JP2018127542A - Polycondensation product, and dispersant for hydraulic composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycondensation product containing a novel phenolic copolymer useful for a dispersant for hydraulic compositions.SOLUTION: The present invention provides a polycondensation product containing a copolymer obtained by polycondensation of a monomer mixture containing a compound A represented by formula (A), and an aromatic compound having a phosphate group or sulfate group and an aldehyde compound, and a dispersant for hydraulic compositions containing the same (Ris H, an alkyl group, an alkoxy group or an alkenyl group; AO is an alkyleneoxy group; m is the number of 1 to 300; Ris H, an alkyl group or an acyl group).SELECTED DRAWING: None

Description

  The present invention relates to a polycondensation product containing a novel phenolic copolymer. More specifically, the present invention relates to a polycondensation product obtained by copolymerizing a monomer mixture containing a phenol alkylene oxide adduct derivative, a phosphate ester or sulfate ester derivative of phenol and an aldehyde.

  Furthermore, the present invention also includes an embodiment of a polycondensation composition having, in addition to the above monomer, an alkylene oxide adduct of hydroxyethylphenol or a derivative thereof as a monomer mixture.

In recent years, with the depletion of high-quality fine aggregates such as river sand, there has been an increase in the use of low-quality aggregates that have not been actively used in the past. . The hydraulic composition using such a low-quality fine aggregate has a tendency to increase the viscosity at the time of freshness and reduce workability even at a general water powder ratio (W / B). . Such a problem is likely to occur particularly when the amount of impurities (eg, clay) contained in the aggregate is large.
Moreover, since the aggregate used as a hydraulic composition material is a natural product, the content of impurities varies. Therefore, when a conventional polycarboxylic acid-based dispersant is used, the amount of the dispersant used to obtain a certain fluidity varies depending on the type of aggregate used and its origin, etc. In actual production of the hard composition, it is necessary to adjust the amount of the dispersant used each time, and various operations become complicated. In addition, when many of the above-mentioned low-quality aggregates are used, it is often necessary to increase the amount of dispersant added to ensure a certain fluidity, which causes an increase in manufacturing costs. .

To solve this problem, fluidity can be improved by using a conventional polycarboxylic acid dispersant and other components in combination, or by optimizing the structure of the polycarboxylic acid dispersant itself. Several prior art examples that enhance the effectiveness as a polycarboxylic acid-based water reducing agent are disclosed.
As an example of the combined use of other components described above, when using a low-quality aggregate containing a swellable clay (for example, smectite, montmorillonite, etc.), a substance containing an inorganic cation (for example, a clay activity-changing substance) Calcium nitrate, substances containing organic cations (eg tetrabutylammonium bromide), polar organic molecules (eg polyethylene glycol, sodium hexametaphosphate, etc.) EO / PO plasticizer (ie polycarboxylic acid water reducing agent) There is a proposal to improve the effectiveness of the polycarboxylic acid-based water reducing agent by using together with (Patent Document 1). When using fine aggregates with low quality, a cationic polymer containing quaternary nitrogen (for example, poly (diallyldimethylammonium) salt) is used as a high-performance water reducing agent or high-performance AE water reducing agent (polycarboxylic acid-based water reducing agent). (Patent Document 2), which is intended to improve the fresh state of concrete viscosity, fluidity retention, etc., when used in combination with a poly-cationic compound (for example, polydiallyldimethylammonium) Chloride) and poly-hydroxyl or hydroxyl carboxylate components (eg, sodium gluconate, etc.) in combination with polycarboxylate dispersants have improved the maintenance of the dose efficiency that the dispersant exhibits in cement mortar. There is another proposal (Patent Document 3).
Further, as a proposal for improving the structure of the polycarboxylic acid dispersant itself, a comb type copolymer containing a main hydrocarbon chain and a side chain containing a gem-bisphosphonate group in addition to a carboxy group and a polyoxyalkylene group is used as a mineral particle. There is a proposal (Patent Document 4) through which the fluidity of the suspension is improved by adopting it as a fluidizing agent for the suspension.

Japanese Patent No. 4491078 Japanese Patent No. 4389233 JP 2011-136844 A Japanese Patent No. 5623672

However, in the proposals so far, satisfactory fluidity has not been achieved without being greatly affected by the type of aggregate used and the amount of impurities.
Thus, with the transition of the aggregate used, there is a need for a new hydraulic composition dispersant that can exhibit a certain fluidity without substantially changing the addition amount regardless of whether the aggregate quality is good or bad. .
On the other hand, there has been no proposal that a phosphate ester or sulfate ester derivative of phenol has been used as a raw material for additives for hydraulic compositions.

  The present invention has been made to improve the performance of the dispersant for hydraulic compositions under such conventional technical background, and has a stable dispersibility regardless of the content of impurities in the aggregate, Contains a dispersant for hydraulic compositions that achieves the desired fluidity without substantially changing the amount added depending on the type of aggregate, and a novel phenolic copolymer useful as such a dispersant for hydraulic compositions It is an object of the present invention to provide a polycondensation product.

  As a result of intensive studies, the present inventors include a polycondensation product using a phosphate ester or sulfate ester derivative of phenols, which has not been studied as a material for additives for hydraulic compositions, as a monomer component. A hydraulic composition having a desired fluidity regardless of the kind and amount of impurities such as clay that can be contained in the aggregate by using a phenolic copolymer as an additive for the hydraulic composition The present invention has been completed.

（式中、
Ｒ_１は水素原子、炭素原子数１乃至２４のアルキル基、炭素原子数２乃至２４のアルケニル基、又は炭素原子数１乃至１０のアルコキシ基を表し、
Ａ_１Ｏは、炭素原子数２乃至４のアルキレンオキシ基を表し、
ｍはアルキレンオキサイドの平均付加モル数であって１乃至３００の数を表し、
Ｒ_２は水素原子、炭素原子数１乃至１０のアルキル基、又は炭素原子数２乃至２４のアシル基を表す。）

（式中、
Ｒ_３は水素原子、炭素原子数１乃至２４のアルキル基、又は炭素原子数２乃至２４のアルケニル基を表し、
Ｘ_１はリン酸エステル基又は硫酸エステル基を表す。）

（式中、
Ｒ_４は水素原子、カルボキシル基、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、フェニル基、ナフチル基又はヘテロ環式基を表し、
ｎは１乃至１００の数を表す。） That is, the present invention comprises a monomer mixture containing compound A represented by the following formula (A), compound B represented by formula (B) and one or more aldehyde compounds C represented by formula (C). The present invention relates to a polycondensation product containing a condensed copolymer.

(Where
R ₁ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
A ₁ O represents an alkyleneoxy group having 2 to 4 carbon atoms,
m is the average number of moles of alkylene oxide added and represents a number from 1 to 300;
R ₂ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms. )

(Where
R ₃ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an alkenyl group having 2 to 24 carbon atoms,
X ₁ represents a phosphate ester group or a sulfate ester group. )

(Where
R ₄ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group, or a heterocyclic group,
n represents a number from 1 to 100. )

（式中、
Ａ_２Ｏ及びＡ_３Ｏは、それぞれ独立して炭素原子数２乃至４のアルキレンオキシ基を表し、
ｐ及びｑは、アルキレンオキサイドの平均付加モル数であって、それぞれ独立して０乃至３００の数を表し且つｐ＋ｑ≧１であり、
Ｘ_２及びＸ_３はそれぞれ独立して水素原子、リン酸エステル基又は硫酸エステル基を表す。） Furthermore, the present invention also includes an embodiment of a polycondensation product including a copolymer obtained by polycondensing a monomer mixture containing a compound D represented by the following formula (D) in addition to the compounds A to C. It is.

(Where
A ₂ O and A ₃ O each independently represents an alkyleneoxy group having 2 to 4 carbon atoms,
p and q are average added moles of alkylene oxide, each independently representing a number from 0 to 300, and p + q ≧ 1;
X ₂ and X ₃ each independently represent a hydrogen atom, a phosphate ester group or a sulfate ester group. )

In the monomer mixture, the polycondensation product is compound A: compound B: compound D = 0.1 to 2: 0.1 to 4: The compound C is contained in a molar ratio with respect to the total molar amount of the compound A, the compound B and the compound D (compound A + compound B + compound D): compound C = 1 to It is preferable to include in the ratio of 10: 10-1.
Further, the polycondensation product may contain two or more kinds of compounds A represented by the formula (A) in the monomer mixture, and further represented by two or more kinds of the formula (B). Compound B may be included.

  The present invention further relates to a dispersant for a hydraulic composition containing the polycondensation product or copolymer described above.

  According to the present invention, it is possible to express excellent dispersion stability with respect to the hydraulic composition without greatly changing the addition amount regardless of the kind and content of impurities in the aggregate, Water that has high water-reducing properties, can shorten the mixing time until the hydraulic composition is fluidized, has good stability over time, low concrete viscosity, and low workability such as setting delay. Dispersants for hard compositions, phenolic copolymers suitably used as the dispersant, and polycondensation products containing the same can be provided.

  The polycondensation product comprising the copolymer of the present invention may also reduce undesirable effects that may be caused by the presence of carbon, typically unburned carbon, in the hydraulic composition. There is an effect that can be done. That is, the polycondensation product or copolymer of the present invention can maintain a high water reduction even when it is blended with a fly ash (FA) blended concrete composition as a dispersant for a hydraulic composition. Particularly, in the cured body of the FA blend composition, the occurrence of darkening of the surface caused by unburned carbon floating on the surface of the concrete can be suppressed, and an effect of providing a cured body excellent in appearance can be provided.

As described above, the polycondensation product or copolymer of the present invention is a hydraulic composition that can suppress deterioration of fluidity of the hydraulic composition that is a concern when impurities such as clay and clay such as bentonite are present. It is a polycondensation product or copolymer useful as an additive.
In the hydraulic composition to which the polycondensation product or copolymer of the present invention is applied, the impurities include clay and clay.
In this specification, clay refers to a collected fine particle portion defined as a passing portion of a metal sieve having a nominal size of 75 μm as defined in JIS Z8801-1.
In addition, in this specification, the clay includes a clay mineral having a layered structure and a clay mineral having no layered structure such as imogolite and allophane. Examples of clay minerals having a layered structure include swellable minerals such as smectite, vermiculite, montmorillonite, bentonite, illite, hectorite, halloysite, mica and brittle mica; kaolin mineral (kaolinite), serpentine, pyrophyllite, talc, chlorite Non-swelling minerals such as light can be mentioned.

  The polycondensation product or copolymer of the present invention is suitably used in a hydraulic composition as an additive for a hydraulic composition, and particularly coal ash such as fly ash, cinder ash, clinker ash, bottom ash and the like. , Silica fume, silica dust, fused silica fine powder, blast furnace slag, volcanic ash, silicic acid white clay, diatomaceous earth, metakaolin, silica sol, and a hydraulic composition containing pozzolanic fine powder such as precipitated silica.

<Polycondensation product and copolymer>
The present invention is a copolymerization of a monomer mixture containing an alkylene oxide adduct of phenols or a derivative thereof (Compound A), a phosphate ester or a sulfate ester derivative of Compound (Compound B), and an aldehyde (Compound C). The polycondensation product containing a copolymer obtained by the above-mentioned process, and the copolymer are used.
In the present invention, “a polycondensation product including a copolymer obtained by polycondensing a monomer mixture”
(1) An embodiment comprising a copolymer (copolymer 1) in which all the components of the monomer mixture, that is, all of the compounds A to D are polycondensed,
(2) An embodiment including a copolymer (copolymer 2) obtained by polycondensation of one or two of compound A, compound B and compound D and compound C in the monomer mixture.
(3) An embodiment including the two types of copolymers (copolymer 1 and copolymer 2) of (1) and (2), and (4) the copolymer of (1) and / or (2) An embodiment containing at least one of unreacted compounds A to D in addition to the polymer (copolymer 1 and / or copolymer 2),
In general, it also includes components including unreacted components and side reactants generated in each polymerization step, preparation step of each component (compound A to compound D), for example, an alkylene oxide addition step, etc. Has been.
Hereinafter, the compounds A to D contained in the monomer mixture will be described in detail.

（式中、
Ｒ_１は水素原子、炭素原子数１乃至２４のアルキル基、炭素原子数２乃至２４のアルケニル基、又は炭素原子数１乃至１０のアルコキシ基を表し、
Ａ_１Ｏは、炭素原子数２乃至４のアルキレンオキシ基を表し、
ｍはアルキレンオキサイドの平均付加モル数であって１乃至３００の数を表し、
Ｒ_２は水素原子、炭素原子数１乃至１０のアルキル基、又は炭素原子数２乃至２４のアシル基を表す。） [Compound A Represented by Formula (A)]
Compound A is an alkylene oxide adduct of phenols or a derivative thereof, and has a structure represented by the following formula (A).

(Where
R ₁ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
A ₁ O represents an alkyleneoxy group having 2 to 4 carbon atoms,
m is the average number of moles of alkylene oxide added and represents a number from 1 to 300;
R ₂ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms. )

The compound A is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to phenol or substituted phenol, and a derivative (alkyl ether or fatty acid ester) of the alkylene oxide adduct is also included in the compound A. .
Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides can be added alone or in combination. When two or more kinds of alkylene oxide are used, Either block addition or random addition may be used.

M is the average number of added moles of alkylene oxide, and represents 1 to 300, preferably 1 to 150. By increasing the number of added moles of A ₁ O, improvement in water reduction can be expected.

The alkyl group having 1 to 24 carbon atoms in R ₁ may have a branched structure or a cyclic structure, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group. , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1- Examples thereof include an adamantyl group, a dodecyl group (lauryl group), a tetradecyl group (myristyl group), a hexadecyl group (palmityl group), an octadecyl group (stearyl group), an icosyl group, a docosyl group (behenyl group), and a tetracosyl group.
Further, examples of the alkenyl group having 2 to 24 carbon atoms include groups having one carbon-carbon double bond in the alkyl group having 1 to 24 carbon atoms. Specifically, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicosenyl group, dococenyl group, A tetracocenyl group etc. are mentioned, These may have a branched structure and a cyclic structure.

The alkyl group having 1 to 10 carbon atoms in R ₂ may have a branched structure or a cyclic structure, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group. , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1- And an adamantyl group.
Examples of the acyl group having 2 to 24 carbon atoms include saturated or unsaturated acyl groups (R ′ (CO) — group, R ′ is a hydrocarbon group having 1 to 23 carbon atoms). For example, saturated acyl groups having 2 to 24 carbon atoms include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid ( Capric acid), dodecanoic acid (lauric acid), tetradecane (myristic acid), pentadecanoic acid (pentadecylic acid), hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecanoic acid, eicosane Acyl groups derived from carboxylic acids and fatty acids such as acids (arachidic acid), docosanoic acid (behenic acid) and tetracosanoic acid (lignoceric acid) are monounsaturated acyl groups such as myristoleic acid, palmitoleic acid, oleic acid, Elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid Acyl groups derived from monounsaturated fatty acids such as nervonic acid, and diunsaturated acyl groups include acyl groups derived from diunsaturated fatty acids such as linoleic acid, eicosadienoic acid and docosadienoic acid, and triunsaturated acyl Examples of the group include acyl groups derived from triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, and eicosatrienoic acid.
Preferable R ₂ includes a hydrogen atom and an acetyl group.

  Compound A represented by the above formula (A) can be used singly or in combination of two or more. By using a combination of two or more compounds as the compound A in the monomer mixture described later, an effect of improving the mortar flow retention rate can be expected.

（式中、
Ｒ_３は水素原子、炭素原子数１乃至２４のアルキル基、又は炭素原子数２乃至２４のアルケニル基を表し、
Ｘ_１はリン酸エステル基又は硫酸エステル基を表す。） [Compound B Represented by Formula (B)]
Compound B is a phosphate ester or sulfate ester derivative of phenols, and has a structure represented by the following formula (B).

(Where
R ₃ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an alkenyl group having 2 to 24 carbon atoms,
X ₁ represents a phosphate ester group or a sulfate ester group. )

  Compound B may be a commercially available compound, or a compound synthesized by a known method using a commercially available phosphorylating agent or sulfating agent for phenol or substituted phenol.

As the alkyl group having 1 to 24 carbon atoms in R _3, the groups exemplified for R ₁ can be used.
Examples of the alkenyl group having 2 to 24 carbon atoms include groups having one carbon-carbon double bond in the above alkyl group having 1 to 24 carbon atoms. Specifically, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, eicosenyl group, dococenyl group, A tetracocenyl group etc. are mentioned, These may have a branched structure and a cyclic structure.
Of these, alkyl groups and alkenyl groups having 1 to 10 carbon atoms are preferred.

When X ₁ represents a phosphate ester group, they are a phosphate monoester and / or a salt thereof, a phosphate diester and / or a salt thereof, or a phosphate triester, or a mixture thereof, and X ₁ is sulfuric acid. When representing ester groups, they are sulfuric monoesters and / or their salts, or sulfuric diesters, or mixtures thereof.
Examples of the phosphate ester salt or sulfate ester salt include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium and magnesium; ammonium salts; organic ammonium salts such as alkyl ammonium and alkanol ammonium. These can include compounds represented by the following formula.
Phosphate monoesters and salts thereof _{R 3 -Ph-O-P (} = O) (- OM) 2
Phosphate diesters and salts thereof _{[R 3 -Ph-O-] 2} P (= O) (- OM)
Phosphate triester _{[R 3 -Ph-O-] 3} P (= O)
-Sulfuric acid monoester and its salt R < ₃ > -Ph-OS (= O) ₂ (-OM)
Sulfuric acid diester [R ₃ —Ph—O—] ₂ S (═O) ₂
(Wherein R ₃ represents the same as defined in the above formula (B), Ph represents a phenylene group, and M represents a hydrogen atom; an alkali metal atom such as sodium or potassium; calcium or magnesium, etc. An alkaline earth metal atom; an ammonium group; an organic ammonium group such as an alkyl ammonium group or an alkanol ammonium group.)

  Compound B represented by the above formula (B) can be used singly or in combination of two or more.

（式中、
Ｒ_４は水素原子、カルボキシル基、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、フェニル基、ナフチル基又はヘテロ環式基を表し、
ｎは１乃至１００の数を表す。）
上記式中、Ｒ_４は水素原子、カルボキシル基、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、フェニル基、ナフチル基又はヘテロ環式基を表し、ｎは１乃至１００の数を表す。
なおこれらアルキル基、アルケニル基、フェニル基、ナフチル基及びヘテロ環式基は、炭素原子数１乃至１０のアルキル基；フェニル基、ナフチル基等のアリール基；塩素原子、臭素原子等のハロゲン原子；スルホ基、スルホン酸塩基等のスルホン酸官能基；アセチル基等のアシル基；ヒドロキシ基；アミノ基；カルボキシル基等の任意の置換基で置換されていてもよい。 [Compound C Represented by Formula (C)]
Compound C is an aldehyde and has a structure represented by the following formula (C).

(Where
R ₄ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group, or a heterocyclic group,
n represents a number from 1 to 100. )
In the above formula, R ₄ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group, or a heterocyclic group, and n is 1 to The number of 100 is represented.
These alkyl groups, alkenyl groups, phenyl groups, naphthyl groups and heterocyclic groups are alkyl groups having 1 to 10 carbon atoms; aryl groups such as phenyl groups and naphthyl groups; halogen atoms such as chlorine atoms and bromine atoms; Sulfonic acid functional groups such as a sulfo group and a sulfonate group; acyl groups such as acetyl groups; hydroxy groups; amino groups; and optionally substituted groups such as carboxyl groups.

Compound C includes, for example, formaldehyde, paraformaldehyde, trioxane, glyoxylic acid, acetaldehyde, trichloroacetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexylaldehyde, heptanal, octylaldehyde, nonylaldehyde, isononylaldehyde, decylaldehyde, Dodecanal, acrolein, crotonaldehyde, pentenal, hexenal, heptenal, octenal, cinnamaldehyde, benzaldehyde, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, anisaldehyde, salicylaldehyde, benzylaldehyde [(C ₆ H ₅ ) ₂ C (OH) —CHO ], Naphthaldehyde, furfural, etc. But among them, formaldehyde, paraformaldehyde, may be selected from the group consisting of benzaldehyde or any mixture of two or more thereof.
Compound C can also be used as a pure crystal or powder, or as a hydrate thereof, and can also be used in the form of an aqueous solution such as formalin, in this case simplifying the metering or mixing of the components Can do.

  The compound C represented by the above formula (C) can be used singly or in combination of two or more.

（式中、
Ａ_２Ｏ及びＡ_３Ｏは、それぞれ独立して炭素原子数２乃至４のアルキレンオキシ基を表し、
ｐ及びｑは、アルキレンオキサイドの平均付加モル数であって、それぞれ独立して０乃至３００の数を表し且つｐ＋ｑ≧１であり、
Ｘ_２及びＸ_３はそれぞれ独立して水素原子、リン酸エステル基又は硫酸エステル基を表す。） [Compound D Represented by Formula (D)]
Compound D is an alkylene oxide adduct of hydroxyethylphenol or a derivative thereof, and has a structure represented by the following formula (D).

(Where
A ₂ O and A ₃ O each independently represents an alkyleneoxy group having 2 to 4 carbon atoms,
p and q are average added moles of alkylene oxide, each independently representing a number from 0 to 300, and p + q ≧ 1;
X ₂ and X ₃ each independently represent a hydrogen atom, a phosphate ester group or a sulfate ester group. )

The compound D is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to hydroxyethylphenol, specifically, at least one of a hydroxyethyl group and a phenolic hydroxy group, or both. Oxide adduct derivatives (phosphate esters or sulfate esters) are also included in Compound D.
The hydroxyethylphenol may be any of o-hydroxyethyl-phenol, m-hydroxyethyl-phenol, and p-hydroxyethyl-phenol. Compound D is preferably a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to o-hydroxyethyl-phenol (and its ester derivative).

Examples of the alkyleneoxy group having 2 to 4 carbon atoms in A ₂ O and A ₃ O include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. A ₂ O and A ₃ O may be composed of only one of these, or may contain two or more groups. When two or more kinds of groups are contained, the addition form thereof may be either random addition or block addition.
P and q are average added moles of alkylene oxide, each independently representing a number of 0 to 300, preferably 0 to 60, and p + q ≧ 1. By increasing the number of moles of A ₂ O _and A ₃ O added, water reduction can be expected.

When X ₂ and X ₃ represent a phosphate group, they are a phosphate monoester and / or a salt thereof, a phosphate diester and / or a salt thereof, a phosphate triester, or a mixture thereof, and X ₂ , when X ₃ represents a sulfate ester group, they are a sulfate monoester and / or a salt thereof, or a sulfate diester, or a mixture thereof.

Examples of the phosphate ester salt or sulfate ester salt include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium and magnesium; ammonium salts; organic ammonium salts such as alkyl ammonium and alkanol ammonium.
When the terminal of the compound D is anionized, that is, phosphorylated or sulfated, when added to the hydraulic composition, the mixing time of the mortar can be shortened.

  The compound D represented by the said formula (D) can be used individually by 1 type and in combination of 2 or more types. By adding the copolymer using Compound D as a monomer component to the hydraulic composition, the resistance to material variation factors is further improved, and good fluidity is obtained regardless of the amount of impurities such as clay. can get.

[Monomer mixture]
In the monomer mixture containing the compound A to compound C or the compound A to compound D used in the polycondensation product of the present invention, the mixing ratio is not particularly limited, but preferably the compound A, compound B and compound D is included in a molar ratio of Compound A: Compound B: Compound D = 0.1-2: 0.1-4: 0-10, and the total of Compound A, Compound B and Compound D It is desirable to contain the compound D in a molar ratio with respect to the molar amount in the ratio of (compound A + compound B + compound D): compound C = 1 to 10: 10-1.
More preferably, it is compound A: compound B: compound D = 0.1-2: 0.1-4: 0-8 (molar ratio), (compound A + compound B + compound D): compound C = 2-6 : 10 to 1 (molar ratio).
When the compounding ratio of compound D is increased in the monomer mixture, fluidity can be ensured even when impurities such as clay are mixed in the hydraulic composition, and shortening of the setting time can be expected. Moreover, the water-reducing property and retainability of the hydraulic composition can be adjusted by adjusting the compounding ratio of Compound B.

[Copolymer and polycondensation product]
The polycondensation product of the present invention comprises a copolymer obtained by polycondensation of a monomer mixture containing the compound A to compound C or the compound A to compound D.
In obtaining the copolymer, the production method and the polymerization method for obtaining the copolymer are not particularly limited.
In addition, in the polycondensation, the order of addition and the addition method of the compound A, the compound B, the compound C, and the compound D are not particularly limited. For example, the polycondensation is performed by adding all of the compounds A to D before the polycondensation reaction. A part of compound A to compound D is added before the condensation reaction, and then the remainder is added dropwise in portions, or a part of compound A to compound D is added before the polycondensation reaction, and the reaction time is constant. The remaining amount after the lapse may be additionally added.

The polycondensation product is, for example, compound A, compound B, compound C and compound D in the presence of a dehydration catalyst, in the absence of a solvent or in a solvent, reaction temperature: 80 ° C. to 150 ° C., normal pressure to pressure, For example, it can be obtained by polycondensation at 0.001 to 1 MPa.
Examples of the dehydration catalyst include hydrochloric acid, perchloric acid, nitric acid, formic acid, methanesulfonic acid, octylsulfonic acid, dodecylsulfonic acid, vinylsulfonic acid, allylsulfonic acid, phenolsulfonic acid, acetic acid, sulfuric acid, diethyl sulfate, dimethyl sulfate, Phosphoric acid, oxalic acid, boric acid, benzoic acid, phthalic acid, salicylic acid, pyruvic acid, maleic acid, malonic acid, nitrobenzoic acid, nitrosalicylic acid, paratoluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfone Examples include acids, fluoroacetic acid, thioglycolic acid, mercaptopropionic acid, activated clay, etc., and these dehydration catalysts can be used alone or in combination of two or more.

  When the polycondensation reaction is carried out in a solvent, examples of the solvent include water, glycol ether compounds such as propylene glycol monomethyl ether (PGME), aromatic compounds such as toluene and xylene, and cyclic aliphatic compounds such as methylcyclohexane. Further, those applicable as the above dehydration catalyst (acid catalyst), for example, acetic acid can also be used as a solvent.

The reaction temperature is preferably 95 ° C to 130 ° C, and the polycondensation reaction can be completed by reacting for 3 to 25 hours.
The polycondensation reaction is preferably carried out under acidic conditions, and preferably the pH of the reaction system is 4 or less.

In addition to compound A, compound B, compound C and compound D, other monomers capable of polycondensation with these compounds may be added to the monomer mixture as long as the effects of the present invention are not impaired.
Other monomers include cresol, catechol, resorcinol, nonylphenol, methoxyphenol, naphthol, methylnaphthol, butylnaphthol, bisphenol A, aniline, methylaniline, hydroxyaniline, methoxyaniline and / or salicylic acid, and 1 to 300 mol of alkylene. Adduct with oxide, phenol, phenoxyacetic acid, methoxyphenol, resorcinol, cresol, bisphenol A, nonylphenol, aniline, methylaniline, N-phenyldiethanolamine, N, N-di (carboxyethyl) aniline, N, N-di ( Carboxymethyl) aniline, phenolsulfonic acid, anthranilic acid and the like.

In order to reduce the content of the unreacted aldehyde component (compound C) in the reaction system after completion of the polycondensation reaction, various conventionally known methods can be employed. For example, a method in which the pH of the reaction system is made alkaline and heat treatment is performed at 60 to 140 ° C., a method in which the reaction system is reduced in pressure (−0.1 to −0.001 MPa) and aldehyde components are removed by volatilization, and a small amount of sulfurous acid is added. Examples thereof include a method of adding sodium hydrogen, ethylene urea, and / or polyethyleneimine.
The dehydration catalyst used in the reaction can be neutralized after completion of the reaction and removed by filtration as a salt form. However, even if the catalyst is not removed, the dispersion for the hydraulic composition of the present invention described later is used. The performance as an agent is not impaired. Examples of the catalyst removal method include phase separation, dialysis, ultrafiltration, use of an ion exchanger, and the like in addition to the above filtration.
In addition, workability | operativity, such as a measurement in the use as a dispersing agent for hydraulic compositions mentioned later, improves by neutralizing a reaction material and diluting with water etc. At this time, basic compounds used for neutralization include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, ammonia, monoethanolamine, diethanolamine, and triethanolamine. Organic amines such as these are used, and one or more of these are used in combination.

The finally obtained copolymer of the present invention has a weight average molecular weight (gel permeation chromatography method (hereinafter referred to as “GPC method”), in terms of polyethylene glycol) in the range of 5,000 to 100,000. More preferably, the weight average molecular weight is in the range of 10,000 to 80,000, particularly in the range of 15,000 to 50,000 in order to exhibit excellent dispersion performance.
As described above, the “polycondensation product” in the present invention may be composed only of a copolymer obtained by polycondensation of a monomer mixture containing compound A to compound D. Components including unreacted components and side reaction products generated in the polymerization step, alkylene oxide addition step and the like are also included.

<Use of polycondensation product and copolymer>
The polycondensation product and copolymer of the present invention can exhibit a wide range of performance as a dispersant in aqueous dispersions of various solid powders. Further, the polycondensation product and copolymer of the present invention can be used as the above-mentioned dispersant as it is (without adding anything), and publicly known and publicly used additives are appropriately employed depending on various applications. It can also be used in the form of a combined admixture.

<Dispersant for hydraulic composition>
Among the above uses, it can be suitably used in the form of a dispersant for a hydraulic composition containing the polycondensation product or copolymer.
In addition, the said hydraulic composition refers to the composition containing the powder (hydraulic powder) which has the physical property hardened | cured by a hydration reaction, for example, cement, gypsum, fly ash, etc. In addition, when hydraulic powder is a cement, a hydraulic composition is also called a cement composition.

The dispersant for hydraulic composition of the present invention can be used in the form of an admixture in which additives for known and publicly used hydraulic compositions are appropriately employed and combined depending on various uses. Specifically, conventionally known cement dispersants, high performance AE water reducing agents, high performance water reducing agents, AE water reducing agents, water reducing agents, air entraining agents (AE agents), foaming agents, antifoaming agents, setting retarders, At least one other additive selected from the group consisting of a setting accelerator, a separation reducing agent, a thickening agent, a shrinkage reducing agent, a curing agent, a water repellent and the like can be blended.
In addition, the dispersing agent for hydraulic compositions containing the polycondensation product or copolymer of the present invention is a form composed of the above polycondensation product or copolymer of the present invention, the polycondensation product of the present invention, or A form in which a copolymer and other publicly known admixtures are blended to form an admixture for hydraulic compositions, or the above-mentioned polycondensation product or copolymer and publicly known publicly used at the time of producing a hydraulic composition such as concrete The admixtures are added separately and finally mixed in the hydraulic composition.

Generally, cement dispersants are appropriately combined and used according to concrete production conditions and performance requirements. The same applies to the cement dispersant of the present invention, which is used as a cement dispersant alone or as a main agent, but as a modification aid for a cement dispersant having a large slump loss, or has an initial water reduction. It can be used in combination as a high cement dispersant.
Examples of known cement dispersants include polycarboxylic acids such as Japanese Patent Publication No. 59-18338, Japanese Patent No. 2628486, Japanese Patent No. 2774445, Japanese Patent No. 323002, Japanese Patent No. 3336456, Japanese Patent No. 3780456, and the like. There are also salts of the copolymer, and also include salts of naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate, lignin sulfonate, sodium gluconate, and sugar alcohol. The blending ratio of the polycondensation product or copolymer of the present invention and a known cement dispersant is, for example, 1:99 to 99: 1 mass%.

Specific examples of the air entraining agent include an anionic air entraining agent, a nonionic air entraining agent, and an amphoteric air entraining agent.
Examples of the setting retarder include inorganic setting retarders and organic setting retarders.
Examples of the accelerator include inorganic accelerators and organic accelerators.
Examples of thickeners / separation reducing agents include cellulose-based water-soluble polymers, polyacrylamide-based water-soluble polymers, biopolymers, nonionic thickeners, and the like.
Examples of antifoaming agents include nonionic antifoaming agents, silicone antifoaming agents, higher alcohols, and mixtures containing these as main components.

When the dispersant for a hydraulic composition of the present invention is applied to, for example, a cement composition, the component constituting the cement composition is a conventionally used concrete component, and cement (for example, ordinary Portland cement, early strength) Portland cement, ultra-high strength Portland cement, low heat / moderate heat Portland cement or blast furnace cement, etc.), aggregate (ie fine aggregate and coarse aggregate), admixture (eg silica fume, calcium carbonate powder, blast furnace slag fine powder, fly Ash, etc.), expansion material and water.
In addition, the admixtures other than the dispersion for the hydraulic composition of the present invention which can be added separately at the time of preparation include the above-mentioned publicly known air entraining agents, setting retarders, accelerators, separation reducing agents, thickening agents, There are a foaming agent, a shrinkage reducing agent, and the like, and these can be appropriately blended. The blending ratio of these components can be appropriately determined according to the type of the selected component and the purpose of use.

The amount of the dispersant for the hydraulic composition of the present invention varies depending on the blending conditions including the above-mentioned concrete material, but when the cement mass or pozzolanic fine powder such as fly ash is used in combination. About 0.05-5.0 mass% is normally added in conversion of solid content with respect to the total mass of cement and fly ash. In order to obtain water reduction and slump flow retention, it is better that the amount added is larger. However, if the amount is too large, setting delay is caused, and in some cases, curing failure may be caused.
The method of use is the same as in the case of ordinary cement dispersants, and is added to the stock solution during concrete kneading or diluted in kneading water in advance. Alternatively, concrete or mortar may be added after kneading and then uniformly kneaded again.

  The following examples illustrate the invention. However, the present invention is not limited to these examples and comparative examples.

In the examples, the physical properties of the samples were measured using the following apparatus under the following conditions.
(1) GPC (gel permeation chromatography)
<Gel permeation chromatography (GPC) measurement conditions>
Column: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (manufactured by Showa Denko KK)
Eluent: 50 mM sodium nitrate aqueous solution and acetonitrile mixture (volume ratio 80/20)
Detector: differential refractometer, calibration curve: polyethylene glycol

Example 1: Preparation of compound A
<EO adduct: No. Used in 1 to 13 polycondensation products>
A stainless steel high-pressure reactor equipped with a thermometer, a stirrer, a pressure gauge, and a nitrogen introduction tube was charged with 80 parts of diethylene glycol monophenyl ether (Hisolv DPH manufactured by Toho Chemical Industry Co., Ltd.) and 0.2 part of 96% potassium hydroxide. The reaction vessel was charged with nitrogen and heated to 150 ° C. in a nitrogen atmosphere. Then, 1700 parts of ethylene oxide was introduced into the reactor in 10 hours while maintaining 150 ° C. under a safety pressure, and then the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction, and polyethylene glycol monophenyl ether (EO) The number of moles added was 90).
Following this procedure, the number of moles of ethylene oxide added was variously changed to prepare various polyethylene glycol monophenyl ethers shown in Table 1 described later. Further, a 20 mol ethylene oxide adduct of phenol (see No. 11) was prepared following the above synthetic procedure, except that the starting material was phenol. High-solve EPH manufactured by Toho Chemical Industry Co., Ltd. was used as the 1 mol ethylene oxide adduct of phenol (see Nos. 4 and 9).

Example 2: Preparation of compound B
<Phosphate ester: No. Used in 1 to 10 and 12 polycondensation products>
In a 1 L reaction vessel equipped with a thermometer, a stirrer, a condenser, and a test tube, 400 g of xylene was charged, and the temperature was raised to reflux xylene. To this, 216 g of 89% phosphoric acid (manufactured by Lhasa Kogyo Co., Ltd.) was added dropwise over 2 hours, and after completion, the mixture was refluxed for 3 hours to dehydrate phosphoric acid. After confirming that the theoretical amount of reaction water had distilled into the test tube, 184 g of phenol was charged into the reaction vessel and refluxed again to advance the esterification reaction. Again, it was confirmed that 90% or more of the reaction water with respect to the theoretical amount was distilled into the test tube, and the reaction was completed. Xylene was removed by distillation under reduced pressure to obtain 330 g (No. 1, 2, 6, 7, 12) of phenol phosphate.
Moreover, it prepared according to the said synthetic | combination procedure except having replaced the phenol with pt-butyl phenol (DIC Corporation make, PTBP) 231g and 89% phosphoric acid 170g. 340 g (No. 3, 4, 8, 9) of pt-butylphenol phosphate ester was obtained. Furthermore, p-octylphenol (POP) manufactured by DIC Co., Ltd., 216 g, 89% phosphoric acid, 139 g was prepared in the same manner, and p-octylphenol phosphate ester 350 g (No. 5, 10). Got.

<Sulfate ester: No. Used in polycondensation products 11 and 13>
A phenol sulfate was obtained by following the above synthesis procedure except that the 89% phosphoric acid was replaced with 98% sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.).

Example 3: Preparation of compound D
<EO adduct: No. Used in 6 to 13 polycondensation products>
A stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet tube was charged with 100 parts of ortho-hydroxyethylphenol (Aldrich reagent) and 0.3 parts of 96% potassium hydroxide, Was replaced with nitrogen and heated to 130 ° C. under a nitrogen atmosphere. Then, 32 parts of ethylene oxide was introduced into the reactor in 4 hours while maintaining 130 ° C. under a safety pressure, and then the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction. A molar EO adduct was obtained.
Following this procedure, ethylene oxide addition moles were variously changed, and various EO adducts of hydroxyethylphenol shown in Table 1 were prepared.
<Phosphate derivative: Used in 12 and 13 polycondensation products>
A glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 3 mol of an ortho-hydroxyethylphenol EO adduct (total 6 mol adduct), and 1 mol at 50 ° C. with nitrogen bubbling. Of phosphoric anhydride was charged over 4 hours and reacted. Thereafter, an aging reaction was carried out at 100 ° C. for 3 hours to terminate the phosphoric esterification reaction, and an ortho-hydroxyethylphenol EO adduct phosphoric ester was obtained.

[Preparation Example 1: Preparation of polycondensation product (No. 1-5)]
In a glass reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, the raw materials (A) and (B) were charged at a molar ratio shown in Table 1. The temperature was raised to 70 ° C., and then 98% sulfuric acid was charged at 1.0 wt% with respect to the total weight of (A) and (B). Next, the raw material (C) was charged all at once into the reaction vessel at the molar ratio shown in Table 1, and then heated to 105 ° C. When reaching 105 ° C., the pH of the reaction product was 2.1 (1% aqueous solution, 20 ° C.). Six hours after reaching 105 ° C., the reaction was completed, 48% caustic soda was charged, and neutralization was performed so that the pH of the 1% aqueous solution of the reaction product was in the range of 5.0 to 7.5. Thereafter, an appropriate amount of water was added so that the solid content of the reaction product was 40% to obtain an aqueous solution of a polycondensation product. About this polycondensation product, GPC measurement was performed and the weight average molecular weight was calculated | required.

[Preparation Examples 6 to 13: Preparation of polycondensation product (No. 6 to 13)]
In a glass reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, the raw materials (A), (B), and (D) were charged at a molar ratio shown in Table 1. This was heated to 70 ° C., and then 98% sulfuric acid was charged at 1.0 wt% with respect to the total weight of (A), (B) and (D). Next, (C) the raw materials were charged all at once into the reaction vessel at the molar ratio shown in Table 1, and the temperature was raised by the same operation as in the above-mentioned cooking example 1, followed by neutralization after the reaction. The solid content was adjusted to 40% to obtain an aqueous solution of a polycondensation product. About this polycondensation product, GPC measurement was performed and the weight average molecular weight was calculated | required.

[Comparative Preparation Example 1: Preparation of polycondensation product of Comparative Example 1]
The polycondensation product of Comparative Example 1 was prepared according to the following procedure (paragraph [0049] [Preparation B.1 of the polycondensate of the present invention] disclosed in Japanese Patent No. 5507809.
1 mol poly (ethylene oxide) monophenyl ether (1000 g / mol), 2 mol phenoxyethanol phosphate (or a mixture of 2-phenoxyethanol dihydrogen phosphate and 2-phenoxyethanol hydrogen phosphate), 16.3 mol water, And 2 moles of H ₂ SO ₄ were stirred in the reaction vessel. Three moles of formaldehyde in the form of a 37% aqueous solution were added dropwise to the solution thus formed. The polycondensation reaction was completed at 105 ° C. for 5 hours. At the end of the reaction, the pH of the reaction mixture was brought to 10.5 using 20% aqueous NaOH. After a further 30 minutes at 105 ° C., the mixture was cooled to room temperature and the solid content was adjusted to about 30% by weight by adding water.
In the thus obtained polycondensation product of Comparative Example 1, the weight average molecular weight Mw measured by GPC was 22,000.

[Comparative Preparation Example 2: Preparation of polycondensation product of Comparative Example 2]
The polycondensation product of Comparative Example 2 was prepared according to the following procedure (paragraph [0069] [Example 1.1]) disclosed in JP-T-2014-503667.
First, 2-phenoxyethanol (96%, 16.92 g) was added to a reactor equipped with a jacket and mechanical impeller set at 70 ° C. _(80% in P 2 _{O 5,} 9.60g) polyphosphoric acid, while stirring the 2-phenoxyethanol was added to the reactor. The mixture was stirred at 80 ° C. for 30 minutes, followed by feeding polyoxyethylene monophenyl ether (96%, Mn = 5000 g / mol, 200 g). The mixture was then heated to 100 ° C. Concentrated sulfuric acid (96%, 6.10 g), formalin (37%, 9.36 g) and paraformaldehyde (94%, 1.92 g) are added to the mixture and the mixture is heated to 110-115 ° C. And stirred for 2 hours. The mixture was then allowed to cool to 60 ° C. and 32% by weight aqueous sodium hydroxide was added to neutralize the mixture to pH 9.1.
In the thus obtained polycondensation product of Comparative Example 2, the weight average molecular weight Mw measured by GPC was 22,000.

*1 No.4,9は2種の(A)成分：（EO平均付加モル数が90の化合物）/（ＥＯ付加モル数が1の化合物）＝0.8/0.2のモル比で併用。
*2 No.11は2種の(A)成分：（EO平均付加モル数が90の化合物）/（ＥＯ平均付加モル数が20の化合物）＝0.5/0.5のモル比で併用。

* 1 Nos. 4 and 9 are used in combination with 2 types of component (A): (compound with an average added mole number of EO of 90) / (compound with an added mole number of EO of 1) = 0.8 / 0.2.
* 2 No. 11 is used in combination with two types of component (A): (compound with 90 average EO addition moles) / (compound with 20 average EO addition moles) = 0.5 / 0.5.

[Test: Fresh mortar test]
<Mortar formulation>
Taiheiyo Cement Co., Ltd. ordinary Portland cement 500g, or a total of 500g of the cement and fly ash, fine aggregate 1350g, fine aggregate and clay, etc. [clay (collected fines) or clay (bentonite, kaolinite)] 1350 g, as the dispersant for hydraulic composition, the above polycondensation products 1 to 20 or the polycondensation products 1 to 2 of the comparative example [each polycondensation product is 0.18 in terms of solid content with respect to the cement mass. 225 g [water / cement ratio (mass ratio) = 0.45] using ion-exchanged water containing mass%, 0.20 mass%, or 0.22 mass% added (see Table 2)] Mortar was prepared (see mortar formulation in Table 2).

The clay (collected fine particles) used in this test is collected fine particles collected from Futtsuyama sand with a particle size of 75 μm or less. The nominal size specified in JIS Z 8801-1 is 75 μm. Used as collected fines).
Moreover, the following commercial item was used for clay.
Bentonite: Reagent (manufactured by Wako Pure Chemical Industries, Ltd.)
Kaolinite: RC-1 (manufactured by Takehara Chemical Industry Co., Ltd.)

<Fresh mortar test>
A fresh mortar test using a mortar according to the formulation shown in Table 2 was performed in accordance with JIS R 5201.
In detail, kneading water (ion-exchange water) prepared by adding a dispersant for hydraulic composition (polycondensation products 1 to 13 or polycondensation products 1 and 2 of comparative examples) in advance to powder ( In addition to cement, or cement and fly ash) and sand (fine aggregate, or fine aggregate and clay, etc.), using a high power mixer (manufactured by Maruto Seisakusho Co., Ltd.), knead at low speed for 45 to 60 seconds. Mix and leave for 30 seconds. The kneading time was appropriately selected as the time for confirming that the mortar was in a fluid state from the start of kneading (the kneading time was common in the blending A to blending E). In 20 seconds from the start of standing, the mortar attached to the wall of the container was scraped off, and after the standing period, the test mortar was prepared by kneading at high speed for 90 seconds.
In addition, in order to avoid the influence of the bubbles in the mortar on the fluidity of the mortar, the mortar used in the test was added with an antifoaming agent (Pronal 753W manufactured by Toho Chemical Industry Co., Ltd.) and the total mass of cement or cement and fly ash. The amount of air was adjusted in combination with an amount of 0.01 wt.

<Measurement of mortar flow and calculation of liquidity retention rate and liquidity fluctuation rate>
For these test mortars just after being kneaded and for test mortars after 30 minutes, a mini-slump cone (cone cylinder having an upper end inner diameter of 50 mm, a lower end inner diameter of 100 mm, and a height of 150 mm) conforming to JIS A 1171 “Test method for polymer cement mortar”. ) Was used to measure the spread of mortar (flow value).
The obtained results are shown in Table 3.

Regarding the test mortars according to Formulation A, Formulation C, and Formulation E, the flow rate immediately after kneading and the rate of change of the flow value after 30 minutes were calculated as the fluidity retention rate by the following formula.
Fluidity retention (%) = [flow value after 30 minutes / flow value immediately after kneading] × 100
The obtained results are shown in Table 3.

In addition, with respect to the test mortar having the same dispersant for hydraulic composition (and the amount used), the flow rate of fluidity, the clay or the flow value of the mortar not added clay or clay (formulation A mortar) The change rate of the flow value of the mortar (Formulation B to Formula E) when clay was added was calculated by the following formula. It can be evaluated that the closer the fluidity fluctuation rate (%) is to 100%, the better the result is that there is less change in fluidity due to the inclusion of clay or clay.
Fluidity fluctuation rate (%) = [flow value when clay or clay is added (blending B to E) / flow value when clay or clay is not added (blending A)] × 100
The obtained results are shown in Table 3.

<Measurement of curing property (exothermic peak)>
The test mortar produced in Formulation A was filled into a plastic container having a diameter of 10 cm and a height of 12 cm, and this was put in the center of a simple insulated box made of urethane foam, and a K-type thermocouple manufactured by Kyowa Denki Co., Ltd. The internal temperature of the mortar was measured using NTB-201A and the diameter of the strand (0.1 mm).
Then, from the history of the internal temperature of the mortar, the time to reach the maximum temperature (exothermic peak time: minutes (h: m)) was confirmed.
The obtained results are shown in Table 3.

<Evaluation of appearance of cured mortar>
Following the procedure of <Fresh Mortar Test> above, the test mortar prepared in Formulation E was filled in a triple mold made by Maruto Seisakusho Co., Ltd., and demolded after 24 hours to obtain a cured mortar. .
About the mortar hardened | cured material obtained in the said procedure, photography was carried out about the placement surface (4 cm x 16 cm), and this placement surface (surface photograph) was divided | segmented into 256 squares of 1 square 5 mm x 5 mm in total. The blackened area ratio (rounded to the first decimal place) was calculated by counting the number of blackened areas in the 256 squares, and the appearance (darkened area) was evaluated according to the following criteria.
Evaluation 1: Blackened area ratio on the surface of the cured body = 5.0% or higher 2: Blackened area ratio on the surface of the cured body = 3.0 to 4.9% or higher 3: Blackened area ratio on the surface of the cured body = 1. 0 to 2.9% or more 4: Blackened area ratio of the surface of the cured body = less than 1.0% Table 3 shows the results obtained.

As shown in Table 3, when Formulation A and Formulations B to D are compared, the hydraulic composition dispersant containing the polycondensation product of the present invention is clay (formulation B), bentonite in fine aggregate. Even when (Blend C) or kaolinite (Blend D) coexists, it is confirmed that the mortar flow value varies less than the blend A not containing these clays and the high fluidity can be maintained.
In addition, even when fly ash is used in combination with bentonite as a hydraulic powder in Formulation E, there is little fluctuation in the mortar flow value, and the flow value is maintained even after 30 minutes and fluidity is maintained. In addition, it was confirmed that darkening of the appearance of the cured product was suppressed as compared with the hydraulic composition dispersant containing the polycondensation product of the comparative example.
On the other hand, in the hydraulic composition dispersant containing the polycondensation products of Comparative Example 1 and Comparative Example 2 that do not contain the copolymer of the present invention, the mortar flow value varies greatly (decreases) depending on the viscosity and the blending of clay. ), And the flow value after 30 minutes also dropped significantly. Moreover, in the system using fly ash in combination, darkening on the surface of the cured body was conspicuous.

  More specifically, compound A (an alkylene oxide adduct of phenols or a derivative thereof) in the monomer mixture improves water reduction as the average number of moles of ethylene oxide added increases, and even if the amount added is reduced by 10%. It was confirmed that the same level of water reduction could be ensured (see Example 2 and Example 7).

  Moreover, in the compound B (phenol phosphate ester or sulfate ester derivative), a result that the appearance of the cured product was improved by having a substituent in the phenyl group was obtained. Further, it was confirmed that the appearance of the cured product was further improved by increasing the chain length of the substituted alkyl group (Examples 3 to 5, 8 to 10).

Furthermore, in the compound D (alkylene oxide adduct of hydroxyethylphenol), it was confirmed that the fluctuation of the mortar flow value can be further reduced in the blends B to E by using a copolymer blended with the compound D (Example 6). ~ 13). In particular, in the anionization of the terminal of Compound D, the phosphate ester greatly improved the fluctuation of the mortar flow value in Formulations B to D (Examples 12 and 13).

Claims (5)

Copolymerization obtained by polycondensing a monomer mixture containing a compound A represented by the following formula (A), a compound B represented by the formula (B) and one or more aldehyde compounds C represented by the formula (C) Polycondensation products, including coalescence.

(Where
R ₁ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,
A ₁ O represents an alkyleneoxy group having 2 to 4 carbon atoms,
m is the average number of moles of alkylene oxide added and represents a number from 1 to 300;
R ₂ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms. )

(Where
R ₃ represents a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, or an alkenyl group having 2 to 24 carbon atoms,
X ₁ represents a phosphate ester group or a sulfate ester group. )

(Where
R ₄ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group, or a heterocyclic group,
n represents a number from 1 to 100. ) The polycondensation product according to claim 1, wherein the monomer mixture further contains a compound D represented by the following formula (D).

(Where
A ₂ O and A ₃ O each independently represents an alkyleneoxy group having 2 to 4 carbon atoms,
p and q are average added moles of alkylene oxide, each independently representing a number from 0 to 300, and p + q ≧ 1;
X ₂ and X ₃ each independently represent a hydrogen atom, a phosphate ester group or a sulfate ester group. ) The monomer mixture is
Compound A, Compound B and Compound D are included at a molar ratio of Compound A: Compound B: Compound D = 0.1-2: 0.1-4: 0-10, and
Compound C is included in a molar ratio with respect to the total molar amount of Compound A, Compound B, and Compound D in the ratio of (Compound A + Compound B + Compound D): Compound C = 1-10: 10-1.
The polycondensation product according to claim 1 or 2. The polycondensation product according to any one of claims 1 to 3, wherein the monomer mixture contains two or more kinds of compounds A represented by the formula (A). A dispersant for a hydraulic composition comprising the polycondensation product according to any one of claims 1 to 4.