meth)acrylic (PI) polymer is a methyl methacrylate and methyl acrylate or ethyl acrylate copolymer.

[0188] According to a second preferred embodiment, when the (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 copolymerizable with methyl methacrylate. Preferably, the comonomer or comonomers are chosen from methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate.

[0189] The weight-average molecular weight, denoted Mw, of the (meth)acrylic polymer (PI) or polymers is generally high and can 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).

[0190] The (meth)acrylic (PI) polymer, if not crosslinked, usually has a melt mass 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 a melt mass flow rate of 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.

[0191] The liquid (meth)acrylic syrup (LSM1) of the first part composition (A) of the (meth)acrylic (MCI) composition according to the invention may comprise a single (meth)acrylic (Ml) monomer, but can also include a mixture of two, three (meth)acrylic (Ml) monomers or even more. This would be a methacrylic (Mla) monomer, a methacrylic (Mlb) monomer, (meth)acrylic (Mlc) monomers, etc.

[0192] If the liquid (meth)acrylic syrup comprises one or more (meth)acrylic (Ml) monomers, the (meth)acrylic (Ml) monomer or each monomer comprises only one (meth)acrylic function per monomer.

[0193] With regard to the (meth)acrylic monomer (Ml), the monomer is selected from alkylacrylic monomers, alkylmethacrylic monomers, hydroxyalkylacrylic monomers, and hydroxyalkylmethacrylic monomers, and mixtures thereof. The terms "alkylacrylic monomer" or "alkylmethacrylic monomer" mean an alkyl ester of acrylic acid or methacrylic acid.

[0194] Preferably, the (meth)acrylic monomer (Ml) is selected 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.

[0195] Advantageously, the (meth)acrylic monomer (Ml) is selected 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.

[0196] 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.

[0197] 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 methyl methacrylate or a mixture of methyl methacrylate with optionally at least one other monomer.

[0198] According to a second, more preferred embodiment, the monomer (Ml) is methyl methacrylate.

[0199] In a first embodiment of the invention, the liquid (meth)acrylic syrup (LSM1) comprises:

[0200] (AaO of 3% by weight to 45% by weight and preferably of 3% by weight to 40% by weight of the (meth)acrylic polymer(s) (PI), and

[0201] (Aa2) from 55% by weight to 97% by weight and preferably from 60% by weight to 97% by weight % by weight of (meth)acrylic monomer(s) (Ml).

[0202] In a second embodiment of the invention, the liquid (meth)acrylic syrup (LSM1) comprises:

[0203] (AaO of 10% by weight to 35% by weight and preferably of 12% by weight to 35% by weight and more preferably of 15% by weight to 30% by weight and even more preferably of 17% by weight to 30% by weight of the (meth)acrylic polymer(s) (PI), and

[0204] (Aa2) from 65% by weight to 90% by weight and preferably from 65% by weight to 88% by weight and more preferably from 70% by weight to 85% by weight and even more preferably from 70% by weight to 83% by weight of the (meth)acrylic monomer(s) (Ml).

[0205] In an advantageous embodiment, the (meth)acrylic polymer or each (PI) and the (meth)acrylic monomer or each (Ml) of the liquid (meth)acrylic syrup comprise at least one of the same (meth)acrylic motif, such a embodiment making it possible to optimize the solubility of the (meth)acrylic polymer or (PI) in the (meth)acrylic monomer or (Ml).

[0206] Preferably, the (meth)acrylic polymer (PI) or each polymer is selected 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 most 45% by weight in the copolymer.

[0207] In a first advantageous embodiment, the liquid (meth)acrylic syrup comprises a (meth)acrylic (PI) polymer, rather than a mixture of (meth)acrylic (PI) polymers.

[0208] In a second advantageous embodiment, the liquid (meth)acrylic syrup comprises a mixture of two (meth)acrylic (PI) polymers.

[0209] Stabilizers may also be present in the liquid (meth)acrylic syrup (LSM1) to prevent spontaneous polymerization of the (meth)acrylic monomer(s) (Ml).

[0210] These stabilizers can in particular be selected 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).

[0211] These stabilizers may be present in the liquid (meth)acrylic syrup (LSM1) in a proportion of at most 3 parts by weight, advantageously at most 2 parts by weight and preferably in a proportion between 0.005 and 1 part by weight, for 100 parts by weight of the sum of the (meth)acrylic polymer(s) (PI) and the (meth)acrylic monomer(s) (Ml) of the liquid (meth)acrylic syrup (LMS1).

[0212] The component (Ab) of at least one organic aldehyde of the first part composition (A) may be aliphatic or aromatic.

[0213] The aliphatic part of the organic aldehyde can be linear, cyclic or branched, but also saturated or unsaturated.

[0214] The organic aldehyde comprises between 3 and 30 carbon atoms. It has a general formula R-CH=O, in which R represents a cyclic hydrocarbon-based chain or a linear or branched hydrocarbon-based chain, R comprising from 2 to 29 carbon atoms, preferably from 3 to 15, optionally comprising one or more unsaturations in the form of double bonds and optionally being substituted by one or more hydroxyl groups.

[0215] Examples include propionaldehyde, butyraldehyde, valeraldehyde, capraldehyde, benzaldehyde, geranial, neral, citronellal and, in general, aldehydes containing hydrocarbon-based groups comprising one or more olefinic-type unsaturations, as well as mixtures of two or more of these in any proportion.

[0216] In one embodiment, the organic aldehyde is selected from propionaldehyde, butyraldehyde, valeraldehyde, capraldehyde, benzaldehyde, geranial, neral, citronellal.

[0217] In one embodiment, the organic aldehyde is selected from 3,7-demethylocta-2,6-dienal.

[0218] The component (Ab), the at least one organic aldehyde of the composition of first part (A), is present between 0.5 parts and 10 parts by weight per 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) or per 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2), preferably between 0.5 parts and 8 parts by weight, more preferably between 0.5 parts and 6 parts by weight.

[0219] The component (Ac), an inhibitor, is also part of the composition of first part (A).

[0220] The inhibitor is preferably chosen from 4-hydroxy-2,2,6,6-tetramethylpiperidin-l-oxyl (4-hydroxy-TEMPO or TEMPOL) or (2,2,6,6-tetramethylpiperidin-l-yl)oxyl (TEMPO).

[0221] The component (Ac), the first-part composition inhibitor (A), is present at between 0.005 parts and 1 part by weight per 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) or per 100 parts by weight of the sum of the syrup Liquid (meth)acrylic (LMS1) and (LSM2), preferably between 0.005 part and 0.5 part by weight.

[0222] The composition of part two (B) according to the invention comprises the components (Ba) a transition metal, (Bb) a reducing agent, (Bc) optionally an inhibitor, and optionally or not component (Bd). Component (Bd) is either, according to a first embodiment, optionally one or more (meth)acrylic monomers (M2) and / or optionally one or more (meth)acrylic polymers (P2), or, according to a second embodiment, a liquid (meth)acrylic syrup (LMS2). The liquid (meth)acrylic syrup (LSM2) according to the second embodiment comprises (Bdi) a (meth)acrylic polymer (P2) and (Bd2) a (meth)acrylic monomer (M2). The (meth)acrylic monomers (M2) and the (meth)acrylic polymer(s) (P2) are chosen according to all the embodiments described above for the choice of the (meth)acrylic polymer (PI) and the (meth)acrylic monomer (Ml).

[0223] In a first preferred embodiment, the (meth)acrylic monomer(s) (M2) and the (meth)acrylic polymer(s) (P2), if present, are the same as the (meth)acrylic polymer (PI) and the (meth)acrylic monomer (Ml).

[0224] In a second preferred embodiment, either the (meth)acrylic monomer(s) (M2) or the (meth)acrylic polymer(s) (P2), if present, are the same as the (meth)acrylic monomer (M1) or the (meth)acrylic polymer (PI). However, the (meth)acrylic monomer(s) (M2) and the (meth)acrylic polymer(s) (P2) are chosen according to all the embodiments described above for the selection of the (meth)acrylic polymer (PI) and the (meth)acrylic monomer(s) (M1), but only one is the same.

[0225] In a third preferred embodiment, the (meth)acrylic monomer(s) (M2) and the (meth)acrylic polymer(s) (P2) of the liquid (meth)acrylic syrup (LMS2) are the same as the (meth)acrylic polymer (PI) and the (meth)acrylic monomer (Ml) of the liquid (meth)acrylic syrup (LMS1).

[0226] In a fourth preferred embodiment, either the (meth)acrylic monomer(s) (M2) or the (meth)acrylic polymer(s) (P2) of the liquid (meth)acrylic syrup (LMS2) are the same as the (meth)acrylic polymer (PI) or the (meth)acrylic monomer (Ml) of the liquid (meth)acrylic syrup (LMS1). However, the (meth)acrylic monomer(s) (M2) and the (meth)acrylic polymer(s) (P2) are chosen according to all the embodiments described above for the selection of the (meth)acrylic polymer (PI) and the (meth)acrylic monomer (Ml), but only one is the same.

[0227] The quantity of each respective component of the respective part compositions is given in parts by weight relative to the weight of the liquid (meth)acrylic syrup (LMS1) or to the sum of liquid (meth)acrylic syrups (LMS1) and (LSM2), which is 100 parts by weight.

[0228] If the second part composition (B) according to the invention does not include (meth)acrylic monomer (M2), (meth)acrylic polymer (P2), or (meth)acrylic liquid syrup (LSM2), the first part composition is taken and includes 100 parts by weight of a (meth)acrylic liquid syrup (LMS1).

[0229] If the second-part composition (B) according to the invention comprises liquid (meth)acrylic syrups (LSM2), it is expressed as 100-n parts by weight of a liquid (meth)acrylic syrup (LMS1) of the first-part composition (A) and n parts by weight of a liquid (meth)acrylic syrup (LMS2), such that the total number of parts for the respective monomers and polymers is constant at 100 parts by weight, and the quantities of all other compounds are given relative to these. The variable n defines a kind of weight ratio between the liquid (meth)acrylic syrup (LMS1) in the first-part composition (A) and the liquid (meth)acrylic syrup (LMS2) in the second-part composition (B).

[0230] In a first preferred embodiment, n is from 0 to 99, corresponding to 0 < n < 99.

[0231] In a second preferred embodiment, n is from 10 to 90, corresponding to 10 < n < 90.

[0232] In a third preferred embodiment, n is from 20 to 80, corresponding to 20 < n < 80.

[0233] In a fourth preferred embodiment, n is from 30 to 70, corresponding to 30 < n < 70.

[0234] In a fifth preferred embodiment, n is from 40 to 60, corresponding to 40 < n < 60.

[0235] In a sixth preferred embodiment, n is from 45 to 55, corresponding to 45 < n < 55.

[0236] In a seventh preferred embodiment, n is from 25 to 60, corresponding to 25 < n < 60.

[0237] The component (Ba), the transition metal of the second part composition (B), can be chosen from the 4th period of the periodic system of elements.

[0238] Advantageously, the transition metal is chosen from manganese, cobalt, iron or copper, and more advantageously from manganese, iron, copper or mixtures thereof.

[0239] The transition metal may be in the form of a metal salt or a mixture of metal salts or an organic complex comprising the transition metal.

[0240] The component (Ba), the transition metal of the second part composition (B), is present in quantities ranging from 0.01 to 4 parts by weight per 100 parts by weight of the liquid (meth)acrylic syrup (LMS1) or per 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2). The quantity of the component (Ba), the transition metal, is calculated in the transition metal portion only.

[0241] The component (Bb,) the reducing agent of the composition of second part (B), may preferably be chosen from ascorbic acid, α-hydroxysulfones, thioureas and saccharin (also called sulfinide benzoic).

[0242] In a first, more preferred embodiment, the reducing agent is saccharin.

[0243] The reducing agent is advantageously soluble in a polar aprotic solvent at 20 °C. Preferably, the polar aprotic solvent is dimethyl sulfoxide (DMSO).

[0244] The quantity of reducing agent in the composition is advantageously between 0.1 parts by weight and 2 parts by weight and even more preferably is less than or equal to 1 part by weight, for 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2).

[0245] The component (Bc), possibly an inhibitor, may also be part of the first part composition (B).

[0246] In one embodiment, the inhibitor of component (Bc) is the same as the inhibitor of component (Ac) of the first part composition (A).

[0247] The inhibitor of component (Bc) is preferably chosen from 4-hydroxy-2,2,6,6-tetramethylpiperidin-l-oxyl (4-hydroxy-TEMPO or TEMPOL) or (2,2,6,6-tetramethylpiperidin-l-yl)oxyl (TEMPO).

[0248] The component (Bc), the possible inhibitor of the composition of second part (B), if present, is present between 0.005 part and 1 part by weight per 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) or per 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2), preferably between 0.01 part and 0.5 part by weight.

[0249] The third part composition (C) according to the invention comprises component (Ca) from 0.01 wt. to 5 wt. parts of a polymerization initiator (INI1). Its function is to ensure the start of the polymerization of the (meth)acrylic monomers (M1) and (M2); it is advantageously a radical initiator.

[0250] The polymerization initiator is selected from among diacyl peroxides, peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyacetals, hydroperoxides or peroxyketals.

[0251] In one embodiment, the polymerization initiator is chosen from a liquid component. This means that either the initiator itself is liquid, or it is of a solution or dispersion, at least within a temperature range between 0 °C and 50 °C.

[0252] In a first preferred embodiment, the polymerization initiator is an organic peroxide comprising 2 to 30 carbon atoms, such as methyl ethyl ketone peroxide (MEKP), methyl isopropyl ketone peroxide (MIKP) or a hydroperoxide (HP).

[0253] In a second preferred embodiment, it is a hydroperoxide or a peroxide comprising at least one hydroperoxide function selected from tert-butyl hydroperoxide, monohydroperoxide, para-menthane hydroperoxide, tert-amyl hydroperoxide, methylethyl ketone peroxide, methylisopropyl ketone peroxide and cumene hydroperoxide or mixtures thereof.

[0254] In a third preferred embodiment, it is monohydroperoxide, methylethylketone peroxide, methylisopropylketone peroxide or para-menthane hydroperoxide.

[0255] In a fourth preferred embodiment, the polymerization initiator is selected from 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) peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, and peroxydicarbonate of dicetyl, dimyristyle 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, 2,5-dimethyl-2,5-Di(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethyl acetate, tert-butyl peroxyisobutyrate, l,l-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, l,l-di(tert-amylperoxy)cyclohexane, l,l-di(tert-butylperoxy)cyclohexane, tert-amyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, the 2,2-di(tert-butylperoxy)butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, peroxide of, dicumyl, di(2- / e / 7-butylpcroxyisopropyl)bcnzcnc, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl and cumyl 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 corresponding mixtures.

[0256] The (meth)acrylic (MCI) composition according to the invention may comprise from 0.01 parts by weight to 5 parts by weight of polymerization initiator.

[0257] According to a particular embodiment, the (meth)acrylic (MCI) composition according to the invention comprises from 0.02 parts by weight to 4.5 parts by weight and advantageously from 0.03 parts by weight to 4 parts by weight of polymerization initiator for 100 parts by weight of liquid (meth)acrylic syrup.

[0258] The (meth)acrylic (MCI) composition according to the invention may also, according to additional aspects, comprise a polymerization activator or accelerator.

[0259] According to a particular embodiment, the (meth)acrylic (MCI) composition according to the invention comprises between 100 ppm and 10,000 ppm, advantageously between 100 ppm and 7,000 ppm and preferably between 200 ppm and 5,000 ppm of polymerization activator or accelerator for 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) or for 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2).

[0260] If the (meth)acrylic composition (MCI) includes a polymerization activator or accelerator, it is a component of the first part composition (A) or the second part composition (B).

[0261] The polymerization activator or accelerator is preferably a tertiary amine. The tertiary amine is advantageously chosen preferably from AA-dimethyl-p-toluidine (DMPT), AA-dihydroxyethyl-p-toluidine (DHEPT), A,A-diethyl-p-toluidine (DEPT) and the para-toluidine ethoxylation product (PTE).

[0262] The present invention also relates to a method for preparing the (meth)acrylic composition (MCI) according to the first and second aspects of the invention.

[0263] According to the third and fourth aspect of the invention, this process comprises the steps of: supplying the respective partial compositions (A), (B) and (C) with their respective components and iv) mixing the supplied partial compositions.

[0264] The respective partial compositions (A), (B) and (C) to be supplied are prepared by supplying the respective components for each partial composition and mixing them accordingly.

[0265] If a monomer or liquid (meth)acrylic syrup is present in a partial composition, it is taken or prepared first, and the other components are added. The components are mixed. This mixing may be done manually or by carried out using mixing means. In one embodiment, the mixing is carried out at a temperature between 10 °C and 30 °C.

[0266] Preferably, the mixing of the respective partial compositions is done in a certain order.

[0267] Preferably, the first part composition (A) and the third part composition (C) are first mixed in a first submixing step (iva). In a second submixing step (ivb), the second part composition (B) is added and mixed with the mixture obtained in the first submixing step (iva).

[0268] Optionally, the mixing is carried out by stirring, and for a period of between 1 minute and 36 hours, advantageously between 2 minutes and 24 hours, more advantageously between 3 minutes and 24 hours and preferably between 4 minutes and 24 hours.

[0269] The (meth)acrylic composition (MCI) comprising the three partial compositions (A), (B) and (C) and any components among the other components possibly added has a viscosity between 10 mPa*s and 10,000 MPa*s at 23 °C.

[0270] Preferably, the viscosity of the (meth)acrylic (MCI) composition at 23 °C is in a range of 50 mPa*s to 10,000 mPa*s, more preferably from 50 mPa*s to 9,000 mPa*s, even more preferably from 50 mPa*s to 8,000 mPa*s, even more preferably from 50 mPa*s to 7,500 Pa*s, even more preferably between 50 mPa*s and 7,000 mPa*s, advantageously between 50 mPa*s and 6,000 mPa*s and more advantageously between 50 mPa*s and 5,000 mPa*s.

[0271] The (meth)acrylic composition (MCI) according to the first aspect or the second aspect is used to prepare a (meth)acrylic polymeric material (MPC1) or a (meth)acrylic polymeric composite material (MPCM1).

[0272] The (meth)acrylic polymeric material (MPC1) or the (meth)acrylic polymeric composite material (MPCM1) is prepared by polymerization of the (meth)acrylic composition (MCI) according to the first aspect or the second aspect.

[0273] The invention relates to a process for preparing a polymeric (meth)acrylic material (MPC1), said process comprising the following steps:

[0274] (i) supply of a (meth)acrylic (MCI) composition according to the first or the second aspect,

[0275] (ii) polymerization of the (meth)acrylic (MCI) composition.

[0276] The invention relates to a process for preparing a polymeric (meth)acrylic composite material (MPCM1), said process comprising the following steps:

[0277] (i) supply of a (meth)acrylic (MCI) composition according to the first or the second aspect,

[0278] (ii) contacting the (meth)acrylic (MCI) composition with a reinforcing material,

[0279] (iii) polymerization of the (meth)acrylic (MCI) composition.

[0280] In one embodiment, the reinforcing material is a fibrous substrate. The fibers of the fibrous substrate in the present invention are long fibers or continuous fibers. The fibrous substrate preferably comprises fibers having an aspect ratio of at least 1,000, preferably at least 2,000, more preferably at least 4,000, advantageously at least 7,000, and most advantageously at least 10,000, or continuous fibers. A fiber is defined by its aspect ratio, which is the ratio of the fiber's length to its diameter.

[0281] The fibrous substrate of the present invention is selected from plant fibers, wood fibers, animal fibers, mineral fibers, synthetic polymer fibers, glass fibers, and carbon fibers and mixtures thereof.

[0282] The fibers of the fibrous material have a diameter between 0.005 pm and 100 pm, preferably between 1 pm and 50 pm, more preferably between 5 pm and 30 pm and advantageously between 10 pm and 25 pm.

[0283] In another embodiment, the reinforcing material is a mineral filler. The mineral filler C may in particular comprise a filler Cl selected from quartz, granite, marble, feldspar, clay, glass, ceramics, mica, graphite, silicates, carbonates, carbides, sulfates, silicates, hydroxides, metal oxides, metals and corresponding mixtures.

[0284] The step of contacting the (meth)acrylic composition (MCI) with a reinforcing material

[0285] With regard to the process of preparing a polymeric (meth)acrylic composite material (MPCM1), several processes could be used, including the step of contacting the (meth)acrylic composition (MCI) with a reinforcing material for a fibrous substrate.

[0286] Mentions can be made of infusion, vacuum-assisted resin infusion (VARI), stretch extrusion, vacuum bag molding, pressure bag molding, autoclave molding, resin transfer molding (RTM) and its variants (HP-RTM, C-RTM, LRTM), reaction injection molding (RIM), reinforced reaction injection molding (R-RIM) and its variants, press molding, compression molding, liquid compression molding (LCM) or sheet prepreg molding (SMC) or bulk prepreg molding (BMC) and filament winding.

[0287] A first preferred manufacturing process for a polymeric (meth)acrylic composite material (MPCM1) is infusion.

[0288] A second preferred manufacturing process of a polymeric (meth)acrylic composite material (MPCM1) is filament winding.

[0289]

[0152] A third preferred manufacturing process is assisted resin infusion through the void

[0290] (VARI).

[0291]

[0153] A fourth preferred manufacturing process is transfer molding of resin

[0292] (RTM) and its variants (HP-RTM, C-RTM, I-RTM) and

[0293] more preferably compression resin transfer molding (C-RTM).

[0294] A fifth preferred manufacturing process for a polymeric (meth)acrylic composite material (MPCM1) is vacuum bag molding, pressure bag molding.

[0295] The present invention relates in a further aspect to a molded part (MPI) comprising the polymeric (meth)acrylic material (MCP1) or a polymeric (meth)acrylic composite material (MPCM1).

[0296] The molded part (MPI) preferably has a length in one dimension of at least 5 m or has at least at one point a thickness of at least 1 cm, preferably 2 cm.

[0297] In one embodiment, the molded part (MPI) has a length in one dimension of at least 10 m.

[0298] In another embodiment, the molded part (MPI) has a length in one dimension of at least 20 m.

[0299] In yet another embodiment, it has a thickness greater than 3 cm at a point.

[0300] In a first preferred embodiment, the (meth)acrylic polymeric composite material (MPCM1) is a (meth)acrylic polymeric composite material reinforced with fibers.

[0301] In a second preferred embodiment, the (meth)acrylic polymeric composite material (MPCM1) is a particle-reinforced (meth)acrylic polymeric composite material.

[0302] The fiber-reinforced (meth)acrylic polymer composite material can be a motor vehicle part, a boat part, a bus part, a train part, a sporting article, an airplane or helicopter part, a spacecraft or rocket part, a photovoltaic module part, a pressure vessel, a construction or building material, a wind turbine part, for example a wind turbine blade beam spar base, a piece of furniture, a piece of construction or building.

[0303] With regard to the use of the polymeric (meth)acrylic composite material (MPCM1), one can mention automotive and motorsport applications such as, for example, a pressure vessel, ballistic and defense applications, marine applications, railway and transport applications, sports, leisure and recreational applications, art and entertainment applications, aeronautical and aerospace applications, construction and civil engineering applications, oil and gas applications, renewable industries applications such as photovoltaic applications and wind energy applications.

[0304] With regard to the use of mechanical parts made of polymeric (meth)acrylic composite material (MPCM1), we can also mention automotive applications, transport applications such as buses or trucks, marine applications, railway applications, sports applications, aeronautical and aerospace applications, photovoltaic applications, computer applications, construction and building applications, telecommunications applications and wind energy applications.

[0305] The polymeric (meth)acrylic composite material (MPCM1) preferably has a length in one dimension of at least 5 m or has at least at one point a thickness of at least 1 cm, preferably 2 cm.

[0306] In one embodiment, the polymeric (meth)acrylic composite material (MPCM1) has a length in one dimension of at least 10 m.

[0307] In another embodiment, the polymeric (meth)acrylic composite material (MPCM1) has a length in one dimension of at least 20 m.

[0308] In yet another embodiment, the polymeric (meth)acrylic composite material (MPCM1) has a thickness greater than 3 cm at a point.

[0309] In a specific embodiment, the polymeric (meth)acrylic composite material (MPCM1) is a part of a wind turbine blade.

[0310] In another specific embodiment, the polymeric (meth)acrylic composite material (MPCM1) is a part of a nautical vessel.

[0311] In another specific embodiment, the polymeric (meth)acrylic composite material (MPCM1) is a part of a pressure vessel. [Processes]

[0312] 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 weight-average molecular weight is expressed in g / mol for the number and average molecular weights Mn and Mw, respectively. For the measurement, the concentration is 1 g / L.

[0313] The viscosity of (meth)acrylic compositions comprising at least components (Aal) and (Aa2) is measured using 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 method of the single-cylinder type rotary viscometer”.

[0314] Stability is measured using the following method. Temper the samples to 25 °C. Pour 200 g of liquid resin into a bottle and continue to maintain it at 25 °C. Check the sample periodically. A thermocouple may be used to monitor the temperature inside the sample throughout the stability test. The sample is considered "compliant," i.e., stable, if the resin remains liquid at 25 °C and no exothermic peak is observed for a period of at least 3 hours, preferably at least 4 hours, and more preferably even longer. Remaining liquid means that the viscosity does not exceed 20 Pa*s at 25 °C.

[0315] Reactivity is measured using the following method. A 20 x 180 mm test tube is filled to a height of 7.5 cm with liquid syrup to which an initiator and an accelerator are added. A thermocouple is placed in the syrup. The tube is immersed to a depth of at least 140 mm in a water bath at 25 °C. The temperature is measured continuously, and the time to the temperature peak is recorded. Examples

[0316] The compounds used for the preparation of the various parts of the (meth)acrylic compositions are as follows:

[0317] in the first part composition (A) and the second part composition (B)

[0318] - as (meth)acrylic polymer (PI) and (P2): a PMMA formed by a copolymer of methyl methacrylate and ethyl acrylate, marketed by the company Altuglas under the name Altuglas® BS 520B,

[0319] - as (meth)acrylic monomer (M1) and (M2): a methacrylate of methyl stabilized with hydroquinone monomethyl ether,

[0320] in the composition of first part (A)

[0321] - as an organic aldehyde (Ab), 3,7-demethylocta-2,6-dienal is used

[0322] - as an inhibitor (Ac), 4-hydroxy-2,2,6,6-tetramethylpiperidin-l- is used oxyle

[0323] - as an accelerator, if present, DMPT (N,N-dimethyl-p- toluidine),

[0324] in the composition of part two (B)

[0325] - as a transition metal (Ba) a metal containing is used

[0326] Borchi® OXY-Coat 1101 from BORCHERS

[0327] - saccharin is used as a reducing agent (Bb)

[0328] - as an inhibitor (Bc), if present, 4-hydroxy-2,2,6,6- is used tetramethylpiperidin-1-oxyl,

[0329] in the composition of third part (C)

[0330] - as an initiator, Trigonox® 249VR from Nouryon is used.

[0331] A liquid (meth)acrylic syrup (LSM) is prepared by first dissolving 20 parts by weight of the (meth)acrylic polymer (PI) in 80 parts by weight of the (meth)acrylic monomer (Ml). This LSM syrup is used to prepare the first part composition (A) and the second part composition (B), i.e., it serves respectively as (LSM1) for component (Aa) and (LSM2) for component (Bd).

[0332] Table 1 - Compositions of the first part composition (A) and the second part composition (B) for a methacrylic composition (MCI) according to the invention in parts by weight [Tables 1] Composition of first part (A) Composition of second part (B) (Aa) 50 (Bd) 50 (Ab) 5 (Ba) 0.1 (Ac) 0.03 (Bb) 0.6 (Bc) 0.01

[0333] The composition of first part (A) and the composition of second part (B) remain liquid without significant change for several days.

[0334] As the third-part composition (C), Nouryon's Trigonox® 249VR is used. As a stability test, it is added at a rate of 3 parts by weight to the first-part composition (A) and at a rate of 3 parts by weight to the second-part composition (B). The compositions are maintained at 23 °C.

[0335] The first part composition (A) to which the third part composition (C) has been added remains stable and liquid for several hours and up to two weeks.

[0336] The second part composition (B) to which the third part composition (C) has been added remains stable and liquid for two to three hours, then the temperature begins to increase slightly after three hours indicating slow polymerization, then reaches a peak at 85 °C after 6 hours.

[0337] The composition of first part (A) and the composition of second part (B) are stable, also when mixed with the composition of third part (C).

[0338] Next, 3 parts by weight of composition of third part (C) are added to 50 parts of composition of first part (A). After mixing, 50 parts of composition of second part (B) are added. The temperature begins to rise slightly at first, after three hours it rises more rapidly indicating the start of polymerization, and then it reaches a peak of 100 °C after 4 hours.

[0339] The third-part composition according to the invention has a sufficient pot life and allows enough time to prepare large and / or thick parts. The composition remains sufficiently liquid for a sufficient time to fill a mold or impregnate a fibrous substrate, or both.

Claims

Demands

1. (Meth)acrylic composition (MCI) comprising: a first-part composition (A) comprising: (Aa) 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising: (AaO) 1% by weight to 50% by weight of one or more (meth)acrylic polymers (PI), and (Aa2) 50% by weight to 99% by weight of one or more (meth)acrylic monomers (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer, (Ab) at least one organic aldehyde, (Ac) an inhibitor; a second-part composition (B) comprising: (Ba) a transition metal, (Bb) a reducing agent, (Bc) optionally an inhibitor, (Bd) optionally one or more (meth)acrylic monomers (M2) and / or optionally one or more (meth)acrylic polymers (P2) ; and a third part composition (C) comprising: (Ca) from 0.01 parts by weight to 5 parts by weight of a polymerization initiator.

2. (Meth)acrylic composition (MCI) comprising: a first-part composition (A) comprising: (Aa) 100-n parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising: (AaO) 1% by weight to 50% by weight of one or more (meth)acrylic polymers (PI), and (Aa2) 50% by weight to 99% by weight of one or more (meth)acrylic monomers (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer, (Ab) at least one organic aldehyde, (Ac) an inhibitor; a second-part composition (B) comprising: (B a) a transition metal, (Bb) a reducing agent, (Bc) optionally an inhibitor, (Bd) n parts by weight of a liquid (meth)acrylic syrup (LMS2) comprising: (Bdi) of 1% by weight to 50% by weight of one or more (meth)acrylic polymers (P2), and (Bd2) of 50% by weight to 99% by weight of one or more (meth)acrylic monomers (M2), a third part composition (C) comprising: (Ca) of 0.01 parts by weight to 5 parts by weight of a polymerization initiator; characterized in that 0 < n < 100.

3. (Meth)acrylic (MCI) composition according to claim 1 or 2, characterized in that the liquid (meth)acrylic syrup (LSM1) comprises: (AaO) of 10 wt% to 35 wt% of one or more (meth)acrylic polymers (PI), and (Aa2) of 65 wt% to 90 wt% of one or more (meth)acrylic monomers (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

4. (Meth)acrylic (MCI) composition according to claim 2, characterized in that the liquid (meth)acrylic syrup (LSM2) comprises: (Bdi) of 10% by weight to 35% by weight of one or more (meth)acrylic polymers (P2), and (Bd2) of 65% by weight to 90% by weight of one or more (meth)acrylic monomers (M2).

5. (Meth)acrylic (MCI) composition according to any one of claims 1 to 4, characterized in that the organic aldehyde is selected from propionaldehyde, butyraldehyde, valeraldehyde, capraldehyde, benzaldehyde, geranial, neral, citronellal and mixtures of two or more of these in any proportions.

6. (Meth)acrylic (MCI) composition according to any one of claims 1 to 5, characterized in that the organic aldehyde is present between 0.5 parts and 10 parts by weight per 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) or per 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2).

7. (Meth)acrylic composition (MCI) according to any one of claims 1 to 5, characterized in that the transition metal is selected from manganese, cobalt, iron or copper, and more advantageously from manganese, iron, copper or mixtures thereof.

8. (Method)acrylic (MCI) composition according to any one of claims 1 to 5, characterized in that the transition metal is present between 0.01 part and 4 parts by weight per 100 parts by weight of the liquid (meth)acrylic syrup (LMS1) or per 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2).

9. (Meth)acrylic (MCI) composition according to any one of claims 1 to 5, characterized in that the reducing agent is selected from ascorbic acid, α-hydroxysulfones, thioureas and saccharin.

10. (Meth)acrylic (MCI) composition according to any one of claims 1 to 5, characterized in that the reducing agent is present between 0.1 parts by weight and 2 parts by weight per 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) or per 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2).

11. (Meth)acrylic (MCI) composition according to any one of claims 1 to 5, characterized in that the inhibitor is selected from 4-hydroxy-2,2,6,6-tetramethylpiperidin-l-oxyl or (2,2,6,6-tetramethylpiperidin-l-yl)oxyl.

12. (Method)acrylic (MCI) composition according to any one of claims 1 to 5, characterized in that the inhibitor is present between 0.005 part and 1 part by weight per 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) or per 100 parts by weight of the sum of the liquid (meth)acrylic syrup (LMS1) and (LSM2).

13. (Meth)acrylic (MCI) composition according to claim 1 or 2, characterized in that the polymerization initiator is selected from diacyl peroxides, peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyacetals, a hydroperoxide and a peroxyketal.

14. Composition according to any one of claims 2 to 13, characterized in that the parameter n is from 0 to 99, corresponding to 0 < n < 99.

15. Composition according to any one of claims 2 to 13, characterized in that the parameter n is from 40 to 60, corresponding to 40 < n < 60.

16. A process for preparing the (meth)acrylic composition (MCI) according to any one of claims 1 to 15, comprising the following steps: (i) supplying a first-part composition (A) comprising: (Aa) 100 parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising: (Aa2) 1% by weight to 50% by weight of one or more (meth)acrylic polymers (PI), and (Aa2) 50% by weight to 99% by weight of one or more (meth)acrylic monomers (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer, (Ab) at least one organic aldehyde, (Ac) an inhibitor; (ii) supplying a second-part composition (B) comprising: (Ba) a transition metal, (Bb) a reducing agent, (Bc) optionally an inhibitor, (Bd) optionally a or several (meth)acrylic monomers (M2) and / or possibly one or more (meth)acrylic polymers (P2);and (iii) supply of a third part composition (C) comprising: (Ca) from 0.01 parts by weight to 5 parts by weight of a polymerization initiator, (iv) mixture of the three compositions supplied.;

17. A process for preparing the (meth)acrylic (MCI) composition according to any one of claims 1 to 15, comprising the following steps: (i) supplying a first-part composition (A) comprising: (Aa) 100-n parts by weight of a liquid (meth)acrylic syrup (LMS1) comprising: (AaJ) 1% by weight to 50% by weight of one or more (meth)acrylic polymers (PI), and (Aa2) of 50% by weight to 99% by weight of one or more (meth)acrylic monomers (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer, (Ab) at least one organic aldehyde (Ac) an inhibitor; (ii) supply of a second part composition (B) comprising: (B a) a transition metal, (Bb) a reducing agent, (Bc) optionally an inhibitor, (Bd) n parts by weight of a liquid (meth)acrylic syrup (LMS2) comprising: (Bdi) from 1% by weight to 50% by weight of one or more (meth)acrylic polymers (P2), and (Bd2) from 50% by weight to 99% by weight of one or more (meth)acrylic monomers (M2), and (iii) supply of a third part composition (C) comprising: (Ca) from 0.01 parts by weight to 5 parts by weight of a polymerization initiator, (iv) a mixture of the three compositions supplied; n being from 0 to 100.

18. A process according to any one of claims 16 or 17, characterized in that the mixing step (iv) comprises two submixing steps: (iva) mixing the first part composition (A) and the third part composition (C) and (ivb) adding and mixing the second part composition (B) with the mixture obtained in the first submixing step (iva).

19. Use of the (meth)acrylic composition (MCI) according to any one of claims 1 to 15 to prepare a (meth)acrylic polymeric material (MCP1) or a (meth)acrylic polymeric composite material (MPCM1).

20. (Method)acrylic polymeric material (MCP1) prepared by polymerization of the (meth)acrylic composition (MCI) according to any one of claims 1 to 15.

21. (Method)acrylic polymeric composite material (MPCM1) prepared by polymerization of the (meth)acrylic composition (MCI) according to any one of claims 1 to 15.

22. (Meth)acrylic polymeric composite material (MPCM1) according to claim 21, which is part of a wind turbine blade or part of a nautical vessel or part of a pressure vessel.

23. (Method)acrylic polymeric composite material (MPCM1) according to claim 21, having a length in one dimension of at least 5 m or having at least at one point a thickness of at least 1 cm, preferably 2 cm.

24. A process for preparing a (meth)acrylic polymeric material (MCP1) comprising the following steps: (i) supplying a (meth)acrylic (MCI) composition according to any one of claims 1 to 15, (ii) polymerizing the (meth)acrylic (MCI) composition.

25. A process for preparing a polymeric (meth)acrylic (MCPM1) composite material comprising the following steps: (i) supplying a (meth)acrylic (MCI) composition according to any one of claims 1 to 15, (ii) contacting the (meth)acrylic (MCI) composition with a reinforcing material, (iii) polymerizing the (meth)acrylic (MCI) composition.

26. A process according to claim 25, comprising infusion, vacuum-assisted resin infusion (VARI), stretch extrusion, vacuum bag molding, pressure bag molding, autoclave molding, resin transfer molding (RTM) and its variants (HP-RTM, C-RTM, I-RTM), reaction injection molding (RIM), reinforced reaction injection molding (R-RIM) and its variants, press molding, compression molding, liquid compression molding (LCM) or sheet prepreg molding (SMC) or bulk prepreg molding (BMC) and filament winding.