Composition comprising a multistage polymer and (METH) acrylic polymer, method for the preparation thereof and use thereof

Abstract

A composition comprising a multistage polymer and a (meth) acrylic polymer is provided.SOLUTION: In particular the present invention relates to a composition comprising a multistage polymer in the form of polymer particles made by a multistage process and a (meth) acrylic polymer wherein the (meth) acrylic polymer has an intermediate molecular weight. More particularly, the present invention relates to a polymer composition comprising polymer particles made by a multistage process comprising at least two stages and a (meth) acrylic polymer of intermediate molecular weight, to a process for its preparation, to its use as impact modifier in a polymer composition for composites comprising a thermoset or thermoplastic polymer and the composition and to articles comprising it.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compositions comprising multi-stage polymers and (meth)acrylic polymers, their preparation methods and their uses.

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

[0003] More particularly, the present invention relates to a polymer composition comprising polymer particles made by a multi-stage process comprising at least two stages and a medium molecular weight (meth)acrylic polymer, a method for preparing the same, its use as an impact modifier in polymer compositions for composites comprising the composition with a thermosetting or thermoplastic polymer, and articles comprising the same.

[0004] Mechanical or structural parts or articles or structural adhesives that must absorb high stresses during their use are widely manufactured from polymeric materials. Mechanical or structural parts or articles are usually composites, while structural adhesives can be purely polymeric. A composite is a macroscopic combination of two or more immiscible materials. A composite consists of at least a matrix material that forms a continuous phase for structural bonding, and reinforcement materials with various architectures for mechanical properties.

[0005] The purpose of using composite materials is to achieve performance from them that is not available from their individual components when used alone. Composite materials are therefore widely used in several industrial sectors, such as construction, automotive, aerospace, transportation, leisure, electronics, and sports, especially due to their better mechanical performance (high tensile strength, high tensile modulus, high fracture toughness) compared to homogeneous materials and their lower density.

[0006] The most important class in terms of commercial industrial quantities are composites with organic matrices, the matrix material of which is generally a polymer. The primary matrix or continuous phase of polymer composites is either a thermoplastic or a thermosetting polymer.

[0007] Thermosetting polymers consist of cross-linked three-dimensional structures. The cross-linking is achieved by curing reactive groups within so-called prepolymers. For example, curing can be achieved by heating the polymer chains to cross-link and permanently harden the material.

[0008] To prepare a polymer composite, a prepolymer is mixed with other ingredients such as glass beads or fibers, or other ingredients that are subsequently wetted or impregnated and cured. Examples of thermosetting polymer prepolymers or matrix materials are unsaturated polyester, vinyl ester, epoxy, or phenolic.

[0009] Once cured, thermosetting resins have excellent properties in terms of dimensional stability, mechanical strength, electrical insulation, heat resistance, water resistance, and chemical resistance. Examples of such thermosetting resins include epoxy resins and phenolic resins. However, such cured resins have low fracture toughness and are brittle.

[0010] Thermoplastic polymers consist of linear or branched polymers that are not crosslinked. To produce a composite, the necessary components (e.g., fibrous base material and thermoplastic polymer for the matrix) are mixed and the thermoplastic polymer can be heated to cool for hardening. Wetting or proper impregnation of the fibers with the thermoplastic polymer can only be achieved if the thermoplastic resin is sufficiently fluid.

[0011] Another method for impregnating fibrous base materials is to dissolve the thermoplastic polymer in an organic solvent or to use a syrup based on a monomer or a mixture of monomers and polymers.

[0012] To ensure and obtain satisfactory mechanical performance over a wide temperature range, the impact performance of the thermoplastic polymer matrix must be increased.

[0013] Impact modifiers in the form of core-shell particles are typically made by a multi-step process involving at least one stage containing a rubbery polymer, after which the particles are incorporated into one of the brittle polymer or structural adhesive phases of a composite to enhance the impact resistance of the finished product.

[0014] However, these types of multi-stage polymers are not easy to disperse, especially with a uniform distribution and / or in significant amounts, in any kind of resin or polymer; for example, in epoxy or methacrylic resins, but also in other precursors of polymer phases or monomers for composites and structural adhesives.

[0015] A good uniform dispersion is necessary to obtain satisfactory impact performance.

[0016] The object of the present invention is to propose a multi-stage polymer composition which is quickly and easily dispersible in reactive epoxy, polyester or (meth)acrylic resins / polymers or liquid monomers or resins, while having a viscosity suitable for the required application.

[0017] The object of the present invention is also to propose a multi-stage polymer composition which is easily dispersible in reactive epoxy resins, polyester resins or (meth)acrylic resins / polymers or resins in liquid monomer or polymer powder form.

[0018] 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, polyester or (meth)acrylic resins / polymers or liquid monomers or resins.

[0019] Another object of the present invention is to propose a method for making multi-stage polymer compositions that are easily dispersible in reactive epoxy, polyester or (meth)acrylic resins / polymers or liquid monomers or resins.

[0020] Yet another object of the present invention is a method for producing a dry multi-stage polymer composition that is readily dispersible in reactive epoxy resins, polyester resins or (meth)acrylic resins / polymers or liquid monomers or resins.

[0021] A still further object is to propose an impact-modified cured resin or adhesive composition that has satisfactory impact properties. [Background technology]

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

[0023] 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.

[0024] Document FR2934866 discloses the preparation of specific core-shell polymers with a functional shell containing a hydrophilic monomer. The core-shell polymers are used as impact modifiers for thermosetting polymers.

[0025] Document EP 1632533 describes a process for the preparation of modified epoxy resins: an epoxy resin composition in which rubbery polymer particles are dispersed by contacting the particles with an organic medium in which the rubber particles are dispersed.

[0026] Document EP1666519 discloses a method for producing rubbery polymer particles and resin compositions containing them.

[0027] Document EP2123711 discloses a thermosetting resin composition having rubbery polymer particles dispersed therein and a method for producing the same.

[0028] Document EP 0 066 382 A1 discloses bulk-flowable impact modifier particles. The solidified 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 of more than 800,000 and its weight proportion is between 0.1 and 10% by weight.

[0029] None of the prior art documents discloses multi-stage polymers in combination with (meth)acrylic polymers having intermediate molecular weights in selective weight ratios. Summary of the Invention

[0030] Surprisingly, a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C b) a step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, and c) Polymers (C1) having a glass transition temperature of at least 30°C It has been found that a polymer composition (PC1) comprising at least components a) and b) of composition (PC1) which are part of a multi-stage polymer (MP1), characterized in that polymer (C1) has a weight average molecular weight Mw of at least 100,000 g and that component c) represents up to 40% by weight of the composition based on a), b) and c), can be easily dispersed in a polymer matrix material for a thermosetting or thermoplastic polymer or a precursor thereof.

[0031] Surprisingly, a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer of step (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 of step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C. c) Monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer of step (C) comprising a polymer (C1) having a glass transition temperature of at least 30°C. A method for producing a polymer composition (PC1), comprising: It has also been found that a process characterized in that the polymer (C1) has a weight-average molecular weight Mw of at least 100,000 g / mol and in that component c) represents up to 40% by weight of the composition, based on a), b) and c), results in a polymer composition in the form of polymer particles that are easily dispersed in a polymer matrix material for a thermosetting or thermoplastic polymer or precursors thereof.

[0032] Surprisingly, a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer of step (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 of stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, steps a) and b) together producing a multi-stage polymer (MP1). c) mixing a polymer (C1) having a glass transition temperature of at least 30°C with a multi-stage polymer (MP1) A method for producing a polymer composition (PC1), comprising: It has also been found that a process characterized in that the polymer (C1) has a weight-average molecular weight Mw of at least 100,000 g / mol and in that component c) represents at most 40% by weight of the composition obtained in steps a), b) and c) results in a polymer composition in the form of polymer particles that are easily dispersed in a polymer matrix material for the thermosetting or thermoplastic polymer or precursors thereof.

[0033] Surprisingly, i) polymer (P2) ii) a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C b) a step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, and c) Polymers (C1) having a glass transition temperature of at least 30°C a polymer composition (PC1) comprising In a polymer composition (PC2) comprising It has also been found that polymer compositions (PC2) characterized in that at least components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1), and that polymer (C1) has a weight-average molecular weight Mw of at least 100,000 g and that component c) represents up to 40% by weight of the composition, based on a), b) and c), have satisfactory impact properties.

[0034] According to a first aspect, the present invention provides a method for producing a cellular membrane comprising: a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C b) a step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, and c) Polymers (C1) having a glass transition temperature of at least 30°C In a polymer composition (PC1) comprising 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 multi-stage polymer (MP1), and characterized in that the polymer (C1) has a weight average molecular weight Mw of at least 100,000 g and that component c) represents up to 40% by weight of the composition based on a), b) and c).

[0035] According to a second aspect, the present invention provides a method for producing a cellular membrane comprising: a) Monomer or monomer mixture (A m) by emulsion polymerization to obtain one layer of step (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 of step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C. c) Monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer of step (C) comprising a polymer (C1) having a glass transition temperature of at least 30°C. A method for producing a polymer composition (PC1), comprising: The polymer (C1) has a weight-average molecular weight Mw of at least 100,000 g / mol and component c) represents up to 40% by weight of the composition based on a), b) and c).

[0036] In a third aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer of step (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 of stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, steps a) and b) together producing a multi-stage polymer (MP1); c) mixing a polymer (C1) having a glass transition temperature of at least 30°C with a multi-stage polymer (MP1) A method for producing a polymer composition (PC1), comprising: The polymer (C1) has a weight-average molecular weight Mw of at least 100,000 g / mol and component c) represents at most 40% by weight of the composition obtained in steps a), b) and c).

[0037] In a fourth aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: i) polymer (P2) ii) a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C b) a step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, and c) Polymers (C1) having a glass transition temperature of at least 30°C a polymer composition (PC1) comprising In a polymer composition (PC2) comprising The polymer composition (PC2) is characterized in that the polymer (C1) has a weight-average molecular weight Mw of at least 100,000 g and that component c) represents up to 40% by weight of the composition based on a), b) and c).

[0038] The term "polymer powder" as used means a polymer comprising powder grains in the range of at least 1 μm obtained by agglomeration of a primary polymer comprising particles in the nanometer range.

[0039] The term "primary particles" as used means 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.

[0040] The term "particle size" as used means the volume average diameter of a particle considered to be spherical.

[0041] The term "thermoplastic polymer" as used means a polymer that when heated turns into a liquid or becomes more liquid or less viscous and can assume new shapes with the application of heat and pressure.

[0042] The term "medium molecular weight" as used means a weight average molecular weight Mw in the range of 100,000 g / mol to 1,000,000 g / mol.

[0043] The term "thermoset polymer" as used herein means a prepolymer in a soft, solid, or viscous state that is irreversibly transformed upon curing into an infusible, insoluble polymer network.

[0044] As used herein, the term "polymer composite" refers to a multi-component material that includes a plurality of different phase domains, at least one type of phase domain being continuous, and at least one component being polymeric.

[0045] The term "copolymer" is used to mean that the polymer is made up of at least two different monomers.

[0046] As used herein, "multi-stage polymer" refers to a polymer formed in a sequential manner by a multi-stage polymerization process. Preferred is a multi-stage emulsion polymerization process in which a first polymer is a first stage polymer and a second polymer is a second stage polymer, i.e., the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer, and there are at least two stages that differ in composition.

[0047] The term "(meth)acrylic" as used refers to all types of acrylic and methacrylic monomers.

[0048] The term "(meth)acrylic polymer" as used means that the (meth)acrylic polymer essentially comprises a polymer with (meth)acrylic monomers constituting 50% or more by weight of the (meth)acrylic polymer.

[0049] The term "dry" used means that the proportion of residual water is less than 1.5% by weight, preferably less than 1% by weight.

[0050] In the present invention, a range from x to y means that the upper and lower limits of this range are included, and is at least equal to x to y.

[0051] 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.

[0052] Regarding the polymer composition (PC1) according to the present invention, it comprises a) a polymer (A1) having a glass transition temperature of less than 10°C, b) a polymer (B1) having a glass transition temperature of at least 60°C, and c) a polymer (C1) having a glass transition temperature of at least 30°C.

[0053] Component c) represents up to 40% by weight of the composition, based on a), b) and c). Preferably, component c) represents up to 35% by weight of the composition, based on a), b) and c), more preferably up to 30%, even more preferably less than 30%, advantageously less than 25%, and even more advantageously less than 20%.

[0054] Component c) comprises more than 4% by weight of the composition, based on a), b), and c). Preferably, component c) comprises more than 5% by weight of the composition, based on a), b), and c), more preferably more than 6%, even more preferably more than 7%, advantageously more than 8%, and even more advantageously more than 10%.

[0055] Component c) comprises between 4% and 40% by weight of the composition, based on a), b), and c). Preferably, component c) comprises between 5% and 35% by weight of the composition, based on a), b), and c); more preferably between 6% and 30% by weight, even more preferably between 7% and less than 30% by weight, advantageously between 7% and less than 25% by weight, and even more advantageously between 10% and less than 20% by weight.

[0056] At least components a) and b) of component (PC1) are part of a multi-stage polymer (MP1).

[0057] At least components a) and b) are obtained by a multistage process comprising at least two stages; these two polymers (A1) and (B1) form a multistage polymer.

[0058] The multi-stage polymer (MP1) of the composition (PC1) according to the invention has at least two stages which differ in their polymer composition.

[0059] The multi-stage polymer (MP1) is preferably in the form of polymer particles, which can be considered spherical particles. These particles 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.

[0060] The particles according to the invention, which are primary particles, have a weight average particle size between 15 and 900 nm. Preferably, the weight average particle size of the polymer is between 20 and 800 nm, more preferably between 25 and 600 nm, even more preferably between 30 and 550 nm, even more preferably between 35 and 500 nm, advantageously between 40 and 400 nm, even more advantageously between 75 and 350 nm, advantageously between 80 and 300 nm. Primary polymer particles may agglomerate to give the polymer powder of the invention.

[0061] The primary polymer particles according to the invention have a multilayer structure comprising at least one stage (A) comprising a polymer (A1) having a glass transition temperature below 10°C, at least one stage (B) comprising a polymer (B1) having a glass transition temperature above 60°C, and at least one stage (C) comprising a polymer (C1) having a glass transition temperature above 30°C.

[0062] Preferably, step (A) is the first of at least two steps, step (B) comprising polymer (B1) grafted to step (A) comprising polymer (A1) or another intermediate layer.

[0063] Also, there may be another stage before stage (A) so that stage (A) is also a shell.

[0064] In a first embodiment, the polymer (A1) having a glass transition temperature of less than 10° C. comprises at least 50% by weight 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.

[0065] Concerning polymer (A1) of the first preferred embodiment, it is a (meth)acrylic polymer comprising at least 50% by weight of polymer units derived from acrylic monomers, preferably 60% by weight, more preferably 70% by weight of polymer (A1) being acrylic monomers.

[0066] 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 monomers of C2 to C12 alkyl acrylic monomers or mixtures thereof. Even more preferably, the acrylic monomers in polymer (A1) comprise monomers of C2 to C8 alkyl acrylic monomers or mixtures thereof.

[0067] 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.

[0068] The comonomer(s) in the polymer (A1) are preferably selected from (meth)acrylic and / or vinylic monomers.

[0069] 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, as long as polymer (A1) has a glass transition temperature of less than 10°C.

[0070] In a particular embodiment, polymer (A1) is a homopolymer of butyl acrylate.

[0071] More preferably, the glass transition temperature Tg of the polymer (A1) comprising at least 70% by weight of polymer units derived 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 even more advantageously between -70°C and -20°C.

[0072] In a second preferred embodiment, the polymer (A1) having a glass transition temperature of less than 10° C. comprises at least 50% by weight 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.

[0073] For example, the polymer (A1) of the core of the second embodiment may be an isoprene homopolymer or a butadiene homopolymer, an isoprene-butadiene copolymer, a copolymer of isoprene with up to 98% by weight of a vinyl monomer, or a copolymer of butadiene with up to 98% by weight 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.

[0074] More preferably, the glass transition temperature Tg of the polymer (A1) comprising at least 50% by weight 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.

[0075] In a third preferred embodiment, polymer (A1) is a silicone rubber-based polymer. For example, the silicone rubber is 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 even more advantageously between -135°C and -25°C.

[0076] 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.

[0077] Preferably, polymer (B1) comprises at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. Even more preferably, polymer (B1) comprises at least 80% by weight of monomers C1-C4 alkyl methacrylate and / or C1-C8 alkyl acrylate monomers.

[0078] 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.

[0079] Advantageously, polymer (B1) comprises at least 70% by weight of monomer units derived from methyl methacrylate.

[0080] 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.

[0081] Preferably, the polymer (B1) is grafted onto the polymer prepared in the previous step.

[0082] In certain embodiments, the polymer (B1) is crosslinked. In one embodiment, polymer (B1) comprises a functional comonomer selected from acrylic acid or methacrylic acid, amides derived from these acids, such as dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, 2-aminoethyl acrylate or methacrylate, optionally quaternized, 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 ranging from 400 g / mol to 10,000 g / mol.

[0083] Concerning polymer (C1), this has a weight average molecular weight Mw of at least 100,000 g / mol, preferably greater than 100,000 g / mol, more preferably greater than 105,000 g / mol, even more preferably greater than 110,000 g / mol, advantageously greater than 120,000 g / mol, more advantageously greater than 130,000 g / mol, and even more advantageously greater than 140,000 g / mol.

[0084] The polymer (C1) has a weight average molecular weight Mw of less than 1,000,000 g / mol, preferably less than 900,000 g / mol, more preferably less than 800,000 g / mol, even more preferably less than 700,000 g / mol, advantageously less than 600,000 g / mol, more advantageously less than 550,000 g / mol, even more advantageously less than 500,000 g / mol and most advantageously less than 450,000 g / mol.

[0085] The weight average molecular weight Mw of polymer (C1) is between 100,000 and 1,000,000 g / mol, preferably between 105,000 and 900,000 g / mol, more preferably between 110,000 and 800,000 g / mol, advantageously between 120,000 and 700,000 g / mol, even more advantageously between 130,000 and 600,000 g / mol, and most advantageously between 140,000 and 500,000 g / mol.

[0086] 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% by weight of monomers selected from C1 to C12 alkyl (meth)acrylates. Advantageously, polymer (C1) comprises at least 80% by weight of monomers of C1 to C4 alkyl methacrylate and / or C1 to C8 alkyl acrylate monomers.

[0087] 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.

[0088] Preferably, the polymer (C1) is not crosslinked.

[0089] Preferably, polymer (C1) is not grafted to either polymer (A1) or (B1).

[0090] In one embodiment, polymer (C1) also comprises a functional comonomer.

[0091] The functional comonomer has the formula (1): TIFF2026004304000001.tif27170

[0092] In the above formula, 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.

[0093] 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, 2-aminoethyl acrylate or methacrylate, optionally quaternized, polyethylene glycol (meth)acrylate, the polyethylene glycol group of which preferably has a molecular weight ranging from 400 g / mol to 10,000 g / mol.

[0094] In a first preferred embodiment, the polymer (C1) comprises from 80% to 100% by weight of methyl methacrylate, preferably from 80% to 99.8% by weight of methyl methacrylate and from 0.2% to 20% by weight of a C1-C8 alkyl acrylate monomer, advantageously chosen from methyl acrylate, ethyl acrylate or butyl acrylate.

[0095] In a second preferred embodiment, the polymer (C1) comprises between 0 and 50% by weight of functional monomers. Preferably, the meth)acrylic polymer (C1) comprises between 0 and 30% by weight, more preferably between 1 and 30% by weight, even 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 functional monomers.

[0096] Preferably, the functional monomer of the second preferred embodiment is a (meth)acrylic monomer. The functional monomer has formula (2) or (3). TIFF2026004304000002.tif25170TIFF2026004304000003.tif25170

[0097] In the above formulas, 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; in formula (3), Y is N and R4 and / or R3 are H or an aliphatic or aromatic group.

[0098] Preferably, the functional monomer (2) or (3) is selected from glycidyl (meth)acrylate, acrylic or methacrylic acid, amides derived from these acids, such as dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, 2-aminoethyl acrylate or methacrylate, optionally quaternized, acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkylimidazolidinone (meth)acrylates, polyethylene glycol (meth)acrylates, the polyethylene glycol group of which preferably has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0099] The primary polymer particles according to the invention are obtained by a multistage process comprising at least two stages: at least components a) and b) of composition (PC1) are part of a multistage polymer (MP1).

[0100] Preferably, the polymer (A1) having a glass transition temperature of less than 10° C. produced during step (A) is produced before step (B) or is the first step of a multi-step process.

[0101] Preferably, the polymer (B1) having a glass transition temperature above 60° C. produced during step (B) is produced after step (A) of the multi-step process.

[0102] In a first preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30° C. is the intermediate layer of polymer particles having a multilayer structure.

[0103] Preferably, the polymer (C1) having a glass transition temperature above 30° C. produced during step (C) is produced after step (B) of the multi-step process.

[0104] More preferably, the polymer (C1) having a glass transition temperature above 30° C. produced during step (C) is the outer layer of a primary polymer particle having a multilayer structure.

[0105] There may be further intermediate steps between steps (A) and (B) and / or between steps (B) and (C).

[0106] 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 multi-stage polymer (MP1).

[0107] This is further illustrated in the process for preparing the composition according to the invention comprising polymer (C1) and a multi-stage polymer.

[0108] With respect to the complete polymer particle, the weight proportion r of polymer (C1) of the outer layer comprised in step (C) is at least 5% by weight, more preferably at least 7% by weight, even more preferably at least 10% by weight.

[0109] According to the invention, the proportion r of the outer stage (C) comprising polymer (C1), relative to the complete polymer particle, is at most 30% by weight.

[0110] Preferably, the proportion of polymer (C1) with respect to the primary polymer particles is between 5 and 30% by weight, preferably between 5 and 20% by weight.

[0111] In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30° C. is the outer layer of a primary polymer particle having a multi-layer structure, in other words the multi-stage polymer (MP1).

[0112] Preferably, at least a portion of the polymer (B1) of layer (B) is grafted onto the polymer prepared in the previous layer. When there are only two stages (A) and (B) containing polymers (A1) and (B1), respectively, a portion of the polymer (B1) is grafted onto the polymer (A1). More preferably, at least 50% by weight of the polymer (B1) is grafted. The degree of grafting can be determined by extracting the polymer (B1) with a solvent and weighing it before and after extraction to determine the non-grafted amount.

[0113] The glass transition temperature Tg of each polymer can be estimated by dynamic methods, such as thermomechanical analysis.

[0114] To obtain samples of each polymer (A1) and (B1), they can be prepared individually rather than in a multi-stage process in order to more easily estimate and measure the glass transition temperature Tg of each polymer at each stage. Polymer (C1) can be extracted to estimate and measure the glass transition temperature Tg.

[0115] 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% by weight of the composition. Monomers in the synthesis of each polymer are not considered solvents. Residual monomers in the composition constitute less than 2% by weight of the composition.

[0116] 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% by weight of moisture, preferably less than 1.5% by weight of moisture, more preferably less than 1.2% by weight of moisture.

[0117] The moisture content can be measured by a thermobalance, which heats the polymer composition and measures the weight loss.

[0118] The compositions of the present invention do not contain any voluntarily added solvents. Finally, residual monomers and water from the polymerization of the respective monomers are not considered solvents.

[0119] It relates to a first preferred method for producing the polymer composition (PC1) according to the invention, which comprises: a) Monomer or monomer mixture (A m ) by emulsion polymerization to obtain one layer of step (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 of step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C. c) Monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer of step (C) comprising a polymer (C1) having a glass transition temperature of at least 30°C. Including, The polymer (C1) has a weight-average molecular weight Mw of at least 100,000 g / mol and component c) represents up to 30% by weight of the composition based on a), b) and c).

[0120] Preferably, step a) is carried out before step b).

[0121] More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a).

[0122] 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 of step (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 of step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C. c) Monomer or monomer mixture (C m ) by emulsion polymerization to obtain a layer of step (C) comprising a polymer (C1) having a glass transition temperature of at least 30°C. sequentially including, It is a multistage process characterized in that the polymer (C1) has a weight average molecular weight Mw of at least 100,000 g / mol.

[0123] Preferably, steps a), b) and c) are carried out in that order.

[0124] The respective monomers or monomer mixtures (A1), (B1) and (C1) for forming the layers (A), (B) and (C) containing the polymers (A1), (B1) and (C1), respectively, are m ), (B m ) and (C m ) are as defined above. The properties of polymers (A1), (B1), and (C1) are as defined above.

[0125] Preferably, the first preferred method for producing the polymer composition according to the invention comprises a further step d) of recovering the polymer composition.

[0126] Recovery refers to the partitioning or separation between the aqueous phase and the solid phase, the latter comprising the polymer composition.

[0127] More preferably, according to the present invention, recovery of the polymer composition is carried out by coagulation or spray drying.

[0128] When the polymer (A1) having a glass transition temperature of less than 10°C comprises at least 50% by weight of polymer units derived from alkyl acrylates and step (A) is the innermost layer of a polymer particle having a multi-layer structure, spray drying is the preferred recovery and / or drying method for the method for producing the polymer powder composition according to the present invention.

[0129] When the polymer (A1) having a glass transition temperature of less than 10° C. comprises at least 50% by weight of polymer units derived from isoprene or butadiene and step (A) is the innermost layer of a polymer particle having a multi-layer structure, coagulation is the preferred recovery and / or drying method for the method for producing a polymer powder composition according to the present invention.

[0130] The process for preparing the polymer composition according to the invention may optionally comprise a further step e) of drying the polymer composition.

[0131] Preferably, when step d) of recovering the polymer composition is carried out by coagulation, a drying step e) is carried out.

[0132] Preferably, after drying step e), the polymer composition contains less than 3% by weight of moisture or water, more preferably less than 1.5% by weight, advantageously less than 1%.

[0133] The moisture content of the polymer composition can be measured with a thermobalance.

[0134] Drying of the polymer can be carried out in an oven or vacuum oven while heating the composition at 50° C. for 48 hours.

[0135] It relates to a second preferred method for preparing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer (MP1), which comprises: a) Mixing process of polymer (C1) and multi-stage polymer (MP1); b) optionally recovering the mixture obtained from the previous step in the form of a polymer powder. Including, In step (a) the polymer (C1) and the multi-stage polymer (MP1) are in the form of a dispersion in an aqueous phase.

[0136] The multi-stage polymer (MP1) of the second preferred process for producing the polymer composition (PC1) is made according to the first preferred process without carrying out step c) of said first preferred process.

[0137] 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 5% by weight, preferably at least 10% by weight, more preferably at least 20% by weight, advantageously at least 50% by weight.

[0138] 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% by weight, preferably at most 95% by weight, more preferably at most 90% by weight.

[0139] The amounts of aqueous dispersion of polymer (C1) and aqueous dispersion of multi-stage polymer are selected so that the weight ratio of multi-stage polymer based on the solid portion alone in the resulting mixture is between 5% and 99% by weight, preferably between 10% and 95% by weight, more preferably between 20% and 90% by weight.

[0140] If recovery step b) is not performed, the polymer composition (PC1) is obtained as an aqueous dispersion of polymer particles, the solids content of the dispersion being between 10 and 65% by weight.

[0141] In one embodiment, the recovery step b) of the process for producing a polymer composition comprising polymer (C1) and multi-stage polymer (MP1) is not optional and is preferably done by coagulation or spray drying.

[0142] The process of the second preferred method for producing a polymer composition (PC1) comprising a polymer (C1) and a multi-stage polymer may optionally comprise a further step c) for drying the polymer composition.

[0143] By dry is meant that the polymer composition according to the present invention contains less than 3% by weight moisture, preferably less than 1.5% by weight moisture, more preferably less than 1.2% by weight moisture.

[0144] Moisture can be measured by a thermobalance, which heats the polymer composition and measures the weight loss.

[0145] The second preferred method for producing a polymer composition comprising polymer (C1) and a multi-stage polymer preferably produces a polymer powder. The polymer powder of the present invention is in the form of particles. The polymer powder particles comprise agglomerated primary polymer particles produced by the multi-stage process and polymer (C1).

[0146] As already mentioned, the polymer composition (PC1) according to the invention can also be in the form of larger polymer particles: polymer powder, which polymer powder particles comprise agglomerated primary polymer particles prepared by a multi-stage process according to the first preferred method, or agglomerated primary polymer particles prepared by mixing polymer particles consisting of polymer (C1) with a multi-stage polymer (MP1) obtained in a multi-stage process according to the second preferred method.

[0147] The polymer powder of the present invention has a volume median particle diameter D50 between 1 μm and 500 μm. Preferably, the volume median particle diameter of the polymer powder is between 10 μm and 400 μm, more preferably between 15 μm and 350 μm, advantageously between 20 μm and 300 μm.

[0148] The volume particle size distribution D10 is at least 7 μm, preferably 10 μm.

[0149] The volume particle size distribution D90 is at most 500 μm, preferably at most 400 μm, more preferably at most 350 μm, even more preferably at most 250 μm.

[0150] The present invention also relates to the use of the polymer composition (PC1) according to the invention in the form of a polymer powder as an impact modifier in a polymer, preferably a thermosetting or thermoplastic polymer or a precursor thereof, to obtain an impact-modified polymer composition.

[0151] The present invention also relates to the use of the polymer composition (PC1) according to the invention in the form of a polymer powder as an impact modifier in structural adhesives, preferably thermosetting polymers of the epoxy or (meth)acrylic type.

[0152] The impact-modifying polymer composition (PC2) according to the present invention comprises: i) polymer (P2) ii) a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C b) a step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, and c) Polymers (C1) having a glass transition temperature of at least 30°C a polymer composition (PC1) comprising Including, The polymer (C1) is characterized in that it has a weight average molecular weight Mw of at least 100,000 g.

[0153] The preferred and advantageous variants of the method for producing the polymer composition (PC1) obtained by a multi-stage process or by mixing are the same as those described above.

[0154] Each of the steps (A) and (B) and the polymers (A1), (B1) and (C1), respectively, are the same as those previously described.

[0155] The impact-modifying polymer composition (PC2) according to the present invention comprises between 1% and 50% by weight of the polymer composition (PC1).

[0156] The polymer (P2) can be a thermosetting polymer or a precursor thereof, or a thermoplastic polymer. The polymer (P2) can also be an adhesive, more preferably a structural adhesive.

[0157] With regard to thermosetting polymers, examples include unsaturated polyester resins, polyacrylics, polyurethanes, cyanoacrylates, bismaleimides and epoxy resins crosslinked with a curing agent.

[0158] As regards thermoplastic polymers, mention may be made, by way of example, of (meth)acrylic polymers or polyesters.

[0159] As regards epoxy resin polymers, mention may be made of resorcinol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl-p-aminophenol, bromobisphenol F diglycidyl ether, triglycidyl ether of m-aminophenol, tetraglycidylmethylenedianiline, triglycidyl ether of (trihydroxyphenyl)methane, polyglycidyl ether of phenol-formaldehyde novolac, polyglycidyl ether of ortho-cresol novolac, tetraglycidyl ether of tetraphenylethane, etc. Mixtures of at least two of these resins may also be used.

[0160] The epoxy resin composition according to the present invention comprises between 1% and 50% by weight, preferably between 2% and 30% by weight, more preferably between 5 and 20% of the polymer obtained by the multi-stage process.

[0161] [Evaluation method] [Glass transition temperature] The glass transition (Tg) of a polymer is measured with an instrument capable of performing thermomechanical analysis. The RDAII "RHEOMETRICS DYNAMIC ANALYSER" proposed by Rheometrics was used. Thermomechanical analysis accurately measures the viscoelastic changes of a sample in response to temperature, strain, or applied deformation. The instrument continuously records the deformation of the sample while maintaining a fixed strain during a controlled program of temperature change. The results are obtained by plotting the elastic modulus (G'), loss modulus, and tan δ as a function of temperature. Tg is the higher temperature value read off the tan δ curve where the derived value of tan δ is equal to zero.

[0162] [Molecular weight] The weight average molecular weight (Mw) of the polymer is measured by size exclusion chromatography (SEC).

[0163] [Particle size analysis] The particle size of the primary particles after multi-stage polymerization is measured with a Zetasizer manufactured by Malvern. The particle size of the recovered polymer powder is measured 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 fraction of fine particles.

Claims

1. a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C; b) a step (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 In a polymer composition (PC1) comprising A polymer composition characterized in that at least components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1), characterized in that polymer (C1) has a weight average molecular weight Mw of at least 100,000 g and component c) represents up to 40% by weight of the composition based on a), b) and c).

2. 2. The polymer composition according to claim 1, characterized in that the polymer (C1) has a weight average molecular weight Mw between 100,000 g / mol and 1,000,000 g / mol.

3. 2. The polymer composition according to claim 1, characterized in that the polymer (C1) has a weight average molecular weight Mw of less than 700,000 g / mol.

4. 2. The polymer composition according to claim 1, characterized in that the polymer (C1) has a weight average molecular weight Mw between 140,000 g / mol and 500,000 g / mol.

5. 2. The polymer composition of claim 1, wherein component c) comprises between 5 and 35% by weight of the composition based on a), b) and c).

6. 2. The polymer composition of claim 1, wherein component c) comprises between 7% and less than 25% by weight of the composition based on a), b) and c).

7. 2. Polymer composition according to claim 1, characterized in that component c) preferably represents more than 10% by weight of the composition, based on a), b) and c).

8. 2. The polymer composition of claim 1, wherein component c) comprises between 10% and less than 20% by weight of the composition based on a), b) and c).

9. 2. The polymer composition according to claim 1, characterized in that component c) accounts for between 10 and less than 20% by weight of the composition, based on a), b) and c), and polymer (C1) has a weight average molecular weight Mw of less than 700,000 g / mol.

10. 2. The polymer composition according to claim 1, characterized in that step (A) is the first step and step (B) comprising polymer (B1) is grafted onto step (A) comprising polymer (A1).

11. 11. The polymer composition according to claim 1, wherein the polymer (C1) is a (meth)acrylic polymer.

12. 12. Polymer composition according to any of the preceding claims, characterized in that the polymer (C1) comprises at least 80% by weight of monomers C1-C4 alkyl methacrylate and / or C1-C8 alkyl acrylate monomers.

13. 13. The polymer composition according to claim 1, wherein the polymer (C1) comprises a functional comonomer.

14. 14. Polymer composition according to claim 13, characterized in that the functional monomer is chosen 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.

15. 11. The polymer composition according to claim 1, wherein the polymer (B1) is crosslinked.

16. 11. Polymer composition according to any of claims 1 to 10, characterized in that the polymers (B1) and (C1) are acrylic or methacrylic polymers.

17. 11. Polymer composition according to claim 1, characterized in that the polymer (A1) contains butadiene as a monomer.

18. 11. Polymer composition according to any of claims 1 to 10, characterized in that the polymers (A1), (B1) and (C1) are acrylic or methacrylic polymers.

19. 19. The polymer composition of claim 18, wherein at least 80% by weight 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.

20. a) Monomer or monomer mixture (A ｍ ) by emulsion polymerization to obtain one layer of step (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 of step (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C. c) Monomer or monomer mixture (C ｍ ) by emulsion polymerization to obtain a layer of step (C) comprising a polymer (C1) having a glass transition temperature of at least 30° C.

20. A method for producing the polymer composition of any of claims 1 to 19, comprising:

1. A process according to claim 1, characterized in that the polymer (C1) has a weight average molecular weight Mw of at least 100,000 g / mol and that component c) represents up to 40% by weight of the composition, based on a), b) and c).

21. a) Monomer or monomer mixture (A ｍ ) by emulsion polymerization to obtain one layer of step (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 of stage (B) comprising a polymer (B1) having a glass transition temperature of at least 60°C, steps a) and b) together producing a multi-stage polymer (MP1). c) mixing a polymer (C1) having a glass transition temperature of at least 30° C. with a multi-stage polymer (MP1) 20. A process for producing a polymer composition (PC1) according to any one of claims 1 to 19, comprising:

1. A process according to claim 1, characterized in that the polymer (C1) has a weight average molecular weight Mw of at least 100,000 g / mol and that component c) accounts for a maximum of 40% by weight of the composition obtained in steps a), b) and c).

22. 22. The method according to claim 20 or 21, characterized in that step a) is carried out before step b).

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

24. 22. The method according to any one of claims 20 to 21, characterized in that steps a), b) and c) are carried out in this order.

25. 25. The method according to any of claims 20 to 24, characterized in that the method comprises the further step d) of recovering the polymer composition.

26. 26. The method according to claim 25, characterized in that step d) is carried out by coagulation or spray drying.

27. 25. The method according to any one of claims 20 to 24, characterized in that the polymer (C1) has a weight average molecular weight Mw between 100,000 g / mol and 1,000,000 g / mol.

28. 25. The method according to any one of claims 20 to 24, characterized in that the polymer (C1) has a weight average molecular weight Mw of less than 700,000 g / mol.

29. 25. The method according to any one of claims 20 to 24, characterized in that the polymer (C1) has a weight average molecular weight Mw between 140,000 g / mol and 500,000 g / mol.

30. 25. The method of any of claims 20 to 24, wherein component c) comprises between 10% and less than 20% by weight of the composition based on a), b) and c).

31. 25. The method according to claim 20, wherein component c) represents between 10% and less than 20% by weight of the composition based on a), b) and c) and polymer (C1) has a weight average molecular weight Mw of less than 700,000 g / mol.

32. 32. Use of a polymer composition according to any one of claims 1 to 19 or obtained by the process according to any one of claims 20 to 31 as an impact modifier.

33. i) polymer (P2); ii) a) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C; b) a step (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 a polymer composition (PC1) comprising In a polymer composition (PC2) comprising 1. A polymer composition, characterized in that the polymer (C1) has a weight average molecular weight Mw of at least 100,000 g and that component c) represents up to 40% by weight of the composition, based on a), b) and c).

34. 34. A polymer composition according to claim 33, characterized in that the polymer composition (PC1) is made according to the method of any of claims 20 to 31.

35. 35. Polymer composition according to claim 33 or 34, characterized in that the polymer (P2) is a thermosetting polymer or a precursor thereof, or a thermoplastic polymer or a structural adhesive.

36. 35. The polymer composition according to claim 33 or 34, characterized in that the polymer (C1) has a weight average molecular weight Mw between 100 000 g / mol and 1 000 000 g / mol.

37. 35. The polymer composition according to claim 33 or 34, characterized in that the polymer (C1) has a weight average molecular weight Mw of less than 700 000 g / mol.

38. 35. The polymer composition according to claim 33 or 34, characterized in that the polymer (C1) has a weight average molecular weight Mw of between 140 000 g / mol and 500 000 g / mol.

39. 35. A polymer composition according to claim 33 or 34, characterized in that component c) comprises between 10% and less than 20% by weight of the composition, based on a), b) and c).

40. 35. The polymer composition according to claim 33 or 34, characterized in that component c) represents between 10 and less than 20% by weight of the composition, based on a), b) and c), and polymer (C1) has a weight average molecular weight Mw of less than 700,000 g / mol.

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