Multi-stage polymers, methods for their preparation, compositions containing same and uses thereof - Patents.com

Abstract

The present invention relates to a composition comprising a multi-stage polymer, a method for preparing the same, a composition comprising the same and its use.In particular, the present invention relates to a multi-stage polymer in the form of a polymer particle produced by a multi-stage process, and a composition in the form of a porous polymer powder comprising a (meth)acrylic polymer.More particularly, the present invention relates to a polymer particle produced by a multi-stage process comprising at least two stages, and a polymer composition in the form of a porous polymer powder comprising a (meth)acrylic polymer, a method for preparing the same, its use, and compositions and articles comprising the same.

Description

[Technical field]

[0001] The present invention relates to compositions comprising multistage polymers, methods for their preparation, compositions containing same and uses thereof.

[0002] In particular, the present invention relates to multi-stage polymers in the form of polymer particles made by the multi-stage process, and to compositions in the form of polymer powders comprising (meth)acrylic polymers.

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

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

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

[0006] The polymeric impact modifier may be in the form of polymer particles. Usually, these polymeric impact modifiers are in the form of core-shell particles made by a multi-stage process, at least one stage containing a rubber-like polymer. These particles are then incorporated into polymers or polymer compositions to increase their impact resistance. The polymers or polymer compositions may be thermosetting or thermoplastic.

[0007] Thermosetting polymers consist of cross-linked three-dimensional structures. The cross-links are obtained by curing reactive groups within so-called prepolymers. Curing may be obtained, for example, by heating the polymer chains or prepolymers, permanently cross-linking or solidifying the material.

[0008] Thermoplastic polymers are usually composed of linear or branched polymers that are not crosslinked. They may be slightly crosslinked as long as they are thermally deformable. However, these aforementioned core-shell particles do not disperse easily or quickly in all kinds of resins or polymers or polymer precursors, especially in liquid epoxy resins or liquid monomers, or other liquid polymer precursors.

[0009] A good uniform and fast dispersion is necessary to have sufficient impact performance in the final polymer composition. Easy dispersion preparation and fast dispersion time are also necessary to reduce the process time and achieve an easier and simpler process.

[0010] The aim of the present invention is in particular to propose a polymer composition which is quickly and easily dispersible in liquid resins, such as precursors of thermosetting or thermoplastic polymers, such as epoxy resins or (meth)acrylic monomers, respectively.

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

[0012] A further object of the present invention is to propose a polymer composition in the form of a dry polymer powder which is easily dispersible, in particular in low-polarity liquid resins or in low-polarity (meth)acrylic monomers.

[0013] The object of the present invention is also to propose a multistage polymer composition in the form of a dry polymer powder which is easily dispersible, especially in low-polarity liquid resins or low-polarity (meth)acrylic monomers.

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

[0015] Another object of the present invention is to propose a method for preparing a multi-stage polymer composition in the form of a polymer powder that is easily dispersible in reactive epoxy resins, polyester resins or (meth)acrylic resins / polymers or liquid monomers or resins, in particular low-polarity liquid resins or low-polarity (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 preparing a liquid composition containing a precursor of a thermoset or thermoplastic polymer.

[0017] Yet another object is to reduce the time required to disperse polymer powders in such liquid compositions. [Background technology]

[0018] Document WO2016 / 102666 discloses a composition comprising a multi-stage polymer and a method for preparing the same. The composition also comprises a (meth)acrylic polymer having a weight average molecular weight of less than 100000 g / mol. The (meth)acrylic polymer may comprise functional monomer units.

[0019] Document WO2016 / 102682 discloses a multi-stage polymer composition and a method for preparing the same. The multi-stage polymer comprises a final stage comprising a (meth)acrylic polymer having a weight average molecular weight of less than 100000 g / mol. The (meth)acrylic polymer may comprise functional monomer units.

[0020] Document FR2934866 discloses polymer formulations of specific core-shell polymers having a functional shell containing hydrophilic monomers. The core-shell polymers are used as impact modifiers for thermosetting polymers.

[0021] Document WO2019 / 012052 discloses a composition comprising a multi-stage polymer and a method for preparing the same. The composition also comprises a (meth)acrylic polymer having a weight average molecular weight between 100000 g / mol and 1000000 g / mol. The (meth)acrylic polymer may comprise functional monomer units.

[0022] None of the prior art documents disclose a composition comprising a multi-stage polymer in combination with a (meth)acrylic polymer, where both polymers contain an alicyclic hydrocarbon group having 3 to 20 carbon atoms or have a Hansen solubility parameter δ p <10MPa 1 / 2 No. 5,393,633, or methods for preparing the same. Summary of the Invention

[0023] Surprisingly, a polymer composition (PC1) was found to be a) a polymer (A1) having a glass transition temperature of less than 10° C., b) a polymer (B1) having a glass transition temperature of at least 60° C., and c) a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt. % of the composition based solely on a), b) and c); Including, At least components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1), The polymer (C1) has a weight average molecular weight Mw between 10000 g / mol and 500000 g / mol; It has been found that a polymer composition (PC1), characterized in that the polymer (B1) and the polymer (C1) contain a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, results in a polymer composition that is easily dispersible in a low-polarity liquid composition and that results in a liquid composition having a low viscosity compared to a liquid composition containing a polymer composition that does not contain a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

[0024] Surprisingly, a polymer composition (PC1) was found to be a) a polymer (A1) having a glass transition temperature of less than 10° C., b) a polymer (B1) having a glass transition temperature of at least 60° C., and c) a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt. % of the composition based solely on a), b) and c); Including, At least components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1), The polymer (C1) has a weight average molecular weight Mw between 10000 g / mol and 500000 g / mol; The polymer (B1) and the polymer (C1) are each a polymerizable comonomer (Mc b1 ) and (Mc c1 ), and both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 The polymer composition (PC1) is easily dispersible in a low polarity liquid composition and is characterized by having a polymerizable comonomer (Mc b1 ) and (Mc c1 ) and both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 It has also been found that the polymer composition results in a liquid composition having a lower viscosity compared to a liquid composition comprising a polymer composition having

[0025] Surprisingly, a polymer composition (PC1) comprising a multi-stage polymer in the form of a polymer powder, a) a polymer (A1) having a glass transition temperature of less than 10° C., b) a polymer (B1) having a glass transition temperature of at least 60° C., and c) a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt. % of the composition based solely on a), b) and c); Including, At least components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1), The polymer (C1) has a weight average molecular weight Mw between 10000 g / mol and 500000 g / mol; The polymer (B1) and the polymer (C1) each contain a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or the polymer (B1) and the polymer (C1) each contain a polymerization comonomer (Mc b1 ) and (Mc c1 ), and both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 The polymer composition (PC1) is easily dispersible in a low polarity liquid composition and does not contain a monomer unit having an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a polymerizable comonomer (Mc b1 ) and (Mc c1 ) and both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 It has been found that the polymer composition results in a liquid composition having a lower viscosity compared to any of the liquid compositions comprising the polymer composition having the formula:

[0026] Surprisingly, a process for producing a polymer composition (PC1) in the form of a polymer powder is provided, comprising the steps of: a) Monomer or monomer mixture (A m) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., c) polymerizing by emulsion polymerization of a monomer or monomer mixture (Cm) to obtain a layer in stage (C) comprising a polymer (C1) having a glass transition temperature of at least 30° C., so that said polymer (C1) represents up to 40 wt. % of the composition, based solely on a), b) and c), d) solidifying the composition obtained in steps a) to c). Including, The polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B m ) and a monomer or monomer mixture (C m ) are mixed with the comonomer (Mc b1 ) and (Mc c1 ), and the comonomer (Mc b1 ) and (Mc c1 ) contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 It has also been found that a method characterized by having:

[0027] Surprisingly, a process for producing a polymer composition (PC1) in the form of a polymer powder is provided, comprising the steps of: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (Bm ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., combining both steps a) and b) to obtain a multi-stage polymer (MP1); and c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt % of the composition based solely on a), b) and c); d) solidifying the composition obtained in steps a) to c). Including, The polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B m ) and a monomer or monomer mixture (C m ) are mixed with the comonomer (Mc b1 ) and (Mc c1 ), and the comonomer (Mc b1 ) and (Mc c1 ) contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 It has also been found that a method characterized by having:

[0028] Surprisingly, a method for producing a liquid polymer composition LPC1 is provided, comprising the steps of: a) providing said polymer composition (PC1) in the form of a porous polymer powder having a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g, b) contacting the polymer composition (PC1) with the liquid composition LCl A method comprising: It has also been found that the polymer composition POWl results in a liquid polymer composition that is uniformly and rapidly dispersed in the liquid composition LCl. [Brief description of the drawings]

[0029] [Figure 1] 1 is a graph showing the viscosity of powders using various concentrations of isobornyl acrylate as a monomer. [Diagram 2] 1 is a graph showing the viscosity of powders using various concentrations of isobornyl methacrylate as a monomer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] According to a first aspect, the present invention relates to a polymer composition (PC1), a) a polymer (A1) having a glass transition temperature of less than 10° C., b) a polymer (B1) having a glass transition temperature of at least 60° C., and c) a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt. % of the composition based solely on a), b) and c); Including, The present invention relates to a polymer composition (PC1), characterized in that at least components a) and b) of the composition (PC1) are part of a multistage polymer (MP1), that the polymer (C1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and that the polymer (B1) and the polymer (C1) contain monomer units containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

[0031] According to a second aspect, the present invention relates to a polymer composition (PC1), a) a polymer (A1) having a glass transition temperature of less than 10° C., b) a polymer (B1) having a glass transition temperature of at least 60° C., and c) a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt. % of the composition based solely on a), b) and c); Including, The composition (PC1) is characterized in that at least components a) and b) are part of a multi-stage polymer (MP1), the polymer (C1) having a weight average molecular weight Mw between 10000 g / mol and 500000 g / mol, the polymer (B1) and the polymer (C1) each containing a polymerized comonomer (Mc b1 ) and (Mc c1 ), and both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 The present invention relates to a polymer composition (PC1) characterized in that it has

[0032] According to a third aspect, the present invention relates to a polymer composition (PC1), a) a polymer (A1) having a glass transition temperature of less than 10° C., b) a polymer (B1) having a glass transition temperature of at least 60° C., and c) a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt. % of the composition based solely on a), b) and c); Including, The composition (PC1) is characterized in that at least components a) and b) of the composition (PC1) are part of a multi-stage polymer (MP1), the polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, the polymer (B1) and the polymer (C1) each contain a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or the polymer (B1) and the polymer (C1) each contain a polymerized comonomer (Mc b1 ) and (Mc c1 ), and both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 The present invention relates to a polymer composition (PC1) characterized in that it has

[0033] According to a fourth aspect, the present invention relates to a method for producing a polymer composition (PC1), comprising: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., c) Monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer in stage (C) comprising a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) representing up to 40 wt. % of the composition, based solely on a), b) and c), d) agglomerating the composition obtained in steps a) to c). Including, The polymer (C1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B m ) and a monomer or monomer mixture (C m ) both of which contain a monomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

[0034] In a fifth aspect, the present invention relates to a method for producing a polymer composition (PC1), comprising the steps of: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., combining both steps a) and b) to obtain a multi-stage polymer (MP1); and c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt % of the composition based solely on a), b) and c); d) agglomerating the composition obtained in steps a) to c). Including, The polymer (C1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B m ) comprises a monomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and polymer (C1) comprises a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

[0035] According to a sixth aspect, the present invention relates to a method for producing a polymer composition (PC1), comprising: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., c) Monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer in stage (C) comprising a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) representing up to 40 wt. % of the composition, based solely on a), b) and c), d) agglomerating the composition obtained in steps a) to c). Including, The polymer (C1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B m ) and a monomer or monomer mixture (C m ) are comonomers (Mc b1 ) and (Mc c1), and both comonomers have Hansen solubility parameters δ p <10MPa 1 / 2 The present invention relates to a method for producing a

[0036] In a seventh aspect, the present invention relates to a method for producing a polymer composition (PC1), comprising the steps of: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., combining both steps a) and b) to obtain a multi-stage polymer (MP1); and c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt % of the composition based solely on a), b) and c); d) agglomerating the composition obtained in steps a) to c). Including, The polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B m ) is the Hansen solubility parameter δ p <10MPa 1 / 2 Comonomer having Mc b1 ), the polymer (C1) has a Hansen solubility parameter δ p <10MPa 1 / 2 Polymerizable comonomer (Mc c1 )

[0037] In an eighth aspect, the present invention relates to the use of a polymer composition (PC1) as an impact modifier.

[0038] In a ninth aspect, the present invention relates to the use of a polymer composition (PC1) as a composition with reduced dispersion time.

[0039] In a tenth aspect, the present invention relates to a method for reducing the time for dispersing a polymer powder in a low polarity liquid composition by using a polymer composition (PC1) in the form of a polymer powder.

[0040] In an eleventh aspect, the present invention relates to a polymer composition PC2 comprising the polymer composition (PC1) as impact modifier.

[0041] In a twelfth aspect, the present invention relates to a method for reducing the time required to disperse a polymer composition (PC1) in a liquid composition, comprising: a) providing said polymer composition (PC1) according to any of the preceding aspects in the form of a porous polymer powder POW1 having a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g, b) contacting the polymer composition (PC1) with the liquid composition LCl The present invention relates to a method comprising the steps of:

[0042] The term "polymer powder" used denotes a polymer in the form of a powder comprising grains in the range of at least 1 μm, said grains being obtained by agglomeration of primary polymer particles comprising one or more polymers, said primary polymer particles being in the nanometer range.

[0043] The term "primary particles" as used refers to spherical polymer particles, including particles in the nanometer range. Preferably, the primary particles have a weight average particle size between 20 nm and 800 nm.

[0044] The term "particle size" as used refers to the volume average diameter of the particles considered as spherical.

[0045] The term "thermoplastic polymer" as used refers to a polymer that turns into a liquid or becomes more liquid or less viscous when heated and is capable of assuming new shapes through the application of heat and pressure.

[0046] The term "thermoset polymer" as used refers to a prepolymer in a soft, solid or viscous state that is irreversibly transformed by curing into an infusible, insoluble polymer network.

[0047] The term "copolymer" is used to indicate that the polymer is composed of at least two different monomeric units.

[0048] The term "multi-stage polymer" as used refers to a polymer formed successively by a multi-stage polymerization process. A multi-stage emulsion polymerization process comprising at least two stages differing in composition, where a first polymer is the first stage polymer and a second polymer is the second stage polymer, i.e., the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer, is preferred.

[0049] The term "(meth)acrylic" is used to refer to all types of acrylic and methacrylic monomers.

[0050] The term "(meth)acrylic polymer" as used means that the (meth)acrylic polymer essentially comprises a polymer that includes a (meth)acrylic monomer that constitutes 50 wt % or more of the (meth)acrylic polymer.

[0051] The term "dry" used denotes a residual water ratio of less than 1.5 wt.%, preferably less than 1.2 wt.%.

[0052] In the present invention, a range from x to y means that the upper and lower limits of this range are included, and is equivalent to at least x and up to y.

[0053] In the present invention, when a range is stated to be between x and y, it means that the upper and lower limits of the range are excluded, and is equivalent to being greater than x and less than y.

[0054] The term "total intrusion volume" used refers to the total volume intruded by liquid mercury according to ISO15901-1:2016. This volume is accumulated and the analytical results give the cumulative intrusion volume (cm) in ml / g as a function of applied pressure or pore diameter. 3 / g) are shown. The total indentation volume is the volume indented at the maximum applied pressure that also corresponds to the smallest pore.

[0055] The term "incremental intrusion" as used represents the intruded volume in ml / g between two specific pressures or two pore sizes. This incremental intrusion may also be expressed relative to the total intrusion volume in vol%.

[0056] By easily dispersed in the liquid resin is meant that a uniform dispersion is obtained. The distribution of the polymer composition (PC1) is not uniform if separation occurs after the initial homogenization.

[0057] The term "low polarity" used refers to a solubility parameter δ p <10MPa 1 / 2 The Hansen solubility parameters reflect the physicochemical solubility properties of organic substances, also called solubility. The Hansen solubility parameters may be calculated according to the method proposed by Charles Hansen in his book entitled "Hansen Solubility Parameters: A user's handbook", Second Edition (2007) Boca Raton, Fla.: CRC Press. ISBN 978-0-8493-7248-3. According to this method, three parameters called "Hansen parameters" are calculated: δ d , δ p and δ h is sufficient to predict the behavior of a solvent for a given molecule. 1 / 2 Unit parameter δ dquantifies the energy of the dispersion forces between molecules, i.e., van der Waals forces. MPa 1 / 2 Unit parameter δ p represents the energy of intermolecular dipole interactions. Finally, MPa 1 / 2 Unit parameter δ h quantifies the energy derived from intermolecular hydrogen bonds, i.e., the ability to interact through hydrogen bonds. The sum of the squares of the three parameters is the Hildebrand solubility parameter (δ tot ) squared.

[0058] Rapid dispersion in liquid resin means that a uniform dispersion is obtained much faster than with polymer compositions not having the specific composition and molecular weight of polymer (C1).

[0059] Concerning the polymer composition (PC1) according to the invention, the polymer composition (PC1) may according to a first embodiment be in the form of a polymer powder (POW1), also called polymer powder POW1, comprising a) a polymer (A1) having a glass transition temperature of less than 10°C, b) a polymer (B1) having a glass transition temperature of at least 60°C, and c) a polymer (C1) having a glass transition temperature of at least 30°C, characterized in that at least components a) and b) of the composition (PC1) are part of a multi-stage polymer (MP1), the polymer (C1) having a weight average molecular weight Mw between 10000 g / mol and 500000 g / mol, and the polymer (B1) and the polymer (C1) comprise monomer units comprising an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

[0060] Component c) represents up to 40 wt% of the composition based on a), b) and c). Preferably, component c) represents up to 35 wt%, more preferably up to 30 wt% of the composition based on a), b) and c).

[0061] In a first advantageous embodiment, component c) represents less than 30 wt. % of the composition, based on a), b) and c).

[0062] In a second advantageous embodiment, component c) represents less than 25 wt. % of the composition based on a), b) and c).

[0063] In a third advantageous embodiment, component c) represents less than 20 wt. % of the composition based on a), b) and c).

[0064] Preferably, component c) comprises more than 4 wt.% of the composition based on a), b) and c), more preferably, component c) comprises more than 5 wt.% of the composition based on a), b) and c).

[0065] In a first advantageous embodiment, component c) represents more than 6 wt. % of the composition, based on a), b) and c).

[0066] In a second advantageous embodiment, component c) represents more than 8 wt. % of the composition based on a), b) and c).

[0067] In a third advantageous embodiment, component c) represents more than 10 wt. % of the composition based on a), b) and c).

[0068] Each of the upper and lower limits given in the previous two paragraphs for the amount of component c) may be combined in any combination of one upper limit and one lower limit.

[0069] Preferably, component c) comprises between 4 wt% and 40 wt% of the composition based on a), b) and c), more preferably, component c) comprises between 5 wt% and 35 wt% of the composition based on a), b) and c).

[0070] In a first advantageous embodiment, component c) represents between 6 wt. % and 30 wt. % of the composition based on a), b) and c).

[0071] In a second advantageous embodiment, component c) represents less than 7 wt. % and 25 wt. % of the composition based on a), b) and c).

[0072] In a third advantageous embodiment, component c) represents between 10 wt. % and 20 wt. % of the composition based on a), b) and c).

[0073] At least components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1).

[0074] At least components a) and b) are obtained by a multistage process comprising at least two stages (A) and (B), respectively, these two polymers (A1) and (B1) forming a multistage polymer.

[0075] Concerning the polymer powder of the invention (POW1), the polymer powder has a volume median particle diameter D50 between 1 μm and 700 μm. Preferably, the volume median particle diameter of the polymer powder is between 10 μm and 600 μm, more preferably between 15 μm and 550 μm, advantageously between 20 μm and 500 μm.

[0076] The particle size distribution by volume D10 is at least 7 μm, preferably 10 μm, more preferably 15 μm.

[0077] The particle size distribution by volume D90 is at most 1000 μm, preferably at most 950 μm, more preferably at most 900 μm, even more preferably at most 800 μm.

[0078] The porosity of the polymer composition (PC1) in the form of a polymer powder POW1 is expressed as the total indentation volume, or the total cumulative indentation (cumulative indentation volume) in milliliters (ml) of mercury per mass (g) of said polymer powder (POW1). It is measured according to the standard ISO 15901-1: Mercury porosity and evaluation of pore size distribution and porosity of solid materials by gas adsorption - Part 1: Mercury porosity. Preferably, the porous polymer powder (POW1) of the invention has a total indentation volume or total cumulative indentation 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 indentation takes into account pore size diameters up to 0.005 μm. Preferably, the total indentation volume or total cumulative indentation takes into account pore size diameters between 100 μm and 0.005 μm, or pressures between 0.01 MPa and 400 MPa.

[0079] The porous polymer powder (POW1) of the present invention has a total indentation volume or total cumulative indentation of at most 10 ml / g. Preferably, the total indentation 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 advantageously at most 4 ml / g and most advantageously at most 3.5 ml / g.

[0080] Each upper and lower limit given in the previous two paragraphs for the total indentation volume or total cumulative indentation of the porous polymer powder of the present invention (POW1) may be combined in any combination of one upper limit and one lower limit.

[0081] Preferably, the porous polymer powder (POW1) of the present invention has a total indentation volume or total cumulative indentation 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, more advantageously between 1.3 ml / g and 4 ml / g and most advantageously between 1.3 ml / g and 3.5 ml / g.

[0082] Incremental intrusion (incremental intrusion volume) is the volume between two specific pore diameters. Incremental intrusion may also be expressed as an absolute value in ml / g, or as a relative value as a percentage of the total intrusion volume or total cumulative intrusion (taking into account pore size diameters between 100 μm and 0.005 μm).

[0083] Preferably, the porous polymer powder (POW1) of the present invention has a cumulative indentation for pore sizes above 10 μm (greater than 10 μm) of at least 0.9 ml / g, more preferably at least 1 ml / g.

[0084] Preferably, the porous polymer powder (POW1) of the present invention has an incremental indentation between pore sizes of 10 μm and 1 μm of at least 0.1 ml / g, more preferably at least 0.12 ml / g, even more preferably at least 0.15 ml / g.

[0085] The apparent bulk density of the polymer powder (POW1) is 0.60 g / cm 3 Preferably, the apparent bulk density is less than 0.45 g / cm 3 less than 0.43 g / cm 3 less than 0.41 g / cm 3 is less than.

[0086] The apparent bulk density of the polymer powder (POW1) is 0.1 g / cm 3 Preferably, the apparent bulk density is 0.11 g / cm 3 More preferably 0.12 g / cm 3 Greater than 0.13 g / cm 3 Greater than.

[0087] The apparent bulk density of the polymer powder (POW1) is 0.1 g / cm 3 ~0.60g / cm 3 Preferably, the apparent bulk density of the polymer powder (POW1) is between 0.15 g / cm 3 ~0.45g / cm 3Advantageously, the apparent bulk density of the polymer powder POW1 is between 0.2 g / cm 3 ~0.4g / cm 3 It is between.

[0088] All the different properties of the respective preferred embodiments of the porous polymer powder (POW1) can be combined in any combination.

[0089] Concerning the polymer composition (PC1) according to the invention, the polymer composition (PC1) is, according to a second embodiment, a continuous phase comprising a) a polymer (A1) having a glass transition temperature of less than 10° C., b) a polymer (B1) having a glass transition temperature of at least 60° C., and c) a polymer (C1) having a glass transition temperature of at least 30° C., in which at least components a) and b) of the composition (PC1) are part of a multi-stage polymer (MP1), the polymer (C1) having a weight average molecular weight Mw between 10000 g / mol and 500000 g / mol, the polymer (B1) and the polymer (C1) comprising monomer units comprising an alicyclic hydrocarbon group having 3 to 20 carbon atoms or the polymer (B1) and the polymer (C1) each comprising a polymerized comonomer (Mc b1 ) and (Mc c1 ), and both comonomers have a Hansen solubility parameter δ p <10MPa 1 / 2 and d) a liquid composition LC1 as the continuous phase in which the polymer composition (PC1) is dispersed.

[0090] The multi-stage polymer (MP1) of the composition (PC1) according to the invention has at least two stages (A) and (B), each of which comprises a polymer (A1) and a polymer (B1), respectively, which differ in polymer composition.

[0091] In a variant, polymer (C1) is also part of the multi-stage polymer (MP1), in which case the composition of polymer (C1) is different from the composition of polymer (A1) and polymer (B1).

[0092] The multi-stage polymer (MP1) is preferably in the form of polymer particles PAR. These particles PAR are also called core-shell particles. For example, the first stage containing polymer (A1) forms the core, and the second or all subsequent stages form the respective shells. Such multi-stage polymers (MP1), also called core-shell particles, are preferred. When the multi-stage polymer (MP1) contains only polymer (A1) and polymer (B1), it is a core-shell particle containing only one shell. When the multi-stage polymer (MP1) contains polymer (A1), polymer (B1) and polymer (C1), it is a core-shell particle containing at least two shells.

[0093] The particles PAR contained in the polymer composition (PC1) in the form of a polymer powder (POW1) according to one embodiment or dispersed according to another embodiment are primary particles.

[0094] The particles PAR have a weight average particle size between 15 nm and 900 nm. Preferably, the weight average particle size of the polymer particles is between 20 nm and 800 nm, more preferably between 25 nm and 600 nm, even more preferably between 30 nm and 550 nm, even more preferably between 35 nm and 500 nm, advantageously between 40 nm and 400 nm, even more advantageously between 75 nm and 350 nm, advantageously between 80 nm and 300 nm.

[0095] According to a first preferred embodiment, the primary polymer particles PAR are agglomerated to give rise to a polymer composition (PC1) or a part of a polymer composition (PC1), which in turn is in the form of a polymer powder, as previously described.

[0096] The polymer composition (PC1) according to the present invention comprises a multi-stage polymer (MP1) comprising at least a) one stage (A) comprising a polymer (A1) having a glass transition temperature below 10°C, and at least b) one stage (B) comprising a polymer (B1) having a glass transition temperature above 60°C.

[0097] In a first preferred embodiment, stage (A) is the first of at least two stages, and stage (B) comprising polymer (B1) is grafted to stage (A) comprising polymer (A1) or another intermediate layer.

[0098] In a second preferred embodiment, there may be another stage before stage (A) so that stage (A) is also a shell.

[0099] In a third preferred embodiment, polymer (C1) having a glass transition temperature above 30° C. is also part of the multi-stage polymer (MP1). At least one stage (C) is also present. Preferably, stage (C) occurs after stage (B). More preferably, stage (C) is the final stage and polymer (C1) is the outer shell of the multi-stage polymer (MP1).

[0100] In a first embodiment, the polymer (A1) having a glass transition temperature of less than 10° C. comprises at least 50 wt.% of polymer units derived from one or more alkyl acrylates, and stage (A) is the innermost layer of a polymer particle having a multi-layer structure. In other words, stage (A) comprising polymer (A1) is the core of the polymer particle.

[0101] Concerning the polymer (A1) of the first preferred embodiment, the polymer is a (meth)acrylic polymer comprising at least 50 wt% of polymer units derived from acrylic monomers. Preferably, 60 wt% and more preferably 70 wt% of the polymer (A1) are acrylic monomers.

[0102] The acrylic monomers in the polymer (A1) comprise monomers selected from C1-C18 alkyl acrylates or mixtures thereof. More preferably, the acrylic monomers in the polymer (A1) comprise monomers of C2-C12 alkyl acrylic monomers or mixtures thereof. Even more preferably, the acrylic monomers in the polymer (A1) comprise monomers of C2-C8 alkyl acrylic monomers or mixtures thereof.

[0103] Polymer (A1) may contain one or more comonomers copolymerizable with the acrylic monomer, so long as polymer (A1) has a glass transition temperature of less than 10°C.

[0104] The comonomer(s) in the polymer (A1) are preferably selected from (meth)acrylic and / or vinyl monomers.

[0105] Most preferably, the acrylic or methacrylic comonomers of polymer (A1) are selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, provided that polymer (A1) has a glass transition temperature of less than 10°C.

[0106] In a particular embodiment, the polymer (A1) is a homopolymer of butyl acrylate.

[0107] More preferably, the glass transition temperature Tg of the polymer (A1) containing at least 70 wt % of polymer units derived from a C2 to C8 alkyl acrylate is between -100°C and 10°C, even more preferably between -80°C and 0°C, advantageously between -80°C and -20°C, and more advantageously between -70°C and -20°C.

[0108] In a second preferred embodiment, the polymer (A1) having a glass transition temperature of less than 10° C. comprises at least 50 wt.% of polymer units derived from isoprene or butadiene, and stage (A) is the innermost layer of a polymer particle having a multi-layer structure. In other words, stage (A) comprising polymer (A1) is the core of the polymer particle.

[0109] By way of example, the polymer (A1) of the core of the second embodiment may be an isoprene homopolymer or a butadiene homopolymer, an isoprene-butadiene copolymer, a copolymer of isoprene with up to 98 wt% of a vinyl monomer and a copolymer of butadiene with up to 98 wt% of a vinyl monomer. The vinyl monomer may be styrene, an alkylstyrene, an acrylonitrile, an alkyl(meth)acrylate, or butadiene or isoprene. In a preferred embodiment, the core is a butadiene homopolymer.

[0110] More preferably, the glass transition temperature Tg of the polymer (A1) comprising at least 50 wt. % of polymer units derived 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.

[0111] In a third preferred embodiment, the polymer (A1) is a silicone rubber-based polymer. For example, the silicone rubber is polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (A1) 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.

[0112] The polymer (A1) having a glass transition temperature of less than 10° C. comprises polymerized monomer units. The polymer (A1) in general, as well as the polymer (A1) of each of the first, second and third preferred embodiments, is preferably polymerized from the respective monomer or monomer mixture (A1) which gives rise to the monomer units constituting the polymer (A1). m ) is prepared from

[0113] As regards the polymer (B1), mention may be made of a copolymer containing a monomer having a double bond and / or a vinyl monomer, at least one of which contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms or has a Hansen solubility parameter δ p <10MPa 1 / 2Preferably, the polymer (B1) is a copolymer comprising at least two different polymerized monomers. Preferably, the polymer (B1) is a (meth)acrylic copolymer, which means that at least 50 wt% of the monomer units of the copolymer (B1) are (meth)acrylic.

[0114] The copolymer (B1) is a comonomer (Mc b1 ), and the comonomer (Mc b1 ) contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or b1 ) is the Hansen solubility parameter δ p <10MPa 1 / 2 The comonomer (Mc b1 ) may be present in an amount of between 1 wt% and 99 wt%, preferably between 1 wt% and 90 wt%, more preferably between 1 wt% and 50 wt%. Preferably, the Hansen solubility parameter δ p <9MPa 1 / 2 It is.

[0115] In a first even more preferred embodiment, the copolymer (B1) contains between 1 wt % and 40 wt % of a comonomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms (Mc b1 ) containing comonomer units. Comonomers containing alicyclic hydrocarbon groups having 3 to 20 carbon atoms (Mc b1 ) is preferably a (meth)acrylic monomer.

[0116] In a second even more preferred embodiment, the copolymer (B1) has a Hansen solubility parameter δ between 1 wt% and 40 wt% p <10MPa 1 / 2 Comonomer having Mc b1 ) Comonomer (Mc b1 ) is preferably a (meth)acrylic monomer.

[0117] In a third even more preferred embodiment, the copolymer (B1) contains between 1 wt % and 40 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms and has a Hansen solubility parameter δp <10MPa 1 / 2 Comonomer having Mc b1 ) Comonomer (Mc b1 ) is preferably a (meth)acrylic monomer.

[0118] In a fourth even more preferred embodiment, the copolymer (B1) contains between 10 wt % and 40 wt % of a comonomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms (Mc b1 ).

[0119] In a fifth even more preferred embodiment, the copolymer (B1) contains between 20 wt % and 40 wt % of a comonomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms (M b1 ).

[0120] In a sixth even more preferred embodiment, the copolymer (B1) contains between 5 wt% and 35 wt% of a comonomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms (Mc b1 ).

[0121] In a seventh even more preferred embodiment, the copolymer (B1) contains between 10 wt % and 40 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms or has a Hansen solubility parameter δ p <9MPa 1 / 2 Comonomer having Mc b1 ) Comonomer (Mc b1 ) is preferably a (meth)acrylic monomer.

[0122] In an eighth even more preferred embodiment, the copolymer (B1) contains between 10 wt % and 40 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms or has a Hansen solubility parameter δ p <10MPa 1 / 2 Comonomer having Mc b1 ) Comonomer (Mc b1 ) is preferably a (meth)acrylic monomer.

[0123] In a ninth even more preferred embodiment, the copolymer (B1) contains between 20 wt % and 40 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or has a Hansen solubility parameter δ p <10MPa 1 / 2 Comonomer having Mc b1 ) Comonomer (Mc b1 ) is preferably a (meth)acrylic monomer.

[0124] In a tenth even more preferred embodiment, the copolymer (B1) contains between 5 wt % and 35 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or has a Hansen solubility parameter δ p <10MPa 1 / 2 Comonomer having Mc b1 ) Comonomer (Mc b1 ) is preferably a (meth)acrylic monomer.

[0125] Most preferably, the other acrylic or methacrylic comonomers (Mc b2 ) is selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, so long as the copolymer (B1) has a glass transition temperature of at least 60°C.

[0126] Advantageously, the copolymer (B1) contains a comonomer (Mc b2 ), which contains at least 50 wt. %, and more advantageously 60 wt. %, of monomer units derived from methyl methacrylate.

[0127] Preferably, the glass transition temperature Tg of the copolymer (B1) is between 60° C. and 150° C. The glass transition temperature of the copolymer (B1) 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.

[0128] Preferably, the copolymer (B1) is grafted onto the polymer prepared in the previous step.

[0129] In a particular embodiment, the copolymer (B1) is crosslinked.

[0130] The copolymer (B1) having a glass transition temperature of at least 60° C. comprises polymerized monomer units. The copolymer (B1) generally and in each embodiment comprises the respective monomer or comonomer (Mc b1 ) and (Mc b2 ) Monomer mixture (B m ) to give copolymer (B1) having monomer units contained in copolymer (B1) after polymerization.

[0131] Regarding the polymer (C1), the polymer has a weight average molecular weight Mw between 10000 g / mol and 500000 g / mol.

[0132] The polymer (C1) has a weight average molecular weight Mw higher than 10 000 g / mol, preferably higher than 10 500 g / mol, more preferably higher than 11 000 g / mol, even more preferably higher than 12 000 g / mol, advantageously higher than 13 000 g / mol, more advantageously higher than 14 000 g / mol, even more advantageously higher than 15 000 g / mol.

[0133] The polymer (C1) has a weight average molecular weight Mw of less than 500000 g / mol, preferably less than 450000 g / mol, more preferably less than 400000 g / mol, even more preferably less than 400000 g / mol, advantageously less than 350000 g / mol, more advantageously less than 300000 g / mol, even more advantageously less than 250000 g / mol and most advantageously less than 200000 g / mol.

[0134] Preferably, the weight average molecular weight Mw of the polymer (C1) is between 10500 g / mol and 450000 g / mol, more preferably between 11000 g / mol and 400000 g / mol, even more preferably between 12000 g / mol and 350000 g / mol, advantageously between 13000 g / mol and 300000 g / mol, more advantageously between 14000 g / mol and 250000 g / mol and most advantageously between 15000 g / mol and 200000 g / mol.

[0135] In a first advantageous embodiment, the weight average molecular weight Mw of the (meth)acrylic polymer MP1 is between 10500 g / mol and 200000 g / mol, more preferably between 11000 g / mol and 190000 g / mol, even more preferably between 12000 g / mol and 180000 g / mol, advantageously between 13000 g / mol and 150000 g / mol, more advantageously between 14000 g / mol and 135000 g / mol and most advantageously between 15000 g / mol and 120000 g / mol.

[0136] In a second advantageous embodiment, the weight average molecular weight Mw of the (meth)acrylic polymer MP1 is between 15000 g / mol and 450000 g / mol, more preferably between 16000 g / mol and 400000 g / mol, even more preferably between 17000 g / mol and 350000 g / mol, advantageously between 18000 g / mol and 300000 g / mol, more advantageously between 19000 g / mol and 250000 g / mol and most advantageously between 20000 g / mol and 200000 g / mol.

[0137] Preferably, the polymer (C1) is a copolymer containing (meth)acrylic monomers, at least one of which contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

[0138] Further, with regard to the polymer (C1), mention may be made of a copolymer containing a monomer having a double bond and / or a vinyl monomer, at least one of which contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms or has a Hansen solubility parameter δ p <10MPa 1 / 2 Preferably, the polymer (C1) is a (meth)acrylic copolymer, which means that at least 50 wt.% of the monomer units of the polymer (C1) are (meth)acrylic.

[0139] The copolymer (C1) is a copolymer of the comonomer (Mc c1 ), and the comonomer (Mc c1 ) contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or the comonomer (Mc c1 ) is the Hansen solubility parameter δ p <10MPa 1 / 2 The comonomer (Mc c1 ) may be present between 1 wt% and 99 wt%, preferably between 1 wt% and 90 wt%, more preferably between 1 wt% and 50 wt%. c1 ) Hansen solubility parameter δ p <9MPa 1 / 2 It is.

[0140] In a first even more preferred embodiment, the copolymer (C1) contains between 1 wt. % and 40 wt. % of a comonomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms (Mc c1 ) containing comonomer units. Comonomers containing alicyclic hydrocarbon groups having 3 to 20 carbon atoms (Mc c1 ) is preferably a (meth)acrylic monomer.

[0141] In a second even more preferred embodiment, the copolymer (C1) has a Hansen solubility parameter δ between 1 wt.% and 40 wt.% p <10MPa 1 / 2 Comonomer having Mc c1 ) Comonomer (Mc c1) is preferably a (meth)acrylic monomer.

[0142] In a third even more preferred embodiment, the copolymer (C1) contains between 1 wt % and 40 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms and has a Hansen solubility parameter δ p <10MPa 1 / 2 Comonomer having Mc c1 ) Comonomer (Mc c1 ) is preferably a (meth)acrylic monomer.

[0143] In a fourth even more preferred embodiment, the copolymer (C1) contains between 10 wt. % and 40 wt. % of a comonomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms (Mc c1 ).

[0144] In a fifth even more preferred embodiment, the copolymer (C1) contains between 20 wt. % and 40 wt. % of a comonomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms (Mc c1 ).

[0145] In a sixth even more preferred embodiment, the copolymer (C1) contains between 5 wt. % and 35 wt. % of a comonomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms (Mc c1 ).

[0146] In a seventh even more preferred embodiment, the copolymer (C1) contains between 10 wt % and 40 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms or has a Hansen solubility parameter δ p <9MPa 1 / 2 Comonomer having Mc c1 ) Comonomer (Mc c1 ) is preferably a (meth)acrylic monomer.

[0147] In an eighth even more preferred embodiment, the copolymer (C1) contains between 10 wt % and 40 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms or has a Hansen solubility parameter δ p <10MPa1 / 2 Comonomer having Mc c1 ) Comonomer (Mc c1 ) is preferably a (meth)acrylic monomer.

[0148] In a ninth even more preferred embodiment, the copolymer (C1) contains between 20 wt % and 40 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms or has a Hansen solubility parameter δ p <10MPa 1 / 2 Comonomer having Mc c1 ) Comonomer (Mc c1 ) is preferably a (meth)acrylic monomer.

[0149] In a tenth even more preferred embodiment, the copolymer (C1) contains between 5 wt % and 35 wt % of an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or has a Hansen solubility parameter δ p <10MPa 1 / 2 Comonomer having Mc c1 ) Comonomer (Mc c1 ) is preferably a (meth)acrylic monomer.

[0150] Most preferably, the acrylic or (meth)acrylic comonomer (Mc c2 ) is selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, so long as the copolymer (C1) has a glass transition temperature of at least 30°C.

[0151] Preferably, the glass transition temperature Tg of the copolymer (C1) is between 30° C. and 150° C. The glass transition temperature of the copolymer (C1) is more preferably between 40° C. and 150° C., advantageously between 45° C. and 150° C., and even more advantageously between 50° C. and 150° C.

[0152] Preferably, the copolymer (C1) is not crosslinked.

[0153] Preferably, copolymer (C1), especially when it is part of multi-stage polymer (MP1), is not grafted to either polymer (A1) or (B1). By not grafted, it is meant that at least 50 wt% of copolymer (C1) in multi-stage polymer (MP1) is solubilizable in the solvent of copolymer (C1). Preferably, at least 75 wt% of copolymer (C1) in multi-stage polymer (MP1) is solubilizable in the solvent of copolymer (C1).

[0154] The copolymer (C1) having a glass transition temperature of at least 30° C. comprises polymerized monomer units. The copolymer (C1) in general and in each embodiment comprises a comonomer (Mc c1 ) and (Mc c2 ) each monomer or monomer mixture (C m ) is prepared from

[0155] In a first preferred embodiment, the monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms is a (meth)acrylic monomer.

[0156] In a second preferred embodiment, the alicyclic hydrocarbon group of the monomer unit has 6 to 20 carbon atoms.

[0157] The monomer unit containing an alicyclic hydrocarbon group is selected from the group consisting of cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, bornyl acylate, bornyl methacrylate, norbornyl acylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, fenchyl acrylate, fenchyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyl adamantyl acrylate, dimethyl adamantyl methacrylate, cyclodecyl acrylate, and cyclodecyl methacrylate.

[0158] The copolymers (B1) and (C1) each contain an alicyclic hydrocarbon group having 3 to 20 carbon atoms or have a Hansen solubility parameter δ p <10MPa 1 / 2 The monomer units, selected according to, may be the same or different.

[0159] In a first preferred embodiment, the polymers (B1) and (C1) each contain an alicyclic hydrocarbon group having 3 to 20 carbon atoms or have a Hansen solubility parameter δ p <10MPa 1 / 2 The monomer units selected according to are the same units.

[0160] In a second preferred embodiment, the polymers (B1) and (C1) each contain an alicyclic hydrocarbon group having 3 to 20 carbon atoms or have a Hansen solubility parameter δ p <10MPa 1 / 2 The monomer units are at least 50 wt % identical.

[0161] In a third preferred embodiment, the polymers (B1) and (C1) each contain an alicyclic hydrocarbon group having 3 to 20 carbon atoms or have a Hansen solubility parameter δ p <10MPa 1 / 2 The monomer units are selected according to less than 50 wt % identical.

[0162] Preferably, the Hansen solubility parameter δ p is 9.5MPa in all embodiments. 1 / 2 has a value less than (δ p <9.5MPa 1 / 2 ).

[0163] More preferably, the Hansen solubility parameter δ p is 9MPa for all embodiments. 1 / 2 has a value less than (δ p <9MPa 1 / 2 ).

[0164] All the different properties of the respective preferred and advantageous embodiments of the polymers (A1), (B1) and (C1) and their respective monomers can be combined in any combination.

[0165] The multi-stage polymer (MP1) is obtained by a multi-stage process comprising at least two stages. At least components a) and b) of the composition (PC1) are part of the multi-stage polymer (MP1).

[0166] Preferably, the polymer (A1) having a glass transition temperature below 10° C. made in stage (A) is made before stage (B) or is the first stage of a multi-stage process.

[0167] Preferably, the copolymer (B1) having a glass transition temperature above 60° C. prepared in stage (B) is prepared after stage (A) of the multi-stage process.

[0168] If copolymer (C1) is also part of the multi-stage polymer (MP1), preferably copolymer (C1) having a glass transition temperature of at least 30° C. produced during stage (C) is produced after stage (B) of the multi-stage process.

[0169] In a first preferred embodiment, the copolymer (B1) having a glass transition temperature of at least 60° C. is an intermediate layer of polymer particles having a multilayer structure.

[0170] In this first preferred embodiment, the copolymer (C1) having a glass transition temperature higher than 30° C. that is prepared in stage (C) is prepared after stage (B) of the multi-stage process.

[0171] More preferably, the copolymer (C1) having a glass transition temperature higher than 30° C. made in stage (C) is a multistage polymer (MP1) having a multi-layer structure or the outer layer of a primary polymer particle.

[0172] There may be further intermediate stages either between stage (A) and stage (B) and / or between stage (B) and stage (C).

[0173] Copolymer (C1) and copolymer (B1) are not the same polymer even though their compositions are very close and some of their properties overlap. The essential difference is that copolymer (B1) is always part of a multistage polymer (MP1).

[0174] This is further illustrated with a process for preparing a polymer composition (PC1) according to the invention comprising a copolymer (C1) and a multistage polymer (MP1).

[0175] The weight proportion r of copolymer (C1) of the outer layer comprised in stage (C), relative to the complete polymer particle, is at least 5 wt%, more preferably at least 7 wt%, even more preferably at least 10 wt%.

[0176] According to the invention, the ratio r of the outer stage (C) comprising the copolymer (C1), relative to the complete polymer particle, is at most 40 wt.%.

[0177] Preferably, the proportion of copolymer (C1) taking into account the primary polymer particles is between 5wt% and 30wt%, preferably between 5wt% and 20wt%.

[0178] In a second preferred embodiment, the copolymer (B1) having a glass transition temperature of at least 60° C. is a primary polymer particle having a multi-layer structure, in other words the outer layer of the multi-stage polymer (MP1).

[0179] Preferably, at least a portion of the copolymer (B1) of layer (B) is grafted onto the polymer made in the previous layer. If there are only two stages (A) and (B) containing polymers (A1) and (B1), respectively, a portion of the copolymer (B1) is grafted onto the polymer (A1). More preferably, at least 50 wt% of the polymer (B1) is grafted. The grafting ratio may be determined by extracting the copolymer (B1) with a solvent and determining the non-grafted amount by weight measurement before and after extraction.

[0180] The glass transition temperature Tg of each polymer can be estimated by dynamic methods, for example, thermomechanical analysis.

[0181] To obtain samples of each of the polymers (A1), (B1) and (C1), which are prepared separately and without a multi-stage method, the individual glass transition temperatures Tg of each polymer in each stage can be more easily estimated and measured. The copolymer (C1) may be extracted to estimate and measure the glass transition temperature Tg and / or molecular weight.

[0182] Preferably, the polymer composition of the present invention is solvent-free when in powder form. By solvent-free, it is meant that the solvent present in the end constitutes less than 1 wt% of the composition. The monomers of the synthesis of each polymer are not considered as solvents. Residual monomers in the composition are present in the composition at less than 2 wt% of the composition.

[0183] Preferably, the polymer composition according to the invention is dry if in powder form, meaning that the polymer composition according to the invention contains less than 3 wt% moisture, preferably less than 1.5 wt% moisture, more preferably less than 1.2 wt% moisture.

[0184] Moisture may be measured by a thermobalance, in which the polymer composition is heated and the weight loss is measured.

[0185] The composition in powder form according to the invention does not contain any voluntarily added solvents. The final residual monomers and water from the polymerization of the respective monomers are not considered as solvents.

[0186] The polymer composition (PC1) of the invention, when in the form of a polymer powder (POW1), comprises polymer particles PAR. When several different types of particles are present, they are called PAR1, PAR2, etc. respectively. The polymer particles PAR constitute at least 50 wt% of the polymer powder composition (POW1). More preferably, the polymer particles PAR1 constitute at least 60 wt%, even more preferably at least 70 wt% of the polymer powder composition POW1.

[0187] In a first preferred embodiment, the polymer composition (PC1) in the form of a polymer powder (POW1) of the invention consists exclusively of polymer particles PAR1. The polymer particles PAR1 consist of a multistage polymer (MP1) comprising components a), b) and c).

[0188] In a second preferred embodiment, the polymer composition (PC1) in the form of a polymer powder (POW1) of the invention comprises at least 60 wt. % of polymer particles PAR1. The polymer particles PAR1 consist of a multistage polymer (MP1) comprising at least components a) and b).

[0189] In a third preferred embodiment, the polymer composition (PC1) in the form of a polymer powder (POW1) of the invention comprises polymer particles PAR1. The polymer particles PAR1 consist of a multistage polymer (MP1) comprising components a), b) and c).

[0190] In a fourth preferred embodiment, the polymer composition (PC1) in the form of the polymer powder POW1 of the invention comprises two different types of particles PAR1 and PAR2. The polymer particles PAR1 consist of a multi-stage polymer (MP1) comprising components a) and b). The polymer particles PAR2 consist of or comprise a polymer (C1).

[0191] Regarding the first preferred method for producing the polymer composition (PC1) according to the invention, the method comprises the steps of: a) Monomer or monomer mixture (A m) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., c) polymerizing by emulsion polymerization of a monomer or monomer mixture (Cm) to obtain a layer in stage (C) comprising a polymer (C1) having a glass transition temperature of at least 30° C., d) agglomerating the composition obtained in steps a) to c). Includes.

[0192] Preferably, step a) is carried out before step b).

[0193] More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a).

[0194] Advantageously, the first preferred method for preparing the polymer composition (PC1) according to the invention comprises: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., c) polymerizing by emulsion polymerization of a monomer or monomer mixture (Cm) to obtain a layer in stage (C) comprising a polymer (C1) having a glass transition temperature of at least 30° C., d) agglomerating the composition obtained in steps a) to c). It is a multi-step process comprising the steps of:

[0195] Preferably, steps a), b), c) and d) are carried out in that order.When emulsion polymerization is used, the polymer composition at the end of the polymerization is obtained as an aqueous dispersion.

[0196] The respective monomers or monomer mixtures (A1), (B1) and (C1) for forming the layers in stages (A), (B) and (C) respectively contain polymers (A1), (B1) and (C1), m ), (B m ) and (C m ) is as previously defined. m ), (B m ) and (C m ) includes each monomer as a polymerized monomer unit in the polymer chain of each of the polymers (A1), (B1) and (C1). The properties of the polymers (A1), (B1) and (C1) are each the same as defined above.

[0197] Regarding the second preferred method for producing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer (MP1), the method comprises the steps of: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., combining both steps a) and b) to obtain a multi-stage polymer (MP1); and c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30° C.; d) agglomerating the composition obtained in steps a) to c). Includes.

[0198] Preferably, the polymer (C1) is in the form of an aqueous dispersion. The aqueous dispersion comprises the polymer (C1) in the form of polymer particles.

[0199] Regarding the third preferred method for producing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer (MP1), the method comprises the steps of: a) providing a multi-stage polymer (MP1) comprising one stage (A) comprising a polymer (C1) having a glass transition temperature of at least 30°C, and a polymer (A1) having a glass transition temperature of less than 10°C, and one stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C; b) mixing or blending polymer (C1) and multi-stage polymer (MP1); c) agglomerating the composition obtained in step b) wherein the polymer (C1) and the multi-stage polymer (MP1) in step b) are in the form of a dispersion in an aqueous phase. Each aqueous dispersion comprises the polymer (C1) and the multi-stage polymer (MP1) in the form of polymer particles.

[0200] Preferably, the multistage polymer (MP1) and polymer (C1) are already prepared as aqueous dispersions.

[0201] The amounts of aqueous dispersion of polymer (C1) and aqueous dispersion of multi-stage polymer (MP1) are selected so that the weight ratio of multi-stage polymer based solely on the solid portion in the resulting mixture is at least 60 wt%, preferably at least 65 wt%, more preferably at least 68 wt% and advantageously at least 70 wt%.

[0202] The amounts of aqueous dispersion of polymer (C1) and aqueous dispersion of multi-stage polymer (MP1) are selected so that the weight ratio of multi-stage polymer, based solely on the solid portion in the resulting mixture, is at most 99 wt%, preferably at most 95 wt%, more preferably at most 90 wt%.

[0203] The amounts of aqueous dispersion of polymer (C1) and aqueous dispersion of multi-stage polymer are selected so that the weight ratio of multi-stage polymer based only on the solid portion in the resulting mixture is between 60 wt% and 99 wt%, preferably between 65 wt% and 95 wt%, more preferably between 68 wt% and 90 wt%.

[0204] A preferred method for producing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer results in a polymer powder POW1. The polymer powder POW1 is in the form of granules (large particles). The polymer powder granules or particles comprise agglomerated primary polymer particles made by a multi-stage process comprising a multi-stage polymer (MP1) and a polymer (C1), or agglomerated primary polymer particles comprising a multi-stage polymer (MP1) and a polymer (C1).

[0205] The agglomeration step may be accomplished by coagulation or atomization.

[0206] In a preferred process, the flocculation step is preferably coagulation.

[0207] The aqueous composition comprising the multi-stage polymer (MP1) and polymer (C1) before the onset of coagulation has a solids content of less than 35 wt%. If the solids content is higher than 35 wt%, water is added to adjust the solids content. Preferably, the solids content is less than 34 wt%, more preferably less than 33 wt%, advantageously less than 32 wt%.

[0208] The solids content is measured or estimated gravimetrically by weighing before and after complete evaporation of the water.

[0209] In a first preferred embodiment, the solids content of the aqueous composition comprising multi-stage polymer (MP1) and polymer (C1) before the onset of coagulation is between 5 wt% and 35 wt%, more preferably between 6 wt% and 34 wt%, even more preferably between 7 wt% and 33 wt%, advantageously between 8 wt% and 32 wt%.

[0210] In a second preferred embodiment, the solids content of the aqueous composition comprising multi-stage polymer (MP1) and polymer (C1) before the onset of coagulation is between 20 wt% and 35 wt%, more preferably between 20 wt% and 34 wt%, even more preferably between 20 wt% and 33 wt%, advantageously between 20 wt% and 32 wt%.

[0211] In a third preferred embodiment, the solids content of the aqueous composition comprising multi-stage polymer (MP1) and polymer (C1) before the onset of coagulation is between 5 wt% and 20 wt%, more preferably between 6 wt% and 20 wt%, even more preferably between 7 wt% and 20 wt%, advantageously between 8 and 20 wt%.

[0212] In a fourth preferred embodiment, the solids content of the aqueous composition comprising multi-stage polymer (MP1) and polymer (C1) before the onset of coagulation is between 10 wt% and 25 wt%, more preferably between 11 wt% and 24 wt%, even more preferably between 12 wt% and 23 wt%, advantageously between 13 wt% and 22 wt%.

[0213] In a fifth preferred embodiment, the solids content of the aqueous composition comprising multi-stage polymer (MP1) and polymer (C1) before the onset of coagulation is between 15 wt% and 27 wt%, more preferably between 17 wt% and 27 wt%, even more preferably between 19 wt% and 27 wt%, advantageously between 21 wt% and 27 wt%.

[0214] Coagulation may be carried out by means of a salt or an inorganic acid.

[0215] In a first preferred embodiment, the coagulation is carried out by means of an inorganic acid.

[0216] The process for preparing the polymer composition (PC1) according to the invention may optionally comprise a further step e) of drying the polymer composition.

[0217] Preferably, after drying step e), the polymer composition contains less than 3 wt. %, more preferably less than 1.5 wt. %, advantageously less than 1.2% moisture or water.

[0218] The moisture content of the polymer composition may be measured with a thermobalance.

[0219] Drying of the polymer may be carried out in an oven or vacuum oven with heating of the composition at 50° C. for 48 hours.

[0220] The liquid composition LC1 of the eighth aspect of the invention is a precursor of a thermosetting or thermoplastic polymer. It may be a monomer, a mixture of monomers, a polymerizable or curable oligomer, a mixture of polymerizable or curable oligomer and monomer, or a mixture of polymer and monomer, which is liquid at 25° C. Preferably, the liquid has a viscosity of 1000 Pa or less. * Less than 0.5 mPa, more preferably less than 0.5 mPa * s~1000Pa * The dynamic viscosity is measured at a shear rate of 1 1 / s.

[0221] For example, the liquid composition LC1 may be selected from compositions for preparing vinyl ester, unsaturated polyester or epoxy resins, or the liquid composition LC1 may be, for example, a styrene-based or (meth)acrylic monomer, or a mixture thereof or a liquid composition comprising said monomers.

[0222] In one embodiment, the liquid composition LC1 comprises at least one (meth)acrylic monomer (M2a), wherein the (meth)acrylic monomer is selected from cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, bornyl 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, dimethyl adamantyl acrylate, dimethyl adamantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate, or mixtures thereof. Preferably, the polymer composition (PC1) comprises between 0.5 wt% and 50 wt%, more preferably between 0.5 wt% and 45 wt%, and even more preferably between 1 wt% and 40 wt% of the composition comprising the liquid composition LC1 and the polymer composition (PC1).

[0223] In one embodiment, the liquid composition LC1 comprises a) a polymer composition (PC1), and b) Monomer (M2b) The weight ratio of the polymer composition (PC1) to the monomer (M2) in the liquid composition LC1 is between 1 / 99 and 25 / 75.

[0224] Preferably, the monomer (M2b) is a (meth)acrylic monomer. More preferably, the monomer (M2b) has a Hansen solubility parameter δ p <10MPa 1 / 2 has.

[0225] The present invention also relates to the use of the polymer composition (PC1) in the form of a polymer powder according to the invention as an impact modifier in a polymer, preferably a thermosetting or thermoplastic polymer or a precursor thereof, to obtain an impact-modified polymer composition.

[0226] The present invention also relates to the use of the polymer composition (PC1) in the fields of UV curing, 3D printing and adhesive compositions.

[0227] [Evaluation method] Glass transition temperature The glass transition (Tg) of a polymer is measured by an instrument capable of performing thermomechanical analysis. The RDAII "RHEOMETRICS DYNAMIC ANALYSER" provided by Rheometrics was used. Thermomechanical analysis precisely measures the viscoelastic changes of a sample as a function of applied temperature, strain or deformation. The instrument continuously records the deformation of the sample during a controlled program of temperature change, while the strain is kept constant. The results are obtained by plotting the elastic modulus (G'), loss modulus and tan delta as a function of temperature. Tg is the highest temperature value read on the tan delta curve where the derived value of tan delta is equal to zero.

[0228] molecular weight The weight average molecular weight (Mw) of the polymer is measured by size exclusion chromatography (SEC). Polystyrene standards are used for calibration. The polymer is dissolved in THF at a concentration of 1 g / L. The chromatography column uses modified silica. The flow rate is 1 ml / min and a refractive index detector is used.

[0229] Particle size analysis The size of the primary particles after multi-stage polymerization is measured using dynamic light scattering with a Malvern Zetasizer, resulting in the volume average particle size (diameter). The particle size of the recovered polymer powder is measured by laser diffraction using a Malvern Mastersizer 3000 manufactured by MALVERN. A Malvern Mastersizer3000 instrument equipped with a 300 mm lens measuring the range of 0.5 to 880 μm is used to estimate the volume average powder particle size, particle size distribution, and fine particle ratio.

[0230] Hansen solubility parameters, especially Hansen solubility parameters δ p is estimated according to the method described in WO2020 / 001835.

[0231] Apparent Density Standard ISO 60:1977 is used. The sample is refined by passing it through a specified funnel into a measuring cylinder of 100 cubic centimeter capacity, the excess is removed using a straightedge and the mass of the contents is determined by weighing.

[0232] viscosity Viscosity can be easily measured with a rheometer or viscometer. Dynamic viscosity is measured at 25 °C. If the liquid has Newtonian behavior, it means that there is no shear thinning, and the dynamic viscosity is independent of the shear of the rheometer or the speed of movement of the viscometer. If the liquid composition has non-Newtonian behavior, it means that there is no shear thinning, and the dynamic viscosity is independent of the shear of the rheometer or the speed of movement of the viscometer. -1 The shear rate is measured. EXAMPLES

[0233] A polymer composition (PC) in the form of a core-shell multistage polymer comprising a core and two shell layers is prepared according to the method described in WO2020 / 260638 for Comparative Example 1. However, for Example 1, 30 wt% of the MMA in the synthesis of the two shell layers of Comparative Example 1 is replaced with isobornyl acrylate (IBOA).

[0234] Both products obtained are coagulated with sulfuric acid and dried. Table 1 TIFF2024546284000001.tif62170Table 2 - Powder properties TIFF2024546284000002.tif53170

[0235] The two powders are tested with various concentrations of isobornyl acrylate (Figure 1) and isobornyl methacrylate (Figure 2) as monomers. The viscosity in Pa*s at 25°C and a shear rate of 1 / s is given as a function of the concentration in wt%. Comparative Example 1 is represented by square symbols and Example 1 by diamond symbols. The results are shown in Figures 1-2.

[0236] The compositions according to the invention result in a much significantly lower viscosity of the liquid composition. The compositions can be dispersed at much higher concentrations.

Claims

1. A polymer composition (PC1) comprising: a) a polymer (A1) having a glass transition temperature of less than 10°C; b) a polymer (B1) having a glass transition temperature of at least 60°C, and c) a polymer (C1) having a glass transition temperature of at least 30° C., said polymer (C1) comprising up to 40 wt % of the composition based solely on a), b) and c). Including, characterised in that at least components a) and b) of composition (PC1) are part of a multistage polymer (MP1), the polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, The polymer (B1) and the polymer (C1) each contain a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or the polymer (B1) and the polymer (C1) each contain a polymerization comonomer (Mc ｂ１ ) and (Mc ｃ１ ), and both comonomers have a Hansen solubility parameter δ ｐ <10 MPa １／２ characterized in that it has Polymer composition (PC1).

2. The polymer composition (PC1) according to claim 1, wherein the polymer (B1) and the polymer (C1) contain a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

3. The polymer (B1) and the polymer (C1) each contain a polymerizable comonomer (Mc ｂ１ ) and (Mc ｃ１ ), and both comonomers have a Hansen solubility parameter δ ｐ <10 MPa １／２ 2. The polymer composition (PC1) according to claim 1, characterized in that it has

4. The polymer (B1) and the polymer (C1) each contain a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a polymerizable comonomer (Mc ｂ１ ) and (Mc ｃ１ ), and both comonomers have a Hansen solubility parameter δ ｐ <10 MPa １／２ 2. The polymer composition (PC1) according to claim 1, characterized in that it has

5. 2. The polymer composition according to claim 1, wherein each of the polymer (B1) and the polymer (C1) contains between 1 wt % and 90 wt % of a monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

6. 2. The polymer composition (PC1) according to claim 1, characterized in that the monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms is selected from the group consisting of 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, dimethyl adamantyl acrylate, dimethyl adamantyl methacrylate, cyclodecyl acrylate, and cyclodecyl methacrylate.

7. 2. The polymer composition (PC1) according to claim 1, characterized in that the polymer composition (PC1) in the form of a porous polymer powder POW1 has a total indentation volume between 1.2 ml / g and 10 ml / g, more preferably between 1.25 ml / g and 8 ml / g.

8. The monomer units containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the polymers (B1) and (C1), or their Hansen solubility parameters δ ｐ <10 MPa １／２ 2. Polymer composition (PC1) according to claim 1, characterized in that the monomer units selected according to are the same units.

9. The monomer units containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms in the polymers (B1) and (C1), or their Hansen solubility parameters δ ｐ <10 MPa １／２ 2. Polymer composition (PC1) according to claim 1, characterized in that the monomer units selected according to are the same for less than 50 wt%.

10. 10. A method for producing the polymer composition of claim 1, comprising: a) a monomer or a mixture of monomers (A ｍ ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B ｍ ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60° C., c) a monomer or a mixture of monomers (C ｍ ) by emulsion polymerization to obtain a layer in stage (C) comprising a polymer (C1) having a glass transition temperature of at least 30°C, said polymer (C1) representing up to 40 wt% of the composition based solely on a), b) and c). d) agglomerating the compositions obtained in steps a) to c). Including, The polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B ｍ ) and a monomer or monomer mixture (C ｍ ) both contain a monomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monomer or monomer mixture (B ｍ ) and a monomer or monomer mixture (C ｍ ) are each a comonomer (Mc ｂ１ ) and (Mc ｃ１ ), and both comonomers have a Hansen solubility parameter δ ｐ <10 MPa １／２ 10. A method comprising:

11. 10. A method for producing the polymer composition of claim 1, comprising: a) a monomer or a mixture of monomers (A ｍ ) by emulsion polymerization to obtain one layer in stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10° C., b) Monomer or monomer mixture (B ｍ ) by emulsion polymerization to obtain a layer in stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, Steps a) and b) are combined to give a multi-stage polymer (MP1); and c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30°C, said polymer (C1) comprising up to 40 wt% of the composition based solely on a), b) and c); d) agglomerating the compositions obtained in steps a) to c). Including, The polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B ｍ ) and a monomer or monomer mixture (C ｍ ) both contain a monomer containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monomer or monomer mixture (B ｍ ) and a monomer or monomer mixture (C ｍ ) are each a comonomer (Mc ｂ１ ) and (Mc ｃ１ ), and both comonomers have a Hansen solubility parameter δ ｐ <10 MPa １／２ 10. A method comprising:

12. 11. The method of claim 10, wherein the aggregation step is carried out by coagulation.

13. 11. Use of the polymer composition (PC1) according to claim 1 or of the polymer composition (PC1) obtainable by the process according to claim 10 as an impact modifier.

14. Liquid composition LC1, a) a polymer composition (PC1) according to claim 1, and b) Monomer (M2) wherein the weight ratio of polymer composition (PC1) to monomer (M2) in the liquid composition LC1 is between 1 / 99 and 25 / 75.

15. 15. Liquid composition LC1 according to claim 14, characterized in that the monomer (M2) is selected 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, or mixtures thereof.

16. Use of the polymer composition (PC1) according to claim 1 or of the polymer composition (PC1) obtained by the method according to claim 10 in the fields of UV curing, 3D printing and adhesive compositions.

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