COMPOSITION COMPRISING A COMPOUND HAVING TWO POLYMERIZABLE GROUPS, A MULTI-STAGE POLYMER, AND A THERMOPLASTIC POLYMER, METHOD FOR PREPARATION THEREOF, USE THEREOF, AND ARTICLES COMPRISING THE COMPOUND

Abstract

The present invention relates to a composition comprising a compound having two polymerizable groups, a multi-stage polymer, and a thermoplastic polymer, a method for preparing the same, and its use. In particular, the present invention relates to a composition comprising a compound having two polymerizable groups, a multi-stage polymer in the form of polymer particles made by a multi-stage process, and a (meth)acrylic polymer. More particularly, the present invention relates to a polymer composition comprising a compound having two polymerizable groups, polymer particles made by a multi-stage process including at least two stages, and a (meth)acrylic polymer, a method for preparing the same, its use in making impact-modified polymer compositions containing thermosetting resins, and compositions and articles containing the same.

Description

[Technical Field]

[0001] The present invention relates to a composition comprising a compound having two polymerizable groups, a multi-stage polymer, and a thermoplastic polymer, a method for preparing the composition, and uses of the composition.

[0002] In particular, the present invention relates to a composition comprising a compound having two polymerizable groups, a multi-stage polymer in the form of polymer particles made by a multi-stage process, and a (meth)acrylic polymer.

[0003] More particularly, the present invention relates to a polymer composition comprising a compound having two polymerizable groups, polymer particles made by a multi-stage process comprising at least two stages, and a (meth)acrylic polymer, a method for preparing the polymer composition, the use of the polymer composition in making an impact-modified polymer composition comprising a thermosetting resin, and compositions and articles comprising the polymer composition. [Background technology]

[0004] Many of today's articles are made from polymeric materials or contain polymers or polymer compositions. These articles must withstand mechanical stresses during use. Therefore, these articles need to be improved in terms of impact resistance.

[0005] One class of polymeric materials is thermosetting polymers, which are used, for example, in adhesives or polymer composites.

[0006] Thermosetting polymers consist of cross-linked three-dimensional structures. The cross-links can be obtained by curing reactive groups in so-called prepolymers. For example, curing can be achieved by heating the polymer chains to permanently cross-link and solidify the material.

[0007] To prepare polymer thermoset composites, prepolymers are mixed with other ingredients such as glass beads or fibers, or other ingredients that are wetted or impregnated and then cured. Examples of prepolymer or matrix materials for thermoset polymers are unsaturated polyester, vinyl ester, epoxy, or phenolic.

[0008] 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.

[0009] To ensure and obtain sufficient mechanical performance over a wide temperature range, the impact performance of the thermosetting polymer matrix must be improved.

[0010] One form of impact modifier is a core-shell particle, also known as a multistage polymer, produced by a multistage process, where at least one stage contains a rubber-like polymer. The particle is then incorporated into a brittle polymer for composites or one of the stages of a structural adhesive to improve the impact resistance of the final product.

[0011] However, these types of multi-stage polymers are not easy to disperse in all types of resins or polymers or even monomers, especially in small or large amounts with uniform distribution and / or in a reasonable amount of time, for example, curable resins such as unsaturated polyesters or vinyl esters, but also other precursors to polymer phases or monomers for composites and structural adhesives.

[0012] To have sufficient impact performance, a good uniform dispersion of the multi-stage polymer is required. The dispersion also needs to have adequate stability (pot life).

[0013] The object of the present invention is to propose a composition suitable for the preparation of toughened cured thermoset polymers, including multistage and thermoplastic polymers, which are homogeneous and stable while having a viscosity suitable for the required application.

[0014] An additional object of the present invention is to provide a composition suitable for preparing cured thermoset polymers, including thermoset polymer precursors, multi-stage polymers, and thermoplastic polymers, which can be easily and quickly prepared.

[0015] Another object of the present invention is to propose a method for producing a composition suitable for preparing a cured thermosetting polymer, comprising a precursor of the thermosetting polymer, a multi-stage polymer and a thermoplastic polymer, which is homogeneous, stable and has a viscosity suitable for the required application.

[0016] Yet another object of the present invention is a method for producing a cured, reinforced polymer composition having satisfactory impact properties.

[0017] The object of the present invention is to propose a method with reduced preparation time for compositions suitable for preparing cured thermosetting polymers, including multistage polymers.

[0018] A further object is to propose an impact-modified cured polymer having sufficient impact properties or an adhesive composition having sufficient impact and adhesive strength properties.

[0019] Background of the Invention prior art Document WO2016 / 102666 discloses a composition comprising a multistage polymer and a method for preparing the composition, the composition also comprising a (meth)acrylic polymer having a weight average molecular weight of less than 100,000 g / mol.

[0020] 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.

[0021] Document EP 2441784 A1 discloses a vinyl ester composition comprising polymeric particles, which are core-shell polymers with a shell comprising an aromatic vinyl monomer and a vinyl cyan monomer.

[0022] In document EP 1632533, a process for producing modified epoxy resins is described in which rubber-like polymer particles are dispersed in an epoxy resin composition by a process in which the particles are contacted with an organic medium in which the rubber particles are dispersed.

[0023] Document WO2019 / 011984 discloses a resin composition. The resin composition includes a resin system, a curing agent system, and a particle system. The particle system is a multi-stage polymer.

[0024] None of the prior art documents discloses the compositions or processes as claimed. Summary of the Invention

[0025] Surprisingly, a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); It has been found that composition (PC1) comprising, in which polymer (B1) has a weight-average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol, component b) represents up to 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c), can be easily dispersed in precursors of polymer matrix materials of thermosetting polymers.

[0026] Surprisingly, a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); It has also been found that composition (PC1) comprising the polymer (B1) has a weight-average molecular weight Mw of between 10,000 and 500,000 g / mol, component b) represents up to 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 and 100 phr, relative to 100 phr of component c), has good stability and remains homogeneous for a long period of time. By long period of time, we mean at least 2 weeks at 23°C, and by homogeneous, we mean that no significant separation occurs between the individual components.

[0027] Surprisingly, a method for producing composition (PC1) comprising the steps of: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a composition (Ci) comprising: ii) mixing composition (Ci) with a composition (Ciia) comprising at least one other component or compound present in composition (PC1); and iii) optionally mixing the composition obtained in step ii) with other components or compounds present in composition (PC1) that have not yet been added in step ii); It has also been found that a method comprising the steps of:

[0028] Surprisingly, a method for producing composition (PC1) comprising the steps of: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a polymer composition comprising: ii) c) providing a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), It has also been found that a process comprising the step of: iii) mixing components a), b) and c) in a ratio of the sum of components a) and b) to 100 phr of component c) between 0.5 and 100 phr results in a process that reduces the preparation time of composition (PC1) compared to a composition that does not contain component b).

[0029] Surprisingly, a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) said thermoplastic polymer (B1) in a maximum of 40% by weight of the composition based on a) and b); c) a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); It has also been found that the use of a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol in a composition (PC1) comprising, in which the sum of components a) and b) is between 0.5 phr and 100 phr relative to 100 phr of component c), reduces the preparation time of the composition (PC1) compared to a composition that does not contain component b).

[0030] Surprisingly, a method for producing a polymer composition (PC2) comprising the steps of: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a polymer composition (Ci) comprising ii) c) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), iii) mixing components a), b) and c) in a ratio of the sum of components a) and b) to 100 phr of component c) between 0.5 phr and 100 phr; and iv) polymerizing or curing the mixture. It has also been found that a method comprising:

[0031] Surprisingly, a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2); It has also been found that polymer composition (PC2) comprising, characterized in that the weight-average molecular weight Mw of polymer (B1) is between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c), has sufficient reinforcing properties. DETAILED DESCRIPTION OF THE INVENTION

[0032] According to a first aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); wherein the weight-average molecular weight Mw of polymer (B1) is between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c).

[0033] According to a second aspect, the present invention provides a method for producing a composition (PC1), comprising: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a composition (Ci) comprising: ii) mixing composition (Ci) with composition (Ciia) comprising at least one other component or compound present in composition (PC1); and iii) optionally mixing the composition obtained in step ii) with other components or compounds present in composition (PC1) that have not yet been added in step ii); The present invention relates to a method, comprising:

[0034] In a third aspect, the present invention provides a method for producing a composition (PC1), comprising the steps of: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a polymer composition (Ci) comprising ii) c) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), iii) mixing compositions (Ci) and (Ciib) comprising components a), b) and c) in a ratio of the sum of components a) and b) to 100 phr of component c) between 0.5 phr and 100 phr.

[0035] In a fourth aspect, the present invention provides a method for reducing the preparation time of a composition (PC1), comprising: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a polymer composition (Ci) comprising ii) c) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), iii) mixing components a), b) and c) in a ratio of the sum of components a) and b) to 100 phr of component c) between 0.5 phr and 100 phr; The present invention relates to a method, comprising:

[0036] In a fifth aspect, the present invention provides a method for producing a composition comprising: a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2); wherein the weight-average molecular weight Mw of polymer (B1) is between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c).

[0037] According to a sixth aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); in the preparation of an impact-modified polymer composition (PC2), characterized in that the weight-average molecular weight Mw of polymer (B1) is between 10,000 g / mol and 500,000 g / mol, component b) represents up to 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c).

[0038] The term "polymer powder" used refers to 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 refers to spherical polymer particles, including particles in the nanometer range. Preferably, the primary particles have a weight average particle size between 50 and 500 nm.

[0040] The term "particle size" as used refers to the volume mean diameter of the particle considered as a sphere.

[0041] The term "thermoplastic polymer" as used refers to a polymer that when heated turns into a liquid, becomes more liquid, or becomes less viscous and can assume new shapes by heat and pressure. Within the scope of the present invention, a thermoplastic polymer can also be crosslinked if it is still capable of being thermoformed.

[0042] The term "thermoset polymer" as used refers to a polymer (e.g., an oligomer or monomer having at least two reactive groups, or a mixture of both) that is made from a prepolymer in a soft, solid, or viscous state and that is irreversibly transformed upon curing into an infusible, insoluble polymer network.

[0043] The term "polymer composite" as used refers to a multi-component material that contains multiple distinct phase domains, at least one type of phase domain being the continuous phase, and at least one component being a polymer.

[0044] The term "copolymer" is used to indicate that the polymer is made up of at least two different monomers.

[0045] The term "multi-stage polymer" as used herein refers to a polymer formed sequentially by a multi-stage polymerization process. Preferred is a multi-stage emulsion polymerization process in which a first polymer is a first stage polymer and a second polymer is a second stage polymer, i.e., in at least two stages differing in composition, the second polymer being formed by emulsion polymerization in the presence of the first emulsion polymer.

[0046] The term "(meth)acrylic" as used refers to all types of acrylic and methacrylic monomers.

[0047] The term "(meth)acrylic polymer" as used herein means that the (meth)acrylic polymer essentially includes polymers with (meth)acrylic monomers constituting 50% or more by weight of the (meth)acrylic polymer.

[0048] The term "dry" as used refers to a residual water content of less than 1.5% by weight, preferably less than 1.25% by weight.

[0049] The term "total intrusion volume" used refers to the total volume of liquid mercury intrusion according to ISO 15901-1:2016. This volume is cumulated and analytical results indicate the cumulative intrusion volume in ml / g (cm) depending on the applied pressure or pore size. 3 The total intrusion volume is the volume intruded at the maximum pressure, which corresponds to the smallest pore size.

[0050] The term "incremental intrusion" as used refers to the amount intruded in ml / g between two specific pressures or two pore sizes. This incremental intrusion can also be expressed as vol% of the total intrusion.

[0051] The term "phr" as used refers to weight percentage. For example, 1 phr of compound A taking into account compound B in a composition means that 1 kg of compound A is added to or present in 100 kg taking into account compound B.

[0052] In the present invention, when a range is stated as x to y (from x to y), it means that the upper and lower limits of the range are included, and correspond to at least x and at most y.

[0053] In the present invention, by saying that a range is between x and y (between x and y), it is meant that the upper and lower limits of this range are excluded, corresponding to greater than x and less than y.

[0054] With regard to the composition according to the invention (PC1), said composition is preferably a polymer composition.

[0055] The polymer composition (PC1) comprises a) a multistage polymer (MP1), b) a thermoplastic polymer (B1), and c) a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), characterized in that the weight average molecular weight Mw of polymer (B1) is between 10,000 g / mol and 500,000 g / mol, component b) represents up to 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr per 100 phr of component c).

[0056] The multi-stage polymer (MP1) comprises a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, and a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C.

[0057] A thermoplastic polymer (B1) having a glass transition temperature of at least 30°C.

[0058] Component b) of composition (PC1) represents up to 40% by weight of a composition based only on a) and b). A composition based only on a) and b) is referred to as composition (Ci). Preferably, component b) of composition (Ci) represents up to 35% by weight of a composition based only on a) and b), more preferably up to 30% by weight, even more preferably less than 30% by weight, advantageously less than 25% by weight, and even more advantageously less than 20% by weight.

[0059] Component b) of composition (Ci) represents more than 0.5% by weight of the composition based only on a) and b). Preferably, component b) of composition (Ci) represents more than 1% by weight of the composition based only on a) and b), more preferably more than 2%, even more preferably more than 4%, advantageously more than 8% and even more advantageously more than 10% by weight.

[0060] Component b) represents between 0.5% and 40% by weight of the composition based solely on a) and b). Preferably, component b) represents between 5% and 35% by weight of the composition based solely on a) and b), 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.

[0061] At least component a) of composition (PC1) or composition (Ci) is part of a multistage polymer (MP1).

[0062] At least component a) is obtained by a multistage process comprising at least two stages (SA1) and (SA2), whereby the two polymers (A1) and (A2) form a multistage polymer (MP1).

[0063] In composition (PC1), the sum of components a) and b) relative to 100 phr of component c) is between 0.5 phr and 100 phr. Preferably, the sum of components a) and b) relative to 100 phr of component c) is between 1 phr and 100 phr.

[0064] In a first more preferred embodiment of composition (PC1), the sum of components a) and b) relative to 100 phr of component c) is between 1 phr and 50 phr, even more preferably between 1 phr and 25 phr, even more preferably between 1 phr and 20 phr, advantageously between 1 phr and 15 phr.

[0065] In a second more preferred embodiment of composition (PC1), the sum of components a) and b) relative to 100 phr of component c) is between 2 phr and 100 phr, even more preferably between 5 phr and 100 phr, even more preferably between 10 phr and 100 phr, advantageously between 15 phr and 100 phr.

[0066] In a third more preferred embodiment of composition (PC1), the sum of components a) and b) relative to 100 phr of component c) is between 15 phr and 100 phr, even more preferably between 17 phr and 100 phr, even more preferably between 19 phr and 100 phr, advantageously between 21 phr and 100 phr.

[0067] In a fourth more preferred embodiment of composition (PC1), the sum of components a) and b) relative to 100 phr of component c) is between 20 phr and 100 phr, even more preferably between 30 phr and 100 phr, even more preferably between 40 phr and 100 phr, advantageously between 50 phr and 100 phr.

[0068] In one embodiment, composition (PC1) is a liquid. In that case, the viscosity of composition (PC1) is between 1 mPa·s and 1,000 Pa·s. The viscosity is measured at 25°C. The viscosity is a dynamic viscosity. If shear thinning is expected, the dynamic viscosity value is taken at a shear rate of 1 1 / sec. The viscosity is measured using a rheometer.

[0069] Preferably, the viscosity of the liquid composition (PC1) is between 5 mPa·s and 900 Pa·s, more preferably between 10 mPa·s and 800 Pa·s, at a temperature of 25° C. and a shear rate of 1 1 / s.

[0070] The multi-stage polymer (MP1) of the composition (PC1) according to the invention has at least two stages (SA1) and (SA2) each comprising a polymer (A1) and (A2), respectively, each of which has a different polymer composition.

[0071] The multi-stage polymer (MP1) is preferably in the form of polymer particles that are considered spherical particles. These particles are also called core / shell particles. The first stage (SA1) forms the core, and the second stage (SA2) forms the shell. Optionally, all subsequent stages form additional shells. Such multi-stage polymers (MP1), also called core / shell particles, are preferred.

[0072] The core / shell particles have a weight-average particle size (diameter) 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, and even more preferably between 35 and 500 nm, advantageously between 40 and 400 nm, more advantageously between 75 and 350 nm, and advantageously between 80 and 300 nm. The polymer core / shell particles themselves can be agglomerated to obtain a polymer powder rich in such polymer core / shell particles.

[0073] The multi-stage polymer (MP1) has a multi-layer structure comprising at least one stage (SA1) comprising a polymer (A1) having a glass transition temperature below 10°C and at least one stage (SA2) comprising a polymer (A2) having a glass transition temperature above 60°C.

[0074] In an optional variant, the multi-stage polymer (MP1) may also already comprise a stage (SB1) comprising a polymer (B1) having a glass transition temperature above 30° C. In this optional variant, component b) of composition (Ci) is combined with component a) of the composition of the invention. This variant is explained in more detail in the process section.

[0075] Preferably, step (SA1) is the first of at least two steps, step (SA2) comprising polymer (A2) being grafted to step (SA1) comprising polymer (A1), or to another optional intermediate layer.

[0076] In a further variant, step (SA1) can be preceded by another step, so that step (SA1) is also a shell, for example on a seed.

[0077] In a first embodiment, the polymer (A1) having a glass transition temperature of less than or equal to 10° C. comprises at least 50% by weight of polymer units derived from alkyl acrylates, and the stage (SA1) is the innermost layer of a multistage polymer (MP1) or a polymer particle having a multilayer structure. In other words, the stage (SA1) comprising the polymer (A1) is the core of the multistage polymer (MP1) or polymer particle.

[0078] Regarding polymer (A1) of the first preferred embodiment, polymer (A1) is a (meth)acrylic polymer containing 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.

[0079] The acrylic monomer units 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.

[0080] Polymer (A1) may contain one or more comonomers copolymerizable with the acrylic monomer, as long as the glass transition temperature of polymer (A1) is below 10°C.

[0081] The comonomer(s) in the polymer (A1) are preferably selected from (meth)acrylic and / or vinylic monomers.

[0082] 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 the glass transition temperature of polymer (A1) is below 10°C.

[0083] In a particular embodiment, polymer (A1) is a homopolymer of butyl acrylate.

[0084] 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 acrylate is between -100°C and 10°C, even more preferably between -80°C and 0°C, advantageously between -80°C and -20°C, and even more advantageously between -70°C and -20°C.

[0085] 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 (SA1) comprising polymer (A1) is the core of the polymer particle.

[0086] 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 up to 98% by weight of a vinyl monomer with isoprene, or a copolymer of up to 98% by weight of a vinyl monomer with butadiene. 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.

[0087] 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 -85°C and 0°C, and most advantageously between -80°C and -20°C.

[0088] In a third preferred embodiment, the polymer (A1) is a silicone rubber-based polymer. For example, the silicone rubber is polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (A1) of the second embodiment is between -150°C and 0°C, even more preferably between -145°C and -5°C, advantageously between -140°C and -15°C, and even more advantageously between -135°C and -25°C.

[0089] As regards the polymer (A2), mention may be made of homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers. Preferably, the polymer (A2) is a (meth)acrylic polymer, comprising more than 50% by weight of monomer units derived from (meth)acrylic monomers, and optionally a (meth)acrylic monomer as a styrene comoner, for example styrene.

[0090] Preferably, polymer (A2) comprises at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. Even more preferably, polymer (A2) comprises at least 80% by weight of C1-C4 alkyl methacrylate monomers and / or C1-C8 alkyl acrylate monomers.

[0091] Most preferably, the acrylic or methacrylic monomers of polymer (A2) are selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, as long as the glass transition temperature of polymer (A2) is at least 60°C.

[0092] Advantageously, polymer (A2) comprises at least 70% by weight of monomer units derived from methyl methacrylate.

[0093] Preferably, the glass transition temperature Tg of polymer (A2) is between 60° C. and 150° C. The glass transition temperature of polymer (A2) 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.

[0094] Preferably, polymer (A2) of the multi-stage polymer (MP1) is grafted onto polymer (A1) prepared in a previous stage.

[0095] In certain embodiments, the polymer (A2) is crosslinked.

[0096] In one embodiment, polymer (A2) comprises a functional comonomer selected from acrylic acid or methacrylic acid, amides derived from these acids, such as, for example, optionally quaternized, dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, 2-aminoethyl acrylate or methacrylate, polyethylene glycol (meth)acrylate, water-soluble vinyl monomers, such as N-vinylpyrrolidone, or mixtures thereof. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0097] With regard to the thermoplastic polymer (B1), the weight average molecular weight Mw of the thermoplastic polymer (B1) is between 10,000 g / mol and 500,000 g / mol.

[0098] The thermoplastic polymer (B1) has a weight average molecular weight Mw of more than 10,000 g / mol, preferably more than 10,500 g / mol, more preferably more than 11,000 g / mol, even more preferably more than 12,000 g / mol, advantageously more than 13,000 g / mol, more advantageously more than 14,000 g / mol, and even advantageously more than 15,000 g / mol.

[0099] The thermoplastic polymer (B1) has a weight average molecular weight Mw of less than 500,000 g / mol, preferably less than 450,000 g / mol, more preferably less than 400,000 g / mol, even more preferably less than 400,000 g / mol, advantageously less than 350,000 g / mol, more advantageously less than 300,000 g / mol, even more advantageously less than 250,000 g / mol and most advantageously less than 200,000 g / mol.

[0100] Preferably, the weight average molecular weight Mw of polymer (B1) is between 10,500 and 450,000 g / mol, more preferably between 11,000 and 400,000 g / mol, even more preferably between 12,000 and 350,000 g / mol, advantageously between 13,000 and 300,000 g / mol, more advantageously between 14,000 and 250,000 g / mol, and most advantageously between 15,000 and 200,000 g / mol.

[0101] In a first more preferred embodiment, the weight average molecular weight Mw of polymer (B1) is between 15,000 and 300,000 g / mol, more preferably between 15,000 and 200,000 g / mol, even more preferably between 15,000 and 190,000 g / mol, advantageously between 15,000 and 180,000 g / mol, more advantageously between 15,000 and 160,000 g / mol, and most advantageously between 15,000 and 150,000 g / mol.

[0102] In a second more preferred embodiment, the weight average molecular weight Mw of polymer (B1) is between 15,000 and 450,000 g / mol, more preferably between 18,000 and 400,000 g / mol, even more preferably between 20,000 and 350,000 g / mol, advantageously between 22,000 and 300,000 g / mol, more advantageously between 25,000 and 250,000 g / mol, and most advantageously between 30,000 and 200,000 g / mol.

[0103] Preferably, polymer (B1) is a copolymer comprising (meth)acrylic monomers. More preferably, polymer (B1) is a (meth)acrylic polymer. Even more preferably, polymer (B1) comprises at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. Advantageously, polymer (B1) comprises at least 80% by weight of C1-C4 alkyl methacrylate monomers and / or C1-C8 alkyl acrylate monomers.

[0104] Preferably, the glass transition temperature Tg of polymer (B1) is between 30° C. and 150° C. The glass transition temperature of polymer (B1) 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.

[0105] Preferably, the polymer (B1) is not crosslinked.

[0106] Preferably, when polymer (B1) is part of a multi-stage polymer, polymer (B1) is not grafted to either polymer (A1) or (A2). This means that the monomer or monomers used to prepare polymer (B1) do not contain a crosslinking or grafting agent. However, it cannot be excluded that some of polymer (B1) is bound to the previous stage polymer. This is due to reactive groups for crosslinking or grafting still present from the previous stage, or due to entanglement of the polymer chains. Polymer (B1) can be at least partially recovered by extraction with a solvent.

[0107] The weight average molecular weight Mw of polymer (B1) is measured by size exclusion chromatography (SEC). If polymer (B1) is part of a multi-stage polymer, it can be extracted with a solvent and the molecular weight measured. Alternatively, polymer (B1) can be synthesized under the same conditions without the presence of the previous stage, avoiding the extraction step and obtaining a "pure" polymer (B1) for measurement.

[0108] In one embodiment, polymer (B1) also comprises a functional comonomer.

[0109] The functional comonomer is represented by the formula (1): JPEG0007824769000001.jpg28170 [wherein R1 is selected from H or CH3, and R2 is H or an aliphatic or aromatic radical having at least one atom that is not C or H] It has.

[0110] Preferably, the functional monomer is selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids, such as, optionally quaternized, dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, 2-aminoethyl acrylate or methacrylate, and polyethylene glycol (meth)acrylate. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0111] In a first preferred embodiment, the polymer (B1) 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 chosen from methyl acrylate, ethyl acrylate or butyl acrylate.

[0112] In a second preferred embodiment, the polymer (B1) comprises between 0 and 50% by weight of functional monomers. Preferably, the meth)acrylic polymer (B1) comprises between 0 and 30% by weight of functional monomers, 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.

[0113] Preferably, the functional monomer of the second preferred embodiment is a (meth)acrylic monomer. The functional monomer is represented by formula (2) or (3): JPEG0007824769000002.jpg52170 [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 radical 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 radical].

[0114] Preferably, the functional monomer (2) or (3) is selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids, such as, optionally quaternized, dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, 2-aminoethyl acrylate or methacrylate, etc.; acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkylimidazolidinone (meth)acrylates, and polyethylene glycol (meth)acrylates. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0115] The multistage polymer (MP1) or core / shell polymer particles are obtained by a multistage process comprising at least two stages: At least components a1) and a2) of composition (PC1) are part of the multistage polymer (MP1).

[0116] Preferably, the polymer (A1) having a glass transition temperature below 10° C., produced during step (SA1), is produced before step (SA2) or is the first step of a multi-step process.

[0117] Preferably, the polymer (A2) having a glass transition temperature above 60° C., produced during step (SA2), is produced after step (SA1) of the multi-stage process.

[0118] In a first preferred embodiment, a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C is produced by a process that results in polymer particles of polymer (B1). The weight-average particle size (diameter) of these polymer (B1) particles is between 15 and 900 nm. Preferably, the weight-average particle size of the polymer (B1) particles is between 20 and 800 nm, more preferably between 25 and 600 nm, even more preferably between 30 and 550 nm, and even more preferably between 35 and 500 nm, advantageously between 40 and 400 nm, more advantageously between 75 and 350 nm, and advantageously between 80 and 300 nm. The polymer particles themselves can be agglomerated with multi-stage polymer (MP1) particles to obtain a polymer powder enriched with both polymer particles. This results in a composition (Ci) comprising components a) and b).

[0119] In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30° C. is a polymer particle having a multilayer structure, in other words the outer layer of a multistage polymer (MP1).

[0120] The polymer (B1) having a glass transition temperature above 30° C., produced during step (SB1), is produced after step (SA2) of the multi-stage process. Additional intermediate steps may be present between steps (SA1) and (SA2) and / or between steps (SA2) and (SB1). This also results in a composition (Ci) comprising components a) and b).

[0121] At least a portion of polymer (B1) can be grafted onto the polymer produced in the previous layer or entangled with the polymer chains of the previous layer. If there are only two stages (SA1) and (SA2) containing polymers (A1) and (A2), respectively, a portion of polymer (B1) can be grafted onto polymer (A2) or entangled with the chains of polymer (A2).

[0122] In one embodiment, at least 50% by weight of the polymer (B1) is grafted.

[0123] In another embodiment, less than 50% by weight of the polymer (B1) is grafted.

[0124] In yet another embodiment, less than 20% by weight of polymer (B1) is grafted.

[0125] In yet another embodiment, between 5% and 60% by weight of polymer (B1) is grafted.

[0126] In yet another embodiment, less than 5% by weight of polymer (B1) is grafted.

[0127] In yet another embodiment, 0% by weight of polymer (B1) is grafted.

[0128] The grafting rate can be determined by extracting with a solvent for polymer (B1) and determining the ungrafted amount by weighing before and after extraction.

[0129] Polymer (B1) and polymer (A2) are not the same polymer, even though their compositions are very similar and some of their properties overlap. The essential difference is that polymer (A2) is always part of multi-stage polymer (MP1). As explained above, there are embodiments in which polymer (B1) can also be part of a multi-stage polymer, but polymer (B1) is not spontaneously grafted onto multi-stage polymer (MP1).

[0130] The glass transition temperature Tg of each polymer can be estimated by dynamic methods such as thermomechanical analysis.

[0131] To obtain samples of each of the polymers (A1) and (A2), they are prepared individually rather than by a multi-stage process, so that the glass transition temperature Tg of each polymer in each stage can be more easily estimated and measured individually. Polymer (B1) can be extracted to facilitate the estimation and measurement of the glass transition temperature Tg.

[0132] Regarding component (LC1) of composition (PC1), component (LC1) is preferably a liquid.

[0133] The viscosity is between 0.5 mPa·s and 10 Pa·s at 25°C. Preferably, the viscosity is between 1 mPa·s and 10 Pa·s, more preferably between 10 mPa·s and 10 Pa·s, even more preferably between 50 mPa·s and 10 Pa·s, advantageously between 100 mPa·s and 10 Pa·s. The viscosity of (LC1) is the dynamic viscosity. If shear thinning is suspected, the dynamic viscosity value is taken at a shear rate of 1 1 / sec. The viscosity is measured using a rheometer.

[0134] Component (LC1) can also be a mixture of several compounds, one of which is a compound (C1) having at least two polymerizable groups (PG1) and (PG2).

[0135] The component (LC1) or the liquid component (LC1) may further comprise a monomer (M1) or a mixture of monomers (Mx), which monomer (M1) or the mixture of monomers (Mx) comprises at least one carbon-carbon double bond.

[0136] The monomers (M1) can be chosen from (meth)acrylic, allylic or styrenic monomers, or for (Mx), mixtures thereof.

[0137] In a variant, the monomers (M1) may be chosen from (meth)acrylic monomers, allylic monomers, or mixtures thereof for (Mx).

[0138] Preferably, the monomer (M1) is selected from styrene, α-methylstyrene, vinyltoluene, divinylbenzene, alkyl(meth)acrylates having an alkyl group containing 1 to 10 carbon atoms, and hydroxyethyl(meth)acrylate, as well as difunctional (meth)acrylates such as butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and di(meth)acrylates having a glycol structure, and polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate.

[0139] In a first more preferred embodiment, the monomer (M1) is selected from alkyl(meth)acrylates having an alkyl group containing 1 to 10 carbon atoms, and hydroxyethyl(meth)acrylate, as well as difunctional (meth)acrylates such as butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and di(meth)acrylates having a glycol structure, and polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate.

[0140] In a second more preferred embodiment, the monomers (M1), or mixtures thereof for (Mx), are styrene-free.

[0141] In a third more preferred embodiment, the monomers (M1), or mixtures thereof for (Mx), do not contain styrene-based monomers.

[0142] The two polymerizable groups (PG1) and (PG2) of the compound (C1) are preferably carbon double bonds.

[0143] The two polymerizable groups (PG1) and (PG2) of the compound (C1) are more preferably α,β-unsaturated carbonyl groups.

[0144] The two polymerizable groups (PG1) and (PG2) of compound (C1) can be chosen from acrylate groups, methacylate groups or condensation products containing maleic acid, itaconic acid or fumaric acid.

[0145] Preferably, compound (C1) is a vinyl ester or an unsaturated polyester.

[0146] In a first more preferred embodiment, compound (C1) is a vinyl ester. Vinyl esters are typically reaction products obtained by reacting polyepoxides (such as epoxy resins) with ethylenically unsaturated double bond-containing monocarboxylic acids, such as (meth)acrylic acid. They have the same backbone as polyepoxides in their main chains and are curable due to the presence of unsaturated double bonds within their molecules. The backbone is preferably one or more types selected from the group consisting of bisphenol A, bisphenol F, phenol novolac, cresol novolac, hydrogenated bisphenol A, hydrogenated bisphenol F, aliphatic ester, aliphatic ether, and aromatic ester type backbones.

[0147] In a second more preferred embodiment, compound (C1) is an unsaturated polyester. The unsaturated polyester is the reaction product of at least one dibasic organic acid or anhydride with at least one polyhydric alcohol.

[0148] Optionally, component (LC1) can contain a radical polymerization initiator, for example, an organic peroxide can be added.

[0149] The present invention also relates to a method for producing composition (PC1).

[0150] Regarding the first preferred method for preparing the composition (PC1) according to the invention, said method comprises: i)a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) a step (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a composition (Ci) comprising: ii) mixing composition (Ci) with composition (Ciia) comprising at least one other component or compound present in composition (PC1); and iii) optionally mixing the composition obtained in step ii) with other components or compounds present in composition (PC1) that have not yet been added in step ii); Includes:

[0151] The composition (Ciia) comprises: - polyepoxides, or - polyepoxides and organic acids with double bonds, or - vinyl ester, or - vinyl esters and monomers (M1) or mixtures of monomers (Mx), - unsaturated polyester, or - unsaturated polyester and monomer (M1) or mixture of monomers (Mx) may include:

[0152] Other components or compounds optionally added in step iii) are a monomer (M1) or a mixture of monomers (Mx), or a polymerization initiator. The monomer (M1) or the mixture of monomers (Mx) is added in step iii) if these monomers are not present in the composition (Ciia) and have not been added in step ii), or if these monomers are present in the composition (Ciia) of step ii), additional monomer (M1) or the mixture of monomers (Mx) is added in step iii).

[0153] In a first preferred embodiment, the composition (Ciia) comprises a polyepoxide.

[0154] In a second preferred embodiment, the composition (Ciia) comprises a polyepoxide and an organic acid having a double bond.

[0155] In a third preferred embodiment, the composition (Ciia) comprises a vinyl ester.

[0156] In a fourth preferred embodiment, the composition (Ciia) comprises a vinyl ester and a monomer (M1) or a mixture of monomers (Mx).

[0157] In a fifth preferred embodiment, the composition (Ciia) comprises an unsaturated polyester.

[0158] In a sixth preferred embodiment, the composition (Ciia) comprises an unsaturated polyester and a monomer (M1) or a mixture of monomers (Mx).

[0159] In steps ii) and iii) of the first preferred method for preparing the composition (PC1), a compound (C1) having at least two polymerizable groups (PG1) and (PG2) is added and formed.

[0160] Preferably, steps i) to iii) are performed in the order listed.

[0161] Regarding the second preferred method for preparing the composition (PC1) according to the invention, said method comprises: i)a) a1) one stage (A1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) one stage (A2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a composition (Ci) comprising: ii) c) providing a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), or a composition (Ciib) comprising one or more precursors of compound (C1), iii) mixing the composition of i) with the composition of ii) Includes:

[0162] Composition (Ciib) is - polyepoxides, or - polyepoxides and organic acids with double bonds, or - vinyl ester, or - vinyl esters and monomers (M1) or mixtures of monomers (Mx), - unsaturated polyester, or - unsaturated polyester (poleyster) and a monomer (M1) or a mixture of monomers (Mx) may include:

[0163] The second preferred method for preparing composition (PC1) can also comprise an optional additional step iv) of adding other ingredients or compounds.

[0164] Preferably, steps i) to iii) are performed in the order listed.

[0165] In a first preferred embodiment, the composition (Ciib) comprises a polyepoxide.

[0166] In a second preferred embodiment, the composition (Ciib) comprises a polyepoxide and an organic acid having a double bond.

[0167] In a third preferred embodiment, the composition (Ciib) comprises a vinyl ester.

[0168] In a fourth preferred embodiment, the composition (Ciib) comprises a vinyl ester and a monomer (M1) or a mixture of monomers (Mx).

[0169] In a fifth preferred embodiment, the composition (Ciib) comprises an unsaturated polyester.

[0170] In a sixth preferred embodiment, the composition (Ciib) comprises an unsaturated polyester and a monomer (M1) or a mixture of monomers (Mx).

[0171] Regarding the third preferred method of producing the composition (PC1) according to the invention, said method comprises: i)a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) a step (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; providing a polymer composition comprising: ii) c) providing a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), iii) mixing components a), b) and c) Includes:

[0172] Compound (C1) is a polyepoxide, a vinyl ester or an unsaturated polyester.

[0173] In a first preferred embodiment, compound (C1) is a polyepoxide.

[0174] In a second preferred embodiment, compound (C1) is a vinyl ester.

[0175] In a third preferred embodiment, compound (C1) is an unsaturated polyester.

[0176] In a more preferred embodiment, compound (C1) is a vinyl ester.

[0177] In all embodiments, the components can be mixed by stirring. The stirring can be performed with a stirrer.

[0178] An important condition of the mixing step is the temperature: preferably, the temperature of the mixing step is between 0°C and 50°C, more preferably between 5°C and 45°C, even more preferably between 10°C and 40°C, most preferably between 10°C and 35°C, advantageously between 10°C and 30°C.

[0179] The time required for the mixing step is shorter compared to a composition that does not contain a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C.

[0180] The mixing time is preferably less than 120 minutes, advantageously less than 90 minutes (lab scale). This parameter is influenced by the amounts used. For the same proportions of components, a smaller absolute amount for all amounts may result in a shorter time.

[0181] A different method for producing composition (PC1) preferably uses multistage polymer (MP1) or composition (Ci) in the form of polymer powder POW1 having a total intrusion volume, as measured by mercury porosimetry, of at least 1.2 ml / g.

[0182] The porosity of the polymer powder POW1 is expressed as the total or cumulative intrusion in milliliters (ml) of mercury per mass (g) of said polymer powder POW1. It is measured according to the standard ISO 15901-1: Evaluation of pore size distribution and porosity of solid materials by mercury porosity and gas adsorption - Part 1: mercury porosity. The total cumulative intrusion is taken into account up to a pore size diameter of 0.005 μm.

[0183] The polymer powder POW1 has a total intrusion or total cumulative intrusion of at most 10 ml / g. Preferably, the total intrusion or total cumulative intrusion of the polymer powder POW1 of the invention is between 1.2 ml / g and 10 ml / g.

[0184] The incremental indentation (incremental indentation) is the volume between two specific pore sizes. The incremental indentation can likewise be expressed as an absolute value in ml / g, or as a relative value as a percentage of the total indentation or total cumulative indentation. Preferably, the polymer powder POW1 has a relative incremental indentation of up to 85% for pore sizes greater than 10 μm (greater than 10 μm). Preferably, the polymer powder POW1 has a cumulative indentation of at least 0.9 ml / g for pore sizes greater than 10 μm (greater than 10 μm).

[0185] The present invention also relates to the use of composition (PC1), which is used for the preparation of a reinforced polymer composition (PC2).

[0186] The polymer composition (PC2) is prepared by polymerizing the compound (C1) of the component (LC1) having at least two polymerizable groups (PG1) and (PG2). After polymerization of the compound (C1), a polymer (P2) is obtained.

[0187] The present invention provides a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) a step (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2); wherein the weight-average molecular weight Mw of polymer (B1) is between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 and 100 phr relative to 100 phr of component c).

[0188] The polymer (P2) is a thermosetting polymer.

[0189] The polymer composition (PC2) may optionally contain other components such as fibers or mineral fillers. Preferably, the other components of the polymer composition (PC2) are selected from fibers or mineral fillers. In that case, the polymer composition (PC2) is a polymer composite.

[0190] The polymer composition (PC2) can be used as an adhesive, more preferably as a structural adhesive, or in polymer composites, or in applications such as coatings, decorative castings, flooring, polymer concrete, solid surfaces, artificial marble, or in marine applications, building and construction, wind energy applications.

[0191] Evaluation method Glass transition temperature The glass transition (Tg) of a polymer is measured using an instrument capable of thermomechanical analysis. We used the RDAII "RHEOMETRICS DYNAMI CANALYSER" proposed by the Rheometrics Company. Thermomechanical analysis precisely measures the viscoelastic changes of a sample in response to temperature, strain, or applied deformation. The strain is 0.1%. The temperature range is between -125°C and 150°C, and the temperature is changed at a rate of 2°C / min. The instrument continuously records the deformation of the sample while holding the strain fixed during a controlled program of temperature variation. Results are obtained by plotting the elastic modulus (G'), loss factor, and tan δ as a function of temperature. Tg is the maximum temperature value read on the tan δ curve at which the derivative of tan δ equals zero.

[0192] molecular weight The weight average molecular weight (Mw) of the polymer is measured using size exclusion chromatography (SEC). Polystyrene standards are used for calibration. The polymer is dissolved in THF at a concentration of 1 g / L. The chromatography column uses modified silica. The flow rate is 1 ml / min and a differential refractive index detector is used.

[0193] Particle size analysis The particle size of the primary particles after multi-stage polymerization is measured using a Zetasizer. The particle size of the recovered polymer powder is measured using a Malvern Mastersizer 3000. The weight-average powder particle size, particle size distribution, and ratio of fine particles are estimated using a Malvern Mastersizer 3000 instrument equipped with a 300 mm lens measuring the range of 0.5 to 880 μm.

[0194] porosity The porosity of the polymer powder POW1 is expressed as the total or cumulative intrusion in milliliters (ml) of mercury per mass (g) of said polymer powder POW1, measured according to the standard ISO 15901-1: Evaluation of pore size distribution and porosity of solid materials by mercury porosity and gas adsorption - Part 1: mercury porosity. [Example]

[0195] Raw materials: As component (LC1) the commercial resins ATLAC 430, ATLAC 590 and ATLAC P600 from the company Aliancys are used.

[0196] Multistage polymer (MP1) was prepared according to the following synthesis: First Stage (SA1) - Polymer Type (A1) Polymerization: A 20-liter high-pressure reactor was charged with an initial kettle charge of 116.5 parts deionized water, 0.1 parts emulsifier, potassium salt of beef tallow fatty acid, 21.9 parts 1,3-butadiene, 0.1 parts t-dodecyl mercaptan, and 0.1 parts p-menthane hydroperoxide. The solution was heated with stirring to 43°C, at which point a redox catalyst solution (4.5 parts water, 0.3 parts sodium tetrapyrophosphate, 0.004 parts ferrous sulfate, and 0.3 parts dextrose) was added, effectively initiating polymerization. The solution was then further heated to 56°C and held at this temperature for 3 hours. Three hours after the start of polymerization, the second monomer charge (77.8 parts BD, 0.2 parts t-dodecyl mercaptan), half of the additional emulsifier, and the reducing agent charge (30.4 parts deionized water, 2.8 parts emulsifier, potassium salt of beef tallow fatty acid, 0.5 parts dextrose), and additional initiator (0.8 parts p-menthane hydroperoxide) were added continuously over 8 hours. Following completion of the second monomer addition, the remaining emulsifier, reducing agent charge, and initiator were added continuously over an additional 5 hours. Thirteen hours after the start of polymerization, the solution was heated to 68°C and allowed to react until at least 20 hours had elapsed since the start of polymerization, producing polybutadiene rubber latex R1. The resulting polybutadiene rubber latex (A1) contained 38% solids and had a weight average particle size of approximately 160 nm.

[0197] Second Stage (SA2)—Polymer Type (A2) Polymerization: A 3.9-liter reactor was charged with 75.0 parts polybutadiene rubber latex R1, 37.6 parts deionized water, and 0.1 parts sodium formaldehyde sulfoxylate, on a solids basis. The solution was stirred, purged with nitrogen, and heated to 77°C. When the solution reached 77°C, a mixture of 22.6 parts methyl methacrylate, 1.4 parts divinylbenzene, and 0.1 parts t-butyl hydroperoxide initiator was added continuously over 70 minutes, followed by an 80-minute hold. 30 minutes after the start of the hold period, 0.1 parts sodium formaldehyde sulfoxylate and 0.1 parts t-butyl hydroperoxide were added all at once to the reactor. After the 80-minute hold period, the stabilized emulsion was added to the graft copolymer latex. A stabilized emulsion was prepared by mixing 3.2 parts deionized water (based on the mass of the graft copolymer), 0.1 part oleic acid, 0.1 part potassium hydroxide, and 0.9 parts octadecyl-3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate. The resulting core-shell polymer (A1+A2) had a weight-average particle size of approximately 180 nm. The final multistage polymer (MP1) was then recovered, and the polymer composition was coagulated and dried to obtain a powder of core / shell-1.

[0198] According to a preferred embodiment, a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C is prepared as an additional stage to the multistage polymer (MP1) - Polymerization of Polymer Composition Type C1: Synthesis of Polymer (B1): Semi-continuous process: 10,000 g of the core-shell polymer (A1 + A2) still dispersed in deionized water, 0.01 g of FeSO4, 0.032 g of ethylenediaminetetraacetic acid sodium salt (dissolved in 10 g of deionized water), 3.15 g of sodium formaldehyde sulfoxylate dissolved in 110 g of deionized water, and 21.33 g of emulsifier potassium salt of tallow fatty acid (dissolved in 139.44 g of water) were charged to a reactor with stirring, and the mixture was stirred until the added ingredients were completely dissolved, except for the core-shell polymer. Three successive vacuum nitrogen purges were performed, and the reactor was placed under low vacuum. The reactor was then heated. At the same time, a mixture containing 1,066.7 g of methyl methacrylate and 10.67 g of n-octyl mercaptan was degassed with nitrogen for 30 minutes. The reactor was heated to 63°C and maintained at that temperature. Then, using a pump, the monomer mixture was introduced into the reactor over 180 minutes. In parallel, a solution of 5.33 g of ter-butyl hydroperoxide (dissolved in 100 g of deionized water) was introduced (same addition time). The lines were rinsed with 50 g and 20 g of water. The reaction mixture was then heated to a temperature of 80°C, and after the addition of the monomers was completed, it was left for 60 minutes to allow the polymerization to complete. The reactor was cooled to 30°C. The weight average molecular weight of copolymer B1 was M w = 28,000 g / mol.

[0199] The final polymer composition consisting of multistage polymer (MP1) and polymer (B1) was then recovered, and the polymer composition was coagulated and dried to obtain the power of core / shell-2.

[0200] Mixing of ingredients: Place 100 g of ingredient (LC1) into an aluminum container. Add various amounts of powdered multi-stage polymer (MP1), which may or may not already contain thermoplastic polymer (B1). Stir at 150-200 rpm for 60 minutes.

[0201] Rheology: The viscosity of the composition is measured with an Anton Parr rheometer, cone and plate type (module CP-50) at 25°C.

[0202] Dispersion test: 5% by weight of powdered component MP1 or MP1+B1 is added to 95% of component LC1. Under standard conditions, mixing at 100-200 RPM is applied using a dispersion blade. After 60 minutes, the appearance of the dispersion is evaluated according to the presence of undispersed powder particles (small grains), agglomeration of powder particles, single-phase or two-phase dispersion, and the presence of air bubbles. If the dispersion is poor, an additional 60 minutes of mixing at 500 RPM is applied. The same procedure is carried out for the amount of component MP1 or MP1+B1.

[0203] Sample preparation for producing parts for mechanical testing: A standard BPO / amine-based (benzoyl peroxide / dimethylaniline) curing agent was used. The dosage was chosen to obtain a gel time of approximately 30 minutes at room temperature.

[0204] Mechanical evaluation: Tensile properties such as elongation at break, tensile strength, and Young's modulus were evaluated using a ZWICK Z050 TH AllroundLine with a 50 kN cell according to the ISO 527 standard.

[0205] Lap shear evaluation: Evaluation was carried out using a ZWICK Z050 TH AllroundLine with a 50kN cell in accordance with the EN 1465 standard. Aluminum plates were used as the substrate.

[0206] Example of a composition: The composition is made of the following compounds: TIFF0007824769000003.tif120170

[0207] The compositions according to the invention (comprising thermoplastic polymers (B1) of compound b)) can be prepared easily and quickly with different compounds c). The resulting dispersions are inventively homogeneous. TIFF0007824769000004.tif57170

[0208] In Table 2, a significant improvement in toughness is observed for the polymers obtained from the compositions according to the invention. Crack growth resistance K 1c and fracture toughness G 1c As shown by the above, the fracture toughness is significantly improved.

Claims

1. a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a component (LC1) containing a compound (C1) having at least two polymerizable groups (PG1) and (PG2); A composition (PC1) comprising: stage (SA1) is the innermost layer of the multistage polymer (MP1); the polymer (B1) has a weight-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c), The two polymerizable groups (PG1) and (PG2) of the compound (C1) are α,β-unsaturated carbonyl groups, The polymer (B1) is a (meth)acrylic polymer. Composition (PC1).

2. a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a component (LC1) containing a compound (C1) having at least two polymerizable groups (PG1) and (PG2); A composition (PC1) comprising: stage (SA1) is the innermost layer of the multistage polymer (MP1); the polymer (B1) has a weight-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c), the two polymerizable groups (PG1) and (PG2) of compound (C1) are selected from acrylate groups, methacrylate groups, or condensation products containing maleic acid, itaconic acid, or fumaric acid, The polymer (B1) is a (meth)acrylic polymer. Composition (PC1).

3. a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a component (LC1) containing a compound (C1) having at least two polymerizable groups (PG1) and (PG2); A composition (PC1) comprising: stage (SA1) is the innermost layer of the multistage polymer (MP1); the polymer (B1) has a weight-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c), Compound (C1) is a vinyl ester, The polymer (B1) is a (meth)acrylic polymer. Composition (PC1).

4. 4. The composition according to claim 1, wherein the polymer (B1) comprises at least 70% by weight of monomers selected from C1 to C12 alkyl (meth)acrylates.

5. The polymer (B1) is represented by the formula (1) [In the formula, R １ is H or CH ３ and R ２ is H or an aliphatic or aromatic radical having at least one atom that is not C or H.

5. The composition according to claim 1, further comprising a functional comonomer having the formula:

6. 6. The composition according to claim 1, wherein component (LC1) additionally comprises a monomer (M1) or a mixture of monomers (Mx).

7. A process for producing a composition (PC1) according to any one of claims 1 to 6, comprising the steps of: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a composition (Ci) comprising: ii) mixing composition (Ci) with composition (Cii) comprising at least one other component or compound present in composition (PC1); and iii) optionally mixing the composition obtained in step ii) with other components or compounds present in composition (PC1) that have not yet been added in step ii); A method comprising:

8. A process for producing a composition (PC1) according to any one of claims 1 to 6, comprising the steps of: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a polymer composition (Ci) comprising ii) c) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); iii) mixing compositions (Ci) and (Ciib) comprising components a), b) and c) in a ratio of between 0.5 phr and 100 phr of the sum of components a) and b) per 100 phr of component c). A method comprising:

9. A method for reducing the preparation time of composition (PC1), comprising: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a polymer composition (Ci) comprising ii) c) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); iii) mixing compositions (Ci) and (Ciib) containing components a), b) and c) in proportions such that the sum of components a) and b) per 100 phr of component c) is between 0.5 and 100 phr; Including, stage (SA1) is the innermost layer of the multistage polymer (MP1); The two polymerizable groups (PG1) and (PG2) of the compound (C1) are α,β-unsaturated carbonyl groups, The polymer (B1) is a (meth)acrylic polymer. method.

10. A method for reducing the preparation time of composition (PC1), comprising: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a polymer composition (Ci) comprising ii) c) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); iii) mixing compositions (Ci) and (Ciib) containing components a), b) and c) in proportions such that the sum of components a) and b) per 100 phr of component c) is between 0.5 and 100 phr; Including, stage (SA1) is the innermost layer of the multistage polymer (MP1); the two polymerizable groups (PG1) and (PG2) of compound (C1) are selected from acrylate groups, methacrylate groups, or condensation products containing maleic acid, itaconic acid, or fumaric acid, The polymer (B1) is a (meth)acrylic polymer. method.

11. A method for reducing the preparation time of composition (PC1), comprising: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30° C. and a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) represents a maximum of 40% by weight of the composition based on a) and b); providing a polymer composition (Ci) comprising ii) c) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); iii) mixing compositions (Ci) and (Ciib) containing components a), b) and c) in proportions such that the sum of components a) and b) per 100 phr of component c) is between 0.5 and 100 phr; Including, stage (SA1) is the innermost layer of the multistage polymer (MP1); Compound (C1) is a vinyl ester, The polymer (B1) is a (meth)acrylic polymer. method.

12. Compositions (Ciia) and (Ciib) polyepoxides, or a polyepoxide and an organic acid having a double bond, or unsaturated polyester, or Unsaturated polyester and monomer (M1) or mixture of monomers (Mx) 12. The method according to any one of claims 7 to 11, comprising:

13. A process for producing a composition (PC1) according to any one of claims 1 to 6, comprising the steps of: i) a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; providing a polymer composition comprising: ii) c) providing a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); iii) mixing components a), b) and c) A method comprising:

14. 14. The method according to any one of claims 7 to 13, characterized in that the multistage polymer (MP1) provided is in the form of a polymer powder having a total intrusion volume, as measured by mercury porosimetry, of at least 1.2 ml / g.

15. Use of a composition according to any one of claims 1 to 6 or a composition obtainable by the process according to any one of claims 7 to 14 in the preparation of an impact-modified polymer composition (PC2).

16. a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2); A polymer composition (PC2) comprising: Polymer composition (PC2), characterized in that stage (SA1) is the innermost layer of multistage polymer (MP1), polymer (B1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c), the two polymerizable groups (PG1) and (PG2) of compound (C1) are α,β-unsaturated carbonyl groups, and polymer (B1) is a (meth)acrylic polymer.

17. a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2); A polymer composition (PC2) comprising:

1. A polymer composition (PC2) characterized in that stage (SA1) is the innermost layer of a multistage polymer (MP1), polymer (B1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of a composition based only on a) and b), the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c), the two polymerizable groups (PG1) and (PG2) of compound (C1) are selected from acrylate groups, methacrylate groups, or condensation products comprising maleic acid, itaconic acid, or fumaric acid, and polymer (B1) is a (meth)acrylic polymer.

18. a) a1) one stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; a multi-stage polymer (MP1) comprising: b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; c) a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2); A polymer composition (PC2) comprising: Polymer composition (PC2), characterized in that stage (SA1) is the innermost layer of multistage polymer (MP1), polymer (B1) has a weight average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) represents a maximum of 40% by weight of the composition based only on a) and b), the sum of components a) and b) is between 0.5 phr and 100 phr, relative to 100 phr of component c), compound (C1) is a vinyl ester and polymer (B1) is a (meth)acrylic polymer.

19. 19. Use of the polymer composition (PC2) according to any one of claims 16 to 18 as an adhesive or in polymer composites; or in the applications of coatings, decorative castings, flooring, polymer concrete, solid surfaces and artificial marble, or in marine applications, building and construction, wind energy applications.

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