MULTI-STAGE POLYMER, PREPARATION METHOD THEREOF AND ADHESIVE COMPOSITION COMPRISING THE SAME

Abstract

MULTI-STAGE POLYMER, PREPARATION METHOD THEREOF AND ADHESIVE COMPOSITION COMPRISING THE SAME The present invention relates to a multi-stage polymer, its composition and its preparation method. In particular, the present invention relates to a multi-stage polymer composition comprising functional groups, its preparation method, its use as an impact resistance modifier and an adhesive composition comprising it. More particularly, the present invention relates to a multi-stage polymer composition comprising functional groups, its preparation method, its use as an impact resistance modifier and a (meth)acrylic adhesive composition comprising it.

Description

Title of the invention: MULTI-STAGE POLYMER, PREPARATION METHOD THEREOF AND ADHESIVE COMPOSITION COMPRISING THE SAME Technical field

[0001] The present invention relates to a multi-stage polymer, its composition and its preparation method.

[0002] In particular, the present invention relates to a multi-stage polymer composition comprising functional groups, a process for its preparation, its use as an impact resistance modifier and an adhesive composition comprising it.

[0003] More particularly, the present invention relates to a multi-stage polymer composition comprising functional groups, its preparation process, its use as an impact resistance modifier and a (meth)acrylic adhesive composition comprising it. [Technical problem]

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

[0005] One class of polymeric additives is processing aids, another is polymeric impact resistance modifiers.

[0006] The polymeric impact modifiers may be in the form of polymeric particles. Typically, these polymeric impact modifiers are in the form of core-shell particles that are prepared by a multi-stage process, at least one stage comprising a rubber-like polymer. These particles are then incorporated into the polymers or polymer compositions, in order to increase their impact resistance and other properties such as toughness for example. The polymers or polymer compositions may be thermosetting or thermoplastic.

[0007] Thermosetting polymers consist of crosslinked three-dimensional structures. Crosslinking is achieved by curing reactive groups in the so-called prepolymer. Curing, for example, can be achieved by heating the polymer chains or the prepolymer in order to crosslink and permanently harden the material.

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

[0009] Structural adhesives are materials with high strength and performance. Their primary function is to hold structures together and be able to withstand high loads.

[0010] Thermosetting acrylic adhesives are rubber-cured systems that cure rapidly at room temperature to produce a crosslinked structural adhesive suitable for bonding metals, engineering plastics, composites, and many other substrates with minimal surface preparation. The two materials to be bonded may be of different natures. They exhibit high tensile shear and peel strength, chemical resistance, and impact resistance. These formulations typically utilize the addition of core-shell, block, and graft polymers, which can swell in size in the adhesive formulation but do not dissolve. These additives further impart improved leveling and flow properties to the adhesive.

[0011] The core-shell polymer must be distributed homogeneously throughout the adhesive to ensure satisfactory impact performance of the adhesive. This homogeneous distribution is not readily achieved with all types of core-shell impact modifiers. In addition, the elongation at break is relatively low for standard acrylic structural adhesives.

[0012] The objective of the present invention is to provide a polymer composition comprising a multi-stage polymer which is rapidly and easily dispersible in liquid and / or reactive resins suitable for (meth)acrylic adhesive compositions.

[0013] It is a further object of the present invention to provide a multi-stage polymer composition which is readily dispersible in liquid and / or reactive resins in the form of a polymer powder suitable for (meth)acrylic adhesive compositions.

[0014] An additional objective of the present invention is to provide an adhesive polymer composition which exhibits a good compromise between good tensile strength and high elongation at break and strength.

[0015] Another object of the present invention is to provide a process for preparing a structural adhesive polymer composition which comprises a multi-stage polymer (MPI) having a core-shell type structure, which is readily dispersible in liquid and / or reactive resins.

[0016] Another object of the present invention is the use of a composition comprising a multi-stage polymer having a core-shell type structure, with a homogeneous distribution of the multi-stage polymer for preparing a structural (meth)acrylic adhesive. [BACKGROUND OF THE INVENTION]Prior Art

[0017] Document WO2016 / 102682 discloses a multi-stage polymer composition and a method for preparing it. The multi-stage polymer comprises a final stage which comprises a (meth)acrylic polymer which has a mass average molecular weight of less than 100,000 g / mol.

[0018] Document FR2934866 discloses core-shell particles having a shell comprising hydrophilic monomers.

[0019] Document WO2019 / 012052 discloses an adhesive composition comprising a multi-stage polymer and a method for preparing the same. The composition further comprises a (meth)acrylic polymer which has a mass average molecular weight between 100,000 g / mol and 1,000,000 g / mol.

[0020] Document WO2019 / 012052 discloses a composition comprising a multi-step polymer and a method for preparing the same. The composition further comprises a (meth)acrylic polymer which has a mass average molecular weight between 100,000 g / mol and 1,000,000 g / mol.

[0021] None of the cited prior art documents discloses a polymeric composition according to the invention or in particular an adhesive composition comprising it. [Brief description of the invention]

[0022] Unexpectedly it has also been discovered that a polymer composition (PCI) comprising

[0023] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0024] b) a polymer (Bl) having a glass transition temperature of at least 10°C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on a), b) and c) only,

[0025] component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0026] c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0027] characterized in that either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRi C(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N,

[0028] is rapidly and easily dispersible in liquid and / or reactive resins suitable for (meth)acrylic adhesive compositions and can be used, for example in adhesive compositions, in particular (meth)acrylic adhesive compositions as an impact resistance modifier.

[0029] Unexpectedly it has been discovered that a composition comprising:

[0030] a) a first part (PI) composition comprising

[0031] al) at least one (meth)acrylic monomer (Ml),

[0032] a2) a polymer composition (PCI) comprising

[0033] a2a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0034] a2b) a polymer (B 1) having a glass transition temperature of at least 10°C, said polymer (B1) representing at least 2% by weight and at most 40% by weight of the composition based on a2a), a2b) and a2c) only,

[0035] component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0036] a2c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a2a), a2b) and a2c) only;

[0037] and

[0038] b) a second part composition (P2) comprising

[0039] bl) a polymerization initiator,

[0040] characterized in that either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRi C(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N, leads to a composition suitable for a (meth)acrylic adhesive having increased elongation at break, shear strength adhesion and strength. Description of the embodiments

[0041] According to a first aspect, the present invention relates to a composition (PCI) comprising:

[0042] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0043] b) a polymer (Bl) having a glass transition temperature of at least 10°C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on a), b) and c) only,

[0044] component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0045] c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0046] characterized in that either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRi C(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.

[0047] According to a second aspect, the present invention relates to a method of manufacturing a composition (PCI), said method comprising the steps of:

[0048] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (SA) comprising the polymer (Al) having a glass transition temperature of less than 10 °C,

[0049] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (SB) comprising a polymer (Bl) having a glass transition temperature of at least 10 °C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on components a), b) and c) only,

[0050] c) either the polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in a step (C) comprising a polymer (Cl) having a glass transition temperature of at least 60°C or the addition of polymer (Cl) having a glass transition temperature of at least 60°C after step b), said polymer (Cl) representing at most 40% by weight of the composition on the basis of a), b) and c) of the first aspect only,

[0051] characterized in that said mixture of monomers (Bm) or mixture of monomers (Cm) comprises, or the mixture of monomers (Bm) and the mixture of monomers (Cm) or the polymer (Cl) comprise between 1% by weight and 40% by weight of a monomer or a copolymerized functional monomer (FC1) of the following general formula CH2=CRiC(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.

[0052] According to a third aspect, the present invention relates to a method of manufacturing a composition (PCI), said method comprising the steps of:

[0053] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (SA) comprising the polymer (Al) having a glass transition temperature of less than 10 °C,

[0054] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (SB) comprising a polymer (Bl) having a glass transition temperature of at least 10 °C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on components a), b) and c) only,

[0055] c) either the polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in a step (C) comprising a polymer (Cl) having a glass transition temperature of at least 60°C or the addition of polymer (Cl) having a glass transition temperature of at least 60°C after step b), said polymer (Cl) representing at most 40% by weight of the composition on the basis of a), b) and c) of the first aspect only,

[0056] d) agglomeration of the composition obtained in steps a) to c);

[0057] characterized in that said mixture of monomers (Bm) or mixture of monomers (Cm) comprises, or the mixture of monomers (Bm) and the mixture of monomers (Cm) or the polymer (Cl) comprise between 1% by weight and 40% by weight of a monomer or a copolymerized functional monomer (FC1) of the following general formula CH2=CRiC(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.

[0058] In a fourth aspect the present invention relates to the use of a polymer composition (PCI) comprising:

[0059] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0060] b) a polymer (Bl) having a glass transition temperature of at least 10°C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on a), b) and c) only,

[0061] component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0062] c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0063] characterized in that either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRi C(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N;

[0064] as an impact resistance modifier, preferably in an adhesive composition.

[0065] In a fifth aspect the present invention relates to the use of a polymer composition (PCI) comprising:

[0066] a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0067] b) a polymer (Bl) having a glass transition temperature of at least 10°C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on a), b) and c) only,

[0068] component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0069] c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0070] characterized in that either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRi C(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N;

[0071] for increasing the elongation at break and the fracture toughness of an adhesive composition or a structural adhesive composition.

[0072] In a sixth aspect, the present invention relates to an adhesive composition (ADC) comprising a polymer composition (PCI), said polymer composition (PCI) comprising:

[0073] a) a polymer (Al) having a glass transition temperature of less than 10

[0074] b) a polymer (Bl) having a glass transition temperature of at least 10°C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on a), b) and c) only,

[0075] component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0076] c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;

[0077] characterized in that either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH.2=CRi C(=O)R2, where Ri is H or CH3 and R2 is a group having at least one atom which is not C or H, preferably the at least one atom which is not C or H is nitrogen.

[0078] According to a seventh aspect, the present invention relates to a composition suitable as a (meth)acrylic adhesive composition (MADC) comprising:

[0079] a) a first part (PI) composition comprising

[0080] al) at least one (meth)acrylic monomer (Ml),

[0081] a2) a polymer composition (PCI) comprising

[0082] a2a) a polymer (Al) having a glass transition temperature of less than 10°C,

[0083] a2b) a polymer (B 1) having a glass transition temperature of at least 10°C, said polymer (B1) representing at least 2% by weight and at most 40% by weight of the composition based on a2a), a2b) and a2c) only,

[0084] component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI),

[0085] a2c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a2a), a2b) and a2c) only;

[0086] and

[0087] b) a second part composition (P2) comprising

[0088] bl) a polymerization initiator,

[0089] characterized in that either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRi C(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.

[0090] In an eighth aspect, the present invention relates to a method of preparing a methacrylic adhesive composition (MADC) comprising the steps of:

[0091] i) providing a composition of the seventh aspect,

[0092] iv) polymerizing or curing the composition.

[0093] The expression "polymer powder" as used denotes a polymer in the form of a powder comprising powder grains of the order of at least 1 μm, said powder grains being obtained by agglomeration of primary polymer particles comprising a polymer or polymers, said primary polymer particles being of the order of a nanometer.

[0094] The term "primary particle" as used refers to a spherical polymer particle comprising a nanometer-sized particle. Preferably, the primary particle has a weight average particle size between 20 nm and 800 nm.

[0095] The term "particle size" as used means the volume average diameter of a particle considered to be spherical.

[0096] The term "thermoplastic polymer" as used means a polymer that is converted to a liquid or becomes more liquid or less viscous when heated and that can take on new shapes by the application of heat and pressure.

[0097] The term "thermosetting polymer" as used means a prepolymer in a flexible, solid, or viscous state that generally irreversibly transforms into an infusible and insoluble polymer network upon curing.

[0098] The term "impact modifier" as used herein refers to a material which, when incorporated into a polymeric material, increases the impact resistance and toughness of that polymeric material by means of phase microdomains of a rubbery material or rubber polymer.

[0099]

[072] The term "rubber", in the present context, means the state thermodynamics of the polymer above its glass transition temperature.

[0100] The term "copolymer", in the present context, means that the polymers consist of at least two different monomers.

[0101] A "multi-stage polymer" as used herein refers to a polymer formed sequentially by a multi-stage polymerization process. Preferred is a multi-stage emulsion polymerization process in which 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, with at least two stages that are different in composition.

[0102] The term "(meth)acrylic" as used refers to all kinds of acrylic and methacrylic monomers.

[0103] The term "(meth)acrylic polymer" as used means that the (meth)acrylic polymer essentially comprises polymers comprising (meth)acrylic monomers which represent 50% by weight or more of the (meth)acrylic polymer.

[0104] The term "dry" as used means that the proportion of residual water is less than 1.5% by weight and preferably less than 1.2% by weight.

[0105] By specifying that a range is from x to y in the present invention, this means that the upper and lower limits of this range are included, which is equivalent to at least x and up to y.

[0106] By specifying that a range is between x and y in the present invention, this means that the upper and lower limits of this range are excluded, which is equivalent to more than x and less than y.

[0107] The term "phr" means parts by weight per hundred parts by weight.

[0108] Concerning the polymer composition (PCI) according to the invention, it can be found according to a first embodiment in the form of a polymer powder, also called polymer powder (P0W1), comprising a) the polymer (Al) having a glass transition temperature of less than 10°C, b) the polymer (Bl) having a glass transition temperature of at least 10°C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on a), b) and c) only, and a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only, at least component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), and

[0109] either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRiC(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.

[0110] According to a second embodiment the polymer composition (PCI) may be in the form of a polymer powder, also called polymer powder POW1, comprising a) the polymer (Al) having a glass transition temperature of less than 10°C, b) the polymer (Bl) having a glass transition temperature of at least 10°C, said polymer (Bl) represents at least 2% by weight and at most 40% by weight of the composition based on a), b) and c) only, and a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only, components a), b) and c) of the composition (PCI) are part of a multi-stage polymer (MPI), and the polymer (Cl) comprises between 1 % by weight and 40% by weight of copolymerized functional monomer (FC1) of general formula CH2=CRiC(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.

[0111] Preferably, component b) represents at most 3% by weight of a composition based on a), b) and c). More preferably, component c) represents at least 4% by weight of the composition based on a), b) and c) and even more preferably at least 5% by weight. More preferably the polymer composition (PCI) comprises between 5% by weight and 35% by weight of polymer (Bl) of the composition based on a), b) and c).

[0112] Preferably, component c) represents at most 40% by weight of a composition based on a), b) and c). More preferably, component c) represents at most 35% by weight of the composition based on a), b) and c) and even more preferably at most 30% by weight.

[0113] In a first embodiment, advantageously, component c) represents less than 29% by weight of a composition based on a) b) and c).

[0114] In a second embodiment, component b) advantageously represents less than 26% by weight of a composition based on a) b) and c).

[0115] In a third embodiment, advantageously, component c) represents less than 23% by weight of a composition based on a) b) and c).

[0116] Preferably component b) represents more than 5% by weight of a composition based on a), b) and c). More preferably component b) represents more than 6% by weight of the composition based on a) and b).

[0117] In a first embodiment, component b) advantageously represents more than 7% by weight of a composition based on a) b) and c).

[0118] In a second embodiment, component b) advantageously represents more than 8% by weight of a composition based on a) b) and c).

[0119] In a third embodiment, advantageously, component c) represents more than 9% by weight of a composition based on a) b) and c).

[0120] The respective upper and lower limits given in the preceding paragraphs for the amount of component b) may be combined in any combinations of an upper limit and a lower limit.

[0121] Preferably component c) represents between 5% by weight and 30% by weight of the composition based on a), b) and c). More preferably component b) represents between 6% by weight and 25% by weight of the composition based on a), b) and c).

[0122] In a first embodiment, advantageously, component b) represents between 6% by weight and 23% by weight of a composition based on a) b) and c).

[0123] In a second embodiment, component c) advantageously represents between 8% by weight and 21% by weight of a composition based on a) b) and c).

[0124] In a third embodiment advantageously component b) represents between 6% by weight and 19% by weight of a composition based on a) b) and c).

[0125] Component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI).

[0126] Component c) represents at most 40% by weight of the composition based on a), b) and c). Preferably, component c) represents at most 35% by weight of the composition based on a), b) and c); more preferably at most 30% by weight, even more preferably less than 30% by weight, advantageously less than 25% by weight and most preferably less than 20% by weight.

[0127] Preferably component c) represents more than 2% by weight of the composition based on a), b) and c). More preferably component c) represents more than 3% by weight of the composition based on a), b) and c); even more preferably more than 4% by weight, even more preferably more than 5% by weight, advantageously more than 6% by weight and most preferably more than 7% by weight.

[0128] The respective upper and lower limits given in the two preceding paragraphs for the amount of component c), may be combined in any combinations of an upper limit and a lower limit.

[0129] Preferably component c) represents between 2% by weight and 40% by weight of the composition based on a), b) and c). More preferably component c) represents between 3% by weight and 35% by weight of the composition based on a), b) and c); even more preferably between 4% by weight and 30% by weight, even more preferably between 5% by weight and 30% by weight, advantageously between 6% by weight and 25% by weight and more preferably between 7% by weight and 20% by weight.

[0130] At least component a) and component b) are obtained by a multi-step process comprising at least two steps respectively (SA) and (SB); and these two polymers (Al) and (Bl) form a multi-step polymer (MPI).

[0131] In one embodiment, the polymer (Cl) is also part of the multi-stage polymer (MPI).

[0132] The multi-stage polymer (MPI) of the polymer composition (PCI) according to the invention has at least two stages respectively (SA) and (SB); and these two stages, respectively comprising the polymer (A1) and the polymer (B1) are different with respect to their polymer composition.

[0133] The multi-stage polymer (MPI) is preferably in the form of polymer particles (PAR). These particles (PAR) are also called core- shell. For example, the first stage (SA) comprising the polymer (Al) forms the core, the second or all subsequent stages form the respective shells. Such a multi-stage polymer (MPI), which is also called a core-shell particle, is preferred. If the multi-stage polymer (MPI) comprises only the polymer (Al) and the polymer (Bl), it is a core-shell particle comprising only a shell.

[0134] In a first preferred embodiment, the multi-stage polymer (MPI) of the composition (PCI) consists of the polymer (Al) forming the core and the polymer (Bl) forming the shell, it is a core-shell particle comprising only a shell.

[0135] In a second preferred embodiment, the multi-stage polymer (MPI) of the composition (PCI) consists of a seed, forming the core together with the polymer (Al), and the polymer (Bl) forming the shell, it is also considered as a core-shell particle comprising only a shell.

[0136] In a third preferred embodiment, the multi-stage polymer (MSP) consists of the polymer (Al) forming the core or an inner stage or a shell and the polymer (Bl) is the shell covering the polymer (Al) or formed subsequently, it is a core-shell particle potentially comprising several shells.

[0137] In a fourth preferred embodiment, the multi-stage polymer (MPI) of the polymer composition (PCl) consists of the polymer (Al) forming the core or an inner stage or a shell and the polymer (Bl) forms a shell covering the polymer (Al) and the polymer (Cl) a shell covering the polymer (Bl), the polymer (Cl) being the outer shell.

[0138] In a fourth preferred embodiment, the multi-stage polymer (MPI) of the polymer composition (PCI) consists of a seed and the polymer (Al), both together forming the core or an inner stage and the polymer (Bl) forms a shell covering the polymer (Al) and the polymer (Cl) a shell covering the polymer (Bl), the polymer (Cl) being the outer shell.

[0139] The above-mentioned particles (PAR) have a weight average particle size between 15 nm and 900 nm. Preferably, the weight 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 preferably between 75 nm and 350 nm, and advantageously between 80 nm and 300 nm.

[0140] According to a first preferred embodiment, the primary polymer particles (PAR) are agglomerated and give the polymer composition (PCI) or a part of the polymer composition (PCI). In this case, the polymer composition (PCI) of the invention is in the form of a polymer powder, as described above.

[0141] With regard to the polymer powder (POW1), it has a volume median particle size D50 between 1 pm and 700 pm. Preferably, the volume median 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.

[0142] The D10 of the volume particle size distribution is at least 10 pm and preferably 15 pm, more preferably 20 pm.

[0143] The D90 of the volume particle size distribution is at most 1000 pm and preferably 950 pm, more preferably at most 925 pm and even more preferably at most 900 pm.

[0144] In one embodiment, the porosity of the polymer composition (PCI) in the form of a polymer powder (P0W1) is expressed as total intruded volume or total cumulative intrusion (cumulative intruded volume) in milliliters (ml) of mercury per mass (g) of said polymer powder (P0W1). This is measured according to ISO 15901-1: Evaluation of pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption - Part 1: Mercury porosimetry. Preferably the polymer powder (P0W1) of the invention has a total intruded volume or total cumulative intrusion of at least 0.6 ml / g, preferably 0.65 ml / g, more preferably 0.07 ml / g, even more preferably 0.75 ml / g. The total cumulative intrusion is considered up to a pore size diameter of 0.005 pm.Preferably the total intruded volume or total cumulative intrusion is considered between a pore size diameter of 100 pm and 0.005 pm or a pressure between 0.01 MPa and 400 MPa.

[0145] The polymer powder (POW1) of the invention has a total intruded volume or a total cumulative intrusion of at most 10 ml / g. Preferably the total intruded volume is at most 8 ml / g, more preferably at most 7 ml / g, even more preferably at most 6 ml / g, advantageously at most 5 ml / g, more preferably at most 4 ml / g and most preferably at most 3.5 ml / g.

[0146] The respective upper and lower limits given in the two preceding paragraphs for the total intruded volume or the total cumulative intrusion of the porous polymer powder (POW 1) of the invention, can be combined in any combinations of an upper limit and a lower limit.

[0147] In a first embodiment, the polymer (Al) having a glass transition temperature of less than 10°C comprises at least 50% by weight of polymer units originating from an alkyl acrylate or alkyl acrylates and step (A) is the innermost layer of the polymer particle having the multilayer structure. In other words, the step (SA) comprising the polymer (Al) is the core of the polymer particle.

[0148] With regard to the polymer (Al) of the first preferred embodiment, this is a (meth)acrylic polymer comprising at least 50% by weight of polymeric units originating from acrylic monomers. Preferably, 60% by weight and more preferably 70% by weight of the polymer (Al) are acrylic monomers.

[0149] The acrylic monomer in the polymer (Al) comprises monomers selected from C1-C18 alkyl acrylates or mixtures thereof. More preferably, the acrylic monomer in the polymer (Al) comprises monomers from C2-C12 alkyl acrylic monomers or mixtures thereof. Even more preferably, the acrylic monomer in the polymer (Al) comprises monomers from C2-C8 alkyl acrylic monomers or mixtures thereof.

[0150] The polymer (Al) may comprise a comonomer or comonomers which are copolymerizable with the acrylic monomer, as long as the polymer (Al) has a glass transition temperature of less than 10°C.

[0151] The comonomer or comonomers in the polymer (Al) are preferably chosen from (meth)acrylic monomers and / or vinyl monomers.

[0152] Most preferably, the acrylic or methacrylic comonomers of the polymer (Al) are selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as the polymer (Al) has a glass transition temperature of less than 10°C.

[0153] In a specific embodiment, the polymer (Al) is a butyl acrylate homopolymer.

[0154] More preferably, the glass transition temperature Tg of the polymer (Al) comprising at least 70% by weight of polymeric units originating from 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.

[0155] In a second preferred embodiment, the polymer (Al) having a glass transition temperature below 10°C comprises at least 50% by weight of polymer units originating from isoprene or butadiene and the step (SA) is the innermost layer of the polymer particle having the multilayer structure. In other words, the step (SA) comprising the polymer (Al) is the core of the polymer particle.

[0156] By way of example, for the polymer (Al) of the core of the second embodiment, there may be mentioned isoprene homopolymers or butadiene homopolymers, isoprene-butadiene copolymers, isoprene copolymers comprising at most 98% by weight of a vinyl monomer and butadiene copolymers comprising at most 98% by weight of a vinyl monomer. The vinyl monomer may be styrene, an alkylstyrene, acrylonitrile, an alkyl (meth)acrylate or butadiene or isoprene. In a preferred embodiment, the core is a butadiene homopolymer.

[0157] More preferably, the glass transition temperature Tg of the polymer (Al) comprising at least 50% by weight of polymeric units originating 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.

[0158] In a third preferred embodiment, the polymer (Al) is a silicone rubber-based polymer. The silicone rubber is, for example, a polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (Al) 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.

[0159] The polymer (Al) having a glass transition temperature of less than 10 °C comprises monomer units, which have been polymerized or copolymerized. The polymer (Al) in general and the respective polymers (Al) of the first, second and third preferred embodiment are prepared from the respective monomer or monomer mixture (Am) giving the monomer units composing the polymer (Al).

[0160] As regards the polymer (Bl), homopolymers and copolymers comprising monomers having double bonds and / or vinyl monomers may be mentioned. Preferably, the polymer (Bl) is a (meth)acrylic polymer.

[0161] Preferably, the polymer (Bl) is a (meth)acrylic polymer, which means that at least 50% by weight of the monomer units of the polymer (Bl) are (meth)acrylic monomers.

[0162] In one embodiment, the polymer (Bl) comprises between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH.2=CRiC(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N. In this case, the polymer (Bl) is a copolymer.

[0163] In a first embodiment, the polymer (B 1) having a glass transition temperature of at least 10 °C comprises at least 50% by weight of polymer units originating from acrylates or methacrylates and step (B) is an intermediate or external layer of the polymer particle having the multilayer structure. In other words, step (SB) comprising the polymer (B1) is never the core of the polymer particle.

[0164] In a second embodiment, the polymer (B 1) having a glass transition temperature of at least 10 °C comprises at least 50% by weight of polymer units originating from acrylates or (meth)acrylates and the step (SB) is an intermediate layer of the polymer particle having the multilayer structure. In other words, the step (SB) comprising the polymer (B1) is not the outer core of the polymer particle.

[0165] With regard to the polymer (B1) of the first and second embodiments mentioned above, this is a (meth)acrylic polymer comprising at least 50% by weight of polymeric units originating from (meth)acrylic monomers, comprising the copolymerized functional monomer (FC1), if any. Preferably, 60% by weight and more preferably 70% by weight of the polymer (B1) are (meth)acrylic monomers.

[0166] In a first preferred embodiment, the polymer (Bl) comprises at least 80% by weight of polymeric units originating from (meth)acrylic monomers.

[0167] In a first preferred embodiment, the polymer (Bl) comprises at least 90% by weight of polymeric units originating from (meth)acrylic monomers.

[0168] In a third preferred embodiment, the polymer (Bl) comprises from 80% by weight to 100% by weight of polymeric units originating from (meth)acrylic monomers.

[0169] The (meth)acrylic monomers in the polymer (Bl) may comprise monomers selected from C1-C18 alkyl (meth)acrylates or mixtures thereof. More preferably, the (meth)acrylic monomers in the polymer (Bl) comprise, in addition to the copolymerized functional monomer (FC1), where appropriate, monomers from C1-C12 alkyl (meth)acrylic monomers or mixtures thereof. Even more preferably, the acrylic monomer in the polymer (Bl) comprises monomers from C1-C8 alkyl (meth)acrylic monomers or mixtures thereof.

[0170] The polymer (Bl) may comprise, as a comonomer, the copolymerized functional monomer (FC1) which is copolymerizable with the (meth)acrylic monomer or monomers, as long as the polymer (Bl) has a glass transition temperature of at least 10°C.

[0171] Most preferably, the acrylic or methacrylic monomers of the polymer (Bl) are selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as the polymer (Bl) has a lower glass transition temperature of at least 10°C.

[0172] If present, the polymer (B1) preferably comprises between 1% by weight and 35% by weight of the copolymerized functional monomer (FC1), more preferably between 2% by weight and 30% by weight, and advantageously between 4% by weight and 27% by weight.

[0173] In one embodiment, the polymer (B1) comprises from 5% by weight to 20% by weight of the copolymerized functional monomer (FC1).

[0174] In another embodiment, the polymer (B1) comprises from 5% by weight to 25% by weight of the copolymerized functional monomer (FC1).

[0175] The polymer (Bl) may comprise a crosslinking agent or a grafted crosslinking agent.

[0176] In a specific embodiment, the polymer (B1) is a copolymer comprising methyl methacrylate and the copolymerized functional monomer (FC1).

[0177] In another specific embodiment, the polymer (B1) is a copolymer of methyl methacrylate, the copolymerized functional monomer (FC1) and another preferred acrylic or methacrylic comonomer.

[0178] In another further specific embodiment, the polymer (B1) is a copolymer of methyl methacrylate, the copolymerized functional monomer (FC1) and a crosslinking agent.

[0179] Most preferably the acrylic or methacrylic monomers of the polymer (Bl) in addition to the copolymerized functional monomer (FC1) are selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof, as long as the polymer (Bl) has a glass transition temperature of at least 10°C.

[0180] Preferably, the polymer (B 1) is crosslinked.

[0181] Advantageously, the polymer (Bl) comprises at least 40% by weight of monomer units originating from methyl methacrylate.

[0182] In a first advantageous embodiment, the polymer (B 1) comprises at least 50% by weight of monomer units originating from methyl methacrylate.

[0183] In a second advantageous embodiment, the polymer (B1) comprises at least 60% by weight of monomer units originating from methyl methacrylate.

[0184] In a third advantageous embodiment, the polymer (B1) comprises from 60% by weight to 99% by weight of monomer units originating from methyl methacrylate.

[0185] In one variant, the polymer (Bl) may be a terpolymer or higher. In this case, the respective monomers are from a monomer mixture (Bm) comprising at least two monomers from the preferred list.

[0186] As regards the polymer (Cl), it has a mass average molecular weight Mw of between 10,000 g / mol and 500,000 g / mol.

[0187] The polymer (Cl) 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.

[0188] The polymer (Cl) 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.

[0189] Preferably, the mass average molecular weight Mw of the polymer (Cl) 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.

[0190] In a first advantageous embodiment, the mass average molecular weight Mw of the (meth)acrylic polymer MPI 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.

[0191] In a second advantageous embodiment, the mass average molecular weight Mw of the (meth)acrylic polymer MPI 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.

[0192] Preferably, the polymer (Cl) is a homopolymer or a copolymer comprising (meth)acrylic monomers. More preferably, the polymer (Cl) is a (meth)acrylic polymer. Even more preferably, the polymer (Cl) comprises at least 60% by weight of monomers selected from C1 to C12 alkyl (meth)acrylates. Advantageously, the polymer (Cl) comprises at least 60% by weight of C1 to C4 alkyl methacrylate monomers and / or C1 to C8 alkyl acrylate monomers.

[0193] Preferably, the glass transition temperature Tv of the polymer (Cl) is between 60°C and 150°C. The glass transition temperature of the polymer (Cl) is more preferably between 65°C and 150°C, advantageously between 70°C and 150°C and more advantageously between 75°C and 150°C.

[0194] Preferably, the polymer (Cl) is not crosslinked.

[0195] Preferably, the polymer (Cl) is not grafted onto any of the polymers (Al) and (Bl), especially if it is part of the multi-stage polymer (MPI). "Ungrafted" means that at least 40% by weight of the polymer (Cl) in the multi-stage polymer (MPI) can be solubilized in a solvent of the polymer (Cl), it can be extracted.

[0196] Preferably, at least a portion of the copolymer (Cl) is extractable. More preferably, at least 5% by weight of the polymer (Cl) is extractable.

[0197] In a first more preferred embodiment, at least 10% by weight of the polymer (Cl) is extractable.

[0198] In a second more preferred embodiment, at least 50% by weight of the polymer (Cl) is extractable.

[0199] In a third more preferred embodiment, at least 80% by weight of the polymer (Cl) is extractable.

[0200] In one embodiment, the polymer (Cl) further comprises a functional comonomer.

[0201] If present, the polymer (Cl) preferably comprises between 1% by weight and 35% by weight of the copolymerized functional monomer (FC1), more preferably between 2% by weight and 30% by weight, and advantageously between 4% by weight and 27% by weight.

[0202] In one embodiment, the polymer (Cl) comprises from 5 wt% to 20 wt% of the copolymerized functional monomer (FC1).

[0203] In another embodiment, the polymer (Cl) comprises from 5% by weight to 25% by weight of the copolymerized functional monomer (FC1).

[0204] The respective preferred and advantageous embodiments of all the different characteristics of the polymers (Al) and (B 1) and (Cl) and their respective monomers, can be combined in any combination.

[0205] In the polymer composition (PCI), either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRiC(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.

[0206] In a first preferred embodiment, the polymer (Bl) of the polymer composition (PCI) comprises a copolymerized functional monomer (FC1).

[0207] In a second preferred embodiment, the polymer (Cl) of the polymer composition (PCI) comprises the copolymerized functional monomer (FC1).

[0208] In a third preferred embodiment, the polymer (B1) and the polymer (Cl) of the polymer composition (PCI) comprise a copolymerized functional monomer (FC1). In this case, in which both polymers, the polymer (B1) and the polymer (Cl) of the polymer composition (PCI) comprise a copolymerized functional monomer (FC1), the range between 1 wt% and 40 wt% of copolymerized functional monomer (FC1) preferably refers to the sum of the two polymers. This also applies to the preferred embodiments.

[0209] Preferably, the range of copolymerized functional monomer (FC1) in the respective polymers for the three preferred embodiments mentioned above, is between 1 wt% and 35 wt% of the copolymerized functional monomer (FC1), more preferably between 2 wt% and 30 wt%, and advantageously between 4 wt% and 27 wt% and more advantageously between 5 wt% and 25 wt%.

[0210] The functional comonomer (FC1) has the formula (1)

[0211] [Chemical formula 1] Ri

[0212] in which Ri is selected from H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom not being carbon C or hydrogen H preferably being nitrogen N, and even more preferably, the at least one atom not being C or H which is nitrogen, is covalently bonded to the carbon of the carbonyl group of the functional comonomer (FC1) of formula (1).

[0213] Preferably the functional comonomer (FC1) is chosen from amides derived from acrylic or methacrylic acid, such as, for example, N,N-dimethylacrylamide or N,N-diethylacrylamide.

[0214] More preferably, the functional comonomer (FC1) has the formula (2)

[0215] [Chemical formula 2]

[0216] wherein Ri is selected from H or CH3 and R3 and R4 are independently aliphatic groups comprising from 1 to 4 carbon atoms.

[0217] In a first more preferred embodiment, the functional comonomer (FC1) has the formula (3)

[0218] [Chemical formula 3] CH: (3)

[0219] wherein R3 and R4 are independently aliphatic groups comprising from 1 to 4 carbon atoms.

[0220] In a second more preferred embodiment, the functional comonomer (FC1) has the formula (4)

[0221] [Chemical formula 4]

[0222] wherein R3 and R4 are independently aliphatic groups comprising from 1 to 4 carbon atoms.

[0223] In a third more preferred embodiment, the functional comonomer (FC1) has the formula (5)

[0224] [Chemical formula 5] T U (5}

[0225] In a fourth more preferred embodiment, the functional comonomer (FC1) has the formula (6)

[0226] [Chemical formula 6]

[0227] The functional comonomer (FC1) can also be a mixture of two different monomers according to formulas (1) to (6).

[0228] The glass transition temperature Tg of the respective polymers can be estimated, for example, by dynamic methods such as thermomechanical analysis.

[0229] In order to obtain a sample of the respective polymers (Al), (Bl) and (Cl), these can be prepared alone under the same conditions, but not by a multi-step process, to more easily estimate and measure the glass transition temperature Tv individually of the respective polymers of the respective steps. The polymer (C3) can be extracted to estimate and measure the glass transition temperature Tv.

[0230] A first preferred method for manufacturing the polymer composition (PCI) is a multi-step method which comprises the successive steps of:

[0231] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (SA) comprising the polymer (Al) having a glass transition temperature of less than 10 °C,

[0232] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (SB) comprising a polymer (Bl) having a glass transition temperature of at least 10 °C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on components a), b) and c) only,

[0233] c) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in a step (C) comprising a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition on the basis of a), b) and c) of the first aspect only,

[0234] characterized in that said mixture of monomers (Bm) or mixture of monomers (Cm) comprises, or the mixture of monomers (Bm) and the mixture of monomers (Cm) or the polymer (Cl) comprise between 1% by weight and 40% by weight of a monomer or a copolymerized functional monomer (FC1) of the following general formula CH2=CRiC(=O)R2, where Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.

[0235] Preferably, steps a), b) and c) are carried out in this order. When emulsion polymerization is used, the polymer composition at the end of the polymerization is obtained as an aqueous dispersion.

[0236] An additional step d) of agglomeration of the composition obtained in steps a) to c) may be added. An additional or supplementary step of drying the polymer composition may also be added.

[0237] The respective monomers or monomer mixtures (Am), (Bm) and (Cm) for the formation of the layers in steps (SA), (SB) and (SC) respectively comprising the polymers (Al), (Bl) and (Cl), respectively, are the same as those defined previously. The monomers or monomer mixtures (Am), (Bm) and (Cm) comprise the respective monomers which are in the form of polymerized monomer units in the polymer chain of the respective polymers (Al), (Bl) and (Cl). The characteristics of the polymers (Al), (Bl) and (Cl), respectively, are the same as those defined previously.

[0238] A second preferred method for manufacturing the polymer composition (PCI) is a multi-step method which comprises the successive steps of:

[0239] a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (SA) comprising the polymer (Al) having a glass transition temperature of less than 10 °C,

[0240] b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (SB) comprising a polymer (Bl) having a glass transition temperature of at least 10 °C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on components a), b) and c) only, both steps jointly leading to a multi-stage polymer (MPI),

[0241] c) adding a polymer (Cl) having a glass transition temperature of at least 60°C after step b) to the multi-step polymer (MPI)

[0242] d) agglomeration of the composition obtained in steps a) to c).

[0243] Preferably, the polymer (Cl) is in the form of an aqueous dispersion. The aqueous dispersion comprises the polymer (Cl) in the form of polymeric particles.

[0244] The polymer composition (PCI) may be in the form of a polymer powder not comprising 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.

[0245] Preferably, the polymer composition (PCI) is in the form of a polymer powder which is dry. "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.

[0246] Humidity can be measured by a thermobalance which heats the polymer composition and measures the weight loss.

[0247] According to the sixth aspect, the present invention relates to an adhesive composition (ADC).

[0248] According to the seventh aspect, the present invention relates to a composition suitable as a (meth)acrylic adhesive composition (MADC).

[0249] Preferably, the adhesive composition (ADC) is a (meth)acrylic adhesive composition (MADC).

[0250] Additionally, the first part (PI) composition of the (meth)acrylic adhesive composition (MADC) may optionally comprise one or more additional compounds, in particular selected from the group consisting of: - at least one monomer (M2) different from the (meth)acrylic monomer (Ml) as defined; - a flexibility agent; - a polymerization accelerator; - an adhesion promoter; - a charge; - a rheology modifier; - and their mixtures.

[0251] The second part composition (P2) of the (meth)acrylic adhesive composition (MADC) comprises at least b1) a polymerization initiator.

[0252] In addition, the second part composition (P2) of the (meth)acrylic adhesive composition (MADC) may optionally comprise one or more additional compounds, in particular selected from the group consisting of: - a (meth)acrylic monomer (M3); - a diluent (non-reactive diluent or reactive diluent); - a plasticizer; - an adhesion promoter; - a rheology modifier; - a charge; - and their mixtures.

[0253] the content of the polymer composition (PCI) in the first part composition preferably being from 11% by weight to 25% by weight, plus preferably from 5% by weight to 22% by weight, advantageously from 7% by weight to 20% by weight.

[0254] As regards the (meth)acrylic monomer (Ml) according to the invention, this may be chosen from a methacrylic monomer or an acrylic monomer or a mixture thereof.

[0255] The (meth)acrylic monomer (Ml) is preferably selected from acrylic acid, methacrylic acid, acrylic ester monomers, methacrylic ester monomers and mixtures thereof.

[0256] Preferably, the (meth)acrylic monomer (Ml) is chosen from acrylic acid, methacrylic acid, alkylacrylic monomers, alkylmethacrylic monomers and mixtures thereof, the alkyl group having from 1 to 22 carbons, linear, branched or cyclic; the alkyl group preferably having 1 to 12 carbons, linear, branched or cyclic.

[0257] Advantageously, the (meth)acrylic monomer (Ml) is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, allyl acrylate, allyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate and mixtures thereof.

[0258] For example, SR 286 and SR 489, marketed by SARTOMER, may be mentioned.

[0259] In a preferred embodiment, at least 40% by weight, preferably at least 45% by weight, of the (meth)acrylic monomer (Ml) is methyl methacrylate.

[0260] The (meth)acrylic monomer(s) (M2) is (are) different from the (meth)acrylic monomer (Ml).

[0261] The (meth)acrylic monomer (M2) may be selected from acrylic ester monomers or methacrylic ester monomers which have at least one atom which is not carbon or hydrogen in the group of the alcohol portion of the ester (without taking into account the atoms of the ester group itself). Preferably, the atom is oxygen. An example is hydroxyethyl methacrylate or polyether chains comprising acrylic monomers.

[0262] The (meth)acrylic monomers (M2) are, for example, chosen from the group consisting of: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- and 3-hydroxypropyl acrylate, 2- and 3-hydroxypropyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2- or 3-ethoxypropyl acrylate, 2- or 3-ethoxypropyl methacrylate, 2 (2-ethoxyethoxy)ethyl acrylate, methoxy-polyethylene glycol methacrylate (preferably comprising 2 to 8 repeating units (EO)), methoxy-polyethylene glycol acrylate (preferably comprising 2 to 8 repeating units (EO)), methacrylate polyethylene glycol (preferably comprising 2 to 8 repeating units (EO), polyethylene glycol acrylate (preferably comprising 2 to 8 repeating units (EO), polypropylene glycol methacrylate (preferably comprising 2 to 8 repeating units (EO),polypropylene glycol acrylate (preferably comprising 2 to 8 repeating units (EO), and mixtures thereof.

[0263] Mention may be made, for example, of SR 550 and SR 256 marketed by SARTOMER.

[0264] The (meth)acrylic monomer (M3) may be identical to the (meth)acrylic monomer (Ml).

[0265] In a first preferred embodiment, the (meth)acrylic monomer (M3) is methyl methacrylate.

[0266] As regards the flexibility agent according to the invention, the latter may be chosen from a block copolymer, for example chosen from a block copolymer of styrene (SBC) and styrene-isoprene-styrene (SIS).

[0267] The flexibility agent may also be selected from a liquid elastomer. The liquid elastomer may have a weight average molecular weight Mw in the range of 1000 g / mol to 100,000 g / mol, preferably 1000 g / mol to 15,000 g / mol, more preferably 1000 g / mol to 9000 g / mol and may be functionalized with ethylenically unsaturated groups.

[0268] In a first preferred embodiment, the liquid elastomer is selected from urethane oligomers. Preferably, the urethane oligomers comprise at least two double bonds, preferably from 2 to 9 double bonds. Preferably, the double bonds are part of an acryl group, a methacryl group or an allyl group.

[0269] In a preferred embodiment, the flexibility agent is selected from urethane (meth)acrylate oligomer and a mixture thereof. A urethane (meth)acrylate oligomer may be any of the type known to those skilled in the art in the coatings or adhesives industries. In general, urethane (meth)acrylate oligomers are generally the reaction products of a isocyanate component containing at least two isocyanate functional groups with a (meth)acrylate component containing at least one (meth)acrylate functional group and at least one group (such as, for example, hydroxyl or amino) reactive with the isocyanate functional group. Details of the urethane (meth)acrylate oligomer can be found, for example, in US2012 / 0302695. Mention may be made, for example, of CN 965, CN 981, CN 9400, CN966H90 marketed by SARTOMER.

[0270] As regards the polymerization accelerator according to the invention, this may be chosen from those known to those skilled in the art in the coatings or adhesives industries. Mention may be made, for example, of tertiary amines such as N,N-dimethyl-p-toluidine (DMPT), N,N-dihydroxyethyl-p-toluidine (DHEPT), organically soluble transition metal catalysts or mixtures thereof.

[0271] As regards the adhesion promoter according to the invention, this may be chosen from those known to those skilled in the art in the coatings or adhesives industries. Mention may be made, for example, of aminosilane, metacryloylsilane, phosphates, methacrylated phosphate ester, epoxidized silane.

[0272] As regards the rheology modifier according to the invention, this may be chosen from those known to those skilled in the art in the coatings or adhesives industries. Mention may be made, for example, of silica (in particular fumed silica), a micronized amide wax (such as, for example, the CRAYVALLAC series marketed by Arkema).

[0273] As regards the initiator according to the invention, this may be chosen from those known to those skilled in the art in the coatings or adhesives industries. Mention may be made, for example, of peroxides or hydroperoxides (such as, for example, diacylperoxides, dialkylperoxides), peroxyesters, peroxyacetals, azo compounds, and mixtures thereof.

[0274] The initiator for starting the polymerization may be chosen from isopropyl carbonate, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, tert-butyl per(2-ethylhexanoate), cumyl hydroperoxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxyisobutyrate, tert-butyl peracetate, tert-butyl perpivalate, amyl perpivalate, tert-butyl peroctoate, azobisisobutyronitrile (AIBN), azobisisobutyramide, 2,2'-azobis(2,4-dimethylvaleronitrile) or 4,4'-azobis(4-cyanopentanoic acid). The use of a mixture of radical initiators chosen from the above list would not depart from the scope of the invention.

[0275] It will be apparent to those skilled in the art which polymerization accelerator to use taking into account the chosen initiator.

[0276] In a first preferred embodiment, the initiator is benzoyl peroxide or a dibenzoyl peroxide.

[0277] As regards the diluent according to the invention, this can be chosen from liquid epoxy resins.

[0278] As regards the plasticizer according to the invention, this may be chosen from those known to those skilled in the art in the coatings or adhesives industries. Mention may be made, for example, of plasticizers based on phthalate, polyol ester (such as, for example, pentaerythritol tetravalenate, marketed by Perstop), epoxidized oil, and mixtures thereof.

[0279] Additional aspects of the present invention relate to the use of the (meth)acrylic adhesive composition (MADC) as a structural adhesive and a structural adhesive comprising the polymer composition (PCI). [Evaluation procedures]

[0280] Glass transition temperature

[0281] The glass transitions (Tg) of polymers are measured with a device capable of performing thermomechanical analysis. A RDAII “RHEOMETRICS DYNAMIC ANALYSER” analyzer supplied by Rheometrics Company was used. Thermomechanical analysis accurately measures the viscoelastic changes of a sample as a function of temperature, stress or strain applied. The device continuously records the deformation of the sample, maintaining the fixed stress, during a controlled temperature variation program.

[0282] The results are obtained by graphical representation, as a function of temperature, of the modulus of elasticity (G'), of the loss modulus and of tan delta. Tv is the highest temperature value read on the loss angle curve, when the derivative of the loss angle is equal to zero.

[0283] Molecular weight

[0284] The mass average molecular weight (Mw) of the polymers is measured by size exclusion chromatography (SEC). Polystyrene standards are used for calibration. The polymer is dissolved in THF at a concentration of 1 g / l. The chromatography column uses modified silica. The flow rate is 1 ml / min and a refractive index detector is used.

[0285] Particle size analysis

[0286] The particle size of the primary particles after multi-stage polymerization is measured with a Malvern Zetasizer using light scattering dynamic. , The volume average particle size (diameter) is taken as the result.

[0287] The particle size of the polymer powder after recovery is measured with a Malvern Mastersizer 3000 from MALVERN with laser diffraction.

[0288] For estimation of weight average powder particle size, particle size distribution and proportion of fine particles, a Malvern Mastersizer 3000 apparatus with 300 mm objectives is used, measuring a range of 0.5 to 880 pm.

[0289] Extraction

[0290] The extractable part of the polymer composition is measured gravimetrically. The sample is treated with stirring for 4 hours at 20 °C in THF at 10 g / L. The solution is filtered and after evaporation of the solvent from the filtered solution, the recovered polymer is weighed and its ratio is calculated.

[0291] Tensile properties

[0292] Mechanical properties under tensile stress are evaluated based on ISO 527-2:2012 (Plastics - Determination of tensile properties). Type 1BA specimens are used and tested in a tensile testing machine (Zwick Roell Z050 type Xforce P load cell of 50 kN) at 5 mm / min. The measured strain is based on the machine displacement (nominal strain). Young's modulus of elasticity is evaluated using an extensometer (Zwick Roell BT-2EXMACRO.ETH.011) between 0.05% and 0.25% strain at 1 mm / min. Thickness and width are measured before testing and the samples are conditioned at 25 °C for at least 12 hours before testing. This test is carried out in quintuplicate.

[0293] Solidity

[0294] Plane strain fracture toughness (K1C) is evaluated with compact tension (CT) configuration specimens based on ASTM D 5045-99 (Standard Test Methods for Plane Strain Toughness and Strain Energy Release Rate of Plastics). The test is conducted at 10 mm / min, in a tensile testing machine (Zwick Roell Z050 type Xforce HP+ 0.5 kN load cell). A natural crack is generated by tapping once on a new razor blade placed in the machined clean notch. The ligament and thickness are measured before testing and the specimens are conditioned at 25 °C for at least 12 hours before testing. This test is conducted in quintuplicate. Measurements were made at -25 °C and -40 °C. The samples are too ductile to be measured at room temperature.

[0295] Evaluation of multi-stage polymer dispersion (core / shell type powder)

[0296] The composition comprising the multi-stage polymer (core / shell powder) was evaluated for ease of dispersion in neat methyl methacrylate. This was evaluated by visual inspection as the time required to reach a homogeneous dispersion state for the core / shell when added to the methacrylate part (first step of the preparation of Part A methacrylate composition). Particular attention was paid to the complete disappearance of the core / shell powder agglomerates. A poor result regarding this test is qualified as difficult and time-consuming while a good result is qualified as easy and rapid.

[0297] Multi-stage polymer dispersion in a cured adhesive composition.

[0298] The quality of the dispersion was evaluated by atomic force microscopy (AFM). The sample is prepared at -90 °C with an RMC cryo-ultramicrotome. The samples are observed on a Bruker Dimension 3100 in Tapping mode.

[0299] Adhesive properties

[0300] Surface preparation of the specimens for adhesion testing is based on EN 13887-2003 (Structural adhesives - Guide for surface preparation of metals and plastics prior to adhesive bonding). 6061 series aluminum specimens were degreased with isopropanol. Lap shear tests based on EN 1465-2009 (Adhesives - Determination of tensile shear strength of single lap adhesive bonded joints) are performed with a tensile testing machine at 23 °C or a 0.2 mm thick joint, at 1 mm / min. The maximum force is divided for the actual joint area to obtain the maximum stress, which is used to compare each specimen. The specimens were conditioned at room temperature for at least 12 hours before testing. The test is performed in quintuplicate. Examples

[0301] Comparative Example 1 - Multi-step synthesis of polymer particles without copolymerized functional monomer:

[0302] First stage A - polymerization of an Al type polymer: into a 20 liter high pressure reactor are charged: demineralized water 116.5 parts, beef tallow fatty acid potassium salt emulsifier 0.1 part, 1,3-butadiene 21.9 parts, t-dodecyl mercaptan 0.1 part, and p-menthane hydroperoxide 0.1 part as initial tank charge. The solution was heated, with stirring, to 43 °C after which a redox catalyst solution was charged (4.5 parts of water, 0.3 parts of sodium tetrapyrophosphate, 0.004 parts of ferrous sulfate and 0.3 parts of dextrose), which effectively initiates the polymerization. The solution was then further heated to 56°C and maintained at this temperature for three hours. Three hours after polymerization began, a second charge of monomer (77.8 parts BD, 0.2 parts t-dodecyl mercaptan), half of an additional charge of emulsifier and reducing agent (30.4 parts deionized water, 2.8 parts emulsifier potassium salt of beef tallow fatty acids, 0.5 parts dextrose), and additional initiator (0.8 parts p-menthane hydroperoxide) were added continuously over eight hours. After the second monomer addition was complete, the remaining charge of emulsifier and reducing agent, as well as the initiator, were added continuously over another five hours.Thirteen hours after initiation of polymerization, the solution was heated to 68 °C and allowed to react until at least twenty hours had elapsed since initiation of polymerization, producing polybutadiene rubber latex, RI. The resulting polybutadiene rubber latex (Al) contained 38% solids and had a weight average particle size of approximately 160 nm.

[0303] Second Stage B - Polymerization of Type B1 Polymer: Into a 3.9 liter reactor are charged 75.0 parts, on a solids basis, of polybutadiene rubber latex RI, 37.6 parts of deionized water, and 0.1 part of sodium formaldehyde sulfoxylate. The solution was stirred, purged with nitrogen, and heated to 77°C. When the solution reached 77°C, a mixture of 22.6 parts of methyl methacrylate, 1.4 parts of 1,4-butanediol dimethacrylate (BDMA), and 0.1 part of t-butyl hydroperoxide initiator was added continuously over a period of 70 minutes, followed by a holding period of 80 minutes. Thirty minutes after the start of the holding period, 0.1 part of sodium formaldehyde sulfoxylate and 0.1 part of t-butyl hydroperoxide were added to the reactor at once. After the 80-minute holding period, a stabilizing emulsion was added to the graft copolymer latex.The stabilizing emulsion was prepared by mixing 3.2 parts of deionized water (based on the mass of graft copolymer), 0.1 part of oleic acid, 0.1 part of potassium hydroxide, and 0.9 parts of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. The resulting core-shell polymer (A+B) has a weight-average particle size of about 180 nm.

[0304] Third step C - Polymerization of polymer type Cl

[0305] Synthesis of polymer Cl: semi-continuous process: 10,000 g of core-shell type polymer (A+B) in demineralized water, 0.01 g of FeSO4 and 0.032 g of ethylenediaminetetraacetic acid, sodium salt (dissolved in 10 g of demineralized water), 3.15 g of sodium formaldehyde sulfoxylate dissolved in 110 g of demineralized water and 21.33 g of sodium salt emulsifier are charged into a reactor, with stirring. potassium of beef tallow fatty acid (dissolved in 139.44 g of water), and the mixture is stirred until the added raw materials are completely dissolved except for the core-shell polymer. Three vacuum-nitrogen purges are carried out successively and the reactor is left under a light vacuum. The reactor is then heated. At the same time, a mixture comprising 1066.7 g of methyl methacrylate and 10.67 g of n-octyl mercaptan was degassed with nitrogen for 30 minutes. The reactor is heated to 63 °C and maintained at this temperature. Then, the monomer mixture was introduced into the reactor over 180 min by means of a pump. At the same time, a solution of 5.33 g of tert-butyl hydroperoxide (dissolved in 100 g of deionized water) is introduced (same addition time). The lines were rinsed with 50 g and 20 g of water.Then, the reaction mixture was heated to a temperature of 80 °C and the polymerization was then carried out until complete for 60 minutes after the completion of the monomer addition. The reactor is cooled to 30 °C. The mass average molecular weight of the Cl copolymer is Mw = 28,000 g / mol. .

[0306] The final polymer composition consisting of the multi-stage polymer (MPI) and the polymer (Cl) is then recovered, the polymer composition being dried by spray drying to obtain a core / shell type powder 1.

[0307] Comparative Example 2: The same syntheses as in Comparative Example 1 are carried out, but the third step C is not carried out. A core / shell powder 2 is obtained.

[0308] Example of the invention 1: the same syntheses as in comparative example 1 were carried out, however, in the synthesis of the second step b, 2.26 parts of MMA are replaced by N,N-dimethylacrylamide (DMA). A core / shell powder 3 is obtained.

[0309] Adhesive compositions

[0310] [Table 1]

[0311] Table 1: Composition of Part A containing the methacrylate monomers Component Supplier Content (%) Methyl methacrylate (M MA) Arkema 53 2-Ethylhexyl acrylate (2 EHA) Arkema 4 Hydroxyethyl methacrylate (HEMA) Arkema 4 Flexibility agent CN1993 CG Sartomer 20.5 Adhesion promoter Sipomer® PAM200 2.5 Catalyst Bisomer® PTE 1 Core / shell type powder Arkema 15

[0312] 53 g of methyl methacrylate (MMA) are poured into a 250 ml beaker. 15 g of core / shell powder additive 1 to 3 respectively are added to the MMA with continuous stirring at 200 rpm for 15 min. Then, 4 g of 2EHA, 4 g of HEMA, 20.5 g of CN1993CG, 2.5 g of Sipomer® PAM200 and 1 g of Bisomer® PTE are added and stirred again for 15 min. The resulting homogeneous Part A composition is kept in a sealed container.

[0313] [Table 2]

[0314] Table 2: Composition of Part B comprising the polymerization initiator Component Function Supplier Content (%) 50% benzoyl peroxide paste RET IC BP50 white Polymerization initiator Arkema 40 Epoxy resin DGEB A liquid Araldite L Y556 Reactive diluent Huntsman 60

[0315] 22 g of LY556 resin are poured into a 250 ml beaker together with 40 g of BP50 with continuous stirring for 30 min at 500 rpm. The resulting homogeneous Part B composition is kept in a sealed container.

[0316] The methacrylate Part A composition and the polymerization initiator Part B composition are mixed together in a 10:1 ratio (10 parts of Part A to 1 part of Part B) with stirring at 1200 rpm for 1 min.

[0317] The resulting homogeneous methacrylate adhesive mixture is poured into PTFE molds to be cured at room temperature for 24 hours. The same adhesive mixture is used to prepare the lap shear specimens using the same curing conditions. The resulting core / shell content of this adhesive formulation is 13.6% by weight.

[0318] It should be noted that a reference “pure resin” composition is simply prepared using the same protocol described above but without adding the powder of core / shell to the composition of Part A (0% core / shell composition by weight).

[0319] The application results corresponding to the inventive example 1 are presented in Table 3. It can be concluded that the innovative core / shell 3 of the present invention exhibits superior performance to the prior art core / shell 1 and core / shell 2 references in the present methacrylate adhesive formulation. More particularly, the core / shell 3 allows higher shear stresses (lap shear test) and elongation at break to be achieved while also increasing the fracture toughness.

[0320] [Table 3]

[0321] Table 3: application results corresponding to the examples Pure resin Comparative example 1 Comparative example 2 Example of the invention 1 Core / shell 1 Core / shell 2 Core / shell 3 Core / shell content 0% by weight 13.6% by weight 13.6% by weight 13.6% by weight Adhesive properties Tensile lap shear at 23°C / [MPa] 6 15.5 10 17.5 Tensile properties E-modulus at 23°C / [MPa] 1600 760 1200 800 Elongation at break at 23°C / [%] 14 25 18 32 Elongation at break at -40°C / [%] 7.6 7.6 6.1 8.5 Tensile strength Klc at 23 °C / [MPa*m1 / 2] 2.2 4.3 3.9 5.0 Klc at -40 °C / [MPa*m1 / 2] 1.5 4.0 3.3 4.8

Claims

Claims

1. A polymer composition (PCI) comprising: a) a polymer (Al) having a glass transition temperature of less than 10°C, b) a polymer (Bl) having a glass transition temperature of at least 10°C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on a), b) and c) only, wherein component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only;characterized in that either the polymer (Bl), or the polymer (Cl), or the polymer (Bl) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRiC(=O)R2, in which Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.;

2. A polymer composition (PCI) according to claim 1, characterized in that the polymer composition (PCI) comprises polymer core-shell particles.

3. Polymer composition (PCI) according to claim 1 or 2, characterized in that the polymer composition (PCI) is in the form of a polymer powder.

4. Polymer composition (PCI) according to any one of claims 1 to 3, characterized in that the polymer composition (PCI) comprises between 5% by weight and 35% by weight of polymer (Bl) of the composition based on a), b) and c).

5. Polymer composition (PCI) according to any one of claims 1 to 3, characterized in that the polymer composition (PCI) comprises between 3% by weight and 35% by weight of polymer (Cl) of the composition based on a), b) and c).

6. PCI polymer composition according to any one of claims 1 to 5 characterized in that the polymer (Bl) is a (meth)acrylic polymer comprising at least 50% by weight of polymer units originating from (meth)acrylic monomers.

7. PCI polymer composition according to any one of claims 1 to 6, characterized in that the polymer (Bl) comprises between 1% by weight and 35% by weight of the copolymerized functional monomer (FC1), more preferably between 2% by weight and 30% by weight, and advantageously between 4% by weight and 27% by weight.

8. PCI polymer composition according to any one of claims 1 to 6, characterized in that the polymer (Cl) comprises between 1% by weight and 35% by weight of the copolymerized functional monomer (FC1), more preferably between 2% by weight and 30% by weight, and advantageously between 4% by weight and 27% by weight.

9. A PCI polymer composition according to any one of claims 1 to 6, characterized in that the polymer (B1) of the polymer composition (PCI) comprises a copolymerized functional monomer (FC1).

10. A PCI polymer composition according to any one of claims 1 to 6, characterized in that the polymer (Cl) of the polymer composition (PCI) comprises a copolymerized functional monomer (FC1).

11. A PCI polymer composition according to any one of claims 1 to 6, characterized in that the polymer (B1) and the polymer (Cl) of the polymer composition (PCI) comprise a copolymerized functional monomer (FC1).

12. PCI polymer composition according to one of claims 1 to 11, characterized in that the functional comonomer (FC1) is chosen from amides derived from acrylic or methacrylic acid, such as for example N,N-dimethylacrylamide or N,N-diethylacrylamide.

13. A method of manufacturing a polymer composition (PCI) according to any one of claims 1 to 12, comprising the steps of: a) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Am) to obtain a layer in a step (SA) comprising the polymer (Al) having a glass transition temperature of less than 10 °C, b) polymerization by emulsion polymerization of a monomer or a mixture of monomers (Bm) to obtain a layer in a step (SB) comprising a polymer (Bl) having a glass transition temperature of at least 10 °C, said polymer (Bl) representing at least 2% by weight and at most 40% by weight of the composition based on components a), b) and c) only, c) either the polymerization by emulsion polymerization of a monomer or a mixture of monomers (Cm) to obtain a layer in a step (C) comprising a polymer (Cl) having a glass transition temperature of at least 60 °C or the addition of polymer (Cl) having a glass transition temperature of at least 60 °C after step b), said polymer (Cl) representing at most 40% by weight of the composition based on a), b) and c) only, characterized in that said mixture of monomers (Bm) or mixture of monomers (Cm) includes,or the monomer mixture (Bm) and the monomer mixture (Cm) or the polymer (Cl) comprise between 1% by weight and 40% by weight of a monomer or a copolymerized functional monomer (FC1) of the following general formula CH2=CRiC(=O)R2, in which Ri is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.,

14. Method according to claim 13, characterized in that the method comprises an additional step d) of agglomeration of the composition.

15. A method according to claim 13 or 14, characterized in that the method comprises an additional step of drying the polymer composition.

16. Use of the polymer composition (PCI) according to any one of claims 1 to 12 or obtained by the process according to any one of claims 13 to 15 as an impact resistance modifier.

17. Use according to claim 16 in an adhesive composition (ADC).

18. Use according to claim 16 in a (meth)acrylic adhesive composition (MADC).

19. Adhesive composition (ADC) comprising the polymer composition (PCI) according to any one of claims 1 to 12 or obtained by the process according to any one of claims 13 to 15.

20. A methacrylic adhesive composition (MADC) comprising the polymer composition (PCI) according to any one of claims 1 to 12 or obtained by the process according to any one of claims 13 to 15.

21. A composition suitable as a (meth)acrylic adhesive composition comprising: a) a first part composition (PI) comprising a1) at least one (meth)acrylic monomer (M1), a2) a polymer composition (PCI) comprising a2a) a polymer (A1) having a glass transition temperature of less than 10°C, a2b) a polymer (B1) having a glass transition temperature of at least 10°C, said polymer (B1) representing at least 2% by weight and at most 40% by weight of the composition based on a2a), a2b) and a2c) only, wherein component a) and component b) of the composition (PCI) are part of a multi-stage polymer (MPI), a2c) a polymer (Cl) having a glass transition temperature of at least 60°C, said polymer (Cl) representing at most 40% by weight of the composition based on a2a), a2b) and a2c) only;and b) a second part composition (P2) comprising b1) a polymerization initiator, characterized in that either the polymer (B1), the polymer (Cl), or the polymer (B1) and the polymer (Cl) comprise between 1% by weight and 40% by weight of copolymerized functional monomer (FC1) of the following general formula CH2=CRiC(=O)R2, in which R1 is H or CH3 and R2 is a group comprising at least one atom which is not C or H, the at least one atom which is not C or H preferably being a nitrogen N.;

22. Use of the composition according to claim 21 as a structural adhesive.

23. 40 Structural adhesive comprising the polymer composition (PCI) according to any one of claims 1 to 12 or obtained by the method according to any one of claims 13 to 15.

24. A process for preparing a methacrylic adhesive composition (MADC) comprising the steps of: i) providing a composition according to claim 21, ii) polymerizing or curing the composition.