Composition comprising multistage polymer and (meth) acrylic polymer, method for preparation thereof and use thereof

Abstract

The present invention relates to a composition comprising a multistage polymer, a (meth) acrylic polymer and a monomer or prepolymer, to a method for the production thereof and to the use thereof. In particular, the present invention relates to a process for preparing a composition comprising a multistage polymer in the form of polymer particles, a (meth) acrylic polymer and a monomer or prepolymer. More specifically, the present invention relates to a liquid polymer composition comprising a multistage polymer, a (meth) acrylic polymer and a monomer or prepolymer, a process for the preparation thereof, the use thereof, in particular as a masterbatch.

Description

Technical Field

[0001] The present invention relates to a composition comprising a multi-stage polymer, a (meth)acrylic polymer and a monomer or a prepolymer, a preparation method thereof and use thereof.

[0002] In particular, the present invention relates to a method for preparing a composition comprising a multistage polymer in the form of polymer particles, a (meth)acrylic polymer and a monomer or prepolymer.

[0003] More specifically, the present invention relates to a liquid polymer composition comprising a multistage polymer, a (meth)acrylic polymer and a monomer or prepolymer, a method for its preparation, and its use, in particular as a masterbatch.

[0004] Technical issues

[0005] Polymers are also widely used as additives in polymer compositions. These so-called polymer additives are usually added as granules or also as powders to solid polymers or molten polymers or liquid resins or liquid compositions.

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

[0007] The polymer impact modifier can be in the form of polymer particles. Typically, these polymer impact modifiers are in the form of core-shell particles made by a multistage process, wherein at least one stage comprises a rubber-like polymer. Afterwards, these particles are incorporated into a polymer or polymer composition to improve its impact resistance. The polymer or polymer composition can be a thermosetting polymer or a thermoplastic polymer.

[0008] Thermosetting polymers consist of a cross-linked three-dimensional structure. Cross-linking is achieved by curing reactive groups within the so-called prepolymer. Curing can be achieved, for example, by heating the polymer chains or prepolymers so that the material permanently cross-links and hardens.

[0009] Thermoplastic polymers consist of linear or branched polymers that are usually not crosslinked. They may be slightly crosslinked as long as they can be deformed by heat.

[0010] However, these core-shell particles are not easy to disperse or are quickly dispersed in all types of resins or polymers or polymer precursors, especially in liquid epoxy resins or liquid monomers or other liquid polymer precursors. Good, even and fast dispersion is necessary for having satisfactory impact properties in the final polymer composition. Also need easy dispersion preparation and fast dispersion time to reduce method time and obtain easier and simpler method. The concentration of core-shell particles should also be high, so that composition can be used as masterbatch.

[0011] One object of the present invention is to propose a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor, said precursor comprising a multistage polymer.

[0012] Another object of the present invention is to propose a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor, wherein the precursor comprises a large amount of a multistage polymer. By large amount it is meant that the composition comprises at least 10 phr of the multistage polymer relative to the precursor (e.g., for 100 parts of epoxy prepolymer or monomer).

[0013] It is also an object of the present invention to propose a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor comprising a multistage polymer that is stable over time. Stable over time means that no visible macroscopic phase separation occurs, preferably over a period of at least 1 month.

[0014] Another object of the present invention is to propose a process for preparing a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor and a multistage polymer.

[0015] Yet another object of the present invention is a process for preparing a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor, said precursor comprising a plurality of multistage polymers.

[0016] Still another object of the present invention is a process for preparing a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor, said precursor comprising a multistage polymer, in a short time.

[0017] Yet another object of the present invention is to prepare a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor comprising a multistage polymer that is stable over time and has a sufficient shelf life without separation.

[0018] Yet another object of the present invention is the use of a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor and a multistage polymer as a masterbatch.

[0019] Still another object is to provide a method for reducing the time to disperse a multistage polymer in a composition comprising a thermosetting polymer precursor or a thermoplastic polymer precursor.

[0020] [Background of the invention] Prior art

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

[0022] Document EP 1632533 describes a method for producing a modified epoxy resin. The epoxy resin composition has rubbery polymer particles dispersed therein, the particles being dispersed by contacting the particles with an organic medium in which the rubber particles are dispersed.

[0023] Document EP1666519 discloses a method for producing rubbery polymer particles and a resin composition containing the rubbery polymer particles.

[0024] Document EP2123711 discloses a thermosetting resin composition in which rubbery polymer particles are dispersed and a method for producing the same.

[0025] Document WO2017 / 121479 discloses a liquid composition comprising a monomer, a (meth)acrylic polymer and a multi-stage polymer.

[0026] Document WO2019 / 012052 discloses a composition comprising a multi-stage polymer and a method for preparing the same. The composition also comprises a (meth) acrylic polymer having a mass average molecular weight between 100,000 g / mol and 1,000,000 g / mol.

[0027] None of the cited prior art documents discloses such a masterbatch composition and in particular a method for its preparation. Summary of the invention

[0028] Surprisingly, a composition (C1) has been found comprising:

[0029] a) 100 phr of a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1) or a mixture of both,

[0030] b) between 10 and 100 phr of a polymer composition (PC1) comprising

[0031] b1) A stage comprising a polymer (B1) having a glass transition temperature below 10°C

[0032] (SB1),

[0033] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0034] b3) and a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B3) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3);

[0035] Characterized in that at least component b1) and component b2) of the composition (PC1) are part of a multistage polymer (MP1), and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol; can be easily and quickly prepared and used as a masterbatch.

[0036] Surprisingly, a process for preparing composition (C1) has also been found, comprising the following steps:

[0037] a) providing a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1) or a mixture of both;

[0038] b) providing a polymer composition (PC1) comprising

[0039] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0040] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0041] b3) and a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B3) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3);

[0042] c) contacting the provided components of a) and b);

[0043] d) providing a mixing device;

[0044] e) mixing the components using the mixing device provided,

[0045] Characterized in that at least components b1) and b2) of the composition (PC1) are part of a multistage polymer (MP1), and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol; a homogeneous and stable composition (C1) is produced, which contains, for 100 parts of a composition (C2) comprising monomers (M1) or prepolymers (PRE1) or a mixture of both, between 10 phr and 100 phr of the polymer composition (PC1).

[0046] Surprisingly, a process for preparing composition (C1) has also been found, comprising the following steps:

[0047] a) providing a polymer composition (PC1) comprising:

[0048] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0049] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0050] b3) and a polymer (B3) having a glass transition temperature of at least 30° C. and a mass average molecular weight Mw between 10 000 g / mol and 500 000 g / mol, based solely on b1), b2) and b3), said polymer (B3) comprising up to 40% by weight of the composition,

[0051] b) contacting the polymer composition (PC1) with a composition (C2) comprising monomers (M1) or prepolymers (PRE1),

[0052] c) providing a mixing device,

[0053] d) mixing the contacted components using a provided mixing device;

[0054] A composition (C1 ) is obtained in which the polymer composition (PC1 ) is dispersed uniformly and more rapidly in the composition (C2) compared to a composition not comprising the polymer (B3).

[0055] Surprisingly, a method has also been found for reducing the time to disperse the polymer composition (PC1) in the composition (C2), comprising the following steps:

[0056] a) providing a polymer composition (PC1) comprising

[0057] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0058] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0059] b3) and a polymer (B3) having a glass transition temperature of at least 30° C. and a mass average molecular weight Mw between 10 000 g / mol and 500 000 g / mol, based solely on b1), b2) and b3), said polymer (B3) comprising up to 40% by weight of the composition,

[0060] b) contacting the polymer composition (PC1) with the composition (C2),

[0061] This is faster than the same process using a polymer composition without compound b3). DETAILED DESCRIPTION

[0062] According to a first aspect, the present invention relates to a composition (C1) comprising

[0063] a) 100 phr of a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1) or a mixture of both,

[0064] b) polymer composition between 10 and 100 phr (PC1)

[0065] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0066] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0067] b3) and a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B3) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3);

[0068] Characterized in that at least component b1) and component b2) of the composition (PC1) are part of a multistage polymer (MP1), and in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0069] According to a second aspect, the present invention relates to a method for preparing a composition (C1), said method comprising the following steps:

[0070] a) providing a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1) or a mixture of both;

[0071] b) providing a polymer composition (PC1) comprising:

[0072] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0073] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0074] b3) and a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B3) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3);

[0075] c) contacting the provided components of a) and b);

[0076] d) providing a mixing device;

[0077] e) mixing the components of a) and b) using the provided mixing device, characterized in that at least components b1) and b2) of the composition (PC1) are part of a multistage polymer (MP1), and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol; and characterized in that the amount of polymer composition (PC1) is selected so that for 100 parts of a composition (C2) comprising monomers (M1) or prepolymers (PRE1) or a mixture of both, between 10 phr and 100 phr of the polymer composition (PC1) are in the composition (C1).

[0078] In a third aspect, the present invention relates to the use of a polymer composition (C1 ) as a masterbatch, said polymer composition (C1 ) comprising:

[0079] a) 100 phr of a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1),

[0080] b) between 10 and 100 phr of a polymer composition (PC1) comprising:

[0081] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0082] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0083] b3) and a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B3) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3);

[0084] characterised in that at least component b1) and component b2) of the composition (PC1) are part of a multistage polymer (MP1), and in that the polymer (B3) has a mass average molecular weight Mw between 10000 g / mol and 500000 g / mol;

[0085] In a fourth aspect, the present invention relates to the use of a method for preparing a composition (C1) for preparing a masterbatch, the method comprising the following steps:

[0086] a) providing a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1) or a mixture of both;

[0087] b) providing a polymer composition (PC1) comprising:

[0088] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0089] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0090] b3) and a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B2) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3);

[0091] c) contacting the provided components of a) and b);

[0092] d) providing a mixing device;

[0093] e) mixing the components of a) and b) using the provided mixing device, characterized in that at least components b1) and b2) of the composition (PC1) are part of a multistage polymer (MP1), and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol; and characterized in that the amount of polymer composition (PC1) is selected so that for 100 parts of monomer (M1) or prepolymer (PRE1), between 10 phr and 100 phr of polymer composition (PC1) are in the composition (C1).

[0094] In a fifth aspect, the present invention relates to a method for reducing the dispersion time of a polymer composition (PC1) comprising between 10 and 100 phr of a multistage polymer (MP1) in 100 parts of a composition (C2) comprising monomers (M1) or prepolymers (PRE1) or a mixture of both, the multistage polymer (MP1) comprising:

[0095] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0096] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C.;

[0097] The method comprises the following steps:

[0098] i) contacting the components

[0099] ii) Provide a mixing device

[0100] iii) mixing the components using the provided mixing device;

[0101] Characterized in that the composition (PC1) further comprises b3) a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B3) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3); and characterized in that the polymer (B3) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol.

[0102] This process of the fifth aspect preferably produces a composition (C1 ) of the preceding aspect.

[0103] In a sixth aspect, the present invention relates to a method for reducing the time for preparing a masterbatch comprising between 10 and 100 phr of a polymer composition (PC1) in 100 parts of a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1), said polymer composition (PC1) comprising a multistage polymer (MP1), said multistage polymer (MP1) comprising:

[0104] b1) a stage (B1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0105] b2) a stage (B2) comprising a polymer (B2) having a glass transition temperature of at least 60° C.;

[0106] The method comprises the following steps:

[0107] i) contacting the components

[0108] ii) Provide a mixing device

[0109] iii) mixing the components using the provided mixing device;

[0110] Characterized in that the composition (PC1) further comprises b3) a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B3) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3); and characterized in that the polymer (B3) has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol.

[0111] This method of the sixth aspect preferably produces a composition (C1 ) of the first aspect.

[0112] The term "polymer powder" as used refers to a polymer in powder form comprising powder particles in the range of at least 1 μm, obtained by agglomeration of primary polymer particles comprising one or more polymers, said primary polymer particles being in the nanometer range.

[0113] The term "primary particles" as used refers to spherical polymer particles comprising particles in the nanometer range. Preferably, the weight average particle size of the primary particles is between 20 nm and 800 nm.

[0114] The term "particle size" as used herein refers to the volume average diameter of the particles considered as spherical.

[0115] The term "thermoplastic polymer" as used herein refers to a polymer that becomes liquid or more fluid or less viscous when heated and can assume new shapes through the application of heat and pressure.

[0116] The term "thermosetting polymer" as used herein refers to a prepolymer in a soft, solid or viscous state that is irreversibly converted to a non-fusible, insoluble polymer network by curing.

[0117] As used herein, the term "epoxy resin" is understood to be any organic compound having at least one oxirane-type functional group that can be polymerized or cured by ring opening. Various examples of epoxy resins are described herein.

[0118] The term "masterbatch" as used herein is understood to be a composition comprising a high concentration of an additive in a carrier material. The additive is dispersed in the carrier material.

[0119] As used herein, the term "impact modifier" is understood to be a material which, once incorporated into a polymeric material, improves the impact resistance and toughness of the polymeric material by forming phase microdomains of rubbery materials or rubbery polymers.

[0120] The term "rubber" is used to refer to the thermodynamic state of a polymer above the glass transition.

[0121] As used herein, the term "polymer composite" refers to a multi-component material comprising a plurality of distinct domains, wherein at least one domain type is a continuous phase, and wherein at least one component is a polymer.

[0122] The term "copolymer" is used to mean a polymer composed of at least two different monomers.

[0123] As used herein, "multistage polymer" refers to a polymer formed in a sequential manner by a multistage polymerization process. Preferred is a multistage emulsion polymerization process wherein the first polymer is a first stage polymer and the 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, having at least two stages that differ in composition.

[0124] The term "(meth)acrylic" is used to refer to all types of acrylic and methacrylic monomers.

[0125] The term "(meth)acrylic polymer" used means that the (meth)acrylic polymer comprises a polymer substantially containing 50% by weight or more of a (meth)acrylic monomer constituting the (meth)acrylic polymer.

[0126] The term "dry" is used to mean that the proportion of residual water is less than 1.5% by weight, preferably less than 1.2% by weight.

[0127] The range from x to y mentioned in the present invention means including the upper and lower limits of the range, which corresponds to at least x and at most y.

[0128] The range between x and y mentioned in the present invention means excluding the upper limit and the lower limit of the range, which is equivalent to being greater than x and less than y.

[0129] The term "phr" means parts per hundred by weight.

[0130] Easily dispersible in the liquid resin means that a uniform dispersion is obtained. If separation occurs after initial homogenization, the distribution of the polymer composition (PC1) is not uniform.

[0131] As for the composition (C1) according to the invention, it comprises a) 100 parts of a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1), and b) between 10 and 100 parts by weight of a polymer composition (PC1).

[0132] Preferably, the composition (C2) is liquid. Liquid means that the composition (C2) is liquid at least in the temperature range of 50°C to 80°C, preferably in the temperature range of 40°C to 80°C and more preferably in the temperature range of 20°C to 80°C. This limitation means that the composition (C2) may still be liquid outside these ranges.

[0133] Preferably, the composition (C1) is liquid. Liquid means that the composition (C1) is liquid at least in the temperature range of 50°C to 80°C, preferably in the temperature range of 40°C to 80°C and more preferably in the temperature range of 20°C to 80°C. This limitation means that the composition (C1) may still be liquid outside these ranges, but is in the liquid phase within these ranges.

[0134] In a first preferred embodiment, the composition (C2) comprises monomers (M1).

[0135] In a second preferred embodiment, the composition (C2) comprises a prepolymer (PRE1). In a variant of the second preferred embodiment, the composition (C2) comprises a prepolymer (PRE1) and also a further solvent.

[0136] In a third preferred embodiment, the composition (C2) comprises a mixture of monomers (M1) and prepolymers (PRE1). In a variant of the third preferred embodiment, the composition (C2) comprises a mixture of monomers (M1), prepolymers (PRE1) and further solvents.

[0137] In a fourth preferred embodiment, the composition (C2) is a mixture of a prepolymer (PRE1a) and a prepolymer (PRE1b).

[0138] In a fifth preferred embodiment, the composition (C2) is a mixture of prepolymer (PRE1a) and prepolymer (PRE1b) and an additional solvent.

[0139] In a sixth preferred embodiment, the composition (C1) is a mixture of prepolymers (PRE1a) and (PRE1b), monomers (M1) and further solvents.

[0140] The component a) composition (C2) alone is liquid at least in the temperature range of 50° C. to 80° C. and has a dynamic viscosity between 0.5 mPa*s and 1000 Pa*s.

[0141] In a first preferred embodiment, said composition (C1) comprises between 10 and 100 phr of polymer composition (PC1), more preferably between 10 and 90 phr, still more preferably between 10 and 80 phr, advantageously between 10 and 75 phr, per 100 parts of composition (C2).

[0142] In a second preferred embodiment, the composition (C1) comprises greater than 25 phr of polymer composition (PC1), preferably greater than 30 phr, even more preferably greater than 35 phr, per 100 parts of polymer composition (C2), and advantageously comprises between 35 and 100 phr of polymer composition (PC1) per 100 parts of polymer composition (C2) comprising monomers (M1) or prepolymers (PRE1) or a mixture of both.

[0143] Preferably, the composition (C1) is liquid at least in the temperature interval from 50° C. to 80° C. and has a dynamic viscosity between 1 mPa*s and 20,000 Pa*s.

[0144] The monomer (M1) of the polymer composition (PC1) is a liquid monomer at least in the temperature range between 10° C. and 60° C. The monomer (M1) contains one carbon C═C double bond.

[0145] The monomers (M1) are preferably selected from (meth)acrylic monomers and / or vinyl monomers and mixtures thereof. More preferably, the monomers (M1) of the polymer composition (PC1) are selected from (meth)acrylic monomers.

[0146] In a first preferred embodiment, monomers (M1) comprise at least 50% by weight of methyl methacrylate.

[0147] In a second preferred embodiment, monomer (M1) is a monomer mixture comprising at least 50% by weight of methyl methacrylate and the remainder up to 100% by weight selected from C2-C12 alkyl (meth)acrylates, alkyl acrylates, styrenic monomers and mixtures thereof.

[0148] In a third preferred embodiment, monomer (M1) comprises at least 80% by weight of methyl methacrylate.

[0149] In a fourth preferred embodiment, monomer (M1) is a monomer mixture comprising at least 80% by weight of methyl methacrylate and the remainder up to 100% by weight selected from C2-C12 alkyl (meth)acrylates, alkyl acrylates, styrenic monomers and mixtures thereof.

[0150] In a fifth preferred embodiment, monomer (M1) comprises at least 90% by weight of methyl methacrylate.

[0151] In a sixth preferred embodiment, monomer (M1) is a monomer mixture comprising at least 90% by weight of methyl methacrylate and the remainder up to 100% by weight selected from C2-C12 alkyl (meth)acrylates, alkyl acrylates, styrenic monomers and mixtures thereof.

[0152] In a seventh preferred embodiment, monomer (M1) is exclusively methyl methacrylate.

[0153] The prepolymer (PRE1) of the polymer composition (C2) is preferably selected from epoxy resins. Preferably, the epoxy resin comprises at least two oxirane type functional groups.

[0154] Preferably, the prepolymer (PRE1) of the polymer composition (PC1) comprises or is selected from a liquid epoxy resin or a liquid mixture of epoxy resins.

[0155] The liquid epoxy resins may be based on bisphenol A or bisphenol F, or on phenol novolaks or mixtures thereof in any ratio. They may be mixed with reactive diluents, such as phenyl or cresyl glycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether or hexahydrophthalic acid diglycidyl ester, for example, preferably in an amount of 1 to 50% by weight, more preferably 2 to 40% by weight, based on the total amount of epoxy resin as prepolymer (PRE1) in the composition (C2).

[0156] In the case of an embodiment in which composition (C2) comprises a mixture of prepolymer (PRE1a) and prepolymer (PRE1b), at least one of the two prepolymers of the mixture is an epoxy resin comprising at least two oxirane type functional groups. The other prepolymer may comprise one, two or more oxirane type functional groups. In the mixture of prepolymer (PRE1a) and prepolymer (PRE1b), one of the prepolymers is preferably a glycidyl ether, more preferably a diglycidyl ether comprising a linear aliphatic group or a cyclic aliphatic group.

[0157] In the following, at least one prepolymer of the mixture comprising at least two oxirane type functional groups is referred to as (PRE1a). In the following, the other prepolymer, which may comprise one, two or more oxirane type functional groups, is referred to as (PRE1b).

[0158] (PRE1a) is present in a mixture of prepolymer (PRE1a) and prepolymer (PRE1b). The weight ratio between (PRE1a) / (PRE1b) is between 99 / 1 and 60 / 40, preferably between 99 / 1 and 70 / 30.

[0159] Preferably, the viscosity of (PRE1b) is lower than the viscosity of (PRE1a). The dynamic viscosity of (PRE1b) is preferably less than 1000 mPa*s at 25°C, more preferably between 1 mPa*s and 800 mPa*s at 25°C, still more preferably between 1 mPa*s and 500 mPa*s at 25°C, advantageously between 1 mPa*s and 250 mPa*s at 25°C.

[0160] In a first preferred embodiment, (PRE1a) is a diglycidyl ether comprising an aromatic group, and (PRE1b) is a glycidyl ether or a glycidyl ester comprising a linear aliphatic group or a cyclic aliphatic group.

[0161] In a second preferred embodiment, (PRE1a) is a diglycidyl ether comprising an aromatic group and (PRE1b) is a glycidyl ether comprising a linear aliphatic group or a cyclic aliphatic group.

[0162] In a third preferred embodiment, (PRE1a) is a diglycidyl ether comprising an aromatic group and (PRE1b) is a diglycidyl ether comprising a linear aliphatic group or a cyclic aliphatic group.

[0163] The solvent of the second preferred embodiment and the variant of the third preferred embodiment and the fourth preferred embodiment and the fifth preferred embodiment of composition (C1 ) is selected from ketones or esters.

[0164] The multi-stage polymer (MP1) of the polymer composition (PC1) has at least two stages (SB1) and (SB2), respectively; and the two stages comprising the polymer (B1) and the polymer (B2), respectively, differ in their polymer composition.

[0165] The multistage polymer (MP1) is preferably in the form of polymer particles PAR which can be regarded as more or less spherical particles. These polymer particles PAR are also referred to as core-shell particles. The first stage forms the core, the second stage or all subsequent stages form the corresponding shell. Such multistage polymers (MP1) (which are also referred to as core-shell particles) are preferred.

[0166] The particles PAR contained in the polymer composition (PC1) are primary particles. The weight average particle size (diameter) of the particles PAR is between 15nm and 900nm. Preferably, the weight average particle size of the polymer particles is between 20nm and 800nm, more preferably between 25nm and 600nm, still more preferably between 30nm and 550nm, still more preferably between 35nm and 500nm, advantageously between 40nm and 400nm, even more advantageously between 75nm and 350nm, advantageously between 80nm and 300nm.

[0167] The polymer composition (PC1) comprises a multistage polymer (MP1) and a polymer (B3). The multistage polymer (MP1) comprises at least b1) one stage (SB1) comprising a polymer (B1) having a glass transition temperature of less than 10°C, and at least b2) one stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60°C. Based only on b1), b2) and b3), the polymer (B3) having a glass transition temperature of at least 30°C accounts for at most 40% by weight of the polymer composition (PC1). Preferably, based only on b1), b2) and b3), the polymer (B3) accounts for at most 35% by weight of the composition; more preferably at most 30% by weight, still more preferably less than 30% by weight, advantageously less than 25% by weight, more advantageously less than 20% by weight.

[0168] Preferably, based only on b1), b2) and b3), polymer (B3) represents more than 4% by weight of the composition. More preferably, based only on b1), b2) and b3), polymer (B3) represents more than 5% by weight of the composition; even more preferably more than 6% by weight, still more preferably more than 7% by weight, advantageously more than 8% by weight, more advantageously more than 10% by weight.

[0169] Preferably, based only on b1), b2) and b3), polymer (B3) represents between 4% and 40% by weight of the composition. More preferably, based only on b1), b2) and b3), polymer (B3) represents between 5% and 35% by weight of the composition; even more preferably between 6% and 30% by weight, still more preferably between 7% and less than 30% by weight, advantageously between 7% and less than 25% by weight, more advantageously between 10% and less than 20% by weight.

[0170] In a first preferred embodiment of the polymer composition (PC1), stage (SB1) is the first of at least two stages and stage (SB2) comprising polymer (B2) is grafted onto stage (SB1) comprising polymer (B1) or another intermediate layer.

[0171] In a second preferred embodiment of the polymer composition (PC1), stage (SB1) may also be preceded by a further stage, so that stage (SB1) is also a shell.

[0172] In a third preferred embodiment of the polymer composition (PC1), the polymer (B3) having a glass transition temperature of at least 30° C. is also part of the multistage polymer (MP1). There is also at least one stage (SB3). Preferably, stage (SB3) occurs after stage (SB2). More preferably, stage (SB3) is the last stage and polymer (B3) is the outer shell of the multistage polymer (MP1).

[0173] In a first embodiment, the polymer (B1) having a glass transition temperature below 10° C. comprises at least 50% by weight of polymer units derived from one or more alkyl acrylates, and stage (SB1) is the innermost layer of the polymer particles having a multilayer structure. In other words, stage (SB1) comprising polymer (B1) is the core of the polymer particles.

[0174] As for the polymer (B1) of the first preferred embodiment, it is a (meth)acrylic polymer comprising at least 50 wt% of polymer units derived from acrylic monomers. Preferably 60 wt%, more preferably 70 wt% of polymer (B1) are acrylic monomer units.

[0175] The acrylic monomer in polymer (B1) includes a monomer selected from C1-C18 alkyl acrylates or a mixture thereof. More preferably, the acrylic monomer in polymer (B1) includes C2-C12 alkyl acrylate monomers or a mixture thereof. Still more preferably, the acrylic monomer in polymer (B1) includes C2-C8 alkyl acrylate monomers or a mixture thereof.

[0176] The polymer (B1) may comprise one or more comonomers copolymerizable with the acrylic monomer, as long as the polymer (B1) has a glass transition temperature below 10°C.

[0177] The comonomer(s) in polymer (B1) are preferably selected from (meth)acrylic monomers and / or vinyl monomers.

[0178] Most preferably, the acrylic comonomer or methacrylic comonomer of polymer (B1) 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 (B1) has a glass transition temperature below 10°C.

[0179] In one specific embodiment, polymer (B1) is a homopolymer of butyl acrylate.

[0180] More preferably, the glass transition temperature Tg of the polymer (B1) 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, more advantageously between -70°C and -20°C.

[0181] In a second preferred embodiment, the polymer (B1) having a glass transition temperature below 10° C. comprises at least 50% by weight of polymer units derived from isoprene or butadiene, and stage (SB1) is the innermost layer of the polymer particles having a multilayer structure. In other words, stage (SB1) comprising polymer (B1) is the core of the polymer particles.

[0182] As examples of the polymer (B1) of the core of the second embodiment, mention may be made of isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers, copolymers of isoprene with up to 98% by weight of vinyl monomers, and copolymers of butadiene with up to 98% by weight of vinyl monomers. 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.

[0183] More preferably, the glass transition temperature Tg of the polymer (B1) 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, most advantageously between -70°C and -20°C.

[0184] In a third preferred embodiment, polymer (B1) is a silicone rubber-based polymer. Silicone rubber is, for example, polydimethylsiloxane. More preferably, the glass transition temperature Tg of polymer (B1) 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, more advantageously between -135°C and -25°C.

[0185] The polymer (B1) having a glass transition temperature below 10° C. comprises polymerized monomer units. The polymer (B1) in general and the corresponding polymers (B1) of the first, second and third preferred embodiments are produced from the corresponding monomers or monomer mixtures (B1) that produce the monomer units contained in the polymer (B1). m )preparation.

[0186] As polymer (B2), there may be mentioned a homopolymer and a copolymer containing a monomer having a double bond and / or a vinyl monomer. Preferably, polymer (B2) is a (meth)acrylic polymer.

[0187] Preferably, polymer (B2) comprises at least 70 wt% of monomers selected from C1-C12 alkyl (meth)acrylates. Still more preferably, polymer (B2) comprises at least 80 wt% of C1-C4 alkyl methacrylate monomers and / or C1-C8 alkyl acrylate monomers.

[0188] Most preferably, the acrylic or methacrylic monomer of polymer (B2) is selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as polymer (B2) has a glass transition temperature of at least 60°C.

[0189] Advantageously, polymer (B2) comprises at least 70% by weight of monomer units derived from methyl methacrylate.

[0190] Preferably, the glass transition temperature Tg of polymer (B2) is between 60 and 150°C. The glass transition temperature of polymer (B1) is more preferably between 80 and 150°C, advantageously between 90 and 150°C, more advantageously between 100 and 150°C.

[0191] Preferably, polymer (B2) is grafted onto the polymer prepared in a previous stage.

[0192] In certain embodiments, polymer (B2) is cross-linked.

[0193] In one embodiment, polymer (B2) comprises functional comonomer. Functional copolymer is selected from acrylic acid or methacrylic acid, amide (for example dimethyl acrylamide) derived from the acid, 2-methoxyethyl acrylate or 2-methoxyethyl methacrylate, optionally quaternized 2-aminoethyl acrylate or 2-aminoethyl methacrylate, polyethylene glycol (meth) acrylate, water-soluble vinyl monomer (for example N-vinyl pyrrolidone) or their mixture. Preferably, the polyethylene glycol group of polyethylene glycol (meth) acrylate has a molecular weight range of 400g / mol to 10000g / mol.

[0194] The polymer (B2) having a glass transition temperature of at least 60° C. comprises polymerized monomer units. In general and in the corresponding embodiments, the polymer (B2) is produced from the corresponding monomers or monomer mixtures (B2) from which the monomer units contained in the polymer (B2) are derived. m )preparation.

[0195] As for polymer (B3), it has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0196] Polymer (B3) having a mass average molecular weight Mw of greater than 10000 g / mol, preferably greater than 10500 g / mol, more preferably greater than 11000 g / mol, still more preferably greater than 12000 g / mol, advantageously greater than 13000 g / mol, more advantageously greater than 14000 g / mol, yet more advantageously greater than 15000 g / mol.

[0197] Polymer (B3) having a mass average molecular weight Mw of less than 500000 g / mol, preferably less than 450000 g / mol, more preferably less than 400000 g / mol, still more preferably less than 400000 g / mol, advantageously less than 350000 g / mol, more advantageously less than 300000 g / mol, still more advantageously less than 250000 g / mol, most advantageously less than 200000 g / mol.

[0198] Preferably, the mass average molecular weight Mw of polymer (B3) is between 10500 g / mol and 450000 g / mol, more preferably between 11000 g / mol and 400000 g / mol, even more preferably between 12000 g / mol and 350000 g / mol, advantageously between 13000 g / mol and 300000 g / mol, more advantageously between 14000 g / mol and 250000 g / mol, most advantageously between 15000 g / mol and 200000 g / mol.

[0199] In a first advantageous embodiment, the mass average molecular weight Mw of polymer (B3) is between 10500 g / mol and 200000 g / mol, more preferably between 11000 g / mol and 190000 g / mol, even more preferably between 12000 g / mol and 180000 g / mol, advantageously between 13000 g / mol and 150000 g / mol, more advantageously between 14000 g / mol and 135000 g / mol, most advantageously between 15000 g / mol and 120000 g / mol.

[0200] In a second advantageous embodiment, the mass average molecular weight Mw of polymer (B3) is between 15000 g / mol and 450000 g / mol, more preferably between 16000 g / mol and 400000 g / mol, even more preferably between 17000 g / mol and 350000 g / mol, advantageously between 18000 g / mol and 300000 g / mol, more advantageously between 19000 g / mol and 250000 g / mol, most advantageously between 20000 g / mol and 200000 g / mol.

[0201] Preferably, polymer (B3) is a copolymer comprising (meth) acrylic monomers. More preferably, polymer (B3) is a (meth) acrylic polymer. Still more preferably, polymer (B3) comprises at least 70% by weight of monomers selected from C1-C12 alkyl (meth)acrylates. Advantageously, polymer (B3) comprises at least 80% by weight of C1-C4 alkyl methacrylate monomers and / or C1-C8 alkyl acrylate monomers.

[0202] Preferably, the glass transition temperature Tg of polymer (B3) is between 30 and 150°C. More preferably, the glass transition temperature of polymer (B3) is between 40 and 150°C, advantageously between 45 and 150°C, more advantageously between 50 and 150°C.

[0203] Preferably, polymer (B3) is not crosslinked.

[0204] Preferably, polymer (C1) is not grafted onto either polymer (B1) or polymer (B2), in particular if it is part of a multistage polymer (MP1). By not grafted is meant that at least 50% by weight of polymer (C1) in the multistage polymer (MP1) is soluble in the solvent for polymer (B3).

[0205] In one embodiment, polymer (B3) further comprises a functional comonomer.

[0206] The functional comonomer has the formula (1)

[0207]

[0208] wherein R1 is selected from H or CH3, and R2 is H or an aliphatic or aromatic group having at least one non-C or non-H atom.

[0209] Preferably, the functional monomer is selected from glycidyl (meth) acrylate, acrylic acid or methacrylic acid, amides derived from these acids (e.g. dimethylacrylamide), 2-methoxyethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or methacrylate, polyethylene glycol (meth) acrylate. Preferably, the polyethylene glycol group of the polyethylene glycol (meth) acrylate has a molecular weight range of 400 g / mol to 10000 g / mol.

[0210] In a first preferred embodiment, polymer (B3) 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 C1-C8 alkyl acrylate monomers. Advantageously, the C1-C8 alkyl acrylate monomers are selected from methyl acrylate, ethyl acrylate or butyl acrylate.

[0211] In a second preferred embodiment, polymer (B3) comprises between 0% and 50% by weight of functional monomers. Preferably, (meth)acrylic polymer (B3) comprises between 0% and 30% by weight of functional monomers, more preferably between 1% and 30% by weight, still more preferably between 2% and 30% by weight, advantageously between 3% and 30% by weight, more advantageously between 5% and 30% by weight, most advantageously between 5% and 30% by weight.

[0212] Preferably, the functional monomer of the second preferred embodiment is a (meth)acrylic monomer. The functional monomer has formula (2) or (3)

[0213]

[0214] Wherein in both formula (2) and formula (3), R1 is selected from H or CH3; and in formula (2), Y is O, R5 is H or an aliphatic group or an aromatic group having at least one non-C or non-H atom; and in formula (3), Y is N and R4 and / or R3 are H or an aliphatic group or an aromatic group.

[0215] Preferably, the functional monomer (2) or the functional monomer (3) is selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids (e.g. dimethylacrylamide), 2-methoxyethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or methacrylate, acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkyl imidazolidinone (meth)acrylates, polyethylene glycol (meth)acrylates. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight range of 400 g / mol to 10000 g / mol.

[0216] The polymer (B3) having a glass transition temperature of at least 30° C. comprises polymerized monomer units. In general and in the corresponding embodiments, the polymer (B3) is produced from the corresponding monomers or monomer mixtures (B3) from which the monomer units contained in the polymer (B3) are derived. m) preparation.

[0217] The multistage polymer (MP1) is obtained by a multistage process comprising at least two stages. At least component b1) and component b2) of the polymer composition (PC1) are part of the multistage polymer (MP1).

[0218] Preferably, the polymer (B1) having a glass transition temperature below 10° C. produced during stage (SB1) is produced before stage (SB2) or is the first stage of a multistage process.

[0219] Preferably, the polymer (B2) having a glass transition temperature of at least 60° C. produced during stage (SB2) is produced after stage (SB1) of the multistage process.

[0220] In a first preferred embodiment, the polymer (B2) having a glass transition temperature of at least 60° C. is the middle layer of the polymer particles having a multilayer structure.

[0221] In this first preferred embodiment, the polymer (B3) having a glass transition temperature above 30° C. produced during stage (SB3) is produced after stage (SB2) of the multistage process.

[0222] More preferably, the polymer (B3) having a glass transition temperature above 30° C. produced during stage (SB3) is the outer layer of the multistage polymer (MP1) or primary polymer particles having a multilayer structure.

[0223] There may be additional intermediate stages between stage (SB1) and stage (SB2) and / or between stage (SB2) and stage (SB3).

[0224] Polymer (B3) and polymer (B2) are not identical polymers, even though their compositions may be very close and some of their properties overlap. The essential difference is that polymer (B2) is always part of a multistage polymer (MP1).

[0225] This is further explained in the process for preparing a polymer composition (PC1) comprising a polymer (B3) and a multistage polymer (MP1).

[0226] The weight ratio r of the polymer (B3) of the outer layer contained in stage (SB3) relative to the complete polymer particles having a multilayer structure is at least 5 wt%, more preferably at least 7 wt%, and even more preferably at least 10 wt%.

[0227] According to the present invention, the weight ratio r of the outer stage (SB3) comprising the polymer (B3) relative to the complete polymer particles having a multilayer structure is at most 40% by weight.

[0228] Preferably, the weight ratio r of the polymer (B3) relative to the primary polymer particles having a multilayer structure is between 5% by weight and 30% by weight, preferably between 10% by weight and 20% by weight.

[0229] In a second preferred embodiment, the polymer (B2) having a glass transition temperature of at least 60° C. is the outer layer of the primary polymer particles having a multilayer structure, in other words, the multistage polymer (MP1).

[0230] Preferably, at least a portion of the polymer (B2) of the layer produced during stage (SB2) is grafted onto the polymer produced in the previous layer. If there are only two stages (SB1) and (SB2) comprising polymer (B1) and polymer (B2), respectively, a portion of polymer (B2) is grafted onto polymer (B1). More preferably, at least 50% by weight of polymer (B1) is grafted. The grafting rate can be determined by extracting polymer (B1) with a solvent and determining the ungrafted amount by weight measurement before and after extraction.

[0231] The glass transition temperature Tg of the corresponding polymer can be estimated, for example, by dynamic methods such as thermomechanical analysis.

[0232] In order to obtain samples of the corresponding polymers (B1), (B2) and (B3), they can be prepared separately under the same conditions, but not by the multi-stage method, so that the glass transition temperature Tg of each of the corresponding polymers of the corresponding stage can be estimated and measured more easily. Polymer (B3) can be extracted to estimate and measure the glass transition temperature Tg.

[0233] As for the first preferred method for preparing the polymer composition (PC1), it comprises the following steps:

[0234] a) by emulsion polymerization of a monomer or a monomer mixture (B 1m ) to obtain a layer in stage (SB1), said stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0235] b) by emulsion polymerization of a monomer or a monomer mixture (B 2m ) to obtain a layer in stage (SB2), said stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C.,

[0236] c) by emulsion polymerization of a monomer or a monomer mixture (B 3m ) to obtain a layer in stage (SB3), said stage (SB3) comprising a polymer (B3) having a glass transition temperature of at least 30° C.,

[0237] d) agglomerating the composition obtained in steps a) to c).

[0238] Preferably, step a) is performed before step b).

[0239] More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a).

[0240] Advantageously, the first preferred process for preparing the polymer composition (PC1) is a multi-step process comprising the following steps one after the other:

[0241] a) by emulsion polymerization of a monomer or a monomer mixture (B 1m ) to obtain a layer in stage (SB1), said stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0242] b) by emulsion polymerization of a monomer or a monomer mixture (B 2m ) to obtain a layer in stage (SB2), said stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C.,

[0243] c) by emulsion polymerization of a monomer or a monomer mixture (B 3m) to obtain a layer in stage (SB3), said stage (SB3) comprising a polymer (B3) having a glass transition temperature of at least 30° C.,

[0244] d) agglomerating the composition obtained in steps a) to c).

[0245] Preferably, steps a), b), c) and d) are carried out in this order. Due to the emulsion polymerization, the polymer composition is obtained in the form of an aqueous dispersion at the end of the polymerization.

[0246] The corresponding monomers or monomer mixtures (B1, B2 and B3) used to form the layers in the stages (SB1), (SB2) and (SB3) respectively comprising the polymers (B1), (B2) and (B3) 1m )、(B 2m ) and (B 3m ) is the same as defined above. The monomer or monomer mixture (B 1m )、(B 2m ) and (B 3m ) contains the corresponding monomers as polymerized monomer units in the polymer chains of the corresponding polymers (B1), (B2) and (B3). The properties of polymers (B1), (B2) and (B3) are the same as defined above, respectively.

[0247] A second preferred method for preparing a polymer composition (PC1) comprising a polymer (B3) and a multistage polymer (MP1) comprises the following steps:

[0248] a) by emulsion polymerization of a monomer or a monomer mixture (B 1m ) to obtain a layer in stage (SB1), said stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0249] b) by emulsion polymerization of a monomer or a monomer mixture (B 2m ) to obtain a layer in stage (SB2), said stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C.,

[0250] Steps a) and b) together give a multistage polymer (MP1), and step:

[0251] c) blending the multistage polymer (MP1) with a polymer (B3) having a glass transition temperature of at least 30° C.,

[0252] d) agglomerating the composition obtained in steps a) to c).

[0253] Preferably, polymer (B3) is in the form of an aqueous dispersion. The aqueous dispersion comprises polymer (B3) in the form of polymer particles.

[0254] For a third preferred process for preparing a polymer composition (PC1) comprising a polymer (B3) and a multistage polymer (MP1), it comprises the following steps:

[0255] a) providing a polymer (C1) having a glass transition temperature of at least 30°C and a multistage polymer (MP1) comprising one stage (SB1) comprising a polymer (B1) having a glass transition temperature of less than 10°C and one stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60°C,

[0256] b) mixing or blending the polymer (B3) and the multistage polymer (MP1),

[0257] c) agglomerating the composition obtained in step b)

[0258] The polymer (B3) and the multistage polymer (MP1) in step b) are in the form of dispersions in the aqueous phase. The corresponding aqueous dispersion contains the polymer (B3) and the multistage polymer (MP1) in the form of polymer particles.

[0259] Preferably, the multistage polymer (MP1) and the polymer (B3) are already provided as aqueous dispersions.

[0260] The agglomeration step of the corresponding process for preparing the polymer composition (PC1) may be chosen from coagulation or spray drying.

[0261] In a first preferred embodiment, the agglomeration step is carried out by coagulation in an aqueous phase.

[0262] In a second preferred embodiment, the agglomeration step is carried out by spray drying.

[0263] The amounts of aqueous dispersion of polymer (B3) and of aqueous dispersion of multistage polymer (MP1) are selected in such a way that the weight proportion of the multistage polymer, based on the solid fraction alone in the resulting mixture, is at least 60% by weight, preferably at least 65% by weight, more preferably at least 68% by weight, advantageously at least 70% by weight.

[0264] The amounts of aqueous dispersion of polymer (B3) and aqueous dispersion of multistage polymer (MP1) are selected in such a way that the weight proportion of the multistage polymer, based on the solid fraction alone in the resulting mixture, is at most 99% by weight, preferably at most 95% by weight, more preferably at most 90% by weight.

[0265] The amounts of aqueous dispersion of polymer (C1) and aqueous dispersion of multistage polymer are selected in such a way that the weight proportion of multistage polymer, based on the solid fraction alone in the resulting mixture, is between 60% and 99% by weight, preferably between 65% and 95% by weight, more preferably between 68% and 90% by weight.

[0266] The preferred method for preparing a polymer composition (PC1) comprising a polymer (B3) and a multistage polymer (MP1) produces a polymer powder (POW1). The polymer powder (POW1) is in the form of granules (macroparticles). The polymer powder granules or particles comprise agglomerated primary polymer particles comprising a multistage polymer (MP1) and a polymer (B3) prepared by a multistage process or agglomerated primary polymer particles comprising a multistage polymer (MP1) and a polymer (B3) particle.

[0267] Component a) is a precursor of a thermosetting polymer or a thermoplastic polymer. This can be a monomer (M1), a monomer mixture, a prepolymer (PRE1) as a polymerizable or curable oligomer, a mixture of a polymerizable or curable oligomer and (one or more) monomers, or a mixture of a polymer and (one or more) monomers, which are liquid at 25°C. Preferably, the liquid has a dynamic viscosity of less than 1000 Pa*s, more preferably between 0.5 mPa*s and 1000 Pa*s. The value of the dynamic viscosity is obtained at a shear rate of 1 1 / s. The viscosity is measured with a rheometer.

[0268] The present invention also relates to a process for preparing the composition (C1) according to the invention.

[0269] The method for preparing composition (C1) comprises the following steps:

[0270] a) providing a monomer (M1) or a prepolymer (PRE1);

[0271] b) providing a polymer composition (PC1) comprising

[0272] b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C.,

[0273] b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and

[0274] b3) and a polymer (B3) having a glass transition temperature of at least 30° C. and a mass average molecular weight Mw between 10 000 g / mol and 500 000 g / mol, based solely on b1), b2) and b3), said polymer (B1) comprising up to 40% by weight of the composition,

[0275] c) contacting the polymer composition (PC1) with a resin (RES) comprising monomers (M1) or prepolymers (PRE1) or a mixture of both,

[0276] d) providing a mixing device,

[0277] e) mixing the contacted compounds using the provided mixing device.

[0278] The amount of polymer composition (PC1) is chosen in such a way that for 100 parts of composition (C2) comprising monomers (M1) or prepolymers (PRE1) or a mixture of both, composition (C1) comprises between 10 and 100 phr of polymer composition (PC1).

[0279] In a first preferred embodiment, the polymer composition (PC1) is in the form of a polymer powder.

[0280] Preferably, the polymer composition (PC1) is in the form of a solvent-free polymer powder. Solvent-free means that the solvent finally present accounts for less than 1% by weight of the composition. The monomers synthesized from the corresponding polymer are not considered as solvents. The residual monomers present in the composition are less than 2% by weight of the composition.

[0281] Preferably, the polymer composition (PC1) in the form of polymer powder is dry. Dry means that the polymer composition according to the invention comprises less than 3 wt.-% moisture, preferably less than 1.5 wt.-% moisture, more preferably less than 1.2 wt.-% moisture.

[0282] Moisture content is measured by a thermobalance that heats the polymer composition and measures the weight loss.

[0283] Preferably, the polymer composition (PC1) is in the form of a polymer powder (POW1) having a volume median particle size D50 between 1 μm and 700 μm. Preferably, the volume median particle size of the polymer powder is between 10 μm and 600 μm, more preferably between 15 μm and 550 μm, advantageously between 20 μm and 500 μm.

[0284] The D10 of the volume particle size distribution is at least 7 μm, preferably 10 μm, more preferably 15 μm.

[0285] The D90 of the volume particle size distribution is at most 1000 μm, preferably 950 μm, more preferably at most 900 μm, even more preferably at most 800 μm.

[0286] The method for preparing composition (C1) comprises the step d) providing a mixing device.

[0287] Preferably, the mixing device is a suitable device selected from a three-roll mill, a high viscosity blender, a high shear mixer, an acoustic mixer or a planetary mixer.

[0288] In a first preferred embodiment, the mixing device is a high shear mixer.

[0289] In a second preferred embodiment, the mixing device is an acoustic mixer. "Acoustic mixer" is a term used to describe a broad machine that induces acoustic vibrations.

[0290] In a third preferred embodiment, the mixing device is a planetary mixer.The planetary mixer comprises mixing blades.

[0291] During the mixing step d), the temperature is between 15 and 150°C, preferably between 20 and 150°C, more preferably between 20 and 100°C, still more preferably between 40 and 80°C.

[0292] The time for the mixing step depends on the mixing device. Generally speaking, the time required for the mixing step is less than 2 hours.

[0293] The process for preparing the composition (C1) optionally comprises a step of preheating at least one of the components provided. Preferably, the prepolymer (PRE1) is preheated before contacting the compounds a) and b) provided. The preheating temperature is at least 30° C., preferably at least 40° C. Advantageously, the preheating temperature is between 40° C. and 150° C.

[0294] In one variant, the components of a) and b) provided are contacted in two or more different steps. This means that, in step c1), only a portion of the compound b) provided is contacted with the component a) provided. In step e1), the two components are mixed with a mixing device. Then, in a second step c2), the remainder or another portion of the compound a) is added and then mixed in step e2). If only a portion is added, steps c) and e) are repeated until all the provided compound b) has been contacted. In this variant, steps c) and e) are divided into several substeps c1) to cx) and e1) to ex), where x is the number of portions of compound b) to be added.

[0295] This variant is preferably used if the amount of component b) in component a) is greater than 50 phr.

[0296] The composition (C1) of the present invention can be used as a masterbatch.

[0297] Masterbatches can be used in different applications such as adhesives, composites, wind blades, 3D printing, electronics (PCB or PCL) or sport.

[0298] Composition (C1) is mixed with the further component(s) to adapt the amount of polymer composition (PC1).

[0299] The mixed composition is converted into a polymer by polymerization or curing.

[0300] The present invention also relates to a process for preparing a polymer composition (PC2) from a composition (C1).

[0301] The method comprises the steps of polymerizing or curing the composition (C1).

[0302] The process for preparing a polymer composition (PC2) from composition (C1) further comprises a step of adding an additional amount of composition (C2) before the polymerization or curing step.

[0303] Evaluation Methodology

[0304] Glass transition temperature

[0305] The glass transition (Tg) was measured with equipment capable of thermomechanical analysis. The RDAII "RHEOMETRICSDYNAMIC ANALYSER" from Rheometrics was used. Thermomechanical analysis accurately measures the changes in the viscoelasticity of a sample as a function of applied temperature, strain or deformation. During a controlled temperature change program, the strain is kept fixed and the equipment continuously records the sample deformation.

[0306] The results are obtained by plotting the elastic modulus (G'), loss modulus, and tan delta as a function of temperature. Tg is the highest temperature value read in the tan delta curve when the derivative of tan delta equals zero.

[0307] Molecular weight

[0308] The mass average molecular weight (Mw) of the polymer was measured by size exclusion chromatography (SEC). Polystyrene standards were used for calibration. The polymer was dissolved in THF at a concentration of 1 g / L. The chromatographic column used modified silica. The flow rate was 1 ml / min and a refractive index detector was used.

[0309] Particle size analysis

[0310] The particle size of the primary particles after the multistage polymerization is measured with a Zetasizer from Malvern using dynamic light scattering. The volume average particle size (diameter) is obtained as a result.

[0311] The particle size of the recovered polymer powder was measured by laser diffraction using a Malvern Mastersizer 3000 from Malvern.

[0312] For the estimation of weight average powder particle size, particle size distribution and fine particle ratio, a Malvern Mastersizer 3000 apparatus with a 300 mm lens and a measuring range of 0.5-880 μm was used.

[0313] Viscosity

[0314] The viscosity is the dynamic viscosity. If shear thinning is present, the dynamic viscosity value is taken at a shear rate of 1 1 / s. The viscosity is measured with a rheometer from Anton Parr. A Rheolab QC rotational rheometer is used.

[0315] Raw materials used

[0316] As the first prepolymer (PRE1), DGEBA (bisphenol A diglycidyl ether) was used.

[0317] As a variant, mixtures of prepolymers are also exemplified. In this case, this would be an embodiment comprising (PRE1a) and (PRE1b); DGEBA as (PRE1a) and 1,6-hexanediol diglycidyl ether and 1,4-cyclohexanedimethanol diglycidyl ether as (PRE1b), respectively.

[0318] According to WO 2020 / 260637, a multistage polymer in the form of core-shell particles CS2 comprising polymer (B3) was prepared as a product referred to as core / shell-2.

[0319] According to WO2020 / 260637, a multistage polymer in the form of core-shell particles CS1 was used as a comparative product, however only the first and second stages were carried out on the product referred to as core / shell-1 in the experimental part of WO2020 / 260637.

[0320] The compositions were prepared using a method employing a mixing blade.

[0321] The core-shell particles CS1 and CS2 were blended into DGEBA at 15 wt % each in a reactor equipped with a heating device and a stirring device. The stirrer was a mixing blade.

[0322] Table 1 - Dynamic viscosity at 80°C as a function of mixing time.

[0323]

[0324] As can be seen from Table 1, when not preparing a composition according to the invention or using a method according to the invention, the preparation takes longer in terms of mixing time.

[0325] A method using an acoustic mixer was also used to prepare the composition. TM Resonant acoustic mixer (or "RAM mixer") LabRAM from Acoustic Mixers, Inc. (Butte, Mont.) or PCCA (Houston, Tex.).

[0326] The core-shell polymers CS1 and CS2 were used as component b) polymer composition (PC1) as before. The DGEBA epoxy resin was likewise used as component a) composition (C2).

[0327] The crude mixture of the two components was preheated at 80°C for 15 minutes. A RAM mixer was used for 1 minute.

[0328] CS1 disperses poorly at 10 wt. %, whereas very good dispersibility is obtained with CS2 at the same ratio. Compositions containing even 21 wt. % can be produced with CS2. When added in steps, very good dispersibility of CS2 at 38 wt. % is obtained.

[0329] Compositions of CS2 in prepolymer (PRE1) were prepared as described above. This time, a mixture of prepolymer (PRE1a) and prepolymer (PRE1b) was used, wherein DGEBA was (PRE1a), 1,6-hexanediol diglycidyl ether was (PRE1b1), and 1,4-cyclohexanedimethanol diglycidyl ether was (PRE1b2). The mixing ratios were (PRE1a) / (PRE1b)=95 / 5 parts by weight, respectively. The resulting viscosities are given in Table 2.

[0330] Table 2 – Viscosity at 25°C

[0331]

[0332] As shown in Table 2, the use of a prepolymer (PRE1) mixture allows for lower viscosity reduction for the same amount of core-shell particles, or higher amounts at comparable viscosity levels.

[0333] Polymer composition type (PC2) was prepared from composition (C1) of Table 2 containing 10 wt% CS2. The composition was cured with DDA.

[0334] Table 3: Mechanical properties of the cured compositions

[0335] (PRE1a) / (PRE1b1) (PRE1a) / (PRE1b2) Pure epoxy system <![CDATA[K 1c (MPa.m 1 / 2 )]]> 1.5 1.3 0.68 <![CDATA[G 1c (kJ / m 2 )]]> 2.3 2.5 0.53

[0336] In Table 3, a significant improvement in toughness is observed for the polymers obtained from the compositions according to the invention. 1c and fracture toughness G1c As shown, the fracture toughness is significantly improved.

Claims

1. A composition (C1) comprising: a) 100 parts of a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1) or a mixture of both, b) between 10 and 100 phr of a polymer composition (PC1) comprising: b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C., b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and b3) and a polymer (B3) having a glass transition temperature of at least 30° C., based solely on b1), b2) and b3), the polymer (B3) accounts for up to 40% by weight of the composition; It is characterized in that At least components b1) and b2) of the composition (PC1) are part of a multistage polymer (MP1) and are characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

2. The composition (C1) according to claim 1, characterized in that The composition (C2) is liquid at least in the temperature range of 50°C to 80°C.

3. The composition (C1) according to claim 1 or 2, characterized in that The composition (C1) is liquid at least in the temperature range of 50°C to 80°C.

4. The composition (C1) according to any one of claims 1 to 3, characterized in that The composition (C2) comprises a prepolymer (PRE1).

5. The composition (C1) according to any one of claims 1 to 4, characterized in that The composition (C2) is a mixture of a prepolymer (PRE1a) and a prepolymer (PRE1b).

6. The composition (C1) according to any one of claims 1 to 5, characterized in that Said composition (C1 ) comprises, for 100 parts of composition (C2), between 10 and 90 phr of polymer composition (PC1 ), more preferably still between 10 and 80 phr, advantageously between 10 and 75 phr.

7. The composition (C1) according to any one of claims 1 to 5, characterized in that Said composition (C1 ) comprises between 35 and 100 phr of polymer composition (PC1 ) for 100 parts of polymer composition (C2).

8. The composition (C1) according to claim 1, characterized in that The monomer (M1) is selected from (meth)acrylic monomers and / or vinyl monomers and mixtures thereof.

9. The composition (C1) according to claim 1, characterized in that The prepolymer (PRE1) is selected from epoxy resins.

10. The composition (C1) according to claim 1, characterized in that The composition (C2) is liquid in the temperature interval from 20°C to 80°C and has a dynamic viscosity between 0.5 mPa*s and 1000 Pa*s.

11. The composition (C1) according to claim 1, characterized in that The composition (C1) is liquid at least in the temperature interval from 20° C. to 80° C. and has a dynamic viscosity between 1 mPa*s and 20,000 Pa*s.

12. The composition (C1) according to any one of claims 1 to 5, characterized in that The multistage polymer (MP1) is in the form of core-shell particles having a weight average particle size between 15 nm and 900 nm.

13. The composition (C1) according to any one of claims 1 to 6, characterized in that The polymer (B3) is a (meth)acrylic polymer.

14. The composition (C1) according to any one of claims 1 to 6, characterized in that The composition (C2) comprises an epoxy resin which may be based on bisphenol A or bisphenol F or on a phenolic resin or a mixture thereof.

15. The composition according to claim 5, characterized in that In the mixture of prepolymer (PRE1a) and prepolymer (PRE1b), one of the prepolymers is preferably a glycidyl ether, more preferably a diglycidyl ether comprising linear aliphatic groups or cyclic aliphatic groups.

16. The composition according to claim 5, characterized in that The ratio between (PRE1a) / (PRE1b) is between 99 / 1 and 60 / 40, preferably between 99 / 1 and 70 / 30.

17. A method for preparing a composition (C1) according to any one of claims 1 to 16, comprising the following steps: a) providing a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1) or a mixture of both; b) providing a polymer composition (PC1) comprising b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10° C., b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60° C., and b3) and a polymer (B3) having a glass transition temperature of at least 30° C., based solely on b1), b2) and b3), the polymer (B3) accounts for up to 40% by weight of the composition; c) contacting the provided components of a) and b); d) providing a mixing device; e) mixing the components of a) and b) using the provided mixing device; Characterized in that at least components b1) and b2) of the composition (PC1) are part of a multistage polymer (MP1), and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol; and characterized in that the amount of polymer composition (PC1) is selected so that for 100 parts of a composition (C2) comprising monomers (M1) or prepolymers (PRE1) or a mixture of both, between 10 phr and 100 phr of polymer composition (PC1) are present in the composition (C1).

18. The method according to claim 17, characterized in that The temperature of the mixing step is between 15°C and 150°C, preferably between 20°C and 150°C, more preferably between 20°C and 100°C, still more preferably between 40°C and 80°C.

19. The method according to claim 17 or 18, characterized in that The mixing device is selected from a high viscosity stirrer, a high shear mixer, an acoustic mixer or a planetary mixer.

20. The method according to any one of claims 17 to 19, characterized in that The contacting of the compounds of a) and b) provided is carried out in two different steps.

21. The method according to any one of claims 17 to 19, characterized in that The mixing step took less than 2 hours.

22. The method according to any one of claims 17 to 19, characterized in that The polymer composition (PC1) is provided in the form of a polymer powder having a volume median particle size D50 between 1 μm and 700 μm.

23. The method according to any one of claims 17 to 19, characterized in that The method also includes a preheating step.

24. Use of the composition (C1 ) according to any one of claims 1 to 16 or obtained by the process according to any one of claims 17 to 23 as a masterbatch.

25. Use of a composition (C1) according to any one of claims 1 to 16 or a composition (C1) obtained by a process according to any one of claims 17 to 23 in applications such as adhesives, composite materials, wind blades, 3D printing, electronic devices (PCB or PCL) or sporting goods.

26. A method for reducing the dispersion time of a polymer composition (PC1) comprising between 10 and 100 phr of a multistage polymer (MP1) in 100 parts of a composition (C2) comprising monomers (M1) or prepolymers (PRE1) or a mixture of both, the multistage polymer (MP1) comprising: b1) a stage (B1) comprising a polymer (B1) having a glass transition temperature below 10° C., b2) a stage (B2) comprising a polymer (B2) having a glass transition temperature of at least 60° C.; The method comprises the following steps: i) contacting the components ii) Provide a mixing device iii) mixing the components using the provided mixing device; Characterized in that the composition (PC1) further comprises b3) a polymer (B3) having a glass transition temperature of at least 30°C, the polymer (B3) constituting up to 40% by weight of the composition, based only on b1), b2) and b3); and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

27. A method for reducing the time of preparing a masterbatch comprising between 10 and 100 phr of a polymer composition (PC1) comprising a multistage polymer (MP1) in 100 parts of a composition (C2) comprising a monomer (M1) or a prepolymer (PRE1), the multistage polymer (MP1) comprising: b1) a stage (B1) comprising a polymer (B1) having a glass transition temperature below 10° C., b2) a stage (B2) comprising a polymer (B2) having a glass transition temperature of at least 60° C.; The method comprises the following steps: i) contacting the components ii) Provide a mixing device iii) mixing the components using the provided mixing device; Characterized in that the composition (PC1) further comprises b3) a polymer (B3) having a glass transition temperature of at least 30° C., said polymer (B3) constituting up to 40% by weight of the composition, based solely on b1), b2) and b3); and characterized in that said polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

28. A method for preparing a polymer composition (PC2) from a composition (C1) according to any one of claims 1 to 16, characterized in that The method comprises the following steps: - polymerizing or curing the composition (C1).

29. The method according to claim 28, characterized in that The method further comprises the step of adding an additional amount of composition (C2) before the polymerisation or curing step.

Images