Composition comprising a multi-stage polymer and a (meth)acrylic polymer, method for preparing same, and uses thereof

Abstract

The present invention relates to a composition in the form of a porous polymer powder comprising a multi-stage polymer and a (meth)acrylic polymer, a method for its preparation, and its use. Specifically, the present invention relates to a composition in the form of a porous polymer powder comprising a multi-stage polymer in the form of polymer particles made by a multi-stage method and a (meth)acrylic polymer, wherein the (meth)acrylic polymer has a medium molecular weight. More specifically, the present invention relates to a polymer composition in the form of a porous polymer powder comprising polymer particles prepared by a multi-stage method including at least two stages and a (meth)acrylic polymer, a method for its preparation, its use, and compositions and articles comprising the same.

Description

Field of the Invention

[0001] The present invention relates to a composition in the form of a porous polymer powder comprising a multi-stage polymer and a (meth)acrylic polymer, a method for preparing the same, and uses thereof.

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

[0003] More specifically, the present invention relates to a polymer composition in the form of a porous polymer powder comprising polymer particles prepared by a multi-stage method including at least two stages and a (meth)acrylic polymer, a method for preparing the same, uses thereof, and compositions and articles comprising the same.

[0004] Technical Problem

[0005] Polymers are also widely used as additives in polymer compositions. These so-called polymer additives are usually added to solid polymers, or to molten polymers, or to liquid resins or liquid compositions in the form of particulate matter or powder.

[0006] One class of polymer additives is processing aids, and another class is polymer impact modifiers.

[0007] Polymer impact modifiers can be in the form of polymer particles. Usually these polymer impact modifiers are in the form of core-shell particles prepared by a multi-stage method, wherein at least one stage comprises a rubbery polymer. These particles are then introduced into a polymer or polymer composition to increase its impact resistance. The polymer or polymer composition can be thermosetting or thermoplastic.

[0008] Thermosetting polymers are composed of a crosslinked three-dimensional structure. Crosslinking is obtained by curing reactive groups inside a so-called prepolymer. Curing can be obtained, for example, by heating the polymer chains or prepolymer so as to permanently crosslink and harden the material.

[0009] Thermoplastic polymers are composed of straight-chain or branched polymers that are usually not crosslinked. There can be slight crosslinking as long as they can be deformed by heat. However, these aforementioned core-shell particles are not easily dispersed or quickly dispersed in all types of resins or polymers or polymer precursors, especially, for example, dispersed in liquid epoxy resins or liquid monomers or other liquid polymer precursors.

[0010] In order for the final polymer composition to have satisfactory impact properties, good uniform and rapid dispersion is necessary. In order to reduce the process time and obtain an easier and simpler method, easy preparation of the dispersion system and rapid dispersion time are also required.

[0011] One object of the present invention is to provide a polymer composition in the form of a polymer powder that can be rapidly and easily dispersed, especially in a liquid resin, such as in a precursor of a thermosetting polymer or a thermoplastic polymer, for example in an epoxy resin or a (meth)acrylic monomer, and also in a polymer melt.

[0012] Another object of the present invention is to provide a polymer composition in the form of a dry polymer powder that can be easily dispersed, especially in a liquid resin, such as in an epoxy resin or a (meth)acrylic monomer, and also in a polymer melt.

[0013] Another object of the present invention is to provide a multi-stage polymer composition in the form of a polymer powder that can be easily dispersed in a reactive epoxy resin, a polyester resin, or a (meth)acrylic resin / polymer or a liquid monomer or resin.

[0014] Another object of the present invention is to provide a multi-stage polymer composition in the form of a dry polymer powder that can be easily dispersed in a reactive epoxy resin, a polyester resin, or a (meth)acrylic resin / polymer or a liquid monomer or resin, and also in a polymer melt.

[0015] Another object of the present invention is to provide a method for preparing a multi-stage polymer composition in the form of a polymer powder, which polymer composition can be easily dispersed in a reactive epoxy resin, a polyester resin, or a (meth)acrylic resin / polymer or a liquid monomer or resin, and also in a polymer melt.

[0016] A further object of the present invention is to provide a method for preparing a dry multi-stage polymer composition in the form of a polymer powder, which polymer composition can be easily dispersed in a reactive epoxy resin, a polyester resin, or a (meth)acrylic resin / polymer or a liquid monomer or resin, and also in a polymer melt.

[0017] A further additional object is to provide an impact-modified cured resin or adhesive composition having satisfactory impact properties.

[0018] A further additional 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 a precursor of a thermosetting polymer or a thermoplastic polymer, such as a liquid reactive epoxy resin or a (meth)acrylic monomer, in which the polymer composition is dispersed.

[0019] A further object is to reduce the dispersion time of the polymer powder in such a liquid composition.

[0020] A further additional object is to provide an impact modifier in the form of a polymer powder which can be rapidly and easily dispersed, in particular in a liquid resin, such as in a precursor of a thermosetting polymer or a thermoplastic polymer, such as an epoxy resin or a (meth)acrylic monomer.

[0021] Background of the Invention - Prior Art

[0022] Document WO2016 / 102666 discloses a composition comprising a multi-stage polymer and a method for its preparation. The composition further comprises a (meth)acrylic polymer having a weight-average molecular weight of less than 100,000 g / mol.

[0023] Document WO2016 / 102682 discloses a multi-stage polymer composition and a method for its preparation. The multi-stage polymer comprises a last stage containing a (meth)acrylic polymer having a weight-average molecular weight of less than 100,000 g / mol.

[0024] Document FR 2934866 discloses the preparation of a polymer of a specific core-shell polymer which has a functional shell containing a hydrophilic monomer. The core-shell polymer is used as an impact modifier in a thermosetting polymer.

[0025] Document EP 1632533 describes a method for producing a modified epoxy resin. The epoxy resin composition has rubber-like polymer particles dispersed therein by a method of contacting the particles with an organic medium in which the rubber particles are dispersed.

[0026] Document EP 1666519 discloses a method for producing rubber-like polymer particles and a method for producing a resin composition containing the rubber-like polymer particles.

[0027] Document EP 2123711 discloses a thermosetting resin composition having rubber-like polymer particles dispersed therein and a method for its production.

[0028] Document EP 0066382A1 discloses impact modifier particles which are flowable in bulk. The agglomerated impact modifier particles are coated or agglomerated with a hard non-elastomeric high molecular weight polymer. The hard non-elastomeric high molecular weight polymer has a viscosity-average molecular weight preferably higher than 800,000, and its weight ratio is between 0.1 and 10% by weight.

[0029] Document WO2019 / 012052 discloses a composition comprising a multi-stage polymer and a method for its preparation. The composition further comprises a (meth)acrylic polymer having a weight-average molecular weight between 100,000 g / mol and 1,000,000 g / mol.

[0030] Document WO2019 / 011984 discloses a curable resin composition. The curable polymer resin composition comprises: i. a resin system comprising at least one resin component, ii. a curing agent system, and iii. a particle system comprising multi-stage polymer particles containing a polymer composition (PCI), wherein the polymer composition (PCI) comprises: a) a stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10 °C, b) a 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 component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), and wherein the polymer (C1) has a weight average molecular weight Mw of at least 100,000 g / mol, and component c) accounts for at most 40% by weight based on the total weight of the composition.

[0031] The prior art documents do not disclose a powder composition in powder form comprising a combination of a multi-stage polymer and a (meth)acrylic polymer or a method for preparing the same, which powder composition has a porosity expressed as a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry. Summary of the Invention

[0033] Surprisingly, a polymer composition (PC1) in the form of a polymer powder has been found, which comprises:

[0034] a) a stage (A) comprising a polymer (A1) having a glass transition temperature below 10 °C,

[0035] b) a stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C, and

[0036] c) and a polymer (C1) having a glass transition temperature of at least 30 °C, wherein the polymer (C1) accounts for at most 40% by weight based on the composition of only a), b) and c), wherein at least component a) and component b) of the composition (PC1) are part of a multi-stage polymer (MP1), and wherein the polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and wherein the polymer powder has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry; the polymer composition (PC1) can be easily and rapidly dispersed in a polymer matrix material of a thermosetting polymer or a thermoplastic polymer or their respective precursors such as liquid resins and / or monomers.

[0037] Surprisingly, a method for preparing a polymer composition (PC1) in the form of a polymer powder has also been found, which comprises the following steps:

[0038] a) polymerizing a monomer or monomer mixture (A m ) by emulsion polymerization to obtain a layer of grade (A) comprising a polymer (A1) having a glass transition temperature below 10 °C;

[0039] b) polymerizing a monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer of grade (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C;

[0040] c) polymerizing a monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer of grade (C) comprising a polymer (C1) having a glass transition temperature of at least 30 °C, such that the polymer (C1) accounts for at most 40% by weight of the composition based on only a), b) and c);

[0041] d) coagulating the composition obtained in steps a) to c);

[0042] characterized in that the polymer (C1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol; and producing a polymer composition in the form of a polymer powder, which has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry and which is easily dispersible in a polymer matrix material of a thermosetting polymer or a thermoplastic polymer or their respective precursors such as liquid resins and / or monomers.

[0043] Surprisingly, it has also been found a method for preparing a polymer composition (PC1) in the form of a polymer powder, which comprises the following steps:

[0044] a) polymerizing a monomer or monomer mixture (A m ) by emulsion polymerization to obtain a layer of grade (A) comprising a polymer (A1) having a glass transition temperature below 10 °C;

[0045] b) polymerizing a monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer of grade (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C;

[0046] Both steps a) and b) together produce a multi-stage polymer (MP1), and step

[0047] c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30 °C, the polymer (C1) accounting for at most 40% by weight of the composition based on only a), b) and c);

[0048] d) Coagulate the composition obtained in steps a) to c).

[0049] It is characterized in that the polymer (C1) has a weight-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol; a polymer composition in the form of a polymer powder is produced, which has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry and is easily dispersed in a polymer matrix material of a thermosetting polymer or a thermoplastic polymer or their respective precursors such as liquid resins and / or monomers.

[0050] Surprisingly, a method for preparing a liquid polymer composition LPC1 has also been found, which comprises the following steps:

[0051] a) Provide a polymer composition (PC1) in the form of a porous polymer powder, which has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry,

[0052] b) Bring the polymer composition (PC1) into contact with a liquid composition LC1,

[0053] to produce a liquid polymer composition, wherein the polymer composition POW1 is uniformly and rapidly dispersed in the liquid composition LC1. Surprisingly, a polymer composition (PC1) in the form of a porous polymer powder POW1 has also been found, which has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry and can be used to prepare a liquid polymer composition or a prepolymer composition.

[0054] Surprisingly, a polymer composition (PC1) in the form of a porous polymer powder POW1 has also been found, which has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry and can be used to reduce the time for dispersing the porous polymer powder POW1 in order to obtain a liquid polymer composition or a prepolymer composition.

[0055] Surprisingly, an additional method for reducing the dispersion time of a polymer composition (PC1) in a liquid composition has also been found, which comprises the following steps:

[0056] a) Provide a polymer composition (PC1) in the form of a porous polymer powder POW1, which has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry,

[0057] b) Bring the polymer composition (PC1) into contact with a liquid composition LC1,

[0058] This method is faster than the same method using a polymer composition in the form of a polymer powder with a lower total intrusion volume measured by mercury porosimetry. Detailed Description of the Invention

[0060] According to a first aspect, the present invention relates to a polymer composition (PC1) in the form of a polymer powder, which comprises:

[0061] a) a fraction (A) which comprises a polymer (A1) having a glass transition temperature below 10 °C,

[0062] b) a fraction (B) which comprises a polymer (B1) having a glass transition temperature of at least 60 °C, and

[0063] c) and a polymer (C1) having a glass transition temperature of at least 30 °C, said polymer (C1) representing at most 40% by weight of the composition based only on a), b) and c), characterized in that at least component a) and component b) of the composition (PC1) are part of a multi-stage polymer (MP1), and characterized in that 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 intrusion volume of at least 1.2 ml / g measured by mercury porosimetry.

[0064] According to a second aspect, the present invention relates to a method for preparing a polymer composition (PC1), which comprises the following steps:

[0065] a) polymerizing a monomer or a monomer mixture (A m ) by emulsion polymerization to obtain a layer of a fraction (A) comprising a polymer (A1) having a glass transition temperature below 10 °C;

[0066] b) polymerizing a monomer or a monomer mixture (B m ) by emulsion polymerization to obtain a layer of a fraction (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C;

[0067] c) polymerizing a monomer or a monomer mixture (C m ) by emulsion polymerization to obtain a layer of a fraction (C) comprising a polymer (C1) having a glass transition temperature of at least 30 °C, said polymer (C1) representing at most 40% by weight of the composition based only on a), b) and c);

[0068] d) coagulating the composition obtained in steps a) to c);

[0069] characterized in that 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 intrusion volume of at least 1.2 ml / g measured by mercury porosimetry.

[0070] In a third aspect, the present invention relates to a method for preparing a polymer composition (PC1), which comprises the following steps:

[0071] a) polymerizing a monomer or a monomer mixture (A m ) by emulsion polymerization to obtain a layer of stage (A) comprising a polymer (A1) having a glass transition temperature below 10 °C,

[0072] b) polymerizing a monomer or a monomer mixture (B m ) by emulsion polymerization to obtain a layer of stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C,

[0073] Both step a) and step b) together produce a multi-stage polymer (MP1), and step

[0074] c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30 °C, wherein the polymer (C1) accounts for at most 40% by weight of the composition based on only a), b) and c);

[0075] d) coagulating the composition obtained in steps a) to c);

[0076] characterized in that 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 intrusion volume of at least 1.2 ml / g measured by mercury porosimetry.

[0077] In a fourth aspect, the present invention relates to the use of the polymer composition (PC1) as an impact modifier.

[0078] In a fifth aspect, the present invention relates to the use of the polymer composition (PC1) as a composition for reducing the dispersion time.

[0079] In a sixth aspect, the present invention relates to a method for reducing the dispersion time of a polymer powder in a liquid composition by using the polymer composition (PC1) in the form of a polymer powder.

[0080] In a seventh aspect, the present invention relates to a polymer composition PC2 comprising the polymer composition (PC1) as an impact modifier.

[0081] In an eighth aspect, the present invention relates to a method for reducing the dispersion time of a polymer composition (PC1) in a liquid composition, which comprises the following steps:

[0082] a) providing a polymer composition (PC1) in the form of a porous polymer powder POW1, which has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry,

[0083] b) Contact the polymer composition (PC1) with the liquid composition LC1.

[0084] The term "polymer powder" as used herein refers to a powder form of a polymer comprising powder particles in the range of at least 1 μm, said powder particles being obtained by agglomeration of primary polymer particles comprising one or more polymers, said primary polymer particles being in the nanometer range.

[0085] The term "primary particle" as used herein refers to spherical polymer particles comprising particles in the nanometer range. Preferably, the primary particles have a weight-average particle size of 20 nm to 800 nm.

[0086] The term "particle size" as used herein refers to the volume-average diameter of particles considered to be spherical.

[0087] The term "thermoplastic polymer" as used herein refers to a polymer that becomes liquid or more liquid or less viscous upon heating and can assume a new shape by the application of heat and pressure.

[0088] The term "thermosetting polymer" as used herein refers to a prepolymer in a soft, solid or viscous state that irreversibly becomes an infusible and insoluble polymer network upon curing.

[0089] The term "polymer composite" as used herein refers to a multi-component material comprising a plurality of different phase domains, wherein at least one type of phase domain is a continuous phase and wherein at least one component is a polymer.

[0090] The term "copolymer" as used herein means that the polymer is composed of at least two different monomers.

[0091] The term "multi-stage polymer" as used herein refers to a polymer formed in a sequential manner by a multi-stage polymerization process. Preferably, it is a multi-stage emulsion polymerization process, wherein the first polymer is the first-stage polymer and the 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 and has at least two stages that are different in composition.

[0092] The term "(meth)acrylic" as used herein refers to all types of acrylic and methacrylic monomers.

[0093] The term "(meth)acrylic polymer" as used herein means that the (meth)acrylic polymer substantially comprises a polymer containing 50 wt% or more of (meth)acrylic monomers that constitute the (meth)acrylic polymer.

[0094] The term "dry" as used herein means that the ratio of residual water is less than 1.5 wt% and preferably less than 1.2 wt%.

[0095] When referring to the range from x to y in the present invention, it means including the upper limit value and the lower limit value of the range, which is equivalent to at least x and at most y.

[0096] When referring to the range between x and y in the present invention, it means excluding the upper limit value and the lower limit value of the range, which is equivalent to greater than x and less than y.

[0097] The term "total intrusion volume" used herein represents the total volume intruded by liquid mercury in accordance with ISO 15901-1:2016. This volume is cumulative, and the analysis result shows the cumulative intrusion volume varying with the applied pressure or pore size, with the unit of ml / g (cm 3 / g). The total intrusion volume is the volume intruded at the maximum applied pressure, which also corresponds to the smallest pores.

[0098] The term "incremental intrusion amount" used herein represents the volume intruded between two specific pressures or two pore sizes, with the unit of ml / g. This incremental intrusion amount can also be expressed as a volume percentage relative to the total intrusion volume.

[0099] Easy dispersion in the liquid resin means obtaining a uniform dispersion. If separation occurs after the initial homogenization, then the distribution of the polymer composition (PC1) is non-uniform.

[0100] Rapid dispersion in the liquid resin means obtaining a uniform dispersion faster than that with a polymer composition (PC1) having a porosity lower than the minimum requirement.

[0101] Regarding the polymer composition (PC1) according to the present invention, which is in the form of a polymer powder and is also referred to as polymer powder POW1, it comprises: a) a fraction (A) which comprises a polymer (A1) having a glass transition temperature below 10 °C, b) a fraction (B) which comprises 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 component a) and component b) of the composition (PC1) are parts of a multi-stage polymer (MP1), and it is characterized in that the polymer (C1) has a weight-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the polymer composition (PC1) in the form of a polymer powder has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry.

[0102] Component c) accounts for at most 40% by weight of the composition based on a), b) and c). More preferably, component c) accounts for at most 35% by weight of the composition based on a), b) and c); more preferably at most 30% by weight, still more preferably less than 30% by weight, advantageously less than 25% by weight, and more advantageously less than 20% by weight.

[0103] Preferably, component c) accounts for more than 4% by weight of the composition based on a), b) and c). More preferably, component c) accounts for more than 5% by weight of the composition based on a), b) and c); even more preferably more than 6% by weight, still more preferably more than 7% by weight, advantageously more than 8% by weight, and more advantageously more than 10% by weight.

[0104] The corresponding upper and lower limit values given for the amount of component c) in the previous two paragraphs can be combined in any combination of one upper limit value and one lower limit value.

[0105] Preferably, component c) accounts for between 4% and 40% by weight of the composition based on a), b) and c). More preferably, component c) accounts for between 5% and 35% by weight of the composition based on a), b) and c); even more preferably between 6% and 30% by weight, still more preferably between 7% and less than 30% by weight, advantageously between 7% and less than 25% by weight, and more advantageously between 10% and less than 20% by weight.

[0106] At least component a) and component b) of the composition (PC1) are part of a multi-stage polymer (MP1).

[0107] At least component a) and component b) are obtained by a multi-stage process comprising at least two stages (A) and (B) respectively; and the two polymers (A1) and polymer (B1) form a multi-stage polymer.

[0108] Regarding the polymer powder POW1 of the present invention, it 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, and advantageously between 20 μm and 500 μm.

[0109] The D10 of the particle size distribution by volume is at least 7 μm, and preferably at least 10 μm, more preferably at least 15 μm.

[0110] The D90 of the particle size distribution by volume is at most 1000 μm, and preferably at most 950 μm, more preferably at most 900 μm, and even more preferably at most 800 μm.

[0111] The porosity of the polymer composition (PC1) in the form of polymer powder POW1 is expressed as the total intrusion volume or total cumulative intrusion amount (cumulative intrusion volume) in milliliters (ml) of mercury per gram (g) of the polymer powder POW1. This is measured according to the specification ISO 15901-1: Evaluation of pore size distribution and porosity of solid materials by mercury porosity and gas adsorption - Part 1: Mercury Porosity. The porous polymer powder POW1 of the present invention has a total intrusion volume or total cumulative intrusion amount of at least 1.2 ml / g, preferably at least 1.25 ml / g, more preferably at least 1.3 ml / g, and even more preferably at least 1.35 ml / g. The total cumulative intrusion amount is calculated up to a pore size of 0.005 μm. Preferably, the total intrusion volume or total cumulative intrusion amount is calculated between a pore size of 100 μm and 0.005 μm or between a pressure of 0.01 MPa and 400 MPa.

[0112] The porous polymer powder POW1 of the present invention has a total intrusion volume or total cumulative intrusion amount of at most 10 ml / g. Preferably, the total intrusion 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.

[0113] The respective upper and lower limit values given for the total intrusion volume or total cumulative intrusion amount of the porous polymer powder POW1 of the present invention in the previous two paragraphs can be combined in any combination of one upper limit value and one lower limit value.

[0114] Preferably, the porous polymer powder POW1 of the present invention has a total intrusion volume or total cumulative intrusion amount 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.

[0115] The incremental intrusion amount (incremental intrusion volume) is the volume between two specific pore sizes. The incremental intrusion amount can be expressed as an absolute value in ml / g or as a relative value, i.e., as a percentage of the total intrusion volume or total cumulative intrusion amount (which is calculated between a pore size of 100 μm and 0.005 μm).

[0116] Preferably, the porous polymer powder POW1 of the present invention has a cumulative indentation volume of at least 0.9 ml / g, more preferably at least 1 ml / g, for pore sizes above 10 μm (greater than 10 μm).

[0117] Preferably, the porous polymer powder POW1 of the present invention has a relative incremental indentation volume of at most 85%, more preferably at most 82%, and even more preferably at most 80% for pore sizes above 10 μm (greater than 10 μm).

[0118] Preferably, the porous polymer powder POW1 of the present invention has an incremental indentation volume of at least 0.1 ml / g, more preferably at least 0.12 ml / g, and even more preferably at least 0.15 ml / g between pore sizes of 10 μm and 1 μm.

[0119] Preferably, the porous polymer powder POW1 of the present invention has a relative incremental indentation volume of at least 5%, more preferably at least 8%, and even more preferably at least 10% between pore sizes of 10 μm and 1 μm.

[0120] Preferably, the porous polymer powder POW1 of the present invention has an incremental indentation volume of at least 0.15 ml / g, more preferably at least 0.2 ml / g, and even more preferably at least 0.25 ml / g between pore sizes of 10 μm and 0.1 μm.

[0121] Preferably, the porous polymer powder POW1 of the present invention has a relative incremental indentation volume of at least 10%, more preferably at least 15%, and even more preferably at least 20% between pore sizes of 10 μm and 0.1 μm.

[0122] Preferably, the porous polymer powder POW1 of the present invention has an incremental indentation volume of at least 0.05 ml / g, more preferably at least 0.06 ml / g, and even more preferably at least 0.07 ml / g between pore sizes of 1 μm and 0.1 μm.

[0123] Preferably, the porous polymer powder POW1 of the present invention has a relative incremental indentation volume of at least 5%, more preferably at least 7.5%, and even more preferably at least 10% between pore sizes of 1 μm and 0.1 μm.

[0124] The apparent bulk density of the polymer powder POW1 is less than 0.60 g / cm 3 . Preferably, the apparent bulk density is less than 0.45 g / cm 3 , more preferably less than 0.43 g / cm 3 , and even more preferably less than 0.41 g / cm 3 .

[0125] The apparent bulk density of the polymer powder POW1 is greater than 0.1 g / cm 3 . Preferably, the apparent bulk density is greater than 0.11 g / cm 3 , more preferably greater than 0.12 g / cm 3 , even more preferably greater than 0.13 g / cm 3 .

[0126] The apparent bulk density of the polymer powder POW1 is between 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 .

[0127] The respective preferred embodiments of all the different features of the porous polymer powder POW1 of the present invention can be combined.

[0128] The multi-stage polymer (MP1) of the composition (PC1) according to the present invention has at least two stages (A) and (B) respectively; and these two stages contain polymers (A1) and polymers (B1) with different polymer compositions respectively.

[0129] The multi-stage polymer (MP1) is preferably in the form of polymer particles regarded as spherical particles PAR. These particles PAR are also called core-shell particles. The first stage forms the core, and the second stage or all subsequent stages form the corresponding shell. Such multi-stage polymers, also called core / shell particles, are preferred.

[0130] 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 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, still more preferably between 30 nm and 550 nm, yet still more preferably between 35 nm and 500 nm, advantageously between 40 nm and 400 nm, even more advantageously between 75 nm and 350 nm and advantageously between 80 nm and 300 nm. The primary polymer particles PAR can agglomerate to obtain the polymer composition (PC1) in the form of a polymer powder of the present invention or a part of the polymer composition (PC1).

[0131] The polymer composition (PC1) according to the present invention contains a multi-stage polymer (MP1), which includes at least a) one stage (A) containing a polymer (A1) having a glass transition temperature below 10 °C, and at least b) one stage (B) containing a polymer (B1) having a glass transition temperature greater than 60 °C.

[0132] In a first preferred embodiment, stage (A) is the first stage of at least two stages, and stage (B) containing polymer (B1) is grafted onto stage (A) containing polymer (A1) or another intermediate layer.

[0133] In a second preferred embodiment, another stage may also be present before stage (A), such that stage (A) may also be the shell.

[0134] In a third preferred embodiment, polymer (C1) having a glass transition temperature of greater than 30 °C is also part of the multi-stage polymer (MP1). There is also at least one stage (C). Preferably, stage (C) occurs after stage (B). More preferably, stage (C) is the last stage, and polymer (C1) is the outer shell of the multi-stage polymer (MP1).

[0135] In a first embodiment, polymer (A1) having a glass transition temperature below 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 the polymer particles having a multi-layer structure. In other words, stage (A) containing polymer (A1) is the core of the polymer particles.

[0136] Regarding polymer (A1) of the first preferred embodiment, it 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) are acrylic monomers.

[0137] The acrylic monomers in polymer (A1) include monomers selected from C1-C18 alkyl acrylates or mixtures thereof. More preferably, the acrylic monomers in polymer (A1) include monomers of C2-C12 alkyl acrylates or mixtures thereof. Even more preferably, the acrylic monomers in polymer (A1) include monomers of C2-C8 alkyl acrylates or mixtures thereof.

[0138] Polymer (A1) may contain one or more comonomers copolymerizable with the acrylic monomers, provided that polymer (A1) has a glass transition temperature below 10 °C.

[0139] One or more comonomers in polymer (A1) are preferably selected from (meth)acrylic monomers and / or vinyl monomers.

[0140] Most preferably, the acrylic or methacrylic comonomer of polymer (A1) is 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 below 10°C.

[0141] In a particular embodiment, polymer (A1) is a homopolymer of butyl acrylate.

[0142] More preferably, the glass transition temperature Tg of polymer (A1) comprising at least 70 wt% of polymer units from C2-C8 alkyl acrylates 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.

[0143] In a second preferred embodiment, polymer (A1) having a glass transition temperature below 10°C comprises at least 50 wt% of polymer units from isoprene or butadiene, and stage (A) is the innermost layer of the polymer particles having a multilayer structure. In other words, stage (A) containing polymer (A1) is the core of the polymer particles.

[0144] For example, for the polymer (A1) of the core of the second embodiment, mention may be made of isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers, copolymers of isoprene with up to 98 wt% of vinyl monomers, and copolymers of butadiene with up to 98 wt% of vinyl monomers. The vinyl monomers may be styrene, alkylstyrene, acrylonitrile, (meth)acrylic alkyl esters, or butadiene or isoprene. In a preferred embodiment, the core is a butadiene homopolymer.

[0145] More preferably, the glass transition temperature Tg of polymer (A1) comprising at least 50 wt% of polymer units 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.

[0146] In a third preferred embodiment, polymer (A1) is a polymer based on silicone rubber. The silicone rubber is, for example, polydimethylsiloxane. More preferably, the glass transition temperature Tg of 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.

[0147] The polymer (A1) having a glass transition temperature below 10 °C comprises polymerized monomer units. The polymer (A1) in general and the corresponding polymers (A1) of the first, second and third preferred embodiments are prepared from the corresponding monomers or monomer mixtures (A m ) that give rise to the monomer units constituting the polymer (A1).

[0148] Regarding the polymer (B1), mention may be made of homopolymers and copolymers comprising monomers having double bonds and / or vinyl monomers. Preferably, the polymer (B1) is a (meth)acrylic polymer.

[0149] Preferably, the polymer (B1) comprises at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. Even more preferably, the polymer (B1) comprises at least 80% by weight of monomers of C1-C4 alkyl methacrylates and / or C1-C8 alkyl acrylate monomers.

[0150] Most preferably, the acrylic or methacrylic monomers of the polymer (B1) are selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, provided that the polymer (B1) has a glass transition temperature of at least 60 °C.

[0151] Advantageously, the polymer (B1) comprises at least 70% by weight of monomer units from methyl methacrylate.

[0152] Preferably, the glass transition temperature Tg of the polymer (B1) is between 60 °C and 150 °C. The glass transition temperature of the 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.

[0153] Preferably, the polymer (B1) is grafted onto the polymer prepared in the previous stage.

[0154] In certain embodiments, the polymer (B1) is crosslinked.

[0155] In one embodiment, the polymer (B1) comprises functional comonomers. The functional comonomers are selected from acrylic acid or methacrylic acid, amides derived from the acid, such as dimethylacrylamide, 2-methoxyethyl acrylate or 2-methoxyethyl methacrylate, optionally quaternized 2-aminoethyl acrylate or 2-aminoethyl methacrylate, poly(ethylene glycol) (meth)acrylate, water-soluble vinyl monomers such as N-vinylpyrrolidone, or mixtures thereof. Preferably, the polyethylene glycol group of the poly(ethylene glycol) (meth)acrylate has a molecular weight of from 400 g / mol to 10,000 g / mol.

[0156] The polymer (B1) having a glass transition temperature of at least 60 °C comprises polymerized monomer units. In general and in the corresponding embodiments, the polymer (B1) is prepared from the corresponding monomers or monomer mixtures (B m ) that form the monomer units of the polymer (B1).

[0157] Regarding the polymer (C1), it has a weight-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0158] The polymer (C1) has a weight-average molecular weight Mw greater than 10,000 g / mol, preferably greater than 10,500 g / mol, more preferably greater than 11,000 g / mol, still more preferably greater than 12,000 g / mol, advantageously greater than 13,000 g / mol, more advantageously greater than 14,000 g / mol and still more advantageously greater than 15,000 g / mol.

[0159] The polymer (C1) has a weight-average molecular weight Mw below 500,000 g / mol, preferably below 450,000 g / mol, more preferably below 400,000 g / mol, advantageously below 350,000 g / mol, more advantageously below 300,000 g / mol and still more advantageously below 250,000 g / mol and most advantageously below 200,000 g / mol.

[0160] Preferably, the weight-average molecular weight Mw of the 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 and even more preferably between 12,000 g / mol and 350,000 g / mol, advantageously between 13,000 g / mol and 300,000 g / mol, more advantageously between 14,000 g / mol and 250,000 g / mol and most advantageously between 15,000 g / mol and 200,000 g / mol.

[0161] In a first advantageous embodiment, the (meth)acrylic polymer MP1 has a weight-average molecular weight Mw between 10,500 g / mol and 200,000 g / mol, more preferably between 11,000 g / mol and 190,000 g / mol, and even more preferably between 12,000 g / mol and 180,000 g / mol, advantageously between 13,000 g / mol and 150,000 g / mol, more advantageously between 14,000 g / mol and 135,000 g / mol and most advantageously between 15,000 g / mol and 120,000 g / mol.

[0162] 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, and even more preferably between 17,000 g / mol and 350,000 g / mol, advantageously between 18,000 g / mol and 300,000 g / mol, more advantageously between 19,000 g / mol and 250,000 g / mol and most advantageously between 20,000 g / mol and 200,000 g / mol.

[0163] Preferably, the polymer (C1) is a copolymer comprising (meth)acrylic monomers. More preferably, the polymer (C1) is a (meth)acrylic polymer. Even more preferably, the polymer (C1) comprises at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. Advantageously, the polymer (C1) comprises at least 80% by weight of monomers methyl C1-C4 alkyl (meth)acrylates and / or C1-C8 alkyl acrylate monomers.

[0164] Preferably, the glass transition temperature Tg of the polymer (C1) is between 30 °C and 150 °C. The glass transition temperature of the polymer (C1) is more preferably between 40 °C and 150 °C, advantageously between 45 °C and 150 °C and more advantageously between 50 °C and 150 °C.

[0165] Preferably, the polymer (C1) is uncrosslinked.

[0166] Preferably, the polymer (C1) is not grafted onto either the polymer (A1) or the polymer (B1), especially if it is part of a multi-stage polymer (MP1). By not grafted is meant that at least 50% by weight of the polymer (C1) in the multi-stage polymer (MP1) can be dissolved in a solvent of the polymer (C1).

[0167] In one embodiment, the polymer (C1) further comprises a functional comonomer.

[0168] The functional comonomer has the formula (1):

[0169]

[0170] wherein R1 is selected from H or CH3, and R2 is H or an aliphatic or aromatic group having at least one atom other than C or H.

[0171] 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 2-methoxyethyl methacrylate, optionally quaternized 2-aminoethyl acrylate or 2-aminoethyl methacrylate, polyethylene glycol (meth)acrylate. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight of 400 g / mol to 10,000 g / mol.

[0172] 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 selected from methyl acrylate, ethyl acrylate or butyl acrylate.

[0173] In a second preferred embodiment, the polymer (C1) comprises between 0% and 50% by weight of the functional monomer. Preferably, the (meth)acrylic polymer (C1) comprises between 0% and 30% by weight, more preferably between 1% and 30% by weight, still more preferably between 2% and 30% by weight, advantageously between 3% and 30% by weight, more advantageously between 5% and 30% by weight and most advantageously between 5% and 30% by weight of the functional monomer.

[0174] Preferably, the functional monomer of the second preferred embodiment is a (meth)acrylic monomer. The functional monomer has formula (2) or formula (3):

[0175]

[0176] Wherein in both formula (2) and formula (3), R1 is selected from H or CH3; and in formula (2), Y is O, R5 is H or an aliphatic or aromatic group having at least one atom other than C or H; and in formula (3), Y is N and R4 and / or R3 is H or an aliphatic or aromatic group.

[0177] Preferably, the functional monomer (2) or the functional monomer (3) is selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids, such as dimethylacrylamide, 2-methoxyethyl acrylate or 2-methoxyethyl methacrylate, optionally quaternized 2-aminoethyl acrylate or 2-aminoethyl methacrylate, acrylate or methacrylate monomers comprising phosphonate or phosphate groups, alkylimidazolidinone (meth)acrylate, polyethylene glycol (meth)acrylate. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight of 400 g / mol to 10,000 g / mol.

[0178] The polymer (C1) having a glass transition temperature of at least 30 °C comprises polymerized monomer units. The polymer (C1) is generally and in the respective embodiments prepared from the monomers or monomer mixtures (C m ) that give rise to the monomer units constituting the polymer (C1).

[0179] The respective preferred embodiments of all the different features of the polymers (A1), (B1) and (C1) can be combined in any combination.

[0180] The multistage polymer (MP1) is obtained by a multistage process comprising at least two stages. At least component a) and component b) of the composition (PC1) are part of the multistage polymer (MP1).

[0181] Preferably, the polymer (A1) having a glass transition temperature below 10 °C prepared during stage (A) is prepared before stage (B) or is the first stage of the multistage process.

[0182] Preferably, the polymer (B1) having a glass transition temperature greater than 60 °C prepared during stage (B) is prepared after stage (A) of the multistage process.

[0183] In a first preferred embodiment, the polymer (B1) having a glass transition temperature of at least 60 °C is the intermediate layer of the polymer particles having a multilayer structure.

[0184] In a first preferred embodiment, the polymer (C1) having a glass transition temperature greater than 30 °C prepared during stage (C) is prepared after stage (B) of the multistage process.

[0185] More preferably, the polymer (C1) having a glass transition temperature greater than 30 °C prepared during stage (C) is the outer layer of the multistage polymer (MP1) or of the primary polymer particles having a multilayer structure.

[0186] Between stage (A) and stage (B) and / or between stage (B) and stage (C), additional intermediate stages may be present.

[0187] The polymer (C1) and the polymer (B1) are not the same polymer, even if their compositions may be very close and some of their properties overlap. The essential difference is that the polymer (B1) is always part of the multistage polymer (MP1).

[0188] This is explained in more detail in the process for preparing the polymer composition (PC1) according to the invention comprising the polymer (C1) and the multistage polymer (MP1).

[0189] The weight ratio r of the outer polymer (C1) contained in grade (C) to the weight of the complete polymer particles is at least 5% by weight, more preferably at least 7% by weight and even more preferably at least 10% by weight.

[0190] According to the invention, the ratio r of the outer grade (C) containing polymer (C1) to the complete polymer particles is at most 40% by weight.

[0191] Preferably, the ratio of polymer (C1) to the primary polymer particles is between 5% by weight and 30% by weight and preferably between 5% by weight and 20% by weight.

[0192] In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 60 °C is the outer layer of the primary polymer particles having a multilayer structure (in other words, the multi-stage polymer (MP1)).

[0193] Preferably, at least a part of the polymer (B1) of layer (B) is grafted onto the polymer prepared in the previous layer. If there are only two grades (A) and (B) containing polymers (A1) and (B1) respectively, then a part of the polymer (B1) is grafted onto the polymer (A1). More preferably, at least 50% by weight of the polymer (B1) is grafted. The grafting rate can be determined by extraction with a solvent for polymer (B1) and weighing before and after extraction to determine the amount of ungrafted polymer.

[0194] The glass transition temperature Tg of each polymer can be estimated, for example, by dynamic methods such as thermomechanical analysis.

[0195] In order to obtain samples of each polymer (A1), polymer (B1) and polymer (C1), they can be prepared separately rather than by the multi-stage method, so as to more easily estimate and measure the glass transition temperature Tg of each polymer in each grade. Polymer (C1) can be extracted in order to estimate and measure the glass transition temperature Tg.

[0196] Preferably, the polymer composition of the present invention does not contain a solvent. Solvent-free means that the solvent finally present is less than 1% by weight of the composition. The monomers for synthesizing the corresponding polymers are not regarded as solvents. The residual monomers in the composition are less than 2% by weight of the composition.

[0197] Preferably, the polymer composition according to the invention is dry. Dry means that the polymer composition according to the invention contains less than 3% by weight of humidity and preferably less than 1.5% by weight of humidity and even more preferably less than 1.2% by weight of humidity.

[0198] The humidity can be measured by a thermobalance that heats the polymer composition and measures the weight loss.

[0199] The composition according to the invention does not contain any actively added solvent. The final residual monomers and water from the corresponding monomers are not considered solvents.

[0200] The polymer composition (PC1) in the form of the polymer powder POW1 of the present invention comprises polymer particles PAR. If there are several different kinds of particles, they are respectively called PAR1, PAR2, etc. The polymer particles PAR account for at least 50% by weight of the polymer powder composition POW1. More preferably, the polymer particles PAR1 account for at least 60% by weight of the polymer powder composition POW1, still more preferably at least 70% by weight.

[0201] In a first preferred embodiment, the polymer composition (PC1) in the form of the polymer powder POW1 of the present invention consists only of polymer particles PAR1. The polymer particles PAR1 consist of a multi-stage polymer (MP1) comprising component a), component b) and component c).

[0202] In a second preferred embodiment, the polymer composition (PC1) in the form of the polymer powder POW1 of the present invention comprises at least 60% by weight of polymer particles PAR1. The polymer particles PAR1 consist of a multi-stage polymer (MP1) comprising at least component a) and component b).

[0203] In a third preferred embodiment, the polymer composition (PC1) in the form of the polymer powder POW1 of the present invention comprises polymer particles PAR1. The polymer particles PAR1 consist of a multi-stage polymer (MP1) comprising component a), component b) and component c).

[0204] In a fourth preferred embodiment, the polymer composition (PC1) in the form of the polymer powder POW1 of the present invention comprises two different kinds of particles PAR1 and PAR2. The polymer particles PAR1 consist of a multi-stage polymer (MP1) comprising component a) and component b). The polymer particles PAR2 comprise or consist of polymer (C1).

[0205] Regarding a first preferred method for preparing the polymer composition (PC1) according to the present invention, it comprises the following steps:

[0206] a) Polymerizing a monomer or a monomer mixture (A m ) by emulsion polymerization to obtain a layer of stage (A) comprising a polymer (A1) having a glass transition temperature below 10 °C,

[0207] b) Polymerizing a monomer or a monomer mixture (B m ) by emulsion polymerization to obtain a layer of stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C,

[0208] c) polymerizing a monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer of grade (C) comprising a polymer (C1) having a glass transition temperature of at least 30 °C,

[0209] d) coagulating the composition obtained in steps a) to c).

[0210] Preferably, step a) is carried out before step b).

[0211] More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a).

[0212] Advantageously, a first preferred method for preparing the polymer composition (PC1) according to the invention is a multi-step method, which comprises the following successive steps:

[0213] a) polymerizing a monomer or monomer mixture (A m ) by emulsion polymerization to obtain a layer of grade (A) comprising a polymer (A1) having a glass transition temperature below 10 °C,

[0214] b) polymerizing a monomer or monomer mixture (B m ) by emulsion polymerization to obtain a layer of grade (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C,

[0215] c) polymerizing a monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer of grade (C) comprising a polymer (C1) having a glass transition temperature of at least 30 °C,

[0216] d) coagulating the composition obtained in steps a) to c).

[0217] Preferably, steps a), b), c) and d) are carried out in this order. Due to the use of emulsion polymerization, the polymer composition obtained at the end of the polymerization is an aqueous dispersion.

[0218] The corresponding monomers or monomer mixtures (A m ), (B m ) and (C m ) used to form the respective layers of grades (A), (B) and (C) comprising the polymers (A1), (B1) and (C1) respectively are the same as those defined above. The monomers or monomer mixtures (A m ), (B m ) and (C m)comprising corresponding monomers as polymerization monomer units in the polymer chains of corresponding polymers (A1), (B1) and (C1). The polymers (A1), (B1) and (C1) are respectively the same as those defined above.

[0219] A second preferred method for preparing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer (MP1) comprises the following steps:

[0220] a) polymerizing a monomer or a monomer mixture (A m ) by emulsion polymerization to obtain a layer of stage (A) comprising a polymer (A1) having a glass transition temperature below 10 °C,

[0221] b) polymerizing a monomer or a monomer mixture (B m ) by emulsion polymerization to obtain a layer of stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C,

[0222] Both step a) and step b) together produce a multi-stage polymer (MP1), and step

[0223] c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30 °C,

[0224] d) coagulating the composition obtained in steps a) to c).

[0225] 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.

[0226] A third preferred method for preparing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer (MP1) comprises the following steps:

[0227] a) providing a polymer (C1) having a glass transition temperature of at least 30 °C and a multi-stage polymer (MP1) comprising a stage (A) and a stage (B), the stage (A) comprising a polymer (A1) having a glass transition temperature below 10 °C, and the stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C,

[0228] b) mixing or blending the polymer (C1) and the multi-stage polymer (MP1),

[0229] c) coagulating the composition obtained in step b),

[0230] The polymer (C1) and the multi-stage polymer (MP1) in step b) are in the form of a dispersion in the aqueous phase. The corresponding aqueous dispersion contains the polymer (C1) and the multi-stage polymer (MP1) in the form of polymer particles.

[0231] Preferably, the multi-stage polymer (MP1) and the polymer (C1) have been provided as an aqueous dispersion.

[0232] The amounts of the aqueous dispersion of the polymer (C1) and the aqueous dispersion of the multi-stage polymer (MP1) are selected such that the weight ratio of the multi-stage polymer, based on only the solid part 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%.

[0233] The amounts of the aqueous dispersion of the polymer (C1) and the aqueous dispersion of the multi-stage polymer (MP1) are selected such that the weight ratio of the multi-stage polymer, based on only the solid part in the resulting mixture, is at most 99 wt%, preferably at most 95 wt% and more preferably at most 90 wt%.

[0234] The amounts of the aqueous dispersion of the polymer (C1) and the aqueous dispersion of the multi-stage polymer are selected such that the weight ratio of the multi-stage polymer, based on only the solid part in the resulting mixture, is between 60 wt% and 99 wt%, preferably between 65 wt% and 95 wt% and more preferably between 68 wt% and 90 wt%.

[0235] A preferred method for preparing the polymer composition (PC1) comprising the polymer (C1) and the multi-stage polymer (MP1) yields the polymer powder POW1. The polymer powder POW1 is in the form of particulate matter (large particles). The polymer powder particulate matter or particles include agglomerated primary polymer particles containing the multi-stage polymer (MP1) and the polymer (C1) or agglomerated primary polymer particles containing the multi-stage polymer (MP1) and the polymer (C1) obtained by the multi-stage process.

[0236] Before the onset of coagulation, the aqueous composition comprising the multi-stage polymer (MP1) and the polymer (C1) 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%.

[0237] The solids content is measured or estimated gravimetrically by weighing before and after complete evaporation of the water.

[0238] In a first preferred embodiment, before the onset of coagulation, the solids content of the aqueous composition comprising the multi-stage polymer (MP1) and the polymer (C1) is between 5% and 35% by weight, more preferably between 6% and 34% by weight, still more preferably between 7% and 33% by weight, and advantageously between 8% and 32% by weight.

[0239] In a second preferred embodiment, before the onset of coagulation, the solids content of the aqueous composition comprising the multi-stage polymer (MP1) and the polymer (C1) is between 20% and 35% by weight, more preferably between 20% and 34% by weight, still more preferably between 20% and 33% by weight, and advantageously between 20% and 32% by weight.

[0240] In a third preferred embodiment, before the onset of coagulation, the solids content of the aqueous composition comprising the multi-stage polymer (MP1) and the polymer (C1) is between 5% and 20% by weight, more preferably between 6% and 20% by weight, still more preferably between 7% and 20% by weight, and advantageously between 8% and 20% by weight.

[0241] In a fourth preferred embodiment, before the onset of coagulation, the solids content of the aqueous composition comprising the multi-stage polymer (MP1) and the polymer (C1) is between 10% and 25% by weight, more preferably between 11% and 24% by weight, still more preferably between 12% and 23% by weight, and advantageously between 13% and 22% by weight.

[0242] In a fifth preferred embodiment, before the onset of coagulation, the solids content of the aqueous composition comprising the multi-stage polymer (MP1) and the polymer (C1) is between 15% and 27% by weight, more preferably between 17% and 27% by weight, still more preferably between 19% and 27% by weight, and advantageously between 21% and 27% by weight.

[0243] Coagulation can be carried out using a salt or an inorganic acid.

[0244] In the first preferred embodiment, coagulation is carried out using an inorganic acid.

[0245] The method for preparing the polymer composition (PC1) according to the invention may optionally include an additional step e) of drying the polymer composition.

[0246] Preferably, after the drying step e), the polymer composition contains less than 3% by weight, more preferably less than 1.5% by weight, and advantageously less than 1.2% by weight of humidity or water.

[0247] The humidity of the polymer composition can be measured using a thermobalance.

[0248] The drying of the polymer can be carried out in an oven or a vacuum oven, where the composition is heated at 50 °C for 48 hours.

[0249] The liquid composition LC1 of the eighth aspect of the present invention is a precursor of a thermosetting polymer or a thermoplastic polymer. This can be a monomer, a mixture of monomers, a polymerizable or curable oligomer, a mixture of a polymerizable or curable oligomer and one or more monomers, or a mixture of a polymer and one or more monomers, which are liquid at 25 °C. Preferably, the liquid has a dynamic viscosity of less than 1000 Pa·s, and more preferably between 0.5 mPa·s and 1000 Pa·s. The value of the dynamic viscosity is measured at a shear rate of 1 s -1 and is measured using a rheometer.

[0250] For example, the liquid composition LC1 can be selected from compositions for preparing vinyl esters, unsaturated polyesters or epoxy resins; or it can be, for example, a styrenic monomer, or a (meth)acrylic monomer, or a mixture thereof or a liquid composition containing said monomers.

[0251] Preferably, the polymeric composition (PC1) accounts for between 0.5 and 50% by weight of the composition comprising the liquid composition LC1 and the polymeric composition (PC1).

[0252] The present invention also relates to the use of the polymeric composition (PC1) in the form of a polymer powder according to the present invention as an impact modifier in a polymer to obtain an impact-modified polymeric composition. Preferably, the polymer is a thermosetting polymer or a thermoplastic polymer or a precursor thereof.

[0253] In a first preferred embodiment, the method for reducing the dispersion time comprises the following steps:

[0254] - providing a precursor of a thermosetting polymer or a monomer of a thermoplastic polymer, and

[0255] - contacting the polymeric composition (PC1) with said precursor.

[0256] In a second preferred embodiment, the method for reducing the dispersion time comprises at least the step of providing the polymeric composition (PC1) in the form of a polymer powder, which has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry.

[0257] The method in the second preferred embodiment also optionally comprises the step of providing a precursor of a thermosetting polymer or a monomer of a thermoplastic polymer. Preferably, the precursor is liquid. More preferably, the precursor has a viscosity between 0.5 mPas and 1000 Pa·s at a temperature of 25 °C. This viscosity is the dynamic viscosity.

[0258] In a second preferred embodiment, the method for reducing the dispersion time further optionally includes the step of contacting a polymer composition (PC1) in the form of a polymer powder with the precursor. Preferably, a polymer composition (PC1) in the form of a polymer powder between 0.5 parts by weight and 100 parts by weight is contacted with 100 parts by weight of the precursor.

[0259] The polymer composition (PC2) can be a thermosetting polymer or its precursor, or a thermoplastic polymer. The polymer composition PC2 can also be an adhesive, and more preferably a structural adhesive.

[0260] Evaluation method

[0261] Glass transition temperature

[0262] The glass transition temperature (Tg) of the polymer is measured using a device capable of performing thermomechanical analysis. The RDAII "RHEOMETRIC SDYNAMIC ANALYSER" provided by the Rheometrics Company has been used. Thermomechanical analysis accurately measures the change in the viscoelasticity of the sample with temperature, strain, or the applied deformation. The device continuously records the sample deformation during a controlled temperature change program while keeping the strain fixed.

[0263] The results are obtained by plotting the storage modulus (G'), loss modulus, and tanδ as a function of temperature. Tg is the highest temperature value read from the tanδ curve when the derivative of tanδ is equal to zero.

[0264] Molecular weight

[0265] 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. Modified silica is used for the chromatographic column. The flow rate is 1 ml / min, and a refractive index detector is used.

[0266] Particle size analysis

[0267] The particle size of the primary particles after multi-stage polymerization is measured using dynamic light scattering with a Zetasizer from Malvern. The weight-average particle size (diameter) is used as the result.

[0268] The particle size of the recovered polymer powder is measured using laser diffraction with a Malvern Mastersizer 3000 from MALVERN.

[0269] To estimate the weight-average powder particle size, particle size distribution and the ratio of fine particles, a Malvern Mastersizer 3000 device with a 300 mm lens was used, and the measurement range was 0.5 - 880 μm.

[0270] Dispersion test: Samples of each powder were dispersed in a liquid composition. The results of the dispersion test were given as + + signs to - signs. This indicates the speed and ease with which the powder is dispersed in the liquid composition. The sign "-" indicates poor dispersion, and the powder may still separate, float, sink or undergo other phase separation after the dispersion test. The signs "+" or "++" indicate good immediate dispersion or very good immediate dispersion. In the examples, monomer methyl methacrylate (MMA) was used as the liquid composition. At 25 °C, 1 g of the corresponding powder was added to a glass container containing 99 g of MMA. Without stirring, after 60 seconds, it was observed whether the powder in the mixture was dispersed.

[0271] Apparent density

[0272] Using the specification ISO 60:1977. The sample was poured through a specified funnel into a graduated cylinder with a capacity of 100 cubic centimeters, the excess was removed with a straightedge, and the mass of the contents was determined by weighing.

[0273] Viscosity

[0274] The viscosity can be easily measured using a rheometer or a viscometer. The dynamic viscosity was measured at 25 °C. If the liquid has Newtonian fluid behavior, meaning no shear thinning, the dynamic viscosity is independent of the shear action in the rheometer or the moving speed in the viscometer. If the liquid composition has non-Newtonian fluid behavior, meaning shear thinning, the dynamic viscosity was measured at a shear rate of 25 °C and 1 s -1 and.

Claims

1. A polymer composition (PC1) in the form of a polymer powder, comprising: a) a fraction (A) comprising a polymer (A1) having a glass transition temperature below 10 °C, b) a fraction (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) accounting for at most 40% by weight of the composition based on a), b) and c), Characterized in that at least component a) and component b) of the composition (PC1) are part of a multi-stage polymer (MP1), and characterized in that the polymer (C1) has a weight-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the polymer composition (PC1) in the form of a polymer powder has a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry.

2. The polymer composition according to claim 1, wherein The total intrusion volume is at least 1.35 ml / g measured by mercury porosimetry.

3. The polymer composition according to claim 1 or 2, characterized in that, The total intrusion volume is at most 10 ml / g measured by mercury porosimetry.

4. The polymer composition (PC1) according to claim 1, characterized in that, The total intrusion volume is between 1.25 ml / g and 8 ml / g.

5. The polymer composition (PC1) according to any one of claims 1 to 2, characterized in that The relative incremental intrusion amount of the polymer powder for pore sizes greater than 10 μm is at most 85%.

6. The polymer composition (PC1) according to claim 1 or 2, characterized in that, The incremental intrusion amount of the polymer powder between pore sizes of 10 μm and 1 μm is at least 0.1 ml / g.

7. The polymer composition (PC1) according to claim 1 or 2, characterized in that, The incremental intrusion amount of the polymer powder between pore sizes of 10 μm and 0.1 μm is at least 0.15 ml / g.

8. The polymer composition according to claim 1 or 2, characterized in that, The relative incremental intrusion amount of the polymer powder between pore sizes of 10 μm and 1 μm is at least 5%.

9. The polymer composition (PC1) according to any one of claims 1 to 2, characterized in that The polymer powder has a volume median particle size D50 between 1 μm and 700 μm.

10. The polymer composition (PC1) according to any one of claims 1 to 2, characterized in that, The apparent bulk density of the polymer powder is between 0.1 g / cm 3 and 0.60 g / cm 3 .

11. The polymer composition according to any one of claims 1 to 2, characterized in that, The polymer composition (PC1) in the form of a polymer powder or the polymer powder composition POW1 comprises polymer particles PAR, which account for at least 50% by weight of the polymer composition (PC1) in the form of a polymer powder or the polymer powder composition POW1.

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

13. The polymer composition according to any one of claims 1 to 2, characterized in that, The fraction (A) is the first fraction, and the fraction (B) containing the polymer (B1) is grafted on the fraction (A) containing the polymer (A1).

14. The polymer composition according to any one of claims 1 to 2, characterized in that, The polymers (B1) and (C1) are acrylic polymers or (meth)acrylic polymers.

15. The polymer composition according to any one of claims 1 to 2, characterized in that, The polymer (A1) contains butadiene as a monomer.

16. The polymer composition according to any one of claims 1 to 2, characterized in that, The polymers (A1), (B1) and (C1) are acrylic polymers or (meth)acrylic polymers.

17. The polymer composition according to claim 14, wherein At least 80% by weight of the acrylic monomers or methacrylic monomers of the polymers (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. A method for preparing a polymer composition according to any one of claims 1 to 17, comprising the following steps: a) By subjecting a monomer or monomer mixture (A m ) to emulsion polymerization to obtain a layer of grade (A) comprising a polymer (A1) having a glass transition temperature below 10 °C, b) By subjecting a monomer or monomer mixture (B m ) to emulsion polymerization to obtain a layer of grade (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C c) by subjecting a monomer or monomer mixture (C m ) to emulsion polymerization to obtain a layer of class (C) comprising a polymer (C1) having a glass transition temperature of at least 30 °C d) Coagulate the composition obtained in steps a) to c).

19. A method for preparing a polymer composition (PC1) according to any one of claims 1 to 17, comprising the following steps: a) By subjecting a monomer or monomer mixture (A m ) to emulsion polymerization to obtain a layer of grade (A) containing a polymer (A1) having a glass transition temperature below 10 °C, b) By subjecting a monomer or monomer mixture (B m ) to emulsion polymerization to obtain a layer of grade (B) comprising a polymer (B1) having a glass transition temperature of at least 60 °C, Steps a) and b) together produce a multi-stage polymer (MP1), and step c) blending the multi-stage polymer (MP1) with a polymer (C1) having a glass transition temperature of at least 30 °C, d) Coagulate the composition obtained in steps a) to c).

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

21. The method according to any one of claims 18 to 19, characterized in that, Said step b) is carried out in the presence of the polymer (A1) obtained in step a).

22. The method according to any one of claims 18 to 19, characterized in that, Said steps a), b), c) and d) are carried out in said order.

23. The method according to any one of claims 18 to 19, characterized in that, The solids content before starting said coagulation is less than 35% by weight.

24. The method according to any one of claims 18 to 19, characterized in that, The solids content before starting said coagulation is less than 32% by weight.

25. The method according to any one of claims 18 to 19, characterized in that, In said step d), the solids content before starting said coagulation is between 5% and 35% by weight.

26. The method according to any one of claims 18 to 19, characterized in that, In said step d), the solids content before starting said coagulation is between 20% and 35% by weight.

27. The method according to any one of claims 18 to 19, characterized in that, In said step d), the solids content before starting said coagulation is between 5% and 20% by weight.

28. The method according to any one of claims 18 to 19, characterized in that In said step d), the solids content before starting said coagulation is between 10% and 25% by weight.

29. The method according to any one of claims 18 to 19, characterized in that, In said step d), the solids content before starting said coagulation is between 15% and 27% by weight.

30. The method according to any one of claims 18 to 19, characterized in that, In said step d), said coagulation is carried out using a salt or an inorganic acid.

31. The method according to any one of claims 18 to 19, characterized in that, The method additionally includes a drying step e).

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

33. Use of a polymer composition (PC1) according to any one of claims 1 to 17 as a composition for reducing the dispersion time.

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

35. The method according to claim 34, wherein The method comprises the following steps: - providing a precursor of a thermosetting polymer or a monomer of a thermoplastic polymer, - bringing the polymer composition (PC1) into contact with the precursor.

36. A method for reducing the dispersion time of a polymer composition (PC1) in a liquid composition, comprising the following steps: a) providing a polymer composition (PC1) according to any one of claims 1-17 in the form of a porous polymer powder POW1, having a total intrusion volume of at least 1.2 ml / g measured by mercury porosimetry, b) bringing the polymer composition into contact with a liquid composition LC1.

37. The method according to claim 36, wherein The liquid composition LC1 is selected from compositions for preparing vinyl esters, unsaturated polyesters or epoxy resins; or it is a styrenic monomer, or a (meth)acrylic monomer, or a mixture thereof, or a liquid composition containing said monomers.

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

39. A polymer composition PC2 comprising the polymer composition (PC1) according to any one of claims 1 to 17 as an impact modifier.

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