WO2019221002A1 - (poly)alkylene glycol-containing copolymer - Google Patents

Abstract

The purpose of the present invention is to provide a (poly)alkylene glycol-containing copolymer exhibiting sufficiently suppressed separation in a copolymer solution and having excellent storage stability. The present invention pertains to a (poly)alkylene glycol chain-containing copolymer having structural unit (a) derived from (poly)alkylene glycol-containing monomer (A) represented by formula (1) below, and structural unit (b) derived from hydrophobic monomer (B), wherein the hydrophobic monomer (B) has an ethylenically unsaturated group, and has an octanol/water partition coefficient (Log P value) of 1.0-8.0. In a chromatogram of the copolymer as measured by a differential refractive index detector for gel permeation chromatography (GPC), the areas of peak α and peak β defined below satisfy equation (2) below. (2): α×100/(α+β)≤3.0 <peaks α and β> peak α: a peak corresponding to a weight average molecular weight (Mw) of greater than 200000. peak β: a peak corresponding to a Mw of 200000 or less.

Description

(Poly) alkylene glycol-containing copolymer

The present invention relates to a (poly) alkylene glycol-containing copolymer. More specifically, the present invention relates to a (poly) alkylene glycol-containing copolymer useful for applications such as a dispersant and a cement admixture.

A polymer containing a (poly) alkylene glycol chain (hereinafter, also referred to as a (poly) alkylene glycol polymer) has a hydrophilicity, hydrophobicity, flexibility, etc. by appropriately adjusting the chain length and the alkylene oxide constituting the polymer. Since characteristics such as steric repulsion are imparted, it is used in cement admixture applications added to cement compositions such as cement paste, mortar, and concrete. Such a cement admixture is usually used as a water reducing agent or the like, and exerts an effect of improving the strength and durability of the cured product by reducing the cement composition by increasing the fluidity of the cement composition. Used for that purpose. As a water reducing agent, a water reducing agent such as naphthalene type has been conventionally used. However, since a (poly) alkylene glycol chain can act as a dispersing group for dispersing cement particles due to its steric repulsion, (poly) alkylene A polycarboxylic acid-based water reducing agent containing a glycol chain has been proposed as exhibiting a high water reducing action, and has recently been used as a high-performance AE water reducing agent.

Regarding a conventional polycarboxylic acid polymer containing a (poly) alkylene glycol chain, for example, Patent Document 1 discloses a cement dispersant mainly composed of a polycarboxylic acid polymer (A) or a salt thereof. The weight average molecular weight of the polymer (A) is in the range of 10,000 to 500,000 in terms of polyethylene glycol by gel permeation chromatography, and the value obtained by subtracting the peak top molecular weight from the weight average molecular weight is 0. A cement dispersant characterized by ˜8,000 is disclosed.
Patent Documents 2 to 5 also disclose polycarboxylic acid polymers containing a (poly) alkylene glycol chain.

In addition, a technique for improving cement dispersibility by introducing a hydrophobic group into a polycarboxylic acid polymer containing a (poly) alkylene glycol chain has been developed. For example, Patent Document 6 discloses a polymer (A ) And polymer (B) as an essential component, a cement admixture, wherein the polymer (A) and the polymer (B) are unsaturated ( The structural unit (I) derived from the poly) alkylene glycol ether monomer (a) and the structural unit derived from the unsaturated carboxylic acid monomer (b) having a carboxyl group and / or a salt thereof as an adsorbing group (II) ) As an essential structural unit, and the polymer (A) further includes, as an essential structural unit, a structural unit (III) derived from an unsaturated carboxylic acid ester monomer (c) having a hydrophobic group. Including, absorption per molecule of polymer The number of groups is 1 or more and less than 16, and the number of hydrophobic groups per molecule of the polymer is 1 or more and less than 20, and the polymer (B) has 16 adsorbing groups per molecule of the polymer. A cement admixture characterized in that the ratio (mass%) of the polymer (A) and the polymer (B) in the cement admixture is 40 to 99/60 to 1 in the cement admixture. Has been.

JP-A-9-86990 JP 2011-195842 A JP 2003-206169 A JP 2006-282864 A JP 2007-270072 A JP 2012-067011 A

As described above, various (poly) alkylene glycol-based polymers have been developed conventionally, and structural units derived from conventional (poly) alkylene glycol-based monomers and structural units derived from hydrophobic monomers There is a problem in that the copolymer having a poor stability and separation occurs during the reaction or storage.

This invention is made | formed in view of the said present condition, and it aims at providing the (poly) alkylene glycol containing copolymer by which separation is fully suppressed in a copolymer solution and excellent in storage stability.

The inventor conducted various studies on copolymers having a structural unit derived from a (poly) alkylene glycol monomer and a structural unit derived from a hydrophobic monomer. As a result, the ratio of the high molecular weight in the copolymer was determined. As a result of the reduction, it was found that the separation in the copolymer solution was sufficiently suppressed and the storage stability was excellent, and it was conceived that the above problems could be solved brilliantly, and the present invention has been achieved.

That is, the present invention is a copolymer containing a (poly) alkylene glycol chain, wherein the copolymer is represented by the following formula (1);

(In the formula, R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (AO) are the same or different and each represents an oxyalkylene group, n represents the average number of moles added of the oxyalkylene group, and is a number from 1 to 300. y represents a number from 0 to 4. z Represents a structural unit (a) derived from the (poly) alkylene glycol-containing monomer (A) and a structural unit (b) derived from the hydrophobic monomer (B). The hydrophobic monomer (B) has an ethylenically unsaturated group and has an octanol / water partition coefficient value (Log P value) of 1.0 to 8.0; Gel Permeation Chromatography (GPC) Differential Refractive Index Detector Chromatography In the ram, a (poly) alkylene glycol-containing copolymer satisfying the following formula (2), the areas of the peak α and the peak β defined below.
α × 100 / (α + β) ≦ 3.0 (2)
<Peak α and β>
Peak α: A peak having a weight average molecular weight (Mw) larger than 200,000.
Peak β: A peak having Mw of 200,000 or less.

The hydrophobic monomer (B) is an ester of an unsaturated carboxylic acid and an alcohol, an aromatic vinyl monomer, an olefin monomer, a (meth) acrylamide monomer, or a maleimide monomer. And at least one selected from the group consisting of esters of unsaturated alcohols and carboxylic acids.

The (poly) alkylene glycol-containing copolymer preferably has a structural unit (c) derived from an unsaturated carboxylic acid monomer (C).
In the (poly) alkylene glycol-containing monomer (A), z in the formula (1) is preferably 0.

The proportion of the structural unit (a) is preferably 50% by mass to 99% by mass with respect to 100% by mass of all structural units.

The proportion of the structural unit (b) is preferably 1% by mass to 30% by mass with respect to 100% by mass of all structural units.

The proportion of the structural unit (c) is preferably 0% by mass to 30% by mass with respect to 100% by mass of all structural units.

The (poly) alkylene glycol-containing copolymer includes other (poly) alkylene glycol-containing monomer (A), hydrophobic monomer (B), and unsaturated carboxylic acid monomer (C). The structural unit (e) derived from the monomer (E) may be included, and the proportion of the structural unit (e) is 0% by mass or more and 30% by mass or less with respect to 100% by mass of all the structural units. It is preferable.

The present invention is also a cement admixture containing the (poly) alkylene glycol-containing copolymer.

The present invention is also a cement composition comprising the (poly) alkylene glycol-containing copolymer and cement.

The present invention is further a method for producing a cement composition, wherein the production method is also a method for producing a cement composition including a step of adding the (poly) alkylene glycol-containing copolymer to a hydraulic material.

Although the preferable form of this invention is demonstrated concretely below, this invention is not limited only to the following description, In the range which does not change the summary of this invention, it can change suitably and can apply. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more also corresponds to the preferable form of this invention.

The (poly) alkylene glycol-containing copolymer of the present invention has the above-described structure, and is sufficiently suppressed in the copolymer solution and excellent in storage stability. Therefore, it can be suitably used as a cement admixture or the like. .

It is the conceptual diagram which showed the peak detected with the differential refractive index detector of GPC about the copolymer obtained in Example 3. FIG.

≪ (Poly) alkylene glycol-containing copolymer≫
The (poly) alkylene glycol-containing copolymer of the present invention (hereinafter also referred to as the copolymer of the present invention) is a gel-permeation chromatography (GPC) differential refractive index detector measured for the copolymer. In the chromatogram, the areas of peak α and peak β defined below satisfy the following formula (2).
α × 100 / (α + β) ≦ 3.0 (2)
<Peak α and β>
Peak α: A peak having a weight average molecular weight (Mw) larger than 200,000.
Peak β: A peak having Mw of 200,000 or less.
In the copolymer, by reducing the proportion of the high molecular weight substance having Mw greater than 200,000 corresponding to the peak α, separation can be sufficiently suppressed in the copolymer and its solution. By suppressing separation in the copolymer solution, the separated product can be prevented from adhering to and contaminating the reactor and the storage container. Further, in the copolymer and its solution, it is possible to suppress the occurrence of non-uniform concentration, and to fully exhibit desired performance during use.
The high molecular weight product has a relatively high content of structural units derived from the hydrophobic monomer (B) and / or the unsaturated carboxylic acid monomer (C), and the (poly) alkylene glycol-containing monomer ( It is estimated that the content of the structural unit derived from A) is a (co) polymer having a relatively low content. This is because the UV / RI ratio (value obtained by dividing the UV chromatogram area by the RI chromatogram area) for the peak α and the peak β detected by GPC is larger. It is suggested from becoming.
When the ratio of the high molecular weight corresponding to the peak α increases in the entire copolymer, not only the separation occurs in the copolymer solution, but also the hydrophobicity of the copolymer having an Mw corresponding to the peak β of 200,000 or less. Since the content of the structural unit derived from the polymerizable monomer (B) (and optionally the unsaturated carboxylic acid monomer (C)) is decreased, the desired performance may not be sufficiently exhibited.
On the other hand, since the copolymer of the present invention has a small proportion of such a high molecular weight, it is presumed that the composition ratio of the constituent units in the copolymer is relatively uniform regardless of Mw. . Thus, the copolymer of this invention will be excellent also in the performance at the time of using for a cement composition etc. because the composition of a copolymer is uniform.

The measurement conditions of GPC of the copolymer are as follows.
<GPC analysis conditions>
Device: Waters Alliance (2695)
Analysis software: Waters, Empor2 Professional + GPC option column: Tosoh Co., Ltd., TSKguardcolumns SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL
Detector: differential refractive index (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: A solution prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and adjusting the pH to 6.0 with acetic acid.
Standard substance for preparing calibration curve: polyethylene glycol (peak top molecular weight (Mp) 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470)
Calibration curve: Prepared by a cubic equation based on the Mp value and elution time of the standard.
Flow rate: 1 mL / min Column temperature: 40 ° C
Measurement time: 45 minutes Standard substance sample solution injection amount: 100 μL (eluent solution with polymer concentration of 0.1% by mass)
Polymer sample solution injection amount: 100 μL (eluent solution having a polymer concentration of 0.5% by mass)

<GPC analysis conditions (analysis of polymer)>
The peaks α and β are defined as follows.
In the chromatogram of the differential refractive index detector of GPC measured for the above copolymer, the weight average molecular weight (Mw) of each peak obtained was determined, and the peak with Mw greater than 200,000 was defined as α, and Mw was 20 A peak of 10,000 or less is defined as β.
The peak β is a peak whose Mw is 200,000 or less among peaks that can be analyzed in the chromatogram.
There may be a plurality of peaks α and β, but the molecular weight and area are calculated together.
When the peaks α and β are detected without overlapping completely, the peaks α and β are separated by vertical division at the most concave portion (lowest point) between the peaks. When the lowest point continues in the most concave portion, the peak is vertically divided at the intermediate point.
In addition, immediately before and after elution of the polymer in the chromatogram, the flat and stable portions are connected with a straight line to form a baseline.

The peak areas of the peaks α and β are defined as follows.
(I) When the peak belonging to the peak α is completely separated from the peak belonging to the peak β, the area of the peak α is an area surrounded by the curve of the peak belonging to the peak α and the baseline. In the above case, the area of the peak β is an area surrounded by the curve of the peak belonging to the peak β and the baseline.
(Ii) When the peak belonging to the peak α does not completely separate from the peak belonging to the peak β and overlaps, the peak is separated by vertically dividing at the most concave portion (lowest point) between the peaks α and β. The area of α is an area surrounded by a peak curve belonging to the peak α, a base line, and a perpendicular line extending from the concave portion to the base line. In the above case, the area of the peak β is an area surrounded by a peak curve belonging to the peak β, a base line, and a perpendicular line extending from the most concave portion to the base line. In addition, when the lowest point continues in the said most recessed part, a peak is isolate | separated in the intermediate point.
When there are a plurality of peaks belonging to the peaks α and β, the total area of the plurality of peaks is the area of the peaks α and β.

The area of the peak α and the peak β may be any as long as the above formula (2) is satisfied, but α × 100 / (α + β) is preferably 2.5 or less, more preferably 2.0 or less. More preferably 1.5 or less, even more preferably 1.0 or less, and particularly preferably 0.5 or less.
Moreover, the peak α (a peak having Mw of 200,000 or more) may not be detected. When the peak α is not detected (below the qualitative limit), the above equation (2) becomes α × 100 / (α + β) = 0.0. The case of α × 100 / (α + β) = 0.0 is also one of the preferred embodiments of the present invention.

The copolymer of the present invention comprises a structural unit (a) derived from the (poly) alkylene glycol-containing monomer (A) represented by the above formula (1) and a structural unit derived from the hydrophobic monomer (B) ( b), each of which may be one type or two or more types.
The proportion of the structural unit (a) in the copolymer of the present invention is sufficient to exhibit performances such as hydrophilicity, compatibility, and dispersion force derived from the structural unit (a). It is preferable that it is 50 mass% or more. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more, Most preferably, it is 80 mass% or more. Moreover, in order to fully exhibit the performance derived from another structural unit, it is preferable that it is 99 mass% or less with respect to 100 mass% of all the structural units. More preferably, it is 97 mass% or less, More preferably, it is 95 mass% or less, More preferably, it is 90 mass% or less, Most preferably, it is 85 mass% or less.

The proportion of the structural unit (b) in the copolymer of the present invention is sufficient to exhibit performances such as hydrophobicity, compatibility, and surface activity derived from the structural unit (b). And preferably 1% by mass or more. More preferably, it is 3 mass% or more, More preferably, it is 5 mass% or more, Still more preferably, it is 7.5 mass% or more, Most preferably, it is 10 mass% or more. Further, in order to reduce the proportion of the high molecular weight substance, more sufficiently suppress the separation in the copolymer solution, and sufficiently exhibit the performance derived from other structural units, 30% with respect to 100% by mass of all structural units It is preferable that it is below mass%. More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less, Most preferably, it is 12.5 mass% or less.

The proportion of the structural unit (c) in the copolymer of the present invention may be 0% by mass or more with respect to 100% by mass of all the structural units. In order to sufficiently exhibit performance such as activity, the content is preferably 1% by mass or more with respect to 100% by mass of all structural units. More preferably, it is 3 mass% or more, More preferably, it is 5 mass% or more, Still more preferably, it is 7.5 mass% or more, Most preferably, it is 10 mass% or more. Moreover, in order to fully exhibit the performance derived from another structural unit, it is preferable that it is 30 mass% or less with respect to 100 mass% of all the structural units. More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less, Most preferably, it is 12.5 mass% or less.
In the calculation of the proportion of the structural unit (c) in the copolymer of the present invention, the mass of the structural unit (c) is calculated as the corresponding sodium salt type structural unit. For example, if the structure is derived from (meth) acrylic acid, the mass ratio is calculated as a structure derived from sodium (meth) acrylate, and if the structure is derived from maleic acid, the structure is derived from disodium maleate.

The copolymer of the present invention comprises other monomers (other than the above (poly) alkylene glycol-containing monomer (A), hydrophobic monomer (B) and unsaturated carboxylic acid monomer (C)). You may have the structural unit (e) derived from E).
The proportion of the structural unit (e) in the copolymer of the present invention may be 0% by mass or more with respect to 100% by mass of all the structural units, but sufficiently exhibits the performance derived from the structural unit (e). It is preferable that it is 1 mass% or more. More preferably, it is 2.5 mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 7.5 mass% or more, Most preferably, it is 10 mass% or more. Moreover, in order to fully exhibit the performance derived from another structural unit, it is preferable that it is 30 mass% or less with respect to 100 mass% of all the structural units. More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less, Most preferably, it is 12.5 mass% or less.

The copolymer of the present invention preferably has a weight average molecular weight of 5,000 to 200,000. In order to sufficiently exhibit the performance of the copolymer, it is more preferably 7,000 or more, still more preferably 10,000 or more, still more preferably 15,000 or more, and particularly preferably 20,000 or more. It is. In order to more sufficiently suppress the separation in the copolymer solution, it is more preferably 150,000 or less, still more preferably 100,000 or less, even more preferably 70,000 or less, and particularly preferably 50. , 000 or less.
The weight average molecular weight of a copolymer can be measured by the method as described in an Example.

<(Poly) alkylene glycol-containing monomer (A)>
In the above formula (1), R ¹ to R ³ are the same or different and each represents a hydrogen atom or a methyl group. Preferably, R ¹ and R ² are hydrogen atoms, and R ³ is a hydrogen atom or a methyl group. More preferably, R ¹ and R ² are hydrogen atoms and R ³ is a methyl group.

In the above formula (1), AO represents “the same or different,” and represents an oxyalkylene group having 2 to 18 carbon atoms, which is the same for all oxyalkylene groups of AO present in n in polyalkylene glycol. Means that it may be different.
In the above formula (1), the oxyalkylene group represented by AO is an alkylene oxide adduct, and examples of such alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2- Examples thereof include alkylene oxides having 2 to 8 carbon atoms such as butene oxide, styrene oxide, glycidol and epichlorohydrin. More preferred are alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and still more preferred are ethylene oxide and propylene oxide.
Further, when the polyalkylene glycol is any two or more alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., any of random addition, block addition, alternating addition, etc. Form may be sufficient.
In the above formula (1), the oxyalkylene group represented by AO is preferably selected as appropriate according to the use required for the copolymer of the present invention, but in order to ensure a balance between hydrophilicity and hydrophobicity. The oxyalkylene group in the polyalkylene glycol preferably has an oxyethylene group as an essential component, more preferably 50 mol% or more is an oxyethylene group, and 90 mol% or more is an oxyethylene group. Further preferred.

In the above formula (1), n represents an average addition mole number of the oxyalkylene group and is 1 to 300. From the viewpoint of sufficiently exerting the performance derived from the oxyalkylene group, it is preferably 2 or more, more preferably 10 or more, still more preferably 25 or more, particularly preferably 30 or more, and still more preferably 50. That's it. On the other hand, if it exceeds 300, the viscosity becomes too high during production and use, and workability may not be sufficient. Preferably it is 200 or less, More preferably, it is 150 or less, More preferably, it is 100 or less, Most preferably, it is 75 or less.

R ⁴ in the above formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Preferred is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferred is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and still more preferred is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Particularly preferred is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and most preferred is a methyl group or a hydrogen atom.

Examples of the hydrocarbon group include methyl, ethyl, n-propyl, n-butyl, n-pentyl (amyl), n-hexyl, n-heptyl, n-octyl, and n-nonyl. Group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group Group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2 Ethyl-2-methylpropyl, 1-methylheptyl, 2-ethylhexyl, 1,5-dimethylhexyl, t-octyl, branched nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl Group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, icosyl group and other aliphatic alkyl groups; cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, An alicyclic alkyl group such as a cycloheptyl group, a cyclooctyl group, a cyclohexylpropyl group, a cyclododecyl group, a norbornyl group (C7), an adamantyl group (C10), a cyclopentylethyl group; the alkenyl group includes, for example, a vinyl group, Allyl group, -Butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, alkenyl group such as dodecenyl group, octadecenyl group, icocenyl group; phenyl group, benzyl group, phenethyl group, o -, M- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, benzhydryl group, trityl group, pyrenyl group and other aryl groups, etc. Is mentioned. Among these, a linear, branched or cyclic alkyl group and a phenyl group are preferable.

In the above formula (1), y represents a number from 0 to 2, and z represents 0 or 1. When z is 0, y is preferably 1 or 2.
When z is 1, y is preferably 0.
z is preferably 0. In this case, y is preferably 1 or 2, and more preferably y is 2.

Specific examples of the monomer (A) include (poly) alkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate, and alkoxy-modified alkoxy groups having 1 to 30 carbon atoms at the ends thereof ( Poly) alkylene glycol (meth) acrylate; vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-butene Compounds obtained by adding 1 to 300 moles of alkylene oxide to unsaturated alcohols having 2 to 8 carbon atoms such as -1-ol, 2-methyl-2-buten-1-ol, and 3-allyloxy-1,2-propanediol And compounds in which these ends are hydrophobically modified with a hydrocarbon group having 1 to 30 carbon atoms. Among these, a compound obtained by adding 1 to 300 moles of alkylene oxide to an unsaturated alcohol having 2 to 8 carbon atoms and a compound obtained by hydrophobically modifying these terminals with a hydrocarbon group having 1 to 30 carbon atoms are preferable. More preferred is a compound obtained by adding 1 to 300 moles of an alkylene oxide to an unsaturated alcohol having 2 to 8 carbon atoms, and further preferred is adding an alkylene oxide to methallyl alcohol or 3-methyl-3-buten-1-ol. It has been made.

<Hydrophobic monomer (B)>
The hydrophobic monomer (B) has an ethylenically unsaturated group and has an octanol / water partition coefficient value (Log P value) of 1.0 to 8.0. Since the copolymer of the present invention has such a structural unit (b) derived from the hydrophobic monomer (B), it is compatible with a hydrophobic substance by a hydrophobic interaction, and is inorganic by a surface active action. Various excellent performances such as reducing the viscosity of the powder slurry will be exhibited.
Note that the (poly) alkylene glycol-containing monomer (A) and the unsaturated carboxylic acid monomer (C) described later can be used even if the Log P value is in the range of 1.0 to 8.0. It shall be classified into the monomer (A) or (C).
The Log P value is described in, for example, ChemBioDraw Ultra ver. It can be calculated using the software of No. 14 (Kabumoto Cambridge Software).
The Log P value is more preferably 1.3 or more, still more preferably 1.5 or more, still more preferably 1.85 or more, particularly preferably from the viewpoint of sufficiently exhibiting hydrophobicity. 2 or more. Moreover, when it exceeds 8, there exists a possibility that the isolation | separation in a copolymer solution cannot fully be suppressed at the time of manufacture and a storage. More preferably, it is 6 or less, More preferably, it is 4 or less, Even more preferably, it is 3 or less, Most preferably, it is 2.5 or less.

The hydrophobic monomer (B) is not particularly limited as long as the Log P value is 1.0 to 8.0, but examples thereof include esters of unsaturated carboxylic acids and alcohols, aromatic vinyl monomers, olefins. And amides of unsaturated carboxylic acids and amines, maleimide monomers and esters of unsaturated alcohols and carboxylic acids.

As the ester of the unsaturated carboxylic acid and the alcohol, for example, an ester of an unsaturated carboxylic acid monomer (C) described later and an alcohol having 2 to 18 carbon atoms is preferable.
Examples of the alcohol having 2 to 18 carbon atoms include ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, lauryl alcohol, stearyl alcohol and other alkyl alcohols; Alcohol; unsaturated alcohols such as allyl alcohol, methallyl alcohol, propargyl alcohol, crotyl alcohol, pentenol, hexenol, heptenol, octenol, nonenol, decenol, dodecenol, octadecenol and the like.
The alcohol preferably has 3 to 16 carbon atoms, more preferably 4 to 12, still more preferably 4 to 8, and particularly preferably 4 to 6.
The alcohol is preferably an alkyl alcohol.

As said unsaturated carboxylic acid, the thing similar to the specific example of the unsaturated carboxylic acid-type monomer (C) mentioned later is mentioned. As the unsaturated carboxylic acid, (meth) acrylic acid and maleic acid are preferable.
Examples of the esters of unsaturated carboxylic acid and alcohol include (meth) acrylic acid alkyl ester (alkyl (meth) acrylate) having an alkyl group having 2 to 18 carbon atoms, maleic having an alkyl group having 4 to 20 carbon atoms. Acid monoalkyl esters (monoalkyl malates) and maleic acid dialkyl esters (dialkyl malates) having two alkyl groups with a total carbon number of 4 to 20 are preferred.

Specific examples of the alkyl group include the above-mentioned aliphatic alkyl groups and alicyclic alkyl groups.
The number of carbon atoms of the alkyl group of the alkyl (meth) acrylate is more preferably 3 to 16, further preferably 4 to 12, still more preferably 4 to 8, and particularly preferably 4 to 6.
The number of carbon atoms of the alkyl group of the monoalkyl malate and the total number of carbon atoms of the two alkyl groups of the dialkyl malate are more preferably 5 to 16, and further preferably 6 to 12. More preferably, it is 6 to 10, particularly preferably 6 to 8.

Specific examples of the alkyl (meth) acrylate include ethyl methacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth). Acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( (Meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl acrylate, etc. It is.

Specific examples of the (mono, di) alkyl malate include dipropyl malate, (mono, di) n-butyl malate, (mono, di) isobutyl malate, (mono, di) tert-butyl malate, (mono, Examples thereof include di) sec-butyl malate, (mono, di) 2-ethylhexyl malate, (mono, di) octyl malate, (mono, di) decyl malate, monolauryl malate, monostearyl malate and the like.

Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, methoxy styrene, 2,4-dimethyl styrene, 4-ethyl styrene, 4-isopropyl styrene, 4-butyl styrene, 4- Examples include phenylstyrene, 4-cyclohexylstyrene, 4-benzylstyrene, 4-crotylbenzene, 2-vinylnaphthalene. Styrene, vinyltoluene and α-methylstyrene are preferred.

Specific examples of the olefin monomers include ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene and other alkenes having 2 to 16 carbon atoms; butadiene, isoprene, 1,4- Examples thereof include alkadienes having 4 to 19 carbon atoms such as pentadiene, 1,6-heptadiene, and 1,7-octadiene.

As the amide of an unsaturated carboxylic acid and an amine, an amide of an unsaturated carboxylic acid monomer (C) described later and an amine having 4 to 20 carbon atoms is preferable.
Examples of the amine include methylamine, ethylamine, (iso) propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, heptylamine, diheptylamine, octyl Examples thereof include amines having 1 to 20 carbon atoms such as amine, dioctylamine and dodecylamine.
As the unsaturated carboxylic acid, (meth) acrylic acid is preferable. That is, as the amide of unsaturated carboxylic acid and amine, a (meth) acrylamide monomer is preferable.

Specific examples of the (meth) acrylamide monomer include N-monosubstituted (meth) acrylamides in which the hydrogen atom of the amino group of (meth) acrylamide is substituted with a hydrocarbon group having 4 to 20 carbon atoms, N, N-disubstituted (meth) acrylamide is mentioned.
As said hydrocarbon group, the above-mentioned alkyl group; alkenyl group; aryl group etc. are mentioned.

As the (meth) acrylamide monomer, N-alkyl (meth) acrylamide and N, N-dialkyl (meth) acrylamide are preferable.
Specific examples of the alkyl group that the (meth) acrylamide monomer has are as described above.
The number of carbon atoms of the alkyl group of the N-alkyl substituent of (meth) acrylamide is more preferably 5 to 16, more preferably 6 to 6 as the total number of carbon atoms of two alkyl groups. 12, more preferably 6 to 10, and particularly preferably 6 to 8.

As the (meth) acrylamide monomer, Nn-propylmethacrylamide, N-butyl (meth) acrylamide, N-pentyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-octadecyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-phenylmethyl acrylamide, N-cyclohexyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N, N-dinonyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide and the like are preferable.

Specific examples of the maleimide monomer include N-substituted maleimide in which the hydrogen atom of the amino group of maleimide is substituted with a hydrocarbon group having 1 to 16 carbon atoms. Examples of the hydrocarbon group include an alkyl group; an alkenyl group; an aryl group, and specific examples thereof are as described above.
Examples of the maleimide monomer include N-heptylmaleimide, N-octylmaleimide, N-dodecylmaleimide (N-laurylmaleimide), N-hexadecylmaleimide, N-octadecylmaleimide (N-stearylmaleimide) and the like N- Preferred are alkyl-substituted maleimides; N-aryl-maleimides such as N-phenylmaleimide, N-methylphenylmaleimide, N-ethylphenylmaleimide, N-butylphenylmaleimide, and N-dimethylphenylmaleimide.

The number of carbon atoms of the hydrocarbon group in the N-alkyl-substituted maleimide is more preferably 5 to 16, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6 to 8.

As the ester of the unsaturated alcohol and the carboxylic acid, for example, the ester of the unsaturated alcohol having 2 to 8 carbon atoms and the carboxylic acid having 2 to 16 carbon atoms described in the monomer (A) is preferable. Examples of the carboxylic acid having 2 to 16 carbon atoms include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, and palmitic acid.
Specific examples of the esters of unsaturated alcohols and carboxylic acids include vinyl propionate, vinyl butyrate, vinyl caprylate, vinyl palmitate; 2-methylallyl propionate, 2-methylallyl butyrate, 2-methylallyl caprylate, palmitate 2-methylallyl acid; 3-methyl-3-buten-1-yl acetate, 3-methyl-3-buten-1-yl propionate, 3-methyl-3-buten-1-yl butyrate, 3-methyl caprylate -3-buten-1-yl, 3-methyl-3-buten-1-yl palmitate and the like.
The number of carbon atoms of the carboxylic acid is more preferably 3 to 14, still more preferably 4 to 12, still more preferably 5 to 10, and particularly preferably 6 to 8.

The hydrophobic monomer (B) is preferably an ester of an unsaturated carboxylic acid and an alcohol, an aromatic vinyl monomer, an olefin monomer, a (meth) acrylamide monomer, or a maleimide monomer. And esters of unsaturated alcohols and carboxylic acids, more preferably esters of unsaturated carboxylic acids and alcohols, aromatic vinyl monomers, and olefin monomers, and more preferably Esters of saturated carboxylic acids and alcohols and aromatic vinyl monomers are preferred, and esters of unsaturated carboxylic acids and alcohols are particularly preferred.

<Unsaturated carboxylic acid monomer (C)>
The copolymer of the present invention preferably has a structural unit (c) derived from an unsaturated carboxylic acid monomer (C). As the unsaturated carboxylic acid monomer (C), an unsaturated monocarboxylic acid monomer or an unsaturated dicarboxylic acid monomer is suitable, and as the unsaturated monocarboxylic acid monomer, Any monomer may be used as long as it has one unsaturated group and one group capable of forming a carbanion in the molecule. For example, (meth) acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl Methyl-2-pentenoic acid, itaconic acid, etc .; these monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts are preferred. The unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule. Maleic acid, itaconic acid, mesaconic acid, Citraconic acid, fumaric acid, etc., their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc., their anhydrides or half esters are preferred.
As the unsaturated carboxylic acid monomer (C), (meth) acrylic acid, maleic acid and salts thereof are preferable. More preferred is (meth) acrylic acid, and even more preferred is acrylic acid.

<Other monomer (E)>
The copolymer of the present invention comprises other monomers (other than the above (poly) alkylene glycol-containing monomer (A), hydrophobic monomer (B) and unsaturated carboxylic acid monomer (C)). You may have the structural unit (e) derived from E).
Specific examples of the other monomer (E) will be given below. These are all those having the Log P value of less than 1 or greater than 8.
Esters of unsaturated (mono, di) carboxylic acids and alcohols such as methyl (meth) acrylate, methoxyethyl (meth) acrylate, monopropyl malate, diethyl malate; hydroxyethyl (meth) acrylate, hydroxyprotyl ( Esters of unsaturated (mono, di) carboxylic acids such as meth) acrylates and diols; amides of unsaturated carboxylic acids such as methyl (meth) acrylamide and diethylacrylamide and amines; N-methylmaleimide; Maleimide monomers such as N-ethylmaleimide; vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl- Such as 3-buten-1-ol and 2-methyl-2-buten-1-ol Japanese alcohols; Diesters of alkyl (poly) alkylene glycols and unsaturated dicarboxylic acids obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to alcohols or amines; Unsaturated dicarboxylic acids and 2 to 2 carbon atoms 18 glycols or polyalkylene glycols and diesters having 2 to 500 addition moles of these glycols; (poly) alkylene glycols such as (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di (meth) acrylate Di (meth) acrylates; polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate; (poly) alkylene glycol dimaleates such as polyethylene glycol dimaleate ; Unsaturated sulfonic acids (salts) such as vinyl sulfonate, (meth) allyl sulfonate, 2-methylpropane sulfonic acid (meth) acrylamide and styrene sulfonic acid; unsaturated cyanates such as (meth) acrylonitrile; glycidyl (meth) Epoxys such as allyl ether.

≪Method for producing copolymer≫
The method for producing the (poly) alkylene glycol-containing copolymer of the present invention is not particularly limited, but it can be produced by polymerizing the monomer component. Specific examples and preferred examples of the monomer component are described above. It is as follows. Moreover, the content rate of each monomer component with respect to 100 mass% of all monomer components is the same as the ratio of each structural unit with respect to 100 mass% of the above-mentioned all structural units.

In the production of the copolymer, a chain transfer agent can be used for adjusting the molecular weight of the obtained polymer. Examples of the chain transfer agent include thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid; isopropyl alcohol ( Secondary alcohols such as 2-propanol); phosphorous acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, dithionic acid and salts thereof (sodium sulfite, sulfurous acid, etc.) Examples thereof include hydrophilic chain transfer agents such as lower oxides such as sodium dithionate and the like, hydrogen sulfites (such as sodium hydrogen sulfite) and metabisulfites (such as sodium metabisulfite) and salts thereof. Of these, 3-mercaptopropionic acid, isopropyl alcohol, sodium hypophosphite, and sodium bisulfite are preferable.

A hydrophobic chain transfer agent can also be used as the chain transfer agent. Examples of the hydrophobic chain transfer agent include 3 carbon atoms such as butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 3-mercaptopropionate, etc. A thiol chain transfer agent having the above hydrocarbon group is preferably used.
In order to adjust the molecular weight of the copolymer, it is also effective to use a monomer having a high chain transfer property such as (meth) allylsulfonic acid (salt) as the monomer (E).

The amount of the chain transfer agent used may be appropriately set, but is 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.5 mol or more, based on 100 mol of the total amount of monomer components. In particular, it is 1.0 mol or more, preferably 20 mol or less, still more preferably 10 mol or less, particularly preferably 5 mol or less, and most preferably 3 mol or less.

The polymerization reaction can be performed by a method such as solution polymerization or bulk polymerization using a radical polymerization initiator as necessary. The polymerization can also be carried out batchwise, semi-batchwise, continuous, or combinations thereof. In the polymerization using the above (poly) alkylene glycol-containing monomer (A) as in the copolymer of the present application, semi-batch solution polymerization is preferable from the viewpoint of increasing the yield of the copolymer.
As a solvent for the solution polymerization, water, an organic solvent, or a mixed solvent thereof can be used. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; ester compounds such as ethyl acetate; acetone, methyl ethyl ketone, and the like Ketone compounds; and cyclic ether compounds such as tetrahydrofuran and dioxane. Among organic solvents, hydrophilic solvents such as alcohol are preferable. More preferred is isopropyl alcohol.
As the solvent, water or a mixed solvent of water and an organic solvent is preferable. Thereby, since the solubility of a monomer improves and the reactivity improves more, the copolymer with a more uniform monomer composition is obtained, and the production | generation of a high molecular weight body can be suppressed more fully.
The ratio of the organic solvent to 100% by mass of the mixed solvent is preferably 20 to 80% by mass, more preferably 40 to 60% by mass.
In the above polymerization reaction, when a solvent is used, the concentration of the monomer may be set as appropriate, but the amount of all raw materials used such as the monomer and solvent used from the start to the end of the polymerization reaction Is 100% by mass, the mass concentration of all monomers is preferably 50% by mass or more and 90% by mass or less. More preferably, it is 60 mass% or more, More preferably, it is 62.5 mass% or more, Most preferably, it is 65 mass% or more. Further, it is more preferably 80% by mass or less, still more preferably 75% by mass or less, and particularly preferably 70% by mass or less. Moreover, it is preferable that the fluctuation | variation of a monomer concentration shall be 30 mass% or less from the start to the completion | finish of a polymerization reaction. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it is 5 mass% or less. By setting the monomer concentration within this range, both high productivity of the copolymer and good storage stability can be achieved.

When the aqueous solution polymerization is performed, a water-soluble polymerization initiator, for example, a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate; hydrogen peroxide; 2,2′-azobis- Azoamidine compounds such as 2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, and azonitriles such as 2-carbamoylazoisobutyronitrile Water-soluble azo initiators such as compounds are used. In this case, alkali metal sulfites such as sodium hydrogen sulfite, metabisulphite, sodium hypophosphite, Fe (II) salts such as Mole salt, hydroxymethanesulfine Acid sodium dihydrate, hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), erythorbium It can also be used in combination accelerator acid (salt) and the like. Among these, a combination of persulfate or hydrogen peroxide and an accelerator such as L-ascorbic acid (salt) or Fe (II) salt is preferable. These radical polymerization initiators and accelerators may be used alone or in combination of two or more.
In addition, when performing solution polymerization using a lower alcohol, aromatic or aliphatic hydrocarbon, ester compound or ketone compound as a solvent, or when performing bulk polymerization, benzoyl peroxide, lauroyl peroxide, sodium peroxide, etc. Peroxides; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; radical polymerization of azo compounds such as azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile) Used as an initiator. In this case, an accelerator such as an amine compound can be used in combination. Further, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned various radical polymerization initiators or combinations of radical polymerization initiators and accelerators.

The amount of the radical polymerization initiator used is preferably 0.01 mol or more, more preferably 0.1 mol or more, still more preferably 0.5 mol or more, particularly preferably with respect to 100 mol of the total amount of monomer components. 1.0 mole or more, preferably 20 moles or less, even more preferably 10 moles or less, particularly preferably 5 moles or less, and most preferably 3 moles or less.

In the above polymerization reaction, the polymerization conditions such as the polymerization temperature are appropriately determined depending on the polymerization method used, the solvent, the polymerization initiator, and the chain transfer agent. Moreover, it is preferable that it is 150 degrees C or less. More preferably, it is 40 degreeC or more, More preferably, it is 50 degreeC or more. More preferably, it is 120 degrees C or less, More preferably, it is 100 degrees C or less. Furthermore, from the viewpoint of proceeding the copolymerization reaction more uniformly, it is preferable to set the fluctuation range of the polymerization temperature to 15 ° C. or less from the start to the end of the polymerization reaction. More preferably, it is 10 degrees C or less, More preferably, it is 8 degrees C or less, Especially preferably, it is 6 degrees C or less. By setting the polymerization temperature within this range, both economic efficiency and good storage stability of the copolymer can be achieved.

The method of charging each monomer component into the reaction vessel is not particularly limited, a method in which the entire amount is initially charged into the reaction vessel; a method in which the entire amount is divided or continuously charged into the reaction vessel; a part is initially in the reaction vessel For example, a method may be used in which the remainder is charged and the remainder is divided or continuously charged into the reaction vessel. In addition, by changing the charging rate of each monomer into the reaction vessel in the middle of the reaction continuously or stepwise, and changing the weight ratio of each monomer per unit time continuously or stepwise, the monomer ratio Two or more types of copolymers having different values may be synthesized simultaneously during the polymerization reaction. The radical polymerization initiator may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or may be combined according to the purpose.
Each polymer obtained as described above can be used as it is as a dispersant, but if necessary, it may be further neutralized with an alkaline substance. As the alkaline substance, inorganic salts such as hydroxides or carbonates of monovalent metals or divalent metals; ammonia; organic amines are suitable. Further, after the reaction is completed, the concentration can be adjusted if necessary.

≪Use of copolymer≫
The (poly) alkylene glycol-containing copolymer of the present invention exhibits good performance as a water-insoluble inorganic or organic dispersant. For example, good performance can be exhibited as a dispersant for inorganic pigments such as heavy or light calcium carbonate and clay used for paper coating; a dispersant for water slurry such as cement and coal; In addition, water treatment agents for scale prevention in cooling water systems, boiler water systems, seawater desalination equipment, pulp digesters, and black liquor concentration tanks; scale treatment agents; textile treatments such as dyeing aids and textile antistatic aids Agent; Adhesive; Sealing agent; Flexibility-imparting component for various polymers; Detergent builder and the like. Furthermore, it can be widely applied in the fields of body detergents such as shampoos, rinses, body soaps, fiber processing, building material processing, paints, ceramics and the like. Among them, it is preferable to use for cement admixture. That is, the method of using the (poly) alkylene glycol-containing copolymer of the present invention as a cement admixture is also one aspect of the present invention.
It is particularly useful as a cement admixture for ready-mixed concrete and shotcrete. Thus, the form in which the copolymer is a copolymer for cement admixture is a preferred form of the present invention, and the cement admixture containing the copolymer, the copolymer and cement are combined. Also included in the present invention are a cement composition that includes the cement admixture and cement. Moreover, the manufacturing method of the cement composition including the process of adding the said (poly) alkylene glycol containing copolymer to a hydraulic material is also one of this invention.
Hereinafter, a cement admixture will be described as a typical dispersant.

<Cement admixture>
The cement admixture of the present invention essentially comprises the copolymer of the present invention, but may contain two or more kinds of the above-mentioned copolymers, and one or more kinds of copolymers different from the above-mentioned copolymers. May be included.
The content of the copolymer in the cement admixture (the total content in the case where two or more types of copolymers are included) is not particularly limited, but in order to sufficiently exhibit the performance derived from the copolymer. The solid content (that is, the non-volatile content) in the cement admixture is preferably 30% by mass or more in 100% by mass. More preferably, it is 50 mass% or more, More preferably, it is 60 mass% or more, Most preferably, it is 70 mass% or more.
In the present specification, the “cement admixture” refers to a cement additive added to a cement composition such as cement paste, mortar, and concrete, and may be an agent composed only of the above copolymer. Moreover, it may be an agent containing not only the above copolymer but also other components and additives as required.

The cement admixture may further contain other commonly used cement dispersants and water reducing agents, and can be used in combination. Other cement dispersants (water reducing agents) are not particularly limited. For example, various sulfonic acid-based dispersants (water reducing agents) having a sulfonic acid group in the molecule, polyoxyalkylene chains and carboxyl groups in the molecule. Examples thereof include various polycarboxylic acid-based dispersants (water reducing agents) and various phosphoric acid-based dispersants (water reducing agents) having a phosphate group in the molecule.
When the copolymer of the present invention is used in combination with another cement dispersant (water reducing agent), the content of the copolymer of the present invention is contained in the cement admixture in order to sufficiently exhibit the performance derived from the copolymer. It is preferable that it is 30 mass% or more in total solid content (namely, non-volatile content) of 100 mass%. More preferably, it is 50 mass% or more, More preferably, it is 60 mass% or more, Most preferably, it is 70 mass% or more.

The cement admixture includes, for example, water-soluble polymer substances, polymer emulsions, retarders, early strengthening agents / accelerators, mineral oil-based antifoaming agents, fat-based antifoaming agents, fatty acid-based antifoaming agents, and fatty acid esters. Antifoaming agent, oxyalkylene antifoaming agent, alcohol antifoaming agent, amide antifoaming agent, phosphate ester antifoaming agent, metal soap antifoaming agent, silicone antifoaming agent, AE agent, surfactant Agent, waterproof agent, rust preventive agent, crack reducing agent, expansion agent, cement wetting agent, thickener, separation reducing agent, flocculant, drying shrinkage reducing agent, strength enhancer, self-leveling agent, rust preventive agent, colorant , One or more of cement additives (materials) such as fungicides, blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and gypsum may be included.

The cement admixture can be used for various hydraulic materials, that is, cement compositions such as cement and gypsum, and other hydraulic materials. As a specific example of a hydraulic composition containing such a hydraulic material, water and the above cement admixture, and further containing fine aggregate (sand, etc.) and coarse aggregate (crushed stone, etc.) as necessary, Cement paste, mortar, concrete, plaster, etc. are mentioned. Among these hydraulic compositions, a cement composition using cement as the hydraulic material is most preferable, and a cement composition containing the cement admixture and cement is also one aspect of the present invention.

<Cement composition>
In the cement composition of the present invention, as the cement, Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate resistance and low alkali type thereof); various mixed cements (blast furnace cement, silica cement, fly ash) Cement); white Portland cement; alumina cement; super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement); grout cement; oil well cement; low heat cement (low heat blast furnace cement, fly Ash mixed low heat generation type blast furnace cement, cement with high belite content); ultra high strength cement; cement-based solidified material; eco-cement (cement manufactured using one or more of municipal waste incineration ash and sewage sludge incineration ash) Besides these, blast furnace slag, fly ash, shi Dar ash, clinker ash, husk ash, silica fume, silica powder, and a film obtained by adding a fine powder and gypsum limestone powder. The cement contained in the cement composition of the present invention may be only one type or two or more types.
As the above aggregate, in addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia, etc. Refractory aggregate and the like.

In the cement composition, the unit water amount per 1 m ³ , the amount of cement used, and the water / cement ratio are not particularly limited. For example, the unit water amount is 100 to 200 kg / m ³ , the cement amount used is 200 to 800 kg / m ³ , The water / cement ratio (weight ratio) is preferably 0.1 to 0.7. More preferably, the unit water amount 120 ~ 185 kg / ^{m 3,} use amount of cement 250 ~ 600 kg / ^{m 3,} water / cement ratio (weight ratio) = 0.15 to 0.6. Thus, the cement composition of the present invention can be widely used from poor blends to rich blends, and is effective for both high-strength concrete with a large amount of unit cement and poor blend concrete with a unit cement amount of 300 kg / m ³ or less. It is. The cement composition of the present invention has a relatively low water / cement ratio region, that is, water / cement ratio (weight ratio) = 0.15 to 0.5 (preferably 0.15 to 0.4). Even in a region where the water / cement ratio is low, it can be used satisfactorily.

Further, by using the cement admixture of the present invention, the resulting cement composition has excellent workability for a long time in a wide range of blending, and therefore it can be effectively applied particularly to ready-mixed concrete, shotcrete and the like. On the other hand, it can be applied to concrete for concrete secondary products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, and the like. In addition, it has high fluidity such as medium fluidity concrete (concrete with slump flow value in the range of 350 to 500 mm), high fluidity concrete (concrete with slump flow value in the range of 500 to 700 mm), self-filling concrete, self-leveling material, etc. The cement admixture of the present invention is also effective for required mortar and concrete.

In the above cement composition, the blending ratio of the cement admixture of the present invention is, for example, the copolymer (the total amount when there are a plurality of components) as an essential component of the present invention, the total amount of cement mass in terms of solid content. It is preferably set to be 0.01 to 5% by mass with respect to 100% by mass. If the amount is less than 0.01% by mass, the performance may not be sufficient. On the other hand, if the amount exceeds 5% by mass, the effect will be practically peaked and disadvantageous in terms of economy, or the cement composition may be separated from the material. And may cause abnormal condensation. More preferably, the content is 0.05 to 3% by mass, and still more preferably 0.1 to 1% by mass. In the present specification, the solid content can be measured as follows.
<Method for measuring solid content>
1. Weigh the aluminum dish.
The solid content to be measured is precisely weighed on the aluminum dish precisely weighed in 2.1.
3. A solid content measurement product precisely weighed in 2 is placed in a dryer adjusted to 130 ° C. in a nitrogen atmosphere for 1 hour.
4. After 1 hour, remove from the dryer and allow to cool in a desiccator at room temperature for 15 minutes.
5. After 15 minutes, remove from the desiccator and precisely weigh the aluminum dish and the measurement object.
The solid content is measured by subtracting the mass of the aluminum pan obtained in 1 from the mass obtained in 6.5 and dividing by the mass of the solid content measurement product obtained in 2.

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, “part” means “part by mass” and “%” means “% by mass”.

In Table 3 below, “monomer composition (preparation)” and “monomer composition (finish)” have the following meanings.
“Monomer composition (preparation)”: A composition calculated from the amount of monomers charged in a reaction vessel to produce a copolymer.
“Monomer composition (finished)”: Analyzes the consumption rate in the polymerization reaction of the monomer charged in the reaction vessel to produce the copolymer, and all the consumed monomer is copolymerized by the polymerization reaction. A composition calculated to convert to coalescence.

As an example of the monomer consumption rate analysis method in the polymerization reaction, the analysis conditions and analysis method of LC (liquid chromatography) are described below.
<LC analysis conditions>
Model: Waters Alliance (2695)
Analysis software: Waters, Empor2 Professional column: Waters, Atlantis dC18 guard column + Atlantis dC18, 4.6 x 250 mm, 2
Detector: differential refractive index (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: A solution obtained by dissolving 3.75 g of sodium acetate trihydrate and 52.2 g of acetic acid in a mixed solvent of 9000 g of water and 6000 g of acetonitrile.
Flow rate: 1 mL / min Column temperature: 40 ° C
Analysis method: A concentration calibration curve of each monomer was prepared by a linear equation, and the monomer concentration in the sample was calculated.

<Storage stability test>
An aqueous solution having a copolymer concentration of 30% by mass was prepared, placed in a 20 mL test tube with a lid, and allowed to stand in a thermostat at 50 ° C., and the presence or absence of turbidity or separation of the solution was visually determined.
Regarding storage stability, it is preferable that the solution is uniform and stable for a long time. It is preferred that no separation occurs in the solution, and more preferred that neither turbidity nor separation occur.

[Example 1]
A solution (1a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 68.0 parts of water and 29.2 parts of 2-propanol.
A solution of 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) (Log P value: 1.88) dissolved in 2.8 parts of water and 1.2 parts of 2-propanol (1b ) Was prepared.
Ethylene oxide is added to 65.4 parts of water, 28.0 parts of 2-propanol, and 3-methyl-3-buten-1-ol in a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and The inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere, and then 9.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (1a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (1b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (1a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (1) was obtained. Α × 100 / (α + β) of the obtained copolymer (1) was 0. The results are shown in Table 1.
The obtained copolymer (1) was subjected to a storage stability test. The results are shown in Table 2.

[Example 2]
An aqueous solution (2a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 77.8 parts of water and 19.4 parts of 2-propanol. A solution (2b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.3 parts of water and 0.8 part of 2-propanol.
In a reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube, and a reflux condenser, 74.7 parts of water, 18.7 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and The inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere, and then 9.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (2a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (2b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (2a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (2) was obtained. Α × 100 / (α + β) of the obtained copolymer (2) was 0.31. The results are shown in Table 1.
The obtained copolymer (2) was subjected to a storage stability test. The results are shown in Table 2.

Example 3
A solution (3a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 82.6 parts of water and 14.6 parts of 2-propanol.
A solution (3b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.5 parts of water and 0.6 part of 2-propanol.
In a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, 79.4 parts of water, 17.0 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and The inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere, and then 9.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (3a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (3b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (3a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (3) was obtained. Α × 100 / (α + β) of the obtained copolymer (3) was 0.99. The results are shown in Table 1.
The obtained copolymer (3) was subjected to a storage stability test. The results are shown in Table 2.

Example 4
A solution (4a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 87.5 parts of water and 9.7 parts of 2-propanol.
A solution (4b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.7 parts of water and 0.4 part of 2-propanol.
In a reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen introduction tube, and a reflux condenser, 84.0 parts of water, 9.3 parts of 2-propanol, and 3-methyl-3-buten-1-ol were mixed with ethylene oxide. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and The inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere, and then 9.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (4a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (4b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (4a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (4) was obtained. Α × 100 / (α + β) of the obtained copolymer (4) was 1.50. The results are shown in Table 1.
The obtained copolymer (4) was subjected to a storage stability test. The results are shown in Table 2.

Example 5
A solution (5a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 90.4 parts of water and 6.8 parts of 2-propanol.
A solution (5b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.8 parts of water and 0.3 part of 2-propanol.
In a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser, 86.8 parts of water, 6.5 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and The inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere, and then 9.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (5a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (5b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (5a), 60 ° C. was continuously maintained for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (5) was obtained. Α × 100 / (α + β) of the obtained copolymer (5) was 2.52. The results are shown in Table 1.
The obtained copolymer (5) was subjected to a storage stability test. The results are shown in Table 2.

Example 6
A solution (6a) was prepared by dissolving 0.3 part of L-ascorbic acid and 1.0 part of 3-mercaptopropionic acid in 94.3 parts of water and 2.9 parts of 2-propanol.
A solution (6b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of butyl acrylate (BA) in 3.9 parts of water and 0.1 part of 2-propanol.
In a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, 90.6 parts of water, 2.8 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and The inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere, and then 9.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (6a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (6b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (6a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (6) was obtained. Α × 100 / (α + β) of the obtained copolymer (6) was 2.05. The results are shown in Table 1.
The obtained copolymer (6) was subjected to a storage stability test. The results are shown in Table 2.

Example 7
A solution (7a) in which 2.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 105.7 parts of 2-propanol was prepared.
A solution (7b) was prepared by dissolving 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA) (Log P value: 3.53) in 4.1 parts of 2-propanol.
In a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, 41.5 parts of water, 94.2 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol. 165.9 parts of unsaturated polyalkylene glycol ether monomer (IPN-50) added in an average of 50 moles was charged, and then the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere. .
After 30 minutes, the above mixed solution (7a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (7b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (7a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. In this way, a polymer solution containing the copolymer (7) was obtained. Α × 100 / (α + β) of the obtained copolymer (7) was 0. The results are shown in Table 1.
The obtained copolymer (7) was subjected to a storage stability test. The results are shown in Table 2.

Example 8
A solution (8a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 45.1 parts of water and 57.3 parts of 2-propanol.
A solution (8b) was prepared by mixing 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA).
In a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, ethylene oxide is added to 41.1 parts of water, 52.3 parts of 2-propanol, and 3-methyl-3-buten-1-ol. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and Then, the inside of the reaction vessel was purged with nitrogen under stirring, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 8.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (8a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (8b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (8a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (8) was obtained. Α × 100 / (α + β) of the obtained copolymer (8) was 0.31. The results are shown in Table 1.
The obtained copolymer (8) was subjected to a storage stability test. The results are shown in Table 2.

Example 9
A solution (9a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 41.0 parts of water and 61.4 parts of 2-propanol.
A solution (9b) in which 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA) were mixed was prepared.
Ethylene oxide was added to 37.3 parts of water, 56.0 parts of 2-propanol, and 3-methyl-3-buten-1-ol in a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and Then, the inside of the reaction vessel was purged with nitrogen under stirring, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 8.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (9a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (9b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (9a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (9) was obtained. Α × 100 / (α + β) of the obtained copolymer (9) was 0.58. The results are shown in Table 1.
The obtained copolymer (9) was subjected to a storage stability test. The results are shown in Table 2.

Example 10
A solution (10a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 43.0 parts of water and 59.4 parts of 2-propanol.
A solution (10b) was prepared by mixing 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA).
In a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, 39.2 parts of water, 54.1 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and Then, the inside of the reaction vessel was purged with nitrogen under stirring, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 8.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (10a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (10b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (10a), 60 ° C. was continuously maintained for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (10) was obtained. Α × 100 / (α + β) of the obtained copolymer (10) was 0.81. The results are shown in Table 1.
The obtained copolymer (10) was subjected to a storage stability test. The results are shown in Table 2.

Example 11
A solution (11a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 47.1 parts of water and 55.3 parts of 2-propanol.
A solution (11b) was prepared by mixing 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA).
In a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser, 42.9 parts of water, 50.4 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and Then, the inside of the reaction vessel was purged with nitrogen under stirring, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 8.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (11a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (11b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (11a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (11) was obtained. Α × 100 / (α + β) of the obtained copolymer (11) was 1.14. The results are shown in Table 1.
The obtained copolymer (11) was subjected to a storage stability test. The results are shown in Table 2.

Example 12
A solution (12a) was prepared by dissolving 0.4 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 44.3 parts of water.
A solution (12b) in which 24.7 parts of acrylic acid (AA) and 22.6 parts of butyl acrylate (BA) were mixed was prepared.
A reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube, and a reflux condenser, 2.8 parts of water, and an unsaturated polysiloxane having an average of 50 moles of ethylene oxide added to 3-methyl-3-buten-1-ol Charge 334.6 parts of an 80% aqueous solution of an alkylene glycol ether monomer (IPN-50) and 1.4 parts of a 70% aqueous solution of paratoluenesulfonic acid monohydrate, and then stir in the reaction vessel. After replacing with nitrogen and raising the temperature to 60 ° C. in a nitrogen atmosphere, 13.0 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (12a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (12b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (12a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (12) was obtained. Α × 100 / (α + β) of the obtained copolymer (12) was 0. The results are shown in Table 1.
The obtained copolymer (12) was subjected to a storage stability test. The results are shown in Table 2.

Example 13
A solution (13a) was prepared by dissolving 0.2 part of L-ascorbic acid and 0.6 part of 3-mercaptopropionic acid in 68.2 parts of water and 68.2 parts of 2-propanol.
Ethylene oxide is added to 43.6 parts of water, 43.6 parts of 2-propanol, and 2-methyl-2-propen-1-ol in a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser. 193.5 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (MLA-150) added with an average of 150 moles and 0.8 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and Then, the inside of the reaction vessel was purged with nitrogen under stirring, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 5.4 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (13a) was added over 3.5 hours, 7.0 parts of 90% aqueous solution of acrylic acid (AA) and 18.2 parts of butyl acrylate (BA) were added over 3 hours, respectively. Metered dropwise at a constant rate. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (13a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (13) was obtained. Α × 100 / (α + β) of the obtained copolymer (13) was 0. The results are shown in Table 1.
The storage stability test of the obtained copolymer (13) was performed. The results are shown in Table 2.

Example 14
A solution (14a) in which 3.3 parts of ammonium persulfate was dissolved in 107.3 parts of water was prepared.
A solution (14b) in which 16.5 parts of butyl acrylate (BA) and 19.7 parts of methacrylic acid (MAA) were mixed was prepared.
A solution (14c) was prepared by dissolving 123.8 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23) (PGM-23) and 1.2 parts of 3-mercaptopropionic acid in 53.6 parts of water. .
Charge 35.3 parts of water and 35.3 parts of 2-propanol to a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, and then purge the inside of the reaction vessel with nitrogen under stirring. After heating to 80 ° C. in a nitrogen atmosphere, the above mixed solution (14a) was metered dropwise at a constant rate over 5 hours and the above mixed solutions (14b) and (14c) over 4 hours. . The temperature during this period was constant at 80 ° C.
After completion of the dropwise addition of the mixed solution (14a), the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (14) was obtained. Α × 100 / (α + β) of the obtained copolymer (13) was 0. The results are shown in Table 1.
The obtained copolymer (14) was subjected to a storage stability test. The results are shown in Table 2.

[Comparative Example 1]
A solution (c-1a) in which 0.3 part of L-ascorbic acid and 0.5 part of 3-mercaptopropionic acid were dissolved in 34.5 parts of water was prepared.
A solution (c-1b) was prepared by mixing 9.1 parts of acrylic acid (AA) and 14.7 parts of 2-ethylhexyl acrylate (2EHA).
A solution (c-1c) in which 1.6 parts of ammonium persulfate was dissolved in 39.3 parts of water was prepared.
A reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube, and a reflux condenser is 79.5 parts of water, and an unsaturated polysiloxane having an average of 50 mol of ethylene oxide added to 3-methyl-3-buten-1-ol. Then, 267.4 parts of an alkylene glycol ether monomer (IPN-50) and 3.0 parts of acrylic acid were charged. Subsequently, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere.
After 30 minutes, the above mixed solutions (c-1a) and (c-1c) were metered dropwise at a constant rate over 3.5 hours and the above mixed solution (c-1b) over 3 hours. The temperature during this period was constant at 60 ° C. After completion of the dropwise addition of the mixed solutions (c-1a) and (c-1c), the temperature was maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 7.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the comparative copolymer (1) was obtained. Α × 100 / (α + β) of the obtained comparative copolymer (1) was 4.23. The results are shown in Table 1.
The obtained comparative copolymer (1) was subjected to a storage stability test. The results are shown in Table 2.

[Comparative Example 2]
A solution (c-2a) was prepared by dissolving 0.3 part of L-ascorbic acid and 0.9 part of 3-mercaptopropionic acid in 51.2 parts of water and 51.2 parts of 2-propanol.
A solution (c-2b) was prepared by mixing 15.9 parts of acrylic acid (AA) and 20.7 parts of 2-ethylhexyl acrylate (2EHA).
In a reaction vessel equipped with a thermometer, a stirrer, a dripping device, a nitrogen inlet tube, and a reflux condenser, 46.7 parts of water, 46.7 parts of 2-propanol, and ethylene oxide were added to 3-methyl-3-buten-1-ol. 207.4 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) added with an average of 50 moles and 0.9 part of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were added, and Then, the inside of the reaction vessel was purged with nitrogen under stirring, the temperature was raised to 60 ° C. in a nitrogen atmosphere, and 8.3 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (c-2a) was metered dropwise at a constant rate over 3.5 hours and the above mixed solution (c-2b) over 3 hours. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (c-2a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the comparative copolymer (2) was obtained. Α × 100 / (α + β) of the obtained comparative copolymer (2) was 3.11. The results are shown in Table 1.
The obtained comparative copolymer (2) was subjected to a storage stability test. The results are shown in Table 2.

[Comparative Example 3]
A solution (c-3a) in which 0.2 part of L-ascorbic acid and 0.6 part of 3-mercaptopropionic acid were dissolved in 136.5 parts of water was prepared.
A reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser. 87.1 parts of water and 2-methyl-2-propen-1-ol added with an average of 150 moles of ethylene oxide Charge 193.5 parts of an 80% aqueous solution of an alkylene glycol ether monomer (MLA-150) and 0.8 parts of a 70% aqueous solution of paratoluenesulfonic acid monohydrate, and then stir the inside of the reaction vessel with stirring. After purging with nitrogen and raising the temperature to 60 ° C. in a nitrogen atmosphere, 5.4 parts of a 2% aqueous hydrogen peroxide solution was added.
After 30 minutes, the above mixed solution (c-3a) was added over 3.5 hours, 7.0 parts of a 90% aqueous solution of acrylic acid (AA) and 18.2 parts of butyl acrylate (BA) were added over 3 hours. , Each was metered dropwise at a constant rate. The temperature during this period was constant at 60 ° C.
After completion of the dropwise addition of the mixed solution (c-3a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. In this way, a polymer solution containing the copolymer (13) was obtained. Α × 100 / (α + β) of the obtained copolymer (c-3) was 8.18. The results are shown in Table 1.
The storage stability test of the obtained copolymer (c-3) was conducted. The results are shown in Table 2.

[Comparative Example 4]
A solution (c-4a) in which 3.2 parts of ammonium persulfate was dissolved in 77.4 parts of water was prepared.
41.8 parts of methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 23) (PGM-23), 1.9 parts of 3-mercaptopropionic acid, 11.1 parts of methacrylic acid were dissolved in 23.5 parts of water. A solution (c-4b) was prepared.
A reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser was charged with 253.9 parts of water, and the inside of the reaction vessel was purged with nitrogen under stirring. After the temperature was raised, the above mixed solution (c-4a) was metered dropwise at a constant rate over 5 hours, and the above mixed solution (c-4b) and 37.1 parts of butyl acrylate over 4 hours. . The temperature during this period was constant at 80 ° C.
After completion of the dropwise addition of the mixed solution (c-4a), the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction. Thereafter, the pH of the reaction solution was neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature. Thus, a polymer solution containing the copolymer (c-4) was obtained. Α × 100 / (α + β) of the obtained copolymer (c-4) was 12.3. The results are shown in Table 1.
The storage stability test of the obtained copolymer (c-4) was performed. The results are shown in Table 2.

In Table 1, Mw (α) represents a high molecular weight-derived peak α, Mw (β1) represents a copolymer-derived peak β1, and Mw (β2) represents a weight-average molecular weight of a monomer-derived peak β2.

Claims (7)

1. A copolymer containing a (poly) alkylene glycol chain,
   The copolymer has the following formula (1);
   

   

   (In the formula, R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (AO) are the same or different and each represents an oxyalkylene group, n represents the average number of moles added of the oxyalkylene group, and is a number from 1 to 300. y represents a number from 0 to 4. z Represents a structural unit (a) derived from the (poly) alkylene glycol-containing monomer (A) and a structural unit (b) derived from the hydrophobic monomer (B). Have
   The hydrophobic monomer (B) has an ethylenically unsaturated group and has an octanol / water partition coefficient value (Log P value) of 1.0 to 8.0,
   In the chromatogram of the differential refractive index detector of gel permeation chromatography (GPC) measured for the copolymer, the areas of peak α and peak β defined below satisfy the following formula (2): A (poly) alkylene glycol-containing copolymer.
   α × 100 / (α + β) ≦ 3.0 (2)
   <Peak α and β>
   Peak α: A peak having a weight average molecular weight (Mw) larger than 200,000.
   Peak β: A peak having Mw of 200,000 or less.
2. The hydrophobic monomer (B) is an ester of an unsaturated carboxylic acid and an alcohol, an aromatic vinyl monomer, an olefin monomer, a (meth) acrylamide monomer, or a maleimide monomer. The (poly) alkylene glycol-containing copolymer according to claim 1, further comprising at least one selected from the group consisting of esters of unsaturated alcohols and carboxylic acids.
3. 3. The (poly) alkylene glycol-containing copolymer according to claim 1 or 2, wherein the (poly) alkylene glycol-containing copolymer has a structural unit (c) derived from an unsaturated carboxylic acid monomer (C). Containing copolymer.
4. 4. The (poly) alkylene glycol-containing monomer (A) according to claim 1, wherein z in the formula (1) is 0. Coalescence.
5. A cement admixture comprising the (poly) alkylene glycol-containing copolymer according to any one of claims 1 to 4.
6. A cement composition comprising the (poly) alkylene glycol-containing copolymer according to any one of claims 1 to 4 and cement.
7. A method for producing a cement composition comprising:
   The method for producing a cement composition, comprising the step of adding the (poly) alkylene glycol-containing copolymer according to any one of claims 1 to 4 to a hydraulic material.

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