WO2021251629A1 - Procédé de préparation d'un mélange pour plaque de gypse, mélange préparé par ce procédé et composition pour former une plaque de gypse le comprenant - Google Patents

Procédé de préparation d'un mélange pour plaque de gypse, mélange préparé par ce procédé et composition pour former une plaque de gypse le comprenant Download PDF

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WO2021251629A1
WO2021251629A1 PCT/KR2021/005823 KR2021005823W WO2021251629A1 WO 2021251629 A1 WO2021251629 A1 WO 2021251629A1 KR 2021005823 W KR2021005823 W KR 2021005823W WO 2021251629 A1 WO2021251629 A1 WO 2021251629A1
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gypsum board
admixture
gypsum
monomer
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PCT/KR2021/005823
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Korean (ko)
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주영길
김대진
김주환
최광호
박광영
차철용
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주식회사 실크로드시앤티
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C08F8/36—Sulfonation; Sulfation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a method for manufacturing an admixture for gypsum board, an admixture for gypsum board according thereto, and a composition for forming a gypsum board comprising the same.
  • Gypsum board is mainly used as an interior material for construction, and is widely used because it has excellent fire resistance, sound insulation, and thermal insulation properties and is inexpensive.
  • gypsum boards such as ordinary boards, hard boards, reinforced boards, and decorative boards, and the type of additive, the amount of combination, the addition of reinforcement, etc. may vary according to the required characteristics of each gypsum board.
  • gypsum boards can be manufactured by generally pouring gypsum mixed with water on a base paper, adjusting the thickness and width, and then curing, cutting, and drying.
  • an admixture may be used as a dispersing agent for dispersing gypsum in water, which can reduce the amount of water used and increase drying efficiency when manufacturing gypsum board, thereby increasing productivity.
  • the addition of a dispersant to the gypsum slurry can change the size distribution of the foam foam and the pores left by the foam.
  • the dispersants may delay the setting of the gypsum slurry and further inhibit the high-speed production of gypsum products such as wallboards. Accordingly, if the amount of the dispersant is increased to improve fluidity, there is a problem in that the curing time increases. handling may be difficult. Therefore, a reduction in line speed is necessary to harden the board and maintain its shape.
  • Korean Patent Application Laid-Open No. 10-2008-7001092 discloses a dispersant that provides slurry fluidity and an appropriate bubble size distribution.
  • the system admixture is separately introduced into the mixer and used.
  • mixing PCE and PNS before inputting the admixture has a problem in that a gel is formed, which is practically difficult in actual product production.
  • the physical properties of the admixture provided as a dispersant for gypsum board production are required to improve the fluidity of the gypsum slurry, shorten the curing time, and facilitate the formation of bubbles. Accordingly, the development of an admixture material with improved physical properties that can easily control these physical properties and can solve existing problems is actively in progress.
  • the flow of the gypsum slurry compared to the PNS-based admixture is improved and It aims at shortening the setting time and making it possible to form bubbles of the same size.
  • a gypsum board comprising a sulfonated polystyrene (SPS)-based polymer compound copolymerized with at least one selected from a styrene-based compound, a sulfonated styrene-based compound, and a monomer group
  • SPS sulfonated polystyrene
  • a sulfonated polystyrene (SPS)-based polymer compound in which at least one selected from a styrene-based compound and a monomer group is copolymerized, a sulfonated polystyrene (SPS)-based
  • PS polystyrene
  • SPS sulfonated polystyrene
  • the monomer group may be at least one selected from an aliphatic single double bond monomer, an aromatic single double bond monomer, and a conjugated diene monomer.
  • the SPS-based polymer compound may be polymerized by polymerizing at least one selected from a styrenic monomer, a sulfonated styrene-based monomer, and other monomers.
  • the SPS-based polymer may be polymerized by directly sulfonating the polymer compound obtained by polymerizing at least one selected from the group consisting of a styrene-based monomer and another monomer with a sulfonating agent.
  • the DS (degree of sulfonation) of the sulfonated polystyrene (SPS)-based polymer compound is provided in a range of 10 to 99%.
  • the solvent in the sulfonation reaction is propane, butane, pentane, hexane.
  • a solvent that can be used for the sulfation reaction such as a solvent containing cyclohexane, dibromomethane, dichlorobenzene, and halogen, may be used.
  • At least one selected from acetic anhydride, sulfuric acid, exothermic sulfuric acid and sulfur trioxide may be used as the sulfonating agent in the sulfonation reaction.
  • an admixture for gypsum board manufactured according to the above manufacturing method.
  • composition for forming a gypsum board comprising gypsum, a curing agent, a lightening agent, and water in the admixture for gypsum board.
  • the gypsum may be hemihydrate gypsum (CaSO 4 ⁇ 1/2H 2 O).
  • the composition for forming a gypsum board contains 0.1 to 2 parts by weight of the admixture for the gypsum board, 0.1 to 1 parts by weight of the curing agent, 0.01 to 1 parts by weight of the lightweighting agent, and 60 to 150 parts by weight of water based on 100 parts by weight of the gypsum. do.
  • the curing agent is potassium sulfate (K 2 SO 4 ) and sodium sulfate (Na 2 SO 4 ) At least any one or more is provided.
  • the weight reducing agent is provided with at least one of a sulfate compound, a persulfate compound, a bisulfate compound, a carbonate compound, and a bicarbonate compound.
  • the composition for forming a gypsum board may further include a curing retardant.
  • a gypsum board using the composition for forming a gypsum board.
  • admixture for gypsum board By including the admixture for gypsum board according to the present invention, physical properties such as fluidity, setting time, and bubble size of the gypsum slurry can be adjusted when manufacturing gypsum board. Therefore, compared to the existing PNS-based admixture, it is possible to provide an admixture with improved physical properties.
  • the fluidity of the gypsum slurry is improved compared to the PNS-based admixture, and the setting time is shortened, while the formation of bubbles of the same size is achieved. It is possible.
  • the fluidity of the gypsum slurry can be increased and the setting time can be adjusted within a desired range.
  • gypsum board-forming composition of the present invention By using the gypsum board-forming composition of the present invention, a high-quality gypsum board with improved physical properties can be manufactured while reducing costs by shortening the setting time during the gypsum board manufacturing process.
  • SPS sulfonated polystyrene
  • Acetic anhydride is cooled to 0° C. under inert nitrogen conditions, 95 to 97% sulfuric acid is added, and the mixture is stirred at room temperature until it becomes a transparent solution.
  • the sulfonated polystyrene (SPS)-based polymer compound copolymerized with an acrylic acid monomer.
  • SPS sulfonated polystyrene
  • the sulfonated polystyrene-based high molecular compound contains 5% of an acrylic acid-based monomer. If necessary, the SPS-based polymer compound is separated by washing in distilled water.
  • An admixture for gypsum board was prepared in (3) above
  • An admixture for gypsum board was prepared using a sulfonated polystyrene (SPS)-based polymer compound.
  • SPS sulfonated polystyrene
  • the sulfonated polystyrene-based polymer compound contains 5% of a maleic acid-based monomer.
  • the polymer compound contains 2.5% of the butadiene monomer and 2.5% of the maleic acid-based monomer.
  • the degree of sulfation is determined through mass spectroscopy and nuclear magnetic resonance (NMR) spectroscopy.
  • the present invention can be measured through one of the mass spectrometry methods, MALDI-ToF MS (Matrix-assisted laser desorption ionization time-of-flight mass spectrometry), and more detailed information can be found in the following paper.
  • MALDI-ToF MS Microx-assisted laser desorption ionization time-of-flight mass spectrometry
  • Example 1 Preparation of a composition for forming a gypsum board
  • hemihydrate gypsum that can be used in an actual gypsum board production plant, 70 parts by weight of water, 0.6 parts by weight of the admixture of Preparation Example 1, 0.2 parts by weight of a curing agent (potassium sulfate) and 0.06 parts by weight of a lightening agent (ammonium sulfate)
  • a curing agent potassium sulfate
  • a lightening agent ammonium sulfate
  • Example 2 Preparation of a composition for forming gypsum board
  • a composition for forming a gypsum board was prepared in the same manner as in Example 1, except that the admixture of Preparation Example 2 was used.
  • Example 3 Preparation of composition for forming gypsum board
  • a composition for forming a gypsum board was prepared in the same manner as in Example 1, except that the admixture of Preparation Example 3 was used.
  • Comparative Example 1 Preparation of a composition for forming a gypsum board
  • a composition for forming a gypsum board was prepared in the same manner as in Example 1, except that polynaphthalenesulfonate (PNS)-based admixture used by a gypsum board producer was used.
  • PPS polynaphthalenesulfonate
  • the weight average molecular weight is 10,000.
  • the diameter spread when demolding after 10 seconds was measured.
  • the maximum value and the minimum value among the measurement data were added, and then divided by 2 to obtain a flow value.
  • Evaluation Example 2 Setting time of composition for forming gypsum board (apparent termination evaluation)
  • the composition for forming a gypsum board is poured into a rubber mold having a width of 50 mm ⁇ length 50 mm ⁇ height 50 mm, and the hardness is measured with a Shore durometer (type D). When the measured value is 85, the time is set. It was set as time (apparent termination evaluation).
  • Evaluation Example 3 Evaluation of cell size of gypsum board
  • a gypsum board was prepared from the composition for forming a gypsum board prepared in Example 3 and Comparative Example 1, the cross section was observed under a microscope (500 magnification) to measure the average cell size, and the results are shown in Table 3.
  • the degree of sulfonation (DS) of the sulfonated polystyrene (SPS)-based polymer compound according to the present invention may be provided in the range of 10 to 99% with reference to FIGS. 1 to 3 .
  • the gypsum board prepared in Examples can be lightened by securing sufficient bubble size, and it was also found that the bubble size can be controlled according to the molecular weight of polystyrene. Accordingly, it can be confirmed that by providing the admixture according to the present invention, the problem of small bubble size, which is the existing problem, can be solved, and a higher weight reduction level can be provided compared to the conventional PNS-based admixture.
  • Examples 1 to 3 of the present invention when 1 to 20% of the monomer included in the sulfonated polystyrene (SPS)-based polymer compound is included, preferably 5%, fluidity, coagulation It can be confirmed that there is an improvement in physical properties such as time and bubble size.
  • SPS sulfonated polystyrene
  • the fluidity of the gypsum slurry can be increased and the setting time can be adjusted within a desired range by controlling the type and polymerization degree of the monomers included in the SPS-based polymer compound.
  • productivity is excellent, and it is widely used as an existing admixture to provide superior physical properties than PNS-based admixtures, and can be substituted for it.
  • a layer or member when a layer or member is said to be located “on” another layer or member, this means that the layer or member is adjacent to another layer or member, as well as another layer or member between the two layers or members. Includes cases where another member is present.
  • molecular weight means “weight average molecular weight (Mw)” unless otherwise defined.
  • the C 1 -C 20 alkyl group refers to a linear or branched aliphatic hydrocarbon monovalent group having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isobutyl group, and a sec-butyl group. group, ter-butyl group, pentyl group, iso-amyl group, hexyl group, and the like.
  • the C 2 -C 20 alkenyl group refers to a hydrocarbon group including one or more carbon double bonds in the middle or at the terminal of the C 2 -C 20 alkyl group, and specific examples thereof include an ethenyl group, a propenyl group, a butenyl group. etc. are included.
  • the C 2 -C 20 alkynyl group refers to a hydrocarbon group including at least one carbon triple bond in the middle or at the terminal of the C 2 -C 20 alkyl group, and specific examples thereof include an ethynyl group, a propynyl group, etc. Included.
  • the C 1 -C 20 alkoxy group refers to a monovalent group having the formula of -OA 101 (here, A 101 is the C 1 -C 20 alkyl group), and specific examples thereof include a methoxy group, an ethoxy group , an isopropyloxy group, and the like.
  • the C 3 -C 10 cycloalkyl group refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclo a heptyl group and the like.
  • the C 3 -C 10 cycloalkylene group of the specification and the second having the same structure as the above C 3 -C 10 cycloalkyl group means a group.
  • the C 6 -C 20 aryl group refers to a monovalent group having a carbocyclic aromatic system having 6 to 20 carbon atoms.
  • Specific examples of the C 6 -C 20 aryl group include a phenyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, a fluorenyl group, and the like.
  • the C 1 -C 20 heteroaryl group includes at least one hetero atom selected from N, O, Si, P and S as a ring-forming atom and a monovalent group having a heterocyclic aromatic system having 1 to 20 carbon atoms.
  • the C 1 -C 20 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a carbazolyl group, etc. do.
  • a method for sulfonation of a sulfonated polystyrene (SPS)-based polymer compound includes the following methods.
  • sulfonation may be performed into a sulfonated polystyrene-based polymer compound.
  • the polystyrene-based polymer compound including other monomers may be directly sulfonated with a sulfonating agent to perform sulfonation with the sulfonated polystyrene-based polymer compound.
  • a styrene monomer, monomer A, and monomer B are polymerized under inert nitrogen conditions to prepare a polystyrene-based polymer compound in which A and B are copolymerized as monomers.
  • an acid anhydride is prepared under inert nitrogen conditions to prepare an acetyl sulfate solution.
  • the acetyl sulfate solution may be added to prepare a sulfonated polystyrene-based polymer compound.
  • the mechanism for this is as follows.
  • the present invention intends to provide a sulfonated polystyrene (SPS)-based polymer compound in an admixture for gypsum board in order to satisfy these properties.
  • SPS sulfonated polystyrene
  • the fluidity of the gypsum slurry used depends on the degree of sulfonation (DS) of the sulfonated polystyrene (SPS)-based polymer compound and the type of monomer included in the SPS-based polymer compound and the degree of polymerization. and to adjust the setting time as necessary.
  • gypsum board comprising a sulfonated polystyrene (SPS)-based polymer compound copolymerized with at least one selected from the following Chemical Formula 1, the following Chemical Formula 2 and the monomer group
  • SPS sulfonated polystyrene
  • R 1 and R 2 are hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkyl Nyl group, C 1 -C 20 alkoxy group, C 3 -C 10 cycloalkyl group, C 6 -C 20 aryl group, C 1 -C 20 heteroaryl group, monovalent non-aromatic condensed polycyclic group and monovalent non-aromatic hetero selected from the condensed polycyclic group,
  • a 1 is an integer selected from 1 to 5
  • a 2 is an integer selected from 1 to 4,
  • M + is H + , Li + , Na + , K + or NH 4 + ,
  • ⁇ is an integer selected from 1 to 100,000.
  • polystyrene-based (Polystyrene, PS)-based high molecular compound copolymerized with at least one selected from the following Chemical Formula 1 and the monomer group Sulfonated Polystyrene , SPS
  • a method for producing an admixture for gypsum board containing a polymer compound is provided.
  • R 1 is hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 1 -C 20 alkoxy group, C 3 -C 10 cycloalkyl group, C 6 -C 20 aryl group, C 1 -C 20 heteroaryl group, monovalent non-aromatic condensed polycyclic group and monovalent non-aromatic condensed heteropolycyclic group is selected from
  • a 1 is an integer selected from 1 to 5;
  • the monomer group is provided with at least one selected from an aliphatic single double bond monomer, an aromatic single double bond monomer, and a conjugated diene monomer.
  • the monomers selected from the monomer group may be provided as random copolymers and/or block copolymers by polymerization.
  • the aliphatic single double bond monomer is (meth)acrylic acid, an ester of (meth)acrylic acid having an unsubstituted alkyl side branch, an ester of (meth)acrylic acid having one or more hydroxyl groups, a phosphoric acid ester, a polyolefin and At least one selected from ester-based monomers of acrylic acid substituted with a hetero atom may be provided.
  • the ester-based monomer of (meth)acrylic acid having an unsubstituted alkyl side branch is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n -Butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, ethylhexyl (meth)acrylate, 3,3 ,5-trimethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, cycloalkyl (meth)acrylate such as cyclopentyl (meth)acrylate, isobornyl (meth) acrylates, cyclohexyl (meth)acrylates, and the
  • the ester-based monomer of (meth)acrylic acid having one or more hydroxyl groups is, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, etc.
  • the phosphoric acid ester-based monomer may be, for example, a phosphoric acid ester of polypropylene glycol monomethacrylate, for example, Sipomer PAM 200 commercially available from Rhodia.
  • the polyolefinic monomer is, for example, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 2,2-propylene glycol di(meth)acrylate, butane-1,4-diol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetra ethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, allyl (meth)acrylate, and the like may be provided. have.
  • the ester-based monomer of substituted acrylic acid substituted with a hetero atom is, for example, maleic anhydride-alt-vinyl methyl ether, sodium 2-acrylamidododecylsulfonate, acrylonitrile, methacrylonitrile, acrylamide, meta Crylamide, N-dimethylacrylamide, vinyl acetate, vinyl propionate, vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylimidazole, and N-vinyl -2-methylimidazoline, vinylbenzyl chloride, vinylbenzyl bromide, vinylbenzyl iodide, and the like may be provided.
  • an aromatic single double bond monomer including at least one selected from styrene-based, naphthalene-based, silane-based, acenaphthylene-based, indene-based and vinylcarbazole-based monomers.
  • vinyltoluene alpha-methylstyrene, trifluorostyrene, 2-vinyl pyridium, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4- Diisopropylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 5-tert-butyl-2-methylstyrene, tert-butoxystyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, N,N-dimethylaminoethylstyrene, 1-vinyl-5-hexylnaphthalene, 1-vinylnaphthalene, divinylnaphthalene, divinylbenzene,
  • the conjugated diene monomer may be a butadiene-based monomer.
  • the aforementioned monomer group may be represented by [A] ⁇ in the following formula, and any one or more selected from the aforementioned monomer group may be provided.
  • it may be provided by selecting from monomers of the same type, and may be provided as a copolymer as a heterogeneous monomer, and may be included in a sulfonated polystyrene (SPS)-based polymer compound.
  • SPS sulfonated polystyrene
  • an SPS-based polymer compound represented by the following Chemical Formula 3 may be provided.
  • ⁇ is an integer selected from 1 to 100,000
  • R 1 and R 2 are hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxyl group, nitro group, C 1 -C 20 alkyl group, C 2 -C 20 alkenyl group, C 2 -C 20 alkyl Nyl group, C 1 -C 20 alkoxy group, C 3 -C 10 cycloalkyl group, C 6 -C 20 aryl group, C 1 -C 20 heteroaryl group, monovalent non-aromatic condensed polycyclic group and monovalent non-aromatic hetero selected from the condensed polycyclic group,
  • a 1 is an integer selected from 1 to 5
  • a 2 is an integer selected from 1 to 4,
  • M + is H + , Li + , Na + , K + or NH 4 + ,
  • x is an integer selected from 5 to 50,000
  • y is an integer selected from 0 to 50,000.
  • the fluidity can be increased and the setting time can be adjusted within a desired range.
  • the polymerization degree which is the type and content of the monomer in [A] ⁇
  • the setting time can be adjusted within a desired range.
  • SPS sulfonated polystyrene
  • DS degree of sulfonation
  • SPS sulfonated polystyrene
  • DS can provide the effect of improving the fluidity of the gypsum slurry and shortening the setting time in the range of 10 to 99%.
  • the solvent used in the sulfonation is propane, butane, pentane, and hexane.
  • a sulfonating agent may be used for the sulfonation reaction.
  • at least one selected from acetic anhydride, sulfuric acid, exothermic sulfuric acid, and sulfur trioxide may be provided as the sulfonating agent.
  • the weight average molecular weight of the sulfonated polystyrene-based polymer compound is provided to be 10,000 to 800,000.
  • the bubble size can be adjusted by adjusting the molecular weight as necessary because the bubble size can also be increased according to the weight average molecular weight.
  • the range of the weight average molecular weight of the sulfonated polystyrene (SPS)-based polymer compound is 10,000 to 800,000, and the cell size of the gypsum board can also be controlled according to the molecular weight.
  • an admixture for gypsum board manufactured according to the above manufacturing method.
  • the admixture for gypsum board is provided in an aqueous dispersion type.
  • the aqueous dispersion is made by slowly adding the reaction solution that has undergone the activation step while adding water to a separate container and stirring.
  • the content of water is not particularly limited, but in consideration of workability, etc., the admixture for gypsum board may be freely added within the range of 1 to 60 parts by weight based on 100 parts by weight of water in the final product.
  • the fluidity and setting time of the gypsum slurry can be controlled within a desired range.
  • composition for forming a gypsum board of the present invention includes gypsum, an admixture for gypsum board, a curing agent, a lightening agent, and water, and the admixture for gypsum board is the same as described above, and sulfonated polystyrene ( Sulfonated Polystyrene, SPS)
  • SPS Sulfonated Polystyrene
  • the gypsum included in the composition for forming a gypsum board may be hemihydrate gypsum.
  • Gypsum is a very soft sulfate mineral containing calcium sulfate (CaSO 4 ) as a main component. Gypsum has many paper known, depending on crystal forms, of which yisuseok and (CaSO 4 ⁇ 2H 2 O) to heat to a temperature of 150 °C to 200 °C or half fired by absorbing moisture in the air gypsum (CaSO 4 ⁇ 1 /2H 2 O) can be obtained.
  • the hemihydrate gypsum may be produced by calcining raw gypsum.
  • raw material gypsum natural gypsum or flue gas desulfurization (FGD) gypsum, phospho gypsum, titanium gypsum, citrogypsum, tartarogypsum, borogypsum
  • chemical gypsum such as lactogypsum
  • recycled gypsum recovered from waste gypsum boards and the like may be used as the raw gypsum, but is not limited thereto.
  • an acid or a salt thereof for example, citric acid or a salt thereof, malic acid or a salt thereof, succinic acid or a salt thereof, tartaric acid or a salt thereof, etc. may be blended together during calcination of the raw gypsum. .
  • the acid or salt is mixed together, the amount of water mixture may be reduced when manufacturing a gypsum board using the produced hemihydrate gypsum.
  • the blending amount of the acid or its salt may be 0.01 parts by weight to 10 parts by weight, or 0.1 parts by weight to 5 parts by weight, or 0.5 parts by weight to 1 part by weight based on 100 parts by weight of the raw gypsum.
  • the firing of the raw gypsum may use a firing device such as a kettle, a rotary kiln, etc. used in the art, and the firing device used is particularly limited. no.
  • the calcined hemihydrate gypsum may be further pulverized into a form suitable for use in the composition by using an apparatus such as a ball mill or a tube mill.
  • the composition for forming a gypsum board is based on 100 parts by weight of gypsum, 0.1 to 2 parts by weight of an admixture for gypsum board, 0.1 to 1 parts by weight of a curing agent, 0.01 to 1 parts by weight of a lightening agent, and 60 parts by weight of water. to 150 parts by weight.
  • 0.1 to 2 parts by weight of the above-mentioned admixture for gypsum board may be included, and preferably 0.1 to 1 parts by weight.
  • the weight average molecular weight of the sulfonated polystyrene (SPS)-based polymer compound provides a range of 10,000 to 800,000.
  • SPS sulfonated polystyrene
  • the admixture for gypsum board is a polynaphthalenesulfonate (PNS)-based compound, polycarboxylate ether (PCE), if necessary, together with a sulfonated polystyrene (SPS)-based polymer compound.
  • PPS polynaphthalenesulfonate
  • PCE polycarboxylate ether
  • SPS sulfonated polystyrene
  • Compounds, lignin sulfonate-based compounds, alkylarylsulfonic acid-based compounds, polyoxyethylene-based compounds, alkylaryl ether-based compounds, oxycarboxylic acid-based compounds, polycarboxylic acid-based compounds, and aminosulfonic acid-based compounds at least one compound selected from more can do.
  • it may further include a polycarboxylate ether (PCE)-based compound.
  • the weight ratio of the sulfonated polystyrene (SPS)-based polymer compound and the polycarboxylate ether (PCE)-based compound is 10:90 to 90:10.
  • SPS sulfonated polystyrene
  • PCE polycarboxylate ether
  • the composition for forming a gypsum board includes a curing agent, which promotes a hydration reaction between the gypsum and water, thereby increasing the productivity of the gypsum board.
  • the curing agent may include at least one of an inorganic compound and an organic compound.
  • the inorganic compound may include chlorides such as calcium chloride and potassium chloride; nitrites such as sodium nitrite and calcium nitrite; nitrates such as sodium nitrate and calcium nitrate; sulfates such as calcium sulfate, potassium sulfate, sodium sulfate and aluminum sulfate; hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as calcium carbonate, sodium carbonate and lithium carbonate; Silicates, such as sodium silicate and potassium silicate; alumina-based compounds such as aluminum hydroxide and aluminum oxide; It may be at least one selected from among.
  • potassium sulfate (K 2 SO 4 ) or sodium sulfate (Na 2 SO 4 ) may be provided.
  • the organic compound includes amines such as diethanolamine and triethanolamine; calcium salts of organic acids such as calcium formate and calcium acetate; and maleic anhydride; It may be at least one selected from among.
  • the composition for forming a gypsum board includes 0.1 to 1 parts by weight of a curing agent based on 100 parts by weight of the gypsum.
  • the curability of the gypsum board prepared from the composition for forming a gypsum board may be increased, and the gypsum board may be controlled not to have brittleness due to excessive curing.
  • the composition for forming a gypsum board includes a weight reducing agent.
  • the weight reducing agent controls the density of the gypsum board prepared from the composition for forming a gypsum board, and generates air bubbles in the gypsum board to lighten the gypsum board.
  • the weight reducing agent may include a sulfate compound, a persulfate compound, a bisulfate compound, a carbonate compound, or a bicarbonate compound.
  • the lightweighting agent may include ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), sodium bicarbonate (NaHCO 3 ), ammonium sulfate ((NH 4 ) 2 SO 4 ), or sodium bisulfate. may, but is not limited thereto.
  • the lightweighting agent is an alkyl sulfate compound, an alkyl ether sulfate compound, an alkyl sulfonate compound, an alkyl ether sulfonate compound, an alkyl phosphate compound, an alkyl ether phosphate compound, an alkyl carbonate compound, and an alkyl ether carbonate compound. It may contain anionic surfactants such as
  • the lightweighting agent may include, but is not limited to, anionic surfactants such as lauryl sulfonate, isotridecyl sulfonate, lauryl sulfate, isotridecyl sulfate or stearyl sulfate.
  • anionic surfactants such as lauryl sulfonate, isotridecyl sulfonate, lauryl sulfate, isotridecyl sulfate or stearyl sulfate.
  • the content of the lightweighting agent may be 0.01 parts by weight to 1 part by weight, and preferably the content of the curing agent is 0.01 parts by weight based on 100 parts by weight of the gypsum. to 0.1 parts by weight is provided.
  • the weight of the gypsum board prepared from the composition for forming a gypsum board may be controlled so that the physical properties of the gypsum board are not deteriorated due to excessive bubble generation.
  • the composition for forming a gypsum board includes water.
  • the water reacts with the hemihydrate gypsum by hydration to form a hard dihydrate gypsum.
  • the composition for forming a gypsum board may contain 60 to 150 parts by weight, preferably 60 to 80 parts by weight, based on 100 parts by weight of gypsum.
  • the composition for forming a gypsum board may further include a curing retardant.
  • the curing retardant includes, for example, oxycarboxylic acids such as gluconic acid, citric acid, and glucoheptone, or inorganic salts thereof such as sodium, potassium, calcium, magnesium, and ammonium, glucose, fructose, galactose, saccharose, and chlorine.
  • Silose, arabinose, lipose, oligosaccharides, saccharides such as dextran, boric acid, etc. may be used, and may be added to control the curing rate and setting time in manufacturing gypsum board, but is not limited thereto.
  • the composition for forming a gypsum board may further include a strength improving agent.
  • a strength improving agent for example, silica fume, fly ash, etc. may be used, and may serve to supplement the physical properties of the gypsum board.
  • the content of the curing retardant and the strength improving agent may be 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the gypsum board-forming composition, respectively.
  • the gypsum board is formed including gypsum, the admixture for the gypsum board, a curing agent, a lightening agent, and water, and the sulfonated polystyrene (SPS)-based polymer compound as described above.
  • SPS sulfonated polystyrene
  • the gypsum, the gypsum board admixture, the curing agent, the lightening agent, and the description of the water may refer to the bar described in the present specification.
  • the gypsum board may be provided on the exterior material sheet and the gypsum core.
  • the gypsum board includes a first exterior material sheet, a second exterior material sheet facing the first exterior material sheet, and a gypsum core disposed between the first exterior material sheet and the second exterior material sheet.
  • Each of the exterior material sheets may be a paper exterior material sheet or a fibrous exterior material sheet, but is not limited thereto, and those known in the art may be used without limitation.
  • the gypsum board according to the present invention has high fluidity during manufacture and a short setting time, so productivity can be improved and bubble size can be controlled.
  • the gypsum board may include a sulfonated polystyrene (SPS)-based high molecular compound among the admixture for the gypsum board, and may be controlled to have desired physical properties during manufacturing.
  • SPS sulfonated polystyrene
  • the gypsum board of the present invention may be appropriately molded as necessary and usefully used as a building material.
  • admixture for gypsum board By including the admixture for gypsum board according to the present invention, physical properties such as fluidity, setting time, and bubble size of the gypsum slurry can be adjusted when manufacturing gypsum board. Therefore, compared to the existing PNS-based admixture, it is possible to provide an admixture with improved physical properties.
  • the fluidity of the gypsum slurry is improved compared to the PNS-based admixture, and the setting time is shortened, while the formation of bubbles of the same size is achieved. It is possible.
  • the fluidity of the gypsum slurry can be increased and the setting time can be adjusted within a desired range.
  • gypsum board-forming composition of the present invention By using the gypsum board-forming composition of the present invention, a high-quality gypsum board with improved physical properties can be manufactured while reducing costs by shortening the setting time during the gypsum board manufacturing process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un mélange pour une plaque de gypse; un mélange pour une plaque de gypse préparé par ce procédé; et une composition pour former une plaque de gypse, le comprenant. En particulier, l'invention porte sur une technique réglant le degré de sulfonation (DS) d'un composé polymère à base de polystyrène sulfoné (SPS) et le type et le degré de polymérisation de monomères contenus dans le composé polymère de manière à permettre le réglage de propriétés physiques de mélange, telles que l'aptitude à l'écoulement, le temps de prise et la taille des bulles d'une suspension de plâtre.
PCT/KR2021/005823 2020-06-11 2021-05-10 Procédé de préparation d'un mélange pour plaque de gypse, mélange préparé par ce procédé et composition pour former une plaque de gypse le comprenant WO2021251629A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115850605A (zh) * 2023-01-19 2023-03-28 北京慕湖外加剂有限公司 一种石膏基聚羧酸减水剂及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01188448A (ja) * 1988-01-25 1989-07-27 Fukui Kagaku Kogyo Kk 石膏スラリー用減水剤
WO2007140567A2 (fr) * 2006-06-07 2007-12-13 Roca Bruno Luis Ernesto Procédé de transformation de polystyrène expansé en ionomères de polystyrène sulfoné
US20080011202A1 (en) * 2004-10-15 2008-01-17 Halliburton Energy Services, Inc. Cement compositions comprising aromatic sulfonated polymers and methods of using the same
KR20080034949A (ko) * 2005-07-22 2008-04-22 크레이튼 폴리머즈 리서치 비.브이. 설폰화된 블록 공중합체, 이의 제조방법 및 그 블록공중합체의 다양한 용도
JP2008546619A (ja) * 2005-06-14 2008-12-25 ユナイテッド・ステイツ・ジプサム・カンパニー 石膏スラリー用調整剤及びそれらの使用方法
JP2013544742A (ja) * 2010-10-11 2013-12-19 ビーエーエスエフ コンストラクション ポリマース ゲゼルシャフト ミット ベシュレンクテル ハフツング 石膏スラリーを含有する分散剤

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01188448A (ja) * 1988-01-25 1989-07-27 Fukui Kagaku Kogyo Kk 石膏スラリー用減水剤
US20080011202A1 (en) * 2004-10-15 2008-01-17 Halliburton Energy Services, Inc. Cement compositions comprising aromatic sulfonated polymers and methods of using the same
JP2008546619A (ja) * 2005-06-14 2008-12-25 ユナイテッド・ステイツ・ジプサム・カンパニー 石膏スラリー用調整剤及びそれらの使用方法
KR20080034949A (ko) * 2005-07-22 2008-04-22 크레이튼 폴리머즈 리서치 비.브이. 설폰화된 블록 공중합체, 이의 제조방법 및 그 블록공중합체의 다양한 용도
WO2007140567A2 (fr) * 2006-06-07 2007-12-13 Roca Bruno Luis Ernesto Procédé de transformation de polystyrène expansé en ionomères de polystyrène sulfoné
JP2013544742A (ja) * 2010-10-11 2013-12-19 ビーエーエスエフ コンストラクション ポリマース ゲゼルシャフト ミット ベシュレンクテル ハフツング 石膏スラリーを含有する分散剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARTINS, C. R. ET AL.: "Synthesis in pilot plant scale and physical properties of sulfonated polystyrene", JOURNAL OF THE BRAZILIAN CHEMICAL SOCIETY, vol. 14, no. 5, 2003, pages 797 - 802, XP055771715, DOI: 10.1590/S0103-50532003000500015 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115850605A (zh) * 2023-01-19 2023-03-28 北京慕湖外加剂有限公司 一种石膏基聚羧酸减水剂及其制备方法

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