JP2006104480A - Phosphoric ester polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a dispersant for a hydraulic composition on an industrially practical level which is capable of imparting excellent dispersibility and effects for reducing the viscosity to a hydraulic composition. <P>SOLUTION: The phosphoric ester polymer is obtained by copolymerizing a specific monomer (1) having a polyoxyalkylene group, a phosphoric monoester monomer (2), and a phosphoric diester monomer (3), in which a weight-average molecular weight is 10,000-150,000, and a ratio (Mw/Mn) of a weight-average molecular weight (Mw) to number-average molecular weight (Mn) is 1.0-2.6. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a phosphate ester polymer and a method for producing a dispersant for a hydraulic composition. The present invention further relates to a phosphate ester polymer, a dispersant for a hydraulic composition containing the same, and a hydraulic composition containing the same.

  Among the admixtures for hydraulic compositions, there is one called a high-performance water reducing agent having a large fluidity-imparting effect. Typical examples include naphthalene sulfonic acid formaldehyde condensate salt (naphthalene type), melamine sulfonic acid formaldehyde condensate salt (melamine type), polycarboxylic acid type having a polyoxyalkylene chain, and the like.

  In recent years, concrete, which is a typical hydraulic composition, has become more durable. For example, the amount of water used in concrete has been reduced to increase its strength. Are also expected to increase. In order to reduce the amount of water, it is mainstream to use a polycarboxylic acid-based water reducing agent that is excellent in water reduction and fluidity retention. However, as the amount of water decreases, fresh concrete viscosity (hereinafter also referred to as concrete viscosity) increases, and there is a problem that workability and workability such as pumping, driving and filling into a mold form are lowered. This viscosity increase problem has not been sufficiently solved even with a polycarboxylic acid-based water reducing agent, and an additive having a higher concrete viscosity reducing effect is desired.

Against this background, Patent Document 1 discloses a concrete admixture containing a vinyl copolymer containing a high-chain-length oxyalkylene group and a specific monomer as essential components. Further, Patent Document 2 discloses a monoester or monoether having a polyalkylene glycol chain in order to obtain a cement dispersant capable of exhibiting excellent flow characteristics, high dispersion effect and quick setting regardless of the mixing ratio of water. And a polymer of a monomer having an unsaturated bond and a phosphate group.
JP 11-79811 A JP 2000-327386 A

  However, the polymer of Patent Document 1 has a limit in viscosity reduction, and the polymer of Patent Document 2 is desired to further improve fluidity and viscosity reduction.

  An object of the present invention is to provide an excellent dispersion effect or viscosity reduction effect to a hydraulic composition containing a hydraulic powder, and further to provide both excellent effects, and the dispersion for a hydraulic composition having good performance. Another object of the present invention is to provide a method capable of producing a phosphoric ester polymer that can be used as an agent at an industrially practical level.

  The present invention includes a monomer 1 represented by the following general formula (1) [hereinafter referred to as monomer 1] and a monomer 2 represented by the following general formula (2) [hereinafter referred to as monomer 2]. And a monomer 3 represented by the following general formula (3) (hereinafter referred to as “monomer 3”) at a pH of 7 or less.

[Wherein R ¹ and R ² are a hydrogen atom or a methyl group, R ³ is a hydrogen atom or —COO (AO) _n X, AO is an oxyalkylene group or oxystyrene group having 2 to 4 carbon atoms, n is It is the total average addition mole number of AO, the number of 3-200, X represents a hydrogen atom or a C1-C18 alkyl group. ]

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 12 carbon atoms, m1 represents a number of 1 to 30, and M represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

[Wherein R ⁶ and R ⁸ are each a hydrogen atom or a methyl group, R ⁷ and R ⁹ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number from 1 to 30 and M is hydrogen. Represents an atom, an alkali metal or an alkaline earth metal. ]

  The present invention also relates to a monomer 1 represented by the general formula (1), a monomer 2 represented by the general formula (2), and a single monomer represented by the general formula (3). It is related with the manufacturing method of the dispersing agent for hydraulic compositions which copolymerizes the body 3 at pH 7 or less.

  The present invention also relates to the monomer 1 represented by the general formula (1), the monomer 2 represented by the general formula (2), and the monomer represented by the general formula (3). The present invention relates to a phosphate ester polymer (hereinafter referred to as a first phosphate ester polymer) obtained by copolymerizing a mixed monomer containing 3 at a pH of 7 or less.

The present invention also relates to a phosphate ester copolymer (hereinafter referred to as a second phosphate ester polymer) obtained by copolymerizing the following (X) and (Y) at a pH of 7 or less.
(X) Monomer 1 represented by the general formula (1).
(Y) Phosphate ester obtained by reacting an organic hydroxy compound represented by the following general formula (4) with a phosphorylating agent.

[Wherein, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkylene group having 2 to 12 carbon atoms, and m4 represents a number of 1 to 30. ]

  The present invention also relates to the monomer 1 represented by the general formula (1), the monomer 2 represented by the general formula (2), and the monomer 3 represented by the general formula (3). The weight average molecular weight is 10,000 to 150,000, and the ratio between the weight average molecular weight (hereinafter referred to as Mw) and the number average molecular weight (hereinafter referred to as Mn). The present invention relates to a phosphate ester polymer (hereinafter referred to as a third phosphate ester polymer) having (Mw / Mn) of 1.0 to 2.6.

  Moreover, this invention relates to the dispersing agent for hydraulic compositions containing the phosphate ester type polymer of the said invention. Furthermore, this invention relates to the hydraulic composition containing hydraulic powder, water, and the dispersing agent for hydraulic compositions of the said invention.

  According to the present invention, even when a monomer containing a phosphate ester having a large amount of diester is used, a phosphate ester type suitable as a dispersant for a hydraulic composition capable of suppressing high molecular weight and performance degradation due to crosslinking. A method for producing a polymer is provided. Moreover, the production method of the present invention does not impair the properties as a dispersant for a hydraulic composition. The dispersant containing the phosphate ester polymer obtained by the production method of the present invention can impart an excellent dispersion effect and viscosity reduction effect to a hydraulic composition containing hydraulic powder, and has performance. It is good.

  Even if the phosphate ester polymer of the present invention is a highly durable high-strength hydraulic composition having a low water content and a large amount of hydraulic powder, it has a fluidity equal to or higher than that of a conventional polycarboxylic acid-based water reducing agent. / Or develops low viscosity. As a result, it is possible to impart workability and workability such as excellent pumping, driving and filling into a mold.

<< first phosphate ester polymer >>
The first phosphate ester polymer of the present invention is a phosphate ester obtained by copolymerizing monomer 1 and a mixed monomer including monomer 2 and monomer 3 at a pH of 7 or less. Based polymer. Preferred structures of the monomers 1 to 3 are the same as those described in the section of the third phosphate ester polymer.

As the mixed monomer containing the monomer 2 and the monomer 3, a commercial product containing a monoester and a diester can be used. For example, Phosmer M, Phosmer PE, Phosmer P ( Unichemical), JAMP514, JAMP514P, JMP100 (all Johoku Chemical), light ester P-1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate Available as phosphate (Aldrich reagent).

Moreover, the mixed monomer containing the monomer 2 and the monomer 3 is, for example, an organic hydroxy compound represented by the general formula (4), phosphoric anhydride (P ₂ O ₅ ), and water in a predetermined charging ratio. Can be produced as a reaction product.

  Monomers 2 and 3 are phosphoric acid esters of monomers having unsaturated bonds and hydroxyl groups, and the above-mentioned commercially available products and reaction products include monoester (monomer 2) and diester ( It has been confirmed that it contains compounds other than monomer 3). These other compounds are considered to be a mixture of polymerizable and non-polymerizable compounds, but in the present invention, such a mixture (mixed monomer) can be used as it is.

The contents of monomers 2 and 3 in the mixed monomer can be calculated based on ³¹ P-NMR measurement results.
< ³¹ P-NMR measurement conditions>
・ Inverse-gated-decoupling method
・ Measurement range: 6459.9Hz
・ Pulse delay time 30sec
Observation data point 10336
・ Pulse width (5.833μsec) 35 ° pulse ・ Solvent CD ₃ OH (deuterated methanol) (30% by weight)
・ Number of integration 128

  Under these conditions, the signal of the obtained chart belongs to the following compound, so that it is possible to determine the relative quantitative ratio from the area ratio.

For example, when the organic hydroxy compound is a phosphorous oxide of “2-hydroxyethyl methacrylate”, it can be assigned as follows.
・ 1.8ppm to 2.6ppm: phosphoric acid ・ 0.5ppm to 1.1ppm: Monomer 2 (monoester)
-0.5 ppm to 0.1 ppm: monomer 3 (diester form)
-1.0 ppm to -0.6 ppm: Triester form -11.1 ppm to -10.9 ppm, -12.4 ppm to -12.1 ppm: Pyrophosphate monoester --12.0 ppm to -11.8 ppm: Pyrophosphate diester -11.2 ppm to -11.1ppm: pyrophosphoric acid, other peaks: unknown

  In the present invention, the phosphoric acid content in the mixed monomer was quantified to determine the ratio of the monomer 2 and the monomer 3 in the mixed monomer. Specifically, the calculation is performed as follows.

The absolute amount (% by weight) of the phosphoric acid content in the sample is determined by gas chromatography. Since the relative molar ratio of phosphoric acid, mono-isomer, and di-isomer in the sample can be obtained from the results of P-NMR, the absolute amounts of mono-isomer and di-isomer were calculated based on the absolute amount of phosphoric acid.

[Phosphoric acid content]
The conditions for gas chromatography are as follows.
Sample: Methylation with diazomethane Example) Methylation by adding 1 to 1.5 cc of diazomethane in diethyl ether to 0.1 g of sample Column: Ultra ALLOY, 15 m × 0.25 mm (inner diameter) × 0.15 μmdf
Carrier gas: He, split ratio 50: 1
Column temperature: 40 ° C. (5 min) (hold) → 10 ° C./min (temperature rise) → 15 min after reaching 300 ° C. Hold inlet temperature: 300 ° C.
Detector temperature: 300 ° C
Under the above conditions, a phosphate-derived peak is detected around 9 minutes, and the phosphate content in the unknown sample can be calculated by a calibration curve method.

[Content of mono- and di-form]
Based on the phosphoric acid content determined above, the total amount of mono- and di-isomers in the reagents used in Examples and the like described below was calculated as follows. The pyrophosphoric acid monoester, pyrophosphoric acid diester, and pyrophosphoric acid were calculated by assigning the decomposition products to phosphoric acid and the monoester compound in consideration of hydrolysis during the polymerization process.
・ Ethyleneglycol methacrylate phosphate (Aldrich reagent): 86.4% by weight
・ Hosmer M: 81.8% by weight
-Light ester P1M: 88.8% by weight

When the charge molar ratio of the monomer is calculated based on the breakdown of the mono- and di-forms from the above results and the NMR results, it is as follows in the case of Example 1-1.
Ω-methoxypolyethyleneglycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.) = 33.6 mol%
-Mono (2-hydroxyethyl) phosphate ester = 44.7 mol%
・ Di- (2-hydroxyethyl) phosphate ester = 21.7 mol%

  As described above, industrially, phosphate ester monomers are usually obtained as a mixture containing a monoester (monomer 2) and a diester (monomer 3). Among these, since diesters are likely to have a high molecular weight (gelation) by crosslinking, such a mixture is restricted in production in fields using the properties, for example, thickeners, adhesives, coatings, etc. Can be used suitably without receiving much. On the other hand, in admixtures for hydraulic compositions (dispersants, water reducing agents, etc.), polymers containing phosphate groups are preferable because of their excellent adsorptive power to hydraulic substances, but dispersibility and viscosity are reduced by increasing the molecular weight. The effect is lowered, which is not preferable from the viewpoint of handleability. However, it is industrially disadvantageous to separate the monoester form and the diester form from the mixture of phosphate esters as raw materials from the application and economical properties of the hydraulic composition.

  From the viewpoint of fluidity and viscosity reduction, it is better to use a mixture of phosphate esters containing a large amount of monoester, but even if it contains a large amount of diester, By controlling the polymerization molar ratio, fluidity and viscosity reduction can be adjusted.

<< second phosphate ester polymer >>
The present invention provides a phosphate ester copolymer (second phosphate ester polymer) obtained by copolymerizing the following (X) and (Y) at a pH of 7 or less. For the preferable structure of the monomer 1 and the preferable structure of the phosphate ester (Y), the description of the third phosphate ester polymer can be referred to.
(X) Monomer 1 represented by the general formula (1).
(Y) Phosphate ester obtained by reacting the organic hydroxy compound represented by the general formula (4) with a phosphorylating agent.

  1-20 are preferable, as for m4 in General formula (4), 1-10 are more preferable, and 1-5 are especially preferable.

  This phosphate ester (Y) is obtained by phosphorylating the organic hydroxy compound represented by the general formula (4) with a phosphorylating agent.

  Examples of the phosphorylating agent include orthophosphoric acid, phosphorus pentoxide (anhydrous phosphoric acid), polyphosphoric acid, phosphorus oxychloride and the like, and orthophosphoric acid and phosphorus pentoxide are preferable. These may be used alone or in combination of two or more. Further, the phosphorylating agent (Z) described later is also preferable. In this invention, the quantity of the phosphorylating agent at the time of making an organic hydroxy compound and a phosphorylating agent react can be determined timely according to the target phosphate ester composition.

  Phosphoric acid ester (Y) has an organic hydroxy compound and a phosphorylating agent in a ratio defined by the following formula (I) of 2.0 to 4.0, more preferably 2.5 to 3.5, particularly 2.8. What was obtained by making it react on the conditions of -3.2 is preferable.

In the present invention, in the formula (I), the phosphorylating agent is treated as P ₂ O ₅ .n (H ₂ O) for convenience.

In particular, the phosphorylating agent includes phosphorous pentoxide (Z-1) and at least one selected from the group consisting of water, phosphoric acid and polyphosphoric acid (Z-2) [hereinafter, phosphorylating agent (Z). In this case, too, the formula (I) includes phosphorus pentoxide (Z-1) and at least one selected from the group consisting of water, phosphoric acid and polyphosphoric acid (Z-2). For the sake of convenience, the phosphorylating agent (Z) is treated as P ₂ O ₅ .n (H ₂ O).

Further, the number of moles of the phosphorylating agent defined by the formula (I) means the amount of phosphorous agent introduced into the reaction system as a raw material, particularly the amount of P ₂ O ₅ units derived from the phosphorylating agent (Z) (mole). ). The number of moles of water refers to water (H ₂ O derived from the phosphorylating agent (Z) introduced into the reaction system as a raw material.
) Amount (mole). That is, the reaction system includes water when polyphosphoric acid is represented as (P ₂ O ₅ .xH ₂ O) and orthophosphoric acid is represented as [1/2 (P ₂ O ₅ .3H ₂ O)]. It will contain all the water present in it.

  Moreover, 20-100 degreeC is preferable and, as for the temperature at the time of adding a phosphorylating agent to an organic hydroxy compound, 40-90 degreeC is more preferable. The time required for adding the phosphorylating agent to the reaction system (the time from the start of addition to the end of addition) is preferably 0.1 hour to 20 hours, and more preferably 0.5 hour to 10 hours.

  The temperature of the reaction system after adding the phosphorylating agent is preferably 20 to 100 ° C, more preferably 40 to 90 ° C. The copolymerization can be carried out based on a method for producing a phosphate ester polymer described later.

  After completion of the phosphorylation reaction, the resulting phosphoric acid condensate (an organic compound or a phosphoric acid having a pyrophosphate bond) may be reduced by hydrolysis, or even without hydrolysis, the phosphoric acid of the present invention. It is suitable as a monomer for producing an ester polymer.

<< Third Phosphate Ester Polymer >>
The third phosphate ester polymer of the present invention is obtained by copolymerizing monomers 1, 2 and 3, Mw is 10,000 to 150,000, and Mw / Mn is 1. It is a phosphate ester type polymer which is 0-2.6. In this phosphate ester-based polymer, Mw is 10,000 or more, preferably 12,000 or more, more preferably 13,000 or more, more preferably 14,000 from the viewpoint of the expression of the dispersion effect and the viscosity reduction effect. 5,000 or more, particularly preferably 15,000 or more, and high molecular weight by cross-linking, suppression of gelation and performance are 150,000 or less, preferably 130,000 or less from the viewpoint of dispersion effect and viscosity reduction effect. More preferably, it is 120,000 or less, More preferably, it is 110,000 or less, Most preferably, it is 100,000 or less, From the both viewpoints, Preferably it is 12,000-130,000, More preferably, it is 13,000-120. 1,000, more preferably 14,000 to 110,000, particularly preferably 15,000 to 100,000. It is. It has Mw of this range, and Mw / Mn is 1.0-2.6. Here, the value of Mw / Mn is the degree of dispersion. The closer the value is to 1, the closer the molecular weight distribution is to the monodispersion, and the farther from 1 (the larger) the wider the molecular weight distribution.

  The phosphate ester polymer of the present invention having the Mw / Mn value as described above is a polymer having a branched structure based on a diester structure, but has a great feature that the molecular weight distribution is very narrow. Such a phosphoric ester polymer of the present invention can be suitably produced by the production method of the present invention described later.

  Mw / Mn of the phosphoric ester polymer of the present invention as described above is 1.0 or more from the viewpoint of ensuring practical production ease, dispersibility, viscosity reduction effect, and versatility with respect to materials and temperature. From the viewpoint of achieving both a dispersibility and a viscosity reducing effect, it is 2.6 or less, preferably 2.4 or less, more preferably 2.2 or less, still more preferably 2.0 or less, and particularly preferably 1. From the viewpoint of combining the above two points, it is preferably 1.0 to 2.4, more preferably 1.0 to 2.2, more preferably 1.0 to 2.0, and particularly preferably 1. 0.0 to 1.8.

Mw and Mn of the third phosphate ester polymer of the present invention are those measured by gel permeation chromatography (GPC) method under the following conditions. In addition, Mw / Mn of the phosphate ester type polymer in the present invention is calculated based on the peak of the polymer.
[GPC conditions]
Column: G4000PWXL + G2500PWXL (Tosoh)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2mg / mL
Reference material: Polyethylene glycol equivalent

The phosphate ester polymer satisfying Mw / Mn as described above has an appropriate branched structure by suppressing cross-linking by the monomer 3 which is a diester body, and has a structure in which adsorbing groups are densely present in the molecule. It is thought to form. Further, since the degree of dispersion Mw / Mn is controlled within a predetermined range, it approaches a system in which molecules of the same size are monodispersed, so that it is considered possible to increase the amount of adsorption on the adsorption target substance (for example, cement particles). Satisfying both of these conditions makes it possible to densely pack the substance to be adsorbed, such as cement particles, and is estimated to be effective in achieving both a dispersibility and a viscosity reducing effect.

  Further, in the chart pattern showing the molecular weight distribution obtained by the GPC method under the above conditions, the area having a molecular weight of 100,000 or more is 5% or less of the total area of the chart, so that dispersibility (required addition amount reduction) It is more preferable in terms of the viscosity reducing effect.

[Monomer 1]
For monomer 1, R ³ in general formula (1) is preferably a hydrogen atom, and AO has 2 to 4 carbon atoms.
The oxyalkylene group is preferably an ethyleneoxy group (hereinafter referred to as an EO group), more preferably 70 mol% or more, further 80 mol% or more, further 90 mol% or more, and especially all AO is an EO group. Preferably there is. X is preferably a hydrogen atom or an alkyl group having 1 to 18, more preferably 1 to 12, further 1 to 4, and 1 or 2 carbon atoms, and particularly preferably a methyl group. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable. Here, n in the formula (1) is 3 to 200, preferably 4 to 120, from the viewpoint of the dispersibility of the polymer in the hydraulic composition and the effect of imparting viscosity. In addition, AO is different among n repeating units on average, and random addition, block addition, or a mixture thereof may be included. AO can also contain a propyleneoxy group etc. besides EO group.

[Monomer 2]
Monomer 2 includes phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester, phosphoric acid mono (2-hydroxyethyl) acrylic acid ester, polyalkylene glycol mono (meth) acrylate acid phosphoric acid ester, and the like. It is done. Of these, mono (2-hydroxyethyl) methacrylic acid phosphate is preferable from the viewpoint of ease of production and product quality stability.

[Monomer 3]
Examples of the monomer 3 include phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid di-[(2-hydroxyethyl) acrylic acid] ester, and the like. Among these, di-[(2-hydroxyethyl) methacrylic acid] ester phosphate is preferable from the viewpoint of ease of production and quality stability of the product.

  Any of the monomers 2 and 3 may be alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts, and the like of these compounds.

  M1 of the monomer 2 and m2 and m3 of the monomer 3 are each preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

The third phosphate polymer of the present invention, by ¹ H-NMR under the following conditions, since the double bond derived from the monomer has disappeared, to monomeric 1,2,3 It is suggested that each have a derived unit.
[ ¹ H-NMR conditions]
A polymer dissolved in water and dried under reduced pressure is dissolved in deuterated methanol at a concentration of 3 to 4% by weight, and ¹ H-NMR is measured. The residual rate of double bonds is measured by an integrated value of 5.5 to 6.2 ppm. In addition, the measurement of ¹ H-NMR uses “Mercury 400 NMR” manufactured by Varian, the number of data points is 42052, the measurement range is 6410.3 Hz, the pulse width is 4.5 μs, the pulse waiting time is 10 S, and the measurement temperature is 25.0 ° C. Performed under conditions.

That is, the third phosphate ester polymer of the present invention having the Mw / Mn value as described above has, as its structural unit, a structural unit derived from monomer 1, a structural unit derived from monomer 2, and a single unit. The structural unit derived from the monomer 3 is included. These structural units are structural units derived from the respective monomers incorporated into the polymer by cleavage of the ethylenically unsaturated bonds of the monomers 1, 2 and 3 and addition polymerization. The ratio of these structural units in the polymer depends on the charging ratio, and when the monomers used for copolymerization are only monomers 1 to 3, the molar ratio of each structural unit is the monomer charging molar ratio. It is thought that it almost agrees with

<< Production Method of Phosphate Ester Polymer >>
The present invention relates to a method for producing a phosphate ester polymer in which monomer 1, monomer 2, and monomer 3 are copolymerized at a pH of 7 or less. Any of the above phosphoric ester polymers of the present invention can be produced by this production method. It is also preferable to use a mixed monomer containing monomer 2 and monomer 3.

  The present inventors have found that a polymer derived from a specific phosphate ester is useful for reducing the viscosity of a hydraulic composition which is one of the problems of the present invention. However, it has been found that the prior art does not provide sufficient disclosure for the problem of industrializing such polymers.

  Patent Document 1 discloses that copolymerization of methallylsulfonic acid is useful for adjusting the molecular weight, but in the method of neutralizing and polymerizing in advance disclosed in the examples, the reaction solution is It becomes non-uniform and it is difficult to produce a polymer having industrially stable performance. On the other hand, in Patent Document 2, only a monoester corresponding to the monomer 2 of the present invention is used as the phosphate ester, but a separation and purification step is required to obtain the monoester alone, and the hydraulic property Considering the use and production efficiency of the composition, it is disadvantageous for industrial production. Hereinafter, the manufacturing method of the phosphate ester type polymer obtained using the monomers 1-3 is demonstrated.

  As described above, it has been difficult to use a phosphate ester monomer that is industrially obtained as a mixture for use in a hydraulic composition. However, in the production method of the present invention, the monomer 2 and / or the single monomer is used. The monomer 1 containing the monomer 3 is used for the reaction in a specific pH range, and the monomer 1, the phosphate ester monomer 2 and the monomer 3 are copolymerized. Thus, even if a raw material containing a diester is used, the occurrence of crosslinking (high molecular weight, gelation) is suppressed, and the excellent performance as a dispersant for a hydraulic composition of a phosphate ester polymer can be maintained. This is a very advantageous production method in the field of hydraulic compositions.

  The phosphoric acid ester polymer according to the present invention is represented by the monomer 1 having an oxyalkylene group represented by the general formula (1) and the general formulas (2) and (3) having a phosphoric acid group. It is a polymer obtained by copolymerizing the monomers 2 and 3 to be produced.

  The preferable thing of the monomers 1-3 is as above-mentioned, respectively, and the above-mentioned commercial item and reaction product can also be used.

  In the copolymerization of the monomers, the molar ratio between the monomer 1 and the monomers 2 and 3 is as follows: monomer 1 / (monomer 2 + monomer 3) = 5/95 to 95/5 Furthermore, 10/90 to 90/10 are preferable. The molar ratio of monomer 1, monomer 2 and monomer 3 is as follows: monomer 1 / monomer 2 / monomer 3 = 5 to 95/3 to 90/1 to 80 / 5 to 96/3 to 80/1 to 60 (however, the total is 100) is preferable. In addition, about the monomer 2 and the monomer 3, the molar ratio and mol% shall be calculated based on an acid type compound (hereinafter the same).

Moreover, in this invention, the ratio of the monomer 3 in all the monomers used for reaction can be 1-60 mol%, Furthermore, it can be 1-30 mol%.
Further, the molar ratio of the monomer 2 and the monomer 3 can be set to monomer 2 / monomer 3 = 99/1 to 4/96, and more preferably 99/1 to 5/95.
Since the monomer raw material containing the monomer 3 in such a range is generally expected to be gelled, it is usually used as a raw material for producing a polymer for a dispersant for a hydraulic composition. Not. However, in the present invention, by using the monomer solution containing monomer 2 and / or monomer 3 at a pH of 7 or less for the reaction, gelation is suppressed and suitable as a dispersant for a hydraulic composition. Such a phosphoric acid ester polymer can be produced at an industrially practical level.

Hereinafter, more preferable production conditions will be described from the viewpoints of gelation suppression, adjustment of a suitable molecular weight, and performance design of a dispersant for hydraulic composition. From this point of view, in the present invention, at the time of copolymerization, 4 mol% or more, further 6 mol% or more, particularly 8 mol% or more of the chain transfer agent is added to the total number of moles of monomers 1 to 3. It is preferable to use it. Further, the upper limit of the amount of chain transfer agent used is preferably 100 mol% or less, more preferably 60 mol% or less, still more preferably 30 mol% or less, particularly preferably based on the total number of moles of monomers 1 to 3. May be 15 mol% or less. For more details,
(1) When n of monomer 1 is 3 to 30,
(1-1) When the molar ratio of the monomer 2 and the monomer 3 in the monomers 1 to 3 is 50 mol% or more, the chain transfer agent is 6 to It is preferable to use 100 mol%, in particular 8 to 60 mol%,
(1-2) When the molar ratio of the monomer 2 and the monomer 3 in the monomers 1 to 3 is less than 50 mol%, the chain transfer agent is 4 to 4 with respect to the monomers 1 to 3. It is preferable to use 60 mol%, in particular 5 to 30 mol%,
(2) When n of monomer 1 exceeds 30, the chain transfer agent is preferably used in an amount of 6 to 50 mol%, particularly 8 to 40 mol%, based on monomers 1 to 3.

  In the production method of the present invention, the reaction rate of the monomers 2 and 3 is preferably 60% or more, more preferably 70% or more, further 80% or more, further 90% or more, and particularly preferably 95% or more. The amount of transfer agent used can be selected from this viewpoint. Here, the reaction rate of the monomers 2 and 3 is calculated by the following equation.

The ratio (mol%) of monomer 2 and monomer 3 in the phosphorus-containing compound in the reaction system at the start and end of the reaction should be calculated based on the above ¹ H-NMR measurement results. Can do.

  In the production of the phosphate ester polymer according to the present invention, in addition to the monomers 1 to 3, other monomers capable of copolymerization may be used. Examples of other copolymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, any of these alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts. In addition, acrylic monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and any one or more of alkali metal salts, alkalis Anhydrous compounds such as earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters and maleic anhydride may also be used. Furthermore, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, Examples include 2- (meth) acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. The total proportion of monomers 1 to 3 in all monomers is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 75 to 100 mol%. From the viewpoint of achieving the performance as the dispersant described in the third phosphate ester polymer, it is more than 95 mol% to 100 mol%, more preferably 97 to 100 mol%, particularly 100 mol%. .

  In the production method of the present invention, the reaction temperature of the monomers 1 to 3 is preferably 40 to 100 ° C., more preferably 60 to 90 ° C., and the reaction pressure is 101.3 to 111.5 kPa (1 to 1 in terms of gauge pressure). 0.1 atm), more preferably 101.3 to 106.4 kPa (1-1.05 atm).

  In the production method of the present invention, a monomer solution containing the monomer 2 and / or monomer 3 prepared with an appropriate solvent is preferably added to another monomer in the presence of a predetermined amount of chain transfer agent. The copolymer is copolymerized with the monomer at a pH of 7 or less. Moreover, you may use the other monomer, polymerization initiator, etc. which can be copolymerized.

  In the present invention, the monomer 1, the monomer 2 and the monomer 3 are reacted at a pH of 7 or less. In the present invention, the pH at 20 ° C. of the reaction solution collected during the reaction (from the start of the reaction to the end of the reaction) is defined as the pH during the reaction. Usually, the reaction may be started under conditions that clearly show that the pH during the reaction is 7 or less (monomer ratio, solvent, other components, etc.).

  When the reaction system is non-aqueous, it can be measured by adding an amount of water capable of measuring pH to the reaction system.

In the case of the monomers 1 to 3 that are the subject of the present invention, if the reaction is carried out under the conditions exemplified in the following (1) and (2), the pH during the reaction is usually adjusted under consideration of other conditions. It is considered to be 7 or less. Further, the pH may temporarily exceed 7 in the initial stage of the reaction as long as it does not affect the entire reaction, such as no gel is formed.
(1) A monomer solution having a pH of 7 or less containing all of monomers 1 to 3 is used for the copolymerization reaction of monomers 1 to 3.
(2) The copolymerization reaction of monomers 1 to 3 is started at pH 7 or less. That is, the reaction is started after the reaction system containing the monomers 1 to 3 is brought to pH 7 or lower.

In particular,
(I) The pH of the monomer solution containing the monomers 1 to 3 is adjusted to 7 or less to initiate the copolymerization reaction. (Ii) A monomer solution containing the monomers 1 to 3 (pH is arbitrary but is preferably 7 or less) is dropped into the reaction system.
(Iii) A monomer solution containing monomer 1 (pH is arbitrary but preferably 7 or less) and a monomer solution containing monomer 2 (pH is arbitrary but 7 or less are preferred). ) And a monomer solution containing the monomer 3 (pH is arbitrary but is preferably 7 or less) are separately added dropwise to the reaction system.
(Iv) Reaction is performed by appropriately combining the above. For example, a part of a monomer solution containing the monomers 1 to 3 (pH is arbitrary but preferably 7 or less) is charged into the reaction system, and the remaining monomer solution is dropped into the reaction system. .

In the above (iii) and (iv), it is necessary to control the dropping conditions of the monomer solution to be dropped so as not to deviate from the set monomer molar ratio. Moreover, in said (ii)-(iv), other reaction conditions are considered so that pH of the reaction system containing the dripped monomers 1-3 may be 7 or less, Preferably it is 4 or less.

  The pH of the reaction system can be adjusted with an inorganic acid (phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc.), NaOH, KOH, triethanolamine, or the like, if necessary.

  As described above, in the present invention, in order to make the pH of the reaction system during the reaction 7 or less, the monomer solution containing at least one of the monomer 2 and the monomer 3 in the monomer solution used for the reaction. It is preferable that the pH of the body solution is 7 or less. The monomer solution having a pH of 7 or lower contains at least one of monomer 2 and monomer 3, and contains monomer 1, and further contains a chain transfer agent and other monomers. It may be. Here, the monomer solution containing the monomer 2 and / or the monomer 3 is preferably a water-containing system (that is, the solvent contains water) for pH measurement. May be measured by adding the required amount of water. From the viewpoint of uniformity of the monomer solution, prevention of gelation, and suppression of performance degradation, the pH is 7 or less, preferably 0.1 to 6, and more preferably 0.2 to 4.5. Monomer 1 is also preferably used as a monomer solution having a pH of 7 or less. This pH is at 20 ° C.

  The pH of the reaction system (polymerization system) before the reaction in which the monomer is finally charged is 20 ° C. from the viewpoint of stability when controlling the molecular weight of the polymer and ease of pH control during the reaction. It is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, and particularly preferably 2 or less. Preferably, the pH of the monomer solution containing monomer 2 and / or monomer 3 (pH of the reaction system at the start of the reaction), the pH of the reaction system during the reaction, and the pH of the reaction system at the end of the reaction are Both are 7 or less.

  In addition, when these monomers 1 to 3 are not used in a water-containing state (that is, dropped as a liquid component as they are), the pH of the polymerization system is inevitably 7 or less, and such a method is also suitable. The pH of the final polymerization system before neutralization is preferably 6 or less, more preferably 5 or less, further 4 or less, and particularly preferably 2 or less.

[Chain transfer agent]
The chain transfer agent has a function of causing a chain transfer reaction in radical polymerization (a reaction in which a growing polymer radical reacts with another molecule to move a radical active site). It is a substance to be added.

  Examples of chain transfer agents include thiol chain transfer agents and halogenated hydrocarbon chain transfer agents, and thiol chain transfer agents are preferred.

As the thiol chain transfer agent, those having a —SH group are preferable, and in particular, the general formula HS—R—Eg (wherein R represents a hydrocarbon-derived group having 1 to 4 carbon atoms, and E is − OH, —COOM, —COOR ′ or —SO ₃ M group, M represents a hydrogen atom, monovalent metal, divalent metal, ammonium group or organic amine group, and R ′ represents an alkyl having 1 to 10 carbon atoms. And g represents an integer of 1 to 2). For example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, Examples include octyl thioglycolate, octyl 3-mercaptopropionate, and the like from the viewpoint of chain transfer effect in a copolymerization reaction including monomers 1 to 3. Mercaptoethanol are preferable, more preferably mercaptopropionic acid. These 1 type (s) or 2 or more types can be used.

  Examples of the halogenated hydrocarbon chain transfer agent include carbon tetrachloride and carbon tetrabromide.

  Examples of other chain transfer agents include α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, 2-aminopropan-1-ol and the like. A chain transfer agent can use 1 type (s) or 2 or more types.

[Polymerization initiator]
In the production method of the present invention, it is preferable to use a polymerization initiator, and in particular, the polymerization initiator is 5 mol% or more, further 7 to 50 mol%, particularly 10 to the total number of moles of monomers 1 to 3. It is preferable to use -30 mol%.

  As an aqueous polymerization initiator, persulfuric acid ammonium salt or alkali metal salt or hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) Water-soluble azo compounds such as dihydrate are used. In addition, an accelerator such as sodium bisulfite and an amine compound can be used in combination with the polymerization initiator.

[solvent]
The production method of the present invention can be carried out by a solution polymerization method, and the solvent used at that time contains water or water and methyl alcohol, ethyl alcohol, isopropyl alcohol acetone, methyl ethyl ketone, or the like. Examples of the solvent include hydrous solvents. In view of handling and reaction equipment, water is preferred. Especially when an aqueous solvent is used, a monomer solution containing monomer 2 and / or monomer 3 is used for the reaction at a pH of 7 or less, further 0.1 to 6, particularly 0.2 to 4, and copolymerization reaction Is preferable from the viewpoint of uniformity (handleability) of the monomer mixture, monomer reaction rate, and crosslinking by hydrolysis of the pyro compound of the phosphoric acid compound.

  An example of the manufacturing method of this invention is shown. A predetermined amount of water is charged into a reaction vessel, the atmosphere is replaced with an inert gas such as nitrogen, and the temperature is raised. Prepare monomer 1, monomer 2, monomer 3, chain transfer agent mixed and dissolved in water, and polymerization initiator dissolved in water, and take 0.5 to 5 hours. Drip into the reaction vessel. At that time, each monomer, chain transfer agent and polymerization initiator may be dropped separately, or a mixed solution of monomers can be charged in a reaction vessel in advance and only the polymerization initiator can be dropped. is there. That is, the chain transfer agent, the polymerization initiator, and other additives may be added as an additive solution separately from the monomer solution, or may be added to the monomer solution after being added. From the viewpoint of stability, it is preferable to supply the reaction system as an additive solution separately from the monomer solution. In any case, the pH of the solution containing the monomer 2 and / or the monomer 3 is preferably 7 or less. Further, the copolymerization reaction is carried out with an acid agent or the like while maintaining the pH at 7 or less, and preferably aging is carried out for a predetermined time. The polymerization initiator may be added dropwise at the same time as the monomer, or may be added in portions, but it is preferable to add in portions in terms of reducing unreacted monomers. For example, in the total amount of the polymerization initiator to be finally used, 1/2 to 2/3 polymerization initiator is added simultaneously with the monomer, and the remainder is aged for 1 to 2 hours after the completion of the monomer dropping, It is preferable to add. If necessary, it is further neutralized with an alkali agent (such as sodium hydroxide) after completion of ripening to obtain the phosphate ester polymer according to the present invention. The manufacturing method of this invention is suitable as a manufacturing method of the dispersing agent for hydraulic compositions containing the phosphate ester type polymer of the said invention.

  The total amount of the monomers 1, 2, 3 in the reaction system and other copolymerizable monomers is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, and particularly preferably 20 to 50% by weight. .

<< Dispersant for hydraulic composition >>
The phosphate ester polymer of the present invention can be used as a dispersant for a hydraulic composition in various inorganic hydraulic powders that exhibit curability by a hydration reaction, including various cements. The dispersant for a hydraulic composition containing the polymer of the present invention may be powdery or liquid. In the case of a liquid form, those using water as a solvent or a dispersion medium (such as an aqueous solution) are preferable from the viewpoint of workability and reduction of environmental load. In the dispersant of the present invention, the content of the polymer of the present invention is preferably 10 to 100% by weight, more preferably 15 to 100% by weight, and still more preferably 20 to 100% by weight in the solid content. In the case of a liquid, the solid content concentration is preferably 5 to 40% by weight, more preferably 10 to 40% by weight, and still more preferably 20 to 35% by weight, from the viewpoints of manufacturability and workability. Further, the dispersant of the present invention may be used in a ratio of 0.02 to 1 part by weight and 0.04 to 0.4 part by weight in solid content concentration of the polymer with respect to 100 parts by weight of the hydraulic powder. From the viewpoint of dispersion effect.

  Examples of the cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, and eco-cement (for example, JIS R5214). As hydraulic powder other than cement, blast furnace slag, fly ash, silica fume and the like may be included, and non-hydraulic limestone fine powder and the like may be included. Silica fume cement or blast furnace cement mixed with cement may be used.

  The dispersant for hydraulic composition of the present invention can also contain other additives (materials). For example, resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, alkylbenzene sulfonic acid (salt), alkane sulfonate, polyoxyalkylene alkyl (phenyl) ether, polyoxyalkylene alkyl (phenyl) ether sulfate (salt) ), Polyoxyalkylene alkyl (phenyl) ether phosphates (salts), protein materials, AE agents such as alkenyl succinic acid and α-olefin sulfonate; oxy such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid Delayers such as carboxylic acids, dextrins, monosaccharides, oligosaccharides, polysaccharides, etc .; foaming agents; thickeners; silica sand; AE water reducing agents; calcium chloride, calcium nitrite, calcium nitrate , Cal bromide Soluble calcium salts such as um, calcium iodide, chlorides such as iron chloride and magnesium chloride, sulfates, potassium hydroxide, sodium hydroxide, carbonates, thiosulfates, formic acid (salts), alkanolamines, etc. Strongening agent or accelerator; foaming agent; waterproofing agent such as resin acid (salt), fatty acid ester, oil, fat, silicone, paraffin, asphalt, wax; blast furnace slag; fluidizing agent; dimethylpolysiloxane, polyalkylene glycol fatty acid ester Anti-foaming agents such as mineral oils, oils and fats, oxyalkylenes, alcohols, amides, etc .; antifoaming agents; fly ash; melamine sulfonic acid formalin condensates, aminosulfonic acids, polymaleic acids and other polycarboxylic acids High-performance water-reducing agent such as silica; Silica fume; Rust inhibitor such as nitrite, phosphate, zinc oxide; Methyl cellulose , Celluloses such as hydroxyethyl cellulose, natural products such as β-1,3-glucan and xanthan gum, polyacrylic acid amide, polyethylene glycol, ethylene oxide adduct of oleyl alcohol or a reaction product thereof with vinylcyclohexene diepoxide, etc. Water-soluble polymers such as synthetic systems; polymer emulsions such as alkyl (meth) acrylates.

  Moreover, the dispersing agent for hydraulic compositions of the present invention is not only for ready-mixed concrete and concrete vibration products, but also for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete, for AE, for repair. It is useful in any field of various concrete such as prepacked, trayy, ground improvement, grout, and cold.

<< Hydraulic composition >>
In addition, the hydraulic composition that is the target of the dispersant of the present invention has a water / hydraulic powder ratio [weight percentage (% by weight) of water and hydraulic powder in the hydraulic composition, hereinafter referred to as W / P. Is written. ] May be 65% or less, further 10 to 60%, further 12 to 57%, particularly 15 to 55%, and further 20 to 55%.

  Moreover, although the hydraulic composition of this invention is a paste, mortar, concrete, etc. containing water and hydraulic powder (cement), you may contain an aggregate. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand and crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel and crushed stone. Depending on the application, lightweight aggregates may be used. The term “aggregate” is based on the “concrete overview” (published on June 10, 1998, published by Technical Shoin).

  According to the present invention described above, the monomer 1 represented by the general formula (1), the monomer 2 represented by the general formula (2), and the general formula (3) The manufacturing method of the dispersing agent for hydraulic compositions which copolymerizes with the monomer 3 which is pH7 or less is provided.

  According to the present invention described above, a dispersant for a hydraulic composition, in which the monomer 1 and a mixed monomer including the monomer 2 and the monomer 3 are copolymerized at a pH of 7 or less. A manufacturing method is provided.

  In addition, according to the present invention described above, a phosphate ester-based polymer copolymerizing the monomer 1 and a mixed monomer including the monomer 2 and the monomer 3 at a pH of 7 or less. A method for producing a composition containing a coalescence (phosphate ester polymer composition) is provided.

  Moreover, according to the present invention described above, a reaction product obtained by copolymerizing the monomer 1 and a mixed monomer including the monomer 2 and the monomer 3 at a pH of 7 or less. A dispersant for a hydraulic composition is provided.

<Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3>
A glass reaction vessel (four-necked flask) with a stirrer was charged with 246 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 55 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.) and mono (2-hydroxyethyl) methacrylic acid ester (hereinafter also referred to as hydroxyethyl methacrylate monophosphate ester) (Ethyleneglycol methacrylate phosphate: 27.9 g) and 2.0 g of 3-mercaptopropionic acid (Ethyleneglycol methacrylate phosphate: Aldrich reagent) and phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester (hereinafter also referred to as hydroxyethyl methacrylate diphosphate ester) (Or 1.0 g) was mixed and dissolved in 55 g of water, a predetermined amount of 20% aqueous sodium hydroxide solution was added to adjust the pH (Table 1), and 3.36 g of ammonium persulfate in 45 g of water. Two of the dissolved ones It was added dropwise over a period of respectively 1.5 hours. After aging for 1 hour, 1.68 g of ammonium persulfate dissolved in 15 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the copolymer was neutralized with 20% sodium hydroxide solution.

<Comparative Examples 1-4 to 1-5>
In a glass reaction vessel (four-neck flask) with a stirrer, 205 g of water, 118 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical), mono (2-hydroxyethyl phosphate) ) 34.5 g of a mixture of methacrylic acid ester and phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester (Ethyleneglycol methacrylate phosphate: Aldrich reagent) and 1.5 g (or 5.6 g) of 3-mercaptopropionic acid are charged. Further, a 30% aqueous sodium hydroxide solution was added to adjust the pH to 9.4 (or 8.4). Thereafter, nitrogen was substituted while stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere. Thereafter, 1.8 g of ammonium persulfate dissolved in 9.0 g of water was added dropwise with stirring. During the addition, the reaction product gelled.

  Table 1 summarizes the above examples and comparative examples. In Table 1, Mw is the weight average molecular weight, EO is ethylene oxide, the number is the average number of moles added, and the phosphoric acid monomer reaction rate is the reaction rate of the monomer 2 and the monomer 3 (hereinafter referred to as the following). The same). Moreover, the chain transfer agent and polymerization initiator of the raw material used were used in the molar ratios in the table with respect to a total of 100 moles of monomer components such as monomers 1 to 3 (the same applies hereinafter).

<Test Example 1>
Using the copolymers shown in Table 1 obtained in Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-5, tests for mortars having the formulations shown in Table 2 were performed. The results are shown in Table 3. Evaluation was performed by the following methods for dispersibility and viscosity.
(1) Mortar combination

The materials used in Table 2 are as follows.
C: Ordinary cement (1: 1 mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd.)
W: Ion exchange water S: Mountain sand from Kimitsu, Chiba Prefecture
W / C: percentage by weight (% by weight) of water (W) and cement (C) (the same applies hereinafter)

(2) Preparation of mortar Into a container (1 L stainless beaker: inner diameter 120 mm), about 1/2 amount of S of the composition shown in Table 2 is added, then C is added, and the remaining S is further added as a stirrer. Mixing of dispersant and water mixed in advance after 25 seconds of air kneading at 200 rpm using EYELA Z-2310 (Tokyo Rika Instruments, stirring rod: height 50 mm, inner diameter 5 mm × 6 pieces / length 110 mm) The solution was added over 5 seconds, the material between the wall and the stirring bar was scraped off for 30 seconds after the addition, and water was added and kneaded for 3 minutes to prepare a mortar. In addition, an antifoamer was added as needed, and it adjusted so that entrained air amount might be 2% or less.

(3) Evaluation (3-1) Dispersibility Use of a cone having an upper opening diameter of 70 mm, a lower opening diameter of 100 mm, and a height of 60 mm, and an addition amount of a copolymer necessary for a mortar flow value to be 200 mm ( Dispersibility was evaluated based on the effective weight% of cement (% in the table). In addition, 200 mm of this mortar flow value is an average value of the maximum value of the mortar flow value and the mortar flow value measured in the direction perpendicular to the length of ½ of the line segment that gives the maximum value. The smaller the amount added, the stronger the dispersibility.

(3-2) Viscosity A recorder is connected to the torque tester shown in FIG. 1, and the torque of the mortar is measured. The viscosity was calculated from the torque of the mortar based on the torque-viscosity relational expression created in advance with polyethylene glycol (Mw20,000) shown in FIG. At the time of creating the torque-viscosity relational expression of polyethylene glycol, the torque output voltage value (mV) is recorded from the recorder by the monitor output 60W and the output signal DC0-5V.

  From the results in Table 3, the phosphate ester polymers of Examples 1-1 to 1-3 were copolymerized with the monomer solution containing monomer 2 and / or monomer 3 having a pH of 7 or less. Then, it can be seen that the dispersibility is stronger. On the other hand, when the solution containing the monomers 2 and 3 is copolymerized at a pH of 7 or more, even if it is gelled or a copolymer is obtained, the dispersibility is weak. In the copolymer of the example, the mortar viscosity is equal to or higher than that of the comparative example, and the dispersion agent has a good vanlas.

<Examples 2-1 to 2-12>
A glass reaction vessel with a stirrer (four-necked flask) was charged with 260 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 75 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono (2-hydroxyethyl) methacrylic acid ester and di-[(2-hydroxyethyl) phosphate Methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 18.9 g and 3-mercaptopropionic acid 0.88 g mixed in water 75 g (pH as shown in Table 4), ammonium persulfate 3 Two of 0.000 g dissolved in 45 g of water were added dropwise over 1.5 hours. The pH at the time of reaction is as shown in Tables 4 and 5. This pH was measured by collecting the reaction solution at the end of dropping and cooling to room temperature (20 ° C.). After aging for 1 hour, 1.50 g of ammonium persulfate dissolved in 15 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the copolymer was neutralized with 25 g of 20% sodium hydroxide solution to obtain a copolymer having Mw 37000. The copolymers of Examples 2-2 to 2-12 were synthesized in the same manner.

<Comparative Example 2-1>
A glass reaction vessel with a stirrer (four-necked flask) was charged with 247 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 55 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono (2-hydroxyethyl) methacrylate ester and di-[(2-hydroxyethyl) phosphate Methacrylic acid] ester mixture (Light Ester P1M: Kyoeisha Chemical Co., Ltd.) 29.8 g and 3-mercaptopropionic acid 1.06 g mixed and dissolved in 55 g water 57.5 g 20% aqueous sodium hydroxide solution was added. A monomer solution adjusted to pH 8.0 and a solution of 5.43 g of ammonium persulfate dissolved in 45 g of water were added dropwise over 1.5 hours. However, since the monomer mixture was non-uniform, it was added dropwise while stirring. After completion of dropping, the reaction product gelled.

<Comparative Example 2-2>
In a glass reaction vessel (four-necked flask) with a stirrer, 180 g of water, 94 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical), sodium methallylsulfonate (Wako Pure) Medicine) 8.8 g, 32.1 g of a mixture of mono (2-hydroxyethyl) methacrylic acid phosphate and di-[(2-hydroxyethyl) methacrylic acid] ester (Ethyleneglycol methacrylate phosphate), Furthermore, 36% aqueous 30% sodium hydroxide solution was added.
. 9 g was added to adjust the pH to 8.9. The mixture was cloudy. Then, nitrogen substitution was carried out while stirring the reaction solution, and the temperature was raised to 60 ° C. in a nitrogen atmosphere. Then, what dissolved ammonium persulfate 8.10g in water 36g was dripped over 1 hour, stirring. After completion of dropping, the reaction and aging were carried out at the same temperature for 3 hours to obtain a copolymer having Mw 47000.

<Comparative Example 2-3>
A glass reaction vessel (four-neck flask) with a stirrer was charged with 152 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethyleneglycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.) 225.6 g, methacrylic acid 11.6 g and 3-mercaptopropionic acid 1.8 g were dissolved in water 56.4 g. Two of those prepared (pH is as shown in Table 5) and 2.6 g of ammonium persulfate dissolved in 45 g of water were added dropwise over 4 hours. Thereafter, aging was performed at the same temperature (80 ° C.) for 1 hour. After completion of aging, the mixture was neutralized with 7.9 g of a 48% aqueous sodium hydroxide solution to obtain a Mw42000 copolymer.

  Tables 4 and 5 summarize Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-3. In addition, pH at the time of reaction (20 degreeC) is a thing at the time of completion | finish of reaction.

<Test Example 2>
Using the copolymers of Tables 4 and 5 obtained in Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-3, dispersibility and viscosity were evaluated in the same manner as in Example 1-1 and the like. did. The results are shown in Table 6. However, dispersibility was evaluated by the amount of copolymer added necessary for the mortar flow value to be 180 mm.

  From the results in Table 6, the phosphate ester polymers of Examples 2-1 to 2-12 copolymerized using a monomer solution having a pH of 7 or less containing monomer 2 and / or monomer 3 Strong dispersibility. In addition, it is a dispersant with a good burr for dispersibility and viscosity reduction effect. In Comparative Example 2-3, mortar viscosity was not measured because the mortar flow was only 120 mm even with an addition amount of 1.0%.

  From the results of Example 2-2 and Examples 2-9 to 2-12, the ratio of the chain transfer agent is preferably 4 mol% or more with respect to the total number of moles of monomers 1 to 3. Further, Example 2-2 in which the ratio of the chain transfer agent is 12.5 mol% with respect to the total number of moles of monomers 1 to 3 and Example 2-10 in which the ratio is 25 mol% is the phosphoric acid monomer reaction Since the rate is good and the molecular weight is in a suitable range, it can be said that it is preferable from the comprehensive viewpoint of dispersibility and viscosity reduction effect.

<Example 3>
100 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 110 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono (2-hydroxyethyl) methacrylate and di-[(2-hydroxyethyl) phosphate Methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 64.6 g and 3-mercaptopropionic acid 4.26 g mixed in 110 g of water (pH 0.9 / 20 ° C.) and ammonium persulfate 7 0.04 g dissolved in 45 g water was added dropwise over 1.5 hours. After aging for 1 hour, 3.52 g of ammonium persulfate dissolved in 15 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. Prior to aging, the pH during the reaction was measured in the same manner as in Example 2-1. After completion of aging, the copolymer was neutralized with 34 g of 48% sodium hydroxide solution to obtain a copolymer having Mw 35000.

  Using the copolymer obtained in Example 3, dispersibility and viscosity were evaluated in the same manner as in Example 1-1. The results are shown in Table 7.

<Examples 4-1 to 4-6 and Comparative Examples 3-1 to 3-3>
Using the copolymers shown in Table 9 obtained by copolymerizing monomers at the charging ratios shown in Table 9, dispersibility and viscosity tests for mortar were conducted by the following methods. The results are shown in Table 9. Mw and Mw / Mn of the copolymer are measured by GPC under the above conditions. The copolymer was produced as in Production Example I below.

[Production Example I]
Into a glass reaction vessel (four-necked flask) equipped with a stirrer, 297.0 g of water was charged, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 35.0 g of ω-methoxypolyethyleneglycol monomethacrylate (addition mole number of ethylene oxide 9: NK ester M90G made by Shin-Nakamura Chemical), mono (2-hydroxyethyl) methacrylate and di-[(2-hydroxyphosphate) Ethyl) methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 38.3 g and mercaptopropionic acid 11.0 g mixed with ammonium persulfate 4.73 g dissolved in water 45.0 g 2 Each was dropped over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 2.36 g of ammonium persulfate in 15.0 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. The pH at the end of the reaction was 0.9. After completion of aging, the mixture was neutralized with a 20% aqueous sodium hydroxide solution to pH 5.0 to obtain a copolymer of Example 4-1 having a weight average molecular weight of 21,000. In the same manner, copolymers of Examples 4-2 to 4-6 were produced. Further, the copolymers of Comparative Examples 3-1 to 3-3 were obtained in the same manner as in Comparative Example 2-3.

(1) Mortar combination

The materials used in Table 8 are as follows.
C: Ordinary cement (1: 1 mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd.)
W: Ion exchange water S: Mountain sand from Kimitsu, Chiba Prefecture

(2) Preparation of mortar Into a container (1 L stainless beaker: inner diameter 120 mm), about 1/2 amount of S of the composition shown in Table 2 is added, then C is added, and the remaining S is further added as a stirrer. Mixing of dispersant and water mixed in advance after 25 seconds of air kneading at 200 rpm using EYELA Z-2310 (Tokyo Rika Instruments, stirring rod: height 50 mm, inner diameter 5 mm × 6 pieces / length 110 mm) The solution was added over 5 seconds, the material between the wall and the stirring bar was scraped off for 30 seconds after the addition, and water was added and kneaded for 3 minutes to prepare a mortar. In addition, an antifoamer was added as needed, and it adjusted so that entrained air amount might be 2% or less.

(3) Evaluation (3-1) Dispersibility Using a cone having an upper opening diameter of 70 mm, a lower opening diameter of 100 mm, and a height of 60 mm, the amount of polymer added necessary to achieve a mortar flow value of 200 mm (vs. The dispersibility was evaluated by the weight percentage of effective cement content (indicated in% in the table). In addition, 200 mm of this mortar flow value is an average value of the maximum value of the mortar flow value and the mortar flow value measured in the direction perpendicular to the length of ½ of the line segment that gives the maximum value. The smaller the amount added, the stronger the dispersibility. In this evaluation, the addition amount is desirably 0.3% or less.

(3-2) Viscosity A recorder is connected to the torque tester shown in FIG. 1, and the torque of the mortar is measured. The viscosity was calculated from the torque of the mortar based on the torque-viscosity relational expression created in advance with polyethylene glycol (Mw20,000) shown in FIG. At the time of creating the torque-viscosity relational expression of polyethylene glycol, the torque output voltage value (mV) is recorded from the recorder by the monitor output 60W and the output signal DC0-5V. In this evaluation, it is desirable that the mortar viscosity is 4200 mPa · s or less.

The symbols in the table are as follows.
MEPEG-E: ω-methoxypolyethyleneglycol monomethacrylate HEMA-MPE: mono (2-hydroxyethyl) methacrylic acid ester HEMA-DPE: di-[(2-hydroxyethyl) methacrylic acid] ester MAA: methacrylic acid, Mw: weight average molecular weight, Mn: number average molecular weight

<Examples 5-1 to 5-3>
The following concrete test was conducted using the copolymer of Table 11 obtained by copolymerizing monomers at the charging ratio shown in Table 11. The results are shown in Table 11. Mw and Mw / Mn of the copolymer are measured by GPC under the above conditions. In addition, the symbol in Table 11 means the same thing as Example 4-1. The copolymer was produced as in Production Example II below.

[Production Example II]
726.3 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. 150.0 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 9: NK ester M90G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono (2-hydroxyethyl) methacrylate and di-[(2-hydroxyphosphate) Ethyl) methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 28.2 g and 3-mercaptopropionic acid 5.34 g and ammonium persulfate 9.19 g were dissolved in water 45.0 g. Two of them were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 4.59 g of ammonium persulfate in 15.0 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. The pH at the end of the reaction was 1.3. After completion of aging, the mixture was neutralized with a 20% sodium hydroxide solution to pH 5.5 to obtain a copolymer of Example 5-1 having an Mw of 27000. Similarly, the copolymers of Examples 5-2 and 5-2 were produced.

[Concrete test]
(1) Concrete mix The concrete mix is as shown in Table 10.

The materials used in Table 10 are as follows.
C: Ordinary Portland cement (1: 1 mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd.)
W: Ion-exchange water S: Fine aggregate, mountain sand from Kimitsu, Chiba G: Coarse aggregate, lime crushed stone from Mt. Torigata, Kochi

(2) Preparation of concrete Using a forced biaxial mixer manufactured by IHI as a mixer to be used, concrete was prepared in a concrete volume of 30 liters, stirring time for 10 seconds, and 90 seconds after adding kneaded water. At that time, the addition amount of the copolymer was adjusted so that the slump flow value was 35.0 to 42.0 cm. The slump flow value is an average value of the maximum slump flow value and the slump flow value measured in a direction perpendicular to the length of a half of the line segment giving the maximum value. Table 14 shows the amount of copolymer added necessary to achieve this slump flow. In addition, the slump flow test of concrete is JIS A 1150 (maximum size of coarse aggregate (G) 20 mm, concrete temperature 20-22 ° C., how to pack samples: packed in 3 layers, and each layer with 25 push rods. ). Moreover, the slump test (JIS A 1101) was done about the concrete in the addition amount of the copolymer. Further, the amount of concrete air (JIS A 1128) was adjusted by adding an antifoaming agent or an AE agent so that the amount of entrained air was 3.5 to 5.5% by volume.

(3) Concrete evaluation About the concrete which added the copolymer prepared above, the concrete compressive strength test method (JIS A 1108, underwater curing, 7 days strength) was performed. The results are shown in Table 11.

Examples 6-1 to 6-2
(1) Production of phosphoric acid ester product: 2-hydroxyethyl methacrylate, phosphoric anhydride (P ₂ O ₅ ) and water are reacted at a predetermined charge ratio to obtain phosphoric acid ester products (A) and (B). It was. The details are as follows.

(1-1) Production of phosphoric acid ester (A) In a reaction vessel, 200 g of 2-hydroxyethyl methacrylate and 36.0 g of 85% phosphoric acid (H ₃ PO ₄ ) are charged, and phosphorous pentoxide (phosphoric anhydride). 89.1 g of (P ₂ O ₅ ) was gradually added while cooling so that the temperature did not exceed 60 ° C. After completion, the reaction temperature was set to 80 ° C., the reaction was performed for 6 hours, and after cooling, a phosphoric acid ester (A) was obtained.

(1-2) Production of phosphoric acid ester (B) 300 g of 2-hydroxyethyl methacrylate was charged in a reaction vessel, and 113.9 g of phosphorous pentoxide (anhydrous phosphoric acid) (P ₂ O ₅ ) was heated to 60 ° C. The solution was gradually added while cooling so as not to exceed. After the completion, the reaction temperature was set to 80 ° C., the reaction was performed for 6 hours, and after cooling, a phosphoric acid ester (B) was obtained.

(2) Production of phosphate ester polymer (2-1) Example 6-1
Water (398.5 g) was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethyleneglycol methacrylate (addition mole number of ethylene oxide 23) 410.4g (effective part 60.8%, moisture 35%)
And a mixture of 62.6 g of phosphoric acid ester (A) and 4.14 g of 3-mercaptopropionic acid and 7.68 g of ammonium persulfate dissolved in 43.5 g of water were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 1.69 g of ammonium persulfate in 9.6 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 59.35 g of 32% sodium hydroxide to obtain a phosphate ester polymer having a weight average molecular weight of 36000 (Example 6-1). The pH at the time of monomer polymerization was 1.2, and the reaction rate was 100%.

(2-2) Example 6-2
A glass reaction vessel (four-necked flask) with a stirrer was charged with 335.3 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. A mixture of 75 g of ω-methoxypolyethyleneglycol methacrylate (addition mole number of ethylene oxide 9), 14.1 g of phosphoric ester (B) and 3.21 g of 3-mercaptopropionic acid, and 4.59 g of ammonium persulfate dissolved in 45 g of water The two were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 2.30 g of ammonium persulfate in 15 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 2 hours. After completion of aging, the mixture was neutralized with 19 g of 20% sodium hydroxide to obtain a phosphate ester copolymer (Example 6-2) having a weight average molecular weight of 16000. The monomer polymerization pH was 1.3 and the reaction rate was 99%.

(3) Evaluation Using the obtained phosphate ester polymer, dispersibility and viscosity were evaluated in the same manner as in Example 4-1. The results are shown in Table 12.

Schematic diagram of torque tester and recorder used for viscosity measurement in Examples and Comparative Examples Torque-viscosity relational expression with polyethylene glycol (Mw 20,000) used for viscosity calculation in Examples and Comparative Examples

Claims (3)

A monomer 1 represented by the following general formula (1), a monomer 2 represented by the following general formula (2), and a monomer 3 represented by the following general formula (3) are copolymerized. Phosphorus having a weight average molecular weight of 10,000 to 150,000 and a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) of 1.0 to 2.6 Acid ester polymer.

[Wherein R ¹ and R ² are a hydrogen atom or a methyl group, R ³ is a hydrogen atom or —COO (AO) _n X, AO is an oxyalkylene group or oxystyrene group having 2 to 4 carbon atoms, n is It is the total average addition mole number of AO, the number of 3-200, X represents a hydrogen atom or a C1-C18 alkyl group. ]

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 12 carbon atoms, m1 represents a number of 1 to 30, and M represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

[Wherein R ⁶ and R ⁸ are each a hydrogen atom or a methyl group, R ⁷ and R ⁹ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number from 1 to 30 and M is hydrogen. Represents an atom, an alkali metal or an alkaline earth metal. ]   A dispersant for a hydraulic composition comprising the phosphate ester polymer according to claim 1.   A hydraulic composition containing hydraulic powder, water, and the dispersant for hydraulic composition according to claim 2.

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