A compound having two polymerizable groups, a composition comprising a multistage polymer and a thermoplastic polymer, a method of manufacturing the same, uses the same, and articles comprising the same

Abstract

The present invention relates to a composition comprising a compound having two polymerizable groups, a multistage polymer, and a thermoplastic polymer, a method for manufacturing the same, and the use of the same. In particular, the present invention relates to a composition comprising a compound having two polymerizable groups, a multistage polymer in the form of polymeric particles produced by a multistage process, and a (meth)acrylic polymer. More specifically, the present invention relates to a polymer composition comprising a compound having two polymerizable groups, polymeric particles produced by a multistage process comprising at least two stages, and a (meth)acrylic polymer, a method for producing the same, a thermosetting resin, and the use thereof for producing an impact-modified polymer composition comprising the composition, and articles comprising the same.

Description

Technology Field

[0001] The present invention relates to a composition comprising a compound having two polymerizable groups, a multistage polymer, and a thermoplastic polymer, a method for manufacturing the same, and the use of the same.

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

[0003] More specifically, the present invention relates to a polymer composition comprising a compound having two polymerizable groups, polymeric particles produced by a multistage process comprising at least two stages, and a (meth)acrylic polymer, a method for producing the same, a thermosetting resin, and the use thereof for producing an impact-modified polymer composition comprising the composition, and articles comprising the same. Background Technology

[0004] Prior art

[0005] Document WO2016 / 102666 discloses a composition comprising a multi-stage polymer and a method for preparing the same. The composition also comprises a (meth)acrylic polymer having a mass average molecular weight of less than 100,000 g / mol.

[0006] Document WO2016 / 102682 discloses a multistage polymer composition and a method for preparing the same. The multistage polymer comprises a final stage comprising a (meth)acrylic polymer having a mass average molecular weight of less than 100,000 g / mol.

[0007] Literature EP2441784A1 discloses a vinyl ester composition containing polymer microparticles. The polymer microparticles are core-shell polymers having a shell comprising an aromatic vinyl monomer and a vinyl cyanide monomer.

[0008] Literature EP 1 632 533 describes a method for manufacturing a modified epoxy resin. The epoxy resin composition is dispersed by a process in which rubber-like polymer particles are brought into contact with an organic medium that disperses rubber particles.

[0009] Document WO2019 / 011984 discloses a resin composition. The resin composition comprises a resin system, a curing system, and a particle system. The particle system is a multistage polymer.

[0010] None of the prior art literature discloses a composition or method as claimed. The problem to be solved

[0011] [Technical Challenges]

[0012] Many modern articles are manufactured from polymeric materials or contain polymers or polymeric compositions. These articles must resist mechanical stress during use. Therefore, they must be impact modified.

[0013] One type of polymeric material is thermosetting polymer, which is used, for example, in adhesives or polymeric composites.

[0014] Thermosetting polymers consist of a cross-linked three-dimensional structure. For example, cross-linking is achieved by curing reactive groups within the so-called prepolymer. Curing can be achieved, for example, by heating the polymer chains to permanently cross-link and solidify the material.

[0015] To manufacture polymeric thermosetting composite materials, a prepolymer is mixed with other components, such as glass beads or fibers, or other components that are wetted or impregnated and then cured. Examples of prepolymers or matrix materials for thermosetting polymers are unsaturated polyesters, vinyl esters, epoxy, or phenolic ones.

[0016] Once cured, thermosetting resins possess excellent properties in terms of dimensional stability, mechanical strength, electrical insulation, heat resistance, water resistance, and chemical resistance. Examples of such thermosetting resins are epoxy resins or phenolic resins. However, these cured resins have low fracture toughness and are brittle.

[0017] To ensure and obtain satisfactory mechanical performance over a wide temperature range, the impact performance of the thermosetting polymer matrix must be increased.

[0018] One form of impact modifier is a core-shell particle called a multistage polymer, manufactured by a multistage process having at least one stage including a rubbery polymer. Subsequently, the particle is incorporated into one of the phases of a brittle polymer for composite materials or a structural adhesive to increase the impact resistance of the final product.

[0019] However, this type of multistage polymer is not easy to disperse in a reasonable amount of time, especially in a homogeneous distribution and / or small or large amount, in all types of resins or polymers or even monomers; this is true not only in curable resins such as unsaturated polyesters or vinyl esters, for example, but also in other precursors of polymeric phases or monomers for composites and structural adhesives.

[0020] Good homogeneous dispersion of multi-stage polymers is necessary to have satisfactory impact performance. The dispersion must also have reasonable stability (time of use).

[0021] The object of the present invention is to propose a composition suitable for producing a hardened, toughened thermosetting polymer comprising a multistage polymer and a thermoplastic polymer that is homogeneous and stable while having a viscosity suitable for the required application.

[0022] A further object of the present invention is to provide a composition suitable for manufacturing a cured thermosetting polymer comprising a precursor of a thermosetting polymer, a multistage polymer, and a thermoplastic polymer that can be manufactured easily and quickly.

[0023] Another objective of the present invention is to propose a composition suitable for producing a cured thermosetting polymer comprising a thermosetting polymer precursor, a multistage polymer, and a thermoplastic polymer, which is homogeneous and stable while having a viscosity suitable for the required application.

[0024] Another objective of the present invention is a method for manufacturing a hardened, toughened polymer composition having satisfactory impact properties.

[0025] The object of the present invention is to propose a method for reducing the preparation time of a composition suitable for manufacturing a cured thermosetting polymer comprising a multistage polymer.

[0026] Another objective is to propose an impact-modified cured polymer that satisfies impact properties or an adhesive composition that satisfies impact and adhesive strength properties. means of solving the problem

[0027] [Brief Description of the Invention]

[0028] Surprisingly, as a composition (PC1),

[0029] a) Multistage polymer (MP1) including the following

[0030] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0031] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0032] b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30 °C, and

[0033] c) comprising a component (LC1) including a compound (C1) having at least two polymerizable groups (PG1) and (PG2), and

[0034] A composition (PC1) characterized in that the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) corresponds to a maximum of 40 wt% of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c);

[0035] It was found that this thermosetting polymer can be easily dispersed in a precursor for a polymeric matrix material.

[0036] Surprisingly, also as a composition (PC1),

[0037] a) Multistage polymer (MP1) including the following

[0038] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0039] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0040] b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30 °C, and

[0041] c) comprising a component (LC1) including a compound (C1) having at least two polymerizable groups (PG1) and (PG2), and

[0042] A composition (PC1) characterized in that the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) corresponds to a maximum of 40 wt% of a composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c).

[0043] It was found that it maintains good stability and remains homogeneous over a long period. A long period means at least two weeks at 23°C, and homogeneity means that no significant separation occurs between the components.

[0044] Surprisingly, also as a method for manufacturing composition (PC1),

[0045] i) a step of providing a composition (Ci).

[0046] a) Multistage polymer (MP1) including the following

[0047] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0048] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0049] b) providing the composition (Ci) comprising a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) corresponds to up to 40 wt% of the composition based on a) and b); and

[0050] ii) a step of mixing composition (Ci) with composition (Ciia) comprising at least one other component or compound present in composition (PC1); and

[0051] iii) a method for preparing a composition (PC1) comprising the step of optionally mixing the composition obtained in step ii) with another component or compound present in the composition (PC1) that has not yet been added in step ii).

[0052] It was found that this allows for the production of a stable and homogeneous composition, and likewise, the production time of the composition (PC1) can be reduced compared to a composition that does not contain component b).

[0053] Surprisingly, also as a method for manufacturing composition (PC1),

[0054] i) a step of providing a polymeric composition

[0055] a) Multistage polymer (MP1) including the following

[0056] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0057] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0058] b) a step of providing the polymeric composition comprising a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) corresponds to up to 40 wt% of the composition based on a) and b),

[0059] ii) a step of providing a c) component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2),

[0060] iii) a method for preparing a composition (PC1), comprising the step of mixing components a), b), and c) in a ratio such that the ratio of the sum of components a) and b) to 100 phr of component c) is between 0.5 and 100 phr.

[0061] It was found that this results in a method for reducing the manufacturing time of composition (PC1) compared to a composition that does not contain this component b).

[0062] Surprisingly, also in composition (PC1), as a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol

[0063] a) Multistage polymer (MP1) including the following

[0064] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0065] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0066] b) up to 40 wt% of the thermoplastic polymer (B1) of the composition based on a) and b), and

[0067] c) comprising a component (LC1) including a compound (C1) having at least two polymerizable groups (PG1) and (PG2), and

[0068] And the use of a thermoplastic polymer (B1) in which the sum of components a) and b) is between 0.5 and 100 phr for 100 phr of component c).

[0069] It was found that composition (PC1) reduces the manufacturing time compared to a composition that does not contain component b).

[0070] Surprisingly, also as a method for manufacturing a polymer composition (PC2),

[0071] i) a step of providing a polymeric composition (Ci).

[0072] a) Multistage polymer (MP1) including the following

[0073] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0074] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0075] b) providing the polymeric composition (Ci) comprising a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) corresponds to up to 40 wt% of the composition based on a) and b).

[0076] ii) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2),

[0077] iii) A step of mixing components a), b), and c) in a ratio such that the ratio of the sum of components a) and b) to 100 phr of component c) is between 0.5 phr and 100 phr.

[0078] iv) a method for preparing a polymer composition (PC2), comprising the step of polymerizing or curing the mixture

[0079] It was found that this yields a polymer composition having satisfactory toughening and / or impact properties.

[0080] Surprisingly, also as a polymeric composition (PC2),

[0081] a) Multistage polymer (MP1) including the following

[0082] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0083] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0084] b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30 °C, and

[0085] c) comprising a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2), and

[0086] A polymeric composition (PC2) characterized in that the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) corresponds to a maximum of 40 wt% of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c).

[0087] It was found that it possesses this satisfactory toughening characteristic. Specific details for implementing the invention

[0088] [Detailed Description of the Invention]

[0089] According to a first embodiment, the present invention comprises a composition (PC1),

[0090] a) Multistage polymer (MP1) including the following

[0091] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0092] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0093] b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30 °C, and

[0094] c) comprising a component (LC1) including a compound (C1) having at least two polymerizable groups (PG1) and (PG2), and

[0095] The present invention relates to a composition (PC1) characterized in that the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) corresponds to a maximum of 40 wt% of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c).

[0096] According to a second aspect, the present invention, as a method for manufacturing a composition (PC1),

[0097] i) a step of providing a composition (Ci).

[0098] a) Multistage polymer (MP1) including the following

[0099] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0100] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0101] b) providing the composition (Ci) comprising a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) corresponds to up to 40 wt% of the composition based on a) and b); and

[0102] ii) a step of mixing composition (Ci) with composition (Ciia) comprising at least one other component or compound present in composition (PC1); and

[0103] iii) optionally, a method for preparing a composition (PC1) comprising the step of mixing the composition obtained in step ii) with another component or compound present in the composition (PC1) that has not yet been added in step ii).

[0104] In a third aspect, the present invention is a method for preparing a composition (PC1), wherein

[0105] i) a step of providing a polymeric composition (Ci).

[0106] a) Multistage polymer (MP1) including the following

[0107] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0108] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0109] b) providing the polymeric composition (Ci) comprising a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) corresponds to up to 40 wt% of the composition based on a) and b).

[0110] ii) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2),

[0111] iii) A method for preparing a composition (PC1), comprising the step of mixing a composition (Ci) and (Ciib) containing components a), b), and c) in a ratio such that the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c).

[0112] In a fourth aspect, the present invention provides a method for reducing the preparation time of a composition (PC1), wherein

[0113] i) a step of providing a polymeric composition (Ci).

[0114] a) Multistage polymer (MP1) including the following

[0115] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0116] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0117] b) providing the polymeric composition (Ci) comprising a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) corresponds to up to 40 wt% of the composition based on a) and b).

[0118] ii) providing a composition (Ciib) comprising a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2),

[0119] iii) A method for reducing the preparation time of a composition (PC1), comprising the step of mixing components a), b), and c) in a ratio such that the ratio of the sum of components a) and b) to 100 phr of component c) is between 0.5 phr and 100 phr.

[0120] In a fifth aspect, the present invention is a polymeric composition (PC2).

[0121] a) Multistage polymer (MP1) including the following

[0122] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0123] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0124] b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30 °C, and

[0125] c) comprising a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2), and

[0126] The present invention relates to a polymeric composition (PC2) characterized in that the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) corresponds to a maximum of 40 wt% of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c).

[0127] According to the sixth aspect, the present invention relates to the use of a composition (PC1) for producing an impact-modified polymeric composition (PC2),

[0128] a) Multistage polymer (MP1) including the following

[0129] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0130] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0131] b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30 °C, and

[0132] c) comprising a component (LC1) including a compound (C1) having at least two polymerizable groups (PG1) and (PG2), and

[0133] The present invention relates to the use of a composition (PC1) characterized in that the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) corresponds to a maximum of 40 wt% of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c).

[0134] The term "polymer powder" as used refers to a polymer comprising powder grains in the range of at least 1 μm obtained by the aggregation of a primary polymer comprising particles in the nanometer range.

[0135] The term "primary particle" used refers to spherical polymer particles containing particles in the nanometer range. Preferably, the primary particles have a weight-average particle size between 50 nm and 500 nm.

[0136] The term "particle size" as used refers to the volume-average diameter of a particle considered as spherical.

[0137] As used, the term “thermoplastic polymer” refers to a polymer that becomes liquid or more liquid or less viscous when heated and can take on a new shape by applying heat and pressure. Within the scope of the invention, thermoplastic polymers may also be cross-linked if they can still be thermoformed.

[0138] The term “thermosetting polymer” used refers to a polymer prepared from a soft, solid, or viscous prepolymer (e.g., an oligomer or monomer having at least two reactive groups, or a mixture of both) that is irreversibly transformed into an infusible, insoluble polymer network by curing.

[0139] As used, the term "polymer composite" refers to a multi-component material comprising a plurality of different phase domains in which at least one type of phase domain is a continuous phase and at least one component is a polymer.

[0140] The term "copolymer" used indicates that the polymer consists of at least two different monomers.

[0141] "Multistage polymer" as used refers to a polymer formed in a sequential manner by a multistage polymerization method. A multistage emulsion polymerization method is preferred in which the first polymer is a first monopolymer and the second polymer is a second monopolymer, that is, the second polymer is formed by emulsion polymerization in the presence of a first emulsion polymer and has at least two stages with different compositions.

[0142] The term "(meth)acrylic" as used refers to all types of acrylic and methacrylic monomers.

[0143] The term "(meth)acrylic polymer" used indicates that the (meth)acrylic polymer essentially comprises a polymer comprising (meth)acrylic monomers constituting 50 weight percent or more of the (meth)acrylic polymer.

[0144] The term "dry" as used indicates that the percentage of residual water is less than 1.5 wt%, and preferably less than 1.25 wt%.

[0145] The term "total intruded volume" used refers to the total volume of liquid mercury intruded according to ISO 15901-1:2016. This volume is cumulative, and the analysis results are given as a function of applied pressure or pore diameter in ml / g (cm²). 3 It represents the accumulated intrusion volume in units of / g). The total intrusion volume is the volume intruded at the maximum applied pressure, which corresponds to the smallest pore.

[0146] The term "incremental intrusion" used refers to the volume intruded in ml / g between two specific pressures or two pore sizes. This incremental intrusion may also be expressed relative to the total intrusion volume in vol% units.

[0147] The term "phr" used indicates a part per hundred by weight. For example, 1 phr of compound A considering compound B in the composition means that 1 kg of compound A is added to or present in 100 kg considering compound B.

[0148] In the present invention, the range of x to y includes the upper and lower limits of this range and means that it is equal to x or greater and y or less.

[0149] In the present invention, the range between x and y means that the upper and lower limits of this range are excluded, and it is equivalent to being greater than x and less than y.

[0150] In relation to the composition (PC1) according to the present invention, It is preferably a polymeric composition.

[0151] The polymer composition (PC1) comprises a) a multistage polymer (MP1), b) a thermoplastic polymer (B1), and c) a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), wherein the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, component b) corresponds to a maximum of 40 wt% of the composition based only on a) and b), and the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c).

[0152] The multistage polymer (MP1) comprises a1) one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C and a2) one stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C.

[0153] The thermoplastic polymer (B1) has a glass transition temperature of at least 30°C.

[0154] Component b) of composition (PC1) corresponds to a maximum of 40 wt% of the composition based only on a) and b). The composition based only on a) and b) is referred to as composition (Ci). Preferably, component b) of composition (Ci) corresponds to a maximum of 35 wt% of the composition based only on a) and b); more preferably, a maximum of 30 wt%, even more preferably less than 30 wt%, advantageously less than 25 wt%, and even more advantageously less than 20 wt%.

[0155] Component b) of composition (Ci) corresponds to more than 0.5 wt% of the composition based only on a) and b). Preferably, component b) of composition (Ci) corresponds to more than 1 wt% of the composition based only on a) and b); more preferably more than 2 wt%, even more preferably more than 4 wt%, advantageously more than 8 wt%, and more advantageously more than 10 wt%.

[0156] Component b) corresponds to between 0.5 wt% and 40 wt% of the composition based only on a) and b). Preferably, component b) corresponds to between 5 wt% and 35 wt% of the composition based only on a) and b); more preferably between 6 wt% and 30 wt%, even more preferably between 7 wt% and less than 30 wt%, advantageously between 7 wt% and less than 25 wt%, and even more advantageously between 10 wt% and less than 20 wt%.

[0157] At least component a) of composition (PC1) or composition (Ci) is part of the multi-stage polymer (MP1).

[0158] At least component a) is obtained by a multistage process comprising at least two stages (SA1) and (SA2); and the two polymers (A1) and (A2) form a multistage polymer (MP1).

[0159] In the composition (PC1), the sum of components a) and b) is between 0.5 and 100 phr for 100 phr of component c); preferably, the sum of components a) and b) is between 1 phr and 100 phr for 100 phr of component c);

[0160] In a first more preferred embodiment of the composition (PC1), the sum of components a) and b) is between 1 phr and 50 phr for 100 phr of component c), more preferably between 1 phr and 25 phr, much more preferably between 1 phr and 20 phr, and advantageously between 1 phr and 15 phr.

[0161] In a second more preferred embodiment of the composition (PC1), the sum of components a) and b) is between 2 phr and 100 phr for 100 phr of component c), more preferably between 5 phr and 100 phr, much more preferably between 10 phr and 100 phr, and advantageously between 15 phr and 100 phr.

[0162] In a third more preferred embodiment of the composition (PC1), the sum of components a) and b) is between 15 phr and 100 phr for 100 phr of component c), more preferably between 17 phr and 100 phr, much more preferably between 19 phr and 100 phr, and advantageously between 21 phr and 100 phr.

[0163] In a fourth more preferred embodiment of the composition (PC1), the sum of components a) and b) is between 20 phr and 100 phr with respect to 100 phr of component c), more preferably between 30 phr and 100 phr, much more preferably between 40 phr and 100 phr, and advantageously between 50 phr and 100 phr.

[0164] In one embodiment, the composition (PC1) is a liquid. In that case, the viscosity of the composition (PC1) is between 1 mPa*s and 1000 Pa*s. The viscosity is measured at 25 °C. The viscosity is dynamic viscosity. If shear thinning is required, the dynamic viscosity value is taken at a shear rate of 1 1 / s. The viscosity is measured by a rheometer.

[0165] Preferably, the viscosity of the liquid composition (PC1) is between 5 mPa*s and 900 Pa*s at a temperature of 25°C and a shear rate of 1 1 / s, more preferably between 10 mPa*s and 800 Pa*s.

[0166] According to the present invention Multistage polymer (MP1) of composition (PC1) It has at least two groups (SA1) and (SA2) each comprising polymers (A1) and (A2) having different polymer compositions.

[0167] The multistage polymer (MP1) is preferably in the form of polymeric particles considered to be spherical particles. These particles are also referred to as core / shell particles. The first stage (SA1) forms the core and the second stage (SA2) forms the shell. Optionally, all subsequent stages form additional shells. Such a multistage polymer (MP1), also referred to as core / shell particles, is preferred.

[0168] The core / shell particles have a weight-average particle size (diameter) between 15 nm and 900 nm. Preferably, the weight-average particle size of the polymer is between 20 nm and 800 nm, more preferably between 25 nm and 600 nm, even more preferably between 30 nm and 550 nm, and 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. Polymer core / shell The particles themselves can aggregate to produce polymer powder containing a large amount of these polymer core / shell particles.

[0169] The multilayer polymer (MP1) has a multilayer structure comprising at least one stage (A) comprising a polymer (A1) having a glass transition temperature of less than 10°C and at least one stage (SA2) comprising a polymer (A2) having a glass transition temperature of more than 60°C.

[0170] In a selective modification example, the multistage polymer (MP1) is Additionally, a step (SB1) comprising a polymer (B1) having a glass transition temperature exceeding 30°C may already be included. In this optional variation, component b) of the composition (Ci) is combined with component a) of the composition of the present invention. This variation is described in more detail in the process section.

[0171] Preferably, the first of at least two stages (SA1) is the first stage, and the stage (SA2) containing the polymer (A2) is grafted onto the stage (SA1) containing the polymer (A1) or another optional intermediate layer.

[0172] In additional variations, since there may be another stage prior to stage (SA1), stage (SA1) also becomes, for example, a kind of shell on the seed.

[0173] In the first embodiment, the polymer (A1) having a glass transition temperature of less than or below 10 °C comprises at least 50 wt% of polymeric units derived from alkyl acrylates, and the unit (SA1) is the innermost layer of the multi-stage polymer (MP1) or polymer particles having a multilayer structure. In other words, the unit (SA1) containing the polymer (A1) is the core of the multi-stage polymer (MP1) or polymer particles.

[0174] Regarding the polymer (A1) of the first preferred embodimentThis is a (meth)acrylic polymer comprising at least 50 wt% of polymer units derived from acrylic monomers. Preferably 60 wt%, and more preferably 70 wt%, of the polymer (A1) is an acrylic monomer.

[0175] The acrylic monomer unit in polymer (A1) comprises a monomer selected from C1 to C18 alkyl acrylates or mixtures thereof. More preferably, the acrylic monomer in polymer (A1) comprises a monomer of C2 to C12 alkyl acrylates or a mixture thereof. Even more preferably, the acrylic monomer in polymer (A1) comprises a monomer of C2 to C8 alkyl acrylates or a mixture thereof.

[0176] As long as the polymer (A1) has a glass transition temperature of less than 10°C, the polymer (A1) may include a comonomer or comonomers capable of copolymerizing with an acrylic monomer.

[0177] The comonomer or comonomers in the polymer (A1) are preferably selected from (meth)acrylic monomers and / or vinyl monomers.

[0178] Most preferably, the acrylic or methacrylic comonomer of the polymer (A1) is selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, as long as the polymer (A1) has a glass transition temperature of less than 10°C.

[0179] In a specific embodiment, the polymer (A1) is a homopolymer of butyl acrylate.

[0180] More preferably, the glass transition temperature Tg of a polymer (A1) comprising at least 70 wt% of polymeric units derived from C2 to C8 alkyl acrylates is between -100 °C and 10 °C, much more preferably between -80 °C and 0 °C, advantageously between -80 °C and -20 °C, and more advantageously between -70 °C and -20 °C.

[0181] In a second preferred embodiment, a polymer (A1) having a glass transition temperature lower than 10°C comprises at least 50 wt% of polymer units derived from isoprene or butadiene, and unit (A) is the innermost layer of a polymer particle having a multilayer structure. In other words, a unit (SA1) containing the polymer (A1) is the core of the polymer particle.

[0182] For example, as the polymer (A1) of the core of the second embodiment, isoprene homopolymer or butadiene homopolymer, isoprene-butadiene copolymer, copolymer of isoprene and up to 98 wt% vinyl monomer, and copolymer of butadiene and up to 98 wt% vinyl monomer may be mentioned. The vinyl monomer may be styrene, alkylstyrene, acrylonitrile, alkyl (meth)acrylate, or butadiene or isoprene. In a preferred embodiment, the core is a butadiene homopolymer.

[0183] More preferably, the glass transition temperature Tg of a polymer (A1) comprising at least 50 wt% of polymeric units derived from isoprene or butadiene is between -100 °C and 10 °C, much more preferably between -90 °C and 0 °C, advantageously between -85 °C and 0 °C, and most advantageously between -80 °C and -20 °C.

[0184] In the third preferred embodiment, the polymer (A1) is a silicone rubber-based polymer. For example, the silicone rubber is polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (A1) of the second embodiment is between -150°C and 0°C, even more preferably between -145°C and -5°C, advantageously between -140°C and -15°C, and even more advantageously between -135°C and -25°C.

[0185] In relation to the polymer (A2) Copolymers and homopolymers comprising monomers having double bonds and / or vinyl monomers may be mentioned. Preferably, the polymer (A2) is a (meth)acrylic polymer and comprises more than 50 wt% of monomer units derived from a (meth)acrylic monomer and optionally a styrene comonomer, for example, a (meth)acrylic monomer which is styrene.

[0186] Preferably, the polymer (A2) comprises at least 70 wt% of a monomer selected from C1 to C12 alkyl (meth)acrylates. More preferably, the polymer (A2) comprises at least 80 wt% of a monomer C1 to C4 alkyl methacrylate and / or C1 to C8 alkyl acrylate monomer.

[0187] Most preferably, as long as the polymer (A2) has a glass transition temperature of at least 60°C, the acrylic or methacrylic monomer of the polymer (A2) is selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and mixtures thereof.

[0188] Advantageously, the polymer (A2) contains at least 70 wt% of monomer units derived from methyl methacrylate.

[0189] Preferably, the glass transition temperature Tg of the polymer (A2) is between 60°C and 150°C. The glass transition temperature of the polymer (A2) is more preferably between 80°C and 150°C, advantageously between 90°C and 150°C, and even more advantageously between 100°C and 150°C.

[0190] Preferably, the polymer (A2) of the multistage polymer (MP1) is grafted onto the polymer (A1) prepared in the previous stage.

[0191] In a specific embodiment, the polymer (A2) is cross-linked.

[0192] In one embodiment, the polymer (A2) comprises a functional comonomer. The functional copolymer is selected from acrylic acid or methacrylic acid, amides derived from these acids, such as dimethylacrylamide, 2-methoxy-ethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or methacrylate, polyethylene glycol (meth)acrylate, water-soluble vinyl monomers such as N-vinylpyrrolidone or mixtures thereof. Preferably, the polyethylene glycol group of the polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0193] In relation to the thermoplastic polymer (B1). It has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0194] The thermoplastic polymer (B1) 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, even more advantageously greater than 14,000 g / mol, and much more advantageously greater than 15,000 g / mol.

[0195] The thermoplastic polymer (B1) 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, even more advantageously less than 300,000 g / mol, much more advantageously less than 250,000 g / mol, and most advantageously less than 200,000 g / mol.

[0196] Preferably, the mass average molecular weight Mw of the polymer (B1) 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.

[0197] In a first more preferred embodiment, the mass average molecular weight Mw of the polymer (B1) is between 15,000 g / mol and 300,000 g / mol, more preferably between 15,000 g / mol and 200,000 g / mol, and even more preferably between 15,000 g / mol and 190,000 g / mol, advantageously between 15,000 g / mol and 180,000 g / mol, more advantageously between 15,000 g / mol and 160,000 g / mol, and most advantageously between 15,000 g / mol and 150,000 g / mol.

[0198] In a second more preferred embodiment, the mass average molecular weight Mw of the polymer (B1) is between 15,000 g / mol and 450,000 g / mol, more preferably between 18,000 g / mol and 400,000 g / mol, and even more preferably between 20,000 g / mol and 350,000 g / mol, advantageously between 22,000 g / mol and 300,000 g / mol, more advantageously between 25,000 g / mol and 250,000 g / mol, and most advantageously between 30,000 g / mol and 200,000 g / mol.

[0199] Preferably, the polymer (B1) is a copolymer comprising a (meth)acrylic monomer. More preferably, the polymer (B1) is a (meth)acrylic polymer. Even more preferably, the polymer (C1) comprises at least 70 wt% of a monomer selected from C1 to C12 alkyl (meth)acrylates. Advantageously, the polymer (B1) comprises at least 80 wt% of monomer C1 to C4 alkyl methacrylates and / or C1 to C8 alkyl acrylates.

[0200] Preferably, the glass transition temperature Tg of the polymer (B1) is between 30°C and 150°C. The glass transition temperature of the polymer (B1) is more preferably between 40°C and 150°C, advantageously between 45°C and 150°C, and even more advantageously between 50°C and 150°C.

[0201] Preferably, the polymer (B1) is not crosslinked.

[0202] Preferably, polymer (B1) is not grafted onto either polymer (A1) or (A2), if it is part of a multistage polymer. This means that the monomers or monomers used in the manufacture of polymer (B1) do not contain a crosslinking agent or a graft crosslinking agent. Nevertheless, it cannot be ruled out that a part of polymer (B1) is linked to the polymer of the preceding stage. This is because reactive groups from the crosslinking or grafting are still present from the preceding stage or through entanglement with the polymer chain. Polymer (B1) can be recovered at least partially by extraction with a solvent.

[0203] The mass average molecular weight Mw of polymer (B1) is measured by size exclusion chromatography (SEC). If polymer (B1) is part of a multistage polymer, it can be extracted with a solvent to measure its molecular weight; alternatively, polymer (B1) can be synthesized under the same conditions without the presence of the previous stage, thereby obtaining a "pure" polymer (B1) for measurement while avoiding the extraction step.

[0204] In one embodiment, the polymer (B1) also includes a functional comonomer.

[0205] The functional comonomer has the following formula (1).

[0206]

[0207] In the formula, R1 is selected from H or CH3, and R2 is H, or an aliphatic or aromatic radical having at least one atom that is not C or H.

[0208] Preferably, the functional monomer is selected from glycidyl (meth)acrylate, acrylic acid or methacrylic acid, amides derived from these acids, such as dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or methacrylate, and polyethylene glycol (meth)acrylate. Preferably, the polyethylene glycol group of polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0209] In a first preferred embodiment, the polymer (B1) comprises 80 wt% to 100 wt% of methyl methacrylate, preferably 80 wt% to 99.9 wt% of methyl methacrylate and 0.1 wt% to 20 wt% of C1 to C8 alkyl acrylate monomers. Advantageously, the C1 to C8 alkyl acrylate monomers are selected from methyl acrylate, ethyl acrylate, or butyl acrylate.

[0210] In a second preferred embodiment, the polymer (B1) comprises a functional monomer between 0 wt% and 50 wt%. Preferably, the (meth)acrylic polymer (B1) comprises a functional monomer between 0 wt% and 30 wt%, more preferably between 1 wt% and 30 wt%, even more preferably between 2 wt% and 30 wt%, advantageously between 3 wt% and 30 wt%, more advantageously between 5 wt% and 30 wt%, and most advantageously between 5 wt% and 30 wt%.

[0211] Preferably, the functional monomer of the second preferred embodiment is a (meth)acrylic monomer. The functional monomer has the following formula (2) or (3).

[0212]

[0213] In both of the formulas (2) and (3), R1 is selected from H or CH3; in formula (2), Y is O, and R5 is an aliphatic or aromatic radical having at least one atom other than H, or C or H; in formula (3), Y is N, and R4 and / or R3 is H or an aliphatic or aromatic radical.

[0214] 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 dimethylacrylamide, 2-methoxyethyl acrylate or methacrylate, optionally quaternized 2-aminoethyl acrylate or methacrylate, acrylate or methacrylate monomers containing phosphonate or phosphate groups, alkyl imidazolidinone (meth)acrylate, and polyethylene glycol (meth)acrylate. Preferably, the polyethylene glycol group of polyethylene glycol (meth)acrylate has a molecular weight in the range of 400 g / mol to 10,000 g / mol.

[0215] A multistage polymer (MP1) or core / shell polymer particles are obtained by a multistage process comprising at least two stages. At least components a1) and a2) of composition (PC1) are part of the multistage polymer (MP1).

[0216] Preferably, the polymer (A1) having a glass transition temperature of less than 10°C prepared during stage (SA1) is prepared before stage (SA2) or is the first stage of a multi-stage process.

[0217] Preferably, a polymer (A2) having a glass transition temperature exceeding 60°C, prepared during stage (SA2), is prepared after stage (SA1) of a multi-stage process.

[0218] In a first preferred embodiment, a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C is prepared by a process to provide polymeric particles of the polymer (B1). The weight-average particle size (diameter) of these polymer (B1) particles is between 15 nm and 900 nm. Preferably, the weight-average particle size of the polymer (B1) particles is between 20 nm and 800 nm, more preferably between 25 nm and 600 nm, even more preferably between 30 nm and 550 nm, and 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. The polymer particles themselves may aggregate together with multistage polymer (MP1) particles to provide a polymer powder containing all of such polymeric particles. This yields a composition (Ci) containing components a) and b).

[0219] In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30°C is an outer layer of polymer particles having a multistage structure, i.e., a multistage polymer (MP1).

[0220] A polymer (B1) having a glass transition temperature exceeding 30°C, prepared during step (SB1), is prepared after step (SA2) of a multi-stage process. There may be an additional intermediate step between step (SA1) and step (SA2) and / or between step (SA2) and step (SB1). This also yields a composition (Ci) comprising components a) and b).

[0221] At least a portion of the polymer (B1) may be grafted onto the polymer prepared in the previous layer or entangled with the polymer chains of the previous layer. In the case where there are only two layers (SA1) and (SA2) each containing polymers (A1) and (A2), a portion of the polymer (B1) may be grafted onto the polymer (A1) or entangled with the chains of the polymer (A2).

[0222] In one embodiment, at least 50 wt% of the polymer (B1) is grafted.

[0223] In another embodiment, less than 50 wt% of the polymer (B1) is grafted.

[0224] In another embodiment, less than 20 wt% of the polymer (B1) is grafted.

[0225] In another embodiment, between 5 wt% and 60 wt% of the polymer (B1) is grafted.

[0226] In another embodiment, less than 5 wt% of the polymer (B1) is grafted.

[0227] In another embodiment, 0 wt% of the polymer (B1) is grafted.

[0228] The grafting ratio can be determined by gravimetric measurement before and after extraction to measure the amount of polymer (B1) extracted into a solvent and the amount of non-grafted.

[0229] Polymers (B1) and (A2) are not the same polymer, even though their compositions may be very similar and some of their features overlap. The essential difference is that polymer (A2) is always part of the multistage polymer (MP1). As previously described, polymer (B1) may also be part of the multistage polymer, but there are embodiments in which polymer (B1) is not spontaneously grafted onto the multistage polymer (MP1).

[0230] The glass transition temperature Tg of each polymer can be estimated by dynamic methods, for example, as thermomechanical analysis.

[0231] To obtain samples of each polymer (A1) and (A2), they can be prepared individually without a multi-stage process so that the glass transition temperature Tg of each polymer at each stage can be more easily estimated and measured individually. Polymer (B1) can be extracted to more easily estimate and measure the glass transition temperature Tg.

[0232] In relation to the component (LC1) of the composition (PC1), It is preferably a liquid.

[0233] The viscosity is between 0.5 mPa*s and 10 Pa*s at 25 °C. Preferably, the viscosity is between 1 mPa*s and 10 Pa*s, more preferably between 10 mPa*s and 10 Pa*s, even more preferably between 50 mPa*s and 10 Pa*s, and advantageously between 100 mPa*s and 10 Pa*s. The viscosity of (LC1) is the dynamic viscosity. If shear thinning is required, the dynamic viscosity value is taken at a shear rate of 1 1 / s. The viscosity is measured by a rheometer.

[0234] The component (LC1) may also be a mixture of several compounds, one of which is a compound (C1) having at least two polymerizable groups (PG1) and (PG2).

[0235] The component (LC1) or the liquid component (LC1) may further comprise a monomer (M1) or a mixture of monomers (Mx). The monomer (M1) or the mixture of monomers (Mx) comprises at least one carbon double bond.

[0236] Monomer (M1) may be selected from (meth)acrylic monomers, allyl monomers, or styrene-based monomers or mixtures thereof for (Mx).

[0237] In the modified monomer, (M1) can be selected from (meth)acrylic monomers, allyl monomers, or mixtures thereof for (Mx).

[0238] Preferably, the monomer (M1) is selected from styrene, α-methylstyrene, vinyltoluene, divinylbenzene, alkyl (meth)acrylates having an alkyl group having 1 to 10 carbon atoms, and hydroxyethyl (meth)acrylates, and difunctional (meth)acrylates such as butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and di(meth)acrylates having a glycol structure, and polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate.

[0239] In a first more preferred embodiment, the monomer (M1) is selected from alkyl (meth)acrylates having an alkyl group having 1 to 10 carbon atoms, and hydroxyethyl (meth)acrylates, and difunctional (meth)acrylates such as butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and di(meth)acrylates having a glycol structure, and polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate.

[0240] In a second more preferred embodiment, the monomer (M1) for (Mx) or a mixture thereof does not contain styrene.

[0241] In a third more preferred embodiment, the monomer (M1) for (Mx) or a mixture thereof does not include a styrene-based monomer.

[0242] The two polymerizable groups (PG1) and (PG2) of compound (C1) are preferably carbon double bonds.

[0243] The two polymerizable groups (PG1) and (PG2) of compound (C1) are more preferably α,β-unsaturated carbonyl groups.

[0244] The two polymerizable groups (PG1) and (PG2) of compound (C1) may be selected from acrylate groups, metasylate groups, or condensation products including maleic acid, itaconic acid, or fumaric acid.

[0245] Preferably, compound (C1) is a vinyl ester or an unsaturated polyester.

[0246] In a first more preferred embodiment, compound (C1) is a vinyl ester. A vinyl ester is typically a reaction product obtained by reacting a polyepoxide (e.g., epoxy resin) with an ethylenically unsaturated double-bond-containing monocarboxylic acid, such as (meth)acrylic acid, and has a backbone in its main chain identical to that of a polyepoxide and is curable because unsaturated double bonds are present in the molecule. The backbone is preferably one or more types of backbones selected from the group consisting of backbones of the types of bisphenol A, bisphenol F, phenol novolac, cresol novolac, hydrogenated bisphenol A, hydrogenated bisphenol F, aliphatic esters, aliphatic ethers, and aromatic esters.

[0247] In a second more preferred embodiment, compound (C1) is an unsaturated polyester. The unsaturated polyester is a reaction product of at least one dibasic organic acid or its anhydride and at least one polyhydric alcohol.

[0248] Optionally, component (LC1) may include an initiator for radical polymerization. For example, an organic peroxide may be added.

[0249] The present invention also relates to a method for manufacturing a composition (PC1).

[0250] Preparation of the composition (PC1) according to the present invention In relation to a first preferred method for , this is

[0251] i) a step of providing a composition (Ci).

[0252] a) Multistage polymer (MP1) including the following

[0253] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0254] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0255] b) providing a composition (Ci) comprising a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, such that component b) corresponds to up to 40 wt% of the composition based on a) and b); and

[0256] ii) a step of mixing composition (Ci) with composition (Ciia) comprising at least one other component or compound present in composition (PC1); and

[0257] iii) optionally includes the step of mixing the composition obtained in step ii) with other components or compounds present in the composition (PC1) that has not yet been added in step ii).

[0258] The composition (Cia) is

[0259] - Polyepoxide or

[0260] - Organic acids and polyepoxides having double bonds or

[0261] - Vinyl ester or

[0262] - Vinyl ester and monomer (M1) or mixture of monomers (Mx)

[0263] - Unsaturated polyester or

[0264] - It may include an unsaturated polyester and a monomer (M1) or a mixture of monomers (Mx).

[0265] Other components or compounds optionally added in step iii) are monomers (M1) or mixtures of monomers (Mx) or initiators for polymerization. Monomers (M1) or mixtures of monomers (Mx) are added in step iii) if they were not added in step ii because they were not present in the composition (Ciia), or additional monomers (M1) or mixtures of monomers (Mx) are added in step iii) if they were present in the composition (Ciia) of step ii).

[0266] In a first preferred embodiment, the composition (Ciia) comprises a polyepoxide.

[0267] In a second preferred embodiment, the composition (Ciia) comprises an organic acid having a double bond and a polyepoxide.

[0268] In a third preferred embodiment, the composition (Ciia) comprises a vinyl ester.

[0269] In a fourth preferred embodiment, the composition (Ciia) comprises a vinyl ester and a monomer (M1) or a mixture of monomers (Mx).

[0270] In a fifth preferred embodiment, the composition (Ciia) comprises an unsaturated polyester.

[0271] In a sixth preferred embodiment, the composition (Ciia) comprises an unsaturated polyester and a monomer (M1) or a mixture of monomers (Mx).

[0272] Steps ii) and iii) of the first preferred method for preparing composition (PC1) will preferably add and form a compound (C1) having at least two polymerizable groups (PG1) and (PG2) when steps i) to iii) are performed in the indicated order.

[0273] In relation to a second preferred method for preparing a composition (PC1) according to the present invention, This is

[0274] i) a step of providing a composition (Ci).

[0275] a) Multistage polymer (MP1) including the following

[0276] a1) a single stage (A1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0277] a2) a single stage (A2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0278] b) providing a composition (Ci) comprising a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw of 10,000 g / mol to 500,000 g / mol, such that component b) corresponds to up to 40 wt% of the composition based on a) and b), and

[0279] ii) providing a composition (Ciib) comprising a precursor or precursors for c) a component (LC1) or compound (C1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2),

[0280] iii) includes the step of mixing the composition from i) with the composition from ii).

[0281] Composition (Ciib) is

[0282] - Polyepoxide or

[0283] - Organic acids and polyepoxides having double bonds or

[0284] - Vinyl ester or

[0285] - Vinyl ester and monomer (M1) or mixture of monomers (Mx)

[0286] - Unsaturated polyester or

[0287] - It may include an unsaturated polyester and a monomer (M1) or a mixture of monomers (Mx).

[0288] A second preferred method for preparing a composition (PC1) may also include an optional additional step iv) of adding other components or compounds.

[0289] Preferably, steps i) to iii) are performed in the indicated order.

[0290] In a first preferred embodiment, the composition (Ciib) comprises a polyepoxide.

[0291] In a second preferred embodiment, the composition (Ciib) comprises an organic acid having a double bond and a polyepoxide.

[0292] In a third preferred embodiment, the composition (Ciib) comprises a vinyl ester.

[0293] In a fourth preferred embodiment, the composition (Ciib) comprises a vinyl ester and a monomer (M1) or a mixture of monomers (Mx).

[0294] In a fifth preferred embodiment, the composition (Ciib) comprises an unsaturated polyester.

[0295] In a sixth preferred embodiment, the composition (Ciib) comprises an unsaturated polyester and a monomer (M1) or a mixture of monomers (Mx).

[0296] In relation to a third preferred method for a method of preparing a composition (PC1) according to the present invention, This is

[0297] i) a step of providing a polymeric composition

[0298] a) Multistage polymer (MP1) including the following

[0299] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0300] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0301] b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C,

[0302] ii) a step of providing a c) component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2),

[0303] ii) includes the step of mixing ingredients a), b), and c).

[0304] Compound (C1) is a polyepoxide, vinyl ester, or unsaturated polyester.

[0305] In the first preferred embodiment, compound (C1) is a polyepoxide.

[0306] In the second preferred embodiment, compound (C1) is a vinyl ester.

[0307] In the third preferred embodiment, compound (C1) is an unsaturated polyester.

[0308] In a more preferred embodiment, compound (C1) is a vinyl ester.

[0309] Mixing of each component of all embodiments may be achieved by stirring. Stirring is performed using a stirrer.

[0310] An important condition of the mixing step is temperature. Preferably, the temperature of the mixing step is between 0°C and 50°C, more preferably between 5°C and 45°C, even more preferably between 10°C and 40°C, most preferably between 10°C and 35°C, and advantageously between 10°C and 30°C.

[0311] The time required for the mixing step is shorter compared to a composition that does not contain a thermoplastic polymer (B1) with a glass transition temperature of at least 30°C.

[0312] The mixing time is preferably less than 120 minutes and advantageously less than 90 minutes (laboratory scale). This parameter is affected by the amount used. For the same proportion of ingredients, the time may be shorter if a smaller absolute amount is used for each quantity.

[0313] A different process for preparing the composition (PC1) preferably uses a multistage polymer (MP1) in the form of a polymer powder POW1 having a total intrusion volume of at least 1.2 ml / g when measured by mercury porosity measurement or a composition.

[0314] The porosity of polymer powder POW1 is expressed as the total intrusion volume of mercury or total cumulative intrusion (cumulative intrusion volume) per mass (g) of polymer powder POW1 (in milliliters (ml)). This is measured according to the ISO 15901-1 standard. Evaluation of mercury porosity and porosity of solid materials by mercury porosity and gas adsorption - Part 1: Mercury porosity. Total cumulative intrusion is considered until the pore size diameter becomes 0.005 μm.

[0315] The polymer powder POW1 has a total penetration volume or total cumulative penetration of up to 10 ml / g. Preferably, the polymer powder POW1 of the present invention has a total penetration volume or total cumulative penetration between 1.2 ml / g and 10 ml / g.

[0316] Incremental intrusion (incremental intrusion volume) is the volume between two specific pore diameters. Incremental intrusion can also be expressed as an absolute value in ml / g units, or as a relative percentage of the total intrusion volume or total cumulative intrusion. Preferably, polymer powder POW1 has a relative incremental intrusion of up to 85% for pore sizes greater than 10 µm (greater than 10 µm). Preferably, polymer powder POW1 has a cumulative intrusion of at least 0.9 ml / g for pore sizes greater than 10 µm (greater than 10 µm).

[0317] The present invention also relates to the use of a composition (PC1). The composition (PC1) is used to produce a toughened polymeric composition (PC2).

[0318] A polymeric composition (PC2) is prepared by polymerizing compound (C1) with at least two polymerizable groups (PG1) and (PG2) of component (LC1). After polymerizing compound (C1), a polymer (P2) is obtained.

[0319] The present invention relates to a polymeric composition (PC2), wherein

[0320] a) Multistage polymer (MP1) including the following

[0321] a1) A single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C,

[0322] a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60 °C, and

[0323] b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30 °C, and

[0324] c) comprising a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2), and

[0325] Polymer (B1) is a polymeric composition (PC2) characterized by having a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and component b) corresponds to a maximum of 40 wt% of a composition based only on a) and b), and the sum of components a) and b) is between 0.5 and 100 phr for 100 phr of component c).

[0326] The polymer (P2) is a thermosetting polymer.

[0327] The polymeric composition (PC2) may optionally include other components as fibers or mineral fillers. Preferably, the other components of the polymeric composition (PC2) are selected from fibers or mineral fillers. In that case, the polymeric composition (PC2) is a polymeric composite.

[0328] The polymeric composition (PC2) can be used as an adhesive, and more preferably as a structural adhesive or a polymeric composite; or can be used in applications such as coatings, decorative castings, flooring, polymeric concrete, solid surfaces, artificial marble, or in marine applications, architecture and construction, and wind energy applications.

[0329] [Evaluation Method]

[0330] glass transition temperature

[0331] The glass transition (Tg) of the polymer is measured using equipment capable of performing thermomechanical analysis. The RDAII "RHEOMETRICS DYNAMIC ANALYSER" proposed by Rheometrics Company was used. Thermomechanical analysis accurately measures the viscoelastic change of a sample as a function of applied temperature, strain, or deformation. The strain is 0.1%. The temperature range is between -125 °C and 150 °C, and the temperature is varied at a rate of 2 °C / min. During the controlled temperature change program, the device continuously records sample deformation while keeping the strain constant.

[0332] The result is obtained by drawing as a function of temperature, elastic modulus (G'), loss modulus, and tan delta. Tg is the highest temperature value read from the tan delta curve when the derived tan delta is equal to 0.

[0333] molecular weight

[0334] The mass average molecular weight (Mw) of the polymer 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. Modified silica is used for the chromatography column. The flow rate is 1 ml / min, and a refractive index detector is used.

[0335] Particle size analysis

[0336] After multistage polymerization, the particle size of the primary particles is measured by a Zetasizer.

[0337] The particle size of the polymer powder after recovery is measured using a Malvern Mastersizer 3000 from MALVERN.

[0338] To estimate the weight-average powder particle size, particle size distribution, and the ratio of fine particles, a Malvern Mastersizer 3000 device equipped with a 300 mm lens measuring in the 0.5-880 µm range is used.

[0339] porosity

[0340] The porosity of polymer powder POW1 is expressed as the total intrusion volume or total cumulative intrusion (cumulative intrusion volume) of mercury per mass (g) of polymer powder POW1 (in milliliters (ml)). This is measured according to the ISO 15901-1 standard. Evaluation of mercury porosity, pore size distribution, and porosity of solid materials by mercury porosity and gas adsorption - Part 1: Mercury Porosity.

[0341] [Example]

[0342] raw material:

[0343] Commercial resins ATLAC430, ATLAC590, and ATLAC P600 from Aliancys are used as component (LC1).

[0344] The multi-stage polymer (MP1) is prepared according to the following synthesis: Stage 1 (SA1) - Polymerization of polymer type (A1):In a 20-liter high-pressure reactor, 116.5 parts of deionized water, 0.1 parts of potassium salt of beef tallow fatty acid emulsifier, 21.9 parts of 1,3-butadiene, 0.1 parts of t-dodecyl mercaptan, and 0.1 parts of p-menthan hydroperoxide were charged as the initial kettle charge. The solution was heated to 43 °C while shaking, and at that time, a redox catalyst solution (4.5 parts water, 0.3 parts sodium tetrapyrophosphate, 0.004 parts ferrous sulfate, and 0.3 parts dextrose) was charged to effectively initiate polymerization. Then, the solution was further heated to 56 °C and maintained at this temperature for a period of 3 hours. Three hours after the start of polymerization, a second monomer filler (77.8 parts BD, 0.2 parts t-dodecyl mercaptan), half of the additional emulsifier and reducing agent filler (30.4 parts deionized water, 2.8 parts potassium salt of beef tallow fatty acid emulsifier, 0.5 parts dextrose), and an additional initiator (0.8 parts p-menthan hydroperoxide) were added sequentially over 8 hours. After the completion of the addition of the second monomer, the remaining emulsifier and reducing agent filler + initiator were added sequentially over an additional 5 hours. Thirteen hours after the start of polymerization, the solution was heated to 68°C and reacted until at least 20 hours had passed since the start of polymerization to produce polybutadiene rubber latex, R1. The resulting polybutadiene rubber latex (A1) contained 38% solids and had a weight-average particle size of about 160 nm.

[0345] Stage 2 (SA2) - Polymerization of polymer type (A2): 75.0 parts of polybutadiene rubber latex R1, 37.6 parts of deionized water, and 0.1 parts of sodium formaldehyde sulfoxylate were filled into a 3.9-liter reactor based on solid content. The solution was shaken, purged with nitrogen, and heated to 77°C. When the solution reached 77°C, a mixture of 22.6 parts methyl methacrylate, 1.4 parts divinylbenzene, and 0.1 parts t-butyl hydroperoxide initiator was added continuously over 70 minutes, followed by a holding period of 80 minutes. 30 minutes after the start of the holding period, 0.1 parts of sodium formaldehyde sulfoxylate and 0.1 parts t-butyl hydroperoxide were added to the reactor all at once. After the 80-minute holding period, the stabilizing fluid was added to the graft copolymer latex. 3.2 parts deionized water (based on the mass of the graft copolymer), 0.1 parts oleic acid, 0.1 parts potassium hydroxide, and 0.9 parts octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate were mixed to prepare a stabilizing fluid. The resulting core-shell polymer (A1+A2) had a weight-average particle size of approximately 180 nm. The final multistage polymer (MP1) was then recovered, and the polymer composition was coagulated and dried to provide a core / shell-1 powder.

[0346] According to a preferred embodiment, a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C is prepared as an additional stage on a multistage polymer (MP1)—polymerization of polymer composition type C1.

[0347] Synthesis of polymer (B1): Semi-continuous process: 10,000 g of core-shell polymer (A+B) still dispersed in deionized water, 0.01 g of FeSO4 and 0.032 g of ethylenediaminetetraacetic acid, sodium salt (dissolved in 10 g of deionized water), 3.15 g of sodium formaldehyde sulfoxylate dissolved in 110 g of deionized water, and 21.33 g of beef tallow fatty acid emulsifier potassium salt (dissolved in 139.44 g of water) were charged into a reactor while stirring, and the mixture was stirred until the added raw materials, excluding the core-shell polymer, were completely dissolved. Three consecutive vacuum-nitrogen purgings were performed, and the reactor was left under a slight vacuum. Next, the reactor was heated. Simultaneously, a mixture containing 1066.7 g of methyl methacrylate and 10.67 g of n-octyl mercaptan was nitrogen-degassed for 30 minutes. The reactor was heated to 63°C and maintained at that temperature. Next, the monomer mixture was introduced into the reactor using a pump within 180 minutes. In parallel, a solution of 5.33 g of ter-butyl hydroperoxide (dissolved in 100 g of deionized water) was introduced (at the same addition time). The line was rinsed with 50 g and 20 g of water. Then, the reaction mixture was heated to 80°C and subsequently allowed to undergo polymerization for 60 minutes after the end of monomer addition. The reactor was cooled to 30°C. The mass average molecular weight of copolymer B1 is M w = 28,000g / mol.

[0348] Then, a final polymer composition consisting of a multistage polymer (MP1) and a polymer (B1) is recovered, and the polymer composition is solidified and dried to provide a core / shell-2 powder.

[0349] Mixing of ingredients: 100 g of ingredient (LC1) is placed in an aluminum container. Various amounts of multistage polymer (MP1), which may or may not contain a thermoplastic polymer (B1), are added in powder form. Stirring is performed at a speed of 150 to 200 rpm for 60 minutes.

[0350] Rheology: The viscosity of the composition is measured using an Anton Parr Rheometer. A cone plate geometry is used at 25 °C (Module CP-50).

[0351] Dispersion Test: 5 wt% of component MP1 or MP1 + B1 in powder form is added to 95% of component LC1. Under standard conditions, mixing is applied using a dispersion blade at 100 to 200 RPM. After 60 minutes, the dispersion is evaluated as a function of the presence of undispersed powder particles (small grains), aggregation of powder particles, single-phase or two-phase dispersion, and the presence of bubbles. If dispersion is poor, additional mixing is applied at 500 RPM for 60 minutes. The same procedure is performed for amounts of component MP1 or MP1 + B1.

[0352] Sample preparation for manufacturing parts for mechanical testing: A standard BPO / amine system (benzoyl peroxide / dimethylaniline) curing agent was used. A dosage was selected to obtain a gel time of about 30 minutes at room temperature.

[0353] Mechanical evaluation: Tensile properties such as elongation at break, tensile strength, and Young's modulus were evaluated using a ZWICK Z050 TH AllroundLine equipped with a 50kN cell according to ISO 527 specifications.

[0354] Lab shear evaluation: Evaluated using a ZWICK Z050 TH AllroundLine equipped with a 50kN cell according to EN 1465 specifications. An aluminum plate was used as the substrate.

[0355] Example of composition: The composition consists of the following compounds:

[0356] Table 1: Composition and dispersion results of ATLAC resin

[0357]

[0358] A composition based on the present invention (compound b, including a thermoplastic polymer (B1)) can be easily and quickly prepared for different compounds c). The resulting dispersion is inventively homogeneous.

[0359] Table 2: Mechanical properties results of polymerized ATLAC 430

[0360]

[0361] In Table 2, a significant increase in toughness is observed for the polymer obtained from the composition according to the present invention. Crack growth resistance K 1c and fracture toughness G 1c As shown here, destructive toughness increases significantly.

Claims

Claim 1 As a composition (PC1), the composition comprises a) a multistage polymer (MP1) comprising a1) a single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C, and b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C, and c) a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2), wherein the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the compound (C1) is a vinyl ester, and component b) corresponds to a maximum of 40 wt% of the composition based only on a) and b), and the sum of components a) and b) is 0.5 phr per 100 phr of component c). A composition (PC1) characterized by being between 100 phr. Claim 2 A composition (PC1) according to claim 1, wherein the polymer (B1) is a (meth)acrylic polymer. Claim 3 A composition (PC1) according to claim 1, wherein the polymer (B1) comprises at least 70 wt% of a monomer selected from C1 to C12 alkyl (meth)acrylates. Claim 4 In claim 1, the polymer (B1) comprises a functional comonomer of formula (1). A composition (PC1) characterized in that, in the formula, R1 is selected from H or CH3, and R2 is H or an aliphatic or aromatic radical having at least one atom that is not C or H. Claim 5 A composition (PC1) according to claim 1, characterized in that the component (LC1) further comprises a monomer (M1) or a mixture of monomers (Mx). Claim 6 A composition (PC1) according to claim 1, characterized in that two polymerizable groups (PG1) and (PG2) of the compound (C1) are α,β-unsaturated carbonyl groups. Claim 7 A composition (PC1) according to claim 1, characterized in that two polymerizable groups (PG1) and (PG2) of the compound (C1) are selected from acrylate groups or methacrylate groups. Claim 8 delete Claim 9 A method for preparing a composition (PC1) according to any one of claims 1 to 7, comprising: i) a step of providing a composition (Ci), wherein a) a multistage polymer (MP1) comprising a1) a polymer (A1) having a glass transition temperature of less than 10°C, a2) a polymer (A2) having a glass transition temperature of at least 60°C, and b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, wherein component b) corresponds to up to 40 wt% of the composition based on a) and b); and ii) a step of mixing the composition (Ci) with a composition (Ciia) comprising at least one other component or compound present in the composition (PC1); A method for preparing a composition (PC1), comprising: iii) optionally mixing the composition obtained in step ii) with another component or compound present in the composition (PC1) that has not yet been added in step ii). Claim 10 A method for preparing a composition (PC1) according to any one of claims 1 to 7, comprising: i) a step of providing a polymeric composition (Ci), wherein a) a multistage polymer (MP1) comprising a1) a polymer (A1) having a glass transition temperature of less than 10°C, a2) a polymer (A2) having a glass transition temperature of at least 60°C, and b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, wherein component b) corresponds to up to 40 wt% of the composition based on a) and b); and c) a component comprising a compound (C1) which is a vinyl ester, as a compound having at least two polymerizable groups (PG1) and (PG2). A method for preparing a composition (PC1), comprising the steps of: providing a composition (Ciib) comprising (LC1); iii) mixing the composition (Ci) and (Ciib) comprising components a), b), and c) in a ratio such that the sum of components a) and b) is between 0.5 phr and 100 phr for 100 phr of component c). Claim 11 A method for reducing the preparation time of a composition (PC1), comprising: i) a step of providing a polymeric composition (Ci), wherein a) a multistage polymer (MP1) comprising a1) a polymer (A1) having a glass transition temperature of less than 10°C, a2) a polymer (A2) having a glass transition temperature of at least 60°C, and b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C and a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, wherein component b) corresponds to up to 40 wt% of the composition based on a) and b); and c) a composition comprising a component (LC1) comprising a compound (C1) which is a vinyl ester, as a compound having at least two polymerizable groups (PG1) and (PG2). A method for reducing the preparation time of a composition (PC1), comprising the steps of: providing (Ciib); iii) mixing a composition (Ci) and (Ciib) containing components a), b), and c) in a ratio such that the sum of components a) and b) is between 0.5 and 100 phr for 100 phr of component c). Claim 12 A method for preparing a composition (PC1) according to claim 9, wherein the composition (Ciia) comprises a vinyl ester or a vinyl ester and a monomer (M1) or a mixture of monomers (Mx). Claim 13 A method for preparing a composition (PC1) according to claim 10, wherein the composition (Ciib) comprises a vinyl ester or a vinyl ester and a monomer (M1) or a mixture of monomers (Mx). Claim 14 A method for reducing the preparation time of a composition (PC1), characterized in that, in claim 11, the composition (Ciib) comprises a vinyl ester or a vinyl ester and a monomer (M1) or a mixture of monomers (Mx). Claim 15 A method for preparing a composition (PC1) according to any one of claims 1 to 7, comprising: i) a step of providing a polymeric composition, wherein a) a multistage polymer (MP1) comprising: a1) a single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C; a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C; and b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C; ii) a step of providing a component (LC1) comprising a compound (C1) having at least two polymerizable groups (PG1) and (PG2); and ii) a step of mixing the components a), b), and c). Claim 16 A method for preparing a composition (PC1), wherein, in claim 9, the provided multistage polymer (MP1) is in the form of a polymer powder having a total intrusion volume of at least 1.2 ml / g as measured by mercury porosity measurement. Claim 17 A method for preparing a composition (PC1) according to claim 10, wherein the provided multistage polymer (MP1) is in the form of a polymer powder having a total intrusion volume of at least 1.2 ml / g as measured by mercury porosity measurement. Claim 18 A method for reducing the preparation time of a composition (PC1), characterized in that, in claim 11, the provided multistage polymer (MP1) is in the form of a polymer powder having a total intrusion volume of at least 1.2 ml / g as measured by mercury porosity measurement. Claim 19 A method for preparing a composition (PC1) according to claim 15, wherein the provided multistage polymer (MP1) is in the form of a polymer powder having a total intrusion volume of at least 1.2 ml / g as measured by mercury porosity measurement. Claim 20 A composition (PC1) used to produce an impact-modified polymeric composition (PC2) according to any one of claims 1 to 7. Claim 21 Polymeric composition (PC2) As comprising: a) a multistage polymer (MP1) comprising a1) a single stage (SA1) comprising a polymer (A1) having a glass transition temperature of less than 10°C, a2) a single stage (SA2) comprising a polymer (A2) having a glass transition temperature of at least 60°C, and b) a thermoplastic polymer (B1) having a glass transition temperature of at least 30°C, and c) a polymer (P2) comprising units from a compound (C1) having at least two polymerizable groups (PG1) and (PG2), wherein the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol and the compound (C1) is a vinyl ester, and component b) corresponds to up to 40 wt% of a composition based only on a) and b), and the sum of components a) and b) is 0.5 phr for every 100 phr of component c). Polymeric composition (PC2) characterized by being between 100 phr. Claim 22 In claim 21, a polymeric composition (PC2) used as an adhesive, or as a structural adhesive, or as a polymeric composite; or in applications such as coatings, decorative castings, flooring, polymeric concrete, solid surfaces, artificial marble, or in marine applications, architecture and construction, or wind energy applications. Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 delete Claim 31 delete Claim 32 delete Claim 33 delete Claim 34 delete Claim 35 delete Claim 36 delete Claim 37 delete Claim 38 delete Claim 39 delete Claim 40 delete Claim 41 delete Claim 42 delete Claim 43 delete Claim 44 delete Claim 45 delete Claim 46 delete Claim 47 delete Claim 48 delete Claim 49 delete Claim 50 delete Claim 51 delete Claim 52 delete

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