Multilayer polymer, method for preparing the same, composition containing the same, and use thereof

Abstract

The present invention relates to compositions comprising multi-stage polymers, methods for preparing the same, compositions comprising the same, and uses thereof. In particular, the present invention relates to compositions in the form of polymer powders comprising simple multi-stage polymers in the form of polymer particles produced by a multi-stage method. More specifically, the present invention relates to polymer compositions in the form of porous polymer powders comprising polymer particles produced by a two-stage multi-stage method and containing an alicyclic hydrocarbon group (meth)acrylic copolymer as an outer shell, methods for preparing the same, uses thereof, and compositions and articles comprising the same.

Description

Technical Field

[0001] [Technical Field of the Invention] The present invention relates to a composition containing a multi-stage polymer, a method for preparing the same, a composition containing the same, and its use.

[0002] In particular, the present invention relates to a composition in the form of a polymer powder containing a simple multi-stage polymer in the form of polymer particles produced by a multi-stage method.

[0003] More specifically, the present invention relates to a polymer composition in the form of a porous polymer powder containing polymer particles produced by a multi-stage method including two stages and containing an (meth)acrylic copolymer containing an alicyclic hydrocarbon group as an outer shell, a method for preparing the same, its use, and a composition and an article containing the same.

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

[0005] One type of polymer additive is a processing aid, and another type is a polymer impact modifier.

[0006] Polymer impact modifiers can be in the form of polymer particles. Usually, these polymer impact modifiers are in the form of core-shell particles produced by a multi-stage method, and at least one stage contains a rubber-like polymer. Then, these particles are incorporated into a polymer or a polymer composition to increase their impact resistance. The polymer or polymer composition may be thermosetting or thermoplastic.

[0007] Thermosetting polymers consist of a crosslinked three-dimensional structure. Crosslinking is achieved by curing reactive groups within a so-called prepolymer. For example, curing can be achieved by heating polymer chains or a prepolymer to permanently crosslink and cure the material.

[0008] Thermoplastic polymers typically consist of linear or branched polymers that are not crosslinked. These may be slightly crosslinked, insofar as they are deformable by heat. However, these aforementioned core-shell particles are not easy to disperse in all kinds of resins or polymers or polymer precursors, particularly liquid epoxy resins or liquid monomers, or other liquid polymer precursors, nor are they dispersed quickly.

[0009] To achieve satisfactory impact performance in the final polymer composition, good, uniform, and rapid dispersion is necessary. To shorten process time and obtain a simpler and more concise process, easy dispersion preparation and rapid dispersion time are also required.

[0010] An object of the present invention is to propose a polymer composition that can be rapidly and easily dispersed in liquid resins, such as epoxy resins or (meth)acrylic monomers, respectively, including precursors of thermosetting polymers or thermoplastic polymers.

[0011] An object of the present invention is to propose a polymer composition in the form of a polymer powder that can be rapidly and easily dispersed in liquid resins, such as epoxy resins or (meth)acrylic monomers, respectively, including precursors of thermosetting polymers or thermoplastic polymers.

[0012] A further object of the present invention is to propose a polymer composition in the form of a dry polymer powder that can be easily dispersed, particularly in low-polarity liquid resins or low-polarity (meth)acrylic monomers.

[0013] Another object of the present invention is to propose a multi-stage polymer composition in the form of a dry polymer powder that can be easily dispersed, particularly in low-polarity liquid resins or low-polarity (meth)acrylic monomers.

[0014] A further object of the present invention is to propose a multi-stage polymer composition in the form of a dry polymer powder that can be easily dispersed in a reactive epoxy resin, polyester resin, or (meth)acrylic resin / polymer or liquid monomer or resin.

[0015] Another object of the present invention is to propose a simplified method for producing multi-stage polymer compositions in the form of polymer powders that can be easily dispersed in reactive epoxy resins, polyester resins or (meth)acrylic resins / polymers or liquid monomers or resins, particularly low-polarity liquid resins or low-polarity (meth)acrylic monomers.

[0016] A further object of the present invention is the use of a polymer composition in the form of a polymer powder for preparing a liquid composition comprising a precursor of a thermosetting polymer or a thermoplastic polymer.

[0017] Another objective is to reduce the time required to disperse the polymer powder in such a liquid composition. [Background technology]

[0018] [Background of the Invention] Prior Art International Publication No. 2016 / 102666 discloses a composition containing a multi-stage polymer and a method for preparing the same. The composition also includes a (meth)acrylic polymer having a mass-average molecular weight of less than 100,000 g / mol. The (meth)acrylic polymer may contain functional monomer units.

[0019] International Publication No. 2016 / 102682 discloses a multi-stage polymer composition and a method for preparing the same. The multi-stage polymer includes a final stage comprising a (meth)acrylic polymer having a mass-average molecular weight of less than 100,000 g / mol. The (meth)acrylic polymer may contain functional monomer units.

[0020] International Publication No. 2019 / 012052 discloses a composition containing a multi-stage polymer and a method for preparing the same. The composition also includes a (meth)acrylic polymer having a mass-average molecular weight between 100,000 g / mol and 1,000,000 g / mol. The (meth)acrylic polymer may contain functional monomer units.

[0021] Patent application PCT / EP2022 / 087285 discloses a composition comprising a multi-stage polymer composition and a method for preparing the same. The multi-stage polymer comprises two shells, each containing monomer units comprising alicyclic hydrocarbon groups having 3 to 20 carbon atoms, or both comonomers having a Hansen solubility parameter δ p <10MPa 1 / 2 Polymerized comonomers (Mc b1 ) and (Mc c1 ) Contains monomer units from each.

[0022] U.S. Patent Application Publication No. 2022 / 073725 discloses a curable resin composition comprising core-shell type rubber particles and a radically polymerizable compound. The core-shell type rubber particles include a shell layer comprising a polymer having alicyclic hydrocarbon groups.

[0023] No prior art document discloses a composition comprising a simple multi-stage polymer having only one shell on a rubbery polymer, wherein the shell polymer comprises monomer units having alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and more particularly, a shell polymer containing less than 50% by weight of monomer units having alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and more particularly, a powder form having a specific porosity, being grafted, and having an extractable portion. [Overview of the project]

[0024] [Brief description of the invention] Surprisingly, the polymer composition (PC1) is a) Polymers having a glass transition temperature of less than 10°C (A1), b) A polymer (B1) having a glass transition temperature of at least 60°C, comprising at least 10% by weight and up to 40% by weight of a composition based solely on a) and b). Includes, Components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1), and polymer (B1) has a mass-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol. It has been found that a polymer composition (PC1) characterized in that polymer (B1) contains polymer monomer units having alicyclic hydrocarbon groups with 3 to 20 carbon atoms is easily dispersible in a low-polarity liquid composition and yields a liquid composition having lower viscosity compared to a liquid composition containing a polymer composition that does not contain monomer units having alicyclic hydrocarbon groups with 3 to 20 carbon atoms, or compared to a liquid composition containing a polymer composition that contains two or more steps or layers containing monomer units having alicyclic hydrocarbon groups with 3 to 20 carbon atoms.

[0025] Surprisingly, a method for producing a polymer composition (PC1) in the form of a polymer powder, a) Monomer or monomer mixture (A m A step of polymerizing by emulsion polymerization of ) to obtain one layer of step (A) containing a polymer (A1) having a glass transition temperature of less than 10°C; b) Monomer or monomer mixture (B m A step of polymerizing by emulsion polymerization of ) to obtain a layer of step (B) containing a polymer (B1) having a glass transition temperature of at least 60°C; d) A step of agglomerating the composition obtained in steps a) to b). Includes, The polymer (B1) accounts for at least 10% by weight and at most 40% by weight of the composition based only on a) and b), and the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B m ) contains a comonomer (Mc b1 ), and the comonomer (Mc b1 ) contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms. A method characterized by this provides a polymer composition that can be easily dispersed in a low-polarity polymer matrix material for thermosetting polymers, thermoplastic polymers, or liquid resins and / or their respective precursors as monomers, and also, compared to a liquid composition containing a polymer composition that does not contain monomer units containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or compared to a liquid composition containing a polymer composition containing two or more stages or layers containing monomer units containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, it has also been found to provide a liquid composition having a lower viscosity.

[0026] Surprisingly, a method for producing a liquid polymer composition LPC1, a) a step of providing the polymer composition (PC1), b) a step of contacting the polymer composition (PC1) with a liquid composition (LC1) has also been found to provide a liquid polymer composition in which the polymer composition (PC1) is uniformly and rapidly dispersed in the liquid composition (LC1).

[0027] Surprisingly, a method for producing a liquid polymer composition LPC1, a) a step of providing the polymer composition (PC1) in the form of a porous polymer powder having a total intrusion volume of at least 1.2 ml / g as measured by mercury porosimetry, b) a step of contacting the polymer composition (PC1) with a liquid composition (LC1) has also been found to provide a liquid polymer composition in which the polymer composition (PC1) is uniformly and rapidly dispersed in the liquid composition (LC1).

Brief Description of the Drawings

[0028] The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description in conjunction with the accompanying drawings. [Figure 1] Figure 1 is a graph showing the measured viscosity (Pa*s) as a function of shear rate of 1 / s at 25°C for examples and comparative examples according to embodiments of the present invention. [Figure 2] Figure 2 is a graph showing measured viscosity (Pa*s) as a function of shear rate of 1 / s at 25°C for examples and comparative examples according to embodiments of the present invention, at concentrations different from those shown in Figure 1. [Modes for carrying out the invention]

[0029] [Detailed description of the invention] According to a first aspect, the present invention relates to a polymer composition (PC1), a) Polymers having a glass transition temperature of less than 10°C (A1), b) A polymer (B1) having a glass transition temperature of at least 60°C, comprising at least 10% by weight and up to 40% by weight of a composition based solely on a) and b). Includes, Components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1), and polymer (B1) has a mass-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol. The present invention relates to a polymer composition (PC1) characterized in that the polymer (B1) contains polymer monomer units having alicyclic hydrocarbon groups with 3 to 20 carbon atoms.

[0030] According to a second aspect, the present invention relates to a method for producing a polymer composition (PC1), a) Monomer or monomer mixture (A m A step of polymerizing by emulsion polymerization of ) to obtain one layer of step (A) containing a polymer (A1) having a glass transition temperature of less than 10°C, b) Monomer or monomer mixture (Bm A step of polymerizing by emulsion polymerization of ) to obtain a layer of step (B) containing a polymer (B1) having a glass transition temperature of at least 60°C. Includes, The polymer (B1) accounts for at least 10% by weight and up to 40% by weight of the composition based solely on a) and b), and the polymer (B1) has a mass-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and is a monomer or monomer mixture (B m ) contains a comonomer (Mc) which has 3 to 20 carbon atoms and contains an alicyclic hydrocarbon group. b1 The present invention relates to a method characterized by including ).

[0031] In a third aspect, the present invention relates to a method for producing a polymer composition (PC1) in the form of a polymer powder, a) Monomer or monomer mixture (A m A step of polymerizing by emulsion polymerization of ) to obtain one layer of step (A) containing a polymer (A1) having a glass transition temperature of less than 10°C; b) Monomer or monomer mixture (B m A step of polymerizing by emulsion polymerization of ) to obtain a layer of step (B) containing a polymer (B1) having a glass transition temperature of at least 60°C; c) A step of agglomerating the composition obtained in steps a) to b). Includes, The polymer (B1) accounts for at least 10% by weight and up to 40% by weight of the composition based solely on a) and b), and the polymer (B1) has a mass-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and is a monomer or monomer mixture (B m ) contains a comonomer (Mc) which has 3 to 20 carbon atoms and contains an alicyclic hydrocarbon group. b1 The present invention relates to a method characterized by including ).

[0032] In a fourth aspect, the present invention relates to the use of a polymer composition (PC1) as an impact resistance modifier.

[0033] In a fifth aspect, the present invention relates to the use of a polymer composition (PC1) as a composition for shortening dispersion time.

[0034] In a sixth aspect, the present invention relates to a method for reducing the time required to disperse a polymer powder (PC1) in a low-polarity liquid composition by using a polymer composition (PC1) in the form of a polymer powder.

[0035] In a seventh aspect, the present invention relates to a polymer composition (PC2) comprising a polymer composition (PC1) as an impact resistance modifier.

[0036] In the eighth aspect, the present invention provides a method for reducing the time required to disperse a polymer composition (PC1) in a liquid composition, a) A step of providing the polymer composition (PC1) according to the first embodiment in the form of a porous polymer powder POW1 having a total intrusion volume of at least 1.2 ml / g as measured by mercury porosimetry, b) The process of bringing the polymer composition (PC1) into contact with the liquid composition (LC1). This includes methods.

[0037] In the ninth aspect, the present invention is a) The polymer composition (PC1) described in the first embodiment, and b) Liquid composition (LC1) This relates to a liquid polymer composition (LPC1) containing [the specified element].

[0038] The term "polymer powder" as used refers to a polymer in powder form containing powder particles in the range of at least 1 μm, wherein the powder particles are obtained by aggregation of primary polymer particles containing one or more polymers, and the primary polymer particles are in the nanometer range.

[0039] The term "primary particles" used here refers to spherical polymer particles, including particles in the nanometer range. Preferably, the primary particles have a weight-average particle size between 20 nm and 800 nm.

[0040] The term "particle size" used here refers to the volume-average diameter of a particle considered to be spherical.

[0041] The term "thermoplastic polymer" used here refers to a polymer that, when heated, turns into a liquid, becomes more liquid, or loses viscosity, and can take on new shapes through heating and pressurization.

[0042] The term "thermosetting polymer" as used refers to a soft, solid, or viscous prepolymer that irreversibly transforms into an infusible, insoluble polymer network upon curing.

[0043] The term "copolymer" used here means that a polymer consists of at least two different monomer units.

[0044] The term "multi-stage polymer" as used refers to a polymer formed sequentially by a multi-stage polymerization process. A preferred multi-stage emulsion polymerization process includes at least two stages with different compositions, where the first polymer is the first-stage polymer and the second polymer is the second-stage polymer, i.e., the second polymer is formed by emulsion polymerization in the presence of the first emulsion polymer.

[0045] The term "(meth)acrylic" used here refers to all types of acrylic and methacrylic monomers.

[0046] The term "(meth)acrylic polymer" used here essentially means that the (meth)acrylic polymer contains polymers that include (meth)acrylic monomers that make up 50% by weight or more of the (meth)acrylic polymer.

[0047] The term "dry" as used means that the ratio of residual water is less than 1.5% by weight, preferably less than 1.2% by weight.

[0048] In this invention, the range x to y means that the upper and lower limits of this range are included, and is equivalent to at least x to y.

[0049] In this invention, saying that the range is between x and y means that the upper and lower limits of this range are excluded, and is equivalent to saying that it is greater than x and less than y.

[0050] The term "total intrusion volume" used here refers to the total volume injected by liquid mercury, in accordance with ISO 15901-1:2016. This volume is accumulated, and the cumulative intrusion volume is determined by analysis as a function of the applied pressure or pore diameter in ml / g(cm³). 3 It is expressed as ( / g). The total intrusion volume is the volume intruded under maximum pressure, and this corresponds to the smallest pore.

[0051] The term "incremental injection volume" refers to the volume injected in ml / g between two specific pressures or two pore sizes. This incremental injection volume can also be expressed as vol% relative to the total injection volume.

[0052] Easily dispersed in a liquid resin means that a uniform dispersion is achieved. The distribution of the polymer composition (PC1) is not uniform if separation occurs after the initial homogenization.

[0053] The term "low polarity" used refers to the Hansen solubility parameter δ p <10MPa 1 / 2 This refers to compounds that possess [a certain characteristic]. The Hansen solubility parameter, also called solvation capacity, reflects the physicochemical solubility characteristics of organic substances. The Hansen solubility parameter can be calculated according to the method proposed by Charles Hansen in his book, "Hansen Solubility Parameters: A User's Handbook," Second Edition (2007), Boca Raton, F.: CRC Press, ISBN 978-0-8493-7248-3. According to this method, there are three parameters called "Hansen parameters": δ d , δ p and δ h However, this is sufficient to predict the behavior of the solvent with respect to a given molecule. MPa 1 / 2 Unit parameter δ dThis quantifies the energy of intermolecular dispersion forces, i.e., van der Waals forces. MPa 1 / 2 Unit parameter δ p This represents the energy of the intermolecular dipole interaction. Finally, MPa 1 / 2 Unit parameter δ h This quantifies the energy derived from intermolecular hydrogen bonds, i.e., the ability to interact via hydrogen bonds. The sum of the squares of the three parameters is Hildebrand's solubility parameter (δ tot This is equivalent to the square of ).

[0054] Rapid dispersion in a liquid resin means that a much faster and more uniform dispersion is achieved than when using a polymer composition that does not have the specific composition and molecular weight of polymer (B1).

[0055] With respect to the polymer composition (PC1) according to the present invention, the polymer composition (PC1) is in the form of a polymer powder (POW1), also called polymer powder POW1, comprising a) a polymer (A1) having a glass transition temperature of less than 10°C, and b) a polymer (B1) having a glass transition temperature of at least 60°C, wherein the polymer (B1) accounts for at least 10% and up to 40% by weight of the composition based solely on a) and b); and components a) and b) of the composition (PC1) are part of a multistage polymer (MP1), the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the polymer (B1) contains polymerization monomer units including alicyclic hydrocarbon groups having 3 to 20 carbon atoms.

[0056] Component b) accounts for at least 10% by weight of the composition based on a) and b). Preferably, component b) accounts for at least 15% by weight of the composition based on a) and b), and more preferably at least 20% by weight.

[0057] Component b) accounts for a maximum of 40% by weight of the composition based on a) and b). Preferably, component b) accounts for a maximum of 35% by weight of the composition based on a) and b), and more preferably a maximum of 33% by weight.

[0058] In the first advantageous embodiment, component b) accounts for less than 30% by weight of the composition based on a) and b).

[0059] In the second advantageous embodiment, component b) accounts for less than 32% by weight of the composition based on a) and b).

[0060] In a third advantageous embodiment, component b) accounts for less than 33% by weight of the composition based on a) and b).

[0061] Preferably, component b) accounts for more than 20% by weight of the composition based on a) and b). More preferably, component b) accounts for more than 21% by weight of the composition based on a) and b).

[0062] In the first advantageous embodiment, component b) accounts for more than 22% by weight of the composition based on a) and b).

[0063] In the second advantageous embodiment, component b) accounts for more than 23% by weight of the composition based on a) and b).

[0064] In a third advantageous embodiment, component b) accounts for more than 25% by weight of the composition based on a) and b).

[0065] The upper and lower limits given in the previous paragraph for the amount of component b) can be combined in any combination of one upper limit and one lower limit.

[0066] Preferably, component b) accounts for between 20% and 35% by weight of the composition based on a) and b). More preferably, component b) accounts for between 25% and 35% by weight of the composition based on a) and b).

[0067] In the first advantageous embodiment, component b) accounts for between 26% and 35% by weight of the composition based on a) and b).

[0068] In a second advantageous embodiment, component c) accounts for between 26% and 34% by weight of the composition based on a) and b).

[0069] In a third advantageous embodiment, component b) accounts for between 26% and 33% by weight of the composition based on a) and b).

[0070] Components a) and b) of composition (PC1) are part of the multi-stage polymer (MP1).

[0071] At least components a) and b) are obtained by a multi-stage method comprising at least two stages (A) and (B), respectively, and these two polymers (A1) and polymer (B1) form a multi-stage polymer (MP1).

[0072] Regarding the polymer powder (POW1) of the present invention, the polymer powder has a volume median particle size D50 between 1 μm and 700 μm. Preferably, the volume median particle size of the polymer powder is between 10 μm and 600 μm, more preferably between 15 μm and 550 μm, and advantageously between 20 μm and 500 μm.

[0073] The D10 particle size distribution per volume unit is at least 10 μm, preferably 15 μm, and more preferably 20 μm.

[0074] The D90 particle size distribution per volume is a maximum of 1000 μm, preferably 950 μm, more preferably 925 μm, and even more preferably 900 μm.

[0075] The porosity of a polymer composition (PC1) in the form of polymer powder (POW1) is expressed as the total indentation volume, or the total cumulative indentation volume (cumulative indentation volume) in milliliters (ml) of mercury per mass (g) of the polymer powder POW1. This is measured according to the standard ISO 15901-1: Mercury porosity and evaluation of pore size distribution and porosity of solid materials by gas adsorption - Part 1: Mercury porosity. Preferably, the porous polymer powder (POW1) of the present invention has a total indentation volume or total cumulative indentation volume of at least 1.2 ml / g, preferably 1.23 ml / g, more preferably 1.26 ml / g, and even more preferably 1.30 ml / g. The total cumulative indentation volume takes into account pore size diameters down to 0.005 μm. Preferably, the total indentation volume or total cumulative indentation volume takes into account pore size diameters between 100 μm and 0.005 μm, or pressures between 0.01 MPa and 400 MPa.

[0076] The porous polymer powder (POW1) of the present invention has a total indentation volume or total cumulative indentation volume of up to 10 ml / g. Preferably, the total indentation volume is up to 8 ml / g, more preferably up to 7 ml / g, even more preferably up to 6 ml / g, advantageously up to 5 ml / g, more advantageously up to 4 ml / g, and most advantageously up to 3.5 ml / g.

[0077] The upper and lower limits given in the previous two paragraphs for the total injection volume or total cumulative injection volume of the porous polymer powder (POW1) of the present invention can be combined in any combination of one upper limit and one lower limit.

[0078] Preferably, the porous polymer powder (POW1) of the present invention has a total indentation volume or total cumulative indentation amount between 1.2 ml / g and 10 ml / g, more preferably between 1.23 ml / g and 8 ml / g, even more preferably between 1.23 ml / g and 7 ml / g, advantageously between 1.23 ml / g and 6 ml / g, more advantageously between 1.23 ml / g and 5 ml / g, more advantageously between 1.26 ml / g and 4 ml / g, and most advantageously between 1.30 ml / g and 3.5 ml / g.

[0079] The incremental intrusion volume is the volume between two specific pore diameters. The incremental intrusion volume can also be expressed as an absolute value in ml / g units, or as a relative value as a percentage of the total intrusion volume or total cumulative intrusion volume (taking into account pore size diameters between 100 μm and 0.005 μm).

[0080] Preferably, the porous polymer powder (POW1) of the present invention has a cumulative intrusion of at least 0.9 ml / g, more preferably at least 1 ml / g, for pore sizes greater than 10 μm (larger than 10 μm).

[0081] Preferably, the porous polymer powder (POW1) of the present invention has an incremental injection amount of at least 0.1 ml / g, more preferably at least 0.12 ml / g, and even more preferably at least 0.15 ml / g, with a pore size of 10 μm to 1 μm.

[0082] The apparent bulk density of the polymer powder (POW1) is 0.60 g / cm³. 3 It is less than 0.45 g / cm³. Preferably, the apparent bulk density is 0.45 g / cm³. 3 Less than 0.43 g / cm³, preferably 0.43 g / cm³ 3 Less than, and more preferably 0.41 g / cm³ 3 It is less than.

[0083] The apparent bulk density of the polymer powder (POW1) is 0.1 g / cm³. 3 It is more than 0.11 g / cm³. Preferably, the apparent bulk density is 0.11 g / cm³. 3 More preferably 0.12 g / cm³ 3 Even more preferably 0.13 g / cm³ 3 It's incredible.

[0084] The apparent bulk density of the polymer powder (POW1) is 0.1 g / cm³. 3 and 0.60 g / cm³ 3 It is between [a certain range]. Preferably, the apparent bulk density of the polymer powder (POW1) is 0.15 g / cm³. 3 and 0.45 g / cm³ 3It is between these two values. Advantageously, the apparent bulk density of the polymer powder POW1 is 0.2 g / cm³. 3 and 0.4 g / cm³ 3 It is between these two points.

[0085] Each preferred embodiment of all the different properties of the porous polymer powder (POW1) can be combined in any combination.

[0086] With respect to the polymer composition (PC1) according to the present invention, the polymer composition (PC1) according to a second embodiment is a continuous phase comprising a) a polymer (A1) having a glass transition temperature of less than 10°C, and b) a polymer (B1) having a glass transition temperature of at least 60°C, wherein components a) and b) of the composition (PC1) are part of a multi-stage polymer (MP1), the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the polymer (B1) is a continuous phase comprising monomer units including alicyclic hydrocarbon groups having 3 to 20 carbon atoms; and c) the polymer composition (PC1) can be dispersed in a liquid composition LC1 as a continuous phase in which the polymer composition (PC1) is dispersed.

[0087] The multi-stage polymer (MP1) of the composition (PC1) according to the present invention has at least two stages (A) and (B), which each contain polymers (A1) and (B1) with different polymer compositions.

[0088] The multi-stage polymer (MP1) is preferably in the form of polymer particles PAR. These particle PARs are also called core-shell particles. For example, a first stage containing polymer (A1) forms the core, and the second or subsequent stages each form their respective shells. Such multi-stage polymers (MP1), also called core-shell particles, are preferred. If the multi-stage polymer (MP1) contains only polymer (A1) and polymer (B1), it is a core-shell particle containing only one shell.

[0089] In a first preferred embodiment, the multi-stage polymer (MP1) is a core-shell particle comprising a core-forming polymer (A1) and a shell-forming polymer (B1), and containing only one shell.

[0090] In a second preferred embodiment, the multi-stage polymer (MP1) is a core-shell particle comprising a seed, a polymer (A1) that together forms a core, and a polymer (B1) that forms a shell, and containing only one shell.

[0091] The particle PAR contained in the polymer composition (PC1) in the form of a polymer powder (POW1) according to one embodiment, or the dispersed particle PAR according to another embodiment, are primary particles.

[0092] The particle PAR has a weight-average particle size between 15 nm and 900 nm. Preferably, the weight-average particle size of the polymer 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, 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.

[0093] According to the first preferred embodiment, the primary polymer particles PAR are aggregated, giving rise to the polymer composition (PC1) or a portion of the polymer composition (PC1). In this case, the polymer composition (PC1) of the present invention is in the form of a polymer powder, as described above.

[0094] The polymer composition (PC1) according to the present invention comprises a multi-stage polymer (MP1) comprising one stage (A) comprising a polymer (A1) having a glass transition temperature of at least a) less than 10°C, and one stage (B) comprising a polymer (B1) having a glass transition temperature of at least b) more than 60°C.

[0095] In a first preferred embodiment, step (A) is the first of at least two steps, and step (B) containing polymer (B1) covers step (A) containing polymer (A1).

[0096] In a second preferred embodiment, seeds may be added before step (A), in which case step (A) and the seeds together are considered as the first step, and step (B) containing polymer (B1) covers step (A) containing seeds and polymer (A1).

[0097] In a third preferred embodiment, step (A) is the first of two steps, step (B) containing polymer (B1) covers step (A) containing polymer (A1), and the multi-step polymer (MP1) consists of step (A) containing polymer (A1) and step (B) containing polymer (B1).

[0098] Step (B) occurs after step (A). More preferably, step (B) is the final step, and polymer (B1) is the outer shell of the multi-stage polymer (MP1).

[0099] In the first embodiment, the polymer (A1) having a glass transition temperature of less than 10°C comprises at least 50% by weight of polymer units derived from one or more alkyl acrylates, and the layer (A) is the innermost layer of polymer particles having a multilayer structure. In other words, the layer (A) containing the polymer (A1) is the core of the polymer particles.

[0100] With respect to polymer (A1) of the first preferred embodiment, the polymer is a (meth)acrylic polymer containing at least 50% by weight of polymer units derived from an acrylic monomer. Preferably, 60% by weight, more preferably 70% by weight, of polymer (A1) is an acrylic monomer.

[0101] The acrylic monomer in polymer (A1) comprises monomers selected from C1-C18 alkyl acrylates or mixtures thereof. More preferably, the acrylic monomer in polymer (A1) comprises monomers of C2-C12 alkyl acrylic monomers or mixtures thereof. Even more preferably, the acrylic monomer in polymer (A1) comprises monomers of C2-C8 alkyl acrylic monomers or mixtures thereof.

[0102] Polymer (A1) may contain one or more comonomers copolymerizable with acrylic monomers, as long as polymer (A1) has a glass transition temperature of less than 10°C.

[0103] One or more comonomers in polymer (A1) are preferably selected from (meth)acrylic monomers and / or vinyl monomers.

[0104] Most preferably, the acrylic or methacrylate comonomer of polymer (A1) is selected from methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, provided that polymer (A1) has a glass transition temperature of less than 10°C.

[0105] In certain embodiments, polymer (A1) is a homopolymer of butyl acrylate.

[0106] More preferably, the glass transition temperature Tg of the polymer (A1) containing at least 70% by weight of polymer units derived from C2-C8 alkyl acrylates is between -100°C and 10°C, more preferably between -80°C and 0°C, advantageously between -80°C and -20°C, and even more advantageously between -70°C and -20°C.

[0107] In a second preferred embodiment, the polymer (A1) having a glass transition temperature of less than 10°C comprises at least 50% by weight of polymer units derived from isoprene or butadiene, and the layer (A) is the innermost layer of polymer particles having a multilayer structure. In other words, the layer (A) containing polymer (A1) is the core of the polymer particles.

[0108] As an example, the core polymer (A1) of the second embodiment may be an isoprene homopolymer or butadiene homopolymer, an isoprene-butadiene copolymer, a copolymer of isoprene and up to 98% by weight of a vinyl monomer, and a copolymer of butadiene and up to 98% by weight of a vinyl monomer. 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.

[0109] More preferably, the glass transition temperature Tg of the polymer (A1) comprising at least 50% by weight of polymer units derived from isoprene or butadiene is between -100°C and 10°C, more preferably between -90°C and 0°C, advantageously between -80°C and 0°C, and most advantageously between -70°C and -20°C.

[0110] In a third preferred embodiment, polymer (A1) is a silicone rubber-based polymer. For example, the silicone rubber is polydimethylsiloxane. More preferably, the glass transition temperature Tg of polymer (A1) in 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.

[0111] Polymers (A1) having a glass transition temperature of less than 10°C contain polymerized monomer units. The general polymer (A1), as well as each of the polymers (A1) of the first, second and third preferred embodiments, contain each monomer or monomer mixture (A) that gives rise to the monomer units constituting the polymer (A1). m It is prepared from ).

[0112] Regarding polymer (B1), examples include copolymers comprising monomers and / or vinyl monomers having double bonds, wherein at least one monomer contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Preferably, polymer (B1) is a (meth)acrylic polymer, meaning that at least 50% by weight of the monomer units of polymer (B1) are (meth)acrylic monomers.

[0113] Copolymer (B1) is comonomer (Mc b1 ) is included, and the comonomer (Mcb1) contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Comonomer (Mc in copolymer (B1) b1 ) can be present in amounts between 5% and 50% by weight, preferably between 10% and 40% by weight, and more preferably between 20% and 40% by weight.

[0114] In a first, more preferred embodiment, copolymer (B1) is a comonomer (Mc) containing alicyclic hydrocarbon groups having 3 to 20 carbon atoms, in an amount between 25% and 35% by weight. b1 ) contains comonomer units from. Comonomers (Mc) containing alicyclic hydrocarbon groups with 3 to 20 carbon atoms. b1 ) is preferably a (meth)acrylic monomer.

[0115] In a second, more preferred embodiment, copolymer (B1) is a comonomer (Mc) containing alicyclic hydrocarbon groups having 3 to 20 carbon atoms, in an amount between 26% and 35% by weight. b1 ) contains comonomers (Mc b1 ) is preferably a (meth)acrylic monomer.

[0116] In a third, even more preferred embodiment, copolymer (B1) is a comonomer (Mc) containing alicyclic hydrocarbon groups having 3 to 20 carbon atoms, in an amount between 26% and 33% by weight. b1 ) includes.

[0117] Comonomer (Mc b1) is preferably a (meth)acrylic monomer. Copolymer (B1) is at least one other comonomer (Mc b2 ) contains. Preferably, other comonomers (Mc b2 The monomer is selected from acrylic or methacrylic monomers.

[0118] Most preferably, the copolymer (B1) is other acrylic or methacrylate comonomers (Mc b2 The copolymer (B1) is selected from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof, provided that the copolymer (B1) has a glass transition temperature of at least 60°C.

[0119] Advantageously, copolymer (B1) is comonomer (Mc b2 ) comprises at least 50% by weight, more preferably 60% by weight, monomer units derived from methyl methacrylate.

[0120] Preferably, the glass transition temperature Tg of copolymer (B1) is between 60°C and 150°C. More preferably, the glass transition temperature of copolymer (B1) is between 70°C and 140°C, advantageously between 80°C and 130°C, and even more advantageously between 85°C and 125°C.

[0121] Preferably, copolymer (B1) is grafted onto the polymer prepared in the previous step.

[0122] Preferably, the copolymer (B1) is not completely grafted. Not completely grafted means that at least 5% by weight of the copolymer (B1) in the multistage polymer (MP1) can be solubilized in the solvent for copolymer (B1) and extracted. Preferably, at least 10% by weight of the copolymer (B1) in the multistage polymer (MP1) can be solubilized in the solvent for copolymer (B1) and extracted. The percentages are relative to the amount of copolymer (B1) in the multistage polymer (MP1) alone.

[0123] Copolymer (B1) having a glass transition temperature of at least 60°C comprises polymerized monomer units. Copolymer (B1) generally, and in each embodiment, comprises each monomer or comonomer (Mc b1 ) and (Mc b2 ) monomer mixture containing (B m It is prepared from ) and after polymerization yields copolymer (B1) having polymerization monomer units contained in copolymer (B1).

[0124] Preferably, the copolymer (B1) does not contain any portion derived from a chain transfer agent, particularly a mercaptan-based chain transfer agent.

[0125] Furthermore, with respect to polymer (B1) or the extractable portion of polymer (B1), it has a mass-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol.

[0126] The polymer (B1) has a mass-average molecular weight Mw of more than 10,000 g / mol, preferably more than 10,500 g / mol, more preferably more than 11,000 g / mol, even more preferably more than 12,000 g / mol, advantageously more than 13,000 g / mol, more advantageously more than 14,000 g / mol, and even more advantageously more than 15,000 g / mol.

[0127] The polymer (B1) or the extractable portion of 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, more advantageously less than 300,000 g / mol, even more advantageously less than 250,000 g / mol, and most advantageously less than 200,000 g / mol.

[0128] Preferably, the mass-average molecular weight Mw of polymer (B1) or the extractable portion of 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, 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.

[0129] In the first advantageous embodiment, the mass-average molecular weight Mw of the (meth)acrylic polymer (B1) or the extractable portion of the polymer (B1) is between 10,500 g / mol and 200,000 g / mol, more preferably between 11,000 g / mol and 190,000 g / mol, 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.

[0130] In a second advantageous embodiment, the mass-average molecular weight Mw of the (meth)acrylic polymer (B1) or the extractable portion of the polymer (B1) is between 15,000 g / mol and 450,000 g / mol, more preferably between 15,500 g / mol and 400,000 g / mol, even more preferably between 16,000 g / mol and 350,000 g / mol, advantageously between 16,500 g / mol and 300,000 g / mol, more advantageously between 17,000 g / mol and 250,000 g / mol, and most advantageously between 17,500 g / mol and 200,000 g / mol.

[0131] Preferably, the polymer (B1) or the extractable portion of polymer (B1) does not contain any portion derived from the chain transfer agent.

[0132] Preferably, polymer (B1) is a copolymer comprising (meth)acrylic monomers, at least one of which comprises an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

[0133] Furthermore, with respect to polymer (B1), a copolymer comprising monomers and / or vinyl monomers having double bonds can be cited, where at least one of the monomers contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Preferably, polymer (B1) is a (meth)acrylic polymer, meaning that at least 50% by weight of the monomer units of polymer (B1) is (meth)acrylic.

[0134] In the first preferred embodiment, the monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms is a (meth)acrylic monomer.

[0135] In the second preferred embodiment, the alicyclic hydrocarbon group of the monomer unit has 6 to 20 carbon atoms.

[0136] Alicyclic hydrocarbon group or comonomer (Mc b1 Monomer units containing ) are selected from the group consisting of cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, bornyl acrylate, bornyl methacrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phentyl acrylate, phentyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate, and mixtures thereof.

[0137] In the first more preferred embodiment, an alicyclic hydrocarbon group or comonomer (Mc b1 The monomer units containing ) are selected from isobornyl acrylates.

[0138] In a second, more preferred embodiment, an alicyclic hydrocarbon group or comonomer (Mc b1 The monomer units containing ) are selected from cyclohexyl acrylates.

[0139] Each preferred and advantageous embodiment of all the different properties of polymers (A1) and (B1) and their respective monomers can be combined in any combination.

[0140] The multi-stage polymer (MP1) is obtained by a multi-stage method involving at least two stages. Components a) and b) of composition (PC1) are part of the multi-stage polymer (MP1).

[0141] Preferably, the polymer (A1) having a glass transition temperature of less than 10°C, which is produced in step (A), is produced before step (B) or is the first step of a multi-step method.

[0142] The copolymer (B1) having a glass transition temperature of at least 60°C, which is produced in step (B), is produced after step (A) of the multi-step method.

[0143] More preferably, the copolymer (B1) having a glass transition temperature of at least 60°C, which is fabricated in step (B), is the outer layer of the multi-step polymer (MP1).

[0144] There may be further intermediate steps between steps (A) and (B).

[0145] In relation to complete polymer particles or multilayer polymers (MP1), the weight ratio r of the outer layer copolymer (B1) contained in the layer (B) is at least 10% by weight, more preferably at least 20% by weight, and even more preferably at least 25% by weight.

[0146] According to the present invention, in relation to complete polymer particles, the ratio r of the outer layer (B) containing the copolymer (B1) is at most 40% by weight.

[0147] Preferably, the ratio of polymer (B1) considering polymer particles or multi-stage polymer (MP1) is between 20% and 35% by weight, preferably between 25% and 35% by weight.

[0148] In a preferred embodiment, the copolymer (B1) having a glass transition temperature of at least 60°C is the outer layer of primary polymer particles having a multilayer structure, in other words, a multilayer polymer (MP1).

[0149] Preferably, at least a portion of the copolymer (B1) in layer (B) is grafted onto the polymer produced in the previous layer. If only two layers (A) and (B) containing polymers (A1) and (B1) respectively are present, a portion of copolymer (B1) is grafted onto polymer (A1). More preferably, at least 25% by weight of polymer (B1) is grafted. The grafting ratio can be determined by determining the amount of ungrafted copolymer (B1) by solvent extraction and weight measurement before and after extraction.

[0150] In the first more preferred embodiment, at least 30% by weight of copolymer (B1) is grafted.

[0151] In a second, more preferred embodiment, at least 40% by weight of copolymer (B1) is grafted.

[0152] In a third, more preferred embodiment, at least 50% by weight of copolymer (B1) is grafted.

[0153] Preferably, at least a portion of the copolymer (B1) of layer (B) is extractable. More preferably, at least 3% by weight of the polymer (B1) is extractable.

[0154] In the first more preferred embodiment, at least 5% by weight of the copolymer (B1) is extractable.

[0155] In a second, more preferred embodiment, at least 10% by weight of the copolymer (B1) is extractable.

[0156] In a third, more preferred embodiment, at least 15% by weight of the copolymer (B1) is extractable.

[0157] The percentages of the graft portion and the extractable portion of copolymer (B1) are given as percentages relative to the amount of copolymer (B1) alone.

[0158] The glass transition temperature (Tg) of each polymer can be estimated by dynamic methods, such as thermomechanical analysis.

[0159] To obtain samples of each polymer (A1) and (B1), they can be prepared individually and without a multi-step method, making it easier to estimate and measure the individual glass transition temperature (Tg) of each polymer at each step. Copolymer (B1) can be extracted to estimate and measure its glass transition temperature (Tg) and / or molecular weight.

[0160] Preferably, the polymer composition of the present invention, if in powder form, is solvent-free. Solvent-free means that the final solvent present accounts for less than 1% by weight of the composition. The monomers of each polymer synthesis are not considered solvents. Residual monomers in the composition are present at less than 2% by weight of the composition.

[0161] Preferably, the polymer composition according to the present invention is dry if it is in powder form. Dry means that the polymer composition according to the present invention contains less than 3% by weight of humidity, preferably less than 1.5% by weight of humidity, and more preferably less than 1.2% by weight of humidity.

[0162] Humidity can be measured by a thermobalance, which measures the weight loss when the polymer composition is heated.

[0163] The powder-based compositions according to the present invention do not contain any solvents added at will. The final residual monomers from the polymerization of each monomer and water are not considered solvents.

[0164] Preferably, the polymer composition (PC1) of the present invention contains less than 1000 ppm of sulfur. This is due to the fact that polymer (B) preferably does not contain any portion derived from a chain transfer agent, particularly a mercaptan-based chain transfer agent. The sulfur content is measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES).

[0165] More preferably, the polymer composition (PC1) contains less than 900 ppm of sulfur, and even more preferably less than 800 ppm of sulfur.

[0166] Regarding a first preferred method for producing a polymer composition (PC1) according to the present invention, the method is as follows: a) Monomer or monomer mixture (A m A step of polymerizing by emulsion polymerization of ) to obtain one layer of step (A) containing a polymer (A1) having a glass transition temperature of less than 10°C; b) Monomer or monomer mixture (B m A step of polymerizing by emulsion polymerization of ) to obtain a layer of step (B) containing a polymer (B1) having a glass transition temperature of at least 60°C, Includes.

[0167] Preferably, step a) is performed before step b).

[0168] More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a).

[0169] Regarding a second preferred method for producing a polymer composition (PC1) according to the present invention in the form of a polymer powder, the method is as follows: a) Monomer or monomer mixture (A m A step of polymerizing by emulsion polymerization of ) to obtain one layer of step (A) containing a polymer (A1) having a glass transition temperature of less than 10°C; b) Monomer or monomer mixture (B m A step of polymerizing by emulsion polymerization of ) to obtain a layer of step (B) containing a polymer (B1) having a glass transition temperature of at least 60°C; c) A step of agglomerating the composition obtained in steps a) to c), Includes.

[0170] Preferably, step a) is performed before step b), and step b) is performed before step c).

[0171] More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a).

[0172] Preferably, no chain transfer agent, particularly mercaptan-based chain transfer agents, is used during step b).

[0173] Advantageously, a first preferred method for producing the polymer composition (PC1) according to the present invention is: a) Monomer or monomer mixture (A m A step of polymerizing by emulsion polymerization of ) to obtain one layer of step (A) containing a polymer (A1) having a glass transition temperature of less than 10°C, b) Monomer or monomer mixture (B m A step of polymerizing by emulsion polymerization of ) to obtain a layer of step (B) containing a polymer (B1) having a glass transition temperature of at least 60°C, c) A step of agglomerating the composition obtained in steps a) to b), Includes.

[0174] Preferably, steps a), b), and c) are carried out in that order. When emulsion polymerization is used, the polymer composition at the end of polymerization is obtained as an aqueous dispersion.

[0175] Preferably, no chain transfer agent, particularly mercaptan-based chain transfer agents, is used during step b).

[0176] Each monomer or monomer mixture (A) is used to form layers (A) and (B) containing polymers (A1) and (B1), respectively. m ) and (B m ) is the same as previously defined. Monomer or monomer mixture (A m ) and (B m ) contains the respective monomers present as polymerized monomer units in the polymer chains of polymers (A1) and (B1). The properties of polymers (A1) and (C1) are the same as those previously defined.

[0177] A preferred method for producing a polymer composition (PC1) containing a multi-stage polymer (MP1) yields a polymer powder POW1. The polymer powder POW1 is in the form of particles (large particles). The polymer powder particles or particles include aggregated primary polymer particles produced by a multi-stage method containing the multi-stage polymer (MP1), or aggregated primary polymer particles containing the multi-stage polymer (MP1).

[0178] The coagulation process can be carried out by solidification or spray drying.

[0179] In the first preferred embodiment of the method, coagulation is preferred in the aggregation step.

[0180] In a second preferred embodiment of the method, spray drying is preferred in the agglomeration step.

[0181] The aqueous composition containing the multi-stage polymer (MP1) before the start of solidification has a solid content of less than 35% by weight. If the solid content is higher than 35% by weight, water is added to adjust the solid content. Preferably, the solid content is less than 34% by weight, more preferably less than 33% by weight, and advantageously less than 32% by weight.

[0182] The solid content is measured or estimated by gravimetric analysis by weighing before and after complete evaporation of water.

[0183] In the first preferred embodiment, the solids content of the aqueous composition comprising the multistage polymer (MP1) and polymer (C1) before solidification begins is between 5% and 35% by weight, more preferably between 6% and 34% by weight, even more preferably between 7% and 33% by weight, and advantageously between 8% and 32% by weight.

[0184] In a second preferred embodiment, the solids content of the aqueous composition containing the multistage polymer (MP1) and polymer (C1) before solidification begins is between 20% and 35% by weight, more preferably between 20% and 34% by weight, even more preferably between 20% and 33% by weight, and advantageously between 20% and 32% by weight.

[0185] In a third preferred embodiment, the solids content of the aqueous composition containing the multistage polymer (MP1) and polymer (C1) before solidification begins is between 5% and 20% by weight, more preferably between 6% and 20% by weight, even more preferably between 7% and 20% by weight, and advantageously between 8% and 20% by weight.

[0186] In a fourth preferred embodiment, the solids content of the aqueous composition containing the multistage polymer (MP1) and polymer (C1) before solidification begins is between 10% and 25% by weight, more preferably between 11% and 24% by weight, even more preferably between 12% and 23% by weight, and advantageously between 13% and 22% by weight.

[0187] In a fifth preferred embodiment, the solids content of the aqueous composition comprising the multistage polymer (MP1) and polymer (C1) before solidification begins is between 15% and 27% by weight, more preferably between 17% and 27% by weight, even more preferably between 19% and 27% by weight, and advantageously between 21% and 27% by weight.

[0188] Coagulation can be achieved using salt or inorganic acid.

[0189] In the first preferred embodiment, coagulation is carried out by an inorganic acid.

[0190] A method for producing the polymer composition (PC1) according to the present invention may optionally include an additional step e) drying the polymer composition.

[0191] Preferably, after drying step e), the polymer composition contains less than 3% by weight, more preferably less than 1.5% by weight, and advantageously less than 1.2% by weight of moisture or water.

[0192] The humidity of the polymer composition can be measured using a thermobalance.

[0193] The polymer can be dried in an oven or vacuum oven at 50°C for 48 hours while heating the composition.

[0194] The liquid composition (LC1) described in the eighth aspect of the present invention is a precursor of a thermosetting polymer or thermoplastic polymer. This may be a monomer, a mixture of monomers, a polymerizable or curable oligomer, a mixture of a polymerizable or curable oligomer and a monomer, or a mixture of a polymer and a monomer, which are liquid at 25°C. Preferably, the liquid is at 1000 Pa * Less than s, more preferably 0.5 mPa * s and 1000Pa * It has a dynamic viscosity between s. The value of the dynamic viscosity is obtained at a shear rate of 1 1 / s. Viscosity is measured using a rheometer. Viscosity is measured as a function of shear rate, and the value at a shear rate of 1 1 / s is obtained for comparison, as described above.

[0195] For example, the liquid composition (LC1) can be selected from compositions for preparing vinyl esters, unsaturated polyesters, or epoxy resins, or the liquid composition (LC1) can be, for example, a styrene monomer or a (meth)acrylic monomer, a mixture thereof, or a liquid composition containing said monomer.

[0196] In one embodiment, the liquid composition (LC1) comprises at least one (meth)acrylic monomer (M2a), the (meth)acrylic monomer being selected from cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, bornyl acylate, bornyl methacrylate, norbornyl acylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phentyl acrylate, phentyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate, or a mixture thereof.

[0197] Preferably, the polymer composition (PC1) accounts for between 0.5% and 50% by weight, more preferably between 0.5% and 40% by weight, and even more preferably between 1% and 30% by weight, of the liquid polymer composition (LPC1) containing the liquid composition (LC1) and the polymer composition (PC1).

[0198] In one embodiment, the present invention is, a) Polymer composition (PC1) and b) Monomer (M2a) A liquid composition (LC2) containing, The same applies to liquid compositions (LC2) in which the weight ratio of polymer composition (PC1) to monomer (M2a) is between 1 / 99 and 25 / 75.

[0199] Preferably, monomer (M2a) is a (meth)acrylic monomer. Monomer (M2a) can be selected from the same list defined above.

[0200] The present invention also relates to the use of a polymer composition (PC1) in the form of a polymer powder according to the present invention as an impact-improving agent in a polymer for obtaining an impact-improving polymer composition. Preferably, the polymer is a thermosetting polymer or a thermoplastic polymer or a precursor thereof.

[0201] The present invention also relates to the use of polymer compositions (PC1) in the fields of UV curing, 3D printing, adhesives, structural adhesives, coatings, solid surfaces, wind energy, and compositions for composite materials (thermoplastic and thermosetting resins).

[0202] [Evaluation Method] glass transition temperature The glass transition (Tg) of polymers is measured using an instrument capable of performing thermomechanical analysis. The RDAII "RHEOMETRICS DYNAMIC ANALYSER" provided by Rheometrics was used. Thermomechanical analysis accurately measures the viscoelastic change of a sample as a function of applied temperature, strain, or deformation. This instrument continuously records the deformation of the sample during a controlled temperature program, while maintaining a constant strain.

[0203] The results are obtained by plotting the modulus of elasticity (G'), the loss modulus of elasticity, and the tan delta as functions of temperature. Tg is the highest temperature value read from the tan delta curve when the derived value of the tan delta is equal to zero.

[0204] molecular weight The mass-average molecular weight (Mw) of the polymer is measured by size exclusion chromatography (SEC). A polystyrene standard is used for calibration. The polymer is dissolved in THF at a concentration of 1 g / L. A modified silica chromatography column is used. The flow rate is 1 ml / min, and a refractive index detector is used.

[0205] extraction The extractable portion of the polymer composition is measured by gravimetric analysis. The sample is treated in 10 g / L THF (tetrahydrofuran) with stirring at 20°C for 4 hours. The solution is filtered, and after the solvent in the filtered solution is evaporated, the recovered polymer is weighed and its proportion is calculated.

[0206] Particle size analysis The particle size of the primary particles after multi-stage polymerization is measured using dynamic light scattering with a Malvern Zetasizer. The volume-average particle size (diameter) is then obtained. The particle size of the recovered polymer powder is measured by laser diffraction using a Malvern Mastersizer 3000 from MALVERN. To estimate the volume-average powder particle size, particle size distribution, and fine particle ratio, a Malvern Mastersizer3000 instrument equipped with a 300mm lens that measures in the range of 0.5 to 880 μm is used.

[0207] Apparent density Standard ISO 60:1977 is used. The sample is purified through a designated funnel into a 100 cubic centimeter graduated cylinder, the excess is removed using a straight ruler, and the mass of the contents is determined by weighing.

[0208] viscosity Viscosity can be easily measured using a rheometer or viscometer. Dynamic viscosity is measured at 25°C. If the liquid exhibits Newtonian behavior, it means there is no shear reduction, and the dynamic viscosity is independent of shear in the rheometer or migration speed in the viscometer. If the liquid composition exhibits non-Newtonian behavior, it means there is shear reduction, and the dynamic viscosity is 1 s at 25°C. -1 They are compared by their shear rates. [Examples]

[0209] [Examples] A polymer composition (PC) in the form of a core-shell multilayer polymer, comprising a core and two shell layers, was prepared for Comparative Example 1 according to the method described in International Publication No. 2020 / 260638. However, in Comparative Example 2, 30% by weight of the MMA in the synthesis of the two shell layers of Comparative Example 1 was replaced with isobornyl acrylate (IBOA).

[0210] Both resulting products are solidified with sulfuric acid and dried.

[0211] As Example 1, the following product was prepared: Stage 1 (A) - Polymerization of polymer type (A1): 116.5 parts deionized water, 0.1 part potassium salt of beef tallow fatty acid as an emulsifier, 21.9 parts 1,3-butadiene, 0.1 part t-dodecyl mercaptan, and 0.1 part p-menthane hydroperoxide were added to a 20-liter high-pressure reactor as the initial kettle charge. The solution was heated to 43°C while stirring, at which point a redox catalyst solution (4.5 parts water, 0.3 parts sodium tetrapyrophosphate, 0.004 parts ferrous sulfate, and 0.3 parts dextrose) was added to efficiently initiate polymerization. The solution was then further heated to 56°C and held at this temperature for 3 hours. Three hours after the start of polymerization, a second monomer charge (77.8 parts BD, 0.2 parts t-dodecyl mercaptan), half of the additional emulsifier, a reducing agent charge (30.4 parts deionized water, 2.8 parts potassium salt of beef tallow fatty acid as an emulsifier, 0.5 parts dextrose), and an additional initiator (0.8 parts p-menthane hydroperoxide) were added continuously over 8 hours. Following the completion of the second monomer addition, the remaining emulsifier, reducing agent charge, and initiator were added continuously over a further 5 hours. Thirteen hours after the start of polymerization, the solution was heated to 68°C and allowed to react for at least 20 hours from the start of polymerization to produce polybutadiene rubber latex. The resulting polybutadiene rubber latex (A1) contained 38% solids and had a weight-average particle size of approximately 160 nm. Stage 2 (B) - Polymerization of polymer type (B2): 71 parts of polybutadiene rubber latex A1, 37.6 parts of deionized water, and 0.1 part of sodium formaldehyde sulfoxylate were added to a 3.9 liter reactor, on a solids basis. The solution was stirred, purged with nitrogen, and heated to 77°C. When the solution reached 77°C, a mixture of 20.3 parts of methyl methacrylate, 8.7 parts of isobornyl acrylate, and 0.1 part of t-butyl hydroperoxide initiator was added continuously over 70 minutes, followed by holding for 80 minutes. 30 minutes after the start of the holding time, 0.1 parts of sodium formaldehyde sulfoxylate and 0.1 parts of t-butyl hydroperoxide were added to the reactor in one go.After an 80-minute holding time, 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 the graft copolymer), 0.1 parts of oleic acid, 0.1 parts of potassium hydroxide, and 0.9 parts of octadecyl-3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate. The resulting core-shell polymer (MP1) had a weight-average particle size of approximately 180 nm. Next, the final multi-stage polymer (MP1) was recovered by coagulation, and the polymer composition was coagulated with sulfuric acid and dried to obtain MP1 powder.

[0212] TIFF2026523200000001.tif72170

[0213] As shown in Table 1, the core-to-shell weight ratio (CS ratio) is 71 / 29, with the core making up 71% by weight and the shell 29% by weight. When present in the shell polymer, the weight ratio of isobornyl acrylate is 30% by weight.

[0214] TIFF2026523200000002.tif65170

[0215] The two powders from Comparative Example 1 and Example 1 were tested at different concentrations of isobornyl acrylate as the monomer (10% by weight in Figure 1 and 15% by weight in Figure 2). Viscosity (Pa * s) is given as a function of the shear rate of 1 / s at 25°C. Example 1 is represented by a square symbol, and Comparative Example 2 is represented by a diamond symbol. The results are shown in Figures 1 and 2.

[0216] Viscosity is compared at a shear rate of 1 / s in Table 3.

[0217] TIFF2026523200000003.tif93170

[0218] The compositions obtained by the present invention and the methods of the present invention result in a significantly reduced viscosity of the liquid composition. This allows for dispersion at much higher concentrations while maintaining the same viscosity.

Claims

1. A polymer composition (PC1), a) A polymer having a glass transition temperature of less than 10°C (A1) b) A polymer (B1) having a glass transition temperature of at least 60°C, wherein the polymer (B1) constitutes at least 10% by weight and up to 40% by weight of the composition based solely on a) and b). Includes, Components a) and b) of composition (PC1) are part of a multi-stage polymer (MP1), and polymer (B1) has a mass-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol. The polymer (B1) is characterized by containing polymerization monomer units that include alicyclic hydrocarbon groups having 3 to 20 carbon atoms. Polymer composition (PC1).

2. The polymer composition (PC1) according to claim 1, characterized in that a portion of polymer (B1) is grafted onto polymer (A1).

3. The polymer composition (PC1) according to claim 2, characterized in that at least 25% by weight of polymer (B1) is grafted onto it.

4. The polymer composition (PC1) according to claim 1, characterized in that at least 3% by weight of the polymer (B1) in the multi-stage polymer (MP1) can be solubilized in the solvent of the copolymer (B1) and extracted.

5. The polymer composition according to any one of claims 1 to 4, characterized in that each polymer (B1) does not contain a portion derived from a chain transfer agent, particularly a mercaptan-based chain transfer agent.

6. The polymer composition (PC1) according to any one of claims 1 to 5, characterized in that the polymer composition (PC1) contains less than 1000 ppm of sulfur.

7. The polymer composition according to any one of claims 1 to 7, characterized in that each polymer (B1) contains monomer units having alicyclic hydrocarbon groups having 3 to 20 carbon atoms in an amount between 25% and 35% by weight.

8. A polymer composition (PC1) according to any one of claims 1 to 7, characterized in that the monomer unit containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms is selected from cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phentyl acrylate, phentyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, cyclodecyl acrylate, and cyclodecyl methacrylate.

9. The polymer composition (PC1) according to any one of claims 1 to 8, characterized in that the polymer composition (PC1) in the form of porous polymer powder (POW1) has a total indentation volume of at least 1.2 ml / g as measured by mercury porosimetry.

10. The polymer composition (PC1) according to any one of claims 1 to 9, characterized in that the polymer composition (PC1) in the form of porous polymer powder (POW1) has a total intrusion volume or total cumulative intrusion volume between 1.2 ml / g and 10 ml / g as measured by mercury porosimetry.

11. The polymer composition (PC1) in the form of porous polymer powder (POW1) is characterized in that, as measured by mercury porosimetry, the polymer composition (PC1) has a cumulative intrusion amount of at least 0.9 ml / g for pore sizes greater than 10 μm, as described in any one of claims 1 to 10.

12. The polymer composition (PC1) in the form of porous polymer powder (POW1) is characterized in that, as measured by mercury porosimetry, it has an incremental injection amount of at least 0.1 ml / g between pore sizes of 10 μm and 1 μm, according to any one of claims 1 to 11.

13. A polymer composition (PC1) in the form of porous polymer powder (POW1) is present at a concentration of 0.1 g / cm³. ３ and 0.60 g / cm³ ３ A polymer composition (PC1) according to any one of claims 1 to 12, characterized by having an apparent bulk density between .

14. Polymer (B1) is a comonomer (Mc ｂ１ A copolymer containing the comonomer (Mc ｂ１ The polymer composition (PC1) according to any one of claims 1 to 13, characterized in that it contains an alicyclic hydrocarbon group having 3 to 20 carbon atoms.

15. Comonomer (Mc) in copolymer (B1) ｂ１ The polymer composition (PC1) according to claim 14, characterized in that the amount of ) is between 5% and 50% by weight, preferably between 10% and 40% by weight, and more preferably between 20% and 40% by weight.

16. A method for producing a polymer composition according to any one of claims 1 to 15, a) Monomer or monomer mixture (A ｍ A step of polymerizing by emulsion polymerization of ) to obtain one layer of step (A) containing a polymer (A1) having a glass transition temperature of less than 10°C; b) Monomer or monomer mixture (B ｍ A step of polymerizing by emulsion polymerization of ) to obtain a layer of step (B) containing a polymer (B1) having a glass transition temperature of at least 60°C. Including; The polymer (B1) accounts for at least 10% by weight and at most 40% by weight of the composition based only on a) and b), and further the polymer (B1) has a mass average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and the monomer or monomer mixture (B ｍ ) contains a comonomer (Mc ｂ１ ) containing an alicyclic hydrocarbon group having 3 to 20 carbon atoms, characterized in that method.

17. A method for producing a polymer composition according to any one of claims 1 to 15, a) Monomer or monomer mixture (A ｍ A step of polymerizing by emulsion polymerization of ) to obtain one layer of step (A) containing a polymer (A1) having a glass transition temperature of less than 10°C; b) Monomer or monomer mixture (B ｍ A step of polymerizing by emulsion polymerization of ) to obtain a layer of step (B) containing a polymer (B1) having a glass transition temperature of at least 60°C; c) A step of agglomerating the composition obtained in steps a) to b). Includes, The polymer (B1) constitutes at least 10% by weight and up to 40% by weight of the composition based solely on a) and b), and furthermore, the polymer (B1) has a mass-average molecular weight Mw between 10,000 g / mol and 500,000 g / mol, and is a monomer or monomer mixture (B ｍ ) contains a comonomer (Mc) with an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ｂ１ ) characterized by including method.

18. The method according to claim 16 or 17, characterized in that the coagulation step is carried out by solidification.

19. The method according to claim 16 or 17, characterized in that the coagulation step is carried out by spray drying.

20. The method according to claim 16 or 17, characterized in that no chain transfer agent, particularly a mercaptan-based chain transfer agent, is used during step b).

21. Use of a polymer composition (PC1) according to any one of claims 1 to 15, or a polymer composition (PC1) obtained by the method according to any one of claims 16 to 20, as an impact resistance modifier.

22. Use of a polymer composition (PC1) according to any one of claims 1 to 15, or a polymer composition (PC1) obtained by the method according to any one of claims 16 to 20, as a composition for shortening dispersion time.

23. A method for shortening the dispersion time of polymer powder in a low-polarity liquid composition by using a polymer composition (PC1) according to any one of claims 1 to 15 in the form of a polymer powder.

24. A polymer composition (PC2) comprising the polymer composition (PC1) according to any one of claims 1 to 15 as an impact resistance modifier.

25. A method for reducing the time required to disperse a polymer composition (PC1) in a liquid composition, a) A step of providing the polymer composition (PC1) according to the first embodiment in the form of a porous polymer powder POW1 having a total indentation volume of at least 1.2 ml / g as measured by mercury porosimetry, b) A step of bringing the polymer composition (PC1) into contact with the liquid composition (LC1) Methods that include...

26. a) A polymer composition (PC1) according to any one of claims 1 to 15, and b) Liquid composition (LC1) A liquid polymer composition (LPC1) containing the above.

27. A liquid composition (LC2), a) A polymer composition (PC1) according to any one of claims 1 to 15, or a polymer composition (PC1) obtained by the method according to any one of claims 16 to 20, and b) Monomer (M2a) Includes, A liquid composition (LC2) in which the weight ratio of polymer composition (PC1) to monomer (M2a) is between 1 / 99 and 25 / 75.

28. The liquid composition (LC2) according to claim 27, characterized in that the monomer (M2) is selected from cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, trimethylcyclohexyl acrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, phentyl acrylate, phentyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, cyclodecyl acrylate, cyclodecyl methacrylate, or a mixture thereof.

29. Use of a polymer composition (PC1) according to any one of claims 1 to 15 or a polymer composition (PC1) obtained by the method according to any one of claims 16 to 20 in the fields of UV curing, 3D printing, adhesives, structural adhesives, coatings, solid surfaces, wind energy, and compositions for composite materials (thermoplastic resins and thermosetting resins).

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