KR102272945B1 - A method for producing an admixture for a gypsum board and an admixture thereof, composition for forming a gypsum board - Google Patents

Abstract

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. In detail, it provides a sulfonated polystyrene (SPS)-based compound, and by controlling the DS (degree of sulfonatiion) of the SPS-based compound, it relates to a technology capable of controlling physical properties such as bubble size, fluidity and setting time of gypsum board. will be.

Description

A method for manufacturing an admixture for gypsum board, an admixture therefor, and a composition for forming a gypsum board comprising the same {A method for producing an admixture for a gypsum board and an admixture thereof, composition for forming a gypsum board}

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.

In detail, it provides an admixture for gypsum board containing a sulfonated polystyrene (SPS)-based compound. In particular, by controlling the DS (degree of sulfonation) of the SPS-based compound, bubble size, fluidity, and setting time of the gypsum board are provided. It provides a technology capable of controlling physical properties, such as

Gypsum board is widely used as an interior material for construction, mainly because it has excellent properties such as fire protection, sound insulation, and heat insulation, and is inexpensive. There are various types of gypsum boards, such as ordinary boards, hard boards, reinforced boards, and decorative boards, and depending on the required characteristics of each gypsum board, the type of additive, the amount of combination, the addition of reinforcement, etc. may vary.

These various types of gypsum boards can be generally manufactured by pouring gypsum mixed with water on a base paper, adjusting the thickness and width, and then curing, cutting, and drying. In this case, as an additive, an admixture may be used as a dispersant for dispersing gypsum in water, which can reduce the amount of water used, and increase drying efficiency when manufacturing gypsum board, thereby increasing productivity.

On the other hand, it is known that 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. In addition, 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 the fluidity, there is a problem in that the curing time increases, and when the wallboard is not sufficiently cured with a cutting knife, the shape of the product is not fixed, and after cutting the board handling may be difficult. Therefore, a reduction in line speed is necessary to harden the board and maintain its shape. As such, in the complex relationship between the chemical properties of the dispersant or admixture, the foam size, and the fluidity of the slurry, it is still a problem to be solved to prepare a gypsum slurry that satisfies both the foam size distribution and the fluidity without delaying the curing time.

Korean Patent Application Laid-Open No. 10-2008-7001092 discloses a dispersant that provides slurry fluidity and an appropriate bubble size distribution, but PCE-based and PNS-based admixtures are separately used as the dispersant does not form desired bubbles with PCE-based alone. Start using it by putting it in a mixer. However, using a mixture of PCE and PNS before adding the admixture has a problem in that a gel is formed, which is somewhat limited.

Accordingly, the development of an admixture material capable of resolving the existing problems by being able to easily control physical properties such as the bubble size of the gypsum board, the fluidity of the admixture, and the setting time, is still actively in progress.

An object of the present invention is to improve the physical properties of the admixture by providing a sulfonated polystyrene (SPS)-based admixture for gypsum board.

In particular, the purpose of controlling the DS (degree of sulfonation) of the SPS-based compound is to improve the flow compared to the PNS-based admixture, shorten the setting time, and form bubbles of the same size.

According to an embodiment of the present invention, there is provided a method for preparing an admixture for gypsum board comprising a sulfonated polystyrene (SPS)-based compound by sulfonation reaction with polystyrene and sulfuric acid.

According to an embodiment of the present invention, it is provided that the DS (degree of sulfonation) of the sulfonated polystyrene (SPS)-based compound is 15 to 99%.

The sulfonation may be carried out by a method of polymerization using the monomer styrene sulfonic acid, or may be carried out by a method of directly sulfonating a sulfonating agent into polystyrene, which is a polymer.

According to an embodiment of the present invention, the solvent in the sulfonation reaction is propane, butane, pentane, pentane, hexane. At least one selected from cyclohexane, acetone, dibromomethane and dichlorobenzene is provided.

According to an embodiment of the present invention, at least one selected from acetic anhydride, sulfuric acid, exothermic sulfuric acid and sulfur trioxide is provided as a sulfonating agent in the sulfonation reaction.

According to an embodiment of the present invention, the polystyrene has a weight average molecular weight of 10,000 to 800,000.

According to one embodiment of the present invention, there is provided an admixture for gypsum board prepared according to the above manufacturing method.

According to one embodiment of the present invention, there is provided a composition for forming a gypsum board comprising gypsum, a curing agent, a lightening agent, and water in the admixture for gypsum board.

According to an embodiment of the present invention, the gypsum may be hemihydrate gypsum (CaSO ₄ ·1/2H ₂ O).

In this case, the composition for forming a gypsum board is provided in an amount of 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 to 150 parts by weight of water based on 100 parts by weight of gypsum. .

In this case, the admixture for gypsum board may further include a polycarboxylate ether (PCE)-based compound. In addition, it is provided that the weight ratio of the sulfonated polystyrene (SPS)-based compound and the polycarboxylate ether (PCE)-based compound is 10:90 to 90:10.

According to an embodiment of the present invention, the curing agent may include at least one of _{potassium sulfate (K 2} SO ₄ ) and sodium sulfate (Na ₂ SO _{4 ).}

According to an embodiment of the present invention, the composition for forming a gypsum board may further include a curing retardant.

According to one embodiment of the present invention, there is provided a gypsum board using the composition for forming a gypsum board.

By including the SPS-based admixture according to the present invention, when manufacturing gypsum board, fluidity and setting time can be adjusted in gypsum board manufacturing according to the SPS-based sulfuration degree (DS).

Including the SPS-based admixture according to the present invention, when manufacturing gypsum board, fluidity and setting time according to the weight average molecular weight (Mw) of polystyrene provided by the SPS system, as well as the bubble size, can be controlled.

Therefore, there is an effect of providing an admixture with improved physical properties compared to the existing PNS-based admixture.

By using the gypsum board-forming composition of the present invention, it is possible to manufacture a high-quality gypsum board with improved physical properties while reducing costs by shortening the setting time during the gypsum board manufacturing process.

In addition, by controlling the molecular weight of the SPS-based compound, gypsum boards of various weights suitable for use can be manufactured without additional processes or additives.

1 is a FT-IR result of measuring whether a sulfonic group is synthesized in polystyrene in a sulfonated polystyrene (SPS)-based compound according to the present invention.
2 is an FT-IR result of polystyrene not subjected to a sulfonation reaction.
3 is a graph showing the results of Table 1. FIG.
4 is a graph showing the results of Table 2.

Hereinafter, specific details and possible implementation examples for carrying out the present invention will be described. However, with respect to the configuration not specifically specified below, as long as it does not go against the purpose of the present invention, information known in the art may be applied.

In the present specification, when a layer or member is said to be located “on” another layer or member, this means not only when a layer or member is adjacent to another layer or member, but also when another layer or member is located between two layers or members. Includes cases where another member is present.

In addition, when it is said that a part "includes" a certain component in the present specification, this means that other components may be further included rather than excluding other components unless otherwise stated.

As used herein, "molecular weight" means "weight average molecular weight (Mw)" unless otherwise defined.

[General definition of a substituent]

In the present specification, 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.

In the present specification, the C ₂ -C ₂₀ alkenyl group refers to a hydrocarbon group including at least one carbon double bond 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. In the present specification, 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, and the like.} Included.

In the present specification, the C ₁ -C ₂₀ alkoxy group refers to a _{monovalent group having a chemical formula of -OA 101} (where 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.

In the present specification, 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.

In the present specification, 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.

In the present specification, 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 is a monovalent group having a heterocyclic aromatic system having 1 to 20 carbon atoms. means Specific examples of the C ₁ -C ₆₀ 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.

[Method for manufacturing admixture for gypsum board and admixture]

According to an embodiment of the present invention, there is provided a method for preparing an admixture for gypsum board comprising a sulfonated polystyrene (SPS)-based compound represented by the following Chemical Formula 1 by sulfonation reaction with polystyrene and sulfuric acid.

<Formula 1>

In Formula 1,

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.

In the production of gypsum board, dispersible flow value and setting time (apparent termination) are important factors.

When the fluidity is improved, it is possible to prevent premature setting of gypsum during slurry mixing, thereby increasing equipment efficiency, and finally providing improved curing performance.

In the case of setting time, if the setting or curing time is not sufficiently hardened, the shape of the final product is not fixed, and it is uneconomical because the time required for production also increases. Therefore, in the production of gypsum board, it is important to have high fluidity and shorten the setting time at the same time.

Accordingly, the present invention aims to control the fluidity and setting time of the gypsum slurry used according to the degree of sulfation of the polystyrene (PS)-based compound in order to provide the above physical properties.

According to an embodiment of the present invention, the DS (degree of sulfonatiion) indicating the degree of sulfation of the sulfonated polystyrene (SPS)-based compound may be 15 to 99%. Preferably 15 to 95% may be provided. When it is lowered to 15% or less of the above range, there is a problem that the SPS-based compound is not dispersed in water, and when it exceeds 99%, there is a problem in that fluidity is disadvantageous and setting time is long. Therefore, DS can provide the effect of improving the fluidity of the gypsum slurry and shortening the setting time in the range of 15 to 99%.

On the other hand, there are various methods for sulfonation of polystyrene, and there are mainly two methods.

First, a polymerization method using the monomer styrene sulfonic acid (Jessica, E., "Sulfonation of Polystyrene: Toward the "Ideal" Polyelextrolyte". JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY, 2013, vol51, 11, 2416-2424).

Second, a method for sulfonation of polystyrene, a polymer (Crisriane, R., "Synthesis in Pilot Scale and Physical Properties of Sulfonated Polystyrene". J. Braz. Chem. Soc., 2003, Vol. 14) , No. 5, 797-802).

In the present invention, any of the above two methods may be adopted. That is, the sulfonation may be carried out by a method of polymerization using the monomer styrene sulfonic acid or by a method of directly sulfonating polystyrene, which is a polymer, using a sulfonating agent, but is not limited thereto.

In the former case, as an embodiment, a method for polymerization including the monomer styrene sulfonic acid may be provided.

Further, in the latter case, in one embodiment, the procedure of the method for direct sulfonation to polystyrene is provided as follows.

First, a process of preparing an acetyl sulfate solution is provided. An acid anhydride is prepared under inactivated nitrogen conditions to prepare an acetyl sulfate solution.

In the next step, after dissolving the polymer polystyrene in an organic solvent, the acetyl sulfate solution may be added to prepare sulfonated polystyrene. The mechanism for this is as follows.

[Mechanism: Acetyl sulfate solution preparation]

[Mechanism: Sulfonation reaction]

According to an embodiment of the present invention, the solvent in the sulfonation reaction is propane, butane, pentane, pentane, hexane. At least one selected from cyclohexane, acetone, dibromomethane, and dichlorobenzene is provided, but is not limited thereto.

According to an embodiment of the present invention, a sulfonating agent may be used for the sulfonation reaction, and in this case, at least one selected from acetic anhydride, sulfuric acid, exothermic sulfuric acid, and sulfur trioxide may be provided as the sulfonating agent. In addition, it is not particularly limited as long as it is a sulfonating agent capable of achieving the desired reaction, and preferably sulfuric acid and acetic anhydride may be provided for the sulfonation reaction.

According to an embodiment of the present invention, the polystyrene has a weight average molecular weight of 30,000 to 400,000.

Preferably, the polystyrene has a weight average molecular weight in the range of 35,000 to 350,000, and according to Tables 1 and 2 to be described later, it can be seen that the fluidity is improved and the setting time is shortened in the above range. Accordingly, it can be confirmed that the physical properties are improved compared to the currently commercially available PNS-based admixtures.

In addition, according to Table 3, since the cell size may also increase according to the weight average molecular weight, the cell size may be adjusted by adjusting the molecular weight as necessary.

That is, in the present invention, the cell size of the gypsum board can be controlled according to the molecular weight within the weight average molecular weight range of 10,000 to 800,000 of the polystyrene of the sulfonated polystyrene (SPS)-based compound.

According to one embodiment of the present invention, there is provided an admixture for gypsum board prepared according to the above manufacturing method.

In this case, it is provided that the admixture is of an aqueous dispersion type. The aqueous dispersion is made by slowly adding the reaction solution that has undergone the activation step while putting water in a separate container and stirring. The content of water is not particularly limited, but in consideration of workability, etc., the admixture may be freely added within a range including 1 to 60 parts by weight based on 100 parts by weight of water in the final product.

Accordingly, by providing the admixture according to the present invention, it is possible to solve the problems of fluidity and small bubble size during gypsum board manufacture, which have emerged in providing the existing admixture for gypsum board manufacture.

Accordingly, since the cell size can be adjusted by controlling the polystyrene molecular weight of the SPS-based compound as needed, gypsum boards of various weights suitable for use can be manufactured without additional processes or additives.

[Composition for forming gypsum board]

The composition for forming a gypsum board of the present invention includes gypsum, an admixture, a curing agent, a lightening agent and water, and the admixture is sulfonated with polystyrene and sulfuric acid, and sulfonated polystyrene represented by the following formula (1) (Sulfonated Polystyrene, SPS) ) and an admixture for gypsum board containing a compound.

<Formula 1>

In Formula 1,

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.

According to an embodiment of the present invention, the gypsum included in the composition for forming a gypsum board may be hemihydrate gypsum.

Gypsum is a very soft sulfate mineral mainly composed of calcium sulfate (CaSO _{4 ).} 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 ℃ to 200 ℃ or half fired by absorbing moisture in the air gypsum (CaSO ₄ · 1 /2H ₂ O) can be obtained.

According to an embodiment of the present invention, the hemihydrate gypsum may be produced by calcining raw gypsum. As the raw gypsum, natural gypsum or flue gas desulfurization (FGD) gypsum, phospho gypsum, titanium gypsum, citrogypsum, tartarogypsum, borogypsum) , chemical gypsum such as lactogypsum can be used. Alternatively, recycled gypsum recovered from waste gypsum boards or the like may be used as the raw gypsum, but is not limited thereto.

According to an embodiment of the present invention, 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. . When the acid or salt is blended together, the amount of coma can be reduced when manufacturing 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 parts by weight based on 100 parts by weight of the raw gypsum.

According to an embodiment of the present invention, the calcination of the raw gypsum may be performed within a temperature range of 150°C to 200°C, for example, at a temperature of 160°C to 180°C.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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.

The admixture represented by Formula 1 may include 0.1 to 2 parts by weight of the admixture for gypsum board, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the gypsum composition for forming a gypsum board.

In addition, the weight average molecular weight of polystyrene provides a range of 10,000 to 800,000. When the weight average molecular weight of the polystyrene satisfies the above-mentioned range, the composition for forming a gypsum board has high fluidity and can provide an effect of shortening the curing time and controlling the size of the foam.

According to an embodiment of the present invention, the admixture is a polynaphthalenesulfonate (PNS)-based compound, a polycarboxylate ether (PCE)-based compound, a lignin sulfonate-based compound, and an alkyl in addition to the sulfonated polystyrene (SPS)-based compound. At least one compound selected from an arylsulfonic acid-based compound, a polyoxyethylene-based compound, an alkylarylether-based compound, an oxycarboxylic acid-based compound, a polycarboxylic acid-based compound, and an aminosulfonic acid-based compound may be further included. Preferably, it may further include a polycarboxylate ether (PCE)-based compound.

In this case, it is provided that the weight ratio of the sulfonated polystyrene (SPS)-based compound and the polycarboxylate ether (PCE)-based compound is 10: 90 to 90: 10. Preferably, it may be 40:60 to 60:40, and more preferably 45:55 to 55:45. Accordingly, as can be seen from the results of Tables 1 and 2 below, it is possible to provide a composition for forming a gypsum board having improved fluidity and setting speed compared to the conventional PNS system by using it together with a polycarboxylate ether (PCE) system. .

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, 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. Preferably potassium sulfate (K ₂ SO ₄ ) or sodium sulfate (Na ₂ SO ₄ ) may be provided.

In addition, 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.

According to an embodiment of the present invention, the composition for forming a gypsum board includes 0.1 to 1 part by weight of a curing agent based on 100 parts by weight of the gypsum. When the content of the curing agent satisfies the above-mentioned range, 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.

According to an embodiment of the present invention, 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.

According to an embodiment of the present invention, the weight reducing agent may include a sulfate compound, a persulfate compound, a bisulfate compound, a carbonate compound, or a bicarbonate compound.

For example, 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. can

According to another embodiment of the present invention, 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

For example, 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.

According to an embodiment of the present invention, in the composition for forming a gypsum board, 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. When the content of the weight reducing agent satisfies the above-mentioned range, 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. According to an embodiment of the present invention, the composition for forming a gypsum board includes water. The water reacts with the hemihydrate gypsum by hydration to form a hard gypsum dihydrate.

According to an embodiment of the present invention, in the composition for forming a gypsum board, 60 to 150 parts by weight of the water is provided, preferably 60 to 80 parts by weight, based on 100 parts by weight of gypsum. .

According to an embodiment of the present invention, 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 such as sodium, potassium, calcium, magnesium, and ammonium thereof, glucose, fructose, galactose, saccharose, and chlorine Sugars, such as silose, arabinose, lipose, oligosaccharide, and dextran, boric acid, etc. can be used. The curing retardant may be added to control the curing rate during manufacturing of the gypsum board, but is not limited thereto.

According to an embodiment of the present invention, the composition for forming a gypsum board may further include a strength improving agent. As the strength improving agent, for example, silica fume, fly ash, etc. may be used. The strength improving agent 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, for example, 0.5 to 5 parts by weight, based on 100 parts by weight of the gypsum board-forming composition.

[Gypsum board]

According to one embodiment of the present invention, gypsum, the gypsum board admixture, curing agent, lightweighting agent, and water, and the sulfonated polystyrene (SPS)-based compound represented by the same Chemical Formula 1 as described above. There is provided a gypsum board using a composition for forming a gypsum board comprising:

Accordingly, the description of the gypsum, the curing agent, the lightening agent, the sulfonated polystyrene-based compound, and the admixture may refer to the bar described in the present specification.

According to an embodiment of the present invention, the gypsum board may be provided on the exterior material sheet and the gypsum core.

According to an embodiment of the present invention, 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. may include

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.

Accordingly, the gypsum board according to the present invention has high fluidity during manufacture and a short setting time, thereby improving productivity. In addition, the gypsum board may include a sulfonated polystyrene (SPS)-based compound among the admixtures, so that the bubble size can be controlled during manufacturing.

Furthermore, it has excellent fluidity, curability, hardness, etc., and is environmentally friendly and harmless to the human body as compared to using only the existing PNS-based admixtures.

Accordingly, the gypsum board of the present invention may be appropriately molded as necessary and usefully used as a building material.

Hereinafter, the following examples illustrate the present invention without limiting the scope of the present invention.

[Example]

Preparation Example: Preparation of SPS-based compounds

1) Preparation of Acetyl Sulfate Solution

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 clear solution.

2) Sulfonation

After dissolving polystyrene in an organic solvent in a flask, nitrogen was purged for 30 minutes while heating the flask to 40°C. Then, the acetyl sulfate solution was added using a funnel, and then stirred at 40° C. for 2 hours. Then, when the solution had a transparent yellow color, 2-propanol was added for 30 minutes, and then the reaction was terminated by cooling at room temperature to obtain a polymerized sulfonated polystyrene (SPS)-based compound. The obtained compound is separated by washing with distilled water, if necessary.

3) SPS-based compounds

prepared in Preparation Example 2) above An admixture was prepared using a sulfonated polystyrene (SPS)-based compound.

Experimental Example 1: IR measurement (synthesis of sulfonic groups)

prepared in Preparation Example 2) above Whether a sulfonic group was synthesized in polystyrene in a sulfonated polystyrene (SPS)-based compound was analyzed using FT-IR measurement. The results for this are shown in FIG. 1 . Also, in this case, the DS value is 35%. For comparison, FT-IR values of polystyrene not subjected to sulfonation are shown in FIG. 2 .

In addition, the sulfonation degree (DS) of the sulfonated polystyrene (SPS)-based compound can be inferred from the amount of the acetyl sulfate solution added. A more accurate measurement method can be measured through NMR (Nuclear magnetic resonance) spectroscopy and MALDI-ToF MS (Matrix-assisted laser desorption ionization time-of-flight mass spectrometry) if necessary. You can check the contents.

Longhe Zhang, Bryan, C., "Sulfonation Distribution in Sulfonated Polystyrene Ionomers Measured by MALDI-ToF MS". ACS Macro Lett, 2013, 2, 217-221

Example 1: Preparation of a composition for forming a gypsum board

Based on 100 parts by weight of 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 an admixture, 0.2 parts by weight of a curing agent (potassium sulfate) and 0.06 parts by weight of a lightening agent (ammonium sulfate) are added, The composition for forming the gypsum board of Example 1 was prepared by mixing for 10 seconds with a mixer.

In this case, in the case of the admixture, sulfonated polystyrene (SPS, solution) and a polycarboxylate ether (PCE)-based compound were provided in a weight ratio of 50:50.

In addition, the sulfonated polystyrene (SPS) is according to Preparation Example 1, in particular, for preparing the SPS-based compound, the weight average molecular weight of the provided polystyrene is 10,000.

Examples 2 to 6 and Comparative Example 1

The compositions for forming gypsum boards of Examples 2 to 6 and Comparative Example 1 were prepared in the same manner as in Example 1, except that the weight average molecular weight or compound (DS) described in Table 1 below was provided as an admixture. As the admixture in Comparative Example 1, a polynaphthalenesulfonate (PNS) system used by a gypsum board producer was used, and in this case, the weight average molecular weight was 10,000.

Evaluation Example 1: Evaluation of fluidity and apparent termination of composition for forming gypsum board

The fluidity and apparent termination of the compositions for forming gypsum boards prepared in Examples 1 to 6 and Comparative Example 1 were measured according to the following method. Accordingly, the results for the fluidity are shown in Tables 1 and 3, and the results for the apparent termination are shown in Tables 2 and 4.

<Evaluation of Flow>

After pouring the composition for forming a gypsum board into a circular mold having a diameter of 70 mm and a height of 40 mm, the diameter spread when demolding was measured 10 seconds later. At this time, the circular spread slurry was measured in three places at intervals of 60 degrees, the maximum value and the minimum value among the measurement data were added, and then divided by 2 to obtain a flow value.

DS
Mw 15% 20% 30% 40% 60% 80% 95% 100% Example 1
(10,000) 128.6 124.3 121 116.4 111.2 108 107.6 107.5 Example 2
(35,000) 130 125.7 121.5 117.2 112.9 108.6 108.6 108 Example 3 (190,000) 137 134.5 132.2 129.8 127.4 122.7 119.1 118 Example 4 (280,000) 135 132.0 129 126 123 117 115 112 Example 5 (350,000) 131 128.0 126 123 121 116 113 110 Example 6
(800,000) 125.5 123.1 121.5 117 112.5 108.1 103.1 100.8 Comparative Example 1 118

(*Unit: mm)

<Condensation time test>

First, the composition for forming 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), and the time is set when the measured value is 85. time (apparent termination time).

DS
Mw 15% 20% 30% 40% 60% 80% 95% 100% Example 1
(10,000) 129 132 135 135 140 142 145 146 Example 2
(35,000) 130 133 137 139 142 146 150 151 Example 3 (190,000) 134 136 140 143 146 151 153 156 Example 4 (280,000) 142 145 149 154 159 161 162 163 Example 5 (350,000) 147 149 155 162 169 174 178 180 Example 6
(800,000) 149 154 160 171 178 181 184 184 Comparative Example 1 161

(*unit: seconds)

Evaluation Example 2: Evaluation of cell size of gypsum board

A gypsum board was prepared from the composition for forming a gypsum board prepared in Examples 1 to 6 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 .

Example (DS 30%) Average cell size (mm) Example 1
(10,000) 0.38 Example 2 (35,000) 0.42 Example 3 (190,000) 0.55 Example 4 (280,000) 0.61 Example 5 (350,000) 0.65 Example 6 (800,000) 0.75 Comparative Example 1 0.50

First, referring to FIG. 1 , in the case of a sulfonated polystyrene (SPS)-based compound according to the present invention, a degree of sulfonatiion (DS) may be provided in the range of 15 to 99%.

In the case of Table 1 for confirming the fluidity, it can be seen that the fluidity is improved as the DS value of the SPS decreases, and it can be confirmed that the DS of the Examples has superior fluidity compared to the Comparative Example in the range of 15% to 60%. In particular, it was confirmed that the DS value is best at about 15 to 35%, and when it is lowered to 15% or less, it is difficult to lower it below that because SPS is not dispersed in water.

In the case of Table 2 for confirming the setting time, it can be confirmed that the setting time is shortened as the DS value of the SPS decreases, and in the case of the Example, it can be confirmed that the setting time is shortened overall compared to the comparative example.

In the case of Table 3 for observing the bubble size, the gypsum boards prepared from the compositions of Examples 1 to 6 can be lightened by securing sufficient size of the bubble size, which can also be adjusted according to the molecular weight of polystyrene. could see that Accordingly, it can be confirmed that by providing the SPS-based admixture as an admixture, the existing problem of small bubble size can be solved, and a higher weight reduction level can be provided compared to the conventional PNS-based admixture.

Therefore, when manufacturing gypsum board according to the present invention, productivity is excellent, and it is widely used as an existing admixture to provide superior physical properties than PNS-based admixtures, and of course it can be substituted.

As described above, although the present invention has been described with reference to the limited examples and drawings, the present invention is not limited to the above examples, which are various modifications and variations from these descriptions by those of ordinary skill in the art to which the present invention pertains. Transformation is possible. Accordingly, the spirit of the present invention should be understood only by the claims set forth below, and all equivalents or equivalent modifications thereof will fall within the scope of the spirit of the present invention.

Claims (12)

It comprises a sulfonated polystyrene (SPS)-based compound represented by the following formula (1) by sulfonation reaction with polystyrene and sulfuric acid,
The sulfonated polystyrene (SPS)-based compound has a DS (degree of sulfonatiion) of 15 to 80% of an admixture for gypsum board.
<Formula 1>

In Formula 1,
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. delete The method of claim 1,
The sulfonation is an admixture for gypsum board that is carried out by a method of polymerization including the monomer styrene sulfonic acid. The method of claim 1,
The sulfonation is an admixture for gypsum board that is carried out by a method of sulfonation in polystyrene. The method of claim 1,
Admixture for gypsum board further comprising at least one selected from acetic anhydride, sulfuric acid, exothermic sulfuric acid, and sulfur trioxide as a sulfonating agent in the sulfonation reaction. The method of claim 1,
The weight average molecular weight of the polystyrene is 10,000 to 800,000 admixture for gypsum board. delete The method of claim 1,
The admixture for gypsum board will further include water,
With respect to 100 parts by weight of water, the admixture for gypsum board comprising 1 to 60 parts by weight of the admixture. The method of claim 1,
A composition for forming a gypsum board comprising gypsum, a curing agent, a lightening agent, and water in the admixture for gypsum board. 10. The method of claim 9,
The admixture composition for forming a gypsum board further comprising a polycarboxylate ether (PCE)-based compound. 10. The method of claim 9,
A composition for forming a gypsum board in which the weight ratio of the sulfonated polystyrene (SPS)-based compound and the polycarboxylate ether (PCE)-based compound is 10:90 to 90:10. A gypsum board using the composition for forming a gypsum board according to claim 9.

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