Composition comprising a multistage polymer and a (METH) acrylic polymer, preparation method thereof and uses thereof

Abstract

The present invention provides a composition comprising a multistage polymer in the form of a porous polymer powder and a (meth)acrylic polymer in the form of a porous polymer powder, a process for its preparation and its use.SOLUTION: The present invention provides a multistage polymer in the form of a polymer particle made by a multistage process and a composition in the form of a porous polymer powder comprising a (meth)acrylic polymer, wherein the (meth)acrylic polymer has a medium molecular weight. More particularly, the invention provides polymer particles made by a multi-stage process comprising at least two stages, and polymer compositions in the form of porous polymer powders comprising (meth)acrylic polymers, processes for their preparation, their use, and compositions and articles comprising the same.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition comprising a multistage polymer and a (meth)acrylic polymer in the form of a porous polymer powder, its preparation process and its use.

[0002] In particular, the present invention relates to a multi-stage polymer in the form of polymer particles made by a multi-stage process, and a composition in the form of a porous polymer powder comprising a (meth)acrylic polymer, wherein the (meth)acrylic polymer has a medium molecular weight.

[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, a method for preparing the same, its use, and compositions and articles comprising the same.

[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 to either solid or molten polymers, or to liquid resins or compositions.

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

[0006] The polymeric impact modifier may be in the form of polymer particles. Typically, these polymeric impact modifiers are in the form of core-shell particles made by a multi-stage process, with 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-linking is achieved by curing reactive groups within so-called prepolymers. Curing may be achieved, for example, by heating the polymer chains or prepolymers, permanently cross-linking or solidifying the material.

[0008] Thermoplastic polymers are usually composed of uncrosslinked linear or branched polymers. 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] 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 processing time and achieve an easier and simpler process.

[0010] The object of the present invention is to propose a polymer composition in the form of a polymer powder that is rapidly and easily dispersible in liquid resins, such as precursors of thermosetting or thermoplastic polymers, such as, for example, epoxy resins or (meth)acrylic monomers, respectively, and at the same time in polymer melts.

[0011] 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 liquid resins, such as, for example, epoxy resins or (meth)acrylic monomers, and at the same time in polymer melts.

[0012] The object of the present invention is also to propose a multi-stage polymer composition in the form of a reactive epoxy resin, polyester resin or (meth)acrylic resin / polymer or polymer powder that can be easily dispersed in liquid monomers or resins.

[0013] A further object of the present invention is to propose a multi-stage polymer composition in the form of a dry polymer powder that can be easily dispersed in reactive epoxy resins, polyester resins or (meth)acrylic resins / polymers or liquid monomers or resins, and at the same time also in polymer melts.

[0014] Another object of the present invention is to propose a method for preparing multi-stage polymer compositions in the form of polymer powders that are easily dispersible in reactive epoxy resins, polyester resins or (meth)acrylic resins / polymers or liquid monomers or resins, and at the same time in polymer melts.

[0015] Yet another object of the present invention is a process for producing a dry multi-stage polymer composition in the form of a polymer powder that can be easily dispersed in reactive epoxy resins, polyester resins or (meth)acrylic resins / polymers or liquid monomers or resins, as well as in polymer melts.

[0016] A still further object is to propose impact-modified cured resin or adhesive compositions having sufficient impact properties.

[0017] 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 comprising precursors of thermosetting or thermoplastic polymers, such as liquid reactive epoxy resins or (meth)acrylic monomers, in which the polymer composition is dispersed.

[0018] Yet another object is to reduce the time required to disperse polymer powders in such liquid compositions.

[0019] A still further object is to propose impact modifiers in the form of polymer powders that can be rapidly and easily dispersed in liquid resins, such as precursors of thermosetting or thermoplastic polymers, in particular epoxy resins or (meth)acrylic monomers, respectively. [Background technology]

[0020] Document WO2016 / 102666 discloses a composition comprising a multistage 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 100,000 g / mol.

[0021] Document WO2016 / 102682 discloses a multi-stage polymer composition and a method for preparing the same, wherein the multi-stage polymer comprises a final stage comprising a (meth)acrylic polymer having a weight average molecular weight of less than 100,000 g / mol.

[0022] Document FR2934866 discloses polymer formulations of specific core-shell polymers having a functional shell containing a hydrophilic monomer. The core-shell polymers are used as impact modifiers for thermosetting polymers.

[0023] Document EP 1632533 describes a method for producing modified epoxy resins: an epoxy resin composition in which rubber-like polymer particles are dispersed by contacting the particles with an organic medium which disperses the rubber particles.

[0024] Document EP 1666519 discloses a method for producing rubbery polymer particles and resin compositions containing them.

[0025] Document EP 2123711 discloses a thermosetting resin composition having rubbery polymer particles dispersed therein and a method for producing the same.

[0026] EP 0 066 382 A1 discloses bulk-flowable impact modifier particles. The coagulated impact modifier particles are coated with or agglomerated with a hard, non-elastomeric, high-molecular-weight polymer. The hard, non-elastomeric, high-molecular-weight polymer preferably has a viscosity-average molecular weight greater than 800,000 and its weight proportion is between 0.1 and 10 wt %.

[0027] Document WO2019 / 012052 discloses a composition comprising a multistage polymer and a method for preparing the same. The composition also comprises a (meth)acrylic polymer having a weight average molecular weight between 100,000 g / mol and 1,000,000 g / mol.

[0028] Document WO2019 / 011984 discloses a curable resin composition comprising: i. a resin system including at least one resin component; ii. a curing agent system; and iii. a particle system including multi-stage polymer particles comprising a polymer composition (PCI) including a) one stage (A) including a polymer (A1) having a glass transition temperature of less than 10°C; b) one stage (B) including 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, wherein at least components a) and b) of composition (PCI) are part of a multi-stage polymer (MPI), wherein polymer (C1) has a weight average molecular weight Mw of at least 10,000 g / mol, and component c) accounts for up to 40 wt% of the composition based on the total weight.

[0029] None of the prior art documents discloses a powder composition comprising a multistage polymer in combination with a (meth)acrylic polymer in the form of a powder having a porosity measured by mercury intrusion and ultimately expressed as a total intrusion volume of 1.2 ml / g, or a method for preparing the same. Summary of the Invention

[0030] Surprisingly, a polymer composition (PC1) in the form of a polymer powder, a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C; b) one stage (B) comprising 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, It has been found that polymer composition (PC1), characterized in that at least components a) and b) of composition (PC1) are part of a multistage polymer (MP1), in which polymer (C1) has a weight average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol, and in which the polymer powder has a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g, can be easily and rapidly dispersed in polymer matrix materials for thermosetting or thermoplastic polymers, or their respective precursors, such as liquid resins and / or monomers.

[0031] Surprisingly, a method for producing a polymer composition (PC1) in the form of a polymer powder, 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) polymerizing by emulsion polymerization 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 at most 40 wt.% of the composition, based solely on a), b) and c), d) solidifying the composition obtained in steps a) to c). Including, It has also been found that a process characterized in that the polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol results in a polymer composition in the form of a polymer powder which has a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g and which disperses easily in polymer matrix materials for thermosetting or thermoplastic polymers or their respective precursors, such as liquid resins and / or monomers.

[0032] Surprisingly, a method for producing a polymer composition (PC1) in the form of a polymer powder, 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, Combining 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, It has also been found that a process characterized in that the polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol results in a polymer composition in the form of a polymer powder which has a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g and which disperses easily in polymer matrix materials for thermosetting or thermoplastic polymers or their respective precursors, such as liquid resins and / or monomers.

[0033] Surprisingly, a method for producing a liquid polymer composition LPC1 was disclosed, which comprises the steps of: a) providing a 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.

[0034] Surprisingly, it has also been found that a polymer composition (PC1) in the form of a porous polymer powder POW1 having a total indentation volume as measured by mercury porosimetry of at least 1.2 ml / g can be used to prepare liquid polymer or prepolymer compositions.

[0035] Surprisingly, it has also been found that using a polymer composition (PC1) 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, it is possible to reduce the time for dispersing the porous polymer powder POW1 to obtain a liquid polymer or prepolymer composition.

[0036] Surprisingly, a method for reducing the time required to disperse a polymer composition (PC1) in a liquid composition was discovered, which comprises: a) providing a polymer composition (PC1) 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 Including, A method has also been discovered that is faster than the same method using a polymer composition in the form of a polymer powder that has a reduced total indentation volume as measured by mercury porosimetry. DETAILED DESCRIPTION OF THE INVENTION

[0037] According to a first aspect, the present invention provides a polymer composition (PC1) in the form of a polymer powder, comprising: a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C; b) one stage (B) comprising 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), and that the polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and that the polymer powder has a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g.

[0038] According to a second aspect, the present invention provides 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) polymerizing by emulsion polymerization 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, said polymer (C1) representing at most 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 0,000 g / mol, and the polymer powder has a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g.

[0039] In a third aspect, the present invention provides 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, Combining 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 polymer powder has a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g.

[0040] In a fourth aspect, the present invention relates to the use of a polymer composition (PC1) as an impact modifier.

[0041] In a fifth aspect, the present invention relates to the use of a polymer composition (PC1) as a composition with reduced dispersion time.

[0042] In a sixth aspect, the present invention relates to a method for reducing the time required to disperse a polymer powder in a liquid composition by using a polymer composition (PC1) in the form of a polymer powder.

[0043] In a seventh aspect, the present invention relates to a polymer composition PC2 comprising the polymer composition (PC1) as impact modifier.

[0044] In an eighth aspect, the present invention provides a method for reducing the time required to disperse a polymer composition (PC1) in a liquid composition, comprising: a) providing a polymer composition (PC1) 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:

[0045] 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 aggregation of primary polymer particles comprising one or more polymers, said primary polymer particles being in the nanometer range.

[0046] The term "primary particles" 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.

[0047] The term "particle size" as used refers to the volume average diameter of a particle considered to be spherical.

[0048] The term "thermoplastic polymer" as used refers to a polymer that when heated turns into a liquid or becomes more liquid or less viscous and can assume new shapes through the application of heat and pressure.

[0049] The term "thermoset polymer" as used herein refers to a prepolymer in a soft, solid, or viscous state that is irreversibly transformed by curing into an infusible, insoluble polymer network.

[0050] The term "polymer composite" as used herein refers to a multi-component material that includes a plurality of distinct phase domains, at least one of the phase domains being a continuous phase, and at least one component being a polymer.

[0051] The term "copolymer" is used to indicate that the polymer is made up of at least two different monomers.

[0052] The term "multi-stage polymer" as used herein refers to a polymer formed sequentially by a multi-stage polymerization process. Multi-stage emulsion polymerization processes 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, are preferred.

[0053] The term "(meth)acrylic" is used to refer to all types of acrylic and methacrylic monomers.

[0054] The term "(meth)acrylic polymer" as used means that the (meth)acrylic polymer essentially comprises a polymer containing (meth)acrylic monomers that constitute 50 wt% or more of the (meth)acrylic polymer.

[0055] The term "dry" used denotes a residual water ratio of less than 1.5 wt.%, preferably less than 1.2 wt.%.

[0056] In the present invention, a range of x and y means that the upper and lower limits of this range are included, and is equivalent to at least x and up to y.

[0057] In the present invention, when a range is stated to be between x and y, it means that the upper and lower limits of this range are excluded, and is equivalent to being greater than x and less than y.

[0058] The term "total intrusion volume" used refers to the total volume intruded by liquid mercury according to ISO 15901-1:2016. This volume is accumulated and analytical results provide the cumulative intrusion volume (cm) in ml / g as a function of applied pressure or pore diameter. 3 / g) is shown. The total indented volume is the volume indented at the maximum applied pressure, which also corresponds to the smallest pore.

[0059] The term "incremental intrusion" as used refers to 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%.

[0060] Easily dispersed in liquid resin means that a uniform dispersion is obtained. The distribution of the polymer composition (PC1) is not uniform if separation occurs after the initial homogenization.

[0061] Rapid dispersion in the liquid resin means that uniform dispersion is obtained much more quickly than with a polymer composition (PC1) that does not have the required minimum porosity.

[0062] Regarding the polymer composition (PC1) according to the invention, the polymer composition is in the form of a polymer powder, also referred to as polymer powder POW1, and comprises a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C, b) one stage (B) comprising 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, wherein at least components a) and b) of composition (PC1) are part of a multistage polymer (MP1), wherein polymer (C1) has a weight average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol, and wherein polymer composition (PC1) in the form of a polymer powder has a total intrusion volume, measured by mercury porosimetry, of at least 1.2 ml / g.

[0063] 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%, even more preferably less than 30 wt%, advantageously less than 25 wt%, and even more advantageously less than 20 wt% of the composition based on a), b) and c).

[0064] Preferably, component c) represents more than 4 wt% of the composition based on a), b) and c), more preferably, component c) represents more than 5 wt%, even more preferably, more than 6 wt%, even more preferably, more than 7 wt%, advantageously, more than 8 wt%, and even more advantageously, more than 10 wt% of the composition based on a), b) and c).

[0065] 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.

[0066] Preferably, component c) represents between 4 and 40 wt% of the composition based on a), b) and c), more preferably between 5 and 35 wt%, even more preferably between 6 and 30 wt%, even more preferably between 7 and less than 30 wt%, advantageously between 7 and less than 25 wt%, and even more advantageously between 10 and less than 20 wt% of the composition based on a), b) and c).

[0067] At least components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1).

[0068] At least components a) and b) are obtained by a multistage process comprising at least two stages (A) and (B), respectively, and these two polymers (A1) and (B1) form a multistage polymer.

[0069] Regarding the polymer powder POW1 of the invention, the polymer powder has a volume median particle size D50 between 1 μm and 700 μm. Preferably, the volume median particle size 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.

[0070] The particle size distribution by volume D10 is at least 7 μm, preferably 10 μm, more preferably 15 μm.

[0071] 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.

[0072] The porosity of a 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. This is measured according to standard ISO 15901-1: Mercury Porosity and Evaluation of Pore Size Distribution and Porosity of Solid Materials by Gas Adsorption—Part 1: Mercury Porosity. The porous polymer powder POW1 of the present 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, and 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.

[0073] 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, and most advantageously at most 4 ml / g.

[0074] The upper and lower limits given in the previous two paragraphs for the total indentation volume or total cumulative indentation of the porous polymer powder POW1 of the present invention may be combined in any combination of one upper limit and one lower limit.

[0075] Preferably, the porous polymer powder POW1 of the 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 1.35 ml / g and 6 ml / g, more advantageously between 1.35 ml / g and 5 ml / g, and most advantageously between 1.35 ml / g and 4 ml / g.

[0076] The incremental indentation (incremental indentation volume) is the volume between two specific pore diameters. The incremental indentation may also be expressed as an absolute value in ml / g, or as a relative value as a percentage of the total indentation volume or total cumulative indentation (taking into account pore size diameters between 100 μm and 0.005 μm).

[0077] Preferably, the porous polymer powder POW1 of the present invention has a cumulative indentation of at least 0.9 ml / g, more preferably at least 1 ml / g for pore sizes above 10 μm (greater than 10 μm).

[0078] Preferably, the porous polymer powder POW1 of the present invention has a relative incremental indentation for pore sizes above 10 μm (greater than 10 μm) of at most 85%, more preferably at most 82%, even more preferably at most 80%.

[0079] 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.

[0080] Preferably, the porous polymer powder POW1 of the present invention has a relative incremental indentation between pore sizes of 10 μm and 1 μm of at least 5%, more preferably at least 8%, even more preferably at least 10%.

[0081] Preferably, the porous polymer powder POW1 of the present invention has an incremental indentation between pore sizes of 10 μm and 0.1 μm of at least 0.15 ml / g, more preferably at least 0.2 ml / g, even more preferably at least 0.25 ml / g.

[0082] Preferably, the porous polymer powder POW1 of the invention has a relative incremental indentation between pore sizes of 10 μm and 0.1 μm of at least 10%, more preferably at least 15%, even more preferably at least 20%.

[0083] Preferably, the porous polymer powder POW1 of the present invention has an incremental indentation between pore sizes of 1 μm and 0.1 μm of at least 0.05 ml / g, more preferably at least 0.06 ml / g, even more preferably at least 0.07 ml / g.

[0084] Preferably, the porous polymer powder POW1 of the invention has a relative incremental indentation between pore sizes of 1 μm and 0.1 μm of at least 5%, more preferably at least 7.5%, even more preferably at least 10%.

[0085] The apparent bulk density of 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 polymer powder POW1 is 0.1 g / cm 3 Preferably, the apparent bulk density is 0.11 g / cm 3 Greater than 0.12 g / cm 3 Greater than, even more preferably 0.13 g / cm 3 Greater than.

[0087] The apparent bulk density of polymer powder POW1 is 0.1 g / cm 3 and 0.60 g / cm 3 Preferably, the apparent bulk density of the polymer powder POW1 is between 0.12 g / cm 3 and 0.45 g / cm 3 It is between.

[0088] All the different properties of the respective preferred embodiments of the porous polymer powder POW1 according to the invention can be combined.

[0089] The multi-stage polymer (MP1) of the composition (PC1) according to the invention has at least two stages (A) and (B), each comprising a polymer (A1) and a polymer (B1), respectively, which differ in polymer composition.

[0090] The multi-stage polymer (MP1) is preferably in the form of polymer particles PAR, which are considered spherical particles. These particles PAR are also called core-shell particles. The first stage forms the core, and the second or all subsequent stages form their respective shells. Such multi-stage polymers, also called core-shell particles, are preferred.

[0091] The particles PAR contained in the polymer composition (PC1) in the form of a polymer powder according to the present invention are primary particles. The particles PAR have a weight-average particle size of between 15 and 900 nm. Preferably, the weight-average particle size of the polymer particles is between 20 and 800 nm, more preferably between 25 and 600 nm, even more preferably between 30 and 550 nm, and even more preferably between 35 and 500 nm, advantageously between 40 and 400 nm, even more advantageously between 75 and 350 nm, and advantageously between 80 and 300 nm. The primary polymer particles PAR aggregate to form the polymer composition (PC1) or a part of the polymer composition (PC1) in the form of a polymer powder according to the present invention.

[0092] 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 of less than 10°C, and at least b) one stage (B) comprising a polymer (B1) having a glass transition temperature of more than 60°C.

[0093] 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.

[0094] In a second preferred embodiment, there may be another stage before stage (A) so that stage (A) is also a shell.

[0095] In a third preferred embodiment, polymer (C1) having a glass transition temperature greater than 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).

[0096] 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 multilayer structure. In other words, stage (A) comprising polymer (A1) is the core of the polymer particle.

[0097] Regarding 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 polymer (A1) being acrylic monomers.

[0098] The acrylic monomers in polymer (A1) comprise monomers selected from C1 to C18 alkyl acrylates or mixtures thereof. More preferably, the acrylic monomers in polymer (A1) comprise C2 to C12 alkyl acrylic monomers or mixtures thereof. Even more preferably, the acrylic monomers in polymer (A1) comprise C2 to C8 alkyl acrylic monomers or mixtures thereof.

[0099] Polymer (A1) may contain one or more comonomers copolymerizable with the acrylic monomer, as long as polymer (A1) has a glass transition temperature of less than 10°C.

[0100] The comonomer(s) in polymer (A1) are preferably selected from (meth)acrylic and / or vinyl monomers.

[0101] 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.

[0102] In a particular embodiment, polymer (A1) is a homopolymer of butyl acrylate.

[0103] More preferably, the glass transition temperature Tg of the polymer (A1) comprising at least 70 wt. % of polymer units derived from C2-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 even more advantageously between -70°C and -20°C.

[0104] 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 multilayer structure. In other words, stage (A) comprising polymer (A1) is the core of the polymer particle.

[0105] As examples, 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, or a copolymer of butadiene with up to 98 wt% of a vinyl monomer. The vinyl monomer may be styrene, alkylstyrene, acrylonitrile, alkyl (meth)acrylate, or butadiene or isoprene. In a preferred embodiment, the core is a butadiene homopolymer.

[0106] 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.

[0107] 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 even more advantageously between -135°C and -25°C.

[0108] The polymer (A1) having a glass transition temperature of less than 10° C. comprises polymerized monomer units. The polymer (A1) in general, and the polymer (A1) of each of the first, second and third preferred embodiments, comprises the respective monomer or monomer mixture (A1) from which the monomer units constituting the polymer (A1) are derived. m ) is prepared from

[0109] As regards the polymer (B1), mention may be made of homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers.Preferably, the polymer (B1) is a (meth)acrylic polymer.

[0110] Preferably, polymer (B1) comprises at least 70 wt.% of monomers selected from C1-C12 alkyl (meth)acrylates. Even more preferably, polymer (B1) comprises at least 80 wt.% of monomers C1-C4 alkyl methacrylate and / or C1-C8 alkyl acrylate monomers.

[0111] Most preferably, the acrylic or methacrylic monomers of polymer (B1) are selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as polymer (B1) has a glass transition temperature of at least 60°C.

[0112] Advantageously, polymer (B1) comprises at least 70% by weight of monomer units derived from methyl methacrylate.

[0113] Preferably, the glass transition temperature Tg of polymer (B1) is between 60° C. and 150° C. The glass transition temperature of polymer (B1) is more preferably between 80° C. and 150° C., advantageously between 90° C. and 150° C., and even more advantageously between 100° C. and 150° C.

[0114] Preferably, polymer (B1) is grafted onto the polymer prepared in the previous step.

[0115] In a particular embodiment, the polymer (B1) is crosslinked.

[0116] In one embodiment, polymer (B1) comprises a functional comonomer selected from acrylic or methacrylic acid, amides derived from this acid, such as dimethylacrylamide, 2-methoxy-ethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or methacrylate, polyethylene glycol (meth)acrylate, water-soluble vinyl monomers, such as N-vinylpyrrolidone, or mixtures thereof. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0117] The polymer (B1) having a glass transition temperature of at least 60° C. comprises polymerized monomer units. The polymer (B1) in general and in each embodiment comprises the respective monomer or monomer mixture (B1) from which the monomer units constituting the polymer (B1) are derived.m ) is prepared from

[0118] With regard to polymer (C1), the polymer has a weight average molecular weight Mw between 10 000 g / mol and 500 000 g / mol.

[0119] The polymer (C1) has a weight average molecular weight Mw of 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, even more advantageously greater than 15 000 g / mol.

[0120] The polymer (C1) has a weight 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, even more advantageously less than 250,000 g / mol and most advantageously less than 200,000 g / mol.

[0121] Preferably, the weight average molecular weight Mw of polymer (C1) is between 10,500 g / mol and 450,000 g / mol, more preferably between 11,000 g / mol and 400,000 g / mol, 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.

[0122] In a first advantageous embodiment, the weight-average molecular weight Mw of the (meth)acrylic polymer MP1 is between 10,500 g / mol and 200,000 g / mol, more preferably between 11,000 g / mol and 190,000 g / mol, 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.

[0123] In a second advantageous embodiment, the weight-average molecular weight Mw of the (meth)acrylic polymer MP1 is between 15,000 g / mol and 450,000 g / mol, more preferably between 16,000 g / mol and 400,000 g / mol, 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.

[0124] Preferably, polymer (C1) is a copolymer comprising (meth)acrylic monomers. More preferably, polymer (C1) is a (meth)acrylic polymer. Even more preferably, polymer (C1) comprises at least 70 wt. % of monomers selected from C1-C12 alkyl (meth)acrylates. Advantageously, polymer (C1) comprises at least 80 wt. % of monomers C1-C4 alkyl methacrylate and / or C1-C8 alkyl acrylate monomers.

[0125] Preferably, the glass transition temperature Tg of polymer (C1) is between 30° C. and 150° C. The glass transition temperature of polymer (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.

[0126] Preferably, the polymer (C1) is not crosslinked.

[0127] Preferably, polymer (C1), especially when part of multi-stage polymer (MP1), is not grafted to either polymer (A1) or (B1), whereby not grafted means that at least 50 wt % of polymer (C1) in multi-stage polymer (MP1) can be solubilized in the solvent for polymer (C1).

[0128] In one embodiment, the polymer (C1) also comprises a functional comonomer.

[0129] The functional comonomer is represented by the formula (1): I have TIFF2026035638000001.tif35170.

[0130] wherein R1 is selected from H or CH3, and R2 is H or an aliphatic or aromatic group having at least one atom that is not C or H.

[0131] Preferably, the functional monomer is selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids, such as dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or methacrylate, polyethylene glycol (meth)acrylate, etc. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0132] In a first preferred embodiment, the polymer (C1) comprises 80% to 100% by weight of methyl methacrylate, preferably 80% to 99.9% by weight of methyl methacrylate, and 0.1% to 20% by weight of a C1-C8 alkyl acrylate monomer. Advantageously, the C1-C8 alkyl acrylate monomer is chosen from methyl acrylate, ethyl acrylate or butyl acrylate.

[0133] In a second preferred embodiment, the polymer (C1) comprises between 0 and 50 wt% of functional monomers. Preferably, the meth)acrylic polymer (C1) comprises between 0 and 30 wt%, more preferably between 1 and 30 wt%, even more preferably between 2 and 30 wt%, advantageously between 3 and 30 wt%, more advantageously between 5 and 30 wt%, and most advantageously between 5 and 30 wt% of functional monomers.

[0134] Preferably, the functional monomer of the second preferred embodiment is a (meth)acrylic monomer. The functional monomer is represented by formula (2) or (3): I have TIFF2026035638000002.tif62170.

[0135] wherein in both formulas (2) and (3), R1 is selected from H or CH3; in formula (2), Y is O and R5 is H or an aliphatic or aromatic group having at least one atom that is not C or H; and in formula (3), Y is N and R4 and / or R3 are H or an aliphatic or aromatic group.

[0136] Preferably, the functional monomer (2) or (3) is selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids, such as dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or methacrylate, acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkylimidazolidinone (meth)acrylates, polyethylene glycol (meth)acrylates, etc. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0137] The polymer (C1) having a glass transition temperature of at least 30° C. comprises polymerized monomer units. The polymer (C1) in general and in each embodiment comprises the respective monomer or monomer mixture (C1) from which the monomer units constituting the polymer (C1) are derived. m ) is prepared from

[0138] All the different properties of the respective preferred embodiments of the polymers (A1), (B1) and (C1) may be combined in any combination.

[0139] The multi-stage polymer (MP1) is obtained by a multi-stage process comprising at least two stages. At least components a) and b) of composition (PC1) are part of the multi-stage polymer (MP1).

[0140] Preferably, the polymer (A1) having a glass transition temperature of less than 10° C. made in stage (A) is made before stage (B) or is the first stage of a multi-stage process.

[0141] Preferably, the polymer (B1) having a glass transition temperature above 60° C. produced in stage (B) is produced after stage (A) of the multi-stage process.

[0142] In a first preferred embodiment, the polymer (B1) having a glass transition temperature of at least 60° C. is the intermediate layer of polymer particles having a multilayer structure.

[0143] In this first preferred embodiment, the polymer (C1) having a glass transition temperature higher than 30° C. produced in stage (C) is produced after stage (B) of the multi-stage process.

[0144] More preferably, the polymer (C1) having a glass transition temperature higher than 30° C. made in stage (C) is a multistage polymer (MP1) having a multilayer structure or the outer layer of a primary polymer particle.

[0145] There may be further intermediate stages either between stage (A) and stage (B) and / or between stage (B) and stage (C).

[0146] Polymer (C1) and polymer (B1) are not the same polymer, even though their compositions are very close and some of their properties overlap. The essential difference is that polymer (B1) is always part of a multistage polymer (MP1).

[0147] This is further illustrated by a process for preparing a polymer composition (PC1) according to the invention comprising a polymer (C1) and a multistage polymer (MP1).

[0148] The weight fraction r of polymer (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%.

[0149] According to the invention, the ratio r of the outer stage (C) comprising polymer (C1), relative to the complete polymer particle, is at most 40 wt.%.

[0150] Preferably, the proportion of polymer (C1) taken into account in the primary polymer particles is between 5 wt% and 30 wt%, preferably between 5 wt% and 20 wt%.

[0151] In a second preferred embodiment, the polymer (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).

[0152] Preferably, at least a portion of the polymer (B1) of layer (B) is grafted onto the polymer produced in the previous layer. When only two stages (A) and (B) containing polymers (A1) and (B1), respectively, are present, a portion of the polymer (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 polymer (B1) with a solvent and determining the non-grafted amount by weighing before and after extraction.

[0153] The glass transition temperature Tg of each polymer can be estimated by dynamic methods such as thermomechanical analysis.

[0154] To obtain samples of each of the polymers (A1), (B1) and (C1), they are prepared singly and without a multi-stage process, so that the individual glass transition temperatures Tg of each polymer in each stage can be more easily estimated and measured. Polymer (C1) may be extracted to estimate and measure its glass transition temperature Tg.

[0155] Preferably, the polymer compositions of the present invention are solvent-free. By solvent-free, we mean that the solvent ultimately present constitutes less than 1 wt% of the composition. Monomers in the synthesis of each polymer are not considered solvents. Residual monomers in the composition constitute less than 2 wt% of the composition.

[0156] Preferably, the polymer composition according to the present invention is dry, meaning that the polymer composition according to the present invention contains less than 3 wt% moisture, preferably less than 1.5 wt% moisture, more preferably less than 1.2 wt% moisture.

[0157] The moisture content may be measured by a thermobalance, which heats the polymer composition and measures the weight loss.

[0158] The compositions according to the present invention do not contain any voluntarily added solvents. The final residual monomers and water from the polymerization of the respective monomers are not considered solvents.

[0159] The polymer composition (PC1) in the form of polymer powder POW1 of the present invention comprises polymer particles PAR. When multiple different types of particles are present, these are referred to as PAR1, PAR2, etc. 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%, and even more preferably at least 70 wt% of the polymer powder composition POW1.

[0160] In a first preferred embodiment, the polymer composition (PC1) in the form of a polymer powder POW1 according to the invention consists solely of polymer particles PAR1, which consist of a multistage polymer (MP1) comprising components a), b) and c).

[0161] In a second preferred embodiment, the polymer composition (PC1) in the form of a polymer powder POW1 according to the invention comprises at least 60 wt. % of polymer particles PAR1, which consist of a multistage polymer (MP1) comprising at least components a) and b).

[0162] In a third preferred embodiment, the polymer composition (PC1) in the form of a polymer powder POW1 according to the invention comprises polymer particles PAR1, which consist of a multistage polymer (MP1) comprising components a), b) and c).

[0163] In a fourth preferred embodiment, the polymer composition (PC1) in the form of a polymer powder POW1 according to the invention comprises two different types of particles PAR1 and PAR2. The polymer particles PAR1 consist of a multistage polymer (MP1) comprising components a) and b). The polymer particles PAR2 comprise or consist of a polymer (C1).

[0164] Regarding the first preferred method for producing the polymer composition (PC1) according to the invention, the method 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) solidifying the composition obtained in steps a) to c). Includes:

[0165] Preferably, step a) is carried out before step b).

[0166] More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a).

[0167] 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) solidifying the composition obtained in steps a) to c). It is a multi-step process that includes the steps of:

[0168] 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.

[0169] the respective monomers or monomer mixtures (A1), (B1) and (C1) for forming the layers in stages (A), (B) and (C), respectively, containing polymers (A1), (B1) and (C1), m ), (B m ) and (C m ) is as defined above. m ), (B m ) and (C m ) includes each monomer as a polymerized monomer unit in the polymer chain of each polymer (A1), (B1), and (C1). The properties of polymers (A1), (B1), and (C1) are each the same as defined above.

[0170] Regarding the second preferred method for producing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer (MP1), the method 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, Combining 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) solidifying the composition obtained in steps a) to c). Includes:

[0171] 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.

[0172] Regarding the third preferred method for producing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer (MP1), the method comprises: 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) solidifying 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.

[0173] Preferably, the multi-stage polymer (MP1) and polymer (C1) are already prepared as aqueous dispersions.

[0174] 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 on the solid portion alone in the resulting mixture is at least 60 wt%, preferably at least 65 wt%, more preferably at least 68 wt%, advantageously at least 70 wt%.

[0175] 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 on the solid portion alone in the resulting mixture is at most 99 wt%, preferably at most 95 wt%, more preferably at most 90 wt%.

[0176] The amounts of aqueous dispersion of polymer (C1) and aqueous dispersion of multistage polymer are selected so that the weight ratio of multistage polymer based on the solid portion alone 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%.

[0177] 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).

[0178] The aqueous composition comprising the multistage 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%, and advantageously less than 32 wt%.

[0179] The solids content is measured or estimated gravimetrically by weighing before and after complete evaporation of the water.

[0180] In a first preferred embodiment, the solids content of the aqueous composition comprising the multistage polymer (MP1) and the 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%.

[0181] In a second preferred embodiment, the solids content of the aqueous composition comprising multistage 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%.

[0182] In a third preferred embodiment, the solids content of the aqueous composition comprising multistage 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%.

[0183] In a fourth preferred embodiment, the solids content of the aqueous composition comprising the multistage polymer (MP1) and the 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%.

[0184] 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%.

[0185] Coagulation may be carried out by means of a salt or an inorganic acid.

[0186] In a first preferred embodiment, the coagulation is carried out by means of an inorganic acid.

[0187] The process for producing the polymer composition (PC1) according to the invention may optionally comprise a further step e) of drying the polymer composition.

[0188] 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 wt. % humidity or water.

[0189] The moisture content of the polymer composition may be measured with a thermobalance.

[0190] Drying of the polymer may be carried out in an oven or vacuum oven while heating the composition at 50° C. for 48 hours.

[0191] The liquid composition LC1 of the eighth aspect of the present 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, preferably less than 0.5 mPa * s and 1000 Pa * The dynamic viscosity is measured at a shear rate of 1 1 / sec.

[0192] 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 monomer or a (meth)acrylic monomer, or a mixture thereof or a liquid composition comprising said monomers.

[0193] Preferably, the polymer composition (PC1) comprises between 0.5 and 50 wt % of the composition comprising the liquid composition LC1 and the polymer composition (PC1).

[0194] 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.

[0195] In a first preferred embodiment, the method for reducing the dispersion time comprises the steps of providing a precursor of a thermosetting polymer or a monomer of a thermoplastic polymer, and contacting said precursor with a polymer composition (PC1).

[0196] In a second preferred embodiment, the method for reducing dispersion time comprises providing a polymer composition (PC1) in the form of a polymer powder having a total indentation volume, measured at least by mercury porosimetry, of at least 1.2 ml / g.

[0197] In the second preferred embodiment, the method also optionally includes providing a precursor of a thermosetting polymer or a monomer of a thermoplastic polymer. Preferably, the precursor is a liquid. More preferably, the precursor has a viscosity between 0.5 mPas and 1000 Pas at a temperature of 25°C. * The viscosity is the dynamic viscosity.

[0198] In a second preferred embodiment, the method for reducing the dispersion time also comprises the step of contacting said precursor with a polymer composition (PC1) optionally in the form of a polymer powder. Preferably, between 0.5 and 100 parts by weight of polymer composition (PC1) in the form of a polymer powder is contacted with 100 parts by weight of said precursor.

[0199] The polymer composition (PC2) may be a thermoset polymer or a precursor thereof, or a thermoplastic polymer. The polymer composition PC2 may also be an adhesive, more preferably a structural adhesive.

[0200] [Evaluation method] Glass transition temperature The glass transition (Tg) of a polymer is measured using an instrument capable of performing thermomechanical analysis. The RDAII "RHEOMETRICS DYNAMIC ANALYSER" provided by Rheometrics was used. Thermomechanical analysis accurately 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 maintaining constant strain. 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.

[0201] 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.

[0202] 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 weight 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 weight-average powder particle size, particle size distribution, and fine particle ratio.

[0203] For the dispersion test, a sample of each powder is dispersed in a liquid composition. The results of the dispersion test are indicated by ++ and - symbols. This indicates how quickly and easily the powder disperses in the liquid composition. A - symbol indicates poor dispersion; the powder remains separated after the dispersion test and may either float, settle, or undergo other phase separation. A + or ++ symbol indicates good or very good immediate dispersion. In this example, monomer methyl methacrylate (MMA) is used as the liquid composition. 1 g of each powder is added to a glass container containing 99 g of MMA at 25°C. The mixture is observed after 60 seconds without stirring to determine whether the powder disperses or does not.

[0204] Apparent Density

[0205] Standard ISO 60:1977 is used. The sample is purified 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.

[0206] viscosity

[0207] Viscosity can be easily measured with a rheometer or viscometer. Dynamic viscosity is measured at 25°C. If a 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 a liquid composition has non-Newtonian behavior, it means that there is shear thinning, and the dynamic viscosity is less than 1 s at 25°C. -1 It is measured at a shear rate of .

Claims

1. a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C; b) one stage (B) comprising 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); A polymer composition (PC1) in the form of a polymer powder comprising: A polymer composition characterized in that at least components a) and b) of composition (PC1) are part of a multistage polymer (MP1), and that polymer (C1) has a weight average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol, and that polymer composition (PC1) in the form of a polymer powder has a total indentation volume, measured by mercury porosimetry, of at least 1.2 ml / g.

2. 2. The polymer composition of claim 1, characterized in that it has a total intrusion volume of at least 1.35 ml / g as measured by mercury porosimetry.

3. 3. Polymer composition according to claim 1 or 2, characterized in that it has a total intrusion volume of at most 10 ml / g, as measured by mercury porosimetry.

4. 2. Polymer composition (PC1) according to claim 1, characterized in that it has a total intrusion volume 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 1.35 ml / g and 6 ml / g, more advantageously between 1.35 ml / g and 5 ml / g, and most advantageously between 1.35 ml / g and 4 ml / g.

5. 5. Polymer composition (PC1) according to any one of claims 1 to 4, characterized in that the relative incremental indentation of the polymer powder for pore sizes above 10 μm is up to 85%.

6. 3. Polymer composition (PC1) according to claim 1 or 2, characterized in that the incremental indentation of the polymer powder between pore sizes of 10 μm and 1 μm is at least 0.1 ml / g, more preferably at least 0.12 ml / g, even more preferably at least 0.15 ml / g.

7. 3. Polymer composition (PC1) according to claim 1 or 2, characterized in that the incremental indentation of the polymer powder between pore sizes of 10 μm and 0.1 μm is at least 0.15 ml / g, more preferably at least 0.2 ml / g, even more preferably at least 0.25 ml / g.

8. 3. Polymer composition according to claim 1 or 2, characterized in that the relative incremental indentation between pore sizes of 10 μm and 1 μm is at least 5%, more preferably at least 8%, even more preferably at least 10%.

9. 9. Polymer composition (PC1) according to any one of claims 1 to 8, characterized in that the polymer powder has a volume median particle size D50 between 1 μm and 700 μm.

10. The apparent bulk density of the polymer powder is 0.1 g / cm ３ and 0.60 g / cm ３ 9. Polymer composition (PC1) according to any one of claims 1 to 8, characterized in that it is between

11. 8. The polymer composition according to claim 1, wherein the polymer composition (PC1) or the polymer powder composition POW1 in the form of a polymer powder according to the invention comprises polymer particles PAR that constitute at least 50 wt. % of the polymer composition (PC1) or the polymer powder composition POW1 in the form of a polymer powder composition.

12. 12. The polymer composition according to claim 11, characterized in that the polymer particles PAR have a weight average particle size (diameter) between 15 nm and 900 nm.

13. 13. A polymer composition according to any one of claims 1 to 12, characterized in that stage (A) is the first stage and stage (B) comprising polymer (B1) is grafted to stage (A) comprising polymer (A1).

14. 14. The polymer composition according to claim 1, wherein the polymers (B1) and (C1) are acrylic or (meth)acrylic polymers.

15. 15. Polymer composition according to any one of claims 1 to 14, characterized in that the polymer (A1) comprises butadiene as a monomer.

16. 15. Polymer composition according to any one of claims 1 to 14, characterized in that the polymers (A1), (B1) and (C1) are acrylic or (meth)acrylic polymers.

17. 17. The polymer composition according to claim 14 or 16, characterized in that at least 80 wt. % of the acrylic or methacrylic monomers of polymer (A1), (B1) or (C1) are selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof.

18. 18. A method for producing a polymer composition according to any one of claims 1 to 17, 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., d) solidifying the composition obtained in steps a) to c). A method comprising:

19. A process for producing a polymer composition (PC1) according to any one of claims 1 to 17, 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, 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; d) solidifying the composition obtained in steps a) to c). A method comprising:

20. 20. The method according to claim 18 or 19, characterized in that step a) is carried out before step b).

21. 21. The process according to any one of claims 18 to 20, characterized in that step b) is carried out in the presence of the polymer (A1) obtained in step a).

22. 20. The method according to claim 18 or 19, characterized in that steps a), b), c) and d) are carried out in that order.

23. 23. The method according to any one of claims 18 to 22, characterized in that the solids content before the onset of solidification is less than 35 wt%.

24. 23. The method according to any one of claims 18 to 22, characterized in that the solids content before the onset of solidification is less than 32 wt%.

25. 23. The method according to any one of claims 18 to 22, characterized in that in step d) the solids content before the onset of solidification is between 5 wt% and 35 wt%.

26. 23. The method according to any one of claims 18 to 22, characterized in that in step d) the solids content before the onset of solidification is between 20 and 35 wt%.

27. 23. The method according to any one of claims 18 to 22, characterized in that in step d) the solids content before the onset of solidification is between 5 wt. % and 20 wt. %.

28. 23. The method according to any one of claims 18 to 22, characterized in that in step d) the solids content before the onset of solidification is between 10 wt. % and 25 wt. %.

29. 23. The method according to any one of claims 18 to 22, characterized in that in step d) the solids content before the onset of solidification is between 15 wt% and 27 wt%.

30. 30. The method according to any one of claims 18 to 29, characterized in that in step d) the coagulation is carried out by means of a salt or an inorganic acid.

31. 31. The method according to any one of claims 18 to 30, further comprising a drying step e).

32. 32. Use of a polymer composition (PC1) according to any one of claims 1 to 17 or obtainable by the process according to any one of claims 18 to 31 as an impact modifier.

33. 18. Use of a polymer composition (PC1) according to any one of claims 1 to 17 as a composition with reduced dispersion time.

34. 18. A method for reducing the time for dispersing a polymer powder in a liquid composition by using a polymer composition (PC1) according to any one of claims 1 to 17.

35. - providing a precursor of a thermosetting polymer or a monomer of a thermoplastic polymer, - contacting said precursor with a polymer composition (PC1) 35. The method of claim 34, comprising:

36. A method for reducing the time required to disperse a polymer composition (PC1) in a liquid composition, comprising: a) providing a polymer composition (PC1) 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 with a liquid composition LCl A method comprising:

37. 37. The method according to claim 36, characterized in that the liquid composition LC1 is selected from compositions for preparing vinyl ester, unsaturated polyester or epoxy resins, or the liquid composition LC1 can be, for example, a styrene-based or (meth)acrylic monomer, or a mixture thereof or a liquid composition comprising said monomers.

38. 38. The method according to claim 36 or 37, characterized in that the polymer composition (PC1) accounts for between 0.5 and 50 wt % of the composition comprising the liquid composition LC1 and the polymer composition (PC1).

39. Polymer composition PC2, which comprises the polymer composition (PC1) as an impact modifier.

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