(Meth)acrylic polymer compositions, methods for preparing same and uses thereof

Abstract

The present invention relates to an impact-resistant (meth)acrylic polymer composition. In particular, the present invention relates to an impact-resistant polymer composition suitable for glazing or lightening applications. The present invention also relates to a method for producing such a polymer composition suitable for glazing or lightening applications. More specifically, the present invention relates to an impact-resistant (meth)acrylic polymer composition, and also to a method for preparing such an impact-resistant (meth)acrylic polymer composition and its use in glazing or lightening applications.

Description

[Technical Field]

[0001] The present invention relates to an impact-resistant (meth)acrylic polymer composition.

[0002] In particular, the present invention relates to impact resistant polymer compositions suitable for glazing or lightening applications. The present invention also relates to methods for producing such polymer compositions suitable for glazing or lightening applications.

[0003] More specifically, the present invention relates to impact resistant (meth)acrylic polymer compositions and also to methods for preparing such impact resistant (meth)acrylic polymer compositions and their use in glazing or lightening applications.

[0004] Acrylic and (meth)acrylic polymers, often simply referred to as PMMA, are widely used for their transparency and scratch resistance. They are particularly valued for their excellent optical properties, especially gloss and high transparency with at least 90% visible light transmittance. However, they are also brittle thermoplastics that are vulnerable to impact. This property is related to the fact that PMMA's glass transition temperature is approximately 110°C, meaning that polymer chains in this material cannot easily move at ambient temperatures. For some applications, improved impact performance is required while maintaining its transparency.

[0005] Impact resistance in the case of acrylic and (meth)acrylic polymers, both commonly referred to simply as polymethyl methacrylate (PMMA), is generally improved by the incorporation of impact additives into the acrylic resin.

[0006] One of the most common known impact additives is the core-shell additive, which is provided in the form of multi-layered spherical particles. These particles are prepared by emulsion polymerization in a multi-stage process and recovered in powder form by micronization. They generally contain a layer sequence of "hard" and "soft" layers. Thus, bi-layered (soft-hard) or tri-layered (hard-soft-hard) particles, or occasionally even more layers, can be found.

[0007] In the case of cast acrylic sheets, which are obtained by polymerizing a monomer mixture in a mold, the impact additive is pre-dispersed in the monomer mixture. In the case of extruded acrylic sheets, the impact additive is compounded with the acrylic resin in the extruder. In either case, a good dispersion of the impact additive within the acrylic resin is necessary to maintain a consistent and uniform level of impact strength. The proportion of impact modifier is also limited by its amount dissolved in the monomer, since the impact additive swells and the mixture is no longer liquid. This amount limitation leads to a limit on the level of impact modification.

[0008] Sheet materials are used in a variety of environments, including temperature changes, and therefore the material must remain transparent to environmental changes, particularly temperature changes.

[0009] Laminates are also sometimes used. Glass laminates have the disadvantage of being very heavy.

[0010] Laminate materials are more complex than monolayer sheets and are typically more expensive to manufacture. Glass-clad laminates and plastic laminates are also very expensive to manufacture, but are less heavy to handle.

[0011] The sheet materials used in glazing are transparent and, if soiled, can be cleaned using solvents or other chemicals, so the material must be solvent resistant.

[0012] There is a need for lightweight impact resistant glazing for use in impact resistant applications.

[0013] There is a need for lightweight impact resistant glazing for use in impact resistant applications that maintains its clarity regardless of temperature.

[0014] It is an object of the present invention to provide (meth)acrylic polymer compositions with improved impact resistance, especially for glazing and lightening applications.

[0015] Another object of the present invention is also to provide a (meth)acrylic polymer composition for lightweight impact resistant glazing.

[0016] An additional object of the present invention is to avoid or significantly reduce the weight or thickness of (meth)acrylic polymer compositions suitable for impact resistant applications.

[0017] Yet another object is to provide a method for producing a (meth)acrylic polymer composition suitable for impact resistant applications.

[0018] A still further object is to provide a method for producing a (meth)acrylic polymer composition for lightweight impact resistant glazing.

[0019] Another further object is the use of the (meth)acrylic polymer composition for impact resistant glazing.

[0020] A further object is to provide a (meth)acrylic impact resistant polymer composition that maintains its bright surface appearance and its transparency over the temperature interval from -30°C to 60°C.

[0021] Another further object is to provide an impact resistant composition that can be thermoformed yet maintains its bright surface appearance and its transparency over the temperature interval from -30°C to 60°C.

[0022] A still further object is to provide a method for producing a (meth)acrylic polymer composition suitable for impact resistant applications, which maintains its bright surface appearance and its transparency over the temperature interval from -30°C to 60°C. [Background technology]

[0023] Document WO2012 / 130595 discloses the use of coated moldings made of high molecular weight impact-modified polymethyl methacrylate polymers as windows for passenger cars or special-purpose vehicles. A molding composition is disclosed that contains 0.5 to 35% by weight of at least one type of core-shell-shell particles as an impact modifier.

[0024] Document WO2012 / 085487 discloses a transparent, impact-resistant crosslinked acrylic composition consisting of a brittle matrix with a glass transition temperature above 0°C and elastomeric domains with characteristic dimensions of less than 100 nm, consisting of flexible macromolecular sequences with a glass transition temperature below 0°C, the elastomeric domains being part of a block copolymer consisting of PRC.

[0025] Document WO 2014 / 154543 discloses an impact-resistant PMMA composition with improved optical properties, especially at high temperatures. The composition comprises core-shell-shell particles with a total radius ranging from 70.0 to 125.0 nm and a refractive index difference of only 0.01 units less than that of the PMMA matrix.

[0026] None of the prior art documents discloses the claimed polymer composition or the process for obtaining it or its use. Summary of the Invention

[0027] Surprisingly, it has been found that a polymer composition comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0°C and an elastomeric domain having a characteristic dimension of less than 100 nm and consisting of a flexible polymer sequence (II) having a glass transition temperature below 0°C, wherein the flexible polymer sequence (II) has a weight average molecular weight Mw between 150,000 g / mol and 800,000 g / mol, is suitable for impact-resistant applications, in particular for impact-resistant sheets.

[0028] Surprisingly, it has also been found that polymer compositions comprising crosslinked (meth)acrylic compositions comprising a brittle matrix (I) having a glass transition temperature above 0° C. and elastomeric domains having a characteristic dimension of less than 100 nm and consisting of flexible polymeric sequences (II) having a glass transition temperature below 0° C., wherein the flexible polymeric sequences (II) have a weight-average molecular weight Mw between 150,000 g / mol and 800,000 g / mol, can be used for impact-resistant glazing applications.

[0029] Surprisingly, it has also been found that in a polymer composition comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0°C and an elastomer domain having a characteristic dimension of less than 100 nm and consisting of a flexible polymer sequence (II) having a glass transition temperature below 0°C, wherein the flexible polymer sequence (II) has a weight average molecular weight Mw between 150,000 g / mol and 800,000 g / mol, an impact-resistant sheet having good solvent resistance and transparency over a wide temperature range can be obtained by using the polymer composition as a sheet.

[0030] Surprisingly, it has also been found that a process for producing a polymer composition comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0° C. and elastomeric domains having a characteristic dimension of less than 100 nm, which are made of flexible polymeric sequences (II) having a glass transition temperature below 0° C., characterized in that the flexible polymeric sequences (II) have a weight-average molecular weight Mw between 150,000 g / mol and 800,000 g / mol, by a cast sheet process, can give impact-resistant sheets having good solvent resistance and transparency over a wide temperature range.

[0031] According to a first aspect, the present invention relates to a polymer composition comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0° C. and elastomeric domains having a characteristic dimension of less than 100 nm and consisting of flexible polymeric sequences (II) having a glass transition temperature below 0° C., characterized in that the flexible polymeric sequences (II) have a weight average molecular weight Mw of between 150,000 g / mol and 800,000 g / mol.

[0032] According to a second aspect, the present invention relates to the use of a polymer composition comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0° C. and elastomeric domains having a characteristic dimension of less than 100 nm and consisting of flexible polymeric sequences (II) having a glass transition temperature below 0° C., characterized in that the flexible polymeric sequences (II) have a weight average molecular weight Mw of between 150,000 g / mol and 800,000 g / mol for impact resistance applications.

[0033] According to a third aspect, the present invention provides a method for producing a polymer composition comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0 ° C and elastomeric domains with a characteristic dimension of less than 100 nm, which are made of flexible macromolecular sequences (II) having a glass transition temperature below 0 ° C, characterized in that the flexible macromolecular sequences (II) have a weight average molecular weight Mw between 150,000 g / mol and 800,000 g / mol, a) General formula Z(-T) n preparing a polymer sequence (II) by mixing an alkoxyamine of the formula (wherein Z represents a polyvalent group, T represents a nitroxide, and n is an integer of 1 or more) with a monomer for forming the polymer sequence (II); b) mixing the polymeric sequence (II) of step a) with methyl methacrylate, optionally with a crosslinking agent, optionally with at least one comonomer M and optionally with at least one radical initiator; c) mixing the composition comprising the polymeric sequence (II) and methyl methacrylate, if not already done in step b), with a crosslinking agent, optionally at least one comonomer M and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated according to a temperature cycle to obtain a cast sheet; The present invention relates to a method, comprising:

[0034] According to a fourth aspect, the present invention relates to a polymer composition suitable for impact-resistant applications, comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0° C. and elastomeric domains having a characteristic dimension of less than 100 nm and consisting of flexible polymeric sequences (II) having a glass transition temperature below 0° C., characterized in that the flexible polymeric sequences (II) have a weight-average molecular weight Mw of between 150,000 g / mol and 800,000 g / mol.

[0035] The term "copolymer" is used to mean that the polymer is made up of at least two different monomers.

[0036] The term "(meth)acrylic monomers" as used refers to all types of acrylic and methacrylic monomers.

[0037] The term "(meth)acrylic polymer" as used means that the (meth)acrylic polymer essentially comprises a polymer with (meth)acrylic monomers constituting 50% or more by weight of the (meth)acrylic polymer.

[0038] The term "impact modifier" as used is understood to be a material that, once incorporated into a polymeric material, increases the impact resistance and toughness of that polymeric material through the phase microdomains of rubbery materials or rubber polymers.

[0039] The term "rubber" as used refers to the thermodynamic state of a polymer above its glass transition.

[0040] The term "rubber polymer" as used means a polymer that has a glass transition temperature (Tg) below 0°C.

[0041] The term "crosslinked" as used herein refers to a polymer copolymer in which some of its chains are linked to one another through covalent bonds or chemical or physical interactions, and these linked chains are largely dispersed in three-dimensional space.

[0042] The term "transparent" as used herein means that the composition has a high light transmittance of at least 80% in the visible light.

[0043] In the present invention, a range from x to y means that the upper and lower limits of this range are included, and is at least equal to x to y.

[0044] In the present invention, when a range is stated to be between x and y, it means that the upper and lower limits of this range are excluded, and is equivalent to being greater than x and less than y.

[0045] The polymer composition of the present invention comprises a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0°C and an elastomer domain having a characteristic dimension of less than 100 nm, the elastomer domain being made of a flexible polymer sequence (II) having a glass transition temperature below 0°C, wherein the flexible polymer sequence (II) has a weight average molecular weight Mw between 150,000 g / mol and 800,000 g / mol.

[0046] In a particular embodiment, the polymer composition of the present invention comprises a crosslinked (meth)acrylic composition consisting of a brittle matrix (I) having a glass transition temperature Tg above 0°C and an elastomeric domain having a characteristic dimension of less than 100 nm, the elastomeric domain consisting of a flexible polymer sequence (II) having a glass transition temperature below 0°C, wherein the flexible polymer sequence (II) has a weight average molecular weight Mw between 150,000 g / mol and 800,000 g / mol.

[0047] Regarding matrix (I), it exhibits an overall Tg greater than 0°C as measured by differential scanning calorimetry (DSC) and is compatible with homopolymers or copolymers of methyl methacrylate. Preferably, the glass transition temperature Tg is greater than 10°C, more preferably greater than 20°C, even more preferably greater than 40°C, even more preferably greater than 40°C, advantageously greater than 50°C, and more advantageously greater than 60°C.

[0048] The matrix (I) is composed of methyl methacrylate and optionally - a linear, cyclic or branched C-C alkyl group of the formula CH2=CH-C(=O)-O-R1, where R1 is a hydrogen atom or a halogen atom, or optionally substituted with a hydroxyl, alkoxy, cyano, amino or epoxy group; 40alkyl group), such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyalkyl acrylates or acrylonitrile; - a linear, cyclic or branched C1-C alkyl group of the formula CH2=C(CH3)-C(=O)-O-R2, where R2 is a hydrogen atom or a halogen atom, or optionally substituted with a hydroxyl, alkoxy, cyano, amino or epoxy group; 40 alkyl group), such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, hydroxyalkyl methacrylates or methacrylonitrile; vinyl aromatic monomers, such as styrene or substituted styrenes, such as α-methylstyrene, monochlorostyrene or tert-butylstyrene and one or more monomers Mo1 selected from the group consisting of:

[0049] The comonomer is selected in such a way that the nature and amount of the comonomer ensures that the lower limit of the glass transition temperature Tg is met.

[0050] Preferably, methyl methacrylate (MMA) is the main monomer in the polymer of matrix (I), so that matrix (I) comprises a proportion of methyl methacrylate of 51% to 100% by weight, preferably between 75% and 100% by weight, advantageously between 90% and 100% by weight.

[0051] Regarding the flexible polymeric sequences (II), said polymeric sequences (II) are also referred to as block B in the present invention. These flexible polymeric sequences (II) exhibit a glass transition temperature (denoted as Tg and measured by DSC) of less than 0° C. Preferably, Tg is less than −5° C., more preferably less than −10° C., and even more preferably less than −15° C.

[0052] Preferably, these flexible polymeric sequences (II) exhibit a glass transition temperature (denoted Tg and measured by DSC) above -100°C. More preferably, the Tg is above -90°C, even more preferably above -80°C, and even more preferably above -70°C. More preferably, these flexible polymeric sequences (II) exhibit a glass transition temperature between -100°C and 0°C, even more preferably between -90°C and -5°C, even more preferably between -80°C and -10°C, and even more preferably between -70°C and -15°C.

[0053] Furthermore, the weight average molecular weight of the flexible polymer sequence (II) having a glass transition temperature below 0° C. is between 150,000 g / mol and 800,000 g / mol.

[0054] Preferably, the weight-average molecular weight of the flexible polymeric sequence (II) with a glass transition temperature below 0° C. is between 175,000 and 700,000 g / mol, more preferably between 200,000 and 650,000 g / mol, advantageously between 225,000 and 600,000 g / mol.

[0055] In a first preferred embodiment, the weight average molecular weight Mw of the flexible polymeric sequence (II) with a glass transition temperature below 0° C. is between 240,000 g / mol and 600,000 g / mol.

[0056] In a second preferred embodiment, the weight average molecular weight Mw of the flexible polymeric sequence (II) with a glass transition temperature below 0° C. is between 255,000 g / mol and 600,000 g / mol.

[0057] The polydispersity index PI of the molecular weight Mw / Mn of the flexible polymeric sequence (II) or block B is greater than 2, preferably greater than 2.1, more preferably greater than 2.2, even more preferably greater than 2.3, even more preferably greater than 2.4, even more preferably greater than 2.5, advantageously greater than 2.5, more advantageously greater than 2.6 and even more advantageously greater than 3.

[0058] The polydispersity index PI of the molecular weight Pi=Mw / Mn is between 2.0 and 10.0, preferably between 2.1 and 10, more preferably between 2.2 and 10, even more preferably between 2.3 and 10, even more preferably between 2.4 and 10, even more preferably between 2.4 and 10, advantageously between 2.5 and 10.0, more advantageously between 3.0 and 10.0, even more advantageously between 3.0 and 6.0, even more advantageously between 3.0 and 5.0.

[0059] The polymer sequence (II) is - a linear, cyclic or branched C-C alkyl group of the formula CH2=CH-C(=O)-O-R1, where R1 is a hydrogen atom or a halogen atom, or optionally substituted with a hydroxyl, alkoxy, cyano, amino or epoxy group; 40 alkyl group), such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyalkyl acrylates or acrylonitrile; - a linear, cyclic or branched C1-C alkyl group of the formula CH2=C(CH3)-C(=O)-O-R2, where R2 is a hydrogen atom or a halogen atom, or optionally substituted with a hydroxyl, alkoxy, cyano, amino or epoxy group; 40alkyl group), such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, hydroxyalkyl methacrylates or methacrylonitrile; vinyl aromatic monomers, such as styrene or substituted styrenes, α-methylstyrene, monochlorostyrene or tert-butylstyrene It is prepared from one or more monomers Mo2 selected from:

[0060] The polymer sequence (II) is not prepared from a diene. Those skilled in the art will appreciate that, if transparency is required for the target application, in order to provide the highest possible transparency, the total Tg of block B (to obtain a block B with a Tg below 0° C., it is necessary to use at least one monomer exhibiting a Tg below 0° C., for example butyl acrylate or 2-ethylhexyl acrylate); - the refractive index of block B (which must be as close as possible to the refractive index of the matrix (I)) We know how to combine these monomers to tailor the

[0061] The polymeric sequence (II) may consist solely of monomers exhibiting a Tg below 0° C. (after the monomers have been polymerized), such as butyl acrylate or 2-ethylhexyl acrylate. The polymeric sequence (II) may also consist of at least one alkyl acrylate and a vinyl aromatic monomer. Advantageously, the polymeric sequence (II) consists of butyl acrylate and styrene in a butyl acrylate / styrene weight ratio between 70 / 30 and 90 / 10, preferably between 75 / 25 and 85 / 15.

[0062] The content of block B (polymeric sequence (II)) in the polymer composition is between 1 and 30% by weight, preferably between 2 and 20% by weight, more preferably between 2 and 15% by weight, based on the polymer composition comprising the crosslinked (meth)acrylic composition and the polymeric sequence (II).

[0063] As for the compounds that enable crosslinking (crosslinking agents), they are preferably polyfunctional acrylic monomers, such as polyol polyacrylates, alkylene glycol polyacrylates or allyl acrylates, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate or 1,4-butylene glycol diacrylate, polyfunctional methacrylic monomers, such as polyol polymethacrylates, alkylene glycol polymethacrylates or allyl methacrylates, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate or 1,4-butylene glycol dimethacrylate, divinylbenzene or trivinylbenzene. In a first preferred embodiment, it is 1,4-butylene glycol dimethacrylate (BDMA).

[0064] The content of crosslinking agent is between 0.05 and 10% by weight relative to the crosslinked acrylic composition that is the subject of the present invention.

[0065] Preferably, the content of crosslinking agent is between 0.05 and 10% by weight relative to the MMA and monomers M1 of the crosslinked acrylic composition that is the subject of the present invention.

[0066] More preferably, the content of crosslinker is between 0.4% and 8% by weight, more preferably between 0.5% and 5% by weight, still more preferably between 0.6% and 5% by weight, still more preferably between 0.8% and 5% by weight, still more preferably between 0.9% and 5% by weight, and even more preferably between 1% and 5% by weight, relative to the MMA and monomer M01 of the crosslinked acrylic composition that is the subject of the present invention.

[0067] The compositions according to the invention have a swelling index in acetone at 20°C of less than 200%, preferably less than 190%, even more preferably less than 180%, and most preferably less than 175%.

[0068] The compositions according to the invention have a swelling index between 0% and 200%, preferably between 0% and 190%, even more preferably between 0% and 180%, and most preferably between 0% and 175%.

[0069] The composition according to the invention is preferably in the form of a sheet. Preferably, it is a cast sheet. The sheet may be a flat sheet or a non-flat sheet. A non-flat sheet can be obtained, for example, by first producing a flat sheet and then thermoforming this flat sheet to obtain a non-flat sheet in the form of a slightly curved sheet.

[0070] The thickness of the sheet is between 1 mm and 50 mm, preferably the thickness is between 1 mm and 45 mm, more preferably between 1 mm and 40 mm, even more preferably between 1 mm and 35 mm, advantageously between 2 mm and 35 mm.

[0071] The content of block B (polymer sequence (II)) in the sheet is between 1 and 30% by weight, preferably between 2 and 20% by weight, more preferably between 2 and 15% by weight, based on the polymer composition comprising the crosslinked (meth)acrylic composition and the polymer sequence (II).

[0072] A method for producing a polymer composition comprising a crosslinked (meth)acrylic composition comprising or consisting of a brittle matrix (I) having a glass transition temperature above 0 ° C and elastomeric domains with a characteristic dimension of less than 100 nm, which consist of flexible macromolecular sequences (II) having a glass transition temperature below 0 ° C, characterized in that the flexible macromolecular sequences (II) have a weight average molecular weight Mw between 150,000 g / mol and 800,000 g / mol, said method comprising: a) preparing a polymer sequence (II); b) mixing the polymeric sequence (II) of step a) with methyl methacrylate, optionally with a crosslinking agent, optionally with at least one comonomer M01, and optionally with at least one radical initiator; c) mixing the composition comprising the polymeric sequence (II) and methyl methacrylate, if not already done in step b), with a crosslinking agent, optionally at least one comonomer M01 and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated according to a temperature cycle to obtain a cast sheet; Includes:

[0073] According to a first preferred embodiment of the method of the present invention for producing a polymer composition, the method comprises the following steps: a) General formula Z(-T) n preparing a polymer sequence (II) by mixing an alkoxyamine of the formula (wherein Z represents a polyvalent group, T represents a nitroxide, and n is an integer of 1 or more) with a monomer for forming the polymer sequence (II); b) mixing the polymeric sequence (II) of step a) with methyl methacrylate, optionally with a crosslinking agent, optionally with at least one comonomer M01, and optionally with at least one radical initiator; c) mixing the composition comprising the polymeric sequence (II) and methyl methacrylate, if not already done in step b), with a crosslinking agent, optionally at least one comonomer M01 and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated according to a temperature cycle to obtain a cast sheet; A method for preparing a cast sheet made of a methyl methacrylate homo- or copolymer impact-reinforced using a polymer sequence (II) comprising:

[0074] According to a second preferred embodiment of the method of the present invention for producing a polymer composition, the method comprises the following steps: a) General formula Z(-T)n preparing a polymer sequence (II) by mixing an alkoxyamine of the formula (wherein Z represents a polyvalent group, T represents a nitroxide, and n is an integer of 1 or more) with a monomer for forming the polymer sequence (II); b1) mixing the polymeric sequence (II) of step a) with methyl methacrylate; b2) partially polymerizing the mixture of polymeric sequence (II) and methyl methacrylate, optionally adding additional methyl methacrylate. c) mixing the partially polymerized composition with a crosslinker, optionally at least one comonomer M01 and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated according to a temperature cycle to obtain a cast sheet; A method for preparing a cast sheet made of a methyl methacrylate homo- or copolymer impact-reinforced using a polymer sequence (II) comprising:

[0075] According to a third preferred embodiment of the method of the present invention for producing a polymer composition, the method comprises the following steps: a1) General formula Z(-T) n preparing an alkoxyamine of the formula: (wherein Z represents a polyvalent group, T represents a nitroxide, and n is an integer of 1 or greater); a2) preparing a polymeric sequence (II) by mixing the alkoxyamine of a1) with a monomer for forming the polymeric sequence (II); b1) mixing the polymeric sequence (II) of step a2) with methyl methacrylate; b2) partially polymerizing the mixture of polymeric sequence (II) and methyl methacrylate, optionally adding additional methyl methacrylate. c) mixing the partially polymerized composition with a crosslinker, optionally at least one comonomer M01 and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated according to a temperature cycle to obtain a cast sheet; A method for preparing a cast sheet made of a methyl methacrylate homo- or copolymer impact-reinforced using a polymer sequence (II) comprising:

[0076] The crosslinker and comonomer M01 are the same as defined above.

[0077] As for the alkoxyamine, it can be any type of alkoxyamine, it can also be a polyalkoxyamine capable of generating several nitroxide radicals, or alternatively a polymeric alkoxyamine or polymeric polyalkoxyamine derived from a polymerization process between at least one monomer and an alkoxyamine.

[0078] Thus, according to a first embodiment of the present invention, at least one of the alkoxyamines is monofunctional.

[0079] According to a second aspect of the invention, at least one of the alkoxyamines is polyfunctional.

[0080] The alkoxyamine or polyalkoxyamine has the general formula Z(-T) n where Z is a polyvalent group, T is a nitroxide, and n is an integer greater than or equal to 1, preferably from 2 to 10, advantageously from 2 to 8, more preferably from 2 to 4 (limits included).

[0081] n represents the functionality of the alkoxyamine, i.e. the number of nitroxide radicals T that can be released by the alkoxyamine according to the following mechanism: TIFF0007820092000001.tif10167

[0082] The reaction is activated by temperature. In the presence of monomers, activated alkoxyamines initiate polymerization. The following scheme illustrates the preparation of an alkoxyamine-based copolymer polyM2-polyM1-polyM2 (n=2). After activation of the alkoxyamine, monomer M1 is polymerized first, followed by monomer M2 once the block polyM1 is completed: TIFF0007820092000002.tif37168

[0083] The principles of preparing block copolymers are also valid for n greater than or equal to 1.

[0084] Z represents a polyvalent group, i.e., a group capable of releasing several radical sites after activation. The activation in question occurs by cleavage of the covalent bond ZT.

[0085] By way of example, Z may be selected from the following groups (I) to (VIII): TIFF0007820092000003.tif20165

[0086] In the above formula, R3 and R4 may be the same or different and represent a linear or branched alkyl group containing 1 to 10 carbon atoms, phenyl or thienyl group, which may alternatively be substituted with a halogen atom, such as F, Cl or Br, or alternatively with a linear or branched alkyl group containing 1 to 4 carbon atoms, or alternatively with a nitro, alkoxy, aryloxy, carbonyl or carboxyl group; a benzyl group, a cycloalkyl group containing 3 to 12 carbon atoms, or a group containing one or more unsaturations; B represents a linear or branched alkylene group containing 1 to 20 carbon atoms; m is an integer ranging from 1 to 10; TIFF0007820092000004.tif17161

[0087] In the above formula, R5 and R6 may be the same or different and represent an aryl, pyridyl, furyl or thienyl group, which may be substituted with a halogen atom, such as F, Cl or Br, or alternatively with a linear or branched alkyl group containing 1 to 4 carbon atoms, or alternatively with a nitro, alkoxy, aryloxy, carbonyl or carboxyl group; D represents a linear or branched alkylene group, a phenylene group or a cycloalkylene group containing 1 to 6 carbon atoms; p is an integer ranging from 1 to 10; TIFF0007820092000005.tif45164

[0088] In the above formula, R7, R8 and R9 may be the same or different and have the same meaning as R3 and R4 in formula (I), and q, r and s are integers ranging from 1 to 10; TIFF0007820092000006.tif21170

[0089] In the above formula, R 10 have the same meaning as R5 and R6 in formula (II), t is an integer ranging from 1 to 4, and u is an integer between 2 and 6 (the aromatic group is substituted); TIFF0007820092000007.tif20168

[0090] In the above formula, R 11 is the group R of formula (IV) 10 where v is an integer between 2 and 6; TIFF0007820092000008.tif31151

[0091] In the above formula, R 12 , R 13 and R 14 represent phenyl groups, which may be identical or different and which may be substituted with halogen atoms, for example Cl or Br, or alternatively with linear or branched alkyl groups containing from 1 to 10 carbon atoms; W represents an oxygen, sulfur or selenium atom, with w equal to 0 or 1; TIFF0007820092000009.tif20162

[0092] In the above formula, R 15 has the same meaning as R3 in formula (I), and R 16 has the same meaning as R5 or R6 in formula (II); TIFF0007820092000010.tif21155

[0093] In the above formula, R 17 and R 18 may be the same or different and represent a hydrogen atom, a linear or branched alkyl group containing 1 to 10 carbon atoms, or an aryl group, which may be substituted with a halogen atom or a heteroatom.

[0094] T represents nitroxide, which is =NO · A stable free radical is a radical having a group, i.e., a group in which an unpaired electron is present. The term "stable free radical" refers to a radical that is long-lived, does not react with air and moisture, and can be handled and stored for much longer periods than most free radicals (see, in this regard, Accounts of Chemical Research 1976, 9, 13-19). Thus, a stable free radical differs from free radicals that have a short lifespan (milliseconds to seconds), such as those derived from conventional polymerization initiators such as peroxides, hydroperoxides, or azo initiators. A free radical can be said to be stable if it is not a polymerization initiator and the average radical lifetime is at least one minute.

[0095] T is represented by the following structure: TIFF0007820092000011.tif36138

[0096] In the above formula, R 19 , R 20 , R 21 , R 22 , R 23 and R 24 represents the following group: - Linear or branched C1-C 20 , preferably C1-C10 alkyl, such as substituted or unsubstituted methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl or neopentyl; - Substituted or unsubstituted C6-C 30 Aryl groups, such as benzyl or aryl(phenyl) - Saturated C1-C 30 cyclic group

[0097] In the above formula, the group R 19 and R 22 is an optionally substituted cyclic structure R which may be selected from the following: 19 -CNC-R 22 May form part of: TIFF0007820092000012.tif29169

[0098] In the above formula, x represents an integer between 1 and 12.

[0099] As an example, the following nitroxides can be used: TIFF0007820092000013.tif38153

[0100] Nitroxides of the formula (X) are particularly preferably used: TIFF0007820092000014.tif23159

[0101] R a and R b represent the same or different alkyl groups having 1 to 40 carbon atoms, which may be optionally linked together to form a ring and which may be substituted with a hydroxyl, alkoxy or amino group;

[0102] R L denotes a monovalent group with a molar mass greater than 15.42 g / mol, preferably greater than 30 g / mol. L may have a molar mass between 40 g / mol and 450 g / mol, for example. It is preferably a phosphorus-containing group of general formula (XI): TIFF0007820092000015.tif17143

[0103] In the above formula, X and Y may be the same or different and may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxyl, perfluoroalkyl and aralkyl groups and may contain 1 to 20 carbon atoms; X and / or Y may also be a halogen atom, such as a chlorine, bromine or fluorine atom.

[0104] Advantageously, R L is a phosphonate group of the formula: TIFF0007820092000016.tif18157

[0105] In the above formula, R c and R d are two identical or different alkyl groups, optionally linked to form a ring, containing from 1 to 40 optionally substituted or unsubstituted carbon atoms.

[0106] base R L may also contain at least one aromatic ring, such as a phenyl or naphthyl group, substituted with one or more alkyl groups, for example containing from 1 to 10 carbon atoms.

[0107] Nitroxides of formula (X) are preferred because they allow for good control of the radical polymerization of (meth)acrylic monomers, as taught in WO 03 / 062293. Thus, alkoxyamines of formula (XIII) having nitroxides of formula (X) are preferred: TIFF0007820092000017.tif26161

[0108] In the above formula,

[0109] Z represents a polyvalent group;

[0110] R a and R brepresent the same or different alkyl groups having 1 to 40 carbon atoms, which may be optionally linked to each other to form a ring and may be substituted with a hydroxyl, alkoxy or amino group;

[0111] R L denotes a monovalent group with a molar mass greater than 15.42 g / mol, preferably greater than 30 g / mol. L may have a molar mass between 40 g / mol and 450 g / mol, for example. It is preferably a phosphorus-containing group of general formula (XI): TIFF0007820092000018.tif16145

[0112] In the above formula, X and Y may be the same or different and may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxyl, perfluoroalkyl and aralkyl groups and may contain 1 to 20 carbon atoms; X and / or Y may also be a halogen atom, such as a chlorine, bromine or fluorine atom.

[0113] Advantageously, R L is a phosphonate group of the formula: TIFF0007820092000019.tif20161

[0114] In the above formula, R c and R d are two identical or different alkyl groups, optionally linked to form a ring, containing from 1 to 40 optionally substituted or unsubstituted carbon atoms.

[0115] base R L may also contain at least one aromatic ring, such as a phenyl or naphthyl group, substituted with one or more alkyl groups, for example containing from 1 to 10 carbon atoms.

[0116] Examples of nitroxides of formula (X) that can be supported by alkoxyamines (XIII) include: N-tert-butyl-1-phenyl-2-methylpropyl nitroxide, N-(2-hydroxymethylpropyl)-1-phenyl-2-methylpropyl nitroxide, N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide, N-tert-butyl-1-bis(2,2,2-trifluoroethyl)phosphono-2,2-dimethylpropyl nitroxide, N-tert-butyl[(1-diethylphosphono)-2-methylpropyl]nitroxide, N-(1-methylethyl)-1-cyclohexyl-1-(diethylphosphono)nitroxide, N-(1-phenylbenzyl)-[(1-diethylphosphono)-1-methylethyl]nitroxide, N-phenyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, N-phenyl-1-diethylphosphono-1-methylethyl nitroxide, N-(1-phenyl-2-methylpropyl)-1-diethylphosphonomethylethyl nitroxide, or nitroxides of the formula: TIFF0007820092000020.tif30150

[0117] Particularly preferred are nitroxides of formula (XIV): TIFF0007820092000021.tif35159

[0118] This is N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, commonly known simply as SG1.

[0119] Alkoxyamines (I), in particular alkoxyamines (XIII), can be prepared, for example, by the process described in FR 2791979. One method that can be used consists in coupling a carbon-based radical with a nitroxide. Starting with a halogenated derivative, the coupling can be carried out in the presence of an organometallic system, for example CuX / ligand (X=Cl or Br), according to an ATRA (atom transfer radical addition) type reaction, as described by D. Greszta et al. in Macromolecules 1996, 29, 7661-7670. TIFF0007820092000022.tif19144

[0120] Alkoxyamines that may be used in the context of the present invention are shown below: TIFF0007820092000023.tif37170TIFF0007820092000024.tif50170TIFF0007820092 000025.tif50164TIFF0007820092000026.tif84164TIFF0007820092000027.tif32165 TIFF0007820092000028.tif53152TIFF0007820092000029.tif73148TIFF0007820092 000030.tif64151TIFF0007820092000031.tif66170TIFF0007820092000032.tif56170

[0121] The last two alkoxyamines, called DIAMINS and TRIAMINS, respectively, are the preferred alkoxyamines.

[0122] Advantageously, alkoxyamines known as TRIAMINS are selected for the process according to the invention.

[0123] Regarding step b1) of mixing the polymeric sequence (II) of step a) with methyl methacrylate, this is done so that the polymeric sequence (II) accounts for between 30% and 60% by weight, preferably between 35% and 55% by weight, of the mixture comprising the polymeric sequence (II) and methyl methacrylate.

[0124] Regarding step b2) of partially polymerizing the mixture of polymeric sequence (II) and methyl methacrylate, this is carried out by heating the mixture. The mixture is heated to a temperature higher than 60°C, preferably higher than 70°C. The mixture is heated to a temperature lower than 100°C, preferably lower than 90°C. The polymerization is stopped when the partially polymerized mixture has a viscosity of between 100 and 5000 cPoise at 20°C, as measured by a Brookfield viscometer. The polymerization is stopped by adding methyl methacrylate at a temperature lower than 20°C, preferably lower than 10°C. The amount of methyl methacrylate added is selected so as to obtain a liquid mixture having between 2 and 30% by weight of polymeric sequence (II) in the mixture.

[0125] As regards the radical initiator, this may be selected from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyacetals or azo compounds. Radical initiators that may be suitable are, for example, isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, tert-butyl per-2-ethylhexanoate, cumyl hydroperoxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylperoxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, amyl perpivalate, 1,1-di(t-amylperoxy)cyclohexane, tert-butyl peroctoate, azodiisobutyronitrile (AIBN), azodiisobutyramide, 2,2′-azobis(2,4-dimethylvaleronitrile), 4,4′-azobis(4-cyanopentanoic acid) or 1,1′-azobis(cyanocyclohexane). It would not be outside the scope of the present invention to use mixtures of radical initiators selected from the above list.

[0126] The content of radical initiator relative to the monomer of the mixture poured into the mold varies from 100 ppm to 2000 ppm by weight, preferably between 200 ppm and 1000 ppm by weight, depending on the intended application and thickness.

[0127] The compositions may also contain other compounds not taken into account in calculating the weight ratios between the aforementioned compounds.

[0128] Other ingredients may optionally be added to the mixture that is poured into the mold, including, but not limited to: milky fillers, such as TiO2 or BaSO4, generally used in the form of preformed pastes in dialkyl phthalate type plasticizers; · colored organic dyes or colored inorganic pigments; · Plasticizers; UV-stabilizing additives, such as Tinuvin P from Ciba, used at a content of 0-1000 ppm, preferably 50-500 ppm, in the mixture to be poured into the mold; light or heat stabilizers, such as Tinuvin 770; ·Antioxidants; Flame retardants, such as tris(2-chloropropyl)phosphate; thickeners, such as cellulose acetate butyrate; release agents, such as sodium dioctyl sulfosuccinate, used in a content of 0 to 500 ppm, preferably 0 to 200 ppm, relative to the mixture to be poured into the mold; · Inorganic or organic fillers (eg polyamide, PTFE or BaSO4) to scatter light (eg to result in a sheet that can be edge-lit).

[0129] Sheets of the composition according to the invention or sheets made by the method according to the invention may be coated on at least one surface with a varnish. The composition according to the invention may be part of a multi-layer composition.

[0130] Sheets of the composition of the present invention or sheets made by the method of the present invention can be used as single layer sheets or in multi-layer constructions.

[0131] The multi-layer structure includes as one layer a sheet of or containing the composition of the present invention. The layer can be an outer layer or an inner layer.

[0132] The other layers of the multilayer structure other than the layer made of the sheet with the composition according to the invention can be polymer layers or glass layers.

[0133] Yet another aspect of the present invention is the use of the composition according to the present invention.

[0134] A first preferred embodiment is for impact resistant applications, especially for impact resistant sheeting.

[0135] Areas of use are, for example, lighting and glazing.

[0136] Use of the polymer composition in glazing and safety glazing, preferably in motovehicle glazing, for example glazing (interior or exterior) of cars and caravans, motorcycle windshields and / or glazing of railway vehicles and / or ships, or in glazing of buildings or machinery or glazing of laboratory equipment such as glove boxes.

[0137] Further provided is the use for the manufacture of displays for communication devices, in particular PDAs, mobile phones or cellular phones, preferably smartphones, tablet PCs, TV sets, kitchen appliances and other electronic devices, or for the manufacture of lamp covers, preferably for interior lighting systems or automotive lighting systems.

[0138] [Evaluation method] The glass transition temperature Tg is measured by DSC according to ISO 11357-2 / 2013.

[0139] Molecular weight - The weight average molecular weight (Mw) and number average molecular weight (Mn) of a polymer are measured by size exclusion chromatography (SEC). The polydispersity index PI is calculated as PI = Mw / Mn, as is commonly known.

[0140] Swelling index - A sample is cut from the sheet and its mass m0 is estimated. Usually, a sample with a mass m0 of about 0.5 g or close to 0.5 g is cut. The sample is placed in a vial with a stirrer. 2 ml of acetone is added. It is stirred for 72 hours. Then, the mass m of the sample swollen with acetone is calculated. f The swelling index in % is determined by the ratio (m f -m0) / m0*100. [Example]

[0141] The synthesis of the composition according to the invention in sheet form is carried out in four steps.

[0142] Step 1: Synthesis of alkoxyamines (TRIAMINS)

[0143] 189 g of ethanol, 100 g of N-tertiobutyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, and 26.5 g of pentaerythritol triacrylate are placed in a 500 mL reactor. The mixture is heated at 80°C with stirring for 4 hours. The reaction mixture is then discharged, and the ethanol is evaporated under vacuum at 57°C using a rotary evaporator. 126 g of TRIAMINS is quantitatively obtained.

[0144] Step 2: Synthesis of the macroinitiator

[0145] Two macroinitiators are synthesized using the TRIAMINS prepared in step 1. Synthesis of macroinitiated polyalkoxyamine 1 The following are placed in a 2 liter metal reactor equipped with an impeller stirrer, a heating jacket with oil circulation, and a vacuum / nitrogen inlet: 640g butyl acrylate 96g styrene 6.64g of TRIAMINS

[0146] After the introduction of the reagents, the reaction mixture is degassed by three vacuum / nitrogen flushes. The reactor is then closed, and stirring (50 rpm) and heating (nominal temperature: 125°C) are initiated. The temperature of the reaction mixture reaches 113°C in approximately 30 minutes. The pressure stabilizes at approximately 1.5 bar. The reactor temperature is maintained at the 115°C stage for 522 minutes. After cooling, 742 g of a mixture with a solids content of 70% is recovered. The excess butyl acrylate is then removed by evaporation at 70°C under reduced pressure for 3 hours. The butyl acrylate / styrene weight ratio of the resulting macroradical is 83:17. Analysis of the macroinitiator by GPC, calibrated using a polystyrene sample, gives the following results: Mn: 138750 g / mol; Mw: 453400 g / mol; polydispersity: 3.27. The macroinitiator is diluted with methyl methacrylate at 50°C with stirring to a solution of 45% by weight of macroinitiator.

[0147] The synthesis of macroinitiated polyalkoxyamine 2 is carried out the same as for polyalkoxyamine 1, except that 9.2 g of TRIAMINS are used. Analysis of the macroinitiator by GPC, calibrated using a polystyrene sample, gives the following results: Mn: 100670 g / mol; Mw: 245690 g / mol; polydispersity: 2.44.

[0148] Step 3: Preparation of syrup. The resulting two macroinitiators are further diluted with methyl methacrylate (MMA). 400 g of the macroinitiator solution is 45% by weight and mixed with 1200 g of MMA, degassed by three vacuum / nitrogen flushes, and heated to 70°C to initiate polymerization. A sample is taken and the viscosity is measured at 20°C using a Brookfield viscometer. When the viscosity is 2000 cPoisse, 850 g of MMA is added at 5°C to terminate the polymerization.

[0149] Step 4: Preparation of Cast Sheets: The syrup is mixed with various weight percents of 1,4-butylene glycol dimethacrylate (BGDM) relative to the MMA in the composition, 735 ppm of 1,1'-azobis(cyclohexanecarbonitrile) (VAZO88), 0.05 wt. % of Tinuvin P, and 0.05 wt. % of Tinuvin 770DF, based on the total weight, while stirring, and degassed by vacuum / nitrogen flush.

[0150] The mixture is then poured into a mold consisting of two glass plates closed with a PVC gasket ring. The mold is first heated at a temperature of 71° C. for 450 minutes and then at 90° C. for 270 minutes. The sheet is then subjected to a post-polymerization treatment at a temperature of 125° C. for 60 minutes.

[0151] The mold is opened to retrieve each sheet of 4 mm thickness and samples of different sizes are cut out for carrying out the tests.

[0152] Comparative Example 1: The polymerization of the cast sheet is carried out by mixing MMA as the monomer with an initiator and a crosslinker.

[0153] Example 1: A cast sheet is made according to the process described above using macroinitiated polyalkoxyamine 1 and 0.6 wt% 1,4-butylene glycol dimethacrylate.

[0154] Example 2: A cast sheet is made according to the process described above using macroinitiated polyalkoxyamine 1 and 1 wt% 1,4-butylene glycol dimethacrylate.

[0155] Example 3: A cast sheet is made according to the process described above using macroinitiated polyalkoxyamine 1 and 4 wt% 1,4-butylene glycol dimethacrylate.

[0156] Example 4: A cast sheet is made according to the process described above using macroinitiated polyalkoxyamine 2 and 4 wt% 1,4-butylene glycol dimethacrylate.

[0157] Table 1. Composition and results TIFF0007820092000033.tif158170

[0158] As shown in Table 1, the composition according to this example exhibits excellent impact resistance as indicated by the results of the Charpy impact test, and has better solvent resistance than a crosslinked (meth)acrylic sheet composition having flexibility and not containing the polymer sequence (II). In order to still have satisfactory impact resistance and reduced swelling, there is a compromise between the weight average molecular weight Mw of the flexible polymer sequence (II) having a glass transition temperature below 0°C, the polydispersity index PI, and the content of crosslinker.

Claims

1. 1. A polymer composition comprising a crosslinked (meth)acrylic composition comprising a brittle matrix (I) having a glass transition temperature above 0° C. and elastomeric domains having a size of less than 100 nm and consisting of flexible polymeric sequences (II) having a glass transition temperature below 0° C., wherein the flexible polymeric sequences (II) have a weight average molecular weight Mw between 150,000 g / mol and 800,000 g / mol, and the composition has a swelling index in acetone at 20° C. of less than 200%, The polymer sequence (II) is ・Formula CH ２ =CH-C(=O)-OR １ (In the formula, R １ is a straight-chain, cyclic or branched C optionally substituted with a hydrogen atom, a halogen atom, or a hydroxyl, alkoxy, cyano, amino or epoxy group; １ -C ４０ an acrylic monomer in which the alkyl group is an alkyl group; ・Formula CH ２ =C(CH ３ )-C(=O)-OR ２ (In the formula, R ２ is a straight-chain, cyclic or branched C optionally substituted with a hydrogen atom, a halogen atom, or a hydroxyl, alkoxy, cyano, amino or epoxy group; １ -C ４０ a methacrylic monomer in which the alkyl group is an alkyl group; prepared from one or more monomers Mo2 selected from The polydispersity index PI of the molecular weight Mw / Mn of the flexible polymer sequence (II) is greater than 2.6; composition.

2. 2. The composition according to claim 1, characterized in that the weight-average molecular weight Mw of the flexible polymeric sequence (II) is between 225,000 and 600,000 g / mol.

3. 2. The composition according to claim 1, characterized in that the weight-average molecular weight Mw of the flexible polymeric sequence (II) is between 240,000 and 600,000 g / mol.

4. 2. The composition according to claim 1, characterized in that the weight-average molecular weight Mw of the flexible polymeric sequence (II) is between 255,000 and 600,000 g / mol.

5. 5. Composition according to claim 1, characterized in that the content of crosslinking agent is between 0.4 and 8% by weight relative to the crosslinked acrylic composition.

6. 5. The composition according to claim 1, wherein the content of crosslinking agent is between 1 and 5% by weight relative to the crosslinked acrylic composition.

7. 7. Composition according to any one of claims 1 to 6, characterized in that the content of polymeric sequence (II) in the polymer composition is between 1% and 30% by weight, relative to the polymer composition comprising the crosslinked (meth)acrylic composition and the polymeric sequence (II).

8. 5. Composition according to claim 1, characterized in that the matrix (I) contains methyl methacrylate in a proportion of from 51% to 100% by weight.

9. 9. Composition according to claim 1, characterized in that the matrix (I) contains methyl methacrylate in a proportion of from 90% to 100% by weight.

10. The polymer sequence (II) is ・Vinyl aromatic monomers 10. The composition according to claim 1, wherein the composition is prepared from one or more monomers Mo2, which further comprise:

11. 11. The composition according to claim 1, wherein the composition has a swelling index in acetone at 20°C of less than 190%.

12. 12. The composition according to claim 1, wherein the composition is in the form of a sheet.

13. 13. The composition according to claim 1, wherein the composition is part of a multilayer composition.

14. A method for producing a polymer composition according to any one of claims 1 to 13, comprising the steps of: a) preparing a polymer sequence (II); b) mixing the polymeric sequence (II) of step a) with methyl methacrylate, optionally with a crosslinker, optionally with at least one comonomer M01, and optionally with at least one radical initiator; c) mixing the composition comprising the polymeric sequence (II) and methyl methacrylate, if not already done in step b), with a crosslinking agent, optionally at least one comonomer M01 and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated to obtain a cast sheet; A method comprising:

15. A method for producing a polymer composition according to any one of claims 1 to 13, comprising the steps of: a) General formula Z(-T) ｎ preparing a polymeric sequence (II) by mixing an alkoxyamine of the formula: (wherein Z represents a polyvalent group, T represents a nitroxide, and n is an integer of 1 or more) with a monomer for forming the polymeric sequence (II); b) mixing the polymeric sequence (II) of step a) with methyl methacrylate, optionally with a crosslinker, optionally with at least one comonomer M01, and optionally with at least one radical initiator; c) mixing the composition comprising the polymeric sequence (II) and methyl methacrylate, if not already done in step b), with a crosslinking agent, optionally at least one comonomer M01 and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated to obtain a cast sheet; A method comprising:

16. A method for producing a polymer composition according to any one of claims 1 to 13, comprising the steps of: a) General formula Z(-T) ｎ preparing a polymeric sequence (II) by mixing an alkoxyamine of the formula: (wherein Z represents a polyvalent group, T represents a nitroxide, and n is an integer of 1 or more) with a monomer for forming the polymeric sequence (II); b1) mixing the polymeric sequence (II) of step a) with methyl methacrylate; b2) partially polymerizing the mixture of polymeric sequence (II) and methyl methacrylate, optionally adding additional methyl methacrylate. c) mixing the partially polymerized composition with a crosslinker, optionally at least one comonomer M01 and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated to obtain a cast sheet; A method comprising:

17. A method for producing a polymer composition according to any one of claims 1 to 13, comprising the steps of: a1) General formula Z(-T) ｎ preparing an alkoxyamine of the formula: (wherein Z represents a polyvalent group, T represents a nitroxide, and n is an integer of 1 or greater); a2) preparing the polymeric sequence (II) by mixing the alkoxyamine of a1) with the monomers for forming the polymeric sequence (II); b1) mixing the polymeric sequence (II) of step a2) with methyl methacrylate; b2) partially polymerizing the mixture of polymeric sequence (II) and methyl methacrylate, optionally adding additional methyl methacrylate. c) mixing the partially polymerized composition with a crosslinker, optionally at least one comonomer M01 and at least one radical initiator; d) pouring the mixture obtained in the previous step into a mold, which is then heated to obtain a cast sheet; A method comprising:

18. The selected alkoxyamine has the formula:

18. The method according to claim 14, wherein the TRIAMINS have the formula:

19. Use of a polymer composition according to any one of claims 1 to 13 or obtainable by the method according to any one of claims 14 to 17 for glazing.

20. Use of a polymer composition according to any one of claims 1 to 13 or obtainable by the method according to any one of claims 14 to 17 for lightening applications.

21. A sheet comprising a polymer composition according to any one of claims 1 to 13 or obtainable by the method according to any one of claims 14 to 18.

22. 22. The sheet of claim 21, wherein at least one surface is coated with a varnish.

23. 22. The sheet of claim 21 used in a multi-layer structure.

24. 22. A multilayer structure comprising a sheet according to claim 21 or a composition according to any one of claims 1 to 13.

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