JP2002201240A - Production method for polycarboxylic acid copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing, at a high polymerization rate a polycarboxylic acid copolymer which is suitable for the use as ultrahigh- strength concrete since it can impart excellent water-reducing properties and workability to a cement composition, etc., and can impart excellent strength and durability to a cured item of the cement composition, etc. SOLUTION: This method contains the step of copolymerization of a monomer mixture comprising (A) a (poly)amine monomer, (B) an unsaturated carboxylic acid monomer, and (C) a polyalkylene glycol monomer, provided the copolymerization of the monomer mixture is conducted under the condition that the degree of neutralization of the unsaturated carboxylic acid monomer (B) is 0-60 mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polycarboxylic acid copolymer. More specifically, the present invention relates to a method for producing a polycarboxylic acid copolymer which can be suitably used as a water reducing agent for ultrahigh strength.

[0002]

2. Description of the Related Art Polycarboxylic acid copolymers are widely used as components of cement admixtures in cement compositions such as cement paste, mortar, concrete, and the like.
It is indispensable for constructing civil engineering, building structures and the like from cement compositions. A cement admixture containing such a polycarboxylic acid-based copolymer is used as a water reducing agent, and by improving the fluidity of the cement composition to reduce the water content of the cement composition, the strength and durability of the cured product are improved. Will have the effect of causing Such water reducing agents exhibit higher water reducing performance than conventional naphthalene-based water reducing agents, and thus have many achievements as high-performance AE water reducing agents.

[0003] By the way, so-called ultra-high-strength concrete, which exhibits high performance among concretes, requires high strength and durability in the base portion of civil engineering and building structures and the like, and is used. As such a water reducing agent for ultra-high-strength concrete, a water reducing agent for ultra-high-strength water having a high water reducing performance so that the amount of water in the concrete is sufficiently reduced and high performance is exhibited is used. . As the ultra-high strength water reducing agent, for example, a copolymer of methacrylic acid and methacrylic acid polyethylene oxide ester and the like are used. Because it becomes high concrete,
There is a need for an ultra-high strength water reducing agent that can improve workability.

Japanese Patent Application Laid-Open No. 2000-191356 discloses that
A specific polyamine monomer as compound A;
A specific unsaturated carboxylic acid-based monomer and a specific polyalkylene glycol-based monomer as compound C, compound A: compound B: compound C = 10 to 40% by weight: 10
４０40% by weight: a cement dispersant mainly composed of a water-soluble amphoteric copolymer copolymerized at a ratio of 50５０80% by weight, which can be used as a dispersant for ultra-high-strength concrete, It is disclosed that the workability is excellent.

[0005] However, in all the examples in this publication, the compound A, the compound B and the compound C are copolymerized to obtain a water-soluble amphoteric copolymer. , The polymerization rate is extremely reduced. Therefore, the molecular weight of the water-soluble amphoteric copolymer decreases, and the production efficiency decreases. When such a water-soluble amphoteric copolymer is used for the production of ultra-high-strength concrete, the water-soluble amphoteric copolymer cannot exhibit a sufficient effect in ultra-high-strength concrete requiring high performance. And the performance and quality of the ultra-high-strength concrete will be reduced. Due to this, the strength and durability of hardened materials such as civil engineering and building structures may be reduced, which may cause problems such as reduced safety and increased repair costs. There is room for studying a method for producing a copolymer that can be used to improve workability and exhibit high performance and quality.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is intended to improve the water reduction and workability of a cement composition and the like, and furthermore, the strength and durability of a cured product thereof. Therefore, an object of the present invention is to provide a method for producing a polycarboxylic acid-based copolymer which can be suitably used for ultra-high-strength concrete at a high polymerization rate.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to efficiently produce a polycarboxylic acid copolymer which can be used as a water reducing agent for ultra-high strength. When copolymerizing the monomer mixture comprising the polymer (A), the unsaturated carboxylic acid monomer (B) and the polyalkylene glycol monomer (C) as essential components, the unsaturated carboxylic acid monomer ( It was noted that when B) was 100% neutralized, the polymerization rate was extremely reduced. The reason why the polymerization rate is extremely lowered is considered to be due to the fact that the polymerization rate of the neutralized unsaturated carboxylic acid monomer (B) is much lower than that of the acid type. It was conceived that the polymerization rate would not be improved unless a certain proportion of the carboxylic acid monomer (B) was in the acid form, and the unsaturated carboxylic acid monomer (B)
It has been found that a polycarboxylic acid copolymer obtained by copolymerization with an appropriate neutralization ratio can be suitably used for ultra-high-strength concrete and the like, and has reached the present invention.

That is, the present invention relates to the use of a monomer mixture containing a (poly) amine monomer (A), an unsaturated carboxylic acid monomer (B) and a polyalkylene glycol monomer (C). A method for producing a polycarboxylic acid-based copolymer comprising a polymerization step, wherein the copolymerization step is carried out by setting the neutralization rate of the unsaturated carboxylic acid-based monomer (B) to 0 to 60 mol%.
Is a method for producing a polycarboxylic acid copolymer in which a monomer mixture is copolymerized. Hereinafter, the present invention will be described in detail.

The method for producing a polycarboxylic acid copolymer of the present invention comprises the steps of: (A) an amine monomer (A), an unsaturated carboxylic acid monomer (B) and a polyalkylene glycol monomer (B). And a copolymerization step of a monomer mixture containing C). The (poly) amine monomer (A) is not particularly limited as long as it is an amine having an unsaturated bond or a polyamine. In the present invention, the (poly) amine monomer (A) preferably has an oxyalkylene group. The unsaturated carboxylic acid monomer (B) is not particularly limited as long as it has an unsaturated bond and a group capable of forming a carbanion. The polyalkylene glycol monomer (C) is not particularly limited as long as it has an unsaturated bond and a polyalkylene glycol chain. These monomers may be used alone or in combination of two or more.

The weight ratio of these monomers in the above-mentioned monomer mixture is not particularly limited, and may be appropriately determined depending on the physical properties and applications desired for the polycarboxylic acid copolymer. For example, when a polycarboxylic acid-based copolymer is used as a cement additive, 5 to 40% by weight of (poly) amine-based monomer (A) and 5 to 40% by weight of unsaturated carboxylic acid-based monomer (B) It is preferable to contain 40% by weight and 20 to 90% by weight of the polyalkylene glycol-based monomer (C).
The weight ratio of the monomers (A), (B) and (C) is calculated by adding the total weight of the monomers (A), (B) and (C) to 1
It is the weight% when it is set to 00 weight%. Further, in the present invention, other monomers other than the above-mentioned monomers can be used, but when other monomers are used, the monomers (A), (B) and (C) It is preferable that the total be the main component in the monomer mixture, for example,
When the monomer mixture is 100% by weight, the total of the monomers (A), (B) and (C) is 50 to 100% by weight.
It is preferable that More preferably, 7
0 to 100% by weight, more preferably 90 to 10% by weight.
0% by weight.

[0011] In the present invention, the copolymerization step may adjust the neutralization rate of the unsaturated carboxylic acid monomer (B) to 0 to 60 mol.
% In which the monomer mixture is copolymerized. The neutralization ratio of the unsaturated carboxylic acid monomer (B) is such that when the total number of moles of the unsaturated carboxylic acid monomer (B) is 100 mol%, It is represented by mol% of the system monomer (B). If the degree of neutralization of the unsaturated carboxylic acid monomer (B) exceeds 60 mol%, the degree of polymerization in the copolymerization step does not increase, resulting in a decrease in the pure content and molecular weight of the obtained copolymer and an increase in production efficiency. Or lower. Preferably, it is 0 to 50 mol%, more preferably 0 to 40 mol%, further preferably 0 to 30 mol%, further preferably 0 to 20 mol%, particularly preferably 0 to 1 mol%.
0 mol%, most preferably 0 to 5 mol%.

The neutralization ratio of the unsaturated carboxylic acid monomer (B) is set to 0 to 60 mol% and the copolymerization step is carried out by, for example, an unsaturated carboxylic acid monomer (all of which is an acid type). A method in which B) is subjected to copolymerization without neutralization, or an unsaturated carboxylic acid monomer (B) is neutralized to a salt form such as a sodium salt or an ammonium salt using an alkaline substance. Occasionally, a method in which a neutralization rate of 0 to 60 mol% is applied to copolymerization, and the like can be mentioned.

As the copolymerization method in the above-mentioned copolymerization step, for example, a known polymerization method such as solution polymerization or bulk polymerization can be carried out using a monomer mixture and a polymerization initiator. As the polymerization initiator, known ones can be used and are not particularly limited. Examples thereof include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate;
Hydrogen peroxide; azo compounds such as azobis-2-methylpropionamidine hydrochloride and azoisobutyronitrile; and peroxides such as benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide.
Further, as an accelerator, for example, sodium bisulfite,
Reducing agents such as sodium sulfite, Mohr's salt, sodium pyrobisulfite, formaldehyde sodium sulfoxylate, and ascorbic acid; amine compounds such as ethylenediamine, sodium ethylenediaminetetraacetate, and glycine can also be used in combination. These polymerization initiators and accelerators may be used alone or in combination of two or more.

In the above-mentioned copolymerization step, a chain transfer agent can be used if necessary. As such a chain transfer agent, known ones can be used and are not particularly limited.
For example, mercaptopropionic acid, mercaptopropionic acid 2-ethylhexyl ester, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6
-Dioxaoctane, decanetrithiol, dodecylmercaptan, hexadecanethiol, decanethiol,
Examples include carbon tetrachloride, carbon tetrabromide, α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, 2-aminopropan-1-ol, and the like. These may be used alone or in combination of two or more.

The above-mentioned copolymerization step can be carried out either batchwise or continuously. In addition, in the copolymerization, as the solvent used as necessary, a known solvent can be used and is not particularly limited. Examples thereof include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol;
Benzene, toluene, xylene, cyclohexane, n-
Aromatic or aliphatic hydrocarbons such as heptane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone. These may be used alone,
Two or more kinds may be used in combination. Among them, one or two or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms from the viewpoint of the solubility of the monomer mixture and the obtained polycarboxylic acid copolymer. It is preferable to use

In the copolymerization step, the method of adding the monomer mixture and the polymerization initiator to the reaction vessel is not particularly limited. For example, all of the monomer mixture is charged into the reaction vessel and the polymerization initiator is added. A method of performing copolymerization by adding the mixture into a reaction vessel; charging a part of the monomer mixture into the reaction vessel, and performing the copolymerization by adding the polymerization initiator and the remaining monomer mixture to the reaction vessel. And a method in which a polymerization solvent is charged into a reaction vessel and the total amount of the monomer and the polymerization initiator is added. Among such methods, the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), and the cement dispersibility, which is an effect of increasing the fluidity of the cement composition or the like, can be improved. The copolymerization is preferably performed by a method in which an initiator and a monomer are sequentially dropped into a reaction vessel.

In the above-mentioned copolymerization step, the copolymerization conditions such as the copolymerization temperature are appropriately determined depending on the copolymerization method, solvent, polymerization initiator and chain transfer agent used, and are not particularly limited. Is usually preferably from 0 to 150 ° C. More preferably, 40 to 120 ° C
The temperature is more preferably from 50 to 100 ° C, and particularly preferably from 60 to 85 ° C. The copolymer obtained by the above-mentioned copolymerization step is used as it is as a component such as a cement admixture, and may be further neutralized with an alkaline substance, if necessary. The alkaline substance is not particularly limited and includes, for example, inorganic salts such as hydroxides, chlorides and carbonates of monovalent metals and divalent metals; ammonia;
It is preferable to use an organic amine or the like.

The polycarboxylic acid copolymer of the present invention is produced by a production method comprising the above-mentioned copolymerization step, but the molecular weight of such a copolymer is not particularly limited. Absent. For example, when used as a cement additive, the weight average molecular weight (M) in terms of polyethylene glycol by gel permeation chromatography (hereinafter referred to as “GPC”) is used.
Preferably, w) is from 500 to 500,000.
If it is less than 500, the water reducing performance of the polycarboxylic acid-based copolymer may decrease. If it exceeds 500,000, the water reducing performance and the slump loss preventing ability of the polycarboxylic acid-based copolymer may decrease. More preferably, 5
000 to 300,000, most preferably 8,000
It is in the range of １００100,000. In the present specification, the weight average molecular weight of the copolymer is a value measured under the following GPC measurement conditions.

[0019]GPC molecular weight measurement conditions  Column used: Tosoh TSKguardcolumn
 SWXL + TSKge1 G4000SWXL + G3
000SWXL + G2000SWXL Eluent: 100999 g of water, 6001 g of acetonitrile
Dissolve 115.6 g of sodium acetate trihydrate in a mixed solvent of
And then pH 6.0 with 30% aqueous sodium hydroxide solution.
Use the eluent adjusted to. Eluent flow rate: 0.8 ml / sec Column temperature: 35 ° C. Standard substance: polyethylene glycol, weight average molecular weight
(Mw) 272500, 219300, 85000, 4
6000, 24000, 12600, 4250, 710
0, 1470. Detector: Differential refraction detector made by Waters Japan Analysis software: MILLENNI made by Waters Japan
UM Ver. 2.18

The present invention also relates to a polyamine monomer (a)
5 to 40% by weight, unsaturated carboxylic acid monomer (b)
A method for producing a polycarboxylic acid-based copolymer for cement additives, comprising a step of copolymerizing a monomer mixture containing 40% by weight and 20 to 90% by weight of a polyalkylene glycol-based monomer (c). In the copolymerization step, the neutralization rate of the unsaturated carboxylic acid monomer (b) is set to 0 to 60 m.
ol% is a step of copolymerizing the monomer mixture,
The polyamine-based monomer (a) is an ester of dibasic acid and / or an ester of a dibasic acid and an alcohol having 1 to 4 carbon atoms, based on 1.0 mol of the polyalkylene polyamine.
1.0 mole, and an unsaturated bond obtained by reacting (meth) acrylic acid and / or 0.01 to 0.5 mole of an ester of (meth) acrylic acid with an alcohol having 1 to 30 carbon atoms. A polyamide polyamine-based compound obtained by adding 0 to 300 moles of an alkylene oxide having 2 to 18 carbon atoms to a total of 1 mole of an amino group and an imino group of a polyamide polyamine, wherein the unsaturated carboxylic acid-based monomer (b) Is the following general formula (1);

[0021]

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(Wherein, R represents a hydrogen atom or a methyl group; a hydrogen atom, a metal atom, an ammonium group or an organic amine group). (C) is the following general formula (2);

[0023]

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(Wherein, R ¹ represents a hydrogen atom or a methyl group; R ^{X s} are the same or different and represent an alkylene group having 2 to 18 carbon atoms. R ² represents a hydrogen atom or a 1 to 1 carbon atom. 3
Represents a hydrocarbon group of 0. m represents an average number of added moles of the oxyalkylene group represented by R ^X O, and is a number of 1 to 300. ) Is a method for producing a polycarboxylic acid copolymer for cement additives, which is an (alkoxy) polyalkylene glycol mono (meth) acrylate.

The process for producing the polycarboxylic acid copolymer for cement additives of the present invention comprises the steps of:
-40% by weight, unsaturated carboxylic acid monomer (b) 5-4
0% by weight and polyalkylene glycol monomer (c)
A copolymerization step of a monomer mixture containing 20 to 90% by weight. These monomers may be used alone or in combination of two or more. When the weight ratio of these monomers is out of the above range, the function of the repeating unit formed by each monomer cannot be effectively exerted as described below, and the effect of the present invention is not sufficiently achieved. It cannot be expressed. The weight ratio of the monomers (a), (b) and (c) is 100% by weight of the sum of the weights of the monomers (a), (b) and (c).
% By weight. Further, in the present invention, as will be described later, other monomers other than the above-mentioned monomers can be used, but when other monomers are used, the monomers (a) and (b) It is preferred that the sum of (c) and (c) be the main component in the monomer mixture.

Polycarbonate for cement additive in the present invention
In the case of the boronic acid copolymer, the polyamine monomer (a) is used.
The repeating unit formed is an unsaturated carboxylic acid monomer
(B) or polyalkylene glycol monomer (c)
Combined with the function of the repeating unit formed
Function to improve water-reduction and workability of paint compositions, etc.
And the unsaturated carboxylic acid monomer
The repeating unit formed by (b) is a cement additive
Of polycarboxylic acid copolymer for cement to cement particles
Function, and polyalkylene glycol
The repeating unit formed by the monomer (c)
Cement group by hydrophilicity and steric repulsion of silalkylene group
It will exhibit the function of improving the dispersibility of products etc.
it is conceivable that. In addition, the polyamine monomer (a)
The repeating unit that is formed has multiple nitrogen atoms
And the above function will be exhibited due to this.
it is conceivable that. By performing these functions,
Water reduction and workability of the cement composition, etc.
If the cured product has excellent strength and durability,
Can be done. Therefore, the cement according to the present invention
Cement blend containing polycarboxylic acid copolymer for additive
Can be used in ultra-high strength concrete
Suitable for use as an ultra-high strength water reducing agent.
You. In addition, ultra-high-strength concrete is a cement composition
What is commonly referred to in the field of
Less water content than conventional concrete
So that the cured product has the same or higher strength as before
Concrete, for example, a water / cement ratio of 2
Less than 5%, especially about 18%, hinders normal use
Concrete with workability that does not cause
And the cured product is 100 N / mm ^Two Above compressive strength
Is what it will be.

In the present invention, by performing the copolymerization step with the neutralization ratio of the unsaturated carboxylic acid monomer (b) being 0 to 60 mol%, the polymerization ratio of the monomer mixture is improved,
Due to this, the function and effect when the polycarboxylic acid copolymer for cement additive is used as a water reducing agent for ultra-high strength can be sufficiently exhibited. The copolymerization step in the present invention is the same as the above-described copolymerization step in the method for producing a polycarboxylic acid copolymer.

The monomers constituting the monomer mixture that forms the polycarboxylic acid copolymer for cement additives in the present invention will be described below. The polyamine-based monomer (a) is a polyalkylene polyamine (hereinafter, also referred to as compound (a1)) (1.0 mol) with respect to 1.0 mol of a dibasic acid and / or a dibasic acid and an alcohol having 1 to 4 carbon atoms. [Hereinafter, also referred to as compound (a2)] 0.5
To 1.0 mol, and an ester of (meth) acrylic acid and / or (meth) acrylic acid with an alcohol having 1 to 4 carbon atoms [hereinafter also referred to as compound (a3)] 0.01 to
0.5 moles of an alkylene oxide having 2 to 18 carbon atoms per 1 mole of a total of amino groups and imino groups of a polyamide polyamine having an unsaturated bond obtained by reacting 0.5 moles.
It is a polyamide polyamine-based compound to which 00 mol has been added.

The compound (a1) is not particularly limited as long as it has a plurality of alkylene groups and a plurality of amino groups or imino groups in one molecule. Examples thereof include diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. One, two or more of min, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine and the like. Among them, from the viewpoint of easy availability and production cost, diethylenetriamine, triethylenetetramine, etc. Preferably, it is used.

The compound (a2) is not particularly restricted but includes, for example, malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid,
One or two or more of azelaic acid, sebacic acid and esters of these with an alcohol having 1 to 4 carbon atoms may be mentioned. Among them, from the viewpoint of availability and production cost, adipic acid may be used. preferable.

The compound (a3) is not particularly restricted but includes, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and (meth) acrylic acid. Butyl (meta)
One or two or more esters of acrylic acid and an alcohol having 1 to 4 carbon atoms may be mentioned. The alcohol having 1 to 4 carbon atoms forming the compound (a2) or the compound (a3) is not particularly limited, and examples thereof include one or more of methanol, ethanol, propanol, butanol and isomers thereof. Can be

The compound (a1), the compound (a2) and the compound (a3) are reacted to obtain a polyamide polyamine having an unsaturated bond. Compounds other than these compounds may be additionally used. It does not have to be used.
In order to obtain a polyamide polyamine having an unsaturated bond, the compound (a1), the compound (a2) and the compound (a
It is essential to carry out the polycondensation reaction of 3), and a known polycondensation reaction method can be used. For example, after a polycondensation reaction of the compound (a1) and the compound (a2) first to obtain a polyamide polyamine, a two-stage reaction method in which the polyamide polyamine and the compound (a3) are polycondensed,
From the beginning, compound (a1), compound (a2) and compound (a
3) is carried out by a batch reaction method or the like in which a polycondensation reaction is simultaneously performed. In these reaction methods, each compound may be subjected to the reaction collectively, or may be subjected to the reaction stepwise or sequentially. According to these reaction methods and the like, a polycondensation reaction, that is, an amidation reaction is performed to form a polyamide chain, and a (meth) acrylic acid residue derived from the compound (a3) is located at a terminal of the polyamide chain to form a polyamide polyamine. It will have unsaturated bonds.

The ratio of the number of moles of the compound (a1), the compound (a2) and the compound (a3) forming the polyamide polyamine having an unsaturated bond is as follows:
The compound (a2) is 0.5 to 1.0 mol, and the compound (a3) is 0.01 to 0.5 mol, based on 1.0 mol. As a result, the product of the condensation polymerization of the compound (a1) and the compound (a2) is such that the molar ratio is, on average, compound (a1) / compound (a2) = 2/1 to 1/1. A polyamide polyamine having a certain range of chain length formed by the condensation polymerization reaction, and due to such a structure, the polycarboxylic acid copolymer for cement additive exhibits high water reduction and dispersion stability. become. If the chain length of the polyamide polyamine is shorter than this, that is, if the compound (a2) is less than 0.5 mol with respect to 1.0 mol of the compound (a1), the polycarboxylic acid copolymer for cement additive will Dispersion stability will be reduced. When the chain length of the polyamide polyamine is longer than this, that is, 1.0 mole of the compound (a1) is added to the compound (a2).
If it exceeds 0 mol, the water-reducing property of the polycarboxylic acid-based copolymer for a cement additive will decrease. Compound (a
1) The compound (a2) is used in an amount of from 0.6 to 1.0 mol.
0.98 mol is preferable, and 0.8 to 0.95 mol is more preferable.

As the ratio of the number of moles, the compound (a)
1) The number of moles of the compound (a3) is 0.1 to 1.0 mole.
When the amount is less than 01 mol, the proportion of the polyamine-based monomer (a) incorporated in the polycarboxylic acid-based copolymer for cement additive decreases, and the repeating unit formed from the polyamine-based monomer (a) is reduced. The function exhibited by the device is reduced. On the other hand, if it exceeds 0.5 mol, the structure of the polycarboxylic acid copolymer for cement additive becomes too three-dimensional, so that the effects of the present invention cannot be sufficiently exhibited. It is preferable that the number of moles of the compound (a3) is 0.02 to 0.3 mole per 1.0 mole of the compound (a1). More preferably, 0.
0.5 to 0.2 mol.

A polyamide polyamine compound is obtained by adding 0 to 300 moles of an alkylene oxide having 2 to 18 carbon atoms to 1 mole of the total of amino groups and imino groups of the polyamide polyamine having an unsaturated bond. become. 2 to 2 carbon atoms to be added to amino group or imino group of polyamide polyamine having unsaturated bond
The alkylene oxide of No. 18 is not particularly limited, and examples thereof include one or more of ethylene oxide, propylene oxide, and butylene oxide.

In order to obtain the above-mentioned polyamide polyamine compound, one or both of the amino group and the imino group of the polyamide polyamine having an unsaturated bond has 2 carbon atoms.
Although alkylene oxides of １８18 to １８18 may or may not be added, the addition is preferred. In this case, the alkylene oxide having 2 to 18 carbon atoms is added to a nitrogen atom of an amino group or imino group having an active hydrogen atom. When the number of added moles of the alkylene oxide having 2 to 18 carbon atoms exceeds 300 moles, the number of nitrogen atoms in the polycarboxylic acid-based copolymer for cement additive is increased due to an increase in the molecular weight of the polyamide polyamine-based compound. And the effect of the present invention cannot be sufficiently exhibited. The preferred number of moles of the alkylene oxide having 2 to 18 carbon atoms is 0.2 to 100 moles based on 1 mole of the total amino group and imino group of the polyamide polyamine having an unsaturated bond. More preferably, 0.5 to 50 mol, still more preferably, 1 to 2
0 mol.

The above-mentioned polyamide polyamine compound is converted from compound (a1), compound (a2) and compound (a3) by 2
An example of a reaction formula obtained by a polycondensation reaction in a step reaction is shown below.

[0038]

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In the above reaction formula, EO represents ethylene oxide, -EO-H represents that ethylene oxide is added to a nitrogen atom having an active hydrogen atom in a polyamide polyamine having an unsaturated bond, and q represents Represents the number of moles of diethylenetriamine, r represents the number of moles of adipic acid, and s represents the number of moles of a repeating unit formed from adipic acid and diethylenetriamine.

The unsaturated carboxylic acid monomer (b) in the present invention is a compound represented by the above general formula (1).
The metal atom in M in the general formula (1) is not particularly limited, and includes, for example, a monovalent metal atom such as an alkali metal atom such as lithium, sodium, and potassium;
Divalent metal atoms such as alkaline earth metal atoms such as magnesium; and trivalent metal atoms such as aluminum and iron. The organic amine group is not particularly limited, and examples thereof include an alkanolamine group such as an ethanolamine group, a diethanolamine group, and a triethanolamine group, and a triethylamine group. Further, it may be an ammonium group. Examples of such an unsaturated carboxylic acid monomer (b) include acrylic acid, methacrylic acid and the like; monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like. Among them, methacrylic acid; a monovalent metal salt, a divalent metal salt, an ammonium salt, an organic amine salt, and the like are preferably used from the viewpoint of improving the cement dispersing performance.

The polyalkylene glycol monomer (c) in the present invention is an (alkoxy) polyalkylene glycol mono (meth) acrylate represented by the general formula (2). In the general formula (2),-(R
^When two or more oxyalkylene groups represented by XO)-are present in the same (alkoxy) polyalkylene glycol mono (meth) acrylate,-( ^Rx
O)-an oxyalkylene group represented by-is randomly added,
Any addition form such as block addition and alternate addition may be used.

The oxyalkylene group represented by-(R ^X O)-is an alkylene oxide adduct having 2 to 18 carbon atoms. The structure of such an alkylene oxide adduct is, for example, ethylene oxide or propylene. It is a structure formed by one or more alkylene oxides such as oxide, butylene oxide, isobutylene oxide, 1-butene oxide and 2-butene oxide.
Among such alkylene oxide adducts, ethylene oxide, propylene oxide and butylene oxide adducts are preferred. In addition, it is preferable that an ethylene oxide moiety is added to an ester bond with (meth) acrylic acid from the viewpoint of improving productivity of esterification with (meth) acrylic acid.

M, which is the average number of moles of the oxyalkylene group represented by R ^X O, is a number from 1 to 300.
If m exceeds 300, the polymerizability of the monomer will decrease. The preferred range of m, is 2 or more, - at (R ^X O) in m-, and the average molar number of addition of oxyethylene group is preferably 2 or more. m
Is less than 2 or the average number of moles of added oxyethylene groups is less than 2, there is a possibility that sufficient hydrophilicity and steric hindrance for dispersing cement particles and the like may not be obtained, so that excellent fluidity is obtained. May not be obtained. The range of m is more preferably 10 to 2
50, and more preferably 20 to 150. The average number of moles of oxyethylene groups added is more preferably from 10 to 250, still more preferably 2 to 250.
0 to 150. The average number of moles added means an average value of the number of moles of the organic group added in one mole of the monomer.

When the carbon number of R ² exceeds 30, the hydrophobicity of the polycarboxylic acid copolymer for cement additives becomes too strong, so that good dispersibility cannot be obtained. R ² is preferably a hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of dispersibility. More preferably, it has 1 to 10 carbon atoms, and still more preferably, 1 to 10 carbon atoms.
5, particularly preferably 1 to 3 carbon atoms, most preferably
It is a hydrocarbon group having 1 to 2 carbon atoms. In order to exhibit excellent material separation prevention performance and to moderate the amount of air entrained in the cement composition, it is preferable to use a hydrocarbon group having 5 to 20 carbon atoms. More preferably, it is a hydrocarbon group having 5 to 10 carbon atoms. Among hydrocarbon groups,
Saturated alkyl groups and unsaturated alkyl groups are preferred. These alkyl groups may be linear or branched.

The (alkoxy) polyalkylene glycol mono (meth) acrylate is not particularly limited as long as it is as described above.
Ethanol, 1-propanol, 2-propanol, 1
-Butanol, 2-butanol, 1-pentanol, 2
Having 1 to 30 carbon atoms such as -pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, and stearyl alcohol; Aliphatic alcohols, alicyclic alcohols having 3 to 30 carbon atoms such as cyclohexanol, (meth) allyl alcohol, 3-butene-
Alkoxypoly obtained by adding 1 to 300 moles of an alkylene oxide group having 2 to 18 carbon atoms to any of unsaturated alcohols having 3 to 30 carbon atoms such as 1-ol and 3-methyl-3-buten-1-ol. Alkylene glycols,
An esterified product with (meth) acrylic acid is exemplified.

Examples of the esterified product include the following (alkoxy) polyethylene glycol (poly)
(Alkylene glycols having 2 to 4 carbon atoms) (meth) acrylates and the like. Methoxy polyethylene glycol mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol}
Mono (meth) acrylate, methoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, methoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate Acrylate, ethoxy ト polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, ethoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, ethoxy ｛polyethylene glycol (poly)
Propylene glycol (poly) butylene glycol mono (meth) acrylate, propoxy polyethylene glycol mono (meth) acrylate, propoxy polyethylene glycol (poly) propylene glycol mono (meth) acrylate, propoxy polyethylene glycol (poly) butylene glycol mono (Meth) acrylate, propoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Butoxy polyethylene glycol mono (meth) acrylate, butoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, butoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, butoxy ｛polyethylene glycol (poly) ) Propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, pentoxy polyethylene glycol mono (meth)
Acrylate, pentoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, pentoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, pentoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (Meth) acrylate, hexoxy polyethylene glycol mono (meth) acrylate, hexoxy ｛polyethylene glycol (poly) propylene glycol プ ロ ピ レ ン mono (meth) acrylate, hexoxy ｛polyethylene glycol (poly)
Butylene glycol mono (meth) acrylate, hexoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate.

Heptoxy polyethylene glycol mono (meth) acrylate, heptoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, heptoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate,
Heptoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate, octoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol (poly) propylene glycol mono (meth) acrylate, octoxy polyethylene Glycol (poly) butylene glycol mono (meth) acrylate, octoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate, nonanoxy polyethylene glycol mono (meth) acrylate, nonanoxy polyethylene glycol (poly ) Propylene glycol (mono (meth) acrylate, nonoxy) polyethylene glycol (poly) butylene Recall} mono (meth) acrylate, Nonanokishi {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Decanoxy polyethylene glycol mono (meth) acrylate, decananoxy {polyethylene glycol (poly) propylene glycol} mono (meth)
Acrylate, decanoxy, polyethylene glycol (poly) butylene glycol, mono (meth) acrylate, decanoloxy, polyethylene glycol (poly) propylene glycol (poly) butylene glycol, mono (meth) acrylate, undecanoxy polyethylene glycol mono (meth) acrylate, Undecanoloxy polyethylene glycol (poly) propylene glycol mono (meth) acrylate, undecanoloxy polyethylene glycol (poly) butylene glycol mono (meth) acrylate, undecanoloxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) ) Acrylate, dodecanooxypolyethylene glycol mono (meth) acrylate, dodecanoloxy Ethylene glycol (poly)
Propylene glycol mono (meth) acrylate, dodecanoxy polyethylene glycol (poly) butylene glycol mono (meth) acrylate, dodecanoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate.

Tridecanoloxypolyethylene glycol mono (meth) acrylate, tridecanoloxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, tridecanoloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth)
Acrylate, tridecanoloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, tetradecanoloxypolyethylene glycol mono (meth) acrylate, tetradecanoloxy ｛polyethylene glycol (poly) propylene glycol｝ mono ( (Meth) acrylate, tetradecanoloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, tetradecanoloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, pentadecanoloxypolyethylene glycol mono (meta) ) Acrylate, pentadecanoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylic Over DOO, Pentadekanokishi {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, Pentadekanokishi {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Hexadecanoloxypolyethylene glycol mono (meth) acrylate, hexadecanoloxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, hexadecanoloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, Hexadecanoloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol メ タ mono (meth) acrylate, heptadecanoxy polyethylene glycol mono (meth) acrylate, heptadecanoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) Acrylate, heptadecanoloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate,
Heptadecanoloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, octadecanoxy polyethylene glycol mono (meth) acrylate, octadecanoxy （polyethylene glycol (poly) propylene glycol｝ mono (meth) Acrylates, octadecanoxy, polyethylene glycol (poly) butylene glycol, mono (meth) acrylate, and octadecanoxy, polyethylene glycol (poly) propylene glycol (poly) butylene glycol, mono (meth) acrylate.

Nonadecanoxy polyethylene glycol mono (meth) acrylate, nonadecananoloxy polyethylene glycol (poly) propylene glycol mono (meth) acrylate, nonadecanoxy polyethylene glycol (poly) butylene glycol mono (meth)
Acrylate, nonadecanoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, cyclopentoxypolyethylene glycol mono (meth) acrylate, cyclopentoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) Acrylate, cyclopentoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, cyclopentoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, cyclohexoxy polyethylene glycol mono (meth) acrylate ) Acrylate, cyclohexoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate , Cyclohexoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, cyclohexoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

The monomer mixture forming the polycarboxylic acid copolymer for cement additive in the present invention may further contain, if necessary, a monomer other than the above monomers (a), (b) and (c). Other monomers (d) may be included. The other monomer (d) is not particularly limited, and may be, for example, an unsaturated dicarboxylic acid-based monomer or an (alkoxy) polyalkylene glycol mono (meth) acrylate represented by the general formula (2). Other polyalkylene glycol ester-based monomers (unsaturated monocarboxylic acid polyalkylene glycol ester-based compounds), unsaturated alcohol polyalkylene glycol adducts, etc. These may be used alone or in combination of two or more.

Styrenes such as styrene, bromostyrene, chlorostyrene and methylstyrene; dienes such as 1,3-butadiene, isoprene and isobutylene; (meth)
Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate,
(Meth) acrylic esters such as hexyl (meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate; α-olefins such as hexene, heptene, and decene; methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether Alkyl vinyl ethers such as vinyl acetate; vinyl esters such as vinyl acetate; allyl esters such as allyl acetate.

Maleic acid, itaconic acid, citraconic acid,
Fumaric acid and the like, unsaturated dicarboxylic acids such as monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts, or anhydrides thereof; Half ester with alcohol,
Diester; the above-mentioned unsaturated dicarboxylic acids and C1 to C2
Half amides and diamides with amines 2; oxyalkylenes having 2 to 4 carbon atoms in these alcohols and amines;
A half ester of the alkyl polyalkylene glycol to which the unsaturated dicarboxylic acid is added,
Diester; the above unsaturated dicarboxylic acids and C2-4
Or a half ester or diester of a polyalkylene glycol having an average addition mole number of these glycols of 2 to 300; maleic acid and a glycol having 2 to 4 carbon atoms or an average addition mole number of these glycols of 2 to 30.
Half amide with polyalkylene glycol of 0; triethylene glycol di (meth) acrylate, (poly)
(Poly) alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate.

Bifunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate; triethylene glycol dimaleate and polyethylene glycol dimaleate (Poly) alkylene glycol dimaleates; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate , 3-
(Meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutylsulfonate, (meth) acrylamide methylsulfonic acid, (meth) acrylamide Unsaturated sulfonic acids such as ethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof;

Unsaturated amides such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; allyls such as allyl alcohol; dimethylaminoethyl ( Unsaturated amino compounds such as meth) acrylates; vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, and polyethylene glycol mono (meth) allyl ether.

(Meth) allyl alcohol alkylene oxide adduct, 3-buten-1-ol alkylene oxide adduct, isoprene alcohol (3-methyl-3-buten-1-ol) alkylene oxide adduct, 3-methyl-2 -Unsaturated alcohol polyalkylene glycol adducts such as butene-1-ol alkylene oxide adducts.

Phenoxy polyethylene glycol mono (meth) acrylate, phenoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, phenoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate,
Phenoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, (meth) allyloxy polyethylene glycol mono (meth) acrylate, (meth) allyloxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) ) Acrylate, (meth) allyloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, (meth) allyloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, etc. (Alkoxy) polyethylene glycol (poly) (carbon number) different from (alkoxy) polyalkylene glycol mono (meth) acrylate represented by (2) To 4 alkylene glycol)
(Meth) acrylic esters.

The polycarboxylic acid copolymer for cement additive in the present invention can be suitably used as a component of a cement admixture. The cement admixture is
It means an agent that can be mixed with a cement composition or the like, that is, an agent containing a cement additive or the like. The cement admixture containing the above-mentioned polycarboxylic acid copolymer for cement additive as a main component is one of preferred embodiments of the present invention.

The polycarboxylic acid copolymer for a cement additive in the present invention can be suitably used as a main component of a cement additive constituting a cement admixture. Will be described. The above cement additive can be used in addition to a cement composition such as a cement paste, mortar, concrete and the like. The cement composition is not particularly limited, and examples thereof include commonly used cement compositions including cement, water, fine aggregate, coarse aggregate and the like. Further, fine powders such as fly ash, blast furnace slag, silica fume, limestone and the like may be added.

The cement is not particularly limited, and includes, for example, portland cements such as ordinary, fast, super fast, moderate heat, and white; mixed portland cements such as alumina cement, fly ash cement, blast furnace cement, silica cement, and the like. Is mentioned. The amount of cement and the unit water amount per m ³ of concrete are not particularly limited. For example, in order to produce high-durability and high-strength concrete, the unit water amount is 80 to 185 kg / m ³ ,
It is preferable to set the water / cement ratio to 10 to 70%.
More preferably, the unit water amount is 100 to 175 kg / m ³ ,
Water / cement ratio = 10-65%.

The method and amount of the cement additive to be added to the cement composition are not particularly limited.
The amount of addition is preferably such that the polycarboxylic acid copolymer for cement additive in the present invention is 0.01 to 10% by weight based on 100% by weight of the total amount of cement. If the amount is less than 0.01% by weight, the performance may be insufficient. If the amount is more than 10% by weight, the economical efficiency is deteriorated. In addition, the said weight% is a value of solid content conversion.

The above cement additive can be used in combination with a commonly used cement dispersant. The cement dispersant is not particularly limited, and examples thereof include the following. Lignin sulfonate; polyol derivative;
Naphthalene sulfonic acid formalin condensate; Melamine sulfonic acid formalin condensate; Polystyrene sulfonate;
Aminosulfonic acids such as aminoarylsulfonic acid-phenol-formaldehyde condensate as described in JP-A-1-113419; and polyalkylene glycol mono () as component (a) as described in JP-A-7-267705. A copolymer of a (meth) acrylic ester compound and a (meth) acrylic compound and / or a salt thereof, and as a component (b), a polyalkylene glycol mono (meth) allyl ether compound and maleic anhydride A copolymer and / or a hydrolyzate thereof and / or a salt thereof, as a component (c), a polyalkylene glycol mono (meth) allyl ether-based compound and a maleic acid ester of the polyalkylene glycol-based compound Patent No. 2508113 Cement dispersant containing polymer and / or salt thereof As described in the specification, a component A is a copolymer of a polyalkylene glycol ester of (meth) acrylic acid and a (meth) acrylic acid (salt), and a component B is a specific polyethylene glycol polypropylene glycol-based compound and a component C As a concrete admixture comprising a specific surfactant;
No. 50, polyethylene (propylene) glycol ester of (meth) acrylic acid or polyethylene (propylene) glycol mono (meth) allyl ether, (meth) allylsulfonic acid (salt), and
Copolymer of (meth) acrylic acid (salt).

As described in JP-A 1-222657, polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allyl sulfonic acid (salt),
And a copolymer consisting of (meth) acrylic acid (salt); as described in JP-B-5-36377, polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt), and
Copolymer of (meth) acrylic acid (salt);
Copolymers of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) as described in JP-A-149056; polyethylene glycol esters of (meth) acrylic acid as described in JP-A-5-170501, (Meth) allylsulfonic acid (salt), (meth) acrylic acid (salt), alkanediol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, and α, β-unsaturated having an amide group in the molecule Copolymers composed of monomers; polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) acrylate, alkyl (meth) acrylate, (meth) acrylic acid as described in JP-A-6-191918 (Salt), and (meth) allylsulfonic acid (salt) or Copolymer of p- (meth) allyloxybenzenesulfonic acid (salt); JP-A-5-432
No. 88, a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride, or a hydrolyzate thereof, or a salt thereof; a polyethylene glycol monomer as described in JP-B-58-38380. Copolymers consisting of allyl ether, maleic acid, and monomers copolymerizable with these monomers, or salts or esters thereof.

As described in JP-B-59-18338, polyalkylene glycol mono (meth) acrylate monomers, (meth) acrylic monomers, and
Copolymers composed of monomers copolymerizable with these monomers; (meth) acrylic acid esters having a sulfonic acid group as described in JP-A-62-119147, and copolymerizable therewith if necessary. Copolymer consisting of various monomers or a salt thereof; a copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in JP-A-6-271347, and having an alkenyl group at a terminal Esterification reaction product with a polyoxyalkylene derivative; a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in JP-A-6-298555, and a polyoxyalkylene derivative having a hydroxyl group at a terminal. Esterification product of 3-methyl-3-butene-1- as described in JP-A-62-68806. Alkenyl ether-based monomer, unsaturated carboxylic acid-based monomer obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as alcohol, and a copolymer comprising a monomer copolymerizable with these monomers. Coalescing, or
Polycarboxylic acids (salts) such as salts thereof. These cement dispersants may be used alone or in combination of two or more.

When the above cement dispersant is used in combination,
Although it cannot be unambiguously determined depending on the type of cement dispersant used, the composition and the test conditions, the proportion of the compounding weight of the cement additive and the cement dispersant is 5 to 9%.
5: 95-5 is preferred. More preferably,
10-90: 90-10. Further, the above-mentioned cement additive can be used in combination with other cement additives. The other cement additives are not particularly limited, and include, for example, other known cement additives (materials) as shown below.

(1) Water-soluble polymer substance: Polymerization of unsaturated carboxylic acid such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), and sodium salt of acrylic acid / maleic acid copolymer object;
Polyoxyethylene or polyoxypropylene polymers such as polyethylene glycol and polypropylene glycol or copolymers thereof; methylcellulose,
Nonionic cellulose ethers such as ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, and hydroxypropylcellulose; yeast glucan, xanthan gum, β-1,3 glucans (either linear or branched) Polysaccharides produced by microbial fermentation such as curdlan, paramylon, bakiman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate; sodium alginate; gelatin; Acrylic acid copolymer having an amino group therein and a quaternary compound thereof.

(2) Polymer emulsion: copolymers of various vinyl monomers such as alkyl (meth) acrylate and the like. (3) retarders: gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and oxycarboxylic acids such as inorganic salts or organic salts such as sodium, potassium, calcium, magnesium, ammonium, and triethanolamine; Acids and salts thereof; monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose and isomerized sugars; oligosaccharides such as disaccharides and trisaccharides; oligosaccharides such as dextrins; Sugars, sugars such as molasses containing them;
Sugar alcohols such as sorbitol; magnesium silicofluoride;
Phosphoric acid and salts or borates thereof; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acids;
Tannic acid; phenol; polyhydric alcohols such as glycerin; aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and their alkalis Phosphonic acids such as metal salts and alkaline earth metal salts and derivatives thereof;

(4) Early strength agent / promoter: calcium chloride,
Calcium nitrite, calcium nitrate, calcium bromide,
Soluble calcium salts such as calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide;
Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate; (5) Mineral oil-based antifoaming agents: kerosene, liquid paraffin and the like. (6) Oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like. (7) Fatty acid antifoaming agents: oleic acid, stearic acid, alkylene oxide adducts thereof and the like. (8) Fatty acid ester antifoaming agents: glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

(9) Oxyalkylene-based antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct; diethylene glycol heptyl ether, polyoxyethylene oleyl ether;
(Poly) oxyalkyl ethers such as polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene 2-ethylhexyl ether, and oxyethylene oxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; polyoxypropylene phenyl ether, polyoxy (Poly) oxyalkylene (alkyl) aryl ethers such as ethylene nonylphenyl ether; 2,4,7,9-tetramethyl-5-decyne-
4,7-diol, 2,5-dimethyl-3-hexyne-
Acetylene ethers obtained by addition-polymerizing an alkylene oxide to acetylene alcohol such as 2,5-diol and 3-methyl-1-butyn-3-ol; diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate and the like. (Poly) oxyalkylene fatty acid esters;
(Poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxy such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecyl phenol ether sulfate Alkylene alkyl (aryl) ether sulfates; (poly)
(Poly) such as oxyethylene stearyl phosphate
Oxyalkylenealkyl phosphates; (poly) oxyalkylenealkylamines such as polyoxyethylene laurylamine; polyoxyalkyleneamides;

(10) Alcohol antifoaming agents: octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like. (11) Amide-based antifoaming agent: acrylate polyamine and the like. (12) Phosphate ester antifoam: tributyl phosphate,
Sodium octyl phosphate and the like. (13) Metal soap-based antifoaming agents: aluminum stearate, calcium oleate and the like. (14) silicone antifoaming agent: dimethyl silicone oil,
Silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.

(15) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzenesulfonic acid), LAS (linear alkylbenzenesulfonic acid),
Alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether sulfate or salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or salt thereof, protein material, alkenyl sulfosuccinic acid, α- Olefin sulfonates and the like.

(16) Other surfactants: 6 to 3 molecules per molecule such as octadecyl alcohol and stearyl alcohol.
Aliphatic monohydric alcohol having 0 carbon atoms, alicyclic monohydric alcohol having 6 to 30 carbon atoms in a molecule such as abiethyl alcohol, 6 to 30 carbon atoms in a molecule such as dodecyl mercaptan, etc. Monovalent mercaptans having atoms, nonylphenols and the like, alkylphenols having 6 to 30 carbon atoms in the molecule, dodecylamines and the like having 6 to 30 carbon atoms in the molecule, molecules such as lauric acid and stearic acid Polyalkylene oxide derivatives in which an alkylene oxide such as ethylene oxide or propylene oxide is added in an amount of 10 mol or more to a carboxylic acid having 6 to 30 carbon atoms therein; and may have an alkyl group or an alkoxyl group as a substituent. Alkyl diphenyl ether in which two phenyl groups having a sulfone group are ether-bonded Rusuruhon acid salts; various anionic surfactants; alkylamine acetates, various cationic surfactants such as alkyl trimethyl ammonium chloride; and various nonionic surfactants; various amphoteric surfactants.

(17) Waterproofing agent: fatty acid (salt), fatty acid ester, oil and fat, silicon, paraffin, asphalt,
Wax and the like. (18) Rust inhibitors: nitrites, phosphates, zinc oxide and the like. (19) Crack reducing agents: polyoxyalkyl ethers; alkanediols such as 2-methyl-2,4-pentanediol and the like. (20) Expansive materials: ettringite, coal, etc.

Other known cement additives (materials) include cement wetting agents, thickening agents, separation reducing agents, flocculants,
Drying shrinkage reducing agent, strength enhancer, self-leveling agent, rust inhibitor, color difference agent, fungicide, blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, gypsum, etc. be able to. These known cement additives (materials) may be used alone or in combination of two or more.

The above-mentioned cement additives may be used in combination with the above-mentioned known cement dispersants and cement additives (materials) in addition to those which improve the dispersibility, foam control and the like of the cement composition. The method for adding the cement additive or the cement dispersant to the cement composition is not particularly limited,
For example, it is preferable to mix these cement additives and cement dispersants to form a cement admixture to facilitate mixing into the cement composition.

The cement composition to which the above-mentioned cement admixture is added has excellent fluidity and fluidity retention, so that it has excellent water-reducing properties and workability, and has excellent cured product strength and durability. It will be. Therefore, the cement admixture containing the polycarboxylic acid copolymer for cement additive in the present invention can be suitably used for ultra-high-strength concrete, and exhibits a sufficient effect as a super-high-strength water reducing agent. Can be done.

[0079]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified,% means% by weight.

Production Example 1Combination of polyamine monomer (A)
Success  Gas equipped with thermometer, stirrer, nitrogen inlet tube and reflux condenser
600 g of diethylenetriamine,
730.9 g of pinic acid was charged and mixed by stirring under a nitrogen atmosphere.
Was. The temperature of the reaction mixture was raised to 150 ° C.
The reaction was carried out for 20 hours while removing accompanying reaction water. this
The amount of water generated during the reaction was 197.7 g. Next
1.7 g of hydroquinone methyl ether, methacrylic acid
70.1 g of phosphoric acid was charged and the reaction was continued at 150 ° C.
The reaction is carried out for 10 hours while removing the reaction product water, and the unsaturated bond
1189 g of a polyamide polyamine having the following formula: this
The reaction water generated during the period was 16 g. This insatiable
The total amount of the polyamide polyamine having a sum bond was converted to water 912.
Polyamide having unsaturated bonds dissolved in 4 g
2101.4 g of a min aqueous solution was obtained. This aqueous solution 201
Charge 3.4 g to autoclave and heat up to 50 ° C
And introduce 559.6 g of ethylene oxide over 2 hours
Then, aging was performed at 50 ° C. for 2 hours. This allows
2,573 g of amine type monomer (A) (solid content: 66.1%)
I got

Example 1 127 g of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, and charged under a nitrogen atmosphere.
The temperature was raised to 0 ° C. 30.3 g of the polyamine monomer (A) produced in the above production example, 20 g of methacrylic acid [unsaturated carboxylic acid monomer (B)], methoxypolyethylene glycol monomethacrylate [polyalkylene glycol monomer ( C): Average addition mole number of ethylene oxide 50] 60 g, a liquid mixture of 19.7 g of water, 40 g of a 5% aqueous solution of ammonium thioglycolate, and 40 g of a 5% aqueous solution of ammonium persulfate are placed in a reaction vessel for 2 hours. And dropped. After completion of the dropwise addition, 10 g of a 5% aqueous solution of ammonium persulfate was further added dropwise over 30 minutes, followed by aging for 2 hours to obtain a copolymer having a weight average molecular weight of 13,000. Table 1 shows the polymerization rates of the unsaturated carboxylic acid monomer (B) and the polyalkylene glycol monomer (C). The polymerization rate of each monomer is represented by {(weight of monomer consumed in polymerization) / (weight of charged monomer)} ×
It is a value calculated by 100.

Comparative Example 1 127 g of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser.
The temperature was raised to 0 ° C. 30.3 g of the polyamine-based monomer (A) produced in the above production example, 20 g of sodium methacrylate (a comparative unsaturated carboxylic acid-based monomer (B)), methoxypolyethylene glycol monomethacrylate (polyalkylene glycol-based) Monomer (C): a mixture of 60 g of ethylene oxide (average number of moles of added ethylene 50), 19.7 g of water, 40 g of a 5% aqueous solution of ammonium thioglycolate, and 40 g of a 5% aqueous solution of ammonium persulfate in a reaction vessel. For 2 hours. After completion of the dropping, 10 g of a 5% aqueous solution of ammonium persulfate was further added dropwise over 30 minutes, and then aged for 2 hours to obtain a weight average molecular weight of 10%.
000 copolymers were obtained. Table 1 shows the polymerization rates of the comparative unsaturated carboxylic acid monomer (B) and polyalkylene glycol monomer (C).

[0083]

[Table 1]

[0084]Mortar preparation method  Pacific ordinary Portland cement (trade name, Pacific Seme
400g) and 800g of Toyoura standard sand with mortar
Low speed rotation by Kisa (trade name: N-50, manufactured by Tesco Corporation)
Roll kneading for 30 seconds. Then, Example 1 or comparison
240 g of water containing the copolymer prepared in Example 1 was kneaded.
Into the mixture of cement and sand
The mortar was prepared by kneading for minutes. The copolymer is cement
The solid content weight% with respect to the weight of the
Was blended. In addition, in the preparation of each mortar
The mixing and kneading conditions with a mortar mixer are uniform
I tried to be.

[0085]Flow value  Six minutes after pouring the prepared mortar, on a stainless steel plate
Placed in a hollow cylindrical container with a diameter of 55 mm and a height of 50 mm
Stuffed. Then lift this hollow cylindrical container vertically
After the mortar spread on the stainless steel plate
Measured in two directions and averaged the flow value (mm)
And The larger the flow value, the higher the liquidity.
are doing. The results are shown in Table 2.

[0086]

[Table 2]

The copolymer prepared in Example 1 and the copolymer prepared in Comparative Example 1 were added in an amount of 0.3% by weight based on the weight of cement.
When the added mortar was prepared, the copolymer of Example 1 obtained a flow value of 110 mm, but the copolymer of Comparative Example 1 showed no flowability at 55 mm.

[0088]

As described above, the method for producing a polycarboxylic acid copolymer of the present invention has the above-mentioned constitution, and therefore, a cement admixture which can be suitably used for cement paste, mortar, concrete, etc., particularly, ultra-high strength concrete. It is possible to produce a polycarboxylic acid-based copolymer that can be used as a component of the agent at a high polymerization rate, thereby improving water reduction and workability, and improving the strength and durability of the cured product. The effect of the polycarboxylic acid-based copolymer that can be obtained can be sufficiently exhibited.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C04B 103: 60 C04B 103: 60 (72) Inventor Takeshi Kenda 5-8 Nishiminaburicho, Suita-shi, Osaka Stock Company N-catalyst F term (reference) 4J027 AC02 AC06 AD04 AJ02 BA06 CB02 CB03 CB05 CB09 CC02

Claims (2)

[Claims] 1. A process for copolymerizing a monomer mixture containing a (poly) amine monomer (A), an unsaturated carboxylic acid monomer (B) and a polyalkylene glycol monomer (C). A method for producing a polycarboxylic acid-based copolymer comprising the step of: (a) setting the neutralization rate of the unsaturated carboxylic acid-based monomer (B) to 0 to 60 mol% in the monomer mixture. A method for producing a polycarboxylic acid-based copolymer, comprising copolymerizing 2. 5 to 40% by weight of a polyamine monomer (a), 5 to 40% by weight of an unsaturated carboxylic acid monomer (b) and 20 to 90% of a polyalkylene glycol monomer (c).
A method for producing a polycarboxylic acid-based copolymer for a cement additive, comprising a step of copolymerizing a monomer mixture containing 1% by weight of the unsaturated carboxylic acid-based monomer. This is a step of copolymerizing the monomer mixture with the neutralization rate of (b) being 0 to 60 mol%, and the polyamine-based monomer (a) is a dibasic compound based on 1.0 mol of the polyalkylene polyamine. 0.5-1.0 mol of an ester of an acid and / or a dibasic acid and an alcohol having 1 to 4 carbon atoms, and (meth) acrylic acid and / or (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms 0 to 300 mol of an alkylene oxide having 2 to 18 carbon atoms per 1 mol of a total of amino groups and imino groups of a polyamide polyamine having an unsaturated bond obtained by reacting 0.01 to 0.5 mol of an ester with Poly added A bromide polyamine compound, the unsaturated carboxylic acid monomer (b) represented by the following general formula (1): ## STR1 ## (Wherein, R represents a hydrogen atom or a methyl group; M represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group), and the polyalkylene glycol monomer (C) is a compound represented by the following general formula (2): (Wherein, R ¹ represents a hydrogen atom or a methyl group. R ^X
Represents the same or different and represents an alkylene group having 2 to 18 carbon atoms. R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. m represents an average number of added moles of the oxyalkylene group represented by R ^X O, and is a number of 1 to 300. )
A method for producing a polycarboxylic acid copolymer for cement additives, which is a (alkoxy) polyalkylene glycol mono (meth) acrylate represented by the formula: