(meth)acrylic composition, method for manufacturing the same, and use thereof

Abstract

This invention relates to (meth)acrylic compositions suitable for preparing (meth)acrylic thermoplastic polymer compositions, methods for preparing (meth)acrylic compositions, and materials obtained by polymerizing such (meth)acrylic compositions. In particular, this invention relates to (meth)acrylic compositions suitable for preparing (meth)acrylic thermoplastic polymer compositions, methods for preparing (meth)acrylic compositions, and (meth)acrylic materials obtained by polymerizing such (meth)acrylic compositions, said (meth)acrylic compositions comprising a liquid polymerizable (meth)acrylic slurry, an impact modifier or toughening agent, and optionally an initiation system for initiating the polymerization of said composition. This invention also relates to (meth)acrylic composite materials comprising polymerized (meth)acrylic compositions, methods for preparing such (meth)acrylic composite materials, and objects comprising such (meth)acrylic composite materials comprising polymerized (meth)acrylic compositions. The present invention also relates to (meth)acrylic compositions suitable for preparing (meth)acrylic thermoplastic polymer compositions or (meth)acrylic composites comprising polymerized (meth)acrylic compositions for applications and uses requiring low dielectric constants.

Description

Technical Field

[0001] This invention relates to (meth)acrylic acid compositions suitable for preparing (meth)acrylic acid thermoplastic polymer compositions, methods for preparing (meth)acrylic acid compositions, and materials obtained by polymerization of such (meth)acrylic acid compositions.

[0002] In particular, the present invention relates to (meth)acrylic compositions suitable for preparing (meth)acrylic thermoplastic polymer compositions, methods for preparing (meth)acrylic compositions, and (meth)acrylic materials obtained by polymerization of such (meth)acrylic compositions, said (meth)acrylic compositions comprising liquid polymerizable (meth)acrylic slurry, impact modifiers or toughening agents, and optionally an initiation system for initiating polymerization of said composition.

[0003] The present invention also relates to (meth)acrylic composite materials comprising polymerized (meth)acrylic compositions, methods for preparing such (meth)acrylic composite materials, and objects comprising such (meth)acrylic composite materials comprising polymerized (meth)acrylic compositions.

[0004] The present invention also relates to (meth)acrylic compositions suitable for preparing (meth)acrylic thermoplastic polymer compositions or (meth)acrylic composites comprising polymerized (meth)acrylic compositions for applications and uses requiring low dielectric constants.

[0005] Technical issues

[0006] Recently, signal transmission in higher frequency regions is being carried out due to the high capacity and high speed of large-capacity information transmission in electronic devices. In order to cope with the high transmission loss in the high frequency region, material technologies characterized by low dielectric constant and low dielectric loss tangent are needed.

[0007] Therefore, the development of insulating materials exhibiting lower dielectric constants and dielectric loss coefficients than those of conventional insulators is underway.

[0008] Reflecting this trend, various attempts have been made to develop materials with low dielectric properties using thermosetting and thermoplastic organic materials.

[0009] Among these trends, there is a growing trend to use insulators that have a lower dielectric constant than composites using thermosetting materials such as epoxy and are less affected by moisture absorption.

[0010] Furthermore, with the introduction of thermoplastic resins, the demand for the development of low dielectric constant (Dk) materials with recyclability is increasing.

[0011] Therefore, LCPs (liquid crystal polymers, approximately 2.9 Dk) and polyamides (approximately 3.2 Dk) made from fully aromatic polyesters have been investigated. Furthermore, among other acrylic polymers, (meth)acrylic polymers polymerized from methyl methacrylate (MMA), such as polymethyl methacrylate (PMMA) (approximately 3.0 Dk), have been found to exhibit moderate to high thermal stability and no field-effect current. However, because PMMA is a solid material, its manufacturing process is limited compared to liquid resins. Therefore, PMMA has not yet been applied to various low-dielectric applications.

[0012] Compositions including (meth)acrylic polymers are widely used. This is primarily due to the properties of these polymers as highly transparent polymer materials with excellent resistance to ultraviolet radiation and weathering. However, (meth)acrylic polymers are also used in applications where transparency is not required, such as in thermoplastic applications and polymer composites.

[0013] Composite materials are macroscopic combinations of two or more immiscible materials. Composite materials consist at least of a matrix material that forms a cohesive continuous phase for structural purposes and reinforcing materials or fillers that provide various frameworks (structures) for mechanical or other properties.

[0014] The purpose of using composite materials is to achieve properties that would not be available if they were used alone from their individual components. Therefore, composite materials are widely used in several industrial sectors, such as construction, automotive, marine or ocean, aerospace, transportation, leisure, electronics, and sports, particularly due to their superior mechanical properties (higher tensile strength, higher tensile modulus, and higher fracture toughness) and lower density compared to homogeneous materials.

[0015] Considering the volume in commercial and industrial scale, the most important category is composite materials with an organic matrix, where the matrix material is typically a polymer. The main matrix or continuous phase of polymer composites is a thermoplastic polymer or a thermosetting polymer.

[0016] One method for preparing thermoplastic polymer-based (meth)acrylic thermoplastic polymer compositions or polymeric (meth)acrylic composites is by using a liquid polymer composition comprising (meth)acrylic monomers, commonly referred to as a "slurry". Such a slurry is used to fill molds blended with mineral fillers or to impregnate reinforcing materials, such as fiber substrates; followed by polymerization.

[0017] At the end of the use of an object or article comprising a (meth)acrylic thermoplastic polymer composition or material or a (meth)acrylic composite material, the object or article shall be readily recyclable.

[0018] The following composition is required: which can be transformed into a polymeric thermoplastic polymer composition with a low dielectric constant and is recyclable.

[0019] The following composition is also required: which can be converted into a polymer thermoplastic polymer composite with a low dielectric constant and is recyclable.

[0020] The following thermoplastic polymer compositions are also required: those with low dielectric constant and recyclability, relatively low material cost, thermoformable, and containing low levels of potentially hazardous products.

[0021] A method is also needed to prepare a composition that can be converted into a polymeric thermoplastic polymeric composition having a low dielectric constant and being recyclable.

[0022] Another object of the present invention is to provide a method for manufacturing a polymeric thermoplastic polymer composition having a low dielectric constant and being recyclable, while having relatively low material costs, being thermoformable, and including low levels of potentially hazardous products.

[0023] Another object of the present invention is to provide a method for manufacturing objects comprising thermoplastic composite materials having a low dielectric constant and being recyclable, while having relatively low material costs, being thermoformable, and comprising low levels of potentially hazardous products. Background Technology

[0024] Document WO97 / 32314 discloses thermoplastic elastomers that can be formulated to have a wide range of dielectric properties. The thermoplastic elastomer materials have a thermoplastic polymer component including polypropylene and an elastomer component including ethylene-propylene-diene monomer (ethylene propylene diene rubber) (EPDM).

[0025] Document US 7,026,032 discloses a polyimide-based composition that can be used as an electronic substrate. The composition is a polymer composite comprising a polyimide component and a fluoropolymer component derived from micropowder.

[0026] Document US2006 / 115670 discloses thermoplastic polyimide resin films, multilayers, and methods for manufacturing printed circuit boards composed therefrom.

[0027] Document US 7,388,057 discloses that epoxy-terminated phenylene ether oligomers can be further reacted with acrylic acid and / or methacrylic acid to produce epoxy di(meth)acrylates. This is used to manufacture thermosetting or photocurable resins and their intermediates, each suitable for electronic applications requiring low dielectric constants, low dielectric loss tangents, and high toughness, and also suitable for various applications such as coating, bonding, and molding.

[0028] Document CN110684470 discloses a method for preparing acrylate adhesives. In addition to methyl methacrylate, the adhesive composition particularly includes acrylic acid and methacrylic acid as monomers.

[0029] Document WO2014 / 184002 discloses an impact modifier for polylactic acid. The impact modifier is a blend of a core-shell polymer and a triblock acrylic copolymer.

[0030] None of the cited prior art discloses a liquid (meth)acrylic slurry comprising one or more (meth)acrylic polymers, one or more (meth)acrylic monomers, and an impact modifier. Nor does the cited prior art disclose (meth)acrylic thermoplastic polymer compositions comprising impact modifiers that offer a good trade-off between low dielectric constant, strength, stiffness, toughness, and impact resistance, as well as a suitable heat deflection (flexure) temperature. Summary of the Invention

[0031] Surprisingly, it has been found that (meth)acrylic composition MC1, including the following, allows for the provision of compositions for preparing (meth)acrylic thermoplastic polymer compositions MTPC1 with low dielectric constants:

[0032] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0033] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0034] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group ((meth)acrylic acid functional group) per monomer.

[0035] (b) 0.5 to 25 parts by weight of impact modifier IM1,

[0036] (c) Optionally 0.01 parts by weight to 5 parts by weight of polymerization initiator

[0037] (d) An accelerator (promoter) optionally between 100 ppm and 10,000 ppm.

[0038] Surprisingly, it was also found that (meth)acrylic acid compositions MC1, including the following, allow for the provision of (meth)acrylic acid thermoplastic polymer compositions MTPC1 that have a good trade-off between low dielectric constants and good trade-offs between strength (particularly tensile strength and flexural strength), stiffness, toughness, and impact resistance:

[0039] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0040] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0041] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0042] (b) 0.5 to 25 parts by weight of impact modifier IM1,

[0043] (c) Optionally, 0.01 parts by weight to 5 parts by weight of a polymerization initiator,

[0044] (d) An accelerator, optionally between 100 ppm and 10,000 ppm.

[0045] Surprisingly, it was also found that the following (meth)acrylic composition MC1 can be used to prepare (meth)acrylic thermoplastic polymer composition MTPC1 with a low dielectric constant:

[0046] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0047] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0048] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0049] (b) 0.5 to 25 parts by weight of impact modifier IM1,

[0050] (c) 0.01 to 5 parts by weight of polymerization initiator

[0051] (d) Accelerators between 100 ppm and 10,000 ppm.

[0052] Surprisingly, a method for preparing the (meth)acrylic thermoplastic polymer composition MTPC1 yields a (meth)acrylic thermoplastic polymer composition MTPC1 with a good trade-off between low dielectric constant, strength, stiffness, toughness, and impact resistance. The method comprises the following steps:

[0053] (i) Providing a (meth)acrylic acid composition MC1, comprising:

[0054] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0055] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0056] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0057] (b) 0.5 to 25 parts by weight of impact modifier IM1,

[0058] (c) 0.01 to 5 parts by weight of polymerization initiator,

[0059] (d) An accelerator, optionally between 100 ppm and 10,000 ppm;

[0060] (ii) Polymerize the (meth)acrylic acid composition MC1. Detailed Implementation

[0061] According to a first aspect, the present invention relates to a (meth)acrylic acid composition MC1, said composition comprising:

[0062] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0063] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0064] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0065] (b) 0.5 to 25 parts by weight of impact modifier IM1,

[0066] (c) Optionally 0.01 parts by weight to 5 parts by weight of polymerization initiator

[0067] (d) An accelerator, optionally between 100 ppm and 10,000 ppm.

[0068] According to a second aspect, the present invention relates to a (meth)acrylic acid composition MC1, said composition comprising:

[0069] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0070] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0071] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0072] (b) 0.5 to 25 parts by weight of impact modifier IM1,

[0073] (c) 0.01 to 5 parts by weight of polymerization initiator

[0074] (d) Accelerators between 100 ppm and 10,000 ppm.

[0075] According to a third aspect, the present invention relates to a method for preparing a (meth)acrylic acid composition MC1, comprising the following steps:

[0076] (i) Provide component (a) a liquid (meth)acrylic slurry comprising:

[0077] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0078] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0079] (ii) For 100 parts (a), add 0.5 to 25 parts by weight of impact modifier IM1 (b), optionally 0.01 to 5 parts by weight of polymerization initiator (c), and optionally 100 ppm to 10,000 ppm of accelerator (d).

[0080] (iii) Mix components (a) to (b) or (a) to (d).

[0081] According to a fourth aspect, the present invention relates to a method for preparing a (meth)acrylic acid composition MC1, the method comprising the following steps:

[0082] (i) Provide component (a) a liquid (meth)acrylic slurry comprising:

[0083] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0084] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0085] (ii) For 100 parts of (a), add 0.5 to 25 parts by weight of component (b) of impact modifier, 0.01 to 5 parts by weight of component (c) of polymerization initiator, and component (d) of accelerator at concentrations between 100 ppm and 10,000 ppm.

[0086] (iii) Mix components (a) through (d).

[0087] According to a fifth aspect, the present invention relates to the use of (meth)acrylic acid composition MC1 for preparing materials having a low dielectric constant, said (meth)acrylic acid composition MC1 comprising:

[0088] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0089] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0090] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0091] (b) 0.5 to 25 parts by weight of impact modifier,

[0092] (c) 0.01 to 5 parts by weight of polymerization initiator

[0093] (d) Accelerators between 100 ppm and 10,000 ppm.

[0094] According to a sixth aspect, the present invention relates to a (meth)acrylic thermoplastic polymer composition MTPC1 prepared by polymerization of a (meth)acrylic composition MC1.

[0095] According to a seventh aspect, the present invention relates to a method for preparing a (meth)acrylic acid thermoplastic polymer composition MTPC1, the method comprising the following steps:

[0096] (i) Providing a (meth)acrylic acid composition MC1 according to the first or second aspect,

[0097] (ii) Optionally, the (meth)acrylic composition MC1 is filled into or poured into a mold.

[0098] (iii) Polymerize (meth)acrylic acid composition MC1.

[0099] According to an eighth aspect, the present invention relates to the use of (meth)acrylic acid composition MC1 for preparing (meth)acrylic acid thermoplastic polymer composition MTPC1 having a low dielectric constant, said (meth)acrylic acid composition MC1 comprising:

[0100] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0101] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0102] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0103] (b) 0.5 to 25 parts by weight of impact modifier,

[0104] (c) 0.01 to 5 parts by weight of polymerization initiator

[0105] (d) Accelerators between 100 ppm and 10,000 ppm.

[0106] According to a ninth aspect, the present invention relates to a method for preparing a (meth)acrylic acid thermoplastic polymer composition MTPC1, the method comprising the following steps:

[0107] (i) Providing a (meth)acrylic acid composition MC1, comprising:

[0108] (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising:

[0109] (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and

[0110] (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer.

[0111] (b) 0.5 to 25 parts by weight of impact modifier IM1,

[0112] (c) 0.01 to 5 parts by weight of polymerization initiator,

[0113] (d) An accelerator, optionally between 100 ppm and 10,000 ppm;

[0114] (ii) Polymerize the (meth)acrylic acid composition MC1.

[0115] According to a tenth aspect, the present invention relates to a (meth)acrylic thermoplastic polymer composition MTPC1 comprising filler FI1 or fibrous material FM.

[0116] According to the eleventh aspect, the present invention relates to a (meth)acrylic composite material MCM1 comprising a (meth)acrylic thermoplastic polymer composition MTPC1.

[0117] According to the twelfth aspect, the present invention relates to articles or objects comprising (meth)acrylic composite material MCM1 or comprising (meth)acrylic thermoplastic polymer composition MTPC1.

[0118] The term "(meth)acrylic monomers" encompasses both acrylic monomers and methacrylic monomers. Similarly, the term "(meth)acrylic polymers" encompasses not only acrylic homopolymers, but also methacrylic homopolymers, acrylic copolymers, and methacrylic copolymers.

[0119] The term “PMMA” as used refers to homopolymers and copolymers of methyl methacrylate (MMA), and for copolymers of MMA, the weight ratio of MMA in PMMA is at least 50 by weight.

[0120] The term "initiator" as used refers to a chemical species that forms a compound or intermediate that initiates the polymerization of monomers, and which can be successively linked with a large number of other monomers to form polymer compounds.

[0121] The term "polymer composite" as used refers to a multi-component material comprising multiple different phase domains, wherein at least one type of phase domain is a continuous phase and at least one component is a polymer.

[0122] The term "thermoplastic" as used refers to a polymer that transforms into a liquid or becomes more liquid or less viscous when heated and can take on a new shape by applying heat and optionally pressure. This also applies to slightly cross-linked thermoplastic polymers that can be thermoformed when heated above their softening temperature.

[0123] The term "low dielectric constant" as used refers to a relative permittivity ε below 2.9 at 1 GHz. r The value of .

[0124] In this invention, the range is described as x to y, which means including the upper and lower limits of the range, equivalent to at least x and at most y.

[0125] In this invention, the range is described as being between x and y, which means excluding the upper and lower limits of the range, equivalent to being greater than x and less than y.

[0126] The liquid (meth)acrylic paste (a) of the composition according to the present invention comprises (a1) (meth)acrylic polymer P1 and (a2) (meth)acrylic monomer M1.

[0127] The liquid (meth)acrylic slurry (a) of the (meth)acrylic composition MC1 of the present invention comprises between 1% and 50% by weight of (meth)acrylic polymer P1 and between 50% and 99% by weight of (meth)acrylic monomer M1. Preferably, the liquid (meth)acrylic paste comprises between 2% and 50% by weight of (meth)acrylic polymer P1 and between 50% and 98% by weight of (meth)acrylic monomer M1, more preferably between 2% and 40% by weight of (meth)acrylic polymer P1 and between 60% and 98% by weight of (meth)acrylic monomer M1, even more preferably between 3% and 40% by weight of (meth)acrylic polymer P1 and between 60% and 97% by weight of (meth)acrylic monomer M1, advantageously between 3% and 35% by weight of (meth)acrylic polymer P1 and between 65% and 97% by weight of (meth)acrylic monomer M1, and even more advantageously between 3% and 30% by weight of (meth)acrylic polymer P1 and between 70% and 97% by weight of (meth)acrylic monomer M1.

[0128] The dynamic viscosity of liquid (meth)acrylic paste is 10 mPa. s to 10000 mPa s, preferably 20 mPa s to 7000 mPa s and favorable 20 mPa s to 5000 mPa Within the range of s and more advantageously 20 mPa s to 2000 mPa s and even more advantageously at 20 mPa s and 1000 mPa The viscosity of the slurry is within the range of s. The viscosity of the slurry can be easily measured using a rheometer or viscometer. Dynamic viscosity is measured at 25°C. If the liquid (meth)acrylic slurry exhibits Newtonian behavior, meaning no shear thinning, the dynamic viscosity is independent of the shear rate in the rheometer or the velocity of the mobile in the viscometer. If the liquid composition exhibits non-Newtonian behavior, meaning shear thinning, the dynamic viscosity is measured at 25°C within 1 s. -1The shear rate is used to measure dynamic viscosity.

[0129] Regarding the liquid (meth)acrylic paste (a), it comprises (a1) (meth)acrylic monomer M1 and (a2) (meth)acrylic polymer P1. Once the (meth)acrylic composition MC1 has been polymerized, the (meth)acrylic monomer M1 polymerizes and is converted into the (meth)acrylic polymer P2, which comprises monomer units of (meth)acrylic monomer M1 and other possible comonomers.

[0130] The liquid (meth)acrylic slurry of the (meth)acrylic composition MC1 according to the present invention may comprise only one (meth)acrylic polymer P1, but may also comprise a mixture of two, three, or even more (meth)acrylic polymers P1. If a mixture of different (meth)acrylic polymers P1 is present, the difference is the composition of the respective (meth)acrylic polymer P1 or the molecular weight of the respective (meth)acrylic polymer P1, or both. This would be (meth)acrylic polymer P1a, (meth)acrylic polymer P1b, (meth)acrylic polymer P1c, etc.

[0131] The (meth)acrylic polymer P1 included in the liquid (meth)acrylic slurry may be particularly selected from:

[0132] Polyalkyl acrylates, including alkyl acrylate homopolymers and alkyl acrylate copolymers, and

[0133] Polyalkyl methacrylates, including alkyl methacrylate homopolymers and alkyl methacrylate copolymers.

[0134] According to a preferred embodiment, the (meth)acrylic polymer P1 is polymethyl methacrylate (PMMA). It is understood that, as described above, polymethyl methacrylate (PMMA) may refer to methyl methacrylate (MMA) homopolymer or MMA copolymer.

[0135] In particular, in cases where the liquid (meth)acrylic slurry comprises a mixture of two or more polymethyl methacrylates P1, the mixture may be formed by mixing at least two MMA homopolymers with different molecular weights, by mixing at least two MMA copolymers having the same monomer composition and different molecular weights, by mixing at least two MMA copolymers with different monomer compositions, or by mixing at least one MMA homopolymer and at least one MMA copolymer.

[0136] According to a first preferred embodiment, the (meth)acrylic polymer P1 is selected from methyl methacrylate homopolymers or methyl methacrylate copolymers or mixtures thereof, wherein methyl methacrylate advantageously constitutes at least 50% by weight of said or each (meth)acrylic polymer P1.

[0137] According to one embodiment of the invention, methyl methacrylate accounts for at least 55% by weight of the (meth)acrylic polymer P1.

[0138] According to another specific embodiment, the (meth)acrylic polymer P1 comprises at least 70% by weight, advantageously at least 80% by weight, preferably at least 90% by weight, and more preferably at least 95% by weight of methyl methacrylate.

[0139] When the (meth)acrylic polymer P1 is a methyl methacrylate (MMA) copolymer, it may include at least one comonomer containing at least one olefinic unsaturation and capable of copolymerizing with methyl methacrylate. Among these comonomers, acrylic acid and methacrylic acid, as well as alkyl (meth)acrylates, are particularly mentioned, wherein the alkyl group contains 1 to 12 carbon atoms. Alkyl (meth)acrylate means an alkyl ester of acrylic acid or methacrylic acid. Examples of comonomers include methyl acrylate and ethyl (meth)acrylate, butyl (meth)acrylate, or 2-ethylhexyl (meth)acrylate.

[0140] Advantageously, the (meth)acrylic polymer P1 is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate with alkyl acrylate or alkyl methacrylate, wherein the alkyl group contains 1 to 12 carbon atoms, advantageously 1 to 6 carbon atoms and preferably 1 to 4 carbon atoms.

[0141] According to a first preferred embodiment, when the (meth)acrylic polymer P1 is a methyl methacrylate (MMA) copolymer, the methyl methacrylate (MMA) copolymer comprises 70% to 99.9% by weight, advantageously 80% to 99.9% by weight, preferably 90% to 99.9% by weight, and more preferably 95% to 99.9% by weight of methyl methacrylate, and 0.1% to 30% by weight, advantageously 0.1% to 20% by weight, preferably 0.1% to 10% by weight, and more preferably 0.1% to 5% by weight of at least one comonomer containing at least one degree of olefinic unsaturation, wherein the comonomer may be copolymerized with methyl methacrylate. Preferably, the comonomer is selected from methyl acrylate and ethyl acrylate.

[0142] In an advantageous variant of the first preferred embodiment, when the (meth)acrylic polymer P1 is a methyl methacrylate (MMA) copolymer, the (meth)acrylic polymer P1 is a copolymer of methyl methacrylate and alkyl acrylate.

[0143] In a preferred variant of the first preferred embodiment, when the (meth)acrylic polymer P1 is a methyl methacrylate (MMA) copolymer, the (meth)acrylic polymer P1 is a copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate.

[0144] According to a second preferred embodiment, when the (meth)acrylic polymer P1 is a methyl methacrylate (MMA) copolymer, the methyl methacrylate (MMA) copolymer comprises 50% to 99.9% by weight, advantageously 52% to 99.9% by weight, preferably 53% to 99.9% by weight, and more preferably 55% to 99.9% by weight of methyl methacrylate, and 0.1% to 50% by weight, advantageously 0.1% to 48% by weight, preferably 0.1% to 47% by weight, and more preferably 0.1% to 45% by weight of at least one comonomer containing at least one degree of olefinic unsaturation, wherein the comonomer may be copolymerized with methyl methacrylate. Preferably, the comonomer is selected from methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, or butyl methacrylate.

[0145] The weight-average molecular weight (denoted as M) of the aforementioned or each (meth)acrylic polymer P1 w The weight-average molecular weight is typically 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).

[0146] (Meth)acrylic polymer P1, if uncrosslinked, typically has a melt mass flow rate (MFR) between 0.1 g / 10 min and 20 g / 10 min (230°C / 3.8 kg), or a melt mass flow rate 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.

[0147] The liquid (meth)acrylic slurry of the (meth)acrylic composition MC1 according to the present invention may include only one (meth)acrylic monomer M1, but may also include a mixture of two, three or even more (meth)acrylic monomers M1. This would be (meth)acrylic monomer M1a, (meth)acrylic monomer M1b, (meth)acrylic monomer M1c, etc.

[0148] Regardless of whether the liquid (meth)acrylic paste includes one or more (meth)acrylic monomers M1, each (meth)acrylic monomer M1 includes only one (meth)acrylic functional group per monomer.

[0149] Regarding (meth)acrylic acid monomers (M1), the monomers are selected from alkyl acrylate (alkyl acrylate) monomers, alkyl methacrylate (alkyl methacrylate) monomers, hydroxyalkyl acrylate (hydroxyalkyl acrylate) monomers, and hydroxyalkyl methacrylate (hydroxyalkyl methacrylate) monomers and mixtures thereof. Alkyl acrylate (alkyl acrylate) monomers or alkyl methacrylate (alkyl methacrylate) monomers refer to alkyl esters of acrylic acid or methacrylic acid.

[0150] Preferably, the (meth)acrylic acid monomer (M1) is selected from hydroxyalkyl acrylic acid monomers, hydroxyalkyl methacrylic acid monomers, alkyl acrylic acid monomers, alkyl methacrylic acid monomers and mixtures thereof, wherein the alkyl group contains 1 to 22 straight-chain, branched or cyclic carbons; the alkyl group preferably contains 1 to 12 straight-chain, branched or cyclic carbons.

[0151] Advantageously, the (meth)acrylic monomer (M1) 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.

[0152] According to a preferred embodiment, at least 50% by weight, and preferably at least 60% by weight, of the (meth)acrylic monomer (M1) is methyl methacrylate.

[0153] According to a first more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, advantageously at least 80% by weight, and even more advantageously at least 90% by weight of monomer (M1) is a mixture of methyl methacrylate and optionally at least one other monomer.

[0154] According to a second more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, advantageously at least 80% by weight, and even more advantageously at least 90% by weight of monomer (M1) is methyl methacrylate and optionally at least one other monomer.

[0155] According to a third more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, advantageously at least 80% by weight, and even more advantageously at least 90% by weight of monomer (M1) is methyl methacrylate.

[0156] According to a fourth more preferred embodiment, at least 80% by weight, preferably at least 85% by weight, more preferably at least 70% by weight, advantageously at least 90% by weight, and even more advantageously at least 95% by weight, of the monomer (M1) is methyl methacrylate.

[0157] In a first variant of the invention, the liquid (meth)acrylic slurry comprises:

[0158] (a1) 3% to 45% by weight and preferably 3% to 40% by weight of (meth)acrylic acid polymer P1, and

[0159] (a2) 55% to 97% by weight and preferably 60% to 97% by weight of (meth)acrylic monomer M1.

[0160] In a second variation of the invention, the liquid (meth)acrylic slurry comprises:

[0161] (a1) 3% to 25% by weight, preferably 4% to 25% by weight, more preferably 5% to 25% by weight, and even more preferably 5% to 24% by weight of (meth)acrylic acid polymer P1, and

[0162] (a2) 75% to 97% by weight and preferably 75% to 96% by weight and more preferably 75% to 95% by weight and even more preferably 76% to 95% by weight of (meth)acrylic monomer M1.

[0163] In a third variation of the invention, the liquid (meth)acrylic slurry comprises:

[0164] (a1) 10% to 30% by weight, preferably 11% to 28% by weight, more preferably 12% to 27% by weight, and even more preferably 15% to 25% by weight of (meth)acrylic polymer P1, and

[0165] (a2) 70% to 90% by weight, preferably 72% to 89% by weight, more preferably 73% to 88% by weight, and even more preferably 75% to 85% by weight of (meth)acrylic monomer M1.

[0166] In an advantageous variation, the (meth)acrylic polymer P1 and the (meth)acrylic monomer M1 of the liquid (meth)acrylic slurry comprise at least one identical (meth)acrylic unit, such a variation allowing for optimization of the solubility of the (meth)acrylic polymer P1 in the (meth)acrylic monomer M1.

[0167] Preferably, the (meth)acrylic polymer P1 is selected from homopolymers of methyl methacrylate or copolymers of methyl methacrylate and methyl acrylate, copolymers of methyl methacrylate and ethyl acrylate, copolymers of methyl methacrylate and butyl acrylate, or copolymers of methyl methacrylate and butyl methacrylate, wherein the corresponding comonomer is present in the copolymer in up to 45% by weight.

[0168] Preferably, the (meth)acrylic monomer M1 is methyl methacrylate.

[0169] In the first advantageous variant, the liquid (meth)acrylic slurry comprises (meth)acrylic polymer P1, rather than a mixture of (meth)acrylic polymer P1.

[0170] In a second advantageous variant, the liquid (meth)acrylic slurry comprises a mixture of two (meth)acrylic polymers P1.

[0171] In another advantageous variant, the liquid (meth)acrylic paste comprises (meth)acrylic monomer M1, rather than a mixture of (meth)acrylic monomer M1.

[0172] In the fourth advantageous variant, the liquid (meth)acrylic paste comprises a mixture of two (meth)acrylic monomers M1.

[0173] Stabilizers or reaction inhibitors may also be present in liquid (meth)acrylic slurries to prevent the spontaneous polymerization of (meth)acrylic monomer M1.

[0174] These stabilizers may be specifically 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).

[0175] These stabilizers may be present in liquid (meth)acrylic slurry in proportions not exceeding 5 parts by weight, advantageously not exceeding 4 parts by weight, and preferably in proportions between 0.3 and 3 parts by weight per 100 parts by weight of the total of (meth)acrylic polymer P1 and (meth)acrylic monomer M1.

[0176] Regarding the impact modifier IM1, it can be selected from core-shell particles or block copolymers.

[0177] In a first preferred embodiment, the impact modifier IM1 is selected from block copolymer BC1.

[0178] In a second preferred embodiment, the impact modifier IM1 is selected from core-shell particles.

[0179] In a third preferred embodiment, the impact modifier IM1 is selected from a mixture of core-shell particles and block copolymer BC1.

[0180] For 100 parts by weight of liquid (meth)acrylic paste, the block copolymer BC1 is present in the (meth)acrylic composition MC1 in an amount of 0.5 to 25 parts by weight.

[0181] Preferably, for 100 parts by weight of liquid (meth)acrylic paste, the block copolymer BC1 is present in the form of 1 to 15 parts by weight, more preferably 1 to 12 parts by weight, and even more preferably 1 to 10 parts by weight.

[0182] Most preferably, for 100 parts by weight of liquid (meth)acrylic slurry, the block copolymer BC1 is present in 2 to 10 parts by weight.

[0183] Regarding the block copolymer BC1, it comprises at least one block having a glass transition temperature Tg of less than 20°C, preferably less than 10°C, and more preferably less than 0°C.

[0184] Preferably, at least one of the other blocks has a glass transition temperature Tg greater than 20°C, more preferably greater than 30°C, and more preferably greater than 40°C.

[0185] The block copolymer BC1 can be selected from the thermoplastic block copolymer TBC1.

[0186] Advantageously, the block copolymer BC1 is amorphous. More advantageously, the block copolymer BC1 does not contain any semi-crystalline or crystalline blocks.

[0187] Most preferably, the thermoplastic block copolymer TBC1 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 in the thermoplastic acrylic block copolymer are (meth)acrylate monomers.

[0188] Preferably, the thermoplastic acrylic block copolymer has the general formula (A). n B, where:

[0189] ● n is an integer greater than or equal to 1.

[0190] ● A is: an acrylic or methacrylic or styrene homopolymer or copolymer, or polystyrene, or an acrylic / styrene or methacrylic / styrene copolymer having a Tg greater than 50°C, preferably greater than 80°C;

[0191] ● B is an acrylic or methacrylic homopolymer or copolymer with a Tg of less than 20°C.

[0192] Preferably, in block A, the monomer is selected from methyl methacrylate (MMA), phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, styrene, or α-methylstyrene or mixtures thereof. More preferably, block A is PMMA or PMMA copolymerized with acrylic or methacrylic comonomers or polystyrene (PS) or PS modified with styrene comonomers.

[0193] Preferably, block B comprises a monomer selected from methyl acrylate, ethyl acrylate, butyl acrylate (BuA), ethylhexyl acrylate or butyl methacrylate and mixtures thereof, more preferably butyl acrylate, wherein the monomer comprises at least 50% by weight, preferably 70% by weight, of block B.

[0194] Furthermore, blocks A and / or B may include other acrylic or methacrylic comonomers carrying various chemical functional groups (e.g., acid, amide, amine, hydroxyl, epoxy, or alkoxy functional groups) known to those skilled in the art. Block A may also introduce groups such as acrylic acid (AA) or methacrylic acid (MAA) to increase its heat resistance.

[0195] Comonomers such as styrene can also be introduced into block B to achieve a refractive index mismatch with block A.

[0196] Preferably, the thermoplastic acrylic block copolymer has a structure selected from the following: ABA, AB, A3B and A4B.

[0197] The thermoplastic acrylic block copolymer may be, for example, 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 pMMA-pBuA-pMMA.

[0198] Those skilled in the art also know that PMMA-type polymers may include small amounts of acrylate comonomers to improve their thermal stability. “Small” means less than 9% by weight, preferably less than 7% by weight, and more preferably less than 6% by weight.

[0199] Block B comprises 10% to 85% by weight, preferably 25% to 75% by weight, and more preferably 35% to 65% by weight of the total weight of the block copolymer.

[0200] Block B has a weight-average molar mass between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 g / mol and 300,000 g / mol.

[0201] Block copolymers that participate in the composition of the matrix can be obtained by controlled radical polymerization (CRP) or by anionic polymerization; the most suitable method will be selected according to the type of copolymer to be manufactured.

[0202] Preferably, for (A) n B-type block copolymers, which would be CRP, especially in the presence of nitroxide radicals, and for ABA-type structures, such as triblock copolymers MAM, which would be anionic or nitroxide radical polymerization.

[0203] The (meth)acrylic acid composition MC1 according to one aspect of the invention further includes an accelerator between 100 ppm and 10,000 ppm. Preferably, it is between 200 ppm and 8,000 ppm by weight, and advantageously between 300 ppm and 6,000 ppm.

[0204] The accelerator is selected from tertiary amines such as N,N-dimethyl-p-toluidine (DMPT), N,N-dihydroxyethyl-p-toluidine (DHEPT), organic soluble transition metal catalysts, or mixtures thereof.

[0205] According to one aspect of the invention, the (meth)acrylic acid composition MC1 further includes a polymerization initiator that functions to ensure the initiation of polymerization of the (meth)acrylic acid monomer M1.

[0206] The polymerization initiator can be selected from organic peroxides, peroxy esters, peroxy acetals, and azo compounds.

[0207] The polymerization initiator may be specifically selected from diacyl peroxides, peroxy esters, peroxy dicarbonates, dialkyl peroxides, peroxy acetals, hydroperoxides, or peroxy ketals.

[0208] In one embodiment, the polymerization initiator is selected from benzoyl peroxide.

[0209] In another embodiment, the polymerization initiator is selected from diisobutyryl peroxide, cumyl peroxyneodecanate, di(3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanate, cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, tert-amyl peroxyneodecanate, tert-butyl peroxyneodecanate, di-n-butyl peroxydicarbonate, dicet peroxydicarbonate, and dimyristyl peroxydicarbonate. 1,1,3,3-Tetramethyl Butyl Peroxypentanoate, tert-butyl Peroxypentanoate, tert-amyl Peroxypentanoate, tert-butyl Peroxypentanoate, di(3,5,5-trimethylhexanoyl)peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1,1,3,3-Tetramethyl Butyl Peroxy-2-ethylhexanoate, tert-amyl Peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl Peroxy-2-ethylhexanoate, tert-butyl Peroxydiethylacetic acid, tert-butyl Peroxyisobutyrate, 1,1-di-(tert-butylperoxy)-3 3,5-Trimethylcyclohexane, 1,1-Di(tert-amylperoxy)cyclohexane, 1,1-Di-(tert-butylperoxy)cyclohexane, tert-amyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 2,2-Di-(tert-butylperoxy)butane, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di-(2-tert-butyl-peroxyisopropyl) )-Benzene, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, tert-butylisopropylphenyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyn-3, di-tert-butylperoxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-(2-methylbutyronitrile), azobisisobutyramide, 2,2'-azobis(2,4-dimethylpentanitrile), 1,1'-azobis(hexahydrobenzonitrile) or 4,4'-azobis(4-cyanopentanoic acid).

[0210] The (meth)acrylic acid composition MC1 according to the present invention may include 0.01 parts by weight to 5 parts by weight of a polymerization initiator.

[0211] According to a specific embodiment, the (meth)acrylic composition MC1 according to the invention comprises 0.02 to 4 parts by weight, and advantageously 0.03 to 3 parts by weight, of a polymerization initiator per 100 parts by weight of liquid (meth)acrylic paste.

[0212] The polymerization initiator just described can be completely replaced by an initiator system, which consists of a polymerization initiator and a polymerization activator or accelerator.

[0213] According to some aspects, the (meth)acrylic acid composition MC1 according to the present invention may also effectively further include a polymerization activator or accelerator.

[0214] According to specific embodiments, the (meth)acrylic composition according to the invention comprises a polymerization activator or accelerator in amounts between 100 ppm and 10,000 ppm, advantageously between 100 ppm and 7,000 ppm, and preferably between 200 ppm and 5,000 ppm per 100 parts by weight of the (meth)acrylic paste.

[0215] According to the third and fourth aspects, the present invention also relates to a method for preparing (meth)acrylic acid composition MC1.

[0216] According to the present invention, the method includes the following steps: i) providing components (a) to (b) or (a) to (d), ii) adding components (b) or (b) to (d) to (a), and ii) mixing components (a) to (b) or (a) to (d).

[0217] Step iii) of the preparation method according to the present invention is carried out by mixing all the components included in the (meth)acrylic composition MC1, noting that a liquid (meth)acrylic slurry is first prepared, then an impact modifier IM1 and, where appropriate, a polymerization activator or accelerator are introduced into the (meth)acrylic slurry, and finally a polymerization initiator is introduced.

[0218] The mixing can be done manually or using a mixing device.

[0219] Optionally, mixing is carried out by stirring and lasts for a period of time 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.

[0220] Therefore, the manufacturing method according to the invention is specifically carried out and can be easily performed in existing facilities dedicated to the manufacture of (meth)acrylic acid compositions MC1.

[0221] The (meth)acrylic acid composition MC1 comprising compounds (a) to (b) or (a) to (d) has a strength at 23°C and a strength at 50 mPa. s and 10,000 Pa The viscosity between s.

[0222] Preferably, the (meth)acrylic acid composition MC1 comprising compounds a) to d) has a viscosity of 50 mPa at 25°C. The range is from s to 2000 mPas.

[0223] The (meth)acrylic acid composition MC1 according to the present invention can be used to prepare materials with low dielectric constant.

[0224] An additional aspect of the invention is a (meth)acrylic thermoplastic polymer composition MTPC1 prepared by polymerization of a (meth)acrylic composition MC1.

[0225] Another aspect of the present invention relates to a method for preparing a (meth)acrylic acid thermoplastic polymer composition MTPC1.

[0226] Another aspect of the present invention relates to a method for preparing a (meth)acrylic thermoplastic polymer composition MTPC1 having a low dielectric constant.

[0227] The method for preparing the (meth)acrylic thermoplastic polymer composition MTPC1 includes the following steps:

[0228] (i) Provides the (meth)acrylic acid composition MC1 as defined above,

[0229] (ii) Optionally, the (meth)acrylic acid composition MC1 is filled into or poured into the cavity (30).

[0230] (iii) Polymerize (meth)acrylic acid composition MC1.

[0231] Different embodiments of the provided (meth)acrylic acid composition MC1 and its corresponding components can be combined in any combination.

[0232] In a first preferred embodiment of the method for preparing (meth)acrylic thermoplastic polymer compositions, the cavity (30) is part of a mold.

[0233] In a second preferred embodiment of the method for preparing a (meth)acrylic thermoplastic polymer composition, step (ii) involves transferring the (meth)acrylic composition MC1 into a mold.

[0234] In a third preferred embodiment of the method for preparing a (meth)acrylic thermoplastic polymer composition, step (ii) involves transferring the (meth)acrylic composition MC1 into a closed mold.

[0235] Second and third preferred embodiments of the method for preparing (meth)acrylic thermoplastic polymer compositions may include the additional step of applying a vacuum and a slight air pressure at the mold exit to transfer the (meth)acrylic composition MC1 into the mold.

[0236] The (meth)acrylic thermoplastic polymer composition MTPC1 according to the present invention can be used in materials having a low dielectric constant.

[0237] Another aspect of the invention relates to a (meth)acrylic thermoplastic polymer composition MTPC1, which includes filler FI1 or fibrous material FM.

[0238] Another aspect of the invention relates to a (meth)acrylic thermoplastic polymer composition MTPC1 having a low dielectric constant, comprising filler FI1 or fibrous material FM.

[0239] The filler FI1 can be in granular form. Examples include glass beads, hollow glass microspheres, and inorganic compounds such as minerals and salts. Inorganic compounds include quartz, granite, marble, feldspar, clay, ceramics, mica, graphite, silicates, carbonates, sulfates, phosphates, hydroxides, metal oxides, or combinations of two or more thereof. Specific compounds include calcium carbonate (CaCO3), silicon dioxide (SiO2), aluminum hydroxide (AlOH3), and magnesium hydroxide.

[0240] In a first more preferred embodiment, the filler FI1 is selected from glass beads.

[0241] In a second, more preferred embodiment, the filler FI1 is selected from hollow glass microspheres.

[0242] In a third, more preferred embodiment, the filler FI1 is selected from inorganic compounds such as minerals and salts.

[0243] In one specific embodiment, for 100 parts of (meth)acrylic thermoplastic polymer, the (meth)acrylic thermoplastic polymer composition MTPC1 includes filler F1 in amounts between 0.01 phr and 300 phr by weight.

[0244] Regarding fibrous materials (FM), it can be mentioned that they are made from several fibers, unidirectional rovings or continuous filament mats, fabrics, felts or nonwovens, which can be in the form of strips, laps, braids, locks or pieces. Fiber materials can have various forms and sizes, one-dimensional, two-dimensional or three-dimensional. Fiber substrates include components (assemblies) of one or more fibers.

[0245] The source of fibrous materials can be natural or synthetic. As for natural materials, plant fibers, wood fibers, animal fibers, or mineral fibers can be mentioned.

[0246] Natural fibers include, for example, sisal, jute, hemp, flax, cotton, coconut fiber, and banana fiber. Animal fibers include, for example, wool or hair.

[0247] As a synthetic material, polymer fibers selected from thermosetting polymers, thermoplastic polymers, or mixtures thereof may be mentioned.

[0248] Polymer fibers can be composed of polyamides (aliphatic or aromatic), polyesters, polyvinyl alcohol, polyolefins such as polypropylene, polyurethane, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins, and vinyl esters.

[0249] Mineral fibers may also be selected from glass fibers (especially E, R or S2 type), carbon fibers, boron fibers or silica fibers.

[0250] The fiber 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.

[0251] Another aspect of the present invention relates to a (meth)acrylic composite material MCM1, which includes a (meth)acrylic thermoplastic polymer composition MTPC1.

[0252] In a first preferred embodiment, the (meth)acrylic composite material MCM1 is a fiber-reinforced (meth)acrylic composite material.

[0253] In a second preferred embodiment, the (meth)acrylic composite material MCM1 is a particle-reinforced (meth)acrylic composite material.

[0254] In a third preferred embodiment, the (meth)acrylic composite material MCM1 is a glass particle-reinforced (meth)acrylic composite material. In a preferred embodiment, the glass particles are hollow glass beads or hollow glass microspheres.

[0255] In an additional aspect, the present invention relates to articles or objects comprising (meth)acrylic composite material MCM1 or comprising (meth)acrylic thermoplastic polymer composition MTPC1.

[0256] According to one embodiment of the present invention, an article or object is obtained by polymerization of a (meth)acrylic acid composition MC1 in a mold.

[0257] According to another embodiment of the present invention, a molded part MP1 is obtained by polymerization of a (meth)acrylic acid composition MC1 in a mold.

[0258] Articles, objects, or molded parts according to the invention can be used in many fields, particularly in housings, motor vehicles, railways, sports, aviation industry, aerospace, photovoltaic or wind power generation, as well as in marine and medical applications.

[0259] More specifically, articles or objects or molded parts according to the invention can be used in electronic and electrical engineering, electronic integration, printed circuit boards and communication materials.

[0260] For example, the following objects or articles may include molded parts MP1: objects used for telecommunications and signal transmission.

[0261] [method]

[0262] Weight-average molecular weight was measured by size exclusion chromatography (SEC). The chromatographic column was calibrated with PMMA standards having molecular weights between 402 g / mol and 1,900,000 g / mol. For number-average and Mw molecular weights, the average molecular weight is expressed in g / mol. For measurements, the concentration was 1 g / L.

[0263] The viscosity of a (meth)acrylic composition comprising at least components a1) and a2) was measured at 25°C using a Brookfield viscometer according to ISO 2555:2018 “Plastics - Resins in the liquid state or asemulsions or dispersions - Determination of apparent viscosity using a single-cylinder type rotational viscometer method”.

[0264] As a dielectric property, the relative permittivity ε was measured based on test method IPC-TM-650, specifically number 2.5.5.14. r The loss tangent is tan. The loss tangent represents the ratio of the imaginary part to the real part of the complex permittivity. The loss tangent is also referred to by terms such as tangential loss, dissipation factor, or loss factor. As a test instrument, the E4991A RF impedance / material analyzer, used with a dielectric material test fixture, performs dielectric constant and loss tangent measurements up to 1.5 GHz using a parallel-plate method.

[0265] [Example]

[0266] The following compounds are used to prepare various (meth)acrylic acid compositions:

[0267] - As a (meth)acrylic acid polymer P1:

[0268] PMMA, formed from a copolymer of methyl methacrylate and ethyl acrylate, is from Altuglas Corporation and is marketed under the name Altuglas® BS 520B.

[0269] - As a (meth)acrylic monomer M1: methyl methacrylate stabilized with hydroquinone monomethyl ether

[0270] - Benzoyl peroxide (BPO) is used as the initiator.

[0271] - As an accelerator, N,N-dihydroxyethyl-p-toluidine (DHEPT) is used.

[0272] - As an impact modifier: Nanostrenght® M52N, a (meth)acrylic block copolymer from ARKEMA.

[0273] Slurry S1 was prepared as follows: First, 20 parts by weight of PMMA (BS520, a copolymer of MMA containing ethyl acrylate as a comonomer) as P1 was dissolved in 80 parts by weight of methyl methacrylate stabilized with MEHQ (hydroquinone monomethyl ether) as (meth)acrylate monomer M1. Slurry S1 had a viscosity of 104 m at 23°C. The viscosity of Pas.

[0274] Slurry S1 is used to prepare the compositions of the embodiments and comparative examples of the present invention by adding other compounds.

[0275] Then add 0.4 parts of N,N-dihydroxyethyl-p-toluidine to 100 parts of slurry S1.

[0276] According to an embodiment of the invention, Nanostrenght® M52N is added in the amounts shown in Table 1.

[0277] Just before polymerization, add 2 parts of benzoyl peroxide.

[0278] Table 1 - Unless otherwise specified, the prepared compositions are listed in phr.

[0279]

[0280] The mixture from Table 1 is polymerized. Polymerization is carried out in a mold to obtain sheets.

[0281] The dielectric properties and impact resistance of the test sheet were measured. The relative permittivity ε was also considered. r Evaluation was conducted at 1 GHz and 23°C. Impact tests were performed by dropping a steel ball (2.08 ch diameter, 535 g) from a height of 1 m.

[0282] The results obtained are summarized in Table 2.

[0283] Table 2 - Properties of the obtained polymerized compositions

[0284]

[0285] The composition according to the embodiments maintains a low dielectric constant while having improved impact properties.

Claims

1. (Meth)acrylic acid composition MC1, comprising: (a) 100 parts by weight of a liquid (meth)acrylic paste, comprising: (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer. (b) Optionally, 0.5 to 25 parts by weight of impact modifier IM1, (c) Optionally 0.01 parts by weight to 5 parts by weight of polymerization initiator (d) An accelerator, optionally between 100 ppm and 10,000 ppm.

2. The (meth)acrylic acid composition MC1 according to claim 1, characterized in that... It includes, (c) 0.01 to 5 parts by weight of polymerization initiator (d) Accelerators between 100 ppm and 10,000 ppm.

3. The (meth)acrylic acid composition MC1 according to claim 1 or 2, characterized in that... Impact modifier IM1 is selected from a mixture of core-shell particles and block copolymer BC1.

4. The (meth)acrylic acid composition MC1 according to claim 1 or 2, characterized in that... The impact modifier IM1 is selected from block copolymer BC1.

5. The (meth)acrylic acid composition MC1 according to claim 3 or 4, characterized in that... For 100 parts by weight of liquid (meth)acrylic paste, the block copolymer BC1 is present in the form of 1 to 15 parts by weight, more preferably 1 to 12 parts by weight, and even more preferably 1 to 10 parts by weight.

6. The composition according to claim 5, characterized in that... The block copolymer BC1 comprises at least one block having a glass transition temperature Tg of less than 20°C, preferably less than 10°C, and more preferably less than 0°C.

7. The composition according to claim 5, characterized in that... The block copolymer BC1 is a thermoplastic block copolymer TBC1, and preferably a thermoplastic acrylic block copolymer.

8. The composition according to claim 5, characterized in that... Block copolymer BC1 The thermoplastic acrylic block copolymer has the general formula (A) n B, wherein: ● n is an integer greater than or equal to 1. ● A is: an acrylic or methacrylic or styrene homopolymer or copolymer, or polystyrene, or an acrylic / styrene or methacrylic / styrene copolymer having a Tg greater than 50°C, preferably greater than 80°C; ● B is an acrylic or methacrylic homopolymer or copolymer with a Tg of less than 20°C.

9. The composition according to any one of claims 3 to 8, characterized in that... The block copolymer BC1 is selected from 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.

10. The composition according to any one of claims 3 to 9, characterized in that... The block copolymer BC1 has a weight-average molar mass between 10,000 g / mol and 500,000 g / mol.

11. The composition according to any one of claims 3 to 10, characterized in that... The block copolymer BC1 contains block B, which accounts for 10% to 85% by weight of the total weight of the block copolymer.

12. The composition according to any one of claims 1 to 11, characterized in that... Liquid (meth)acrylic paste has a 10 m... Pas and 10,000 mPa The viscosity between s.

13. The composition according to any one of claims 1 to 12, characterized in that... The (meth)acrylic polymer P1 has a weight average molecular weight Mw greater than 40 000 g / mol w .

14. The composition according to any one of claims 1 to 13, characterized in that... (Meth)acrylic monomers (M1) are selected from alkylacrylic monomers, alkylmethacrylic monomers, hydroxyalkylacrylic monomers and hydroxyalkylmethacrylic monomers and mixtures thereof.

15. The composition according to any one of claims 1 to 13, characterized in that... (Meth)acrylic monomers (M1) are 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.

16. The composition according to any one of claims 1 to 13, characterized in that... (Meth)acrylic monomer (M1) is a mixture of at least 90% by weight of methyl methacrylate and optionally at least one other monomer.

17. The composition according to any one of claims 1 to 13, characterized in that the (meth)acrylic monomer (M1) is at least 90% by weight methyl methacrylate.

18. A method for preparing the (meth)acrylic acid composition MC1 according to any one of claims 1 to 17, comprising the following steps: (i) Provide component (a) a liquid (meth)acrylic slurry comprising: (a1) 1% to 50% by weight of one or more (meth)acrylic acid polymers P1, and (a2) 50% to 99% by weight of one or more (meth)acrylic acid monomers M1, each monomer M1 comprising only one (meth)acrylic acid functional group per monomer. (ii) For 100 parts (a), add 0.5 to 25 parts by weight of component (b) of impact modifier IM1. Optional component (c) 0.01 parts by weight to 5 parts by weight of polymerization initiator and optional component (d) accelerator between 100 ppm and 10,000 ppm. (iii) Mix components (a) to (b) or (a) to (d).

19. Use of the (meth)acrylic acid composition MC1 according to any one of claims 1 to 17 for the preparation of materials having a low dielectric constant.

20. Use of the acrylic composition MC1 according to claim 19 for the preparation of materials having a low dielectric constant, meaning a relative dielectric constant ε lower than 2.9 at 1 GHz r .

21. A (meth)acrylic thermoplastic polymer composition MTPC1, prepared by polymerization of a (meth)acrylic composition MC1 according to any one of claims 1 to 17.

22. The (meth)acrylic thermoplastic polymer composition MTPC1 according to claim 21, comprising filler FI1 or fibrous material FM.

23. The thermoplastic polymer composition MTPC1 according to claim 22, characterized in that... (Meth)acrylic thermoplastic polymer composition MTPC1 includes filler FI1 made of glass beads, hollow glass microspheres, inorganic compounds such as minerals and salts.

24. The thermoplastic polymer composition MTPC1 according to claim 22, characterized in that... For 100 parts of (meth)acrylic thermoplastic polymer, the (meth)acrylic thermoplastic polymer composition MTPC1 includes filler F1 between 0.01 phr and 300 phr by weight.

25. Use of the (meth)acrylic thermoplastic polymer composition MTPC1 according to any one of claims 21 and 24 as a material having a low dielectric constant.

26. Use of the acrylic thermoplastic polymer composition MTPC1 according to any one of claims 21 to 24 as a material having a low dielectric constant, meaning a relative dielectric constant ε of less than 2.9 at 1 GHz r .

27. A method for preparing a (meth)acrylic thermoplastic polymer composition MTPC1, comprising the following steps: (i) Providing a (meth)acrylic acid composition MC1 according to any one of claims 1 to 17, (ii) Optionally, the (meth)acrylic composition MC1 is filled into or poured into a mold. (iii) Polymerize (meth)acrylic acid composition MC1.

28. A (meth)acrylic composite material MCM1, comprising the (meth)acrylic thermoplastic polymer composition MTPC1 according to claims 21 to 24.

29. The composite material MCM1 according to claim 28, characterized in that... MCM1 is a fiber-reinforced (meth)acrylic composite material.

30. The composite material MCM1 according to claim 28, characterized in that... MCM1 is a particle-reinforced (meth)acrylic composite material.

31. The composite material MCM1 according to claim 28, characterized in that... MCM1 is a glass particle-reinforced (meth)acrylic composite material.

32. The composite material MCM1 according to claim 28, characterized in that... MCM1, a (meth)acrylic composite material, is a (meth)acrylic composite material reinforced with hollow glass beads or hollow glass microspheres.

33. Articles, objects, or molded parts comprising (meth)acrylic composite material MCM1 according to claims 28 to 32 or comprising (meth)acrylic thermoplastic polymer composition MTPC1 according to claims 21 to 24.

34. The article or object or molded object according to claim 33, used in electronic and electrical engineering, electronic integration, printed circuit boards and communication materials.

35. The article or object or molded object according to claim 33, used for telecommunications and signal transmission.

36. Use of the article, object, or molded component according to claim 34 or 35 in the fields of housing, motor vehicles, railways, sports, aviation industry, aerospace, photovoltaic or wind power generation, as well as in marine and medical applications.

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