Stabilized gypsum particles

Abstract

The present invention relates to a construction chemical composition for the preparation of gypsum articles, the construction chemical composition comprising finely divided calcium sulfate and a polyaryl ether dispersant. The present invention also relates to a method for preparing the construction chemical composition and to an article comprising the construction chemical composition.

Description

[Technical Field]

[0001] The present invention relates to a building chemical composition for the preparation of gypsum-based articles, comprising a dispersant which is fine calcium sulfate and a polyaryl ether. Furthermore, the present invention relates to a method for preparing the building chemical composition and an article comprising the building chemical composition. [Background technology]

[0002] Crushed gypsum plays a crucial role in the manufacture of gypsum wallboard. So-called ball-mill setting accelerators (BMAs) are added as seeding agents to initiate the gypsum hardening reaction and ultimately shorten it. Combined with setting retarders, the addition of BMAs is essential to obtain higher mechanical strength in the final gypsum wallboard in a shorter time. However, the effect of BMAs is considerably limited due to their coarse and non-uniform particle size. Smaller particle sizes are needed to further reduce the hardening time, including improving mechanical performance. Such materials would likely allow for higher production rates of gypsum wallboards, reduced gypsum use, or gypsum wallboards with better mechanical performance.

[0003] An alternative method, in addition to grinding, is given by precipitation starting from soluble calcium and sulfate sources. U.S. Patent Application Publication No. 2015114268 relates to a method for producing calcium sulfate dihydrate by reacting a water-soluble calcium compound with a water-soluble sulfate compound in the presence of water and a polymer containing acid groups and polyether groups. Further disclosed are the calcium sulfate dihydrate that can be produced by this method and its use for the production of gypsum board. Disadvantages of precipitation starting from soluble calcium and sulfate sources are the relatively high cost of the starting materials and the complex process control, which leads to a high overall production cost of the final product.

[0004] A further technique for reducing the particle size of pulverized gypsum is the application of polymer dispersants in the wet grinding process. U.S. Patent No. 7,861,955 discloses wet grinding of gypsum using a polycarboxylate dispersant as a stabilizer to reduce the average particle size of gypsum with a high solids content. However, the application of the resulting gypsum particles does not lead to the acceleration of gypsum formation. Polycarboxylate dispersants generally have a decelerating effect on gypsum formation, thus working in the opposite way to a fine gypsum particle setting accelerator. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Therefore, there is a need in the art for a gypsum-containing composition, particularly a suitable building chemical composition as a setting accelerator for gypsum board, that does not have the aforementioned drawbacks of the prior art.

[0006] Therefore, an object of the present invention is to provide a suitable building chemical composition as a setting accelerator for gypsum compositions, characterized by an accelerated gypsum hardening reaction. Furthermore, the mechanical properties of the resulting gypsum articles should be further improved. Thus, a further object of the present invention is to obtain higher compressive strength of the prepared gypsum articles in a shorter period of time, which is important for manufacturing, transportation, and handling. [Means for solving the problem]

[0007] The above and other objectives are addressed by the subject matter of the present invention.

[0008] According to a first aspect of the present invention, a chemical composition for building, i) fine calcium sulfate particles having a D(0.63) particle size of less than 10.0 μm determined by laser diffraction (Mastersizer 2000 manufactured by Malvern Instruments) according to Mie theory for small particles (particle RI=1.531, dispersant RI=1.330; absorption=0.1; 10 to 20% Obscuration), and ii) a dispersant which is a polyaryl ether comprising, a chemical composition for construction is provided, wherein the mass ratio between the fine calcium sulfate particles and the dispersant is in the range of 0.1:99.9 to 99.9:0.1.

[0009] According to an embodiment of the present invention, the fine calcium sulfate particles are present in the form of calcium sulfate hemihydrate (mineral name: bassanite), calcium sulfate dihydrate (mineral name: gypsum), anhydrous calcium sulfate (mineral name: anhydrite) or a mixture thereof.

[0010] According to another embodiment of the present invention, the polyaryl ether is i) at least one aromatic or heteroaromatic structural unit comprising a polyether side chain, and ii) at least one phosphorylated aromatic or heteroaromatic structural unit a polycondensation product comprising

[0011] The at least one aromatic or heteroaromatic structural unit comprising a polyether side chain is represented by formula (I)

Chemical Formula

[0012] The building chemical composition may further contain an antifoaming agent to reduce the amount of foaming or bubbles generated during the preparation process. Any antifoaming agent suitable for use in an aqueous polyaryl ether dispersant-containing system may be used. Suitable examples of antifoaming agents that may be used include, but are not limited to, silicone antifoaming agents, mineral oil / silica antifoaming agents, low surface tension additives, and mixtures thereof. Examples of silicone antifoaming agents that may be used include, but are not limited to, polysiloxane solutions and non-aqueous emulsions of polysiloxane. Examples of polysiloxane solutions that may be used as antifoaming agents include, but are not limited to, cyclohexanone polysiloxane solutions, diisobutyl ketone polysiloxane solutions, and mixtures thereof. An example of a non-aqueous polysiloxane emulsion that may be used as an antifoaming agent is polysiloxane propylene glycol emulsion. In certain embodiments, the defoaming agent is a diisobutyl ketone polysiloxane solution commercially available from BYK Chemie GmbH (Wesel, Germany) under the trademarks BYK(registered trademark)-066N, BYK(registered trademark)-070, BYK(registered trademark)-077, and BYK(registered trademark)-A500. Further preferred examples of antifoaming agents include kerosene, liquid paraffin, animal oils, vegetable oils, sesame oil, castor oil, their alkylene oxide adducts, oleic acid, stearic acid and its alkylene oxide adducts, diethylene glycol laurate, glycerol monolicinolate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, polyoxyethylene monolaurate, polyoxyethylene sorbitol monolaurate, natural waxes, linear or branched fatty alcohols and their alkoxylated derivatives, octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycol, polyoxyalkylene glycol, polyoxyalkylene amide, acrylate polyamine, tributyl phosphate, sodium octyl phosphate; aluminum stearate, calcium oleate, silicone oil, silicone paste, silicone emulsion, fluorosilicone oil; and polyoxyethylene polyoxypropylene adducts. In preferred embodiments, the antifoaming agent is a polyoxyethylene polyoxypropylene adduct.The amount of defoaming agent used in building chemical compositions may range from about 0.002 to about 10 mass percent of the polyaryl ether dispersant.

[0013] The present invention further relates to a method for preparing a building chemical composition comprising fine calcium sulfate having a D(0.63) particle size of less than 10.0 μm, determined by laser diffraction according to Mie theory, and a dispersant which is a polyaryl ether, aa) A step of providing a suspension comprising calcium sulfate particles having a D(0.63) particle size of 10.0 μm or more, determined by laser diffraction according to Mie theory, water, and a dispersant which is a polyaryl ether, and ab) A step in which the suspension obtained in step aa) is wet-ground to obtain a building chemical composition. Includes, This invention relates to a method in which the mass ratio between fine calcium sulfate particles and a dispersant is in the range of 0.1:99.9 to 99.9:0.1. [Modes for carrying out the invention]

[0014] According to one embodiment of the present invention, calcium sulfate particles exist in the form of calcium sulfate hemihydrate (mineral name: basanyite), calcium sulfate dihydrate (mineral name: gypsum), anhydrous calcium sulfate (mineral name: anhydrous gypsum), or mixtures thereof.

[0015] It is preferable that the calcium sulfate particles exist in the form of calcium sulfate hemihydrate (mineral name: basanyite), calcium sulfate dihydrate (mineral name: gypsum), or a mixture thereof.

[0016] The polyaryl ether is preferably a polycondensation product as defined above.

[0017] According to one embodiment of the present invention, the suspension of step aa) has a solid content in the range of 6.0 to 75.0% by mass.

[0018] Solids content is defined as the ratio of the residual mass of the sample after drying at 40°C until a certain mass is reached, to the initial mass of the sample before heating.

[0019] According to another embodiment of the present invention, the mass ratio between calcium sulfate particles and the dispersant in the suspension of step aa) is in the range of 1.0 to 200.

[0020] According to a further embodiment of the present invention, the suspension of step aa) is, based on the total mass of the suspension, i) 5.0 to 70.0% by mass of calcium sulfate particles, ii) A dispersant that is a polyaryl ether in an amount of 0.01 to 10.0% by mass, and iii) Remaining water up to 100% by mass Includes.

[0021] According to one embodiment of the present invention, the wet grinding described in step a) is carried out in a ball mill, a rotary grinder, or a stirring bead mill.

[0022] According to another embodiment of the present invention, the method further comprises step ac), which involves drying the building chemical composition obtained in step a), thereby obtaining the building chemical composition in powder form.

[0023] The present invention further relates to a method for preparing a building chemical composition comprising fine calcium sulfate having a D(0.63) particle size of less than 10.0 μm, determined by laser diffraction according to Mie theory, and a dispersant which is a polyaryl ether, ba) A step of providing liquid A comprising a calcium source, water, and a dispersant which is a polyaryl ether, bb) A step of providing liquid B comprising a sulfate source, water and a dispersant which is optionally a polyaryl ether, and bc) A process to obtain a building chemical composition by precipitating fine calcium sulfate by mixing liquid A and liquid B. Includes, This invention relates to a method in which the mass ratio between fine calcium sulfate particles and a dispersant is in the range of 0.1:99.9 to 99.9:0.1.

[0024] The calcium source in liquid A is selected from the group consisting of calcium acetate, calcium chloride, calcium hydroxide, calcium nitrate, calcium oxide, calcium sulfamate, calcium thiocyanate, or mixtures thereof.

[0025] The sulfate source in liquid B is selected from the group consisting of aluminum sulfate, potassium sulfate, sodium sulfate, sulfuric acid, or mixtures thereof, and includes various hydrates of the listed sulfates.

[0026] The polyaryl ether is preferably a polycondensation product as defined above.

[0027] According to another embodiment of the present invention, the precipitation described in step bc) is carried out in a continuous microreactor or a spray precipitation reactor.

[0028] According to another embodiment of the present invention, the method further comprises step bd), which involves drying the building chemical composition obtained in step bc) to obtain a building chemical composition in powder form.

[0029] The present invention also relates to building chemical compositions obtained by the above method.

[0030] Furthermore, the present invention relates to the use of the above-mentioned building chemical composition in a method for manufacturing gypsum wallboard, wherein the method is a) A step of providing a composition comprising gypsum, preferably calcium sulfate hemihydrate (mineral name: basanyite), water, and optionally a foam. b) A step of supplying the composition obtained in step a) into a mixing device and thereby preparing a slurry, c) A step of applying the slurry obtained in step b) to the first cardboard sheet, and d) The process of covering the slurry with a second cardboard sheet. Includes, Here, i) At least one of the blended water and the foam contains the building chemical composition according to the present invention, and / or ii) The first cardboard sheet and / or the second cardboard sheet are coated with the building chemical composition according to the present invention, and / or iii) The invention relates to the use of a building chemical composition, in which it is added to a slurry in a mixing device or through a supply valve at the outlet of a mixing device.

[0031] The present invention further relates to the use of polyaryl ethers as dispersants in wet grinding or precipitation processes for the preparation of fine calcium sulfate.

[0032] It is particularly preferable that the polyaryl ether is the polycondensation product described above.

[0033] The present invention further relates to an article comprising the above-mentioned building chemical composition.

[0034] Preferably, the article is a gypsum wallboard or a nonwoven gypsum board.

[0035] The present invention will be described in more detail below.

[0036] architectural chemical compositions The present invention relates to a chemical composition for building construction, i) Fine calcium sulfate particles having a D(0.63) particle size of less than 10.0 μm, determined by laser diffraction according to Mie theory, and ii) Dispersant which is a polyaryl ether Includes, This invention relates to a chemical composition for construction in which the mass ratio between fine calcium sulfate particles and a dispersant is in the range of 0.1:99.9 to 99.9:0.1.

[0037] It is preferable that the fine calcium sulfate particles exist in the form of calcium sulfate hemihydrate (mineral name: basanyite), calcium sulfate dihydrate (mineral name: gypsum), anhydrous calcium sulfate (mineral name: anhydrous gypsum), or mixtures thereof.

[0038] As used herein, the term “gypsum” is used as a general term for the compound calcium sulfate dihydrate (CaSO4·2H2O) and the rock composed of this compound, as well as for the corresponding building material, calcium sulfate hemihydrate (CaSO4·0.5H2O or Basanyite) or anhydrous calcium sulfate (CaSO4 or anhydrous gypsum). Unless otherwise specified, as used herein, the term “gypsum” refers to the compound calcium sulfate in its anhydrous or hydrated form.

[0039] Gypsum (CaSO4·2H2O) exists naturally in large sediments formed when oceans dried up during Earth's history. Furthermore, gypsum (CaSO4·2H2O) is obtained as a product or by-product in various industrial applications. An example of such a process is flue gas desulfurization, in which sulfur dioxide is removed from the combustion off-gases of coal-fired power plants using calcium carbonate or calcium hydroxide slurry.

[0040] When heated to a temperature of 120-130°C, calcium sulfate dihydrate releases some of its crystallized water and converts to calcium sulfate hemihydrate (CaSO4·0.5H2O or basanyite). When calcium sulfate hemihydrate is mixed with water, calcium sulfate dihydrate is modified within a short time.

[0041] Calcium sulfate hemihydrate (basaniite) is an important building material for the manufacture of mortar, screed, molds, and especially gypsum board. Depending on the technical requirements, the calcium sulfate binder requires considerably different qualities. In particular, with respect to treatment life and the time it takes for curing, the binder must be adjustable over a range of periods from a few minutes to several hours. To meet these requirements, the use of mixtures that adjust curing is necessary.

[0042] A further component of the building chemical composition according to the present invention is a dispersant which is a polyaryl ether.

[0043] As used herein, the term "polyaryl ether" refers to polymer compounds comprising an aryl moiety and an ether moiety.

[0044] In particular, the polyaryl ether according to the present invention i) at least one aromatic or heteroaromatic structural unit comprising one or more polyether side chains, and ii) at least one phosphorylated aromatic or heteroaromatic structural unit It is preferable that the polycondensation product contains [a specific compound].

[0045] Preferably, the aromatic or heteroaromatic structural unit comprising one or more polyether side chains comprises one or more polyalkylene glycol side chains, more preferably one or more polyethylene glycol side chains. In particular, it is preferable that the aromatic or heteroaromatic structural unit comprising one or more polyether side chains, preferably one or more polyalkylene glycol side chains, is selected from the group consisting of alkoxylated, more preferably ethoxylated hydroxyl-functionalized aromatics or heteroaromatic compounds. For example, the hydroxyl-functionalized aromatic or heteroaromatic compound is selected from phenoxyethanol, phenoxypropanol, 2-alkoxyphenoxyethanol, 4-alkoxyphenoxyethanol, 2-alkylphenoxyethanol, 4-alkylphenoxyethanol, or mixtures thereof. Further preferred aromatic or heteroaromatic structural units comprising one or more polyether side chains, preferably one or more polyalkylene glycol side chains, are alkoxylated, preferably ethoxylated amino-functionalized aromatics or heteroaromatic compounds, such as N,N-(dihydroxyethyl)aniline, N-(hydroxyethyl)aniline, (dihydroxypropyl)aniline, N-(hydroxypropyl)aniline, or mixtures thereof. Alkoxylated phenol derivatives such as phenoxyethanol and / or phenoxypropanol are even more preferred. A molecular weight M in the range of 300 to 10,000 daltons. w Alkoxylated compounds having the property of polyethylene glycol monophenyl ether are particularly preferred, more preferably ethoxylated phenol derivatives, such as polyethylene glycol monophenyl ether.

[0046] As outlined above, the polyaryl ethers, which are polycondensation products according to the present invention, further comprise at least one phosphorylated aromatic or heteroaromatic structural unit. Therefore, although not limited by theory, the polyaryl ethers have some acidity based on the presence of the phosphorylated aromatic or heteroaromatic structural unit. The phosphorylated aromatic or heteroaromatic structural unit can be obtained by phosphorylating the corresponding alcohol with polyphosphoric acid and / or phosphorus pentoxide according to methods known in the art.

[0047] Preferably, the phosphorylated aromatic or heteroaromatic structural unit is alkoxylated with at least one phosphate ester group, preferably an ethoxylated hydroxyl-functionalized aromatic or heteroaromatic compound, such as phenoxyethanol phosphate and / or poly(ethylene glycol) monophenyl ether phosphate and / or alkoxylated with at least one phosphate ester group, preferably an ethoxylated amino-functionalized aromatic or heteroaromatic compound, such as N,N-(dihydroxyethyl)aniline diphosphate, N,N-(dihydroxyethyl)aniline phosphate, N-(hydroxypropyl)aniline phosphate, N,N-(dihydroxyethyl)aniline phosphate, N-(hydroxypropyl)aniline phosphate, or a mixture thereof. More preferably, an alkoxylated with at least one phosphate ester group is an ethoxylated phenol derivative, such as polyethylene glycol monophenyl ether phosphate, which is even more preferable.

[0048] Furthermore, the polyaryl ether, which is the condensation product according to the present invention, has a molecular weight M in the range of 4,000 to 150,000 daltons, more preferably 10,000 to 100,000 daltons, and even more preferably 15,000 to 75,000 daltons. w It is preferable to have the following: Mass molecular weight M w This is determined by size exclusion chromatography (column combination: Shodex (Japan) OH-Pak SB-G, OH-Pak SB 804, and OH-Pak SB 802.5 HQ; eluent: 80 vol% aqueous solution of HCO2NH4 (0.05 mol / L) and 20 vol% acetonitrile; injection volume 100 μL, throughput rate 0.5 mL / min). Molecular weight M w Linear poly(ethylene oxide)- and polyethylene glycol standards were used for calibration to determine the coefficients.

[0049] At least one aromatic or heteroaromatic structural unit containing a polyether side chain is given by formula (I)

Chem.

Chem.

[0050] More preferably, at least one aromatic or heteroaromatic structural unit including a polyether side chain is defined by formula (I) above (wherein, A is represented by a substituted or unsubstituted aromatic compound having 5 to 10 carbon atoms, which may or may not be the same; B is represented by O; n=1; R 1 and R 2 These are independent of each other, either identical or different, and represented by branched or linear C1-C5 alkyl groups or H; a is either the same or different, and is represented by an integer between 1 and 300; X is either the same or different, and is represented by a branched or linear C1-C10 alkyl group, an aryl group, or H. Represented by, and At least one phosphorylated aromatic or heteroaromatic structural unit is defined by formula (II) above (wherein, D is represented by a substituted or unsubstituted aromatic compound having 5 to 10 carbon atoms, which may or may not be the same; E is represented by O; m=1; R 3 and R 4 These are independently of each other, identical or different, and represented by branched or linear C1-C10 alkyl groups, aryl groups, or H; b is either the same or different, and is represented by an integer between 0 and 300. It is represented by [this].

[0051] More preferably, at least one aromatic or heteroaromatic structural unit including a polyether side chain is defined by formula (I) above (wherein, A is represented by an unsubstituted aromatic compound having 5 to 10 carbon atoms, which may or may not be the same; B is represented by O; n=1; R 1 and R 2 However, they are represented independently by methyl or H; a is either the same or different, and is represented by an integer between 1 and 300; X is represented by H. Represented by, and At least one phosphorylated aromatic or heteroaromatic structural unit is defined by formula (II) above (wherein, D is represented by an unsubstituted aromatic compound having 5 to 10 carbon atoms, which may or may not be the same; E is represented by O; m=1; R 3 and R 4 These are represented independently by methyl or H; b is either the same or different, and is represented by an integer between 0 and 300. It is represented by [this].

[0052] More preferably, at least one aromatic or heteroaromatic structural unit including a polyether side chain is defined by formula (I) above (wherein, A is represented by phenyl; B is represented by O; n=1; R 1 and R 2 It is represented by H; a is either the same or different, and is represented by an integer between 1 and 300; X is represented by H. Represented by, and At least one phosphorylated aromatic or heteroaromatic structural unit is defined by formula (II) above (wherein, D is represented by phenyl; E is represented by O; m=1; R 3 and R4 It is represented by H; b is either the same or different, and is represented by an integer between 0 and 300. It is represented by [this].

[0053] According to a preferred embodiment of the present invention, the polyaryl ether is of formula (III) [ka] (In the formula, Y is independent of each other, either identical or different, and is represented by the above formula (I) or (II). R 5 and R 6 (These are represented by substituted or unsubstituted aromatic or heteroaromatic compounds having H, methyl, COOH, or 5 to 10 C atoms, independently of each other, and either identical or different from each other.) It includes further structural units represented by

[0054] More preferably, the further structural unit is the above formula (III) (wherein, Y is independent of each other, either identical or different, and is represented by the above formula (I) or (II). R 5 and R 6 (These are independent of each other, either identical or different, and represented by H, methyl, or phenyl.) It is represented by [this].

[0055] More preferably, the further structural unit is the above formula (III) (wherein, Y is independent of each other, either identical or different, and is represented by the above formula (I) or (II). R 5 and R 6 (This is represented by H) It is represented by [this].

[0056] The molar ratio (III):[(I)+(II)] between structural units (I), (II), and (III) in the polyaryl ether is preferably in the range of 1:0.5 to 2.0, more preferably in the range of 1:0.9 to 2.0. The molar ratio (I):(II) between structural units (I) and (II) in the polyaryl ether is preferably in the range of 1:10 to 10:1, more preferably in the range of 1:5 to 3:1.

[0057] Polyaryl ethers suitable for the wet grinding process according to the present invention can be obtained by methods known in the art. For example, a method for preparing the polyaryl ether is described in International Publication No. 2010 / 040611A1.

[0058] Preferably, the mass ratio of fine calcium sulfate particles to the dispersant in the building chemical composition according to the present invention is in the range of 0.1:99.9 to 99.9:0.1, more preferably in the range of 60.0:40.0 to 99.0 to 1.0, even more preferably in the range of 50.0:50.0 to 99.0:1.0, and even more preferably in the range of 80.0:20.0 to 98.0 to 2.0, for example, in the range of 85.0:15.0 to 99.9:0.1. It is particularly preferable that the mass ratio of fine calcium sulfate particles to the dispersant is in the range of 85.0:15.0 to 99.9:0.1.

[0059] Furthermore, it is preferable that the building chemical composition according to the present invention is a liquid building chemical composition, and more preferably an aqueous building chemical composition.

[0060] Therefore, a further component of the building chemical composition is water.

[0061] Therefore, the building chemical composition is determined based on the total mass of the building chemical composition. i) Fine calcium sulfate particles in an amount of 0.07 to 70.0 mass%, more preferably 5.0 to 60.0 mass%, even more preferably 10.0 to 60.0 mass%, even more preferably 15.0 to 45 mass%, and even more preferably 20.0 to 35.0 mass%, ii) A dispersant that is a polyaryl ether, in an amount of 0.07 to 70.0% by mass, more preferably 0.1 to 40.0% by mass, even more preferably 0.1 to 5.0% by mass, and even more preferably 0.5 to 3.0% by mass, and iii) Remaining water up to 100% by mass It is preferable to include it.

[0062] In addition to the polyaryl ethers described above, the building chemical composition may contain further dispersants other than polyaryl ethers. Preferably, the slurry described in step aa), ba), or bb) contains at least one dispersant other than polyaryl ether. Non-limiting examples of such dispersants are cationic polymers, polyamines, polyamides, polycondensates containing sulfonic acids, ketone resins, or mixtures thereof.

[0063] Accordingly, according to a preferred embodiment of the present invention, the building chemical composition further comprises a dispersant selected from the group consisting of cationic polymers, polyamines, polyamides, polycondensates containing sulfonic acid, ketone resins, or mixtures thereof.

[0064] As used herein, the term "cationic polymer" refers to a polymer having cationic groups in its main chain or as side chains.

[0065] Non-limiting examples of suitable cationic polymers include 3–97 mol% cationic structural units of formula (IV). [ka] (In the formula, R 7 Each instance, it represents hydrogen and / or methyl, and may be the same or different. R 8 Each time it appears, it may be the same or different, preferably [ka] A quaternary amine, pyridinium, or pyrazole cation selected from the group consisting of the following: During the ceremony, R 9 , R 10 and R 11 Each instance of these terms, whether the same or different, independently represents hydrogen, an aliphatic hydrocarbon moiety having 1 to 20 carbon atoms, an alicyclic hydrocarbon moiety having 5 to 8 carbon atoms, and an aryl and / or polyethylene glycol (PEG) moiety having 6 to 14 carbon atoms. Each instance of l represents an integer between 0 and 2, which may be the same or different. Each instance of m is either the same or different, representing either 0 or 1. n, each time it appears, is either the same or different, and represents an integer between 1 and 10. Each time Y appears, it may be the same or different, indicating the absence of a group, or oxygen, NH and / or NR. 9 This represents, Each time V appears, it may be the same or different. [ka] This represents, During the ceremony, x represents an integer between 0 and 6, which may be the same or different each time it appears. Each instance of X represents a monovalent equivalent of a polyvalent anion selected from halogen atoms, C1-4 alkyl sulfates, C1-4 alkyl sulfonates, C6-14-(alk) aryl sulfonates, and / or sulfates, disulfates, phosphates, diphosphates, triphosphates, and / or polyphosphates, whether the same or different each time it appears. It is a cationic copolymer containing [a specific compound].

[0066] An example of the cationic polymer is described in U.S. Patent Application Publication No. 2016 / 0369024.

[0067] As used herein, the term "polyamine" refers to a polymer containing an amine moiety in its main chain. Preferably, the polyamine is an unsubstituted or polyalkyleneamine substituted with one or more alkyl or hydroxyl groups. [ka] (In the formula, Each instance of x is 0 to 4, more preferably 0 to 2, and even more preferably 0. Each time y appears, it is 1, 2, or 3. R 12 Each instance is H or CH3, more preferably H. R 13 (Each instance is a linear or branched C1-C5 alkyl group, optionally substituted with hydrogen, hydroxyl, or hydroxyl.) It is particularly preferable that this be the case.

[0068] As used herein, the term "polycondensate containing sulfonic acid" refers to a polymer dispersant containing sulfonic acid groups obtained by polycondensation. Non-limiting examples of suitable polycondensates containing sulfonic acid include β-naphthalene sulfonate-formaldehyde condensate (BNS), sulfonated melamine-formaldehyde condensate, or acetone-formaldehyde condensate.

[0069] As used herein, the term “ketone resin” refers to a monomer-based condensation product in which the monomers comprise at least ketone(I) and formaldehyde(II). Preferably, the condensation product further comprises at least one moiety(III) selected from the group consisting of phosphono, sulfite, sulfino, sulfamide, sulfoxy, sulfalkyloxy, sulfinoalkyloxy, phosphonooxy and / or salts thereof, where alkyl can be selected from any branched or unbranched C1-C10 alkyl. Generally, the monomer ratio(I) / (II) / (III) is 1 / 2 to 3 / 0.33 to 1.

[0070] The ketone resin is preferably prepared from cyclohexanone and / or acetone, formaldehyde and sulfite as monomers, and more preferably from cyclohexanone, formaldehyde and sulfite.

[0071] Preferably, the ketone resin has a molecular weight of 10,000 to 40,000 g / mol, more preferably 15,000 to 25,000 g / mol.

[0072] Suitable ketone resins are described, for example, in U.S. Patent Application Publication No. 2016 / 0229748.

[0073] Preferably, the building chemical composition according to the present invention contains at least one dispersant other than a polyaryl ether in an amount of 0.01 to 10.0% by mass, more preferably 0.1 to 6.0% by mass, and even more preferably 1.0 to 3.0% by mass, based on the total mass of the building chemical composition.

[0074] The building chemical composition may further contain stabilizers.

[0075] As used herein, the term “stabilizer” refers to additives that increase the shelf life of liquid building chemical compositions. Non-limiting examples of stabilizers are oligosaccharides and polysaccharides, preferably starch ethers, gellan gum, diutan gum, xanthan gum, chitosan, guar derivatives, or mixtures thereof.

[0076] Preferably, the building chemical composition contains a stabilizer in an amount of 0.01 to 8.0% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 0.2 to 2.0% by mass, based on the total mass of the slurry.

[0077] Furthermore, building chemical compositions can be modified by the presence of additives. Generally, gypsum slurry contains additives that affect its flow properties or curing process. For example, slurry may contain one or more additives selected from the group consisting of cellulose ether, slaked lime, mineral additives, low-density aggregates, fibers, setting accelerators, thickeners, setting retarders, air entrainers, foaming agents, leavening agents, fillers, polyacrylates, dispersants, superabsorbers, and stabilizers.

[0078] Therefore, the building chemical composition is determined based on the total mass of the building chemical composition. i) 0.07 to 70.0 mass%, more preferably 15.0 to 60.0 mass%, and even more preferably 20.0 to 45 mass% of gypsum, ii) A dispersant that is a polyaryl ether, in an amount of 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 0.5 to 3.0% by mass. iii) Optionally, 0.01 to 9.0% by mass, more preferably 0.1 to 6.0% by mass, and even more preferably 1.0 to 3.0% by mass, at least one dispersant other than a polyaryl ether. iv) Optionally, 0.01 to 7.0% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 0.2 to 2.0% by mass of a stabilizer. v) Optionally, an additive in an amount of 4.0% by mass or less, more preferably 0.01 to 3.0% by mass, and even more preferably 0.1 to 2.0% by mass, and vi) Remaining water up to 100% by mass It is preferable to include, or more preferably consist of, these.

[0079] Preferably, the building chemical composition may contain a setting retarder and / or a setting accelerator.

[0080] As used herein, the term “coagulation retarder” refers to additives that delay the hydration of calcium sulfate hemihydrate (basanyite) or anhydrous calcium sulfate (anhydrous gypsum) during the formation of calcium sulfate dihydrate (gypsum). Non-limiting examples of coagulation retarders include fruit acids (e.g., tartaric acid, citric acid) and their salts, glucons, protein hydrolysates, amino acid polycondensates, phosphates, phosphonates, complexing agents, hydroxycarboxylic acids, saccharides, organic phosphates, and mixtures thereof.

[0081] As used herein, the term “coagulation accelerator” refers to an additive that accelerates the hydration of calcium sulfate hemihydrate (basanyite) or anhydrous calcium sulfate (anhydrous gypsum) during the formation of calcium sulfate dihydrate (gypsum). Non-limiting examples of coagulation accelerators include K2SO4 and its finely ground dihydrate.

[0082] method As outlined above, the method according to the present invention is aa) A step of providing a suspension comprising calcium sulfate particles having a D(0.63) particle size of 10.0 μm or more, determined by laser diffraction according to Mie theory, water, and a dispersant which is a polyaryl ether, and ab) A step in which the suspension obtained in step aa) is wet-ground to obtain a building chemical composition. Includes, The mass ratio between fine calcium sulfate particles and the dispersant is in the range of 0.1:99.9 to 99.9:0.1.

[0083] According to step aa) of the method of the present invention, a suspension is provided comprising gypsum, water, and a dispersant which is a polyaryl ether.

[0084] The definition of gypsum shown above is to be used with respect to the term. According to this invention, either natural gypsum or synthetic gypsum is used. Natural gypsum does not require physical or chemical treatment to make it useful for its intended use.

[0085] The definitions given above are similarly applicable to the term polyaryl ether. It is preferable that the polyaryl ether is the polycondensation product described above.

[0086] Preferably, the initial particle size of the gypsum, i.e., the particle size before the wet grinding step a), is in the range of 10.0 to 250.0 μm, more preferably 15.0 to 200.0 μm, and even more preferably 20.0 to 150.0 μm, and is determined according to D(0.63) measured using laser diffraction according to Mie theory.

[0087] According to a preferred embodiment of the present invention, the suspension of step aa) has a solid content of 6.0 to 75.0% by mass, more preferably 20.0 to 65.0% by mass, and even more preferably 30.0 to 60.0% by mass, for example, 35.0 to 50.0% by mass.

[0088] A further component of the suspension described in step aa) of the method of the present invention is water.

[0089] Therefore, the suspension described in step aa) is, based on the total mass of the suspension, i) Fine calcium sulfate particles in an amount of 0.07 to 70.0 mass%, more preferably 5.0 to 60.0 mass%, even more preferably 10.0 to 60.0 mass%, even more preferably 15.0 to 45 mass%, and even more preferably 20.0 to 35.0 mass%, ii) A dispersant that is a polyaryl ether, in an amount of 0.07 to 70.0% by mass, more preferably 0.1 to 40.0% by mass, even more preferably 0.1 to 5.0% by mass, and even more preferably 0.5 to 3.0% by mass, and iii) Remaining water up to 100% by mass It is preferable to include it.

[0090] Furthermore, the suspension described in step aa) may include a dispersant other than a polyaryl ether, selected from the group consisting of cationic polymers, polyamines, polyamides, polycondensates containing sulfonic acid, ketone resins, or mixtures thereof, as described above.

[0091] The suspension described in step aa) may also include the above-mentioned stabilizers and / or further additives.

[0092] Therefore, the suspension described in step aa) is, based on the total mass of the suspension, i) 0.07 to 70.0 mass%, more preferably 15.0 to 60.0 mass%, and even more preferably 20.0 to 45 mass% of gypsum, ii) A dispersant that is a polyaryl ether, in an amount of 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 0.5 to 3.0% by mass. iii) Optionally, 0.01 to 9.0% by mass, more preferably 0.1 to 6.0% by mass, and even more preferably 1.0 to 3.0% by mass, at least one dispersant other than a polyaryl ether. iv) Optionally, 0.01 to 7.0% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 0.2 to 2.0% by mass of a stabilizer. v) Optionally, an additive in an amount of 4.0% by mass or less, more preferably 0.01 to 3.0% by mass, and even more preferably 0.1 to 2.0% by mass, and vi) Remaining water up to 100% by mass It is preferable to include, or more preferably consist of, these.

[0093] According to step a) of the method of the present invention, the slurry obtained in step aa) is subjected to a wet grinding process to obtain fine calcium sulfate particles.

[0094] The suspension described in step aa) is ground by any known grinding or crushing device. Non-limiting examples of suitable grinding devices include ball mills, rotary grinders, agitated bead mills, or any aqueous grinding devices.

[0095] In particular, wet grinding can be carried out in an agitated bead mill. An agitated bead mill includes a grinding chamber containing a grinding medium, as well as a stator and a rotor. Preferably, the agitated bead mill includes a grinding material inlet opening and a grinding material outlet opening for supplying and discharging the ground material into and out of the grinding chamber, and a grinding medium separation device positioned in the grinding chamber upstream of the outlet opening to separate the grinding medium particles from the grinding material before the grinding material is discharged from the grinding chamber through the outlet opening.

[0096] To improve the mechanical grinding performance in the grinding chamber, pins protruding into the grinding chamber are preferably present on the rotor and / or stator. During operation, on the one hand, the direct contribution to grinding performance is given by the impact between the material being ground and the pins. On the other hand, further contributions to grinding performance occur indirectly through the impact between the pins and the grinding medium particles incorporated into the material being ground, and subsequent impacts between the material being ground and the grinding medium particles. Finally, the shear and stretching forces acting on the material being ground also contribute to the crushing of the suspended material being ground.

[0097] Preferably, the final particle size of the fine calcium sulfate particles, i.e., the particle size after the wet grinding process, is less than 10.0 μm, more preferably less than 5.0 μm, and even more preferably in the range of 0.1 to 2.0 μm, determined according to D(0.63) measured using laser diffraction (Mastersizer 2000 from Malvern Instruments) according to Mie theory for small particles (particle RI=1.531, dispersant RI=1.330; absorption=0.1; absorbance of 10-20%).

[0098] According to another embodiment of the present invention, a method for preparing a building chemical composition comprising fine calcium sulfate having a D(0.63) particle size of less than 10.0 μm determined by laser diffraction according to Mie theory, and a dispersant which is a polyaryl ether, ba) A step of providing liquid A comprising a calcium source, water, and a dispersant which is optionally a polyaryl ether, bb) A step of providing liquid B comprising a sulfate source, water and a dispersant which is optionally a polyaryl ether, and bc) A process to obtain a building chemical composition by precipitating fine calcium sulfate by mixing liquid A and liquid B. Includes, A method in which the mass ratio between fine calcium sulfate particles and a dispersant is in the range of 0.1:99.9 to 99.9:0.1.

[0099] The dispersant, which is a polyaryl ether, is present in liquid A, liquid B, or both liquids A and B.

[0100] The calcium source in liquid A is selected from the group consisting of calcium acetate, calcium chloride, calcium hydroxide, calcium nitrate, calcium oxide, calcium sulfamate, calcium sulfate dihydrate, calcium sulfate hemihydrate, anhydrous calcium sulfate, calcium thiocyanate, or mixtures thereof.

[0101] The sulfate source in liquid B is selected from the group consisting of aluminum sulfate, potassium sulfate, sodium sulfate, sulfuric acid, or mixtures thereof, and includes various hydrates of the listed sulfates.

[0102] It is preferable that the polyaryl ether is the polycondensation product described above.

[0103] Preferably, the precipitation described in step bc) is carried out in a continuous microreactor or a spray precipitation reactor.

[0104] In particular, fine calcium sulfate can be precipitated by a microjet reactor (MJR) process according to step bc). A preferred process is described in German Patent No. 102004038029. Particularly preferred is the microjet reactor described in European Patent No. 1165224, in which precipitation is carried out by injecting two liquid media into the reactor chamber by a pump, preferably a high-pressure pump. The reactor chamber is preferably enclosed in a reactor housing. The two liquid media are preferably injected at a common impact point, and each medium is injected through one nozzle. Through the openings of the reactor chamber, a gas, evaporating liquid, cooling liquid, or cooling gas is preferably introduced to maintain the gas atmosphere inside the reactor, especially at the impact point of the liquid jets, and to cool the resulting product. Furthermore, the gas is also beneficial for stabilizing the mixing area and avoiding clogging. The resulting product and excess gas are preferably removed from the reactor housing through further openings by positive pressure on the gas inlet side or by negative pressure on the product and gas discharge side.

[0105] The nozzles of the microjet reactor (MJR) are not particularly limited in terms of their diameter. For example, the nozzles may independently have diameters ranging from 50 μm to 1 mm, such as 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1000 μm. Preferably, the nozzles have a diameter of 300 μm, i.e., 300 μm (liquid A) and 300 μm (liquid B). The polyaryl ether may be present in liquid A and / or liquid B. Preferably, the polyaryl ether is present in liquid A.

[0106] Preferably, liquid A contains 0.1 to 60.0% by mass of a calcium source, more preferably 1.0 to 50.0% by mass, even more preferably 2.0 to 40.0% by mass, and 0.0001 to 20.0% by mass of polyaryl ether, more preferably 0.001 to 15.0% by mass, and even more preferably 0.01 to 10.0% by mass, based on the total mass of raw material 1.

[0107] Furthermore, liquid B preferably contains 0.1 to 60.0% by mass of a sulfate source, more preferably 1.0 to 50.0% by mass, even more preferably 2.0 to 40.0% by mass, and optionally 0.0001 to 20.0% by mass of polyaryl ether, more preferably 0.001 to 15.0% by mass, and even more preferably 0.01 to 10.0% by mass, based on the total mass of raw material 2.

[0108] The flow rate of liquid A and / or liquid B is preferably in the range of 100 mL / min to 800 mL / min, more preferably in the range of 200 mL / min to 650 mL / min, more preferably in the range of 250 mL / min to 550 mL / min, and even more preferably in the range of 280 mL / min to 500 mL / min.

[0109] Furthermore, liquid A and / or liquid B preferably have an upstream pressure in the range of 10 to 350 bar, preferably in the range of 20 to 150 bar, more preferably in the range of 30 to 120 bar, and even more preferably in the range of 40 to 100 bar, for example, 80 bar.

[0110] The suspension according to the present invention may also be precipitated by a micronization process. For example, a preferred micronization process is described in European Patent No. 0065193.

[0111] In the micronization process, a composition comprising calcium sulfate, a dispersant (a polyaryl ether), and a solvent is prepared in a first mixing chamber. Subsequently, the composition is precipitated in a second mixing chamber by the addition of further solvents.

[0112] In a preferred embodiment, a suspension of gypsum in a selected solvent is first introduced into a first tank. A second tank preferably contains a mixed gypsum-free solvent. A polyaryl ether may be present in the first and / or second tanks. The suspension and solvent are supplied to a first mixing chamber. Before entering the mixing chamber, the gypsum suspension and / or solvent may be heated to a desired temperature by a heat exchanger. As a result of turbulent mixing in the first mixing chamber, dissolution of the gypsum occurs, and the resulting solution, after a short residence time of preferably less than 1 second, enters a second mixing chamber, where the gypsum is precipitated in a colloidally dispersed form by the mixture of solvents.

[0113] Alternatively, the suspension according to the present invention may be precipitated by a cross-flow nozzle process. In the cross-flow nozzle process, a first flow containing the gypsum suspension and a solvent is supplied into a mixing chamber, while, preferably, a second flow positioned perpendicular to the first flow is supplied into the mixing chamber, the second flow containing the solvent. A dispersant, which is a polyaryl ether, may be present in the first flow and / or the second flow.

[0114] Furthermore, the suspension according to the present invention may be precipitated by intensive mixing / spray precipitation (HTE) technology. This technology is well known in the art.

[0115] The present invention further relates to the use of polyaryl ethers as dispersants in wet grinding or precipitation processes for the preparation of fine calcium sulfate.

[0116] Preferably, the polyaryl ether is the polycondensation product described above.

[0117] Furthermore, it is preferable that the building chemical composition according to the present invention is a powder having powder particles with a D(0.63) particle size of less than 500.0 μm, preferably <200 μm, and more preferably <100 μm, determined by laser diffraction according to Mie theory.

[0118] The fine calcium sulfate particles according to the present invention are embedded in powder particles after drying.

[0119] The powder is produced in step ac) or bd) by drying the suspension containing the building chemical composition according to the present invention obtained in process step a) or bc).

[0120] Therefore, the powder is i) Fine calcium sulfate particles having a D(0.63) particle size of less than 10.0 μm, determined by laser diffraction according to Mie theory, and ii) Dispersant which is a polyaryl ether A composition according to the present invention, comprising, The composition has a mass ratio between fine calcium sulfate particles and a dispersant in the range of 0.1:99.9 to 99.9:0.1.

[0121] Preferably, the mass ratio of fine calcium sulfate particles to the dispersant in the powder is in the range of 60.0:40.0 to 99.0 to 1.0, more preferably in the range of 50.0:50.0 to 99.0:1.0, and even more preferably in the range of 80.0:20.0 to 98.0 to 2.0, for example, in the range of 85.0:15.0 to 99.9:0.1. It is particularly preferable that the mass ratio of fine calcium sulfate particles to the dispersant is in the range of 85.0:15.0 to 99.9:0.1.

[0122] In addition to or instead of the previous paragraph, the powder, based on the total mass of the powder, i) Fine calcium sulfate particles in an amount of 0.1 to 99.9% by mass, more preferably 50.0 to 99.0% by mass, even more preferably 80.0 to 99.0% by mass, for example, 85.0 to 99.0% by mass, and ii) A dispersant that is a polyaryl ether, in an amount of 0.1 to 99.9% by mass, more preferably 1.0 to 50.0% by mass, and even more preferably 1.0 to 20.0% by mass, for example, 1.0 to 15.0% by mass. It is preferable to include it.

[0123] Furthermore, the powder may also contain additives other than polyaryl ethers, such as further dispersants, stabilizers, and additives that affect flow properties or the curing process. The definitions of such additives are to be referenced above.

[0124] Therefore, the powder is preferably measured based on the total mass of the powder. i) 70.0 to 99.9% by mass, more preferably 75.0 to 99.0% by mass, even more preferably 80.0 to 99.0% by mass, for example, 85.0 to 99.0% by mass of fine calcium sulfate particles. ii) A dispersant that is a polyaryl ether, in an amount of 0.1 to 20.0% by mass, more preferably 1.0 to 18.0% by mass, and even more preferably 1.0 to 15.0% by mass, for example, 1.0 to 12.0% by mass. iii) Optionally, 0.01 to 6.0% by mass, more preferably 0.1 to 3.0% by mass, and even more preferably 1.0 to 1.0% by mass, at least one dispersant other than a polyaryl ether. iv) Optionally, 0.01 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, and a stabilizer, and v) Optionally, an additive in an amount of 1.0% by mass or less, more preferably 0.01 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass. It includes, more preferably, consists of.

[0125] Even more surprising was that the dried setting accelerator of the present invention exhibited higher storage stability than conventional gypsum-based setting accelerators produced by a dry milling process in the presence of starch, surfactants, and / or sugars. The setting-promoting properties of dry-milled gypsum-based setting accelerators deteriorate significantly, especially after storage at high humidity. This is not the case with the dried setting accelerator of the present invention. Therefore, the dried mortar containing the powder also has very good storage stability. A preferred dried mortar mixture contains calcium sulfate as a binder component and is applied, for example, as plaster, jointing material, joint mortar filler, screed, or self-leveling substrate.

[0126] The present invention also relates to articles comprising the above-mentioned chemical compositions for construction.

[0127] Preferably, the articles are selected from the group consisting of gypsum wallboard, nonwoven gypsum board, stucco, mortar plaster, machine-compliant plaster, plaster gypsum, adhesive plaster, joint gypsum, gypsum-based fillers, screed plaster, finishing plaster, and marble plaster.

[0128] It is particularly preferable that the item is gypsum wallboard.

[0129] Accordingly, the present invention also relates to the use of the above-mentioned building chemical compositions in a method for manufacturing gypsum wallboard. Methods for preparing gypsum wallboard are well known in the art and generally involve the preparation of a foamed gypsum slurry, which is then applied to cardboard sheets.

[0130] Therefore, this method, ca) A step of providing a composition comprising gypsum, water, and optionally a foam, cb) A step of supplying the composition obtained in step ca) into a mixing device and thereby preparing a slurry, A step of applying the slurry obtained in step cb) to the first cardboard sheet, and cd) The process of covering the slurry with a second cardboard sheet. It is preferable to include it.

[0131] The building chemical composition may be added to the slurry during steps ca), cb), cc), and / or cd). In particular, the compound water and / or foam added to the composition in step ca) may contain the building chemical composition. The building chemical composition may also be applied to the first and / or second cardboard sheets before steps cc) and cd).

[0132] In addition to or instead of the above, the building chemical composition may be added directly to the slurry in the mixing device during step cb) and / or via a supply valve at the outlet of the mixing device.

[0133] Therefore, at least one of the mixed water and the foam contains a building chemical composition, and / or the building chemical composition is added to the slurry in the mixing device or through a supply valve at the outlet of the mixing device.

[0134] In addition to or instead of the preceding paragraph, the first cardboard sheet and / or the second cardboard sheet are coated with a building chemical composition.

[0135] Preferred methods for adding building chemical compositions are described, for example, in U.S. Patent Application Publication No. 2015114268A, International Publication No. 06115497A1, U.S. Patent Application Publication No. 2006244182A, and U.S. Patent Application Publication No. 2006244183A.

[0136] Furthermore, the present invention also relates to the use of the above-mentioned building chemical compositions in methods for producing gypsum containing dry mortar, nonwoven gypsum board, stucco, mortar plaster, machine-ready plaster, plaster gypsum, adhesive plaster, joint plaster, gypsum-based fillers, screed plaster, finishing plaster and marble plaster.

[0137] In a preferred embodiment, a building chemical composition is used to increase the compressive strength of a manufactured article.

[0138] The compressive strength of the manufactured article is increased after 10, 30, and 60 minutes, preferably after the calcium sulfate-based article has reached a mass consistency, in accordance with DIN 196-1 for investigating strength enhancement.

[0139] The scope and object of the present invention will be better understood based on the following examples, which are intended to illustrate and not limit specific embodiments of the present invention. [Examples]

[0140] Materials used The polyaryl ether (PAE) used in composition IE1 of the present invention is Comparative Example 7 in International Publication No. 2015 / 091461A1.

[0141] The polycarboxylate used in comparative example composition CE1 is BASF's product Melflux PCE 239 L.

[0142] The polycarboxylate used in comparative example composition CE2 is BASF's product Melflux PCE 1493 L.

[0143] The poly-naphthalene sulfonate (PNS) used in various compositions is Bozzetto's product Flube CA 40.

[0144] The β-hemihydrate is Gesso Alabastrino, a product manufactured by Gessi Roccastrada, with an average particle size of 40 μm.

[0145] The natural anhydrous gypsum is Casea's Micro B product, with an average particle size of 35 μm.

[0146] The dihydrate is Casea's product CS-Dihydrat, which has an average particle size of 50 μm.

[0147] Plast Retard L is a product manufactured by Sicit 2000.

[0148] Slurry preparation Comparison Example 1 As a control, a blank gypsum slurry containing no setting accelerator was prepared using 300 g of β-hemihydrate. The amount of water required to correspond to a water-to-binder (w / g) ratio of 0.665, and determined based on the untreated gypsum slurry, was filled into a mixing tank (a mixer conforming to DIN EN 196-1), and then the β-hemihydrate was carefully sprinkled into the water. Furthermore, the amount of Plast Retard L shown in Table 1 was added to the mixture. The slurry was stirred at 285 rpm for 30 seconds. The water-to-binder (w / g) ratio of 0.665 was adjusted to achieve a flow rate of 21.0 cm for control example 1.

[0149] Comparative Examples CE1 and CE2 Preparation of liquid setting accelerators For the preparation of the liquid setting accelerator, a composition of 15% by mass of the dihydrate, 83% by mass of water, and 2.0% by mass of PCE was subjected to wet grinding in a Netzsch Labstar LS 01 using zirconium oxide balls with a diameter of 0.4–0.6 mm and an 85% wet region. Wet grinding was carried out for a total of 240 minutes.

[0150] Application Test A slurry was prepared using 300 g of β-hemihydrate. The amount of water required for a water-to-binder ratio (w / g) of 0.665, determined based on the untreated gypsum slurry, was filled into a mixing tank (a mixer conforming to DIN EN 196-1), and then the β-hemihydrate was carefully sprinkled into the water. Plast Retard L was added to the mixture in the amounts shown in Table 1. During mixing, a liquid setting accelerator was added by spray. The slurry was stirred at 285 rpm for 30 seconds.

[0151] Comparative Example CE3 Preparation of liquid setting accelerators For the preparation of the liquid setting accelerator, a composition of 15% by mass of the dihydrate and 83% by mass of water was subjected to wet grinding in a Netzsch Labstar LS 01 using zirconium oxide balls with a diameter of 0.4–0.6 mm and an 85% wet area. Wet grinding was carried out for a total of 240 minutes.

[0152] Application Test A slurry was prepared using 300 g of β-hemihydrate. The amount of water required for a water-to-binder ratio (w / g) of 0.665, determined based on the untreated gypsum slurry, was filled into a mixing tank (a mixer conforming to DIN EN 196-1), and then the β-hemihydrate was carefully sprinkled into the water. Plast Retard L was added to the mixture in the amounts shown in Table 1. During mixing, a liquid setting accelerator was added by spray. The slurry was stirred at 285 rpm for 30 seconds.

[0153] Comparative Example CE4 Preparation of drying and setting accelerator For comparison, a drying coagulation accelerator was prepared by dry grinding the dihydrate with a particle size of 5 μm in the amounts shown in Table 1 with 5% alkylbenzenesulfonic acid and an amine salt in a ball mill for a total of 4 minutes.

[0154] Application Test A slurry was prepared using 250 g of β-hemihydrate and 0.05 g (0.02% bws) of drying accelerator. The amount of water required to correspond to a water-to-binder (w / g) ratio of 0.685, and determined based on the untreated gypsum slurry, was filled into a mixing tank (a mixer conforming to DIN EN 196-1), and then the β-hemihydrate containing the drying accelerator was carefully sprinkled into the water. Plast Retard L was added to the mixture in the amounts shown in Table 1. The slurry was stirred at 285 rpm for 30 seconds. A water-to-binder (w / g) ratio of 0.665 was adjusted to achieve a flow rate of 21.0 cm for Comparative Example CE4.

[0155] Examples of the present invention IE1, IE2, and IE3 Preparation of liquid setting accelerators For the preparation of the liquid setting accelerator, compositions of dihydrate, water, and PAE in the amounts shown in Table 1 were subjected to wet grinding in a Netzsch Labstar LS 01 using zirconium oxide balls with a diameter of 0.4–0.6 mm and an 85% wet area. Wet grinding was carried out for a total of 240 minutes.

[0156] Application Test The slurry of the present invention was prepared using 300 g of β-hemihydrate. The amount of water required to correspond to a water-to-binder (w / g) ratio of 0.665, and determined based on the untreated gypsum slurry, was filled into a mixing tank (a mixer conforming to DIN EN 196-1), and then the β-hemihydrate was carefully sprinkled into the water. Plast Retard L was added to the mixture in the amounts shown in Table 1. During mixing, each liquid setting accelerator was added by spray. The slurry was stirred at 285 rpm for 30 seconds.

[0157] Embodiment IE4 of the present invention Preparation of liquid setting accelerators For the preparation of the liquid setting accelerator, compositions of hemihydrate, water, and PAE in the amounts shown in Table 1 were subjected to wet grinding in a Netzsch Labstar LS 01 using zirconium oxide balls with a diameter of 0.4–0.6 mm and an 85% wet area. Wet grinding was carried out for a total of 240 minutes.

[0158] Application Test A slurry was prepared using 250 g of β-hemihydrate. The amount of water required for a water-to-binder ratio (w / g) of 0.685, determined based on the untreated gypsum slurry, was filled into a mixing tank (a mixer conforming to DIN EN 196-1), and then the β-hemihydrate was carefully sprinkled into the water. Plast Retard L was added to the mixture in the amounts shown in Table 1. During mixing, a liquid setting accelerator was added by spray. The slurry was stirred at 285 rpm for 30 seconds.

[0159] Embodiment IE5 of the present invention Preparation of liquid setting accelerators For the preparation of the liquid setting accelerator, compositions of natural anhydrous gypsum, water, and PAE in the amounts shown in Table 1 were subjected to wet grinding in a Netzsch Labstar LS 01 using zirconium oxide balls with a diameter of 0.4–0.6 mm and an 85% wet area. Wet grinding was carried out for a total of 240 minutes.

[0160] Application Test A slurry was prepared using 250 g of natural anhydrous gypsum. The amount of water required to correspond to a water-to-binder (w / g) ratio of 0.685, and determined based on the untreated gypsum slurry, was filled into a mixing tank (a mixer conforming to DIN EN 196-1), and then the β-hemihydrate was carefully sprinkled into the water. Plast Retard L was added to the mixture in the amounts shown in Table 1. During mixing, a liquid setting accelerator was added by spray. The slurry was stirred at 285 rpm for 30 seconds.

[0161] The compositions of liquid setting accelerators are summarized in Table 1. Table 2 includes the compositions and properties of application examples containing liquid setting accelerators.

[0162] particle size The particle size was determined using laser diffraction (Mastersizer 2000, Malvern Instruments) according to Mie theory for small particles (particle RI = 1.531, dispersant RI = 1.330; absorption = 0.1; absorbance of 10-20%).

[0163] The results are summarized in Table 2.

[0164] Slump test The flow rate was determined after 60 seconds. After adding the powder components to the liquid, the stucco needed to be immersed for 15 seconds. Next, the slurry was mixed for 30 seconds using a Hobart mixer. After a total time of 45 seconds, the stucco slurry was filled to the top of the ASTM ring and lifted after 60 seconds. Finally, the diameter of the putty was measured on two vertical axes using a caliper ruler.

[0165] curing time Initial hardening was determined by the so-called knife-cut method (similar to DIN EN 13279-2).

[0166] The results are summarized in Table 2.

[0167] As can be inferred from Table 2, the curing time of the composition of the present invention containing PAE as a dispersant for the liquid setting accelerator is significantly shorter than that of the control example without a dispersant for the liquid setting accelerator. Compared to Comparative Examples CE1 and CE2 containing PCE as a dispersant, the curing times of Examples IE1 and IE2 containing the same amount of PAE are also shorter. The effect of the dispersant of the present invention is also demonstrated with respect to hemihydrate (IE4) and natural anhydrous gypsum (IE5) as gypsum components. Comparative Example CE4 shows that the curing time and, consequently, the particle size of the fine calcium sulfate obtained from the wet grinding process of the present invention are superior to that of fine calcium sulfate obtained by the dry grinding method.

[0168] [Table 1]

[0169] [Table 2]

[0170] Mechanical properties To determine the flexural and compressive strengths of the gypsum articles produced from the above slurry, test specimens were prepared as follows: The mass and density of the test specimens prepared with seed dosages of 0.02% and 0.01% are summarized in Tables 3 and 4.

[0171] Test specimen (4 x 4 x 16 cm) 3 A prism was prepared according to DIN 196-1 for the purpose of investigating strength enhancement. Before testing the flexural and compressive strengths, all samples were dried to a constant mass by the following method: After the gypsum slurry hardened, all test specimens were stored for 1 day at 20°C / 65% relative humidity. Then, all samples were removed from the mold and dried at 40°C to a constant mass. The dry density was calculated by weighing and on a volume basis (256 cm³). 3 Tables 3 and 4 contain various measurements of flexural strength and compressive strength, as well as their average values.

[0172] [Table 3]

[0173] [Table 4]

[0174] According to Table 3, the flexural and compressive strengths of compositions prepared in the presence of a dispersant are improved compared to the blank control. The compressive strength of the resulting gypsum article containing PAE is improved compared to the composition containing PCE. Therefore, applying PAE instead of PCE according to the wet grinding process of the present invention has a beneficial effect on the compressive strength of the resulting gypsum article.

Claims

1. A method for preparing a building chemical composition comprising fine calcium sulfate having a D(0.63) particle size of less than 10.0 μm, determined by laser diffraction according to Mie theory, and a dispersant which is a polyaryl ether, aa) A step of providing a suspension comprising calcium sulfate particles having a D(0.63) particle size of 10.0 μm or more, determined by laser diffraction according to Mie theory, water, and a dispersant which is a polyaryl ether. ab) A step of wet grinding the suspension obtained in step aa) to obtain the chemical composition for construction. Includes, At that time, The aforementioned polyaryl ether i) at least one aromatic or heteroaromatic structural unit including a polyether side chain, and ii) A polycondensation product comprising at least one phosphorylated aromatic or heteroaromatic structural unit, wherein the molar ratio i):ii) between structural units i) and ii) in the polyaryl ether is in the range of 1:10 to 3:

1. The mass ratio between the fine calcium sulfate particles and the dispersant is in the range of 85.0:15.0 to 99.9:0.1, and The aforementioned building chemical composition is based on the total mass of the building chemical composition, i) 0.07 to 70.0% by mass of fine calcium sulfate particles, ii) 0.01 to 10.0% by mass of the dispersant, which is a polyaryl ether, and iii) Remaining water up to 100% by mass Includes, The calcium sulfate particles exist in the form of calcium sulfate dihydrate. method.

2. The method according to claim 1, wherein the wet grinding described in step a) is carried out in a ball mill, a rotary grinder, or a stirring type bead mill.

3. The method according to claim 1 or 2, further comprising step a) drying the building chemical composition obtained in step a) to obtain the building chemical composition in powder form.

4. The at least one aromatic or heteroaromatic structural unit, including the polyether side chain, is defined by the formula (I) 【Chemistry 1】 (In the formula, A is represented by identical or different substituted or unsubstituted aromatic or heteroaromatic compounds having 5 to 10 carbon atoms; B is either the same or different, and is represented by N, NH, or O; If B = N, then n = 2; if B = NH or O, then n = 1; R １ and R ２ These are independently of each other, identical or different, and represented by branched or linear C1-C10 alkyl groups, C5-C8 cycloalkyl groups, aryl groups, heteroaryl groups, or H; a is either the same or different, and is represented by an integer between 1 and 300; X is either the same or different, and is represented by branched or linear C1-C10 alkyl groups, C5-C8 cycloalkyl groups, aryl groups, heteroaryl groups, or H. Represented by, and The aforementioned at least one phosphorylated aromatic or heteroaromatic structural unit is defined by formula (II) 【Chemistry 2】 (In the formula, D is represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 carbon atoms, which may or may not be the same; E is either the same or different, and is represented by N, NH, or O; If E = N, then m = 2; if E = NH or O, then m = 1; R ３ and R ４ These are independently of each other, identical or different, and represented by branched or linear C1-C10 alkyl groups, C5-C8 cycloalkyl groups, aryl groups, heteroaryl groups, or H; b is either the same or different, and is represented by an integer between 0 and 300. The method according to any one of claims 1 to 3, as represented by [the specified method].

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