KR101733616B1 - Hybrid-polymer its manufacturing method and cement superplasticizer mortarconcrete admixture using the hybrid-polymer - Google Patents
Hybrid-polymer its manufacturing method and cement superplasticizer mortarconcrete admixture using the hybrid-polymer Download PDFInfo
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- KR101733616B1 KR101733616B1 KR1020150058259A KR20150058259A KR101733616B1 KR 101733616 B1 KR101733616 B1 KR 101733616B1 KR 1020150058259 A KR1020150058259 A KR 1020150058259A KR 20150058259 A KR20150058259 A KR 20150058259A KR 101733616 B1 KR101733616 B1 KR 101733616B1
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
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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
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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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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Abstract
TECHNICAL FIELD The present invention relates to a hybrid polycarboxylic acid polymer and a method for producing the same, and a cement fluidizer and a mortar concrete admixture using the hybrid polycarboxylic acid polymer. In the present invention, The development of hybrid polymeric polymers with excellent dispersibility and workability through the easy synthesis of ester - based macromers and the economic modification of ether - based macromers has been developed and used to prepare cement fluidizers and mortar concrete admixtures.
Description
TECHNICAL FIELD The present invention relates to a hybrid polymer polymer, a method for producing the same, and a cement fluidizer and a mortar concrete admixture using the same. More particularly, the present invention relates to a hybrid polycarboxylic acid polymer and a method for producing the hybrid polymer, and a method for producing the hybrid polymer using the hybrid polycarboxylic acid polymer A cement fluidizing agent and a mortar concrete admixture.
In addition to high strength of concrete, cement and concrete admixtures can achieve high quality cement formulations, such as reduced workload and aggregate separability, and it is easy to construct areas where reinforcing bars are crowded or difficult to vibrate, It is necessary to be able to impart fluidity to the high part so that it can be transported using a high pressure pump.
Various types of admixtures have been used to achieve this purpose. Among them, melamine-based, sulphonic-based, and lignin-based admixtures are not easy to install at a deep slugging rate and work in a skyscraper.
The inventors of the present invention have developed an admixture having excellent dispersibility and workability by using a compound comprising a known polycarboxylic acid polymer.
In the present invention, a hybrid polymer having excellent dispersibility and workability is developed through easy synthesis of an ester-based macromer which satisfies excellent dispersibility and workability and has a high polymerization ratio and an economical ether-based macromer, Cement fluidizer and mortar / concrete admixture were prepared.
It is another object of the present invention to provide a cement fluidizing agent comprising a hybrid polymer polymer having excellent dispersing ability and maintaining ability between cement molecules, and a method for producing the same. Another object of the present invention is to provide a mortar / To provide a concrete admixture.
The hybrid polymer of the present invention can be produced by reacting a compound represented by the formula (d) with a macromonomer represented by the following formula (a) obtained by reacting a compound represented by the formula (b) and a compound represented by the formula (c) (G) obtained by reacting a compound represented by the formula (b) and reacting at least one of the compound represented by the formula (e) and the compound represented by the formula (f) And a copolymer.
(A)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms or aromatic compound containing 6 to 30 carbon atoms , m represents the average molar number of addition of oxyalkylene groups and is a number of 1 to 400)
(B)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, and m is an average number of moles of the oxyalkylene group added and is 1 to 400)
(C)
(Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms, or aromatic compound containing 6 to 30 carbon atoms)
(D)
(R5 to R7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R8 is an alkylene group having 1 to 30 carbon atoms, Z is a hydrogen atom , An alkyl group containing 1 to 30 carbon atoms or an alkylene group containing 2 to 30 carbon atoms)
(E)
(Wherein R 9 to R 11 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, M is a hydrogen atom , A monovalent metal or a divalent metal)
(F)
(R12 and R13 are each independently an alkyl group containing 1 to 30 carbon atoms, and M is a hydrogen atom, a monovalent metal or a divalent metal)
(G)
(R 1 to R 3 and R 5 to R 7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, and R 9 to R 11 each represent a hydrogen atom and 1 to 30 carbon atoms An alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, R4 and R8 are alkylene groups having 1 to 30 carbon atoms, R12 and R13 Is independently an alkyl group containing from 1 to 30 carbon atoms, X is absent or is an alkylene group containing from 1 to 30 carbon atoms, Y is alkyl containing 1 to 30 carbon atoms, 3 to 30 carbon atoms Or an aromatic compound having 6 to 30 carbon atoms, Z is a hydrogen atom, an alkyl group containing 1 to 30 carbon atoms, or an alkylene group containing 2 to 30 carbon atoms, m, n, o, p, q, r, and s are Wherein m and n are 1 to 400, o, p and r are 0 to 400, q and s are 0.1 to 400 moles, and M is a hydrogen atom, a monovalent metal or a divalent metal,
The average addition mole number of the oxyalkylene group of the macromonomer represented by the formula (a) and the compound represented by the formula (d) is 1 to 400.
And the average molecular weight of the high molecular weight polymer represented by the formula (g) is 10,000 to 300,000.
The mixing ratio of the macromonomer represented by the formula (a), the compound represented by the formula (b), the compound represented by the formula (d), the compound represented by the formula (e) (B) and the compound represented by the formula (d), the mole ratio of the macromonomer represented by the formula (a) to the compound represented by the formula (d) And the molar ratio of the compound to be displayed is less than or equal to the sum of the molar ratio of the compound to be displayed.
The compound represented by the formula (e): The compound represented by the formula (f) is a compound represented by the formula (a) 100: 0 to 70: 1 to 100: 0 to 150: 0 to 150.
The cement fluidizing agent and the mortar concrete admixture using the hybrid polymer of the present invention may be characterized in that they include a cement fluidizing agent comprising a polymer represented by the formula (g).
The method for producing a cement fluidizing agent using the hybrid polymer of the present invention comprises reacting a macromonomer represented by the following formula (a) obtained by reacting a compound represented by the following formula (b) with a compound represented by the following formula (c) (e) is reacted with at least one of the compounds represented by the formula (f) without reacting or not reacting the compound represented by the formula (b) (G), which is obtained by subjecting a compound represented by the following formula (g).
(A)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms or aromatic compound containing 6 to 30 carbon atoms , m represents the average molar number of addition of oxyalkylene groups and is a number of 1 to 400)
(B)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, and m is an average number of moles of the oxyalkylene group added and is 1 to 400)
(C)
(Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms, or aromatic compound containing 6 to 30 carbon atoms)
(D)
(R5 to R7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R8 is an alkylene group having 1 to 30 carbon atoms, Z is a hydrogen atom , An alkyl group containing 1 to 30 carbon atoms or an alkylene group containing 2 to 30 carbon atoms)
(E)
(Wherein R 9 to R 11 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, M is a hydrogen atom , A monovalent metal or a divalent metal)
(F)
(R12 and R13 are each independently an alkyl group containing 1 to 30 carbon atoms, and M is a hydrogen atom, a monovalent metal or a divalent metal)
(G)
(R 1 to R 3 and R 5 to R 7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, and R 9 to R 11 each represent a hydrogen atom and 1 to 30 carbon atoms An alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, R4 and R8 are alkylene groups having 1 to 30 carbon atoms, R12 and R13 Is independently an alkyl group containing from 1 to 30 carbon atoms, X is absent or is an alkylene group containing from 1 to 30 carbon atoms, Y is alkyl containing 1 to 30 carbon atoms, 3 to 30 carbon atoms Or an aromatic compound having 6 to 30 carbon atoms, Z is a hydrogen atom, an alkyl group containing 1 to 30 carbon atoms, or an alkylene group containing 2 to 30 carbon atoms, m, n, o, p, q, r, and s are Wherein m and n are 1 to 400, o, p and r are 0 to 400, q and s are 0.1 to 400 moles, and M is a hydrogen atom, a monovalent metal or a divalent metal,
The average molar number of addition of the oxaloalkylene group of the macromonomer represented by the formula (a) and the compound represented by the formula (d) is 1 to 400.
And the average molecular weight of the high molecular weight polymer represented by the formula (g) is 10,000 to 300,000.
The mixing ratio of the macromonomer represented by the formula (a), the compound represented by the formula (b), the compound represented by the formula (d), the compound represented by the formula (e) (B) and the compound represented by the formula (d), the mole ratio of the macromonomer represented by the formula (a) to the compound represented by the formula (d) And the molar ratio of the compound to be displayed is less than or equal to the sum of the molar ratio of the compound to be displayed.
The compound represented by the formula (e): The compound represented by the formula (f) is a compound represented by the formula (a) 100: 0 to 70: 1 to 100: 0 to 150: 0 to 150.
The cement fluidizing agent of the present invention is obtained by modifying a polycarboxylic acid ester-based macromer and an ether-based macromer used in a conventional polycarboxylic acid-based admixture. The cement admixture has dispersibility and workability Is remarkably improved.
The hybrid polymer of the present invention can be obtained by reacting a macromonomer represented by the following formula (a) obtained by reacting a compound represented by the following formula (b) with a compound represented by the following formula (c) (G), which is obtained by reacting at least one of the compound represented by the formula (e) and the compound represented by the formula (f) by reacting the compound represented by the formula (b) . ≪ / RTI >
(A)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms or aromatic compound containing 6 to 30 carbon atoms , m represents the average molar number of addition of oxyalkylene groups and is a number of 1 to 400)
The macromonomer represented by the formula (a) has a structure as described above. When the polymer has a structure similar to that of the polymer represented by the formula (g), the macromonomer represented by the formula (a) depends on the influence of the acid group Enhancement of maintenance performance and shortening of mixing time.
The macromonomer represented by the formula (a) is synthesized through the reaction between the compound represented by the formula (b) and the compound represented by the formula (c), and the control of the synthesis is determined by the acid catalyst and the moles to be reacted. Methane sulfonic acid, p-toluene sulfonic acid, hydrochloric acid, sulfuric acid, etc. may be used as the acid catalyst. The reaction temperature and time are preferably from 50 to 200 ° C for 0.5 to 150 hours, more preferably from 60 to 130 ° C for from 0.5 to 80 hours. In order to confirm the progress of the reaction, the acid value was measured and the reaction rate was calculated as follows, and when the reaction rate was 99% or more, the completion time was set.
When the number of m representing the oxyalkylene group and the alkyl group in the macromonomer represented by the formula (a) is 400 or more, the side chain becomes too long during the synthesis, and thus the synthesis is difficult due to the high viscosity. The performance of formula (g) also falls and m is preferably 1 to 400.
(B)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, and m is an average number of moles of the oxyalkylene group added and is 1 to 400)
The compound used for preparing the macromonomer represented by the formula (a) and the compound represented by the formula (b) can control the molecular weight by the average addition mole number of m, and the ring opening shown in the compound represented by the formula (c) As an additive in the reaction, it has an acid group on the side chain through reaction with an acid anhydride. When the polymer is represented by the formula (g), it can be used simultaneously with the macromonomer represented by the formula (a). When the polymer is used in combination, the performance of the concrete admixture is better than when it is used singly.
(C)
(Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms, or aromatic compound containing 6 to 30 carbon atoms)
Y is selected from the group consisting of maleic acid anhydride, succinic acid anhydride, 1,8-naphthalic acid anhydride, 4-methylphthalic acid anhydride, phthalic anhydride, (2-Dodecen-1-yl) succinic acid anhydride, 2-Cyclohexanedicarboxylic acid anhydride, 2,3-Dimethylmaleic acid anhydride, Homophthalic acid anhydride, Hexahydro-4-methylphthalic anhydride, 3,3-Tetramethyleneglutaric acid anhydride, Phenylsuccinic acid anhydride, Methylsuccinic acid anhydride, 2 4-Methylphthalic anhydride, 2-Octen-1-ylsuccinic acid anhydride, N-Methylisatoic acid anhydride, 4-Amino-1,8-naphthalic acid anhydride, 2-Dimethylglutaric acid anhydride, 3,4-Pyridinedicarboxylic acid anhydride, Bromomaleic acid anhydride, 3-Hydroxyphthalic acid anhydride, 2,3-Dichloromaleic acid anhydride, 5-Bromoisatoic acid anhydride, 4-Bromo-1,8-naphthalic anhydride, 4-Bromo-1,8-naphthalic anhydride, , 3,6-Dichlorophthalic anhydride, and the like.
The compound represented by the formula (c) is applied to the reaction with an unsaturated (poly) oxyalkylene ether through a ring-opening reaction with acid anhydrides (acid anhydrides) and can be applied to the present invention by replacing an acidic group at the terminal group have.
(D)
(R5 to R7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R8 is an alkylene group having 1 to 30 carbon atoms, Z is a hydrogen atom , An alkyl group containing 1 to 30 carbon atoms or an alkylene group containing 2 to 30 carbon atoms)
In the case of the compound represented by the formula (d) used in combination with the macromonomer represented by the formula (a) in the synthesis of the polymer represented by the formula (g), n means the average addition mole number and ranges from 1 to 400 , Methoxypolyethylene glycol and methacrylic acid. The solvent is not particularly limited, and examples thereof include aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-hexane, and tetrahydrofuran May be used alone or in admixture of two or more. The amount to be used is not particularly limited as long as the reaction can proceed sufficiently, but may be added in an amount of 5 to 15% by weight of the total amount. In addition, the reaction was controlled using an acidic catalyst such as para toluene sulfonic acid. The polymerization inhibitor may be selected from among sulfur, oxygen, benzoquinone, hydroquinone and phenothiazine. The reaction time may be 5 to 100 hours, preferably 5 to 90 hours, The reaction was carried out for 8 to 50 hours. The reaction was carried out at 90-150 ° C. The degree of progress of the reaction was measured by measuring the acid value. The reaction was terminated when the reaction rate was 99% or more to obtain the compound represented by the formula (d) .
(E)
(Wherein R 9 to R 11 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, M is a hydrogen atom , A monovalent metal or a divalent metal)
(F)
(R12 and R13 are each independently an alkyl group containing 1 to 30 carbon atoms, and M is a hydrogen atom, a monovalent metal or a divalent metal)
In the case of the compound represented by the formula (d) and the compound represented by the formula (e) used in the synthesis of the polymer represented by the formula (g), one or two of them may be used at the same time, Accordingly, the degree of polymerization can be controlled. The reaction is carried out at 20 to 200 ° C for 0.5 to 150 hours, preferably at 50 to 130 ° C for 0.5 to 80 hours. The polymerization of these reactions can also control the average molecular weight with polymerization regulators.
(G)
(R 1 to R 3 and R 5 to R 7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, and R 9 to R 11 each represent a hydrogen atom and 1 to 30 carbon atoms An alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, R4 and R8 are alkylene groups having 1 to 30 carbon atoms, R12 and R13 Is independently an alkyl group containing from 1 to 30 carbon atoms, X is absent or is an alkylene group containing from 1 to 30 carbon atoms, Y is alkyl containing 1 to 30 carbon atoms, 3 to 30 carbon atoms Or an aromatic compound having 6 to 30 carbon atoms, Z is a hydrogen atom, an alkyl group containing 1 to 30 carbon atoms, or an alkylene group containing 2 to 30 carbon atoms, m, n, o, p, q, r, and s are Wherein m and n are 1 to 400, o, p and r are 0 to 400, q and s are 0.1 to 400 moles, and M is a hydrogen atom, a monovalent metal or a divalent metal,
The polymer represented by the above formula (g) is a polymer having three or more kinds of hybrid polymer, which is a polymer having a macromonomer represented by the formula (a), a compound represented by the formula (b), a compound represented by the formula (d) A compound represented by the formula (f), or a compound represented by the formula (f). (B) and the compound represented by formula (d) in the compound represented by the formula (e), the compound represented by the formula (a) and the compound represented by the formula Is less than or equal to the sum of the molar ratio of the compound represented by formula (f) to the compound represented by formula (f), and the polymer represented by formula (g) And the compound represented by the formula (b) may be used together. The compound represented by the formula (e) and the compound represented by the formula (f) may be used alone or in combination, and at least one of the compound represented by the formula (e) and the compound represented by the formula Should be included.
The polymerization is carried out at a ratio of the average number of moles and is represented by the following formula (a): Macromonomer: compound represented by formula (b): compound represented by formula (d) ) Can be polymerized at a ratio of 0.1 to 400: 0 to 400: 0.1 to 400: 0 to 400: 0 to 400. Particularly preferred is a macromonomer represented by the formula (a): a compound represented by the formula (b): a compound represented by the formula (d): a compound represented by the formula (e) 1 to 100: 0 to 70: 1 to 100: 0 to 150: 0 to 150. If the proportion of the compound represented by the formula (e) or the compound represented by the formula (f) is too low, the dispersing performance is deteriorated. If the ratio is too high, the retaining performance is deteriorated due to the high viscosity.
The polymerization product can be obtained by reacting at 30 to 150 ° C for 0.5 to 150 hours, particularly preferably at 50 to 130 ° C for 0.5 to 80 hours. If the reaction time is too short or too long, the polymerization degree is lowered and the performance is lowered. If the temperature does not reach or exceed a certain temperature during the polymerization, the polymerization may not proceed or the chain may be broken.
In the polymerization of the monomer component, a chain transfer agent and a polymerization initiator may be used. As the chain transfer agent, any appropriate substance can be used. Specifically, thiol chain transfer agents such as thioglycerol, mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid and thiomalic acid can be used. As the polymerization initiator, persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, peroxide-based polymerization initiators such as hydrogen peroxide and benzoyl peroxide can be used.
The high molecular weight polymer represented by the formula (g) prepared by the above method simultaneously contains an ester-based macromer and an ether-based macromer, and exhibits a high polymerization rate of the ester-based macromer, Due to the polymerization time, a hybrid polymer having excellent dispersibility and workability can be obtained.
In addition, the hybrid polymer prepared as described above may be used alone as a cement fluidizing agent, a mortar / concrete admixture, or an AE / AE water reducing agent that improves work performance or freezing / thawing resistance performance, A shrinkage reducing agent for reducing shrinkage occurring during drying, an accelerator for retarding the setting and curing time, a retarder, a rust inhibitor for inhibiting the corrosion of reinforcing steel by chloride, a separating reducing agent for preventing the separation of cement and aggregate, A waterproofing agent for enhancing waterproofness, a foaming agent for lighter weight by generating bubbles, a foaming agent, and an admixture of a thickener for improving viscous / cohesive action, and may be made of a cement fluidizer and a mortar / concrete admixture.
Hereinafter, examples and comparative examples of the present invention will be described in detail.
[Preparation of macromonomer represented by the formula (a)] [
≪ Example 1 (SuH) >
A 1,117.36 g (EO moles: 20) of a methacrylic (poly) alkylene glycol ether compound was placed in a glass reactor and a thermometer, a stirrer and a reflux condenser were placed, and the water contained in the compound was recovered under vacuum Remove. Followed by 42.35 g of succinic anhydride and 5.8 g of methanesulfonic acid. When the addition is completed, the temperature is raised to a temperature of about 90 ° C. After heating for about 22 hours, the acid value was 23.42 ml / g (reaction rate: 99.4%), and the reaction was terminated.
≪ Example 2 (MalH) >
A glass reactor was equipped with a thermometer, a stirrer and a reflux condenser, and 1,420 g of a methallyl (poly) alkylene glycol ether compound (EO molar number: 100) was added and the water contained in the compound was vacuum recovered Remove. Then 52.74 g of maleic anhydride and 7.36 g of methanesulfonic acid are added. When the addition is completed, the temperature is raised to a temperature of about 90 ° C. After heating for about 3 hours, the acid value was 23.30 ml / g (reaction rate: 99.9%) and the reaction was terminated.
≪ Example 3 (PhH) >
A glass reactor was equipped with a thermometer, a stirrer and a reflux condenser, and then 3,120 g of a methallyl (poly) alkylene glycol ether compound (EO molar number: 50) was added and the water contained in the compound was vacuum recovered Remove. Thereafter, 173 g of phthalic anhydride and 3 g of methanesulfonic acid are added. When the addition is completed, the temperature is raised to about 90 ° C. After heating for about 66 hours, the acid value was 22.94 ml / g (reaction rate: 99.3%) and the reaction was terminated.
[Preparation of macromonomer represented by the formula (d)] [
Example 4 (PEG4)
After adding a thermometer, a stirrer, a reflux condenser and a dropping funnel, 1000 g of methoxypolyethylene glycol (molar number of EO added: 60), 224.3 g of methacrylic acid and 826 g of toluene were added, followed by 36.8 g of p-toluenesulfonic acid 3.36 g of butadiene is added, and the reflux reaction proceeds at 105. After about 20 hours, the reaction acid value was 42.1 ml / g (reaction rate: 99.9%), and the reaction was terminated. After toluene was removed, the reaction solution was neutralized with a 50% aqueous solution of sodium hydroxide solution.
Example 5 (PEG5)
After adding a thermometer, a stirrer, a reflux condenser and a dropping funnel, 1000 g of methoxypolyethylene glycol (molar number of EO added: 20), 224.3 g of methacrylic acid and 826 g of toluene were added, and 36.8 g of p- 3.36 g of phenothiazine was added and the reaction was carried out at 105 ° C. After about 20 hours, the reaction acid value was 42.1 ml / g (reaction rate: 99.9%), and the reaction was terminated. After toluene was removed, the reaction solution was neutralized with a 50% aqueous solution of sodium hydroxide solution.
Example 6 (PEG6)
After adding a thermometer, a stirrer, a reflux condenser and a dropping funnel, 552 g of methoxypolyethylene glycol (100 mol of EO added), 123 g of methacrylic acid and 456 g of toluene were added, and 20.1 g of p-toluenesulfonic acid, 1.99 g of azine is added thereto, and then a reflux reaction is carried out at 105 ° C. After about 20 hours, the reaction acid value was 42.1 ml / g (reaction rate: 99.9%). After completion of the reaction, the toluene was removed and neutralized with a 50% aqueous solution of sodium hydroxide solution.
[Production of high molecular weight polymer represented by the formula (g)] [
≪ Example 7 >
After adding a thermometer, a stirrer, a reflux condenser and a dropping funnel to the glass reactor, 117 g of the compound prepared in Example 1 and 90 g of the compound prepared in Example 4 were added to 90 g of ion-exchanged water and heated to 65 ° C. When the temperature reached the target temperature, 1.59 g of 3-mercaptopropionic acid, 6.38 g of acrylic acid, 6.3 g of methacrylic acid and 0.94 g of sodium lactate were added dropwise for 3 to 3.5 hours. After aging for 3 hours, the reaction was terminated and the obtained reaction mixture was cooled to 50 ° C or lower to obtain a copolymer aqueous solution having a weight average molecular weight of 42360.
≪ Example 8 >
A thermometer, a stirrer, a reflux condenser, and a dropping funnel were placed in a glass reactor, and 117 g of the compound prepared in Example 1 and 90 g of the compound prepared in Example 5 were added to 90 g of ion-exchanged water and heated to 75 ° C. When the temperature reached the target temperature, 1.59 g of 3-mercaptopropionic acid, 6.38 g of acrylic acid, 6.3 g of methacrylic acid and 0.94 of sodium peracetate were added dropwise for 3 to 3.5 hours. After aging for 3 hours, the reaction was terminated, and the obtained reaction mixture was cooled to 50 캜 or lower to obtain a copolymer aqueous solution having a weight average molecular weight of 38,193.
≪ Example 9 >
After adding a thermometer, a stirrer, a reflux condenser and a dropping funnel to the glass reactor, 117 g of the compound prepared in Example 1 and 90 g of the compound prepared in Example 6 were added to 90 g of ion-exchanged water and heated to 80 ° C. When the temperature reached the target temperature, 1.59 g of 3-mercaptopropionic acid, 6.38 g of acrylic acid, 6.3 g of methacrylic acid and 0.94 of sodium peracetate were added dropwise for 3 to 3.5 hours. After aging for 3 hours, the reaction was terminated and the obtained reaction mixture was cooled to 50 DEG C or lower to obtain a copolymer aqueous solution having a weight average molecular weight of 35,233.
≪ Comparative Example 1 &
A thermometer, a stirrer, a reflux condenser and a dropping funnel were placed in a glass reactor, and then 210 g of a methallyl (poly) alkylene glycol ether compound, 17.05 g of maleic acid and 100 g of ion-exchanged water were added and heated to 8 캜. Then, the reaction vessel was charged with 9.8 parts of hydrogen peroxide. Then, 9 g of acrylic acid, 0.635 g of L-ascorbic acid and 6.03 g of ion-exchanged water were added dropwise for 3 hours and 3.5 hours, respectively. After completion of the dropwise addition, the reaction solution was maintained at 65 ° C for 1 hour. When the reaction was completed, the solution was adjusted to pH 7 with aqueous NaOH solution to obtain a copolymer aqueous solution.
≪ Comparative Example 2 &
A thermometer, a stirrer, a reflux condenser and a dropping funnel were placed in a glass reactor, and then 210 g of a methallyl (poly) alkylene glycol ether compound, 21.35 g of maleic acid and 142 g of ion-exchanged water were placed and heated to 65 캜. Then, 4.39 g of an aqueous hydrogen peroxide solution was added to the reaction vessel. 5.9 g of 2-hydroxyethyl acrylate, 0.284 g of L-ascorbic acid and 5.4 g of ion-exchanged water were added dropwise for 3 hours and 3.5 hours, respectively. After completion of the dropwise addition, the reaction product was maintained at 65 ° C for 1 hour. After completion of the reaction, the reaction product was cooled to room temperature and adjusted to pH 7 with aqueous NaOH solution to obtain a copolymer aqueous solution.
≪ Comparative Example 3 &
A thermometer, a stirrer, a reflux condenser, and a dropping funnel were placed in a glass reactor, and 43.37 g of a methallyl (poly) alkylene glycol ether compound and 25.48 g of ion-exchanged water were charged and heated to 60 캜. Then, 3.0 g of a 2% hydrogen peroxide aqueous solution is added to the reaction vessel. Then, 1.92 g of acrylic acid was added dropwise over 1.5 hours, and 4.08 g of acrylic acid was added dropwise over 1.5 hours as the dropwise addition was completed. At the same time as dropping acrylic acid for the first time, an aqueous solution consisting of 0.14 g of 3-mercaptopropionic acid, 0.08 g of L-ascorbic acid and 15.94 g of ion-exchanged water was added dropwise over 3.5 hours. When the dropwise addition was completed, the mixture was maintained at the above-mentioned temperature of 60 DEG C for 1 hour, and then cooled to terminate the polymerization reaction. Thereafter, the pH was adjusted to 7 using an aqueous NaOH solution to obtain a copolymer aqueous solution.
≪ Examples 7 to 15 &
Examples 7 to 15 were conducted by using the monomers synthesized in Examples 1 to 3 and adjusting the proportions of the monomers synthesized in Examples 4 to 6. The results of the copolymers made are shown in Table 1.
gravity
AAA: Acrylic acid, MAA: Methacrylic acid
[SuH-PEG4: Monomer synthesized in Example 1 and monomers synthesized in Example 4. MalH-PEG4 and PhH-PEG4 also refer to monomers synthesized in the same manner as in the above method.
≪ Examples 16 to 19 &
The monomer was synthesized by controlling the molecular weight of VPEG used in Example 1. Polymerization was carried out using the monomers synthesized in Examples 4 to 6 by varying kinds of monomers. Table 2 shows the results.
AA: Acrylic acid, MAA: Methacrylic acid, MA: Maleic acid, HEA: 2-hydroxyethylacrylate
[Su11-PEG4: A material having a weight average molecular weight of 1,100 of the methallyl (poly) alkylene glycol ether compound used in Example 1 was used.
[Su5-PEG4: A material having a weight average molecular weight of 500 of the methallyl (poly) alkylene glycol ether compound used in Example 1 was used.
[Average weight molecular weight measurement]
The average weight molecular weights of the samples polymerized in Examples 7 to 19 and Comparative Examples 1 to 3 were measured and shown in Table 3.
The conditions for measuring the weight-average molecular weight of the copolymer are as follows.
1) Device: Products of WATERS Corp. GPC
2) Detector: Differential Spectroscopy (RI) detector (Ditector 2414) (product of WATERS Corp.)
3) Eluent: Type: deionized water (for HPLC), flow rate: 0.8 ml / min
4) Column type: product of WATERS Corp., ultrahydrogel (6 X 40mm)
5) Column temperature: 25 DEG C
6) Standard sample: Polyethylene glycol Maximum Peak-top Molecular Weight (Mp) After using the calibration curve of 1670, 5000, 25300, 440000, 78300, 152000, 326000, 55800
[Preparation of concrete admixture]
Prepared using aqueous copolymer solutions prepared in Examples 4 to 16 and Comparative Examples 1 to 3.
1) The active ingredients of the aqueous solutions prepared in Examples 4 to 16 and Comparative Examples 1 to 3 were measured.
2) After adjusting the effective component of the aqueous solution of the copolymer to 20%, 0.1% of the total weight of the other admixture is added. (Without the other admixture to be added, performance of the copolymer aqueous solution alone can be exhibited.
[Method of measuring active ingredient]
1) Measure the mass of the polymer to be measured.
2) The polymer thus measured is placed in a drier set at 105 DEG C and dried for 3 hours.
3) After 3 hours, remove the polymer sample from the drier and cool for 20 minutes in a desicator at room temperature.
4) When the term is completed, measure the mass of the polymer sample.
5) Perform three runs from 1 to 4 to prepare three specimens.
6) The active ingredient is calculated according to the following formula.
7) The average value of the three calculated specimens is determined as the effective component of the polymer.
The admixture of the present invention based on the above method was applied to a concrete test and compared and analyzed.
[Concrete Test]
1) Slump test: KS F 2402
2) Air flow measurement: KS F 2409
3) Concrete formulation is carried out with the following composition.
- Water: 165kg
- Cement (general Portland cement): 423kg
- Fly ash: 47kg
- Aggregate 1 (Type: Washer): 760kg
- Aggregate 2 (type: 25 mm crushed stone): 946 kg
4) Performance method: Concrete prepared in the above-mentioned formulation was mixed thoroughly and then proceeded to the following test method to measure the initial flow value, the flow value after 60 minutes, and the respective air amount.
[Slump test (KS F 2402)]
1) Wipe the inside of the slump cone with a wet rag and place it on a watertight flat plate.
2) Put the sample about 1/3 of the volume of the slump cone (about 7cm deep) and tweak it 25 times over the whole surface with the compaction rod.
3) Put the sample up to 2/3 of the volume of the slump cone (depth about 16cm) and cut 25 times with the compaction rod. At this time, the depth of the compaction rod into the concrete should be about 9cm.
4) Finally, put the sample over the slump cone and twist it 25 times evenly with the compaction bar.
5) Align the surface of the sample to the top of the slump cone and flatten it.
6) Gently pull the slump cone up.
7) Measure the length of the concrete with the accuracy of 5mm.
[Air volume test (KS F 2409)]
1) Divide the sample into three layers of approximately the same height, tie each layer uniformly 10 times, and tap the sides of the container with a wooden hammer about 5 times.
2) Next, use an extra sample to make it flat. After thoroughly wiping the top of the flange of the container and the bottom of the flange of the lid, attach the lid to the container tightly so that air can leak through the inside and outside of the lid, tighten the air tightly and match the air pressure to the initial pressure.
3) After about 5 seconds, open the operating plate sufficiently. Tap the side of the container with a wooden hammer so that the pressure of each part of the concrete is well filled in every corner. After opening the operating plate again, read the scale of the pressure gauge to 1 decimal place from when the needle is stabilized.
[Compressive strength test]
Based on the concrete formulation mentioned above, the specimens for the compressive strength test are prepared as follows.
1) The number of specimens shall be three or more.
2) The mold is applied with mineral oil before the concrete is hit on the inner surface.
3) When filling the concrete into the mold, fill it with 3 layers using a compaction rod and cut each layer 25 times.
4) The mold is removed after 24-48 hours after pouring the concrete, then cured until the strength test is performed in the wet state at 18 ~ 24 ℃.
(%)
(%)
※ In the above table, the concrete condition indicates the feeling when mixing with a scoop, and it is very good depending on the good condition of light and soft feeling: ◎, good: ○, medium: ◇, bad: marked with ×.
Claims (11)
(A)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms or aromatic compound containing 6 to 30 carbon atoms , m represents the average molar number of addition of oxyalkylene groups and is a number of 1 to 400)
(B)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, and m is an average number of moles of the oxyalkylene group added and is 1 to 400)
(C)
(Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms, or aromatic compound containing 6 to 30 carbon atoms)
(D)
(R5 to R7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R8 is an alkylene group having 1 to 30 carbon atoms, Z is a hydrogen atom , An alkyl group containing 1 to 30 carbon atoms or an alkylene group containing 2 to 30 carbon atoms)
(E)
(Wherein R 9 to R 11 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, M is a hydrogen atom , A monovalent metal or a divalent metal)
(F)
(R12 and R13 are each independently an alkyl group containing 1 to 30 carbon atoms, and M is a hydrogen atom, a monovalent metal or a divalent metal)
(G)
(R 1 to R 3 and R 5 to R 7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, and R 9 to R 11 each represent a hydrogen atom and 1 to 30 carbon atoms An alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, R4 and R8 are alkylene groups having 1 to 30 carbon atoms, R12 and R13 Is independently an alkyl group containing from 1 to 30 carbon atoms and X is an alkylene group containing no more than 1 to 30 carbon atoms and Y is an alkyl group having from 1 to 30 carbon atoms or an alkyl group having from 3 to 30 carbon atoms Or an aromatic compound containing 6 to 30 carbon atoms, Z is a hydrogen atom, an alkyl group containing 1 to 30 carbon atoms or an alkylene group containing 2 to 30 carbon atoms, m , n, o, p, q, r, Wherein m and n are 1 to 400, o, p and r are 0 to 400, q and s are 0.1 to 400 moles, and M is a hydrogen atom, a monovalent metal or a divalent metal.
Wherein the average molar number of addition of the oxyalkylene group of the macromonomer represented by the formula (a) and the compound represented by the formula (d) is 1 to 400.
Wherein the high molecular weight polymer represented by the formula (g) has an average weight molecular weight of 10,000 to 300,000.
The mixing ratio of the macromonomer represented by the formula (a), the compound represented by the formula (b), the compound represented by the formula (d), the compound represented by the formula (e) and the compound represented by the formula (f) The sum of the molar ratios of the macromonomer represented by the formula (a), the compound represented by the formula (b) and the compound represented by the formula (d) according to the molar ratio is represented by the formula (e) Is less than or equal to the sum of the molar ratios of the compounds.
The compound represented by the formula (a) is a compound represented by the formula (b): The compound represented by the formula (d): The compound represented by the formula (e) : 0 to 70: 1 to 100: 0 to 150: 0 to 150.
(A)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms or aromatic compound containing 6 to 30 carbon atoms , m represents the average molar number of addition of oxyalkylene groups and is a number of 1 to 400)
(B)
(R 1 to R 3 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R 4 is an alkylene group having 1 to 30 carbon atoms, X is absent Or an alkylene group containing 1 to 30 carbon atoms, and m is an average number of moles of the oxyalkylene group added and is 1 to 400)
(C)
(Y is one of alkyl containing 1 to 30 carbon atoms, aliphatic cyclic compound containing 3 to 30 carbon atoms, or aromatic compound containing 6 to 30 carbon atoms)
(D)
(Wherein R5 to R7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, R8 is an alkylene group having 1 to 30 carbon atoms, Z is a hydrogen atom , An alkyl group containing 1 to 30 carbon atoms or an alkylene group containing 2 to 30 carbon atoms)
(E)
(Wherein R 9 to R 11 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, M is a hydrogen atom , A monovalent metal or a divalent metal)
(F)
(R12 and R13 are each independently an alkyl group containing 1 to 30 carbon atoms, and M is a hydrogen atom, a monovalent metal or a divalent metal)
(G)
(R 1 to R 3 and R 5 to R 7 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkylene group having 2 to 30 carbon atoms, and R 9 to R 11 each represent a hydrogen atom and 1 to 30 carbon atoms An alkylene group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an allyl group, R4 and R8 are alkylene groups having 1 to 30 carbon atoms, R12 and R13 Is independently an alkyl group containing from 1 to 30 carbon atoms, X is absent or is an alkylene group containing from 1 to 30 carbon atoms, Y is alkyl containing 1 to 30 carbon atoms, 3 to 30 carbon atoms Or an aromatic compound having 6 to 30 carbon atoms, Z is a hydrogen atom, an alkyl group containing 1 to 30 carbon atoms, or an alkylene group containing 2 to 30 carbon atoms, m, n, o, p, q, r, and s are Wherein m and n are 1 to 400, o, p and r are 0 to 400, q and s are 0.1 to 400 moles, and M is a hydrogen atom, a monovalent metal or a divalent metal,
Wherein the average molar number of addition of the oxyalkylene group of the macromonomer represented by the formula (a) and the compound represented by the formula (d) is 1 to 400.
Wherein the average molecular weight of the high molecular weight polymer represented by the formula (g) is 10,000 to 300,000.
The mixing ratio of the macromonomer represented by the formula (a), the compound represented by the formula (b), the compound represented by the formula (d), the compound represented by the formula (e) and the compound represented by the formula (f) The sum of the molar ratios of the macromonomer represented by the formula (a), the compound represented by the formula (b) and the compound represented by the formula (d) according to the molar ratio is represented by the formula (e) The molar ratio of the compound to be added is less than or equal to the sum of the molar ratio of the compound to be added.
The compound represented by the formula (a) is a compound represented by the formula (b): The compound represented by the formula (d): The compound represented by the formula (e) : 0 to 70: 1 to 100: 0 to 150: 0 to 150. The method for producing a cement fluidizing agent according to claim 1,
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