MULTI-STAGE POLYMER, PREPARATION METHOD THEREFOR, COMPOSITION COMPRISING SAME AND USE THEREOF

Abstract

MULTI-STAGE POLYMER, PREPARATION METHOD THEREOF, COMPOSITION COMPRISING IT AND USE THEREOF The present invention relates to a composition comprising a multi-stage polymer, a preparation method therefor, a composition comprising it and use thereof. In particular, the present invention relates to a composition in the form of a polymer powder comprising a multi-stage polymer in the form of polymeric particles prepared by a multi-stage process and a (meth)acrylic polymer. More particularly, the present invention relates to a polymer composition in the form of a porous polymer powder comprising polymeric particles prepared by a multi-stage process comprising at least two stages and a (meth)acrylic polymer, a preparation method therefor, use thereof and compositions and articles comprising it.

Description

Title of the invention: MULTI-STAGE POLYMER, PREPARATION METHOD THEREOF, COMPOSITION COMPRISING IT AND USE THEREOF Technical field

[0001] The present invention relates to a composition comprising a multi-stage polymer, its preparation process, a composition comprising it and its use.

[0002] In particular, the present invention relates to a composition in the form of a polymer powder comprising a multi-step polymer in the form of polymeric particles prepared by a multi-step process and a (meth)acrylic polymer.

[0003] More particularly, the present invention relates to a polymer composition in the form of a porous polymer powder comprising polymer particles prepared by a multi-step process comprising at least two steps and a (meth)acrylic polymer, its preparation process, its use and compositions and articles comprising it. [Technical problem]

[0004] Polymers are widely used also as additives in polymer compositions. These so-called polymer additives are usually added as granules or also as powder, either to solid polymers, or to molten polymers, or to liquid resins, or to liquid compositions.

[0005] One class of polymeric additives is processing aids, another is polymeric impact resistance modifiers.

[0006] The polymeric impact modifiers may be in the form of polymeric particles. Typically, these polymeric impact modifiers are in the form of core-shell particles that are prepared by a multi-step process, at least one step comprising a rubber-like polymer. Then these particles are incorporated into the polymers or polymer compositions to increase their impact resistance. The polymers or polymer compositions may be thermosetting or thermoplastic.

[0007] Thermosetting polymers consist of crosslinked three-dimensional structures. Crosslinking is achieved by curing reactive groups in the so-called prepolymer. Curing, for example, can be achieved by heating the polymer chains or the prepolymer in order to crosslink and cure the material. permanently.

[0008] Thermoplastic polymers consist of linear or branched polymers, which are usually not crosslinked. They can be slightly crosslinked as long as they can be deformed by heat. However, these core-shell particles mentioned above are not easy to disperse or quick to disperse in all kinds of resins or polymers or polymer precursors, including for example in liquid epoxy resins or in liquid monomers or in other liquid polymer precursors.

[0009] A well-homogeneous and rapid dispersion is necessary to have a satisfactory impact resistance performance in the final polymer composition. Easy dispersion and rapid dispersion time are also required to reduce the process time and obtain an easier and simpler process.

[0010] An objective of the present invention is to provide a polymer composition which is rapidly and easily dispersible, in particular in liquid resins such as, for example, precursors for thermosetting polymers or thermoplastic polymers such as, respectively, for example, in epoxy resins or in (meth)acrylic monomers.

[0011] An objective of the present invention is to provide a polymer composition in the form of a polymer powder which is rapidly and easily dispersible, in particular in liquid resins such as, for example, precursors for thermosetting polymers or thermoplastic polymers such as, for example, in epoxy resins or in (meth)acrylic monomers.

[0012] A further objective of the present invention is to provide a polymeric composition in the form of a dry polymer powder which is easily dispersible, in particular in weakly polar liquid resins or weakly polar (meth)acrylic monomers.

[0013] A further object of the present invention is to provide a multi-stage polymer composition in the form of a dry polymer powder which is readily dispersible, especially in weakly polar liquid resins or weakly polar (meth)acrylic monomers.

[0014] An additional object of the present invention is to provide a multi-stage polymer composition in the form of a dry polymer powder which is readily dispersible in reactive epoxy resins, polyester resins or (meth)acrylic resins / polymers or liquid monomers or resins.

[0015] Another object of the present invention is to provide a process for manufacturing a multi-stage polymer composition in the form of a polymer powder which is readily dispersible in reactive epoxy resins, resins of polyester or (meth)acrylic resins / polymers or liquid monomers or resins, in particular in weakly polar liquid resins or weakly polar (meth)acrylic monomers.

[0016] Yet another object of the present invention is the use of a polymer composition in the form of a polymer powder for the preparation of a liquid composition comprising precursors for thermosetting polymers or thermoplastic polymers.

[0017] Yet another objective is to reduce the dispersion time of a polymer powder in such a liquid composition. [CONTEXT OF THE INVENTION]Prior art

[0018] Document WO2016 / 102666 discloses a composition comprising a multi-step polymer and a method of preparing the same. The composition further comprises a (meth)acrylic polymer which has a mass average molecular weight of less than 100,000 g / mol. The (meth)acrylic polymer may comprise a functional monomeric unit.

[0019] Document WO2016 / 102682 discloses a multi-step polymer composition and a method for preparing the same. The multi-step polymer comprises at least one last step which comprises a (meth)acrylic polymer which has a mass average molecular weight of less than 100,000 g / mol. The (meth)acrylic polymer may comprise a functional monomeric unit.

[0020] Document FR 2934866 discloses a polymer preparation of specific core-shell polymers having a functional shell comprising hydrophilic monomers. The core-shell polymers are used as an impact resistance modifier in thermoset polymers.

[0021] Document WO2019 / 012052 discloses a composition comprising a multi-step polymer and a method for preparing the same. The composition further comprises a (meth)acrylic polymer which has a mass average molecular weight of between 100,000 g / mol and 1,000,000 g / mol. The (meth)acrylic polymer may comprise a functional monomeric unit.

[0022] None of the prior art documents discloses a composition comprising a multi-stage polymer combined with a (meth)acrylic polymer, both polymers comprising monomeric units either comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20 or chosen according to its Hansen solubility parameter ôp < 10 MPa1 / 2 or a process for its preparation. [Brief description of the invention]

[0023] Unexpectedly it has been discovered that a polymer composition (PCI) comprising

[0024] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0025] b) a polymer (Bl) having a glass transition temperature of at least 60°C, And

[0026] c) a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of a composition based on a), b) and c) only,

[0027] characterized in that at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0028] and in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol,

[0029] and in that the polymer (Bl) and the polymer (Cl) comprise monomeric units comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20; gives a polymer composition which can be readily dispersed in weakly polar liquid compositions and gives a liquid composition having a lower viscosity compared to a liquid composition with a polymer composition not comprising monomeric units comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20.

[0030] Unexpectedly, it has also been discovered that a polymer composition (PCI) comprising

[0031] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0032] b) a polymer (Bl) having a glass transition temperature of at least 60°C, And

[0033] c) a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of a composition based on a), b) and c) only,

[0034] characterized in that at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0035] and in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol,

[0036] and in that the polymer (Bl) and the polymer (Cl) comprise monomeric units originating from polymerized comonomers (Mcbi) and (Mccl) respectively, the two comonomers having a Hansen solubility parameter ôp < 10 MPa1 / 2; gives a polymer composition which can be readily dispersed in weakly polar liquid compositions and giving a liquid composition having a lower viscosity compared to a liquid composition comprising a polymer composition not comprising monomeric units originating from polymerized comonomers (Mcbi) and (Mcci) respectively, the two comonomers having a Hansen solubility parameter ôp <10 MPa1 / 2.

[0037] Surprisingly, it has been discovered that a polymer composition (PCI) comprising a multi-stage polymer in the form of a polymer powder comprising

[0038] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0039] b) a polymer (Bl) having a glass transition temperature of at least 60°C, And

[0040] c) a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of a composition based on a), b) and c) only,

[0041] characterized in that at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0042] and in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol,

[0043] and in that either the polymer (B 1) and the polymer (Cl) comprise monomeric units comprising an alicyclic hydrocarbon group having a number of carbons from 3 to 20, or in that the polymer (Bl) and the polymer (Cl) comprise monomeric units originating from polymerized comonomers (Mcbi) and (Mcci) respectively, the two comonomers having a Hansen solubility parameter ôp < 10 MPa1 / 2;provides a polymer composition which can be readily dispersed in weakly polar liquid compositions and provides a liquid composition having a lower viscosity compared to either a liquid composition comprising a polymer composition not comprising monomeric units comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20, or a liquid composition comprising a polymer composition not comprising monomeric units originating from polymerized comonomers (Mc bi) and (Mccl) respectively, both comonomers having a Hansen solubility parameter ôp <10 MPa1 / 2;

[0044] Surprisingly, it has also been discovered that a process for manufacturing the polymer composition (PCI) in the form of a polymer powder comprising the steps of

[0045] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in step (A) comprising the polymer (Al) having a glass transition temperature of less than 10°C;

[0046] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C;

[0047] c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in a step (C) comprising a polymer (Cl) having a glass transition temperature of at least 30°C, such that said polymer (Cl) represents at most 40% by weight of the composition on the basis of a), b) and c) only;

[0048] d) coagulation of the composition obtained in steps a) to c);

[0049] characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and the monomer or mixture of monomers (Bm) and the monomer or mixture of monomers (Cm), both mixtures comprising the comonomers (Mcbi) and (Mccl) respectively, said comonomers (Mcbi) and (Mcci) comprising either an alicyclic hydrocarbon group having a carbon number of 3 to 20, or both comonomers having a Hansen solubility parameter ôp <10 MPa1 / 2; gives a polymer composition which can be readily dispersed in a weakly polar polymer matrix material for thermosetting polymers or thermoplastic polymers or their respective precursors as liquid resins and / or monomers.

[0050] Surprisingly, it has also been discovered that a process for manufacturing the polymer composition (PCI) in the form of a polymer powder comprising the steps of

[0051] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in step (A) comprising the polymer (Al) having a glass transition temperature of less than 10°C;

[0052] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C;

[0053] jointly, steps a) and b) leading to a multi-step polymer (MPI) and step

[0054] c) blending the multi-stage polymer (MPI) with a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0055] d) coagulation of the composition obtained in steps a) to c);

[0056] characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and the monomer or mixture of monomers (Bm) and the monomer or mixture of monomers (Cm), the two mixtures comprising the comonomers (Mcbi) and (Mcci) respectively, said comonomers (Mcbi) and (Mcci) comprising either an alicyclic hydrocarbon group having a number of carbons of 3 to 20, or the two comonomers having a Hansen solubility parameter ôp < 10 MPa1 / 2; gives a polymer composition which can be readily dispersed in a low polar polymeric matrix material for thermosetting polymers or thermoplastic polymers or their respective precursors as liquid resins and / or monomers.

[0057] Surprisingly, it has also been discovered that a process for the manufacture of a liquid polymer composition LPC1 comprising the steps of

[0058] a) providing said polymeric composition (PCI) in the form of a porous polymer powder having a total intruder volume of at least 1.2 ml / g as measured by mercury porosimetry,

[0059] b) bringing the polymeric composition (PCI) into contact with a liquid composition LC1,

[0060] produces a liquid polymer composition (PCI) where the polymer composition P0W1 is homogeneously and rapidly dispersed in the liquid composition LC1. Description of the embodiments

[0061] According to a first aspect, the present invention relates to a polymer composition (PCI) comprising

[0062] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0063] b) a polymer (Bl) having a glass transition temperature of at least 60°C, And

[0064] c) a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of a composition based on a), b) and c) only;

[0065] characterized in that at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that the polymer (Bl) and the polymer (Cl) comprise monomeric units comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20.

[0066] According to a second aspect, the present invention relates to a polymer composition (PCI) comprising

[0067] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0068] b) a polymer (Bl) having a glass transition temperature of at least 60°C, And

[0069] c) a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of a composition based on a), b) and c) only;

[0070] characterized in that at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that the polymer (Bl) and the polymer (Cl) comprise monomeric units originating from polymerized comonomers (McH ) and (Mcci) respectively, the two comonomers having a Hansen solubility parameter ôp < 10 MPa1 / 2.

[0071] According to a third aspect, the present invention relates to a polymer composition (PCI) comprising

[0072] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0073] b) a polymer (Bl) having a glass transition temperature of at least 60°C, And

[0074] c) a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of a composition based on a), b) and c) only;

[0075] characterized in that at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and either in that the polymer (Bl) and the polymer (Cl) comprise monomeric units comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20, or in that the polymer (Bl) and the polymer (Cl) comprise monomeric units originating from polymerized comonomers (Mcbl) and (Mccl) respectively, both comonomers having a Hansen solubility parameter ôp < 10 MPa^.

[0076] According to a fourth aspect, the present invention relates to a method for manufacturing a polymer composition (PCI) comprising the steps of

[0077] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (A) comprising the polymer (Al) having a glass transition temperature of less than 10 °C,

[0078] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60 °C,

[0079] c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in a step (C) comprising a polymer (Cl) having a glass transition temperature of at least 30 °C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0080] d) agglomeration of the composition obtained in steps a) to c);

[0081] Characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and the monomer or mixture of monomers (Bm) and the monomer or mixture of monomers (Cm), both of which comprise monomers comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20.

[0082] In a fifth aspect, the present invention relates to a method for manufacturing the polymer composition (PCI) comprising the steps of

[0083] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (A) comprising the polymer (Al) having a glass transition temperature of less than 10 °C,

[0084] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60 °C,

[0085] together, steps a) and b) giving a multi-stage polymer (MPI) and a step

[0086] c) blending the multi-stage polymer (MPI) with a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0087] d) agglomeration of the composition obtained in steps a) to c);

[0088] Characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that the monomer or mixture of monomers (Bm) comprises monomers comprising an alicyclic hydrocarbon group having a number of carbons of 3 to 20 and the polymer (Cl) comprises monomeric units comprising an alicyclic hydrocarbon group having a number of carbons of 3 to 20.

[0089] According to a sixth aspect, the present invention relates to a method for manufacturing the polymer composition (PCI) comprising the steps of

[0090] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (A) comprising the polymer (Al) having a glass transition temperature of less than 10 °C,

[0091] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60 °C,

[0092] c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in a step (C) comprising a polymer (Cl) having a glass transition temperature of at least 30 °C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0093] d) agglomeration of the composition obtained in steps a) to c);

[0094] characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that the monomer or mixture of monomers (Bm) and the monomer or mixture of monomers (Cm), both comprise comonomers (Mcb[) and (Mccl) respectively, the two comonomers having a Hansen solubility parameter ôp < 10 MPa1 / 2.

[0095] In a seventh aspect, the present invention relates to a method for manufacturing the polymer composition (PCI) comprising the steps of

[0096] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (A) comprising the polymer (Al) having a glass transition temperature of less than 10 °C,

[0097] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60 °C,

[0098] together, steps a) and b) giving a multi-stage polymer (MPI) and a step

[0099] c) blending the multi-stage polymer (MPI) with a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0100] d) agglomeration of the composition obtained in steps a) to c);

[0101] characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that the monomer or mixture of monomers (Bm) comprises comonomers (Mcbi) having a Hansen solubility parameter ôp < 10 MPa1 / 2 and the polymer (Cl) comprises monomeric units originating from a polymerized comonomer (Mccl) having a Hansen solubility parameter ôp < 10 MPa1 / 2.

[0102] In an eighth aspect, the present invention relates to the use of a polymer composition (PCI) as an impact resistance modifier.

[0103] In a ninth aspect, the present invention relates to the use of a polymer composition (PCI) as a composition for reduced dispersion time.

[0104] In a tenth aspect, the present invention relates to a method for reducing the dispersion time of a polymer powder in a weakly polar liquid composition using the polymeric composition (PCI) in the form of a polymer powder.

[0105] In an eleventh aspect, the present invention relates to a PC2 polymer composition comprising the polymer composition (PCI) as an impact resistance modifier.

[0106] In a twelfth aspect, the present invention relates to a method for reducing the dispersion time of a polymeric composition (PCI) in a liquid composition comprising the steps of:

[0107] a) providing said polymeric composition (PCI) according to any one of aspects 1 to 3 in the form of a porous polymer powder P0W1 having a total intruder volume of at least 1.2 ml / g as measured by mercury porosimetry,

[0108] b) bringing the polymeric composition (PCI) into contact with a liquid composition LC1.

[0109] The term "polymer powder", in the present context, denotes a polymer in the form of a powder comprising powder grains of the order of at least 1 pm, said powder grains being obtained by agglomeration of primary polymer particles comprising a polymer or polymers, said primary polymer particles being of the order of a nanometer.

[0110] The term "primary particle", as used herein, refers to a spherical polymer particle comprising a nanometer-sized particle. Preferably, the primary particle has a weight average particle size of between 20 nm and 800 nm.

[0111] The term "particle size", as used herein, refers to the volume average diameter of a particle considered to be spherical.

[0112] The term "thermoplastic polymer" as used herein refers to a polymer that becomes liquid or becomes more liquid or less viscous when heated and can be formed into new shapes by the application of heat and pressure.

[0113] The term "thermosetting polymer", as used herein, refers to a prepolymer in a flexible, solid, or viscous state that irreversibly transforms into an infusible and insoluble polymer network upon curing.

[0114] The term "copolymer", in the present context, means that the polymer consists of at least two different monomeric units.

[0115] A "multi-stage polymer" as used herein refers to a polymer formed sequentially by a multi-stage polymerization process. Preferred is a multi-stage emulsion polymerization process in which the first polymer is a first-stage polymer and the second polymer is a second-stage polymer, i.e., the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer, with at least two stages that are different in composition.

[0116] The term “(meth)acrylic”, in the present context, refers to all kinds of acrylic and methacrylic monomers.

[0117] The term “(meth)acrylic polymer” as used means that the polymer (meth)acrylic essentially includes polymers comprising (meth)acrylic monomers that comprise 50% by weight or more of the (meth)acrylic polymer.

[0118] The term "dry", in the present context, means that the proportion of residual water is less than 1.5% by weight and preferably less than 1.2% by weight.

[0119] By specifying that a range is from x to y in the present invention, this means that the upper limit and the lower limit of this range are included, which is equivalent to at least x and up to y.

[0120] By specifying that a range is between x and y in the present invention, it means that the upper limit and the lower limit of this range are excluded, which is equivalent to more than x and less than y.

[0121] The term "total intruded volume" in this context means the total volume into which liquid mercury is introduced according to ISO 15901-1:2016. This volume is cumulative and the analysis results show a cumulative intruded volume in ml / g (cmVg) as a function of the applied pressure or pore diameter. The total intruded volume is the intruded volume at the maximum applied pressure, which also corresponds to the smallest pores.

[0122] The term "incremental intrusion", in the present context, means the intruded volume in ml / g between two certain pressures or between two pore sizes. This incremental intrusion can also be expressed relative to the total intruded volume in % by volume.

[0123] By "readily dispersed in liquid resins" is meant that a homogeneous dispersion is obtained. The distribution of the polymeric composition (PCI) is not homogeneous if separation occurs after initial homogenization.

[0124] The term "weakly polar", in the present context, refers to compounds having a Hansen solubility parameter ôp < 10 MPa1 / 2. Hansen solubility parameters reflect the physicochemical dissolution properties, also called solvation abilities, of organic substances. Hansen solubility parameters can be calculated according to the approach proposed by Charles Hansen in the work entitled "Hansen Solubility Parameters: A user's handbook", Second Edition (2007) Boca Raton, Fia.: CRC Press. ISBN 978-0-8493-7248-3. According to this approach, three parameters, called "Hansen parameters": ôd, ôp and ôh are sufficient to predict the behavior of a solvent with respect to a given molecule. The parameter ôd in MPa1 / 2, quantifies the energy of the dispersion forces between the molecules, that is, the van der Waals forces.The parameter ôp in MPa1 / 2 represents the energy of intermolecular dipolar interactions. Finally, the parameter ôh in MPa1 / 2 quantifies the energy from intermolecular hydrogen bonds, that is, the ability to interact with a hydrogen bond. The sum of the squares of the three parameters corresponds to the square of the solubility parameter of . Hildebrand (ôtot).

[0125] By rapidly dispersed in liquid resins is meant that a homogeneous dispersion is obtained more quickly than with a polymer composition not having the specific composition and molecular weight of the polymer (Cl).

[0126] Concerning the polymer composition (PCI) according to the invention, it can be found according to a first embodiment in the form of a polymer powder (P0W1), also called polymer powder P0W1, comprising a) the polymer (Al) having a glass transition temperature of less than 10 °C, b) the polymer (Bl) having a glass transition temperature of at least 60 °C and c) and the polymer (Cl) having a glass transition temperature of at least 30 °C; wherein at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), and characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that the polymer (Bl) and the polymer (Cl) comprise monomeric units comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20.

[0127] Component c) represents at most 40% by weight of a composition based on a), b) and c). Preferably component c) represents at most 35% by weight of the composition based on a), b) and c); and more preferably at most 30% by weight.

[0128] In a first embodiment, advantageously, component c) represents less than 30% by weight of a composition based on a) b) and c).

[0129] In a second embodiment, advantageously, component c) represents less than 25% by weight of a composition based on a) b) and c).

[0130] In a third advantageous embodiment, component c) represents less than 20% by weight of a composition based on a) b) and c).

[0131] Preferably component c) represents more than 4% by weight of a composition based on a), b) and c). More preferably component c) represents more than 5% by weight of the composition based on a), b) and c).

[0132] In a first embodiment, component c) advantageously represents more than 6% by weight of a composition based on a) b) and c).

[0133] In a second embodiment, component c) advantageously represents more than 8% by weight of a composition based on a) b) and c).

[0134] In a third embodiment, advantageously, component c) represents more than 10% by weight of a composition based on a) b) and c).

[0135] The respective upper and lower limits given in the preceding paragraphs for the amount of component c), may be combined in any combinations of an upper limit and a lower limit

[0136] Preferably component c) represents between 4% by weight and 40% by weight of the composition based on a), b) and c). More preferably component c) represents between 5% by weight and 35% by weight of the composition based on a), b) and c).

[0137] In a first embodiment, advantageously, component c) represents between 6% by weight and 30% by weight of a composition based on a) b) and c).

[0138] In a second embodiment advantageously component c) represents 7% by weight and less than 25% by weight of a composition based on a) b) and c).

[0139] In a third advantageous embodiment, component c) represents between 10% by weight and 20% by weight of a composition based on a) b) and c).

[0140] At least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI).

[0141] At least component a) and component b) are obtained by a multi-step process comprising at least two steps respectively (A) and (B); and these two polymers (Al) and (B 1) form a multi-step polymer.

[0142] As regards the polymer powder (POW1), it has a volume median particle size D50 of between 1 pm and 700 pm. Preferably the volume median particle size of the polymer powder is between 10 pm and 600 pm, more preferably between 15 pm and 550 pm and advantageously between 20 pm and 500 pm.

[0143] The D10 of the volume particle size is at least 7 pm and preferably 10 pm, more preferably 15 pm.

[0144] The D90 of the volume particle size is at most 1000 pm and preferably 950 pm, more preferably at most 900 pm and even more preferably at most 800 pm.

[0145] The porosity of the polymer composition (PCI) in the form of a polymer powder (P0W1) is expressed as total intruded volume or total cumulative intrusion (cumulative intruded volume) in milliliters (ml) of mercury per mass (g) of said polymer powder (P0W1). This is measured according to ISO 15901-1: Evaluation of pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption - Part 1: Mercury porosimetry. Preferably the porous polymer powder (P0W1) of the invention has a total intruded volume or total cumulative intrusion of at least 1.2 ml / g, preferably 1.25 ml / g, more preferably 1.3 ml / g, even more preferably 1.35 ml / g. The total cumulative intrusion is considered up to a pore size diameter of 0.005 pm.Preferably the total intruded volume or total cumulative intrusion is considered between a pore size diameter of 100 pm and 0.005 pm or a . pressure between 0.01 MPa and 400 MPa.

[0146] The porous polymer powder (P0W1) of the invention has a total intruded volume or total cumulative intrusion of at most 10 ml / g. Preferably the total intruded volume is at most 8 ml / g, more preferably at most 7 ml / g, even more preferably at most 6 ml / g, advantageously at most 5 ml / g, more preferably at most 4 ml / g and most preferably at most 3.5 ml / g.

[0147] The respective upper and lower limits given in the two preceding paragraphs for the total intruded volume or the total cumulative intrusion of the porous polymer powder (P0W1) of the invention, can be combined in any combinations of an upper limit and a lower limit.

[0148] Preferably the porous polymer powder (P0W1) of the invention has a total intruded volume or a total cumulative intrusion of between 1.2 ml / g and 10 ml / g, more preferably between 1.25 ml / g and 8 ml / g, even more preferably between 1.3 ml / g and 7 ml / g, advantageously between 1.3 ml / g and 6 ml / g, more advantageously between 1.3 ml / g and 5 ml / g and more advantageously between 1.3 ml / g and 4 ml / g and most advantageously between 1.3 ml / g and 3.5 ml / g.

[0149] Incremental intrusion (incremental intruded volume) is the volume between two certain pore diameters. Incremental intrusion can be expressed as an absolute value also in ml / g or as a relative value as a percentage of total intruded volume or total cumulative intrusion (which is considered between a pore size diameter of 100 pm and 0.005 pm).

[0150] Preferably the porous polymer powder (P0W1) of the invention has a cumulative intrusion for a pore size greater than 10 pm (larger than 10 pm) of at least 0.9 ml / g, more preferably at least 1 ml / g.

[0151] Preferably the porous polymer powder (P0W1) of the invention has an incremental intrusion between a pore size of 10 pm to 1 pm of at least 0.1 ml / g, more preferably at least 0.12 ml / g and even more preferably at least 0.15 ml / g.

[0152] The bulk apparent density of the polymer powder (P0W1) is less than 0.60 g / cm3. Preferably the bulk apparent density is less than 0.45 g / cm3, more preferably less than 0.43 g / cm3, and even more preferably less than 0.41 g / cm3.

[0153] The bulk apparent density of the polymer powder (P0W1) is greater than 0.1 g / cm3. Preferably the bulk apparent density is greater than 0.11 g / cm3, more preferably is greater than 0.12 g / cm3, even more preferably greater than 0.13 g / cm3.

[0154] The bulk apparent density of the polymer powder (P0W1) is between 0.1 g / cm3 and 0.60 g / cm3. Preferably the bulk apparent density of the polymer powder polymer (P0W1) is between 0.15 g / cm3 and 0.45 g / cm3. Advantageously, the bulk apparent density of the polymer powder POW1 is between 0.2 g / cm 3 and 0.4 g / cm3.

[0155] The respective preferred embodiment of all the different characteristics of the porous polymer powder (P0W1), can be combined in any combination.

[0156] As regards the polymer composition (PCI) according to the invention, it may be, according to a second embodiment, dispersed in a continuous phase, comprising a) the polymer (Al) having a glass transition temperature of less than 10°C, b) the polymer (Bl) having a glass transition temperature of at least 60°C, and c) the polymer (Cl) having a glass transition temperature of at least 30°C;wherein at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), and characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that either the polymer (Bl) and the polymer (Cl) comprise monomeric units comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20, or in that the polymer (Bl) and the polymer (Cl) comprise monomeric units originating from polymerized comonomers (Mcbi) and (Mcd) respectively, both comonomers having a Hansen solubility parameter ôp <10 MPa1 / 2; and d) a liquid composition LC1 as a continuous phase in which the polymer composition (PCI) is dispersed. ;

[0157] The multi-stage polymer (MPI) of the composition (PCI) according to the invention has at least two stages respectively (A) and (B); and these two stages, respectively comprising the polymer (A1) and the polymer (B1) are different with respect to their polymer composition.

[0158] Alternatively, the polymer (Cl) is also part of the multi-stage polymer (MPI). In this case, the composition of the polymer (Cl) is different from the composition of the polymer (Al) and the polymer (Bl).

[0159] The multi-stage polymer (MPI) is preferably in the form of PAR polymer particles. These PAR particles are also called core-shell particles. For example, the first stage comprising the polymer (Al) forms the core, the second or all subsequent stages form the respective shells. Such a multi-stage polymer (MPI), which is also called a core-shell particle, is preferred. If the multi-stage polymer (MPI) comprises only the polymer (Al) and the polymer (B 1), it is a core-shell particle comprising only a shell. If the multi-stage polymer (MPI) comprises the polymer (Al), the polymer (Bl) and the polymer (Cl), it is a core-shell particle comprising only a shell. core-shell comprising at least two shells.

[0160] The PAR particles, included in the polymer composition (PCI) in the form of a polymer powder (P0W1) according to one embodiment or dispersed according to another embodiment, are the primary particles.

[0161] The PAR particles have a weighted average particle size of between 15 nm and 900 nm. Preferably, the weighted average particle size of the polymer particle is between 20 nm and 800 nm, more preferably between 25 nm and 600 nm, even more preferably between 30 nm and 550 nm, again, even more preferably between 35 nm and 500 nm, advantageously between 40 nm and 400 nm, even more preferably between 75 nm and 350 nm, and advantageously between 80 nm and 300 nm.

[0162] According to a first preferred embodiment, the primary polymer particles PAR are agglomerated and give the polymer composition (PCI) or a part of the polymer composition (PCI). In this case, the polymer composition (PCI) of the invention is in the form of a polymer powder, as described above.

[0163] The polymer composition (PCI) according to the invention comprises a multi-stage polymer (MPI) comprising at least a) one stage (A) comprising a polymer (Al) having a glass transition temperature of less than 10°C, and at least b) one stage (B) comprising a polymer (Bl) having a glass transition temperature of more than 60°C.

[0164] In a first preferred embodiment, step (A) is the first step of the at least two steps and step (B) comprising the polymer (B1) is grafted onto step (A) comprising the polymer (Al) or another intermediate layer.

[0165] In a second preferred embodiment, there could be another step before step (A), so that step (A) would also be an envelope.

[0166] In a third preferred embodiment, the polymer (Cl) having a glass transition temperature above 30°C is also part of the multi-stage polymer (MPI). At least one step (C) is also present. Preferably step (C) occurs after step (B). More preferably step (C) is the last step and the polymer (Cl) is the outer shell of the multi-stage polymer (MPI).

[0167] In a first embodiment, the polymer (Al) having a glass transition temperature of less than 10°C comprises at least 50% by weight of polymer units originating from an alkyl acrylate or alkyl acrylates and step (A) is the innermost layer of the polymer particle having the multi-layer structure. In other words, step (A) comprising the polymer (Al) is the core of the polymer particle.

[0168] As regards the polymer (Al) of the first preferred embodiment, this is a (meth)acrylic polymer comprising at least 50% by weight of poly units merics from acrylic monomers. Preferably, 60% by weight and more preferably 70% by weight of the polymer (Al) are acrylic monomers.

[0169] The acrylic monomer in the polymer (Al) comprises monomers selected from C1 to C18 alkyl acrylates or mixtures thereof. More preferably, the acrylic monomer in the polymer (Al) comprises monomers from C2 to C12 alkyl acrylic monomers or mixtures thereof. Even more preferably, the acrylic monomer in the polymer (Al) comprises monomers from C2 to C8 alkyl acrylic monomers or mixtures thereof.

[0170] The polymer (Al) may comprise a comonomer or comonomers which are copolymerizable with the acrylic monomer, as long as the polymer (Al) has a glass transition temperature of less than 10°C.

[0171] The comonomer or comonomers in the polymer (Al) are preferably chosen from (meth)acrylic monomers and / or vinyl monomers.

[0172] Most preferably, the acrylic or methacrylic comonomers of the polymer (Al) are selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as the polymer (Al) has a glass transition temperature of less than 10°C.

[0173] In a specific embodiment, the polymer (Al) is a butyl acrylate homopolymer.

[0174] More preferably, the glass transition temperature Tg of the polymer (Al) comprising at least 70% by weight of polymer units originating from the C2 to C8 alkyl acrylate is between -100°C and 10°C, even more preferably between -80°C and 0°C, and advantageously between -80°C and -20°C and more advantageously between -70°C and -20°C.

[0175] In a second preferred embodiment, the polymer (Al) having a glass transition temperature below 10°C comprises at least 50% by weight of polymer units originating from isoprene or butadiene and step (A) is the innermost layer of the polymer particle having the multilayer structure. In other words, step (A) comprising the polymer (Al) is the core of the polymer particle.

[0176] As an example, for the polymer (Al) of the core of the second embodiment, there may be mentioned isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers, isoprene copolymers comprising at most 98% by weight of a vinyl monomer and butadiene copolymers comprising at most 98% by weight of a vinyl monomer. vinyl monomer may be styrene, an alkylstyrene, acrylonitrile, an alkyl (meth)acrylate or butadiene or isoprene. In a preferred embodiment, the core is a butadiene homopolymer.

[0177] More preferably, the glass transition temperature Tv of the polymer (Al) comprising at least 50% by weight of polymeric units originating from isoprene or butadiene is between -100°C and 10°C, even more preferably between -90°C and 0°C, advantageously between -80°C and 0°C and most advantageously between -70°C and -20°C.

[0178] In a third preferred embodiment, the polymer (Al) is a silicone rubber-based polymer. The silicone rubber is, for example, a polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (Al) of the second embodiment is between -150°C and 0°C, even more preferably between -145°C and -5°C, advantageously between -140°C and -15°C and more advantageously between -135°C and -25°C.

[0179] The polymer (Al) having a glass transition temperature of less than 10°C comprises monomeric units, which have been polymerized. The polymer (Al) in general and the respective polymers (Al) of the first, second and third preferred embodiment are prepared from the respective monomer or monomer mixture (Am) producing the monomeric units composing the polymer (Al).

[0180] As regards the polymer (Bl), mention may be made of copolymers comprising monomers comprising double bonds and / or vinyl monomers, at least one of the monomers comprising either an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20, or being chosen according to its Hansen solubility parameter ôp < 10 MPa1 / 2. Preferably, the polymer (Bl) is a (meth)acrylic polymer, which means that at least 50% by weight of the monomeric units of the polymer (Bl) are (meth)acrylic.

[0181] The copolymer (Bl) comprises a comonomer (Mcbi), either said comonomer (Mcbi) comprises an alicyclic hydrocarbon group having a carbon number of 3 to 20, or said comonomer (Mcb[) has a Hansen solubility parameter ôp < 10 MPa1 / 2. The comonomer (Mcb[) in the copolymer (Bl) may be present between 1% by weight and 99% by weight, preferably between 1% by weight and 90% by weight and more preferably between 1% by weight and 50% by weight. Preferably the Hansen solubility parameter ôp < 9 MPa1 / 2.

[0182] In a first even more preferred embodiment, the copolymer (B 1) comprises between 1% by weight and 40% by weight of comonomer units originating from the comonomer (Mcbi) comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20. The comonomer (Mcbi) comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20 is pref- probably a (meth)acrylic monomer.

[0183] In a second even more preferred embodiment, the copolymer (B 1) comprises between 1% by weight and 40% by weight of (Mcb[) having a Hansen solubility parameter ôp < 10 MPa1 / 2. The comonomer (Mcb[) is preferably a (meth)acrylic monomer.

[0184] In a third, even more preferred embodiment, the copolymer (B1) comprises between 1% by weight and 40% by weight of a comonomer (McH) comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20 and having a Hansen solubility parameter ôp < 10 MPa1 / 2. The comonomer (McH) is preferably a (meth)acrylic monomer.

[0185] Most preferably the other acrylic or methacrylic comonomers (Mcb2) of the polymer (Bl) are selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as the copolymer (Bl) has a glass transition temperature of at least 60°C.

[0186] Advantageously, the copolymer (Bl) comprises at least 50% by weight of monomeric units originating from methyl methacrylate as comonomer (Mcb2), more advantageously 60% by weight.

[0187] Preferably, the glass transition temperature Tv of the copolymer (Bl) is between 60°C and 150°C. The glass transition temperature of the copolymer (Bl) is more preferably between 80°C and 150°C, advantageously between 90°C and 150°C and more advantageously between 100°C and 150°C.

[0188] Preferably, the copolymer (Bl) is grafted onto the polymer prepared in the previous step.

[0189] In certain embodiments, the copolymer (Bl) is crosslinked.

[0190] The copolymer (Bl) having a glass transition temperature of at least 60 °C comprises monomeric units, which have been polymerized. The copolymer (Bl) in general and in the respective embodiments is prepared from the respective monomers or monomer mixtures (Bm) comprising the comonomers (Mcb[) and (Mcb2), producing after polymerization the copolymer (Bl) with the monomeric units comprised in the copolymer (Bl).

[0191] As regards the polymer (Cl), it has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol.

[0192] The polymer (Cl) has a mass average molecular weight Mw greater than 10,000 g / mol, preferably greater than 10,500 g / mol, more preferably greater than 11,000 g / mol, even more preferably greater than 12,000 g / mol, advantageously greater than 13,000 g / mol, more advantageously greater than 14,000 g / mol and even more advantageously greater than 15,000 g / mol.

[0193] The polymer (Cl) has a mass average molecular weight Mw of less than 500,000 g / mol, preferably less than 450,000 g / mol, more preferably less than 400,000 g / mol, even more preferably less than 400,000 g / mol, advantageously less than 350,000 g / mol, more advantageously less than 300,000 g / mol and even more advantageously less than 250,000 g / mol and most advantageously less than 200,000 g / mol.

[0194] Preferably, the mass average molecular weight Mw of the polymer (Cl) is between 10,500 g / mol and 450,000 g / mol, more preferably between 11,000 g / mol and 400,000 g / mol and even more preferably between 12,000 g / mol and 350,000 g / mol, advantageously between 13,000 g / mol and 300,000 g / mol, more advantageously between 14,000 g / mol and 250,000 g / mol and most advantageously between 15,000 g / mol and 200,000 g / mol.

[0195] In a first advantageous embodiment, the mass average molecular weight Mw of the (meth)acrylic polymer MPI is between 10,500 g / mol and 200,000 g / mol, more preferably between 11,000 g / mol and 190,000 g / mol and even more preferably between 12,000 g / mol and 180,000 g / mol, advantageously between 13,000 g / mol and 150,000 g / mol, more advantageously between 14,000 g / mol and 135,000 g / mol and most advantageously between 15,000 g / mol and 120,000 g / mol.

[0196] In a second advantageous embodiment, the mass average molecular weight Mw of the (meth)acrylic polymer MPI is between 15,000 g / mol and 450,000 g / mol, more preferably between 16,000 g / mol and 400,000 g / mol and even more preferably between 17,000 g / mol and 350,000 g / mol, advantageously between 18,000 g / mol and 300,000 g / mol, more advantageously between 19,000 g / mol and 250,000 g / mol and most advantageously between 20,000 g / mol and 200,000 g / mol.

[0197] Preferably the polymer (Cl) is a copolymer comprising (meth)acrylic monomers, at least one of the monomers comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20.

[0198] As regards furthermore the polymer (Cl), mention may be made of copolymers comprising monomers comprising double bonds and / or vinyl monomers, at least one of the monomers comprising either an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20, or being chosen according to its Hansen solubility parameter ôp < 10 MPa1 / 2. Preferably, the polymer (Cl) is a (meth)acrylic copolymer, which means that at least 50% by weight of the monomeric units of the polymer (Cl) are (meth)acrylic.

[0199] The copolymer (Cl) comprises a comonomer (Mcci), either said comonomer (Mcci) comprises an alicyclic hydrocarbon group having a number of carbons from 3 to 20, or said comonomer (Mcci) has a Hansen solubility parameter ôp < 10 MPa1 / 2. The comonomer (Mcci) in the copolymer (Cl) may be present between 1% by weight and 99% by weight, preferably between 1% by weight and 90% by weight and more preferably between 1% by weight and 50% by weight. Preferably the Hansen solubility parameter of the comonomer (Mccl) ôp < 9 MPa1 / 2.

[0200] In a first even more preferred embodiment, the copolymer (Cl) comprises between 1% by weight and 40% by weight of comonomer units originating from the comonomer (Mccl) comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20. The comonomer (Mccl) comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20 is preferably a (meth)acrylic monomer.

[0201] In a second even more preferred embodiment, the copolymer (Cl) comprises between 1% by weight and 40% by weight of comonomer (Mccl) having a Hansen solubility parameter ôp < 10 MPa1 / 2. The comonomer (Mccl) is preferably a (meth)acrylic monomer.

[0202] In a third, even more preferred embodiment, the copolymer (Cl) comprises between 1% by weight and 40% by weight of a comonomer (Mcci) comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20 and having a Hansen solubility parameter ôp < 10 MPa1 / 2. The comonomer (Mccl) is preferably a (meth)acrylic monomer.

[0203] Most preferably the acrylic or (meth)acrylic comonomers (Mcc2) of the copolymer (Cl) are selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as the copolymer (Cl) has a glass transition temperature of at least 30°C.

[0204] Preferably, the glass transition temperature Tv of the copolymer (Cl) is between 30°C and 150°C. The glass transition temperature of the copolymer (Cl) is more preferably between 40°C and 150°C, advantageously between 45°C and 150°C and more advantageously between 50°C and 150°C.

[0205] Preferably, the copolymer (Cl) is not crosslinked.

[0206] Preferably, the copolymer (Cl) is not grafted onto any of the polymers (Al) and (Bl), especially if it is part of the multi-stage polymer (MPI). “Ungrafted” means that at least 50% by weight of the copolymer (Cl) in the multi-stage polymer (MPI) can be solubilized in a solvent of the copolymer (Cl). Preferably at least 75% by weight of the copolymer (Cl) in the multi-stage polymer (MPI) can be solubilized in a solvent of the copolymer (Cl).

[0207] The copolymer (Cl) having a glass transition temperature of at least 30°C comprises monomeric units, which have been polymerized. The copolymer (Cl) in general and in the respective embodiments is prepared from the respective monomers or monomer mixtures (Cm) comprising the co monomers (Mccl) and (Mec2), producing the monomeric units included in the copolymer (Cl).

[0208] In a first preferred embodiment, the monomeric units comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20 are (meth)acrylic monomers.

[0209] In a second preferred embodiment, the number of carbons in the alicyclic hydrocarbon group of the monomeric units is from 6 to 20.

[0210] The monomeric units comprising the alicyclic hydrocarbon group are selected from the group consisting of cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, bornyl acrylate, bomyl methacrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, fenchyl acrylate, fenchyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate.

[0211] The monomeric units comprising an alicyclic hydrocarbon group having a number of carbons from 3 to 20 or chosen according to their Hansen solubility parameter ôp < 10 MPa1 / 2 in the polymer (Bl) and (Cl) may be identical or different.

[0212] In a first preferred embodiment, the monomeric units comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20 or chosen according to their Hansen solubility parameter ôp < 10 MPa1 / 2 in the polymer (Bl) and (Cl) are identical or different.

[0213] In a second preferred embodiment, the monomeric units comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20 or chosen according to its Hansen solubility parameter ôp < 10 MPa1 / 2 in the polymer (B 1) and (Cl) are at least 50% by weight identical.

[0214] In a third preferred embodiment, the monomeric units comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20 or chosen according to its Hansen solubility parameter ôp < 10 MPa1 / 2 in the polymer (Bl) and (Cl) are less than 50% by weight identical.

[0215] Preferably, the Hansen solubility parameter ôp has a value less than 9.5 MPa1 / 2 (ôp < 9.5 MPa1 / 2) for all embodiments.

[0216] More preferably, the Hansen solubility parameter ôp has a value less than 9 MPa 1 / 2 (ôp < 9 MPa 1 / 2) for all embodiments.

[0217] The respective preferred and advantageous embodiments of all the features different characteristics of the polymers (Al), (Bl) and (Cl) and their respective monomers, can be combined in any combination.

[0218] The multi-stage polymer (MPI) is obtained by a multi-stage process comprising at least two stages. At least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI).

[0219] Preferably, the polymer (Al) having a glass transition temperature below 10°C prepared during step (A), is prepared before step (B) or is the first step of the multi-step process.

[0220] Preferably, the copolymer (Bl) having a glass transition temperature above 60°C prepared during step (B) is prepared after step (A) of the multi-step process.

[0221] If the copolymer (Cl) is also part of the multi-step polymer (MPI), preferably the copolymer (Cl) having a glass transition temperature of at least 30°C prepared during step (C) is prepared after step (B) of the multi-step process

[0222] In a first preferred embodiment, the copolymer (Bl) having a glass transition temperature of at least 60°C is an intermediate layer of the polymer particle having the multilayer structure.

[0223] In this first preferred embodiment, the copolymer (Cl) having a glass transition temperature above 30°C prepared during step (C), is prepared after step (B) of the multi-step process.

[0224] More preferably, the copolymer (Cl) having a glass transition temperature above 30°C prepared during step (C) is the outer layer of the multi-stage polymer (MPI) or primary polymer particle having the multi-layer structure.

[0225] Additional intermediate steps may be present, either between step (A) and step (B) and / or between step (B) and step (C).

[0226] Copolymer (Cl) and copolymer (Bl) are not the same polymer, even though their composition could be very close and some of their characteristics overlap. The essential difference is that copolymer (Bl) is always part of the multi-stage polymer (MPI).

[0227] This is explained in more detail in the process for the preparation of the polymeric composition (PCI) according to the invention comprising the copolymer (Cl) and the multi-stage polymer (MPI).

[0228] The weight ratio r of the copolymer (Cl) of the outer layer included in step (C) relative to the complete polymer particle is at least 5% by weight, more preferably at least 7% by weight and even more preferably at least 10% by weight.

[0229] According to the invention, the ratio r of the external step (C) comprising the copolymer (Cl) relative to the complete polymer particle is at most 40% by weight.

[0230] Preferably, the ratio of polymer (Cl) to primary polymer particle is between 5 wt% and 30 wt% and preferably between 5 wt% and 20 wt%.

[0231] In a second preferred embodiment, the copolymer (Bl) having a glass transition temperature of at least 60°C is the outer layer of the primary polymer particle having the multi-layer structure, in other words, the multi-stage polymer (MPI).

[0232] Preferably, at least a portion of the copolymer (B1) of layer (B) is grafted onto the polymer prepared in the previous layer. If only two steps (A) and (B) comprising polymers (A1) and (B1) respectively are present, a portion of the copolymer (B1) is grafted onto polymer (A1). More preferably at least 50% by weight of polymer (B1) is grafted. The grafting rate can be determined by extraction with a solvent for copolymer (B1) and gravimetric measurement before and after extraction to determine the ungrafted amount.

[0233] The glass transition temperature Tv of the respective polymers can be estimated, for example, by dynamic methods such as thermomechanical analysis.

[0234] In order to obtain a sample of the respective polymers (Al), (Bl) and (Cl), these can be prepared alone, and not by a multi-step process, to more easily estimate and measure the glass transition temperature Tv individually of the respective polymers of the respective steps. The copolymer (Cl) can be extracted to estimate and measure the glass transition temperature Tv and / or the molecular weight.

[0235] Preferably, the polymer composition of the invention, if in the form of a powder, does not comprise solvents. "No solvents" means that any solvent present represents less than 1% by weight of the composition. The monomers of the synthesis of the respective polymers are not considered solvents. The residual monomers in the composition represent less than 2% by weight of the composition.

[0236] Preferably, the polymer composition according to the invention, if in the form of a powder, is dry. "Dry" means that the polymer composition according to the present invention comprises less than 3% by weight of moisture and preferably less than 1.5% by weight of moisture and, more preferably, less than 1.2% by weight of moisture.

[0237] Humidity can be measured by a thermobalance which heats the polymer composition and measures the weight loss.

[0238] The composition according to the invention in the form of a powder does not comprise any deliberately added solvent. Any residual monomers from the polymerization respective monomers and water are not considered solvents.

[0239] The polymer composition (PCI), if in the form of a polymer powder (POW1) of the invention comprises polymer particles PAR. If several different kinds of particles are present, they are respectively called PARI, PAR2, etc. The polymer particles PAR represent at least 50% by weight of the polymer powder composition (POW1). More preferably, the polymer particles PARI represent at least 60% by weight, even more preferably at least 70% by weight of the polymer powder composition POW1.

[0240] In a first preferred embodiment, the polymer composition (PCI) in the form of a polymer powder (P0W1) of the invention consists only of PARI polymer particles. The PARI polymer particles consist of a multi-stage polymer (MPI) which comprises components a), b) and c).

[0241] In a second preferred embodiment, the polymer composition (PCI) in the form of a polymer powder (P0W1) of the invention comprises at least 60% by weight of PARI polymer particles. The PARI polymer particles consist of a multi-stage polymer (MPI) which comprises at least components a) and b).

[0242] In a third preferred embodiment, the polymer composition (PCI) in the form of a polymer powder (P0W1) of the invention comprises PARI polymer particles. The PARI polymer particles consist of a multi-stage polymer (MPI) which comprises components a), b) and c).

[0243] In a fourth preferred embodiment, the polymer composition (PCI) in the form of a polymer powder POW 1 of the invention comprises two different kinds of particles PARI and PAR2. The polymer particles PARI consist of the multi-stage polymer (MPI) which comprises components a) and b). The polymer particles PAR2 comprise or consist of the polymer (Cl).

[0244] As regards a first preferred method for the manufacture of the polymer composition (PCI) according to the invention, this comprises the steps of

[0245] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in step (A) comprising the polymer (Al) having a glass transition temperature of less than 10°C,

[0246] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C,

[0247] c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in step (C) comprising a polymer (Cl) having a glass transition temperature of at least 30°C,

[0248] d) agglomeration of the composition obtained in steps a) to c).

[0249] Preferably step a) is carried out before step b).

[0250] More preferably, step b) is carried out in the presence of the polymer (Al) obtained in step a).

[0251] Advantageously, the first preferred method for manufacturing the polymer composition (PCI) according to the invention is a multi-step method which comprises the successive steps of

[0252] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in step (A) comprising the polymer (Al) having a glass transition temperature of less than 10°C,

[0253] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C

[0254] c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in step (C) comprising a polymer (Cl) having a glass transition temperature of at least 30°C,

[0255] d) agglomeration of the composition obtained in steps a) to c).

[0256] Preferably, steps a), b), c) and d) are carried out in this order. When emulsion polymerization is used, the polymer composition at the end of the polymerization is obtained as an aqueous dispersion.

[0257] The respective monomers or monomer mixtures (Am), (Bm) and (Cm) for the formation of the layers in steps (A), (B) and (C) respectively comprising the polymers (Al), (Bl) and (Cl), respectively, are the same as those defined previously. The monomers or monomer mixtures (Am), (Bm) and (Cm) comprise the respective monomers which are as monomeric units polymerized in the polymer chain of the respective polymers (Al), (Bl) and (Cl). The characteristics of the polymers (Al), (Bl) and (Cl), respectively, are the same as those defined previously.

[0258] As regards a second preferred method for manufacturing the polymeric composition (PCI) comprising the polymer (Cl) and the multi-step polymer (MPI), this comprises the steps of

[0259] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in step (A) comprising the polymer (Al) having a glass transition temperature of less than 10°C,

[0260] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C,

[0261] jointly, steps a) and b) leading to a multi-step polymer (MPI) and the step

[0262] c) mixing the multi-stage polymer (MPI) with a polymer (Cl) having a glass transition temperature of at least 30°C,

[0263] d) agglomeration of the composition obtained in steps a) to c).

[0264] Preferably, the polymer (Cl) is in the form of an aqueous dispersion. The aqueous dispersion comprises the polymer (Cl) in the form of polymeric particles.

[0265] As regards a third preferred method for manufacturing the polymeric composition (PCI) comprising the polymer (Cl) and the multi-step polymer (MPI), this comprises the steps of

[0266] a) providing a polymer (Cl) having a glass transition temperature of at least 30°C and a multi-stage polymer (MPI) comprising a stage (A) comprising a polymer (Al) having a glass transition temperature of less than 10°C and a stage (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C,

[0267] b) mixing or blending the polymer (Cl) and the multi-stage polymer (MPI),

[0268] c) agglomeration of the composition obtained in steps b)

[0269] the polymer (Cl) and the multi-stage polymer (MPI) in step b) being in the form of an aqueous phase dispersion. The respective aqueous dispersions comprise the polymer (Cl) and the multi-stage polymer (MPI) in the form of polymeric particles.

[0270] Preferably, the multi-stage polymer (MPI) and the polymer (Cl) are already provided as an aqueous dispersion.

[0271] The amounts of the aqueous dispersion of the polymer (Cl) and the aqueous dispersion of the multi-stage polymer (MPI) are chosen such that the weight ratio of the multi-stage polymer on the basis of the solid part only in the mixture obtained is at least 60% by weight, preferably at least 65% by weight, more preferably at least 68% by weight and advantageously at least 70% by weight.

[0272] The amounts of the aqueous dispersion of the polymer (Cl) and the aqueous dispersion of the multi-stage polymer (MPI) are chosen such that the weight ratio of the multi-stage polymer based on the solid part only in the resulting mixture is at most 99% by weight, preferably at most 95% by weight and more preferably at most 90% by weight.

[0273] The amounts of the aqueous dispersion of the polymer (Cl) and the aqueous dispersion of the multi-stage polymer are chosen in such a way that the weight ratio of the multi-stage polymer on the basis of the solid part only in the mixture obtained is between 60% by weight and 99% by weight, preferably between 65% by weight and 95% by weight and more preferably between 68% by weight and 90% by weight.

[0274] The preferred method for manufacturing the polymer composition (PCI) comprising the polymer (Cl) and the multi-stage polymer (MPI) produces the polymer powder P0W1. The polymer powder P0W1 is in the form of grains (large particles). The grain or polymer powder particle comprises agglomerated primary polymer particles prepared by a multi-stage process comprising the multi-stage polymer (MPI) and the polymer (Cl) or agglomerated primary polymer particles comprising the multi-stage polymer (MPI) and the polymer (Cl).

[0275] The agglomeration step can be carried out by coagulation or by atomization.

[0276] For preferred processes, coagulation is preferred in the agglomeration step.

[0277] The aqueous composition comprising the multi-stage polymer (MPI) and the polymer (Cl), before the start of coagulation, has a solids content of less than 35% by weight. If the solids content is greater than 35% by weight, water is added to adjust the solids content. Preferably the solids content is less than 34% by weight, more preferably less than 33% by weight and advantageously less than 32% by weight.

[0278] The solids content is measured or estimated gravimetrically, by weighing before and after complete evaporation of the water.

[0279] In a first preferred embodiment, the solids content of the aqueous composition comprising the multi-stage polymer (MPI) and the polymer (Cl), before the start of coagulation, is between 5% by weight and 35% by weight, more preferably between 6% by weight and 34% by weight, even more preferably between 7% by weight and 33% by weight and advantageously between 8% by weight and 32% by weight.

[0280] In a second preferred embodiment, the solids content of the aqueous composition comprising the multi-stage polymer (MPI) and the polymer (Cl), before the start of coagulation, is between 20% by weight and 35% by weight, more preferably between 20% by weight and 34% by weight, even more preferably between 20% by weight and 33% by weight and advantageously between 20% by weight and 32% by weight.

[0281] In a third preferred embodiment, the solids content of the aqueous composition comprising the multi-stage polymer (MPI) and the polymer (Cl), before the start of coagulation, is between 5% by weight and 20% by weight, more preferably between 6% by weight and 20% by weight, even more preferably between 7% by weight and 20% by weight and advantageously between 8% by weight and 20% by weight.

[0282] In a fourth preferred embodiment, the solids content of the aqueous composition comprising the multi-stage polymer (MPI) and the polymer (Cl), before the start of coagulation, is between 10% by weight and 25% by weight, more preferably between 11% by weight and 24% by weight, even more preferably between 12% by weight and 23% by weight and advantageously between 13% by weight and 22% by weight.

[0283] In a fifth preferred embodiment, the solids content of the aqueous composition comprising the multi-stage polymer (MPI) and the polymer (Cl), before the start of coagulation, is between 15% by weight and 27% by weight, more preferably between 17% by weight and 27% by weight, even more preferably between 19% by weight and 27% by weight and advantageously between 21% by weight and 27% by weight.

[0284] Coagulation can be carried out with a salt or with an inorganic acid.

[0285] In a first preferred embodiment, the coagulation is carried out with an inorganic acid.

[0286] The process for manufacturing the polymer composition (PCI) according to the invention may optionally comprise the additional step e) of drying the polymer composition.

[0287] Preferably, after drying step e), the polymer composition comprises less than 3% by weight, more preferably less than 1.5% by weight, advantageously less than 1.2% of moisture or water.

[0288] The humidity of a polymer composition can be measured with a thermobalance.

[0289] Drying of the polymer may be carried out in an oven or a vacuum oven with heating of the composition for 48 hours at 50°C.

[0290] The liquid composition LC1 of the eighth aspect of the invention is a precursor for thermosetting polymers or thermoplastic polymers. This may be a monomer, a mixture of monomers, a polymerizable or hardenable oligomer, a mixture of a polymerizable or hardenable oligomer with one or more monomer(s), or a mixture of polymers with one or more monomers which are liquid at 25°C. Preferably, the liquid has a dynamic viscosity of less than 1000 Pa*s, and more preferably between 0.5 mPa*s and 1000 Pa*s. The value of the dynamic viscosity is taken at a shear rate of 1 1 / s. The viscosity is measured with a rheometer.

[0291] For example, the liquid composition LC1 may be chosen from compositions for the preparation of vinyl ester resin, unsaturated polyester resin or epoxy resin; or it may be, for example, a styrenic monomer or a (meth)acrylic monomer, or a corresponding mixture or a liquid composition comprising said monomers.

[0292] In one embodiment, the liquid composition LC1 comprises at least one (meth)acrylic monomer (M2a), the (meth)acrylic monomer being chosen from cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, bomyl acrylate, bornyl methacrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, fenchyl acrylate, fenchyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate or mixtures thereof.Preferably the polymeric composition (PCI) represents between 0.5% by weight and 50% by weight of the composition comprising the liquid composition LC1 and the polymeric composition (PCI), more preferably between 0.5% by weight and 45% by weight, even more preferably between 1% by weight and 40% by weight.

[0293] In one embodiment, the liquid composition (LC1) comprises

[0294] a) the polymer composition (PCI) and

[0295] b) a monomer (M2b),

[0296] the ratio of polymer composition (PCI) to monomer (M2) by weight in the liquid composition LC1 being between 1 / 99 and 25 / 75.

[0297] Preferably, the monomer (M2b) is a (meth)acrylic monomer. More preferably, the monomer (M2b) has a Hansen solubility parameter ôp < 10 MPa1 / 2.

[0298] The present invention also relates to the use of the polymer composition (PCI) in the form of the polymer powder according to the invention as an impact resistance modifier in polymers, in order to obtain a polymer composition with modified impact resistance. Preferably the polymers are thermosetting polymers or thermoplastic polymers or their precursors.

[0299] The present invention also relates to the use of the polymer composition (PCI) in the field of compositions for UV curing, 3D printing and adhesives. [Evaluation procedures]

[0300] Glass transition temperature

[0301] The glass transitions (Tv) of polymers are measured with equipment capable of performing thermomechanical analysis. An RDAII “RHEOMETRICS DYNAMIC ANALYSER” analyzer provided by Rheometrics Company was used. Thermomechanical analysis precisely measures the viscoelastic changes of a sample as a function of temperature, stress or strain applied. The device continuously records the deformation of the sample, by maintaining the fixed constraint, during a regulated temperature variation program.

[0302] The results are obtained by plotting the modulus of elasticity (G'), the loss modulus and the loss angle as a function of temperature. Tv is the highest temperature value read in the loss angle curve, when the derivative of the loss angle is equal to zero.

[0303] Molecular weight

[0304] The mass average molecular weight (Mw) of the polymers is measured by size exclusion chromatography (SEC). Polystyrene references are used for calibration. The polymer is dissolved in THF at a concentration of 1 g / L. The chromatography column uses a modified silica. The flow rate is 1 ml / min and a refractive index detector is used.

[0305] Particle size analysis

[0306] The particle size of the primary particles after multi-stage polymerization is measured with a Malvern Zetasizer using dynamic light scattering. The volume average particle size (diameter) is taken as the result.

[0307] The particle size of the polymer powder after recovery is measured with a Malvern Mastersizer 3000 from MALVERN with laser diffraction.

[0308] For the estimation of volume average powder particle size, particle size distribution and proportion of fine particles, a Malvern Mastersizer 3000 apparatus with 300 mm objectives is used, measuring a range of 0.5 to 880 pm.

[0309] The Hansen solubility parameters, and in particular the Hansen solubility parameter ôp are estimated according to the method as described in document WO2020 / 001835.

[0310] Apparent density

[0311] ISO 60:1977 is used. The sample is purified through a specified funnel into a measuring cylinder with a capacity of 100 cubic centimeters, the excess is removed with an adjuster's rule and the mass of the contents is determined by weighing.

[0312] Viscosity

[0313] Viscosity can easily be measured with a rheometer or viscometer. Dynamic viscosity is measured at 25°C. If the liquid has Newtonian behavior, meaning that it does not exhibit shear thinning, the dynamic viscosity is independent of shear in a rheometer or of the speed of the spindle in a viscometer. If the liquid composition has non-Newtonian behavior, meaning that it exhibits shear thinning, the dynamic viscosity is measured at a shear rate of 1s 1 at 25°C. Examples

[0314] A polymer composition (PC) in the form of a core-shell multi-step polymer comprising a core and two shell layers is prepared according to the method as described in WO2020 / 260638 for Comparative Example 1. For Example 1 however, 30 wt% of the MMA in the synthesis of the two shell layers of Comparative Example 1 is replaced by isobornyl acrylate (IBOA).

[0315] The two products obtained are coagulated with sulfuric acid and dried.

[0316]

[0317] [Table 1] [Tables 1] Reference CS report Particle size [nm] 1st shell Polymer (Bl) 2nd shell Polymer (Cl) Extracted polymer / [%] Mw of extracted polymer / [g / mol] Comparative example 71 / 29 177 PMMA-crosslinked PMMA - transfer agent 12 35,000 Example 1 71 / 29 170 PMMA -IBOA (70 / 30) crosslinked PMMA-IBOA (70 / 30)- transfer agent 11 22,000

[0318]

[0319] [Table 2]

[0320] Table 2 - properties of powders Reference D10 / [pm] D50 / [pm] D90 / [pm] MVA / [g / cm3] PH Porosity / [ml / g] Comparative example 1 64 200 520 0.20 5.6 2.45 Example 1 88 265 675 0.31 6.7 1.7

[0321] Both powders are tested at different concentrations of isobornyl acrylate ( [Fig.l]) and isobornyl methacrylate (Figure 2) as monomers. The viscosity in Pa*s at a shear rate of 1 / s at 25°C is given as a function of the concentration in wt%. Comparative Example 1 are the square symbols and Example 1 are the diamond symbols. The results are shown in Figures 1 and 2.

[0322] The composition according to the invention produces a significantly lower viscosity of the liquid compositions. It can be dispersed at a much higher concentration.

Claims

Claims

1. A polymer composition (PCI) comprising a) a polymer (Al) having a glass transition temperature of less than 10°C, b) a polymer (Bl) having a glass transition temperature of at least 60°C, and c) a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of a composition based on a), b) and c) only, characterized in that at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), and characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and characterized in that the polymer (Bl) and the polymer (Cl) comprise monomeric units comprising an alicyclic hydrocarbon group having a carbon number of 3 to 20.

2. Polymer composition (PCI) according to claim 1, characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 12,000 g / mol and 350,000 g / mol.

3. Polymer composition (PCI) according to claim 1, characterized in that the polymer (Bl) and the polymer (Cl) comprise monomeric units originating from polymerized comonomers (Mcbl) and (Mccl) respectively the two comonomers comprise an alicyclic hydrocarbon group having a carbon number of 3 to 20.

4. Polymer composition (PCI) according to claim 1, characterized in that the polymer (Bl) and the polymer (Cl) comprise monomeric units comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20 having a glass transition temperature Tv of between 60°C and 150°C for polymer (Bl) and of between 30°C and 150°C for polymer (Cl).

5. A polymeric composition according to claim 1 or 2 or 4, characterized in that each of the polymer (Bl) and the polymer (Cl) comprises between 1% by weight and 90% by weight of monomeric units comprising the alicyclic hydrocarbon group having a carbon number of 3 to 20.

6. Polymer composition (PCI) according to claim 1 or 2 or 4 or 5, characterized in that the number of carbons in the hy- group alicyclic carbon number of monomeric units is 6 to 20.

7. A polymeric composition according to claim 1 or 2 or 4 or 5, characterized in that each of the polymer (Bl) and the polymer (Cl) comprises between 1% by weight and 50% by weight of monomeric units comprising the alicyclic hydrocarbon group having a carbon number of 3 to 20.

8. Polymeric composition (PCI) according to any one of claims 1 to 2 or 4 to 7, characterized in that the monomeric units comprising an alicyclic hydrocarbon group comprising a number of carbons from 3 to 20 are chosen from cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, fenchyl acrylate, fenchyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate.

9. Polymeric composition (PCI) according to any one of claims 1 to 8, characterized in that the polymeric composition (PCI) is in the form of a porous polymer powder P0W1 having a total intruded volume of at least 1.2 ml / g as measured by mercury porosimetry according to standard ISO 15901-1.

10. A process for manufacturing the polymer composition according to any one of claims 1 to 9 comprising the steps of a) polymerizing by emulsion polymerization a monomer or a mixture of monomers (Am) to obtain a layer in a step (A) comprising the polymer (Al) having a glass transition temperature of less than 10°C, b) polymerizing by emulsion polymerization a monomer or a mixture of monomers (Bm) to obtain a layer in a step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C, c) polymerizing by emulsion polymerization a monomer or a mixture of monomers (Cm) to obtain a layer in a step (C) comprising a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only; d) agglomeration of the composition obtained in steps a) to c); characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that the monomer or mixture of monomers (Bm) and the monomer or mixture of monomers (Cm), together comprise monomers comprising an alicyclic hydrocarbon group having a number of carbons of 3 to 20.

11. A process for manufacturing the polymer composition according to any one of claims 1 to 9 comprising the steps of a) polymerizing by emulsion polymerization a monomer or a mixture of monomers (Am) to obtain a layer in a step (A) comprising the polymer (Al) having a glass transition temperature of less than 10°C, b) polymerizing by emulsion polymerization a monomer or a mixture of monomers (Bm) to obtain a layer in a step (B) comprising a polymer (Bl) having a glass transition temperature of at least 60°C, together, steps a) and b) giving a multi-stage polymer (MPI) and a step c) of mixing the multi-stage polymer (MPI) with a polymer (Cl) having a glass transition temperature of at least 30°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;d) agglomeration of the composition obtained in steps a) to c); characterized in that the polymer (Cl) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol and in that the monomer or mixture of monomers (Bm) and the monomer or mixture of monomers (Cm), together comprise monomers comprising an alicyclic hydrocarbon group having a number of carbons of 3 to 20.;

12. Method according to claim 10 or 11, characterized in that the agglomeration step is carried out by coagulation.

13. Use of the polymer composition (PCI) according to any one of claims 1 to 9 or obtained by the process according to any one of claims 10 to 13 as an impact resistance modifier.

14. Liquid composition LC1 comprising a) the polymer composition (PCI) according to any one of claims 1 to 9 or obtained by the process according to any one of claims 10 to 12 and b) a monomer (M2), characterized in that the ratio of polymer composition (PCI) to monomer (M2) by weight in the liquid composition LC1 is between 1 / 99 and 25 / 75.

15. Liquid composition LC1 according to claim 14, characterized in that the monomer (M2) is chosen from cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, fenchyl acrylate, fenchyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate and corresponding mixtures.

16. Use of the polymer composition (PCI) according to any one of claims 1 to 9 or obtained by the process according to any one of claims 10 to 12 in the field of compositions for UV curing, 3D printing and adhesives.