KR102029757B1 - Method of preparing for polycarboxylic acid-based copolymer for cement composition addictive - Google Patents
Method of preparing for polycarboxylic acid-based copolymer for cement composition addictive Download PDFInfo
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- KR102029757B1 KR102029757B1 KR1020150187482A KR20150187482A KR102029757B1 KR 102029757 B1 KR102029757 B1 KR 102029757B1 KR 1020150187482 A KR1020150187482 A KR 1020150187482A KR 20150187482 A KR20150187482 A KR 20150187482A KR 102029757 B1 KR102029757 B1 KR 102029757B1
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
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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
- C04B24/24—Macromolecular compounds
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a method for producing a polycarboxylic acid-based copolymer used as an additive for cement composition, using an aqueous solution of SFS (Sodium Formaldehyde Sulfoxylate) as a reducing agent and an aqueous solution of iron sulfate as a reaction accelerator in a specific ratio, a monomer mixture, By dropping SFS (Sodium Formaldehyde Sulfoxylate) aqueous solution and iron sulfate aqueous solution in a specific method, it is possible to effectively control the reaction time, to prepare a polycarboxylic acid copolymer for cement composition additives that can minimize the low molecular peak area on GPC In addition, by using the polycarboxylic acid-based copolymer prepared according to the present invention, it is possible to provide a cement composition having excellent workability by increasing the adsorption rate to cement particles, having excellent water-resistance and compressive strength, and delaying curing. .
Description
The present invention relates to a method for producing a polycarboxylic acid copolymer used as an additive for a cement composition, and to preparing a polycarboxylic acid copolymer in which a monomer mixture, an aqueous solution of sodium formaldehyde sulfate and an accelerator are added dropwise in a specific manner. It is about a method.
Cement paste made by mixing cement, water and other additives, mortar made by adding sand to it, and concrete made by additionally adding and mixing coarse gravel Cement compositions including are used in large quantities in various building materials and the like. However, after the cement composition is prepared, over time, due to the hydration reaction between the cement and the water, the cement composition begins to harden and the workability becomes less and less. In this case, when the amount of water used is added to improve the workability, the total amount of water used for the cement composition is limited because it lowers the compressive strength and causes cracking. Accordingly, various cement additives have been developed to maintain the dispersibility of the cement composition while reducing the amount of water used.
Among them, polycarboxylic acid-based copolymers have excellent properties of sensitization, retention, and compressive strength with only a small amount of lignin, naphthalene, and melamine-based compounds, which are conventionally used, and are currently the most widely used cement additives.
Examples of the polycarboxylic acid-based copolymers include water-soluble vinyl copolymers obtained by copolymerizing methacrylates (Japanese Patent Laid-Open No. Hei 1-226757, US Patent 4,962,173, Japanese Laid-Open Hei 4-209613), and maleic anhydride and alkenyl ethers. Copolymers and derivatives thereof (Japanese Patent Laid-Open No. 58-38380, Japanese Patent Laid-Open No. 63-285140, Japanese Patent Laid-Open No. 2-163108) and the like are known.
On the other hand, concrete, especially concrete, is a building material with a limitation that slump deterioration usually occurs after 30 minutes, so that all work must be completed in a short time from concrete mixing to casting. Therefore, cement additives have a higher sensitivity than conventional water reducers due to the use of modern mechanized equipment and traffic congestion due to the recent deterioration of the quality of concrete aggregates. Is required.
Accordingly, the inventors further studied the polycarboxylic acid-based copolymer, and as a result, the inventors have invented a method of manufacturing a polycarboxylic acid-based copolymer having a higher water-resistance and holding power than the conventional water reducing agent and having an improved compressive strength.
The problem to be solved by the present invention is to use a combination of SFS (Sodium Formaldehyde Sulfoxylate) aqueous solution as a reducing agent and iron sulfate aqueous solution as a reaction accelerator in a specific ratio, and a monomer mixture, SFS (Sodium Formaldehyde Sulfoxylate) aqueous solution and iron sulfate aqueous solution By dropping to, it is to provide a method for producing a polycarboxylic acid-based copolymer for cement composition additives that can minimize the low-molecular peak area on GPC and effectively control the reaction time.
Another problem to be solved by the present invention is to increase the adsorption rate to the cement particles by using a cement composition additive comprising a polycarboxylic acid-based copolymer prepared by the above production method, has excellent sensitivity and compressive strength It is to delay the curing to provide a cement composition excellent in workability.
The present invention is to solve the above problems, a) preparing a monomer mixture; b) preparing a reducing agent aqueous solution and a reaction promoter; c) adding the reaction promoter to the reactor in advance, and simultaneously dropping the monomer mixture and the reducing agent aqueous solution using separate dropping apparatuses; And d) polymerizing the loaded monomer mixture in a reactor to provide a method for preparing a polycarboxylic acid copolymer for cement composition additive.
In addition, the present invention provides a polycarboxylic acid-based copolymer for cement composition additive prepared by the above method, and a cement composition additive and cement composition comprising the same.
The present invention is a method for producing a polycarboxylic acid copolymer for cement composition additives, using a combination of SFS (Sodium Formaldehyde Sulfoxylate) as a reducing agent and iron sulfate as a reaction accelerator in a specific ratio, monomer mixture, SFS (Sodium Formaldehyde Sulfoxylate) ) By dropping the aqueous solution and the aqueous solution of iron sulfate in a specific manner, there is an effect that can minimize the low-molecular peak area on the GPC and effectively control the reaction time.
In addition, by using a cement composition additive comprising a polycarboxylic acid-based copolymer prepared by the above production method, it increases the adsorption rate to the cement particles, has excellent water-resistance and compressive strength, delays curing and has excellent workability. Cement compositions can be provided.
Hereinafter, the present invention will be described in more detail to aid in understanding the present invention. At this time, the terms or words used in the present specification and claims should not be construed as being limited to the ordinary or dictionary meanings, and the inventors appropriately define the concept of terms in order to explain their invention in the best way. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that it can.
The present invention comprises the steps of a) preparing a monomer mixture; b) preparing a reducing agent aqueous solution and a reaction promoter; c) adding the reaction promoter to the reactor in advance, and simultaneously dropping the monomer mixture and the reducing agent aqueous solution using separate dropping apparatuses; And d) polymerizing the loaded monomer mixture in a reactor to provide a method for preparing a polycarboxylic acid copolymer for cement composition additive.
When preparing a polycarboxylic acid copolymer, as an initiator of the polymerization reaction, radicals generated by thermal decomposition of a persulfate compound at a high temperature (˜80 ° C.) or a peroxide compound at a low temperature (˜30 ° C.) may be used as a reducing agent. Use radicals generated when used in combination.
Conventionally, in this case, a method of dropping the first monomer into the reactor in advance and simultaneously dropping the second monomer and the reducing agent over a predetermined time was used.
However, unlike the conventional manufacturing method, the present invention is characterized by first preparing a monomer mixture and a reducing agent aqueous solution, and simultaneously dropping them into the reactor using a separate dropping device.
In the polycarboxylic acid copolymer production method for cement composition additive of the present invention as described above, because the monomer mixture of the first monomer and the second monomer is added dropwise throughout the reaction, the first monomer is added dropwise to the reactor in advance. Compared with the conventional production method in which 2 monomers are added dropwise throughout the reaction, the reaction heat can be controlled and the polymer can be uniformly polymerized, thereby improving the workability of the cement composition.
Therefore, according to the production method of the present invention, the low molecular peak area on the GPC can be reduced by 2 to 3% compared to the conventional production method, the cement comprising a polycarboxylic acid copolymer prepared by the production method In the case of using the composition additive, it is possible to provide a cement composition having excellent workability by increasing the adsorption rate to the cement particles, having excellent water-resistance and compressive strength, and delaying curing.
In addition, the polycarboxylic acid copolymer production method for cement composition additives of the present invention further uses a reaction accelerator, characterized in that the reaction promoter is added to the reactor in advance.
In particular, the use of the reaction accelerator in advance in the reactor is more effective in accelerating the decomposition of peroxides by promoting the decomposition of peroxides by continuously participating in the whole reaction process compared to the method of simultaneously dropping with the monomer mixture and the reducing agent aqueous solution. This is because the reaction time for securing the conversion rate can be shortened and adjusted more effectively accordingly.
Meanwhile, the cement composition herein refers to a cement paste prepared by adding water to the cement, a mortar prepared by adding fine aggregate sand thereto, and concrete prepared by additionally mixing and mixing coarse aggregate gravel thereto. It means to include all cement compositions known to.
According to one embodiment of the invention, the monomer mixture of step a) may include two or more monomers and peroxides, and the monomer mixture may be an alkoxypolyalkylene glycol mono (meth) acrylic acid ester monomer and And (meth) acrylic acid monomers.
Specifically, the alkoxypolyalkylene glycol mono (meth) acrylic acid ester monomer is characterized in that represented by the following formula (1).
[Formula 1]
Where
R 1 is hydrogen or methyl;
R 2 O is one or a mixture of two or more oxyalkylenes having 2 to 4 carbon atoms;
R 3 is alkyl having 1 to 4 carbon atoms;
m is an integer of 50-200 by the average added mole number of an oxyalkylene group.
Here, the R 2 O is composed of two or more mixed compositions of oxyalkylene having 2 to 4 carbon atoms, and may be included in a block or random phase.
In addition, in the case where the average added mole number of the oxyalkylene group is 50 to 200, there is an effect of expressing excellent dispersibility and slump retention, and more specifically, may be 50 to 150.
The alkoxy polyalkylene glycol mono (meth) acrylic acid ester monomer represented by the formula (1) is, for example, methoxy polyethylene glycol mono (meth) acrylate, methoxy polypropylene glycol mono (meth) acrylate, methoxy poly Butylene glycol mono (meth) acrylate, methoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, methoxy polyethylene glycol polybutylene glycol mono (meth) acrylate, methoxy polypropylene glycol polybutylene glycol mono ( Meth) acrylate, methoxy polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, ethoxy polybutyl Len glycol mono (meth) acrylate, ethoxy polyethylene glycol polypropylene glycol Mono (meth) acrylate, ethoxy polyethylene glycol polybutylene glycol mono (meth) acrylate, ethoxy polypropylene glycol polybutylene glycol mono (meth) acrylate, or ethoxy polyethylene glycol polypropylene glycol polybutylene glycol It may be at least one monomer selected from the group consisting of mono (meth) acrylates.
In addition, the (meth) acrylic acid monomer is characterized in that represented by the following formula (2).
[Formula 2]
R 2 -COOM 1
Where
R 2 is a hydrocarbon group having 2 to 5 carbon atoms containing an unsaturated bond;
M 1 is a hydrogen atom, a monovalent or divalent metal, an ammonium group or an organic amine salt.
The (meth) acrylic acid monomer represented by the formula (2) is, for example, at least one selected from the group consisting of acrylic acid, methacrylic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts of these acids. It may be a monomer.
In addition, the peroxide included in the monomer mixture of step a) serves as a polymerization initiator to generate a radical to initiate a polymerization reaction by reaction with a reducing agent, such as ammonium persulfate, sodium persulfate, potassium persulfate, or the like. Persulfate; Hydrogen peroxide; Azo compounds such as azobis-2methylpropionamidine hydrochloride and azoisobutyronitrile; Peroxides, such as a benzoyl peroxide, lauroyl peroxide, and cumene hydroperoxide, can be used.
The amount of the suitable polymerization initiator may be 0.3 to 3% by weight based on the total weight of the monomer mixture.
In addition, in order to adjust the molecular weight of the obtained polycarboxylic acid-based copolymer, the monomer mixture of step a) may further include a chain transfer agent, and specifically, a thiol chain transfer agent may be used.
The thiol-based chain transfer agent used at this time is selected from the group consisting of mercapto ethanol, thioglycerol, thioglycolic acid, 2-mercapto propionic acid, 3-mercapto propionic acid, thioxalic acid, thioglycolic acid octyl, and 3-mercapto propionic acid octyl It may be one or more species.
Suitable amount of such thiol-based chain transfer agent may be 0.1 to 3% by weight based on the total weight of the monomer mixture.
In addition, according to an embodiment of the present invention, the reducing agent aqueous solution of step b) may include water and a reducing agent.
Specifically, the reducing agent may be used alone or in combination of two or more thereof, such as sodium hydrogen sulfite, sodium sulfite, molar salts, sodium pyro sulfite, ascorbic acid, erythorbic acid or SFS (Sodium Formaldehyde Sulfoxylate), more specifically As the SFS (Sodium Formaldehyde Sulfoxylate) is preferably used.
An appropriate amount of SFS (Sodium Formaldehyde Sulfoxylate) may be 50 to 100% by weight relative to the peroxide (peroxide) contained in the monomer mixture. If the amount of SFS used is less than 50% by weight, peroxides do not generate sufficient radicals, resulting in a low polymerization rate, resulting in reduced conversion into polymers, resulting in wider low molecular peaks on the GPC, resulting in a superior erosion of the cement composition. Force and retention force, and when the amount of SFS used is more than 100% by weight, the workability of the cement composition may be poor because the content of the monomer constituting the copolymer is reduced.
In addition, the production method of the present invention is characterized by using iron sulfate as a reaction accelerator (iron sulfate). The iron sulfate may be used alone or in combination with iron (II) sulfate (FeSO 4 , ferrous sulfate) or iron (III) sulfate (Fe 2 (SO 4 ) 3 , ferric sulfate).
The present invention uses the iron sulfate in combination with SFS (Sodium Formaldehyde Sulfoxylate), it has the effect of reducing the reaction time for securing the conversion compared to the case of using SFS alone. This is because iron sulfate serves to accelerate the decomposition of organic peroxides to accelerate the generation of radicals.
In addition, the present invention can be used by combining the SFS (Sodium Formaldehyde Sulfoxylate) and iron sulfate in an optimum ratio. The iron sulfate may be used in an amount of 2 to 16 wt%, more specifically 4 to 10 wt%, based on the weight of the peroxide. If the amount of iron sulfate is less than 2% by weight, there may be a problem that the reaction time for the conversion rate is long, if the amount of iron sulfate is more than 16% by weight, the progress of the reaction is accelerated excessively to the polymer having a large molecular weight Generated and may not be desirable.
In addition, according to one embodiment of the present invention, the monomer mixture of step c) and the reducing agent aqueous solution may be added dropwise for 2 to 4 hours. If it is dropped in less than 2 hours, there may be a problem of exothermic generation and side reactions due to the addition of a large amount of monomer, and if it is dropped in excess of 4 hours, the cause of deterioration of properties may be caused by the formation of a polymer having a non-uniform molecular weight distribution. Can be.
The polycarboxylic acid copolymer of the present invention may be prepared by copolymerizing the monomer components using a polymerization initiator, and the copolymerization method may be carried out by a method such as solution polymerization or bulk polymerization, but is not particularly limited thereto. .
For example, in the case of polymerization using water as a solvent, the solution polymerization initiator used may be a water-soluble polymerization initiator such as persulfate of ammonium or alkali metal or hydrogen peroxide, and lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester compound. Alternatively, for polymerization using a ketone compound as a solvent, hydroperoxides such as benzoyl peroxide and lauroyl peroxide cumene hydroperoxide, aromatic azo compounds such as azobisisobutyronitrile and the like can be used as the polymerization initiator. At this time, accelerators, such as an amine compound, can also be used together. In addition, when using a water-lower alcohol mixed solvent, it can select suitably from the said various polymerization initiator or the combination of a polymerization initiator, and an accelerator, and can use.
Appropriate polymerization temperature may vary depending on the type of solvent or polymerization initiator used, and may be specifically selected from the range of 0 to 120 ℃, in the case of the present invention is preferably carried out at a low temperature of 20 to 40 ℃.
When the polymerization temperature is less than 20 ℃, the polymerization reaction is insufficient to increase the low molecular peak area on the GPC, the performance as a cement composition additive may be deteriorated, when the polymerization temperature exceeds 40 ℃ polycarboxylic acid copolymer Too large a molecular weight of the mortar and slump loss may be severe.
In addition, the present invention can provide a polycarboxylic acid-based copolymer for cement composition additive prepared by the method for producing a polycarboxylic acid-based copolymer for cement composition additive.
According to one embodiment of the present invention, when considering the dispersibility, the polycarboxylic acid-based copolymer, when the weight average molecular weight is measured by GPC (Gel Permeation Chromatography) method, specifically, may be 30,000 to 70,000, More specifically, it may be 40,000 to 60,000. When the weight average molecular weight is 30,000 to 70,000, the initial dispersibility is excellent to improve the initial susceptibility, not only to maintain the slump retention of the composition, but also to improve the curing delay to form a concrete composition having high strength early.
In addition, the present invention can provide a cement composition additive comprising the polycarboxylic acid copolymer for the cement composition additive and a cement composition comprising the cement composition additive.
According to an embodiment of the present invention, the additive of the cement composition may be included 0.01 to 10% by weight based on the cement composition, specifically, 0.05 to 5% by weight, more specifically 0.1 to 5% by weight may be included. have.
When the additive of the cement composition is included in the above range, it may be advantageous to provide an excellent cement composition even in the region of high susceptibility. In other words, if it exceeds 10% by weight, it is not preferable in terms of economical efficiency because it does not have an effect as much as the added amount, and if it is less than 0.05% by weight, particularly less than 0.01% by weight, it may be difficult to achieve desired performance such as slump retention, water loss, and compressive strength. have.
As described above, the present invention uses a cement composition additive comprising a polycarboxylic acid copolymer prepared by the production method of the present invention, thereby increasing the adsorption rate to cement particles, delaying curing with excellent sensitivity and compressive strength. It is possible to provide a cement composition excellent in workability.
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
Example One
160 g of water was injected into a 1 L glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the inside of the reaction vessel was replaced with nitrogen to maintain 30 ° C. under a nitrogen atmosphere. Into the reactor, a solution of 0.13 g of iron sulfate dissolved in 10 g of water was continuously maintained at 30 ° C. The monomer mixture (A) comprises 429 g of methoxypolyethylene glycol monomethacrylate (45 moles of average added moles of ethylene oxide), 48 g of acrylic acid, 6.67 g of 30% hydrogen peroxide, 4 g of 2-mercaptoethanol, and 80 g of water. Mixed. The reducing agent solution (B) was prepared by dissolving 1 g of SFS (Sodium Formaldehyde Sulfoxylate) in 50 g of water. (A) and (B) were simultaneously added dropwise to the reactor for 4 hours, and then maintained at 40 ° C for 2 hours to complete the polymerization. The reaction was neutralized with 7.65 g of 32% NaOH.
Example 2
In Example 1, a copolymer was prepared in the same manner as in Example 1 except that (A) and (B) were simultaneously added dropwise to the reactor for 2 hours.
Example 3
In Example 1, a copolymer was prepared in the same manner as in Example 1 except that 2 g of SFS (Sodium Formaldehyde Sulfoxylate) was used.
Comparative example One
In Example 1, a copolymer was prepared in the same manner as in Example 1, except that 1 g of D-araboascorbic acid was used instead of SFS (Sodium Formaldehyde Sulfoxylate).
Comparative example 2
In Example 1, a copolymer was prepared in the same manner as in Example 1 except that 0.2 g of SFS (Sodium Formaldehyde Sulfoxylate) was used.
Comparative example 3
In Example 1, a copolymer was prepared in the same manner as in Example 1, except that 4 g of SFS (Sodium Formaldehyde Sulfoxylate) was used.
Comparative example 4
In Example 1, a copolymer was prepared in the same manner as in Example 1 except that (A) and (B) were simultaneously added dropwise to the reactor for 1 hour.
Comparative example 5
In Example 1, a copolymer was prepared in the same manner as in Example 1 except that (A) and (B) were simultaneously added dropwise to the reactor for 6 hours.
Comparative example 6
In Example 1, a copolymer was prepared in the same manner as in Example 1, except that the iron sulfate aqueous solution was not added.
The preparation conditions of the Examples and Comparative Examples are shown in Table 1 below.
Experimental Example 1: Mortar Fluidity Test
Medium Portland Cement (Manufactured by Hanil) 665 g, Sand (Standard Yarn) 1350 g, Water (Water Supply) 332.5 g and 2.66 g (50% solids) of the Cement Additives prepared in Examples and Comparative Examples are medium-sized in a mortar mixer for 3 minutes. The mixture was kneaded to prepare mortar.
Each of the prepared mortar was filled with a hollow cone having a diameter of 60 mm and a height of 40 mm, and then the cone was lifted up and removed in a vertical direction.
The measured test results are shown in Table 2 below, and the mortar flow value (mm) was the average of the mortar diameters measured in two directions.
Experimental Example 2: concrete test
Usually, 3.53 kg of Portland cement (manufactured by Hanil), 7.94 kg of sand (standard yarn), 10.01 kg of crushed stone, 1.66 kg of water (water supply) and 11.29 g (50% solids) of the cement additive prepared in Examples and Comparative Examples were kneaded. Each made concrete.
Each concrete produced was measured for slump according to Korean Industrial Standards KSF 2402, and KSF 2449.
The measured test results are shown in Table 2 below.
When SFS (Sodium Formaldehyde Sulfoxylate) was used as a reducing agent in Example 1, the area of the low molecular peak (peak) on GPC was reduced compared to the case where D-araboascorbic acid was used as the reducing agent in Comparative Example 1, thereby adsorbing with cement particles and cement particles. It was confirmed that the dispersion effect of increased mortar flow value and concrete slump value.
When the reducing agent was increased to 100 parts by weight based on Example 1 (Example 3), when the dropping time of the monomer mixture and the reducing agent aqueous solution was reduced to 2 hours (Example 2), the low-molecular peak area on the GPC was also reduced, resulting in mortar flow. It was confirmed that the value and the concrete slump value increased.
However, when the amount of reducing agent added to 10 parts by weight or 200 parts by weight is increased as in Comparative Example 2, peroxides do not generate a sufficient amount of radicals or the content of monomers constituting the copolymer is not appropriate. The low molecular peaks were wide and the mortar flow and concrete slump were low.
In addition, when the dropping time was reduced to 1 hour as in Comparative Example 4, or when the dropping time was increased to 6 hours as in Comparative Example 5, it was found that the low molecular peak, mortar flow value, and concrete slump value on GPC were lower than those in Example. Can be.
When the polymerization was carried out without adding iron sulfate as a reaction accelerator, as in Comparative Example 6, it was found that the reaction was not accelerated, so that the conversion to the polymer was not sufficient within 4 hours, and the effect as a cement composition was not good.
When using a polycarboxylic acid-based copolymer having the same composition as the cement additive, it is necessary to minimize the low molecular peak on the GPC in order to increase the adsorption to the cement particles and the dispersion effect of the cement particles.
When the polymer is polymerized at a low temperature using the Redox initiation method as described above, the present invention uses a combination of SFS (Sodium Formaldehyde Sulfoxylate) aqueous solution as a reducing agent and iron sulfate aqueous solution as a reaction accelerator, and a monomer mixture, SFS (Sodium). Formaldehyde Sulfoxylate) by dropping the aqueous solution and the reaction accelerator in a specific manner, effectively control the reaction time, reduce the low molecular peak of the produced polycarboxylic acid-based copolymer to increase the adsorption to cement particles, dispersibility of cement particles It can be seen that it can be improved to exhibit high fluidity and workability.
The foregoing description of the present invention is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.
Claims (17)
b) preparing a reducing agent aqueous solution and a reaction promoter;
c) adding the reaction promoter to the reactor in advance, and simultaneously dropping the monomer mixture and the reducing agent aqueous solution using separate dropping apparatuses; And
d) polymerizing the loaded monomer mixture in a reactor,
The monomer mixture comprises an alkoxypolyalkylene glycol mono (meth) acrylic acid ester monomer, a (meth) acrylic acid monomer and a peroxide,
The reducing agent aqueous solution is a method for producing a polycarboxylic acid-based copolymer for cement composition additive containing sodium formaldehyde sulfoxylate (SFS: 50 to 100% by weight relative to the peroxide).
The alkoxypolyalkylene glycol mono (meth) acrylic acid ester monomer is a polycarboxylic acid copolymer production method for cement composition additives, characterized in that represented by the following formula (1):
[Formula 1]
Where
R 1 is hydrogen or methyl;
R 2 O is one or a mixture of two or more oxyalkylenes having 2 to 4 carbon atoms;
R 3 is alkyl having 1 to 4 carbon atoms;
m is an integer of 50-200 by the average added mole number of an oxyalkylene group.
The R 2 O is a polycarboxylic acid-based copolymer manufacturing method for cement composition additives, characterized in that consisting of two or more mixed compositions of oxyalkylene having 2 to 4 carbon atoms contained in a block or random phase.
The (meth) acrylic acid monomer is a polycarboxylic acid copolymer production method for cement composition additives, characterized in that represented by the following formula (2):
[Formula 2]
R 2 -COOM 1
Where
R 2 is a hydrocarbon group having 2 to 5 carbon atoms containing an unsaturated bond;
M 1 is a hydrogen atom, a monovalent or divalent metal, an ammonium group or an organic amine salt.
The monomer mixture of step a) is a method for producing a polycarboxylic acid copolymer for a cement composition, characterized in that it further comprises a chain transfer agent.
The reaction promoter of step b) is a method for producing a polycarboxylic acid-based copolymer for cement composition additives comprising iron sulfate (iron sulfate).
The reaction promoter of step b) is a method for producing a polycarboxylic acid-based copolymer for cement composition, characterized in that containing 2 to 16% by weight compared to the peroxide (peroxide).
The method of preparing a polycarboxylic acid copolymer for cement composition additives, characterized in that the monomer mixture and the reducing agent aqueous solution of step c) are added dropwise for 2 to 4 hours.
The polymerization of step d) is a polycarboxylic acid copolymer production method for cement composition additives, characterized in that carried out at 20 to 40 ℃.
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