Composition comprising a multi-layered polymer and a (meth)acrylic polymer, its preparation process and its use

Abstract

Composition comprising a multi-layered polymer and a (meth)acrylic polymer, its preparation process, and its use. The present invention relates to a composition comprising a multi-layered polymer, a (meth)acrylic polymer, and a monomer or prepolymer, its preparation process, and its use. In particular, the present invention relates to a process for preparing a composition comprising a multi-layered polymer in the form of polymeric particles, a (meth)acrylic polymer, and a monomer or prepolymer. More particularly, the present invention relates to a liquid polymer composition comprising a multi-layered polymer, a (meth)acrylic polymer, and a monomer or prepolymer, its preparation process, and its use, particularly as a masterbatch.

Description

Title of the invention: Composition comprising a multi-layered polymer and a (meth)acrylic polymer, its preparation process and its use. Technical field

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

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

[0003] More particularly, the present invention relates to a liquid polymer composition comprising a multi-stage polymer, a (meth)acrylic polymer and a monomer or prepolymer, its preparation process, its use particularly as a masterbatch. [Technical problem]

[0004] Polymers are also widely used as additives in polymer compositions. These so-called polymer additives are usually added as granules or also as powder, either to solid polymers, molten polymers, liquid resins, or liquid compositions.

[0005] One class of polymeric additives are processing auxiliaries, another are polymeric shock strength modifiers.

[0006] Polymeric impact resistance modifiers can be in the form of polymer particles. Typically, these polymeric impact resistance modifiers are in the form of core-shell particles prepared by a multi-stage process, at least one stage comprising a rubber-type polymer. These particles are then incorporated into the polymers or polymer compositions to increase their impact resistance. The polymers or polymer compositions can be thermosetting or thermoplastic.

[0007] Thermosetting polymers consist of cross-linked three-dimensional structures. Cross-linking is achieved by hardening reactive groups in the so-called prepolymer. Hardening, for example, can be achieved by heating the polymer chains or the prepolymer in order to cross-link and permanently harden the material.

[0008] Thermoplastic polymers consist of linear or branched polymers, which are not usually cross-linked. They may be slightly cross-linked as long as they can be deformed by heat.

[0009] However, these core-shell particles mentioned above are not easily or quickly dispersed in all kinds of resins, polymers, or polymer precursors, particularly, for example, in liquid epoxy resins, liquid monomers, or other liquid polymer precursors. A homogeneous and rapid dispersion is necessary to achieve satisfactory impact resistance performance in the final polymer composition. Easy dispersion and a rapid dispersion time are also required to reduce process time and obtain a simpler and easier process. The concentration of the core-shell particles must also be high so that the compositions can be used as masterbatches.

[0010] An objective of the present invention is to provide a composition comprising precursors for thermosetting polymers or thermoplastic polymers comprising a multi-layered polymer.

[0011] A further objective of the present invention is to provide a composition comprising precursors for thermosetting polymers or thermoplastic polymers comprising a large quantity of a multi-layered polymer. By "large quantity" is meant at least 10 parts per 100 parts of a composition comprising a multi-layered polymer for the purpose of providing precursors (for example, for 100 parts of epoxy prepolymer or monomer).

[0012] An objective of the present invention is also to provide a composition comprising precursors for thermosetting polymers or thermoplastic polymers comprising a multi-layered polymer that is stable over time. Stability over time means that no visible macroscopic phase separation occurs, preferably for a period of at least one month.

[0013] Another objective of the present invention is to propose a method for manufacturing a composition comprising precursors for thermosetting polymers or thermoplastic polymers and a multi-stage polymer.

[0014] A further objective of the present invention is a method for manufacturing a composition comprising precursors for thermosetting polymers or thermoplastic polymers comprising a large amount of a multi-layered polymer.

[0015] Yet another objective of the present invention is a method for manufacturing a composition comprising precursors for thermosetting polymers or thermoplastic polymers comprising a multi-stage polymer in a short time.

[0016] A further objective of the present invention is a method for manufacturing a composition comprising precursors for thermosetting polymers or thermoplastic polymers comprising a multi-stage polymer which is stable over time and has a sufficient storage life without separation.

[0017] Yet another additional objective of the present invention is the use of a composition comprising precursors for thermosetting polymers or thermoplastic polymers and a multi-stage polymer as a master blend.

[0018] Yet another objective is to provide a method for reducing the dispersion time of a multi-stage polymer in a composition comprising precursors for thermosetting polymers or thermoplastic polymers. [CONTEXT OF THE INVENTION] Prior art

[0019] Document WO2016 / 102682 discloses a multi-layered polymer composition and its preparation process. The multi-layered polymer includes a final layer comprising a (meth)acrylic polymer having a mass average molecular weight of less than 100,000 g / mol.

[0020] Document EP 1 632 533 describes a process for the production of a modified epoxy resin. The epoxy resin composition has rubber-like polymer particles dispersed therein by a process that brings the particles into contact with an organic medium which disperses the rubber particles.

[0021] Document EP 1 666 519 discloses a process for the production of a rubbery polymer particle and a process for a resin composition containing it.

[0022] Document EP 2 123 711 discloses a thermosetting resin composition comprising rubbery polymer particles dispersed therein and a process for the production thereof.

[0023] Document WO2017 / 121749 discloses a liquid composition comprising a monomer, a (meth)acrylic polymer and a multi-stage polymer.

[0024] Document WO2019 / 012052 discloses a composition comprising a multi-stage polymer and its preparation process. The composition further comprises a (meth)acrylic polymer having a mass average molecular weight between 100,000 g / mol and 1,000,000 g / mol.

[0025] None of the prior art documents cited disclose such a masterbatch composition or in particular a process for its preparation. [Brief description of the invention]

[0026] Unexpectedly, it was discovered that a composition (Cl) comprising a. 100 phr of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both, b. between 10 phr and 100 phr of a polymeric composition (PCI) comprising bl) a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0027] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0028] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition based on bl), b2) and b3) only;

[0029] characterized in that at least component b 1) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI), 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 prepared easily and rapidly and used as a masterbatch.

[0030] Surprisingly, it was also discovered that a process for manufacturing a composition (Cl) comprising the steps of:

[0031] a) supply of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both;

[0032] b) supply of a polymeric composition (PCI) comprising

[0033] bl) a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0034] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0035] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition based on bl), b2) and b3) only;

[0036] c) bringing the supplied components of a) and b);

[0037] d) supply of a mixing means;

[0038] e) mixing the components with the supplied mixing means,

[0039] characterized in that at least component b 1) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI), and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol; produces a stable homogeneous composition (Cl) comprising between 10 phr and 100 phr of a polymeric composition (PCI) per 100 parts of composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both.

[0040] Unexpectedly, it was also discovered that a process for manufacturing a composition (Cl) comprising the steps of

[0041] a) supply of a polymeric composition (PCI) comprising

[0042] bl) a stage (SB1) comprising a polymer (Bl) having a transition temperature vitreous temperature below 10 °C,

[0043] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0044] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C and having a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol of, said polymer (B3) representing at most 40% by weight of a composition based on bl), b2 and b3) only,

[0045] b) contacting the polymeric composition (PCI) with a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1),

[0046] c) supplying a mixing means,

[0047] d) mixing of the components brought into contact with the mixing means provided;

[0048] produces a composition (Cl) where the polymeric composition (PCI) is dispersed from homogeneously and more rapidly in composition (C2) compared with a composition not including the polymer (B3).

[0049] Surprisingly, a process has also been discovered for reducing the dispersion time of a polymeric composition (PCI) in a composition (C2) comprising the steps of:

[0050] a) supply of a polymeric composition (PCI) comprising

[0051] bl) a stage (SB1) comprising a polymer (Bl) having a transition temperature vitreous temperature below 10 °C,

[0052] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0053] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C and having a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol of, said polymer (B3) representing at most 40% by weight of a composition based on bl), b2 and b3) only,

[0054] b) contacting the polymeric composition (PCI) with a composition (C2),

[0055] which is faster than the same process using a polymeric composition without compound b3). Description of the implementation methods

[0056] According to a first aspect, the present invention relates to a composition (Cl) comprising a. 100 phr of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both, b. between 10 phr and 100 phr of a polymeric composition (PCI) bl) a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0057] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0058] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition based on bl), b2) and b3) only;

[0059] characterized in that at least component b 1) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI), and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0060] According to a second aspect, the present invention relates to a method for manufacturing a composition (Cl), said method comprising the steps of

[0061] a) supply of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both;

[0062] b) supply of a polymeric composition (PCI) comprising

[0063] bl) a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0064] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0065] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition based on bl), b2) and b3) only;

[0066] c) bringing the supplied components of a) and b) into contact);

[0067] d) supply of a mixing means;

[0068] e) mixing of components a) and b) with the supplied mixing means,

[0069] characterized in that at least component b1) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI), 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; and characterized in that the amount of the polymeric composition (PCI) is chosen so that between 10 phr and 100 phr of a polymeric composition (PCI) are in the composition (Cl) for 100 parts of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both.

[0070] In a third aspect, the present invention relates to the use of a polymer composition (Cl) comprising a. 100 phr of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) b. between 10 phr and 100 phr of a polymeric composition (PCI) comprising bl) a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0071] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0072] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition based on bl), b2) and b3) only;

[0073] characterized in that at least component bl) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI), and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol;

[0074] as a masterbatch.

[0075] In a fourth aspect, the present invention relates to a method for manufacturing a composition (Cl), said method comprising the steps of

[0076] a) supply of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both;

[0077] b) supplying a polymeric composition (PCI) comprising

[0078] bl) a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0079] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0080] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B2) representing at most 40% by weight of the composition on the basis of bl), b2) and b3) only;

[0081] c) bringing the supplied components of a) and b);

[0082] d) supply of a mixing means;

[0083] e) mixing of components a) and b) with the mixing means provided,

[0084] characterized in that at least component b1) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI), 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 the polymeric composition (PCI) is chosen such that between 10 parts per 100 parts per 100 parts of a polymeric composition (PCI) are in the composition (Cl) per 100 parts of a monomer (Ml) or of a prepolymer (PRE1) or one for the preparation of a masterbatch.

[0085] In a fifth aspect, the present invention relates to a method for reducing the dispersion time of a polymeric composition (PCI) of between 10 phr and 100 phr comprising a multi-stage polymer (MPI):

[0086] bl) a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0087] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C,

[0088] in 100 parts of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both;

[0089] said process includes the step of i. bringing the components into contact ii. supply of a mixing medium iii. mixing of the components with the mixing means provided; characterized in that the composition (PCI) further comprises b3) a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition on the basis of bl), b2) and b3) only; and characterized in that the polymer (B3) has an average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0090] In a sixth aspect, the present invention relates to a method for reducing the time to prepare a masterbatch comprising between 10 phr and 100 phr of polymeric composition (PCI) composed of a multi-stage polymer (MPI) comprising

[0091] bl) a stage (Bl) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0092] b2) a stage (B2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C,

[0093] in 100 phr of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1);

[0094] said process includes the step of

[0095] i) bringing the components into contact

[0096] ii) supplying a mixing means

[0097] iii) mixing of the components with the mixing means provided;

[0098] characterized in that the composition (PCI) further comprises b3) a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition based on bl), b2) and b3) only; and characterized in that the polymer (B3) has an average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0099] The term "polymer powder", in the present context, refers to a polymer in the form of a powder comprising powder grains of the order of at least 1 pm, said powder grains being obtained by agglomeration of primary polymer particles comprising a polymer or polymers, said primary polymer particles being on the order of nanometers.

[0100] The term "primary particle" in this context refers to a spherical polymer particle comprising a particle on the order of a nanometer. Preferably, the primary particle has a weight-average particle size of between 20 nm and 800 nm.

[0101] The term "particle size", in the present context, refers to the volume average diameter of a particle considered to be spherical.

[0102] The term “thermoplastic polymer”, in the present context, refers to a polymer which becomes liquid or becomes more liquid or less viscous when heated and which can take on new shapes by the application of heat and pressure.

[0103] The term “thermosetting polymer”, in this context, refers to a prepolymer in a soft, solid or viscous state which is irreversibly transformed into an infusible and insoluble polymer network by hardening.

[0104] The term “epoxy resin,” in this context, refers to 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 in this application.

[0105] The term "masterbatch", in this context, refers to a composition which comprises an additive at a high concentration in a vehicle material. The additive is dispersed in the vehicle material.

[0106] The term “impact resistance modifier”, in this context, refers to a material which, when incorporated into a polymer material, increases the impact resistance and strength of that polymer material by means of phase microdomains of a rubbery material or a rubber polymer.

[0107]

[072] The term “rubber”, in the present context, refers to the state Thermodynamics of the polymer above its glass transition.

[0108] The term “polymer composite”, in this context, refers to a multicomponent material comprising several different phase domains in which at least one type of phase domain is a continuous phase and in which at least one component is a polymer.

[0109] The term "copolymer" as used refers to the fact that the polymer is made up of at least two different monomers.

[0110] A “multi-stage polymer,” in this context, means a polymer formed sequentially by a multi-stage polymerization process. Preferably, a multi-stage emulsion polymerization process is used in which the first polymer is a first-stage polymer and the second polymer is a second-stage polymer; that is, the second polymer is formed by emulsion polymerization in the presence of the first polymer in emulsion, with at least two stages that differ in composition.

[0111] The term “(meth)acrylic”, in the present context, refers to all kinds of acrylic and methacrylic monomers.

[0112] The term "(meth)acrylic polymer" as used refers to the fact that the (meth)acrylic polymer essentially comprises polymers comprising (meth)acrylic monomers which make up 50% or more by weight of the (meth)acrylic polymer.

[0113] The term “dry”, in the present context, means that the proportion of residual water is less than 1.5% by weight and preferably less than 1.2% by weight.

[0114] By specifying that a range goes from x to y in the present invention, this means that the upper limit and the lower limit of this range are included, which is equivalent to at least x and up to y.

[0115] By specifying that a range is between x and y in the present invention, this means that the upper limit and the lower limit of this range are excluded, which is equivalent to more than x and less than y.

[0116] The term "phr" denotes parts by weight per hundred parts by weight.

[0117] By "easily dispersed in liquid resins," it is meant that a homogeneous dispersion is obtained. The distribution of the polymer composition (PCI) is not homogeneous if separation occurs after initial homogenization.

[0118] As regards the composition (Cl) according to the invention, it comprises a) 100 parts of a composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) and b) between 10 phr and 100 phr by weight of a polymeric composition (PCI).

[0119] Preferably, composition (C2) is liquid. The term "liquid" means that composition (C2) is liquid at least within a temperature range of 50 °C to 80 °C, preferably from 40 °C to 80 °C, and even more preferably from 20 °C to 80 °C. This limitation means that composition (C2) could still be liquid outside these ranges.

[0120] Preferably, the composition (Cl) is liquid. The term "liquid" means that the composition (Cl) is liquid at least within a temperature range of 50 °C to 80 °C, preferably from 40 °C to 80 °C, and even more preferably from 20 °C to 80 °C. This limitation means that the composition (Cl) could still be liquid outside these ranges, but is in the liquid phase within these ranges.

[0121] In a first preferred embodiment, the composition (C2) comprises the monomer (Ml).

[0122] In a second preferred embodiment, the composition (C2) comprises the prepolymer (PRE1). In a variation of the second preferred embodiment, the composition (C2) comprises the prepolymer (PRE1) and furthermore a solvent.

[0123] In a third preferred embodiment, the composition (C2) comprises a mixture of the monomer (Ml) and the prepolymer (PRE1). In a variation of the third preferred embodiment, the composition (C2) comprises a mixture of the monomer (Ml), the prepolymer (PRE1), and more than one solvent.

[0124] In a fourth preferred embodiment, the composition (C2) is a mixture of prepolymers (PREla) and (PRElb).

[0125] In a fifth preferred embodiment, the composition (C2) is a mixture of prepolymers (PREla) and (PRElb) and more than one solvent.

[0126] In a sixth preferred embodiment, the composition (Cl) is a mixture of prepolymers (PREla) and (PRElb), a monomer (Ml) and more than one solvent.

[0127] The component a) composition (C2) alone is a liquid at least over a temperature range of 50 °C to 80 °C and has a dynamic viscosity between 0.5 mPa*s and 1000 Pa*s.

[0128] In a first preferred embodiment, the composition (Cl) comprises between 10 phr and 100 phr of a polymeric composition (PCI) for 100 parts of composition (C2), more preferably between 10 phr and 90 phr, even more preferably between 10 phr and 80 phr and advantageously between 10 phr and 75 phr.

[0129] In a second preferred embodiment, the composition (Cl) comprises more than 25 parts of a polymeric composition (PCI) per 100 parts of composition (C2), preferably more than 30 parts, even more preferably more than 35 parts and advantageously between 35 parts and 100 parts of a polymeric composition (PCI) per 100 parts of polymeric composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both.

[0130] Preferably, the composition (Cl) is liquid at least over a temperature range of 50 °C to 80 °C and has a dynamic viscosity between 1 mPa*s and 20,000 Pa*s.

[0131] The monomer (Ml) of the polymeric composition (PCI) is a liquid monomer at least in the temperature range between 10 °C and 60 °C. The monomer (Ml) comprises a carbon C=C double bond.

[0132] The monomer (Ml) is preferably chosen from (meth)acrylic monomers and / or vinyl monomers and corresponding mixtures. More preferably the monomer (Ml) of the polymeric composition (PCI) is chosen from a (meth)acrylic monomer.

[0133] In a first preferred embodiment the monomer (Ml) comprises at least 50% by weight of methyl methacrylate.

[0134] In a second preferred embodiment, the monomer (Ml) is a mixture of monomers comprising at least 50% by weight of methyl methacrylate and the remainder up to 100% by weight selected from C2 to C12 alkyl (meth)acrylates, an alkyl acrylate, styrenic monomers and corresponding mixtures.

[0135] In a third preferred embodiment the monomer (Ml) comprises at least 80% by weight of methyl methacrylate.

[0136] In a fourth preferred embodiment, the monomer (Ml) is a mixture of monomers comprising at least 80% by weight of methyl methacrylate and the remainder up to 100% by weight selected from C2 to C12 alkyl (meth)acrylates, an alkyl acrylate, styrenic monomers and corresponding mixtures.

[0137] In a fifth preferred embodiment the monomer (Ml) comprises at least 90% by weight of methyl methacrylate.

[0138] In a sixth preferred embodiment, the monomer (Ml) is a mixture of monomers comprising at least 90% by weight of methyl methacrylate and the remainder up to 100% by weight selected from C2 to C12 alkyl (meth)acrylates, an alkyl acrylate, styrenic monomers and corresponding mixtures.

[0139] In a seventh preferred embodiment the monomer (Ml) is only methyl methacrylate.

[0140] The prepolymer (PRE1) of the polymeric composition (C2) is preferably selected from an epoxy resin. Preferably, the epoxy resin comprises at least two oxirane-type functional groups.

[0141] Preferably the prepolymer (PRE1) of the polymer composition (PCI) comprises or is selected from a liquid epoxy resin or a liquid mixture of epoxy resins.

[0142] The liquid epoxy resin may be based on bisphenol A or F or on phenol novolaks or corresponding mixtures in any proportions. They may be mixed with a reactive diluent, such as a phenyl or cresyl glycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether or diglycidyl hexaphthalate, preferably in an amount of 1 to 50% by weight, more preferably 2 to 40% by weight, based on the total amount of epoxy resins as a prepolymer (PRE1) of the composition (C2).

[0143] In the case of the embodiment where the composition (C2) comprises a mixture of prepolymers (PREla) and (PRElb), 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 include one, two, or more oxirane-type functional groups. One of the prepolymers is preferably a glycidyl ether, and more preferably a diglycidyl ether comprising a linear aliphatic or cyclic aliphatic group.

[0144] The at least one prepolymer of the mixture comprising at least two oxirane-type functional groups is referred to hereafter as (PREla). The other prepolymer, which may comprise one, as well as two or more, oxirane-type functional groups, is referred to hereafter as (PRElb).

[0145] (PREla) is in excess in the mixture of polymers (PREla) and (PRElb). The ratio between (PREla) / (PRElb) is between 99 / 1 and 60 / 40, preferably between 99 / 1 and 70 / 30.

[0146] Preferably the viscosity of (PRElb) is lower than the viscosity of (PREla). The dynamic viscosity of (PRElb) is preferably less than 1000 mPa*s at 25 °C, more preferably between 1 and 800 mPa*s at 25 °C, even more preferably between 1 and 500 mPa*s at 25 °C and advantageously between 1 and 250 mPa*s at 25 °C.

[0147] In a first preferred embodiment (PREla) is a diglycidyl ether comprising aromatic groups and (PRElb) is a glycidyl ether or glycidyl ester comprising a linear aliphatic or cyclic aliphatic group.

[0148] In a second preferred embodiment (PREla) is a diglycidyl ether comprising aromatic groups and (PRElb) is a glycidyl ether comprising a linear aliphatic or cyclic aliphatic group.

[0149] In a third preferred embodiment (PREla) is a diglycidyl ether comprising aromatic groups and (PRElb) is a diglycidyl ether comprising a linear aliphatic or cyclic aliphatic group.

[0150] The solvent of the variation of the second and third preferred embodiments, and of the fourth and fifth preferred embodiments of the composition (Cl) is chosen from a ketone and an ester.

[0151] The multi-stage polymer (MPI) of the polymeric composition (PCI) has at least two stages respectively (SB1) and (SB2); and these two stages, comprising respectively polymer (B1) and polymer (B2) are different with respect to their polymer composition.

[0152] The multi-stage polymer (MSP) is preferably in the form of PAR polymer particles considered more or less as spherical particles. These PAR polymer particles are also called core-shell particles. The first stage forms the core, and the second or subsequent stages form the respective shells. Such a multi-stage polymer (MSP), which is also called a core-shell particle, is preferred.

[0153] The PAR particles, included in the polymer composition (PCI), are the primary particles. The PAR particles have a weighted average particle size (diameter) of between 15 nm and 900 nm. Preferably, the weighted average particle size of the polymer particle is between 20 nm and 800 nm, more preferably between 25 nm and 600 nm, even more preferably between 30 nm and 550 nm, again, even more preferably between 35 nm and 500 nm, advantageously between 40 nm and 400 nm, even more advantageously between 75 nm and 350 nm, and advantageously between 80 nm and 300 nm.

[0154] The polymer composition (PCI) comprises a multi-stage polymer (MPI) and a polymer (B3). Said multi-stage polymer (MPI) comprises at least b1) a stage (SB1) comprising a polymer (B1) having a glass transition temperature below 10 °C, and at least b2) a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60 °C. The polymer (B3) having a glass transition temperature of at least 30 °C represents at most 40% by weight of the polymer composition (PCI) based on b1), b2), and b3) only. Preferably, the polymer (B3) represents at most 35% by weight of the composition based on b1), b2), and b3) only; more preferably at most 30% by weight, even more preferably less than 30% by weight, advantageously less than 25% by weight and more advantageously less than 20% by weight.

[0155] Preferably, the polymer (B3) represents more than 4% by weight of the composition based on bl), b2), and b3) only. More preferably, the polymer (B3) represents more than 5% by weight of the composition based on bl), b2), and b3) only; even more preferably, more than 6% by weight; even more preferably, more than 7% by weight; advantageously, more than 8% by weight; and more advantageously, more than 10% by weight.

[0156] Preferably, the polymer (B3) represents between 4% by weight and 40% by weight of the composition based on bl), b2), and b3) only. More preferably, the polymer (B3) represents between 5% by weight and 35% by weight of the composition based on bl), b2), and b3) only; even more preferably between 6% by weight and 30% by weight; even more preferably between 7% by weight and less than 30% by weight; advantageously between 7% by weight and less than 25% by weight; and more advantageously between 10% by weight and less than 20% by weight.

[0157] In a first preferred embodiment of the polymer composition (PCI), the stage (SB1) is the first stage of at least two stages and the stage (SB2) comprising the polymer (B2) is grafted onto the stage (SB1) comprising the polymer (Bl) or another intermediate layer.

[0158] In a second preferred embodiment of the polymeric composition (PCI), there could be another stage before stage (SB1), so that stage (SB1) would also be a bark.

[0159] In a third preferred embodiment of the polymer composition (PCI), the polymer (B3) having a glass transition temperature of at least 30 °C is also part of the multi-stage polymer (MPI). At least one stage (SB3) is also present. Preferably, stage (SB3) occurs after stage (SB2). More preferably, stage (SB3) is the last stage and polymer (B3) is the outer shell of the multi-stage polymer (MPI).

[0160] In a first embodiment, the polymer (B1) having a glass transition temperature below 10°C comprises at least 50% by weight of polymeric units from an alkyl acrylate or alkyl acrylates, and the stage (SB1) is the innermost layer of the polymer particle having the multilayer structure. In other words, the stage (SB1) comprising the polymer (B1) is the core of the polymer particle.

[0161] With regard to the polymer (Bl) of the first preferred embodiment, it is a (meth)acrylic polymer comprising at least 50% by weight of polymeric units derived from acrylic monomers. Preferably, 60% by weight and more preferably 70% by weight of the polymer (Bl) are acrylic monomeric units.

[0162] The acrylic monomer in the polymer (Bl) comprises monomers selected from C18 to C18 alkyl acrylates or corresponding mixtures thereof. More preferably, the acrylic monomer in the polymer (Bl) comprises C2 to C12 alkylacrylic monomers or corresponding mixtures thereof. Even more preferably, the acrylic monomer in the polymer (Bl) comprises C2 to C8 alkylacrylic monomers or corresponding mixtures thereof.

[0163] The polymer (Bl) may comprise a comonomer or comonomers which are copolymerizable with the acrylic monomer, as long as the polymer (Bl) has a glass transition temperature below 10 °C.

[0164] The comonomer or comonomers in the polymer (Bl) are preferably chosen from (meth)acrylic monomers and / or vinyl monomers.

[0165] Most preferably, the acrylic or methacrylic comonomers of the polymer (Bl) are chosen from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and corresponding mixtures, as long as the polymer (Bl) has a glass transition temperature below 10 °C.

[0166] In a specific embodiment, the polymer (Bl) is a butyl acrylate homopolymer.

[0167] More preferably, the glass transition temperature Tg of the polymer (Bl) comprising at least 70% by weight of polymer motifs from the C2 to C8 alkyl acrylate is between -100 °C and 10 °C, even more preferably between -80 °C and 0 °C, and advantageously between -80 °C and -20 °C and more advantageously between -70 °C and -20 °C.

[0168] In a second preferred embodiment, the polymer (Bl) having a glass transition temperature below 10 °C comprises at least 50% by weight of polymeric units derived from isoprene or butadiene, and the stage (SB1) is the innermost layer of the polymer particle having the multilayer structure. In other words, the stage (SB1) comprising the polymer (Bl) is the core of the polymer particle.

[0169] By way of example, for the polymer (B 1) of the core of the second embodiment, isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers, isoprene copolymers comprising a maximum of 98% by weight of a vinyl monomer, and butadiene copolymers comprising a maximum of 98% by weight of a vinyl monomer may be mentioned. The vinyl monomer may be styrene, an alkylstyrene, acrylonitrile, an alkyl (meth)acrylate, butadiene, or isoprene. In a preferred embodiment, the core is a butadiene homopolymer.

[0170] More preferably, the glass transition temperature Tv of the polymer (Bl) comprising at least 50% by weight of polymeric motifs from isoprene or butadiene is between -100 °C and 10 °C, even more preferably between -90 °C and 0 °C, advantageously between -80 °C and 0 °C and most advantageously between -70 °C and -20 °C.

[0171] In a third preferred embodiment, the polymer (Bl) is a silicone rubber-based polymer. The silicone rubber is, for example, a polydimethylsiloxane. More preferably, the glass transition temperature Tv of the polymer (Bl) of the second embodiment is between -150 °C and 0 °C, even more preferably between -145 °C and -5 °C, advantageously between -140 °C and -15 °C, and more advantageously between -135 °C and -25 °C.

[0172] The polymer (Bl) having a glass transition temperature below 10 °C comprises monomeric units that have been polymerized. The polymer (Bl) in general and the respective polymers (Bl) of the first, second, and third preferred embodiment are prepared from the respective monomer or mixture of monomers (Blm) producing the monomeric units composing the polymer (Bl).

[0173] With regard to polymer (B2), homopolymers and copolymers comprising monomers with double bonds and / or vinyl monomers may be mentioned. Preferably, polymer (B2) is a (meth)acrylic polymer.

[0174] Preferably the polymer (B2) comprises at least 70% by weight of monomers selected from C12 Cl alkyl (meth)acrylates. Even more preferably, the polymer (B2) comprises at least 80% by weight of C4 Cl alkyl methacrylate monomers and / or C8 Cl alkyl acrylate monomers.

[0175] Most preferably the acrylic or methacrylic monomers of the polymer (B2) are chosen from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and corresponding mixtures, as long as the polymer (B2) has a glass transition temperature of at least 60 °C.

[0176] Advantageously, the polymer (B2) comprises at least 70% by weight of monomeric motifs derived from methyl methacrylate.

[0177] Preferably, the glass transition temperature Tv of the polymer (B2) is between 60 °C and 150 °C. The glass transition temperature of the polymer (Bl) is more preferably between 80 °C and 150 °C, advantageously between 90 °C and 150 °C and more advantageously between 100 °C and 150 °C.

[0178] Preferably, the polymer (B2) is grafted onto the polymer prepared in the previous stage.

[0179] In some embodiments the polymer (B2) is crosslinked.

[0180] In one embodiment, the polymer (B2) comprises a functional comonomer. The functional copolymer is selected from acrylic acid or methacrylic acid, amides derived from these acids, such as, for example, dimethylacrylamide, 2-methoxyethyl acrylate or 2-methoxyethyl methacrylate, 2-aminoethyl acrylate or 2-aminoethyl methacrylate, which may be quaternized, polyethylene glycol (meth)acrylates, water-soluble vinyl monomers such as N-vinylpyrrolidone, or corresponding mixtures. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylates has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0181] The polymer (B2) having a glass transition temperature of at least 60 °C comprises monomeric units that have been polymerized. The polymer (B2) in general and in the respective embodiments is prepared from the respective monomers or mixtures of monomers (B2m) producing the monomeric units included in the polymer (B2).

[0182] With regard to the polymer (B3), it has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0183] The polymer (B3) has a mass average molecular weight Mw greater than 10,000 g / mol, preferably greater than 10,500 g / mol, more preferably greater than 11,000 g / mol, even more preferably greater than 12,000 g / mol, advantageously greater than 13,000 g / mol, more advantageously greater than 14,000 g / mol and even more advantageously greater than 15,000 g / mol.

[0184] The polymer (B3) has a mass 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 and even more advantageously less than 250,000 g / mol and most advantageously less than 200,000 g / mol.

[0185] Preferably, the average molecular weight by mass Mw of the polymer (B3) is between 10,500 g / mol and 450,000 g / mol, more preferably between 11,000 g / mol and 400,000 g / mol and even more preferably between 12,000 g / mol and 350,000 g / mol, advantageously between 13,000 g / mol and 300,000 g / mol, more advantageously between 14,000 g / mol and 250,000 g / mol and most advantageously between 15,000 g / mol and 200,000 g / mol.

[0186] In a first advantageous embodiment, the average molecular weight by mass Mw of the polymer (B3) is between 10,500 g / mol and 200,000 g / mol, more preferably between 11,000 g / mol and 190,000 g / mol and even more preferably between 12,000 g / mol and 180,000 g / mol, advantageously between 13,000 g / mol and 150,000 g / mol, more advantageously between 14,000 g / mol and 135,000 g / mol and most advantageously between 15,000 g / mol and 120,000 g / mol.

[0187] In a second advantageous embodiment, the average molecular weight by mass Mw of the polymer(B3) is between 15,000 g / mol and 450,000 g / mol, more preferably between 16,000 g / mol and 400,000 g / mol and even more preferably between 17,000 g / mol and 350,000 g / mol, advantageously between 18,000 g / mol and 300,000 g / mol, more advantageously between 19,000 g / mol and 250,000 g / mol and most advantageously between 20,000 g / mol and 200,000 g / mol.

[0188] Preferably, the polymer (B3) is a copolymer comprising (meth)acrylic monomers. More preferably, the polymer (B3) is a (meth)acrylic polymer. Even more preferably, the polymer (B3) comprises at least 70% by weight of monomers selected from C12 alkyl (meth)acrylates. Advantageously, the polymer (B3) comprises at least 80% by weight of C4 alkyl methacrylate monomers and / or C8 alkyl acrylate monomers.

[0189] Preferably, the glass transition temperature Tv of the polymer (B3) is between 30 °C and 150 °C. The glass transition temperature of the polymer (B3) is more preferably between 40 °C and 150 °C, advantageously between 45 °C and 150 °C and more advantageously between 50 °C and 150 °C.

[0190] Preferably, the polymer (B3) is not crosslinked.

[0191] Preferably, the polymer (Cl) is not grafted onto either of the polymers (Bl) and (B2), particularly if it is part of the multi-layer polymer (MLP). "Non-grafted" means that at least 50% by weight of the polymer (Cl) in the multi-layer polymer (MLP) can be solubilized in a solvent of the polymer (B3).

[0192] In one embodiment, the polymer (B3) also comprises a functional comonomer.

[0193] The functional comonomer has the formula (1)

[0194] [Chemical formula 1]

[0195] Ri being chosen from H and CH3 and R2 being H or an aliphatic or aromatic radical having at least one atom that is not C or H.

[0196] Preferably, the functional monomer is selected from glycidyl (meth)acrylate, acrylic acid and methacrylic acid, amides derived from these acids, such as, for example, dimethylacrylamide, 2-methoxyethyl acrylate or 2-methoxyethyl methacrylate, 2-aminoethyl acrylates or 2-aminoethyl methacrylates which are optionally quantified, and polyethylene glycol (meth)acrylates. Preferably, the polyethylene glycol group of polyethylene glycol (meth)acrylates has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0197] In a first preferred embodiment, the polymer (B3) comprises from 80% by weight to 100% by weight of methyl methacrylate, preferably from 80% by weight to 99.9% by weight of methyl methacrylate and from 0.1% by weight to 20% by weight of a C8 Cl alkyl acrylate monomer. Advantageously, the C8 Cl alkyl acrylate monomer is selected from methyl acrylate, ethyl acrylate and butyl acrylate.

[0198] In a second preferred embodiment, the polymer (B3) comprises between 0% and 50% by weight of a functional monomer. Preferably, the (meth)acrylic polymer (B3) comprises between 0% and 30% by weight of the functional monomer, more preferably between 1% and 30% by weight, even more preferably between 2% and 30% by weight, advantageously between 3% and weight and 30% by weight, more advantageously between 5% by weight and 30% by weight and most advantageously between 5% by weight and 30% by weight.

[0199] Preferably, the functional monomer of the second preferred embodiment is a (meth)acrylic monomer. The functional monomer has formula (2) or (3)

[0200] [Chemical formula 2]

[0201] [Chemical formula 3]

[0202] wherein in both formulas (2) and (3), RI is chosen from H and CH3; and in formula (2), Y is O, R5 is H or an aliphatic or aromatic radical having at least one atom that is neither C nor H; and in formula (3), Y is N and R4 and / or R3 is H or an aliphatic or aromatic radical.

[0203] 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, for example, dimethylacrylamide, 2-methoxyethyl acrylate or 2-methoxyethyl methacrylate, 2-aminoethyl acrylates or 2-aminoethyl methacrylates which are optionally quaternized, acrylate or methacrylate monomers comprising a phosphonate or phosphate group, alkylimidazolidinone (meth)acrylates, and polyethylene glycol (meth)acrylates. Preferably, the polyethylene glycol group of polyethylene glycol (meth)acrylates has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0204] The polymer (B3) having a glass transition temperature of at least 30 °C comprises monomeric units that have been polymerized. The polymer (B3) in general and in the respective embodiments is prepared from the respective monomers or mixtures of monomers (B3m) producing the monomeric units included in the polymer (B3).

[0205] The multi-stage polymer (MPI) is obtained by a multi-stage process comprising at least two stages. At least component b1) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI).

[0206] Preferably, the polymer (Bl) having a glass transition temperature below 10 °C formed during stage (SB1) is formed before stage (SB2) or is the first stage of the multi-stage process.

[0207] Preferably, the polymer (B2) having a glass transition temperature of at least 60 °C formed during stage (SB2) is formed after stage (SB1) of the multi-stage process.

[0208] In a first preferred embodiment, the polymer (B2) having a glass transition temperature of at least 60 °C is an intermediate layer of the polymer particle having the multilayer structure.

[0209] In this first preferred embodiment, the polymer (B3) having a glass transition temperature greater than 30 °C prepared during stage (SB3), is prepared after stage (SB2) of the multi-stage process.

[0210] More preferably, the polymer (B3) having a glass transition temperature greater than 30 °C prepared during stage (SB3) is the outer layer of the multi-stage polymer (MPI) or of the primary polymer particle having the multilayer structure.

[0211] There could be additional intermediate floors, between floor (SB 1) and floor (SB2) and / or between floor (SB2) and floor (SB3).

[0212] Polymer (B3) and polymer (B2) are not the same polymer, even though their composition may be very similar and some of their characteristics overlap. The essential difference is that polymer (B2) is always part of the multi-stage polymer (MSP).

[0213] This is explained in more detail in the process for preparing the polymer composition (PCI) polymer (B3) and the multi-stage polymer (MPI).

[0214] The weight ratio r of the polymer (B3) of the outer layer included in the stage (SB3) relative to the complete polymer particle having the multilayer structure is at least 5% by weight, more preferably at least 7% by weight and even more preferably at least 10% by weight.

[0215] According to the invention, the ratio r of the outer stage (SB3) comprising the polymer (B3) relative to the complete polymer particle having the multilayer structure is at most 40% by weight.

[0216] Preferably, the ratio r of the polymer (B3) relative to the primary polymer particle having the multilayer structure is between 5% by weight and 30% by weight and preferably between 10% by weight and 20% by weight.

[0217] 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 particle having the multilayer structure, in other words, the multi-stage polymer (MPI).

[0218] Preferably, at least a portion of the polymer (B2) from the layer prepared during stage (SB2) is grafted onto the polymer prepared in the preceding 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 solvent extraction of polymer (B1) and gravimetric measurement before and after extraction to determine the ungrafted amount.

[0219] The glass transition temperature Tv of the respective polymers can be estimated, for example, by dynamic processes such as thermomechanical analysis.

[0220] To obtain a sample of the respective polymers (B1), (B2), and (B3), these can be prepared individually under the same conditions, but not by a multi-stage process, to more easily estimate and measure the glass transition temperature Tv of the respective polymers in the respective stages. Polymer (B3) can be extracted to estimate and measure the glass transition temperature Tv.

[0221] With regard to a first preferred process for manufacturing the polymer composition (PCI), it comprises the steps of

[0222] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bim) to obtain a layer in the stage (SB1) comprising the polymer (Bl) having a glass transition temperature below 10 °C,

[0223] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (B2m) to obtain a layer in the stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60 °C,

[0224] c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (B3m) to obtain a layer in the stage (SB3) comprising a polymer (B3) having a glass transition temperature of at least 30 °C,

[0225] d) agglomeration of the composition obtained in steps a) to c).

[0226] Preferably step a) is carried out before step b).

[0227] More preferably, step b) is carried out in the presence of the polymer (Al) obtained in step a).

[0228] Advantageously, the first preferred process for manufacturing the polymer composition (PCI) is a multi-stage process comprising the successive steps of:

[0229] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bim) to obtain a layer in the stage (SB1) comprising the polymer (Bl) having a glass transition temperature below 10 °C,

[0230] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (B2m) to obtain a layer in the stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60 °C

[0231] c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (B3m) to obtain a layer in the stage (SB3) comprising a polymer (B3) having a glass transition temperature of at least 30 °C,

[0232] d) agglomeration of the composition obtained in steps a) to c).

[0233] Preferably, steps a), b), c) and d) are carried out in that order. When emulsion polymerization is used, the polymer composition at the end of polymerization is obtained as an aqueous dispersion.

[0234] The respective monomers or monomer mixtures (Bim), (B2m), and (B3m) for layer formation in stages (SB1), (SB2), and (SB3), respectively, comprising polymers (Bl), (B2), and (B3), respectively, are the same as those defined previously. The monomers or monomer mixtures (Bim), (B2m), and (B3m) comprise the respective monomers that are polymerized monomeric motifs in the polymer chain of the respective polymers (Bl), (B2), and (B3). The characteristics of polymers (Bl), (B2), and (B3), respectively, are the same as those defined previously.

[0235] With regard to a second preferred method of manufacturing the polymer composition (PCI) comprising the polymer (B3) and the multi-stage polymer (MPI), this method comprises the steps of

[0236] a) emulsion polymerization of a monomer or a mixture of monomers (Bim) to obtain a layer in stage (SB1) comprising the polymer (Bl) having a glass transition temperature below 10 °C,

[0237] b) emulsion polymerization of a monomer or a mixture of monomers (B2m) to obtain a layer in stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60 °C,

[0238] jointly, steps a) and b) leading to a multi-stage polymer (MSP) and the step

[0239] c) mixing the multi-stage polymer (MSP) with a polymer (B3) having a glass transition temperature of at least 30 °C,

[0240] d) agglomeration of the composition obtained in steps a) to c).

[0241] Preferably, the polymer (B3) being in the form of an aqueous dispersion. The aqueous dispersion comprises the polymer (B3) in the form of polymeric particles.

[0242] With regard to a third preferred method of manufacturing the polymer composition (PCI) comprising the polymer (B3) and the multi-stage polymer (MPI), this method comprises the steps of

[0243] a) supply of a polymer (Cl) having a glass transition temperature of at least 30 °C and a multi-stage polymer (MPI) comprising a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C and a stage (SB2) comprising a polymer (B2) having a glass transition temperature of at least 60 °C,

[0244] b) blending or mixing of the polymer (B3) and the multi-stage polymer (MPI),

[0245] c) agglomeration of the composition obtained in steps b)

[0246] the polymer (B3) and the multi-stage polymer (MPI) in step b) being in the form of an aqueous phase dispersion. The respective aqueous dispersions comprise the polymer (B3) and the multi-stage polymer (MPI) in the form of polymeric particles.

[0247] Preferably, the multi-stage polymer (MPI) and the polymer (B3) are already made available as an aqueous dispersion.

[0248] The agglomeration step of the respective processes for manufacturing the polymeric composition (PCI) can be chosen from coagulation or spray drying.

[0249] In a first preferred embodiment, the agglomeration step is carried out by coagulation in aqueous phase.

[0250] In a second preferred embodiment, the agglomeration step is carried out by spray drying.

[0251] The quantities of the aqueous dispersion of the polymer (B3) and of the aqueous dispersion of the multi-stage polymer (MPI) are chosen such that the weight ratio of the multi-stage polymer on the basis of the solid part only in the mixture obtained is at least 60% by weight, preferably at least 65% by weight, more preferably at least 68% by weight and advantageously at least 70% by weight.

[0252] The quantities of the aqueous dispersion of the polymer (B3) and of the aqueous dispersion of the multi-stage polymer (MPI) are chosen such that the weight ratio of the multi-stage polymer on the basis of the solid part only in the mixture obtained is at most 99% by weight, preferably at most 95% by weight and more preferably at most 90% by weight.

[0253] The amounts of the aqueous dispersion of the polymer (Cl) and of the aqueous dispersion of the multi-stage polymer are chosen such that the weight ratio of the multi-stage polymer on the basis of the solid part only in the mixture obtained is between 60% by weight and 99% by weight, preferably between 65% by weight and 95% by weight and more preferably between 68% by weight and 90% by weight.

[0254] Preferred processes for manufacturing the polymer composition (PCI) comprising polymer (B3) and multi-stage polymer (MPI) produce polymer powder (P0W1). The polymer powder (P0W1) is in the form of grains (large particles). The polymer powder grain or particle comprises agglomerated primary polymer particles prepared by a multi-stage process comprising multi-stage polymer (MPI) and polymer (B3), or agglomerated primary polymer particles comprising multi-stage polymer (MPI) and polymer particles (B3).

[0255] Component a) is a precursor for thermosetting or thermoplastic polymers. This precursor may be a monomer (Ml), a mixture of monomers, a prepolymer (PRE1) such as a polymerizable or curable oligomer, a mixture of a polymerizable or curable oligomer with one or more monomers, or a mixture of polymers with one or more monomers that are liquid at 25 °C. Preferably, the liquid has a dynamic viscosity of less than 1,000 Pa*s, and more preferably between 0.5 mPa*s and 1,000 Pa*s. The dynamic viscosity value is taken at a shear rate of 1 1 / s. The viscosity is measured with a rheometer.

[0256] The present invention also relates to a method for manufacturing the composition (Cl) of the present invention.

[0257] The process for manufacturing a polymeric composite composition (Cl) comprises the steps of:

[0258] a) supply of the monomer (Ml) or the prepolymer (PRE1);

[0259] b) supply of a polymeric composition (PCI) comprising

[0260] bl) a stage (SB1) comprising a polymer (Bl) having a glass transition temperature below 10 °C,

[0261] b2) a stage (SB2) comprising a polymer (B2) having a transition temperature vitreous of at least 60 °C, and

[0262] b3) and a polymer (B3) having a glass transition temperature of at least 30 °C and having a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol of, said polymer (Bl) representing at most 40% by weight of a composition based on bl), b2 and b3) only,

[0263] c) bringing the polymeric composition (PCI) into contact with a resin (RES) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both,

[0264] d) providing a mixing means,

[0265] e) mixing the compounds brought into contact with the mixing means provided.

[0266] The amount of polymer composition (PCI) is chosen so that the composition (Cl) comprises between 10 phr and 100 phr of a polymeric composition (PCI) per 100 parts of composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both.

[0267] In a first preferred embodiment, the polymer composition (PCI) is in the form of polymer powder.

[0268] Preferably, the polymer composition (PCI) is in the form of a polymer powder free from solvents. “No solvents” means that any solvent present represents less than 1% by weight of the composition. Monomers from the synthesis of the respective polymers are not considered solvents. Residual monomers in the composition represent less than 2% by weight of the composition.

[0269] Preferably, the polymer composition (PCI) is in the form of a dry polymer powder. “Dry” means that the polymer composition according to the present invention comprises less than 3% by weight of moisture and preferably less than 1.5% by weight of moisture and, more preferably, less than 1.2% by weight of moisture.

[0270] Humidity can be measured by a thermobalance which heats the polymer composition and measures the weight loss.

[0271] Preferably, the polymeric composition (PCI) is in the form of polymer powder (P0W1), having a volume average particle size D50 of between 1 pm and 700 pm. Preferably, the volume average particle size of the polymer powder is between 10 pm and 600 pm, more preferably between 15 pm and 550 pm, and advantageously between 20 pm and 500 pm.

[0272] The D10 of the volume particle size distribution is at least 7 pm and preferably 10 pm, more preferably 15 pm.

[0273] The D90 of the volume particle size is at most 1000 pm and preferably 950 pm, more preferably at most 900 pm and even more preferably at most 800 pm.

[0274] Said process for manufacturing composition (Cl) includes step d) of supplying a mixing means.

[0275] Preferably the mixing means is a suitable apparatus selected from a three-roller mill, high viscosity mixers, high shear mixers, acoustic mixers or planetary mixers.

[0276] In a first preferred embodiment the mixing means is a high shear mixer.

[0277] In a second preferred embodiment, the mixing means is an acoustic mixer. The term "acoustic mixers" is used to describe a wide-based machine that generates acoustic oscillations.

[0278] In a third preferred embodiment, the mixing means is a planetary mixer. The planetary mixer comprises a mixing blade.

[0279] During mixing step d) the temperature is between 15 °C and 150 °C, preferably between 20 ° and 150 °C, more preferably between 20 °C and 100 °C and even more preferably between 40 ° and 80 °C.

[0280] The duration of the mixing steps depends on the mixing means. In general, the time required for the mixing step is less than 2 hours.

[0281] The manufacturing process for composition (Cl) optionally includes a preheating step of at least one of the supplied components. Preferably, the prepolymer (PRE1) is preheated before being brought into contact with the supplied compounds of a) and b). The preheating temperature is at least 30 °C, preferably at least 40 °C. Advantageously, the preheating temperature is between 40 °C and 150 °C.

[0282] Alternatively, the supplied components of a) and b) are brought into contact in two or more separate steps. This means that only a portion of the supplied compound b) is brought into contact with the supplied components a) in step c1). The two components are mixed in step e1) with the mixing medium. Then the remainder, or again an additional portion, of compound a) is added in a second step c2) and then mixed in step e2). If only a portion is added, then steps c) and e) are repeated until all of the supplied compound b) has been brought into contact. In this variation, steps c) and e) are divided into several substeps c1) to e1) and e1) to e1), where x is the number of portions of compound b) to be added.

[0283] Preferably this variation is used if the quantity of components b) in components a) is greater than 50 phr.

[0284] The composition (Cl) of the invention can be used as a master mixture.

[0285] The masterbatch can be used in various applications such as adhesives, composites, wind turbine blades, 3D printing, electronics (PCB or PCL) or sports.

[0286] Composition (Cl) is mixed with another component or components in order to adjust the amount of polymer composition (PCI).

[0287] The mixed composition is transformed into a polymer, by polymerization or hardening.

[0288] The present invention also relates to a method for preparing a polymeric composition (PC2) from the composition (Cl).

[0289] Said process comprising the following steps: polymerization or hardening of the composition (Cl).

[0290] The process of preparing a polymeric composition (PC2) from the composition (Cl) further includes the step of adding an additional quantity of composition (C2) before the polymerization or hardening step. [Evaluation methods]

[0291] Glass transition temperature

[0292] The glass transitions (Tv) of polymers are measured using a device that performs thermomechanical analysis. A Rheometrics Dynamic Analyzer (RDAII) from Rheometrics Company was used. Thermomechanical analysis precisely measures the viscoelastic changes of a sample as a function of temperature, stress, or applied strain. The device continuously records the strain of the sample, while maintaining a constant stress, during a controlled temperature variation program.

[0293] The results are obtained by graphically representing the modulus of elasticity (G'), the loss modulus, and the loss angle as a function of temperature. Tv is the highest temperature value read from the loss angle curve when the derivative of the loss angle is equal to zero.

[0294] Molecular weight

[0295] The mass average molecular weight (Mw) of the polymers is measured by size exclusion chromatography (SEC). Polystyrene references 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 detector for the refractive index is used.

[0296] Particle size analysis

[0297] The particle size of the primary particles after multi-stage polymerization is measured with a Malvern Zetasizer using dynamic light scattering. The volume-average particle size (diameter) is taken as the result.

[0298] The particle size of the polymer powder after recovery is measured with a Malvern Mastersizer 3000 from MALVERN with laser diffraction.

[0299] For estimating the average powder particle size by weight, the granulometry and the proportion of fine particles, a Malvern Mastersizer 3000 device with 300 mm objectives is used, measuring a range from 0.5 to 880 pm.

[0300] Viscosity

[0301] The viscosity is the dynamic viscosity. In the case of shear fluidization, the value of the dynamic viscosity is taken at a shear rate of 1 1 / s. The viscosity is measured with a rheometer from the Anton Parr company.

[0302] Raw materials used

[0303] As a first prepolymer (PRE1), DGEBA (bisphenol A diglycidyl ether) is used.

[0304] Alternatively, mixtures of prepolymers are also given by way of example. In this case, it would be the embodiment comprising (PREla) and (PRElb); DGEBA as (PREla) and respectively 1,6-hexanediol diglycidyl ether and 1,4-cyclohexanedimethanol diglycidyl ether as (PRElb).

[0305] A multi-stage polymer in the form of CS2 core-shell particles comprising a polymer (B3) was prepared according to document WO2020 / 260638 as the product referred to as core / shell -2.

[0306] A multi-stage polymer in the form of CS1 core-shell particles is used as a comparator product according to document WO2020 / 260638, however, only the first and second stages are produced for a product called core / shell -1 in the experimental part of document WO2020 / 260638.

[0307] Composition prepared with a process with a mixing blade.

[0308] The core-bark particles CS1 and CS2 are mixed at a ratio of 15% by weight in the DGEBA in a reactor equipped with a heating and stirring means. The mixer is a mixing blade.

[0309] Table 1 - dynamic viscosity at 80 °C as a function of mixing time. [Tables 1] Viscosity [Pa*s] Time [min] CS1 CS2 1 3.3 1.90 2 3.3 1.40 3 3.2 1.20 4 3.1 1.15 5 3.0 1.10 8 2.9 1.05 10 2.8 1.05 12 2.7 1.05 15 2.6 1.05 20 2.2 1.05 30 2.1 1.05 45 1.9 1.05

[0310] As can be seen in Table 1, the preparation takes longer with regard to mixing time when the composition is not prepared according to the invention or with the process according to the invention.

[0311] The compositions are also prepared using a process with an acoustic mixer. A LabRAM resonant acoustic mixer (or "RAM mixer") from RESODYN™ Acoustic Mixers, Inc. (Butte, Mont.) or PCCA (Houston, Tex.) is used.

[0312] The core-shell polymers CS1 and CS2, as before, are used as component b) polymer composition (PCI). As component a) composition (C2) a DGEBA epoxy resin is again used.

[0313] The crude mixture of the two components is preheated to 80 °C for 15 min. The RAM mixer is used for 1 min.

[0314] CS1 is poorly dispersed at a concentration of 10 wt%, whereas very good dispersion is obtained with CS2 at the same concentration. With CS2, a composition of up to 21 wt% can be produced. When added in two steps, very good dispersion of CS2 at 38 wt% is obtained.

[0315] The CS2 compositions in a prepolymer (PRE1) are prepared as described previously. This time, mixtures of prepolymers (PRE1a) and (PRE1b), with DGEBA as (PRE1a) and 1,6-hexanediol diglycidyl ether as (PRE1b) and 1,4-cyclohexanedimethanol diglycidyl ether as (PRElb2) are used. The mixing ratio is respectively (PREla) / (PRElb) = 95 / 5 parts by weight. The resulting viscosities are given in Table 2.

[0316] Table 2 - Apparent viscosity at 25 °C [Tables 2] Viscosity [Pa*s] Concentration of C S2 [% by weight] (PRE1) (PREla) / (PRElbl) (PREla) / (PRElb2) 10 27 16 22 15 66 22 35 20 153 41 60 25 282 90 134 30 825 118 218

[0317] As shown in Table 2, the use of blends for the prepolymer (PRE1) makes it possible to reduce lower viscosities for the same quantity of core-shell particles or a greater quantity to a comparable viscosity level.

[0318] A polymeric composition of type (PC2) is prepared from the compositions (Cl) of Table 2 comprising 10 wt% of CS2. The compositions are cured with DDA.

[0319] Table 3: Results of the mechanical properties of a hardened composition [Tables3] (PREla) / (PRElbl) (PREla) / (PRElb2) Pure Epoxy System Klc (MPa.m1 / 2) 1.5 1.3 0.68 Gk (kJ / m2) 2.3 2.5 0.53

[0320] In Table 3, a notable increase in strength is observed for a polymer obtained from a composition according to the invention. Fracture strength increases significantly, as shown by the crack propagation resistance K[c] and the fracture strength Gic.

Claims

Demands

1. Liquid composition (Cl) comprising: a. 100 parts of a composition (C2) comprising a prepolymer (PRE1) which is a mixture of prepolymers (PREla) and (PRElb), (PREla) is in excess in the mixture, b.between 10 phr and 100 phr of a polymeric composition (PCI) comprising bl) 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, said polymer (B3) representing at most 40% by weight of the composition on the basis of bl), b2) and b3) only; characterized in that at least component bl) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI), and characterized in that polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

2. Composition (Cl) according to claim 1, characterized in that composition (C2) is liquid at least over a temperature range of 50 °C to 80 °C.

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

4. Composition (Cl) according to any one of claims 1 to 3, characterized in that composition (C2) is liquid.

5. Composition (Cl) according to any one of claims 1 to 4, characterized in that composition (C2) further comprises a solvent.

6. Composition (Cl) according to any one of claims 1 to 5, characterized in that the composition (Cl) comprises between 10 parts per 100 parts per 100 parts of the polymeric composition (PCI) composition (C2), even more preferably between 10 phr and 80 phr and advantageously between 10 phr and 75 phr.

7. Composition (Cl) according to any one of claims 1 to 5, characterized in that the composition (Cl) comprises between 35 phr and 100 phr of a polymeric composition (PCI) for 100 parts of polymeric composition (C2).

8. Composition (Cl) according to claim 5, characterized in that the composition (C2) further comprises a monomer (Ml), the monomer (Ml) being selected from (meth)acrylic monomers and / or vinyl monomers and corresponding mixtures.

9. Composition (Cl) according to claim 1, characterized in that the prepolymer (PRE1) is selected from an epoxy resin and at least one of the two prepolymers in the mixture is an epoxy resin comprising at least two oxirane-type functional groups.

10. Composition (Cl) according to claim 1, characterized in that the composition (C2) is liquid at least over a temperature range of 20 °C to 80 °C and has a dynamic viscosity between 0.5 mPa*s and 1000 Pa*s.

11. Composition (Cl) according to claim 1, characterized in that the composition (Cl) is liquid at least over a temperature range of 20 °C to 80 °C and has a dynamic viscosity between 1 mPa*s and 20,000 Pa*s.

12. Composition (Cl) according to any one of claims 1 to 5, characterized in that the multi-stage polymer (MPI) is in the form of a core-shell particle having a weight average particle size between 15 nm and 900 nm.

13. Composition (Cl) according to any one of claims 1 to 6, characterized in that the polymer (B3) is a (meth)acrylic polymer.

14. Composition (C1) according to any one of claims 1 to 6, characterized in that composition (C2) comprises an epoxy resin which may be based on bisphenol A or F or on phenol novolaks or corresponding mixtures.

15. Composition according to claim 1, characterized in that in the mixture of prepolymers (PREla) and (PRElb), one of the prepolymers is a glycidyl ether, and more preferably a diglycidyl ether comprising a linear aliphatic or cyclic aliphatic group.

16. A process for manufacturing the liquid (Cl) composition according to any one of claims 1 to 15, comprising the steps of: a) supplying a composition (C2) comprising a prepolymer (PRE1) which is a mixture of prepolymers (PREla) and (PRElb), (PREla) being in excess in the mixture; b) supplying a polymeric composition (PCI) 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, said polymer (B3) representing at most 40% by weight of the composition on the basis of b1), b2), and b3) only; c) bringing the supplied components of a) and b) into contact;d) supplying a mixing medium selected from high viscosity mixers, high shear mixers, acoustic mixers and planetary mixers; e) mixing the components of a) and b) with the supplied mixing medium; characterized in that at least component b1) and component b2) of the composition (PCI) are part of a multi-stage polymer (MPI), 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; and characterized in that the amount of the polymeric composition (PCI) is selected such that between 10 parts per 100 parts of a polymeric composition (PCI) are in the composition (Cl) for 100 parts of composition (C2) comprising a monomer (Ml) or a prepolymer (PRE1) or a mixture of both.

17. A process according to claim 16, characterized in that the temperature at the mixing stage is between 15° and 150°C, preferably between 20° and 150°C, more preferably between 20° and 100°C and even more preferably between 40° and 80°C.

18. A method according to claim 16 or 17, characterized in that the mixing means is selected from high shear mixers, acoustic mixers and planetary mixers.

19. A method according to any one of claims 16 to 18, characterized in that the step of bringing the supplied compounds of a) and b) into contact is carried out in two separate steps.

20. A method according to any one of claims 16 to 18, characterized in that the time required for the mixing step is less than 2 hours.

21. A method according to any one of claims 16 to 18, characterized in that the polymeric composition (PCI) is supplied in the form of a polymer powder having a volume average particle size D50 of between 1 pm and 700 pm.

22. A method according to any one of claims 16 to 18, characterized in that the method further comprises a preheating step.

23. Use of the composition (Cl) according to any one of claims 1 to 15 or obtained by the process according to any one of claims 16 to 22 as a master mixture.

24. Use of the composition (Cl) according to any one of claims 1 to 15 or obtained by the process according to any one of claims 16 to 22 in applications such as adhesives, composites, wind turbine blades, 3D printing, electronics (PCB or PCL) or sport.

25. A method for reducing the dispersion time of a polymeric composition (PCI) comprising a multi-stage polymer (MPI) 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 in 100 parts of a composition (C2) comprising a prepolymer (PRE1) which is a mixture of prepolymers (PRE1a) and (PRE1b), (PRE1a) being in excess in the mixture; said method comprising the step of i. bringing the components into contact ii. providing a mixing means iii. mixing the components with the supplied mixing means; characterized in that the composition (PCI) further comprises b3) a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition on the basis of bl), b2) and b3) only; and characterized in that the polymer (B3) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

26. A process for reducing the preparation time of a masterbatch comprising between 10 parts per hour and 100 parts per hour of polymeric composition (PCI) comprising a multi-stage polymer (MPI) 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 in 100 parts of a composition (C2) comprising a prepolymer (PRE1) which is a mixture of prepolymers (PRE1a) and (PRE1b), (PRE1a) is in excess in the mixture; said process comprising the step of i) bringing the components into contact ii) providing a mixing means iii) mixing the components with the supplied mixing means;characterized in that the composition (PCI) further comprises b3) a polymer (B3) having a glass transition temperature of at least 30 °C, said polymer (B3) representing at most 40% by weight of the composition on the basis of bl), b2) and b3) only; 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 process for preparing a polymeric composition (PC2) from the composition (Cl) according to any one of claims 1 to 15, characterized in that the process comprises the following steps: - polymerization or hardening of the composition (Cl).

28. A process according to claim 27, characterized in that the process further comprises the step of adding an additional quantity of composition (C2) before the polymerization or hardening step.