TWI250138B - Copolymer having superior water-reducing properties for cement and method for preparing the same - Google Patents

Abstract

The present invention provides a copolymer that is obtained by copolymerizing a monomer mixture or further neutralizing the copolymer with an alkaline substance, a method for preparing the same, and a cement composition comprising the same. The copolymer of the present invention increases composition fluidity even at a high water-reducing formulation by improving dispersibility of cement particles, prevents a decrease of fluidity as the function of time, and offers good workability by supplying an adequate amount of air flow continuously.

Description

1250138

发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明, especially a cement copolymer for forming concrete with good strength, which can improve the dispersibility of cement particles, even if the high water-reducing formula is used to increase the fluidity of the cement composition, and prevent the fluidity from decreasing with time. And provide good processability by continuously supplying an appropriate amount of gas. [Prior Art] A cement composition such as concrete or mortar is a hard substance which is hardened by the reaction of cement 10 with water. The physical properties of the cement composition, such as the compressive strength after hardening, vary depending on the amount of water used. Roughly speaking, when the water consumption is increased to improve the workability, the compressive strength is reduced and the crack is caused. Therefore, there is a limit to the amount of water used in cement compositions. The Korean Industrial Standard (KS) F 2560 recommends the use of certain chemical additives to concrete to reduce the amount of water used. The categories of chemical additives are divided into AE (air-entraining) additives, water reducing additives, and high proportions of water reducing additives. The AE additive is a chemical additive that is included in the cement composition to increase the number of small bubbles. When it is mixed with a water-reducing additive or a high-ratio water-reducing additive, it forms a 20 AE water-reducing additive (gas and water reduction). Additives) and a high proportion of AE water reducing additives. When AE water-reducing additives are used, the water consumption can be reduced by about 1% by weight (% by weight), while the high proportion of AE water-reducing additives can reduce the water consumption by more than 18 wt% (% by weight). The water-reducing additive is made of lignin compound. Continued page (Please note and use the continuation page when the invention page is not enough) -8·

1250138, high proportion of water reducing additives are made of naphthalene-formalin condensate and trimeric condensate.

Since the loss of concrete in the cement composition occurs within 30 minutes, all work from concrete mixing to casting needs to be completed in a short time. Recently, due to changes in aggregates, the increase in unit water content, the use of mechanized modern equipment, and the increase in transport volume have led to the need for an excellent enthalpy retention characteristic and a comparative advantage when compared with conventional AE water-reducing additives. A new chemical additive with good water-reducing properties. Yes, additive manufacturers are actively developing high-grade AE water-reducing additives that have good water-reducing properties and low-cost loss of 10 degrees, and can be added to concrete compositions in concrete.

Today, a high proportion of AE water-reducing additives are commercially available, such as naphthalenesulfonic acid furfural condensation salts (naphthyl), melaminesulfonic acid formaldehyde condensation salts (melamine based), and polycarboxylates (polycarboxylic acid groups). ). However, these high ratios of 15 water additives have some problems. For example, although the hardening characteristics of the naphthyl and melamine-based high water-reducing additives are excellent, there is a problem of low fluidity (debt loss). On the other hand, the biggest problem with polycarboxylate high proportion water reducing additives is the slowing of hardening. However, a newly developed polycarboxylate-based concrete additive having excellent fluidity has a good fluidity as long as it is added in a small amount, and solves the problem of hardening retardation. In the case of polycarboxylate-based high-proportion AE water-reducing additives, No. 59-18338, this patent publication discloses a polyolefin-based ethylene glycol mono(meth)acrylate monomer, (methyl). An acrylic monomer, and a copolymer prepared from a monomer copolymerizable with the monomers. In addition, Japanese Patent Laid-Open No. Hei 5-238795-9- 1250138 discloses a polyolefin-based ethylene glycol diester monomer having an unsaturated double bond, a monomer having a separating group, and other specific A copolymer prepared from a monomer. Although these polycarboxylate-based high-proportion AE water-reducing additives have good water-reducing properties and twist retention characteristics, there is still much room for improvement. The cement dispersant disclosed in Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Copolymer. However, the dispersibility of these cement dispersants is unsatisfactory, especially when the 10-high water-reducing formulation is used because the polyethylene glycol mono-propylene ether monomer and the maleic acid monomer are not easily copolymerized. The cement dispersant disclosed in Japanese Patent Publication No. Hei 10-194808, etc., contains a copolymer prepared from a polypropylene glycol polyethylene glycol mono(meth) propylene ether monomer and an unsaturated carboxylic acid monomer. Because this cement disperses 15 agents with a highly hydrophobic polypropylene glycol component, it does not have sufficient dispersibility. Therefore, in order to achieve sufficient dispersibility, it must be added in a large amount, and sufficient dispersibility cannot be obtained when a high water-reducing formula is used. . DISCLOSURE OF THE INVENTION 20 An object of the present invention is to provide a cement copolymer which can improve the dispersion stability of cement particles, and a preparation method thereof. Another object of the present invention is to provide a fluid composition which increases the fluidity of the cement composition, prevents the fluidity from decreasing with time, and continuously supplies an appropriate amount of gas, so that the cement composition is good -10- 1250138

DESCRIPTION OF THE INVENTION MM processable cement copolymer, and a preparation method thereof. In order to achieve the above object, the present invention provides a copolymer for cement having superior water-reducing characteristics obtained by copolymerizing a monomer mixture or further neutralizing the copolymerized monomer mixture with an alkaline substance. Wherein the monomer mixture comprises an alkoxy polyolefin-based ethylene glycol mono(indenyl) acrylate monomer, a (mercapto)acrylic monomer, and a reactive surfactant; the invention also provides a A method of preparing the copolymer for cement. The present invention also provides a cement composition which has excellent fluidity even in the case of using a high water-reducing formulation, which is 0.01 to 10 parts by weight of the above-mentioned cement copolymer for 100 parts of cement. [Embodiment] The present invention will be described in detail later. The present invention copolymerizes a copolymer comprising a carboxylic acid monomer and a reactive surfactant as a unit unit monomer. Therefore, the present invention has better dispersibility than the conventional cement additive, and even if the high water reducing formula is used, the fluidity of the cement composition is increased, the fluidity is prevented from decreasing with time, and the continuous supply of an appropriate amount of gas is caused. This cement composition is made to have good processability. The present invention comprises a reactive surfactant as a unit monomer in the copolymer, having a hydrophilic and a hydrophobic group so as to increase the solubility of the polymer in water. Further, it also enhances the physical absorption of the cement particles to the polymer so as to contribute to the dispersion of the cement particles and maintain the fluidity, and to increase the stability of the divalent ions contained in the cement composition. -11- 1250138 - Description of the Invention If specifically, the carboxylic acid-based copolymer of the present invention comprising a reactive surfactant as a unit monomer, preferably a monomer mixture, wherein the monomer mixture comprises There are: a) 50 to 90% by weight (by weight) of a 5-alkoxy polyolefin-based ethylene glycol mono(meth)acrylate monomer represented by the following Chemical Formula 1; b) 5 to 45 wt% in the following chemical formula 2 A (mercapto)acrylic monomer, or a salt thereof, and c) 0.5 to 40% by weight of a reactive surfactant represented by the following Chemical Formula 3: 10 Chemical Formula 1 R1 CH2 = C-GQO-(f#0 mR3 where: R1 is a hydrogen atom or a sulfhydryl group; R2〇 is a C2 to C4 oxyalkylene which may be the same or different in phase 15, if not simultaneously added in blocks or in any form; R3 is a Q to C4 And the m is an average addition moles of the oxyalkylene group, which is an integer from 1 to 50; the formula 2 R4 I , 2〇ch2=c-gog-m1 wherein: -12- 1250138 Description of the invention that R4 is a hydrogen atom or a sulfhydryl group; and Μ1 is a hydrogen atom, a valence Metal atom, a divalent metal atom, an ammonium, or an organic amine; and Chemical Formula 3 # Η

II 5 CH = G - R6〇-(R7G)r-( S〇3)n-lvi2 wherein: R5 is a hydrogen atom or a fluorenyl group; R6 is an alkyl group, a subphenyl group, or an alkyl group. Phenyl; R70 is an alkylene oxide of (C to C4, which may be the same or different, and may be added in blocks or in any form if 10 is different; r is the average addition mole number of the oxyalkylene group, which is from 1 to 50 Integer; η is 0 or 1; and Μ2 is a hydrogen atom, a monovalent metal atom, an ammonium, or an organic amine. 15 The reactive surfactant represented by Chemical Formula 3 has a double bond which can participate in a radical reaction, so that each monomer During the copolymerization, it can function as a surfactant in the polymer backbone. The hydrophobic portion of the surfactant promotes the adsorption of cement particles, and the ionic portion forms an electric double layer, thereby increasing the zeta potential ( Zeta potential) and enhance the electrostatic repulsion of the dispersed particles 20 and stability. Therefore, the hydrophilicity and steric hindrance of the polyolefin-based ethylene glycol chain will disperse the cement particles, while the surfactant end groups are due to the electrostatic repulsion of the sulfonic acid. Sex, so that it can play excellent dispersion and refueling (air Entraining) Stabilization 1250138 Description of invention #Sell stomach. The monomer represented by Chemical Formula 1 can be obtained from: methoxypolyethylene glycol mono(indenyl) acrylate, methoxypolypropylene glycol mono(meth)acrylate, methoxy Polybutylene glycol mono(mercapto) acrylate, methoxy polyethylene glycol polypropylene glycol mono(indenyl) 5 acrylate, methoxy polyethylene glycol polybutylene glycol mono (meth) acrylate, Nonoxyl polypropylene glycol polybutylene glycol mono(meth)acrylate, methoxy polyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol mono(methyl) Acrylate, ethoxylated polypropylene glycol mono(meth)acrylate, ethoxylated polybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polypropylene glycol mono 10 (meth) acrylate, B Oxypolyethylene glycol polybutylene glycol mono(meth)acrylate, ethoxypolypropylene glycol polybutylene glycol mono(mercapto)acrylate, and ethoxypolyethylene glycol polypropylene glycol polybutylene glycol single (Mercapto) acrylate or the like is selected, and the like can be copolymerized with each other. The content in the copolymer is preferably from 50 15 to 90% by weight. If it exceeds this range, it is difficult to achieve good dispersibility. The monomer represented by Chemical Formula 2 can be derived from: acrylic acid and methacrylic acid, and monovalent metal salt. A divalent metal salt, an ammonium salt, an organic amine salt thereof, or the like, which may be copolymerized with each other. The monomer represented by Chemical Formula 2 is preferably contained in the copolymer in an amount of from 5 20 to 45 wt%. This range, that is, may reduce the ability of the cement composition to prevent loss of twist. The monomer represented by Chemical Formula 3 has both a hydrophobic and a hydrophilic group, and another double bond capable of participating in a radical reaction. Specifically, it can be The following are selected: thiooxy polyolefin based ethylene 2250138 Description of the invention ϋ propylene propylene ether, such as thiooxy polyethylene glycol propylene ether, thiooxy polypropylene glycol propylene ether, thiooxy polybutylene glycol propylene Ether, thiooxy polyethylene glycol 2-butenyl ether, thiooxy polypropylene glycol 2-butenyl ether, thiooxy polybutylene glycol 2-butenyl ether, thiooxy polyethylene glycol 3-butenyl ether, thiooxy poly 5 propylene glycol 3-butenyl ether, thiol Butanediol 3-butenyl ether, thiooxy polyethylene glycol 3-pentenyl ether, thiooxy polypropylene glycol 3-pentenyl ether, and thiooxy polybutylene glycol 3-pentenyl ether Thioxypolyethylene glycol alkyl vinyl phenyl ether, such as thiooxy polyethylene glycol (3-vinyl-5-mercapto)phenyl ether, thiooxy polypropylene glycol (3-vinyl- 5-methyl)phenyl ether, thiooxypolybutylene glycol 10 (3-vinyl-5-mercapto)phenyl ether, thiooxy polyethylene glycol (3-vinyl-5-ethyl) phenyl ether , thiooxy polypropylene glycol (3·vinyl-5-ethyl) phenyl ether, thiooxy polybutylene glycol (3-vinyl-5-ethyl) phenyl ether, thiooxy polypropylene glycol (3· propylene 5-methyl propyl ether, thiooxy polybutylene glycol (3-propenyl-5-propyl) phenyl ether, thiooxy polyethylene glycol (3-propenyl-5-butyl)benzene Ether, thiooxy polypropylene glycol (3-15 propylene-5-butyl) phenyl ether, and thiooxy polybutylene glycol (3-propenyl-5-butyl) phenyl ether; 2-thiooxy poly Olefin ethylene glycol-3-(4-alkylphenoxy)propenyl propylene ether, for example 2-thiol polyethylene glycol-3-(4-mercaptophenoxy) propylene propylene ether, 2- Thiooxypolypropylene Alcohol-3-(4-methylphenoxy)propenyl propylene ether, 2-sulfoxypolybutanediol-3-(4-methylphenoxy)propenyl propylene ether, 2-thiol 20 Polyethylene glycol-3-(4-ethylphenoxy)propenyl propylene ether, 2-sulfoxypolypropylene glycol-3: (4-ethylphenoxy) propylene propylene ether, and 2-sulfol a polybutylene glycol-3-(4-ethylphenoxy)propenyl propylene ether; and a monovalent metal salt, a divalent metal salt, and an organic amine salt thereof. These monomers can be copolymerized with each other. Preferably, the reactive surfactant represented by Chemical Formula 3 is contained in the total amount of -15. 5 to 40 wt ° / 〇 (% by weight). Exceeding this range may reduce the strength retention and refueling capacity of the cement composition. The carboxylic acid-based copolymer or the neutralized salt containing a reactive surfactant as a unit monomer can be represented by the following Chemical Formulas 4a, 4b, 4c and 4d, 5 but not limited thereto. Chemical formula 4a

〇 ¥ &

I Chemical formula 4b c iooo-B^aH2s?CH3 Hr -<c cc] -g-<icoo-<ch2ch20?ch3 3⁄4 蜱col Spring: CH ,\ -1 3 3 o 10 Chemical formula 4c c 1q09(ch2ch2o ¥g^ cc: c:(丨coo-(c^CHo:]nbH3 pv -ci Η -€,coi 丨CHo(CH2oH30},--Mo 3 §4 -16 1250138

Chemical formula 4d G<-c 〇q, (cho^q)? Ch3 •H2- -<c (G c I οοο'^Μαβ^,β

C c(.coi H2- S

In Chemical Formulas 4a to 4d: Μ is a hydrogen atom, or a monovalent or divalent metal atom; R is a hydrogen group 5 or a burnt group; !1,11^,11,0,卩,9 and 1' are molar ratios in which at least one of m and W is not 0, at least one of 〇 and ρ is not 0, and η, q and r are not zero. The ammonium of the reactive surfactant end group may be substituted with a hydrogen atom or a monovalent metal atom. The monomer components of the copolymer of the present invention may be copolymerized by a polymerization initiator. The copolymerization method is not particularly limited, and solution polymerization, mass polymerization, and the like can be employed. For example, when water is used as the polymerization solvent, a water-soluble 15 polymerization initiator such as a persulfate or metal test, or hydrogen peroxide can be used. For example, a lower alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ester compound, or a ketone compound can be used as a polymerization solvent, such as benzoic acid benzoquinone, decyl peroxide, and hydroperoxy benzene. A hydroperoxide of the type, or an aromatic azo compound such as azobisisobutyronitrile is used as a polymerization initiator. Accelerators such as amine compounds can also be employed. -17-1250138 Description of the invention If a mixed solution of water/low alcohol is used, the aforementioned polymerization initiator or a combination of the polymerization initiator and the accelerator may be employed. The polymerization initiator is preferably used in an amount of from 0.5 to 5% by weight based on the total amount of the monomers. The polymerization temperature is preferably selected from the range of 0 to 5 120%, depending on the solvent or polymerization initiator to be used. Alternatively, a sulfur-based chain transfer agent can be used to control the molecular weight of the polymer. In the case of a sulfur-based chain transfer agent, ethanethiol, thioglycerol, thioacetic acid, 2-propionic propionic acid, 3-M-propionic acid, thiosuccinic acid, hydrogen may be used singly or in combination. Octyl thioglycolate, octyl 3-mercaptopropionate, etc. The sulfur-based chain transfer agent is preferably used in an amount of from 0.5 to 5% by weight based on the total weight of the monomers. The obtained polymer can be used as a main component of the cement additive without further processing or, if necessary, neutralized with an inert substance to provide a main component of the cement additive. As the alkaline substance, an inorganic substance such as a hydroxide, a chloride, and a monovalent metal or a divalent metal 15 carbonate, or an organic amine can be used. In view of dispersibility, the copolymer and its neutralized copolymer preferably have a weight average molecular weight of from 10,000 to 30,000, and preferably from 15,000 to 20,000, as measured by GPC (gel permeation chromatography). In the cement composition such as concrete, the cement additive of the present invention is preferably added in an amount of 0.01 to 10 parts per 100 parts of cement, especially when considering a high water reducing formula, and 0.1 to 5 servings are preferred. Based on the weight, if the content exceeds 10 parts, it is not economical. In addition, if the content is less than 〇.〇, the dispersibility, water-reducing property, and gas-filling ability are deteriorated. -18- 1250138

DESCRIPTION OF THE INVENTION MM The cement additive of the present invention can improve the dispersibility of the cement particles, so that the moisture in the concrete can be reduced by 18 wt% or more. Even with the high water-reducing formula, it increases the fluidity of the cement composition, prevents the fluidity from decreasing with time, and has a good processability and good strength by continuously supplying an appropriate amount of gas. The invention will be described in detail by way of the following examples and comparative examples. However, the examples are for illustrative purposes only and are not intended to limit the invention. EXAMPLES Example 1 10 Based on the weight, 250 parts of water is charged into a 2L glass reactor equipped with a thermometer, a stir: a rod, a dropping funnel, a nitrogen feed tube, and a reflux cooling. Device. Nitrogen gas was fed into the reactor while stirring, and the reactor was heated to a temperature of 80 QC under a nitrogen atmosphere. Deionized water containing 2 parts of ammonium persulfate was added to the 15 reactor on a weight basis. After the dissolution of the sulfate, 275.18 parts of methoxypolyethylene glycol monomethacrylic acid (average molar addition of ethylene oxide = 13 moles), 43.69 parts of methacrylic acid, 25.11 parts Acrylic acid, 7.02 parts of polyoxyethylene phenyl phenyl propylene ether ammonium sulfate as a nonionic and anionic reactive surfactant (average addition molar number of ethylene oxide = 10 moles), 4.5 20 parts of 3- A monomer mixture of mercaptopropionic acid, and 130 parts of water and an aqueous initiator solution containing 90 parts of an aqueous solution of 5 wt% ammonium persulfate was added to the reactor in a dropwise manner over 3 hours. Immediately thereafter, 4 parts of an aqueous solution of 5 wt% ammonium persulfate was additionally added. Polymerization was then carried out for 1 hour while maintaining the temperature at 80 °C. -19- 1250138 DESCRIPTION OF THE INVENTION - Stomach After the completion of the polymerization, the obtained polymer was cooled to room temperature and neutralized with a 30 wt% aqueous solution of sodium hydroxide. The prepared water-soluble copolymer salt had a weight average molecular weight of 18,591 as measured by GPC. Example 2 5 A water-soluble copolymer salt was prepared in the same manner as in Example 1 except that the average addition mole number of ethylene oxide of decyloxy polyethylene glycol monomethacrylic acid was changed to 30 moles. . The salt had a weight average molecular weight of 23,486 as measured by GPC. Example 3 10 Perform the polymerization as in Example 1, but change the monomer solution to a weight, containing 266.76 parts of methoxypolyethylene glycol monomethacrylic acid (the average addition of ethylene oxide to the molar) Number = 14 moles), 42.68 parts of methacrylic acid, 24.01 parts of acrylic acid, and 17.55 parts of polyoxyethylene phenyl phenyl propylene ether sulfate ammonium salt (cyclohexyloxyethane) as a nonionic and anionic reactive surfactant A solution of a mixture of an average addition mole number = 10 moles, 4.5 parts of 3-mercaptopropionic acid, and 130 parts of water. After the completion of the polymerization, the obtained polymer was cooled to room temperature and neutralized with a 30 wt% aqueous sodium hydroxide solution. The prepared water-soluble copolymer salt had a weight average molecular weight of 16,931 as measured by GPC. 20 Example 4 Perform the polymerization as in Example 1, but change the monomer solution to a weight, containing 259.04 parts of methoxypolyethylene glycol monomethacrylic acid (the average addition of ethylene oxide to the molar) Number = 14 m), 36.39 parts of methacrylic acid, 20.47 parts of acrylic acid, 35.1 parts of non-ionic and anionic-20-1250138 -

DESCRIPTION OF THE INVENTION HM reaction surfactant of polyoxyethylene phenyl phenyl propylene ether ammonium sulfate (the average addition molar number of ethylene oxide is 2 10 moles), 4.5 parts of 3-weisyl propionic acid, and 130 parts a mixture of water. After the completion of the polymerization, the obtained polymer was cooled to room temperature, 5 and neutralized with a 30 wt% aqueous sodium hydroxide solution. The prepared water-soluble copolymer salt had a weight average molecular weight of 16,605 according to the measurement of GPC. Example 5 Performing the polymerization as in Example 1, but changing the monomer solution to a weight, containing 275.18 parts of methoxypolyethylene glycol monomethacrylic acid 10 (the average addition of ethylene oxide) Ears = 14 moles, 43.69 parts of methacrylic acid, 25.11 parts of acrylic acid, 7.02 parts of sodium acryloxy hydroxypropane salt as an anionic reaction surfactant, 4.5 parts of 3-mercaptopropionic acid, and A solution of a mixture of 130 parts of water. After the completion of the polymerization, the obtained polymer was cooled to room temperature, 15 and neutralized with a 30 wt% aqueous solution of sodium hydroxide. The prepared water-soluble copolymer salt had a weight average molecular weight of 15,415 as measured by GPC. Comparative Example 1 Performing the polymerization as in Example 1, but changing the monomer solution to a weight, containing 280.8 parts of methoxypolyethylene glycol monomethacrylic acid 20 (average addition of ethylene oxide) Molar number = 14 moles, 44.58 parts of methacrylic acid, 25.62 parts of acrylic acid, 4.5 parts of 3-mercaptopropionic acid, and 130 parts of water, but did not include a mixture solution of reactive surfactants. After the completion of the polymerization, the obtained polymer was cooled to room temperature and neutralized with a 30 wt% aqueous sodium hydroxide solution. According to the measurement of GPC, -21-1250138, the prepared water-soluble copolymer salt has a weight average molecular weight of 27,287. Comparative Example 2 A naphthalenesulfonic acid formaldehyde (NSF) condensate conventionally used as a cement additive was prepared. 5 The following shows the main components, contents, and properties of the water-soluble copolymer salt prepared in Examples 1 to 5 and Comparative Example 1 as shown in Table 1. The results shown in the following Table 2 are the test results of the water-soluble copolymer salt and the cement additive of Comparative Example 2 (cement mortar fluidity test and concrete test). [Mortar fluidity test] 10 1 g of Portland cement (manufactured by SsangYong Cement Co., Ltd.), 1000 g of sand, lg (solid content) of each of the cement additives, and 450 g of water (tap water), The mortar was prepared by mixing at a medium speed for 3 minutes in a mortar mixer. Each prepared mortar sample was placed in a hollow cone having a diameter of 60 mm and a height of 40 mm. The cone is taken up and the diameter measured in two directions is averaged to determine the fluidity (mm) of the mortar. [Concrete test] 736 kg of Portland cement (manufactured by SsangYong Cement Co., Ltd.) , 1863 kg of sand, 2330 kg of rubber, 0.25 wt ° / 〇 20 of the cement additive based on the weight of the cement (for the cement additive of Comparative Example 2, 1.00 wt%), with 386.4 kg of water (tap water) mixing to prepare concrete. Each prepared concrete sample was measured for its twist and air content according to Korean Industrial Standards KSF 2402 and KS F 2449. -22- 1250138 _ Description of the invention Table 1 Category Polyolefin-based ethylene glycol (meth) acrylate carboxylic acid (methacrylic acid / acrylic acid) Reactive surfactant active content (wt%) Weight average molecular weight oxirane Ear content (wt%) Content (wt%) Type content (wt%) Example 1 14 78.4 19.6 Nonionic + anion 2 40.1 18,591 Example 2 30 78.4 19.6 2 39.8 23,486 Example 3 14 76.0 19.0 5 40.1 16,931 Example 4 14 73.8 16.2 10 40.1 16,605 Example 5 14 78.4 19.6 Anion 2 40.0 15,415 Comparative Example 1 14 80.0 20 Surface Thin 40.2 27,287

Table 2

Category Addition / Cement (wt%) Cement Paste Fluidity (mm) 坍 (cm) Air Content (%) Initial 30 minutes after initial 90 minutes after initial 60 minutes Example 1 0.25 248 237 22.2 21.7 4.0 3.8 Examples 2 0.25 263 244 22.3 19.8 4.4 4.0 Example 3 0.25 255 246 21.9 2L7 4.7 4.5 Example 4 0.25 260 252 22.0 21.8 5.1 4.7 Example 5 0.25 239 229 21.5 20.3 4.1 3.8 Comparative Example 1 0.25 235 221 19.3 16.0 3.8 2.6 Comparative Example 2 1.00 245 219 17.2 14.9 4.1 3.7 -23- 1250138 DESCRIPTION OF THE INVENTION »Μ As can be seen from the foregoing test results, the mortar containing the cement additives of Examples 1 to 5 is preferred when compared with the cement additives of Comparative Examples 1 and 2. The fluidity, although the initial twist is high, the concrete twist after 90 minutes is low and has an excellent air content. This indicates that the cement additive of the present invention can improve the dispersibility of the cement particles while exhibiting a better dewatering property in a small amount. The cement additive of the present invention improves the dispersibility of the cement particles, and even if the fluidity of the composition is increased in the high water removal zone, the fluidity can be prevented from decreasing with time, and the appropriate amount of gas is continuously supplied, so that a good addition is exerted. 10 Workability. The above embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention. Any modification or variation made without departing from the spirit of the invention is within the scope of the invention. -twenty four-

Claims (1)

1250138 Picking up, patent application scope 1. - A cement binder having superior water-reducing characteristics, which is neutralized with a - alkaline substance by a copolymerization-monomer mixture or further stepwise And the obtained monomer; wherein the monomer mixture comprises: a) 50 to 90% by weight of a monomer represented by the following chemical formula i; 5 b) 5 to 45 wt% of a monomer represented by the following Chemical Formula 2; and 0 0.5 to 40 wt % A reactive surfactant represented by the following Chemical Formula 3: Chemical Formula 1 R1 I CH2-cc〇G-CR2〇)mR3 10 wherein: R1 is a hydrogen atom or a methyl group; R2〇 is a C2 to C4 olefin oxide, They may be the same or different, and may be added in blocks or in any form at different times; l5 R3 is an alkyl group of c4 to c4; and an average addition mole number of 111疋 oxidized dilute hydrocarbon groups, which is an integer from 1 to 50; Wherein: 20 4 R4 is a hydrogen atom or a methyl group; and [771. Μ is a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium, a (when the scope of application of the patent is insufficient, please note Use continuation page) -25- 1250138 ---- Scope of application for patents or organic amines; and Chemical formula 3 R5 Η CH = C - -(R70)"(S03)rrΜ2 where: 5 R5 is a hydrogen atom or a methyl group; R6 is a Q to C3 olefinic group, a phenylene group, or an alkylphenylene group; R70 is an alkylene oxide of (C to C4, which may be the same or different, if not simultaneously added in blocks or in any form; r is oxidized The average addition mole number of the olefin group, which is an integer number of from 1 to 50; η is 0 or 1; and Μ2 is a hydrogen atom, a monovalent metal atom, an ammonium, or an organic amine. 2. A cement copolymer having superior water-reducing characteristics as described in claim 1, wherein a) one or more selected from the group consisting of the following 15 compounds represented by the chemical formula 1 Substance: methoxy polyethylene glycol mono (meth) acrylate, decyloxy polypropylene glycol mono (meth) acrylate, methoxy polybutylene glycol mono (meth) acrylate, methoxy polymerization Ethylene glycol polypropylene glycol mono(meth)acrylate, methoxy polyethylene glycol polybutylene glycol mono(meth)acrylate, methoxypolypropylene glycol polybutylene glycol mono(mercapto)acrylic acid 20 ester, Methoxy polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, B Oxidized polytetramethylene glycol mono(meth)acrylate, ethoxy-62-4250138 Patent application continuation page Polyethylene glycol polypropylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polybutylene Alcohol mono(mercapto) acrylate, ethoxylated polypropylene glycol polybutylene glycol mono(曱) Acrylate, and ethoxy polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylic baked vinegar. 5 3. Water with superior water-reducing characteristics as described in item 1 of the patent application a copolymer for mud, wherein the b) single system represented by Chemical Formula 2 is from the group consisting of acrylic acid, methacrylic acid, monovalent metal salt, divalent metal salt, ammonium salt, and organic amine salt of the acid One or more substances selected for use. 10. The cement copolymer having superior water-reducing characteristics according to claim 1, wherein the c) reactive surfactant represented by the chemical formula 3 is one selected from the group consisting of the following substances; Or above: Thioxypolyethylene glycol propylene ethers, such as thiooxy polyethylene glycol propylene ether, thiooxy polypropylene glycol propylene ether, thiooxy polybutylene glycol propylene ether, thiooxy polymerization Ethylene glycol 2-butenyl ether, thiooxy polypropylene glycol 2-butenyl ether, thiooxy polybutylene glycol 2-butenyl ether, thiooxy polyethylene glycol 3-butenyl ether, Thioethoxy polypropylene glycol 3-butenyl ether, thiooxy polybutanediol 3-butenyl ether, thiooxy polyethylene glycol 3-pentenyl ether, thiooxy poly 20 propylene glycol 3-pentene Ether, and thiooxypolybutanediol 3-pentenyl ether; thiooxypolyethylene glycol alkyl vinyl phenyl ethers, such as thiooxy polyethylene glycol (3-vinyl-5- Methyl)phenyl ether, thiooxypolypropylene glycol (3-vinyl-5-mercapto)phenyl ether, thiooxypolybutylene glycol (3-vinyl-5-mercapto)phenyl ether, thiooxy polymerization Ethylene glycol (3-vinyl-5-ethyl) phenyl ether, thiooxy polypropylene glycol -27-12450138 - Patent application continuation page (3-vinyl-5-ethyl) phenyl ether, thiooxy polymerization Butanediol (3-vinyl-5-ethyl) phenyl ether, thiooxy polypropylene glycol (3-propenyl-5-propane Phenyl ether, thiooxypolybutylene glycol (3-propenyl-5-propyl)phenyl ether, thiooxy polyethylene glycol (3-propenyl-5-butyl)phenyl ether, thiooxy polymerization Propylene glycol (3-propenyl-5-butyl)phenyl ether, and 5 thiooxypolybutylene glycol (3-propenyl-5-butyl)phenyl ether; 2-Theryloxyethylene glycol-3-(4-alkylphenoxy)propene propylene ether, such as 2-sulfoxy polyethylene glycol-3-(4-mercaptophenoxy) propylene Propylene ether, 2-sulfoxypolypropylene glycol-3-(4-methylphenoxy)propene propylene ether, 2-thiooxypolybutylene glycol-3-(4-methylphenoxy)propene propylene ether ,2-thiooxypoly 10 ethylene glycol-3-(4-ethylphenoxy)propene propylene ether, 2-sulfoxypolypropylene glycol-3-(4-ethylphenoxy)propene propylene a bond 'and 2 thiooxypolybutylene glycol-3-(4-ethylphenoxy)propene propylene ether; and neutralizing the above with a monovalent metal salt, a divalent metal salt, an ammonium salt, or an organic amine And the salt obtained. 15 5. A copolymer for cement having superior water-reducing characteristics as described in claim 1 of the patent application, which has a weight average molecular weight of 10,000 to 30,000. 6. A cement composition comprising a) 100 parts by weight of cement, and b) based on the weight, 0.01 to 10 parts of the cement for the 100 parts of the cement as claimed in claim 1 Copolymer. 20 7. A method for preparing a cement copolymer having superior water-reducing characteristics, comprising: a) a step of copolymerizing the following materials: i) 50 to 90 wt% of a monomer represented by the following Chemical Formula 1; Ii) 5 to 45 wt% of a monomer represented by the following Chemical Formula 2; and -28-1250138 ------ Patent Application Continuation iii) 0.5 to 40 wt% of a reaction represented by the following Chemical Formula 3 Sexual surfactant: Chemical formula 1 R1 CH2=CC〇〇-(R%)mR3 5 wherein: R1 is a hydrogen atom or a methyl group; R20 is a C2 to C4 alkylene oxide which may be the same or different, if not simultaneously added in blocks or in any form; R3 is a Q to C4 alkyl group; and 10 m is an average addition mole number of the oxidized alkene group, It is an integer from 1 to 50; Chemical Formula 2 R4 gh2=c-goo-m1 Wherein z 15 R4 is a hydrogen atom or a methyl group; and M1 is a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium, or an organic amine; and the chemical formula 3 R5 Η CH = G - R^O KR^〇)r ~(S〇3)nM^ 20 where: -29- 1250138 Patent Application Continuation R5 is a hydrogen atom or a hydrazine group; R6 is a Q to C3 alkene group, a phenyl group, or an alkylphenyl group; R70 is a Q to C4 oxidized olefins, which may be the same or different, if not simultaneously added in blocks or in any form; 5 r is the average addition mole number of the oxidized olefin group, which is an integer from 1 to 50, η is 0 or 1 ; and Μ2 is a hydrogen atom, a monovalent metal atom, an ammonium, or an organic amine. 8. A method for preparing a water-slurry copolymer having superior water-reducing characteristics as described in claim 7 of the patent application, further comprising: b) a step of neutralizing the copolymer prepared in the step a) with an alkaline substance. 9. The method for preparing a cement copolymer having superior water-reducing characteristics according to claim 8, wherein the alkaline substance of the step b) is a hydroxide, a vapor, or a monovalent or divalent metal. Carbonate, ammonia, or 15 organic amines. 10. A method of preparing a cement copolymer having superior water-reducing characteristics as described in claim 7, wherein the copolymerization step of the step a) is carried out by solution polymerization or mass polymerization. 1L A method for preparing a cement copolymer having superior water-reducing characteristics as described in claim 7 of the patent application, wherein the copolymerization temperature of the step a) is from 0 to 120 °C. 12. A process for the preparation of a copolymer for cement having superior water-reducing characteristics as described in claim 7, wherein a further sulfur-based chain transfer agent is added during the copolymerization of step a). -30-