JP2007084614A - Method for producing phosphoric acid ester-based polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a dispersant for a hydraulic composition, capable of stably producing the dispersant which can give an excellent dispersing effect and viscosity reducing effect to the hydraulic composition, in an industrially practical level with good reproducibility. <P>SOLUTION: This method comprises copolymerizing a specified monomer 1 having a polyoxyalkylene group with a phosphoric acid monoester-based monomer 2 and a phosphoric acid diester-based monomer 3, wherein a mixed solution containing the monomer 1, the monomer 2, and the monomer 3 is prepared at 10-50°C and polymerization of the monomers is started within 72 hr after the preparation of the solution, while a temperature of the mixed solution is maintained in a range of 10-50°C until the polymerization is started, so that a phosphoric acid ester-based polymer which is suitable as the dispersant for the hydraulic composition is obtained. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a phosphate ester polymer suitably used for a dispersant for hydraulic composition.

  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 formwork 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.

Further, as seen in the method for producing a polycarboxylic acid-based dispersant, the polymer obtained by the monomer charging method is greatly different in performance required as a cement dispersant. For example, Patent Document 3 proposes a method in which a monomer component and a chain transfer agent component are charged in a reaction vessel in advance, and a polymerization initiator is added for polymerization. Patent Document 4 proposes a method of polymerizing a solution in which a monomer component and a chain transfer agent are mixed in advance and a polymerization initiator, respectively.
JP 11-79811 A JP 2000-327386 A JP-A-1-226757 JP-A-9-86990

  An object of the present invention is to provide a copolymer that can impart an excellent dispersion effect and viscosity reduction effect to a hydraulic composition containing a hydraulic powder, and serves as a dispersant for a hydraulic composition with good performance. An object is to provide a method that can be produced stably and reproducibly (with little variation in molecular weight depending on the production lot) at an industrially practical level.

The present invention relates to 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 method for producing a phosphate ester polymer using a mixed solution containing monomer 3 represented by the following general formula (3) (hereinafter referred to as monomer 3),
The mixed solution is obtained by mixing the monomers 1 to 3 at a temperature of 10 to 50 ° C.,
Polymerization begins within 72 hours after mixing of monomers 1-3,
In addition, the temperature of the mixed solution is maintained in the range of 10 to 50 ° C. until the polymerization is started.
The present invention relates to a method for producing a phosphate ester polymer.

[Wherein R ¹ and R ² are each 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 average added 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). A method for producing a dispersant for a hydraulic composition using a mixed solution containing the body 3,
The mixed solution is obtained by mixing the monomers 1 to 3 at a temperature of 10 to 50 ° C.,
Polymerization begins within 72 hours after mixing of monomers 1-3,
In addition, the temperature of the mixed solution is maintained in the range of 10 to 50 ° C. until the polymerization is started.
The present invention relates to a method for producing a dispersant for a hydraulic composition.

  The present invention also relates to a hydraulic composition containing hydraulic powder, water, and a dispersant for a hydraulic composition obtained by the production method of the present 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 polymer suitable as a dispersant for a hydraulic composition can be stably produced with good reproducibility. Is provided. Moreover, the production method of the present invention does not impair the properties of the phosphate ester polymer 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.

<< Production Method of Phosphate Ester Polymer >>
The present invention starts a polymerization reaction with a mixed solution obtained by mixing these monomers at a temperature of 10 to 50 ° C., which includes monomer 1, monomer 2, and monomer 3. Until it does, It relates to the manufacturing method of the phosphate ester type polymer which maintains the temperature of this mixed solution in the range of 10-50 degreeC. Any of the phosphate 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. Furthermore, the manufacturing method suitable for industrialization of this polymer was discovered.

  Hereinafter, the manufacturing method of the phosphate ester type polymer using the monomers 1-3 is demonstrated.

  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.

  Preferable monomers 1 to 3 used in the present invention are as follows, and commercially available products and reaction products can also be used.

[Monomer 1]
For monomer 1, R ³ in general formula (1) is preferably a hydrogen atom, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably contains an ethyleneoxy group (hereinafter referred to as EO group). The EO group is 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably all AO is an EO group in the total AO. 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 the average added mole number. In terms of dispersibility of the polymer in the hydraulic composition and the effect of imparting viscosity, n is 3 to 200, preferably 4 to 120. 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]
Examples of the monomer 2 include phosphoric acid monoesters of organic hydroxy compounds. Specific examples include polyalkylene glycol mono (meth) acrylate acid phosphates. For example, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid mono-[(2-hydroxyethyl) acrylic acid ester] and the like can be mentioned. Among these, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester is preferable from the viewpoint of ease of production and product quality stability.

[Monomer 3]
Examples of the monomer 3 include phosphoric acid diesters of organic hydroxy compounds. Specific examples include polyalkylene glycol di (meth) acrylate acid phosphoric acid diester. Examples 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 a salt, and may be an alkali metal salt, alkaline earth metal salt, ammonium salt, alkylammonium salt or 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.

  Moreover, in the manufacturing method of this invention, the mixed monomer containing the monomer 2 and the monomer 3 can be used.

  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.

[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. ]

  That is, a phosphate ester obtained by reacting the organic hydroxy compound represented by the general formula (4) with a phosphorylating agent can be used.

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

  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 described below [hereinafter referred to as phosphorylating agent (Z)] 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.

  In the phosphate ester, the ratio of the organic hydroxy compound and the phosphorylating agent defined by the following formula (I) is 2.0 to 4.0, more preferably 2.5 to 3.5, and particularly 2.8 to 3. What was obtained by making it react on the conditions of 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 is preferably phosphorous pentoxide (Z-1) and phosphorylating agent (Z) containing at least one (Z-2) selected from the group consisting of water, phosphoric acid and polyphosphoric acid. In formula (I), a phosphorylating agent (Z) containing phosphorus pentoxide (Z-1) and at least one (Z-2) selected from the group consisting of water, phosphoric acid and polyphosphoric acid, For convenience, it will be 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 indicates the amount (mole) of water (H ₂ O) derived from the phosphorylating agent (Z) introduced into the reaction system as a raw material. 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 performed based on the above-described method for producing a phosphate ester polymer.

  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.

  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 is 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 ³¹ P-NMR result, the absolute amount of mono-isomer and di-isomer is 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.

  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.

  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 can be 1-60 mol% in all the monomers used for reaction, and also 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.

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.

  As the chain transfer agent, those described later can be used, and it is preferable that the chain transfer agent is introduced into the reaction system as a solution, preferably in a mixed solution containing the monomers 1 to 3. The amount to be contained in the mixed solution may be all or a part of the final charged amount, but it is preferable to contain the whole amount.

  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.

In addition, the ratio (mol%) of the monomer 2 and the monomer 3 in the phosphorus-containing compound in the reaction system at the start of the reaction and at the end of the reaction can be calculated based on the measurement result of ¹ H-NMR. .

  From the viewpoint of expressing dispersibility, the content of unreacted monomer 2 and monomer 3 in the reaction product is 5 mol% or less based on the total amount of monomers 2 and 3 charged. Preferably, it is 3 mol% or less, more preferably 2 mol% or less.

  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 the other copolymerizable monomer include sulfonic acid or carboxylic acid having an unsaturated group, and salts thereof. For example, allyl sulfonic acid, methallyl sulfonic acid, alkali metal salt, alkaline earth metal salt, ammonium salt, or amine salt of any of these can be mentioned. 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 a dispersant described in the coalescence, it is more than 95 mol% to 100 mol%, and more preferably 97 to 100 mol%. Other monomers that can be copolymerized can be contained in the mixed solution and introduced into the reaction system, introduced into the reaction system separately from the mixed solution, or further combined into the reaction system. Also, any of them may be used.

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

  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 1.1 atm) as a gauge pressure. ) And 101.3-106.4 kPa (1-1.05 atm).

  In the present invention, it is preferable to react the monomer 1, the monomer 2 and the monomer 3 at a pH of 7 or less from the viewpoint of preventing gelation. 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 monomers 1 to 3 to be used in the present invention, a mixed solution containing all the monomers 1 to 3 is used for the copolymerization reaction of the monomers 1 to 3. At that time, it is preferable to set the pH during the reaction to 7 or less in consideration of other conditions. For this reason, it is preferable that pH of a mixed solution is 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.

  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.

  In the present invention, in order to make the pH of the reaction system during the reaction 7 or less, the pH of the mixed solution is preferably 7 or less. Here, the mixed solution is preferably a water-containing system (that is, the solvent contains water) for pH measurement, but in the case of a non-aqueous system, a necessary amount of water may be added for measurement. From the viewpoint of uniformity of the mixed 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.

  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 mixed solution (the 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 all 7 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 the chain transfer agent include thiol chain transfer agents and halogenated hydrocarbon chain transfer agents, and thiol chain transfer agents, particularly water-soluble 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. In which 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.

  As described above, the chain transfer agent is preferably used as a solution, but it is more preferable to maintain the temperature of the solution in the range of 10 to 50 ° C. until the polymerization is started. In particular, it is preferable to keep the temperature of the solution in the range of 10 to 50 ° C. until the polymerization is started by allowing the chain transfer agent to coexist in the mixed solution of the monomers 1 to 3.

[Polymerization initiator]
In the production method of the present invention, it is preferable to use a polymerization initiator from the viewpoint of polymerization efficiency such as initiation of polymerization, improvement of reaction rate, shortening of polymerization time and the like. The polymerization initiator is preferably used in an amount of 5 mol% or more, more preferably 7 to 50 mol%, particularly preferably 10 to 30 mol%. The polymerization initiator is preferably introduced into the reaction system separately from the mixed solution.

  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 is carried out by a solvent polymerization method. Examples of the solvent used at that time include water-soluble organic solvents such as water, methyl alcohol, ethyl alcohol, isopropyl alcohol acetone, and methyl ethyl ketone. In view of handling and reaction equipment, water is preferred. In particular, when an aqueous solution 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 a copolymerization reaction is performed. It is preferable to perform it 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. In the production method of the present invention, the polymerization solvent is preferably used in a ratio of 0.1 to 5 times by weight, particularly 0.5 to 4 times by weight, based on the total weight of the monomers.

  In the production method of the present invention, the monomers 1 to 3 are mixed at 10 to 50 ° C. to prepare a mixed solution, and the temperature of the mixed solution is set to 10 to 50 ° C. until the polymerization is started. maintain. That is, in the present invention, the monomers 1 to 3 are maintained at a temperature of 10 to 50 ° C. until the polymerization is started after the three monomers 1 to 3 coexist. ) To carry out the polymerization reaction. When the component for obtaining the mixed solution is heated, the one at 10 to 50 ° C. is used. For example, it is preferable in terms of handling that the monomer 1 is heated and dissolved in water. In that case, the monomer 1 is cooled to 10 to 50 ° C. and then used for mixing with the monomers 2 and 3. It is done. Moreover, it is preferable to mix the solvent used for manufacture of a mixed solution, adjusting temperature beforehand to 10-50 degreeC. If the mixing temperature is 10 ° C. or higher, the freezing point of the monomer 1 is low, and if it is 50 ° C. or lower, hydrolysis of the monomers 2 and 3 can be suppressed. The dispersion effect and viscosity reduction effect of the polymer are improved.

  In this invention, it is preferable that the temperature of all the components for obtaining mixed solutions including a monomer 1-3, a solvent, a chain transfer agent, etc. exists in the range of 10-50 degreeC.

  Moreover, it is preferable to maintain the temperature of a mixed solution at 10-45 degreeC, and also 10-35 degreeC until superposition | polymerization is started. The preparation temperature of the mixed solution and the temperature maintained until the polymerization is started may be the same or different.

  The mixed solution is preferably prepared by mixing a solution containing the monomer 1 and a solution containing the monomer 2 and the monomer 3. In that case, it is preferable that the temperature of each solution is 10-50 degreeC.

  The temperature of the mixed solution is preferably a temperature below the cloud point before the start of the reaction. By using it at a temperature below the cloud point, the monomer distribution in the reaction system becomes uniform, and it is possible to suppress the partial polymerization of the same monomer component by forming a high molecular weight, and the weight of the intended composition ratio. Coalescence can be obtained.

  The mixed solution preferably has a viscosity of 500 mPa · s or less for the purpose of facilitating introduction (for example, dropping) into the reaction system. Such viscosity is preferably adjusted by diluting with water, and is preferably 300 mPa · s or less, and more preferably 200 mPa · s or less, from the viewpoint of uniform solubility or dispersibility upon introduction of the reaction system.

  The mixed solution starts polymerization within 72 hours after its preparation from the viewpoint of inhibiting hydrolysis of the monomer. For example, the mixed solution is preferably introduced into the reaction system containing water within 72 hours. Further, it is preferably within 48 hours, particularly preferably within 24 hours.

  Examples of the solvent of the mixed solution include water or a water-solvent solvent containing water and methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, and the like. Although it may be the same as or different from the solvent used in the reaction system, it is preferable to select in consideration of the influence of introduction of the mixed solution. In particular, the solvent of the mixed solution and the solvent of the reaction system are preferably the same.

  In an industrial polymerization reaction, the transition metal ions may be mixed into the reaction system from monomer raw materials, diluted water, or from raw material storage tanks, reaction tanks, piping corrosion, etc. Prediction is very difficult. For this reason, in this invention, it is preferable to superpose | polymerize in presence of a chelating agent. Use of a chelating agent is also preferable from the viewpoint of suppressing fluctuations in molecular weight.

  As the chelating agent used in the present invention, phosphonic acid or a salt thereof is preferable in that the chelating ability is high even in a small amount.

  In the present invention, the chelating agent is preferably added to the polymerization reaction system at a ratio of 1 to 10,000 mg / kg, particularly 50 to 800 mg / kg. The chelating agent is preferably contained in the mixed solution and introduced into the reaction system. The amount of the chelating agent contained in the mixed solution may be the whole amount or a part of the final charged amount, but the whole amount is preferably contained.

  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 a mixed solution in which the monomers 1 to 3 and the chain transfer agent are mixed and dissolved in water at a predetermined temperature and a solution in which the polymerization initiator is dissolved in water, and react within 72 hours after preparing the monomer mixed solution. Start dripping into the container. Furthermore, dripping is performed over 0.5 to 5 hours. The completion of dropping is preferably within 72 hours after the preparation of the monomer mixed solution. Furthermore, it is preferable to complete within 48 hours, particularly within 24 hours. The temperature of the mixed solution waiting for dripping is maintained at 10 to 50 ° C. At that time, the pH of the mixed solution is preferably 7 or less from the viewpoint of uniformity of the monomer solution, prevention of gelation, and suppression of performance degradation. Further, the copolymerization reaction is preferably performed with an alkali agent or the like while maintaining the pH at 7 or less, and preferably aging is performed for a predetermined time. The polymerization initiator may be added dropwise at the same time as the mixed solution 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 of the polymerization initiator is added simultaneously with the mixed solution, and the remainder is added after aging for 1 to 2 hours after the mixed solution is dropped. It is preferable. 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 phosphate ester polymer obtained by the production method of the present invention can be used as a dispersant for a hydraulic composition even in an acid form, but from the viewpoint of suppressing hydrolysis of an ester due to acidity, it is based on an alkali. Preference is given to the salt form by neutralization. Examples of the alkali include alkali metal salts or hydroxides of alkaline earth metals, ammonia, mono-, di-, and trialkanol (preferably having 2 to 6 carbon atoms) amines.

  The phosphate ester polymer described below is obtained by the method for producing a phosphate ester polymer of the present invention.

  That is, a phosphate ester-based polymer obtained by a production method using a mixed solution containing monomer 1, monomer 2, and monomer 3, wherein the mixed solution is monomer 1 3 was mixed at a temperature of 10 to 50 ° C., and the polymerization was started within 72 hours after the mixing of the monomers 1 to 3 and until the polymerization was started. It is a phosphate ester-type polymer obtained from the manufacturing method which hold | maintains temperature in the range of 10-50 degreeC. Preferred structures of the monomers 1 to 3 are as described above.

  The phosphate ester polymer of the present invention preferably has a weight average molecular weight (hereinafter referred to as Mw) of 10,000 to 150,000. Mw is 10,000 or more, preferably 12,000 or more, more preferably 13,000 or more, more preferably 14,000 or more, and particularly preferably 15,000 from the viewpoint of the expression of the dispersion effect and the viscosity reduction effect. From the viewpoints of high molecular weight by crosslinking, suppression of gelation and performance, from the viewpoint of dispersion effect and viscosity reduction effect, it is 150,000 or less, preferably 130,000 or less, more preferably 120,000 or less, more Preferably it is 110,000 or less, Especially preferably, it is 100,000 or less, From the both viewpoints, Preferably it is 12,000-130,000, More preferably, it is 13,000-120,000, More preferably, it is 14,000. To 110,000, particularly preferably 15,000 to 100,000.

Mw of the phosphate ester polymer of the present invention is measured by a gel permeation chromatography (GPC) method under the following conditions.
[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

  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.

<< 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. ] Is 65% or less, more preferably 10 to 60%, still more 12 to 57%, and particularly 15 to 55% and further 20 to 55% in that the low-viscosity effect is exhibited.

  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 “Concrete Overview” (published on June 10, 1998, published by Technical Shoin).

Example 1
366 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) was added at an appropriate amount of water so that the effective content was 60.8% and the water content was 35%, dissolved at 70 ° C., and then up to 30 ° C. Phosphoric esterified product (A) which is a mixture of 450 g of cooled monomer aqueous solution, mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate 71.6 g and 3-mercaptopropionic acid 4.5 g were mixed (the temperature of each component was 30 ° C.) (preparation of a mixed solution), and the mixture was allowed to stand at 25 ° C. for 1 hour, and ammonium persulfate. Two of 8.4 g dissolved in 48 g of water were added dropwise over 1.5 hours. At that time, the temperature of the mixed solution was maintained at 25 ° C. until it was introduced into the reaction system. After aging for 1 hour, 1.8 g of ammonium persulfate dissolved in 10 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 44.4 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the content of unreacted monomer 2 and monomer 3 was 0.3 mol% with respect to the total amount of monomers 2 and 3 charged.

The phosphoric acid ester (A) used in this example and the following examples and comparative examples was obtained by adding 200 g of 2-hydroxyethyl methacrylate and 36.0 g of 85% phosphoric acid (H ₃ PO ₄ ) in a reaction vessel. 89.1 g of charged phosphorus pentoxide (phosphoric anhydride) (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., reacted for 6 hours, and cooled.

Comparative Example 1
In a glass reaction vessel with a stirrer (four-necked flask), 366 g of water and ω-methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 23) are appropriate so that the effective content is 60.8% and the water content is 35%. Of water, dissolved at 70 ° C., cooled to 30 ° C., 450 g monomer aqueous solution, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphoric acid di-[(2-hydroxy (Ethyl) methacrylic acid] ester mixture 71.6 g of phosphoric acid ester (A) and 3-mercaptopropionic acid 4.5 g were mixed (the temperature of each component was 30 ° C.) (preparation of mixed solution), After the preparation, the mixture was allowed to stand at 25 ° C. for 1 hour, and then purged with nitrogen while stirring. The temperature was raised to 80 ° C. in a nitrogen atmosphere over 1 hour. 30 minutes after reaching 80 ° C., ammonium persulfate. Dropping of an aqueous solution in which 8.4 g was dissolved in 48 g of water was started and dropped over 1.5 hours. After aging for 1 hour, 1.8 g of ammonium persulfate dissolved in 10 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 44.4 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the contents of unreacted monomer 2 and monomer 3 were 0.4 mol% with respect to the total amount of monomers 2 and 3 charged.

Comparative Example 2
366 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Monomer aqueous solution 450 g in which ω-methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 23) was dissolved at 70 ° C. by adding an appropriate amount of water so that the effective content was 60.8% and the water content was 35%. Without cooling the phosphoric acid ester product (A), which is a mixture of phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphoric acid di [(2-hydroxyethyl) methacrylic acid] ester ( Add 71.6 g of temperature (30 ° C.) and 4.5 g of 3-mercaptopropionic acid (temperature is 30 ° C.) over 5 minutes, mix (preparation of mixed solution), and cool to 25 ° C. over 1 hour after preparation. Further, those left for 1 hour (mixed solution) and ammonium persulfate. Two of 8.4 g dissolved in 48 g of water were added dropwise over 1.5 hours. At that time, the temperature of the mixed solution was maintained at 25 ° C. until it was introduced into the reaction system. After aging for 1 hour, 1.8 g of ammonium persulfate dissolved in 10 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 44.4 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the content of unreacted monomer 2 and monomer 3 was 0.3 mol% with respect to the total amount of monomers 2 and 3 charged.

Comparative Example 3
366 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) was added at an appropriate amount of water so that the effective content was 60.8% and the water content was 35%, dissolved at 70 ° C., and then up to 30 ° C. Phosphoric esterified product (A) which is a mixture of 450 g of cooled monomer aqueous solution, mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate 71.6 g and 3-mercaptopropionic acid 4.5 g were mixed (the temperature of each component was 30 ° C.) (preparation of a mixed solution), and the mixture was allowed to stand at 25 ° C. for 96 hours, and ammonium persulfate. Two of 8.4 g dissolved in 48 g of water were added dropwise over 1.5 hours. At that time, the temperature of the mixed solution was maintained at 25 ° C. until it was introduced into the reaction system. After aging for 1 hour, 1.8 g of ammonium persulfate dissolved in 10 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 44.4 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the content of unreacted monomer 2 and monomer 3 was 0.3 mol% with respect to the total amount of monomers 2 and 3 charged.

Example 2
366 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) was added at an appropriate amount of water so that the effective content was 60.8% and the water content was 35%, dissolved at 70 ° C., and then up to 30 ° C. Phosphoric esterified product (A) which is a mixture of 450 g of cooled monomer aqueous solution, mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate 71.6 g and 3-mercaptopropionic acid 4.5 g were mixed (the temperature of each component was 30 ° C.) (preparation of the mixed solution), and the mixture was allowed to stand at 25 ° C. for 20 hours (mixed solution). Ammonium sulfate. Two of 8.4 g dissolved in 48 g of water were added dropwise over 1.5 hours. At that time, the temperature of the mixed solution was maintained at 25 ° C. until it was introduced into the reaction system. After aging for 1 hour, 1.8 g of ammonium persulfate dissolved in 10 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 44.4 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the contents of unreacted monomer 2 and monomer 3 were 0.4 mol% with respect to the total amount of monomers 2 and 3 charged.

Example 3
371 g of water was charged into a glass reaction vessel with a stirrer (four-necked flask), purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) was added at an appropriate amount of water so that the effective content was 60.8% and the water content was 35%, dissolved at 70 ° C., and then up to 30 ° C. Phosphoric esterified product (A) which is a mixture of 500 g of cooled monomer aqueous solution, mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate 34.1 g and 3-mercaptopropionic acid 2.8 g were mixed (the temperature of each component was 40 ° C.) (preparation of a mixed solution), and the mixture was allowed to stand at 25 ° C. for 2 hours, and ammonium persulfate. Two of 7.2 g dissolved in 41 g of water were added dropwise over 1.5 hours. At that time, the temperature of the mixed solution was maintained at 25 ° C. until it was introduced into the reaction system. After aging for 1 hour, 1.6 g of ammonium persulfate dissolved in 9 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 21.2 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the content of unreacted monomer 2 and monomer 3 was 0.3 mol% with respect to the total amount of monomers 2 and 3 charged.

Example 4
A glass reaction vessel (four-necked flask) with a stirrer was charged with 381 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) was added at an appropriate amount of water so that the effective content was 60.8% and the water content was 35%, dissolved at 70 ° C., and then up to 30 ° C. Phosphoric esterified product (A) which is a mixture of 520 g of a cooled monomer aqueous solution, mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate 28.6 g and 2.8 g of 3-mercaptopropionic acid were mixed (the temperature of each component was 45 ° C.) (preparation of a mixed solution) and allowed to stand at 25 ° C. for 8 hours, and ammonium persulfate. Two of 7.2 g dissolved in 41 g of water were added dropwise over 1.5 hours. At that time, the temperature of the mixed solution was maintained at 25 ° C. until it was introduced into the reaction system. After aging for 1 hour, 1.6 g of ammonium persulfate dissolved in 9 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 17.7 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the content of unreacted monomer 2 and monomer 3 was 0.3 mol% with respect to the total amount of monomers 2 and 3 charged.

Example 5
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 471 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 9) was added at an appropriate amount of water so that the effective content was 84.4% and the water content was 10%, dissolved at 70 ° C, and then up to 30 ° C. Phosphoric esterified product (A), which is a mixture of 290 g of cooled monomer aqueous solution, mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate 93.8 g and 11.3 g of 3-mercaptopropionic acid were mixed (the temperature of each component was 30 ° C.) (preparation of a mixed solution), and the mixture was allowed to stand at 25 ° C. for 24 hours, and ammonium persulfate. Two of the 8.2 g dissolved in 46 g of water were added dropwise over 1.5 hours. At that time, the temperature of the mixed solution was maintained at 25 ° C. until it was introduced into the reaction system. After aging for 1 hour, a solution prepared by dissolving 3.3 g of ammonium persulfate in 19 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the solution was neutralized with 58.2 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the content of unreacted monomer 2 and monomer 3 was 0.8 mol% with respect to the total amount of monomers 2 and 3 charged.

Example 6
489 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. ω-Methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 9) was added at an appropriate amount of water so that the effective content was 84.4% and the water content was 10%, dissolved at 70 ° C, and then up to 30 ° C. Phosphoric esterified product (A), which is a mixture of 290 g of cooled monomer aqueous solution, mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate 53.2 g and 9.1 g of 3-mercaptopropionic acid were mixed (the temperature of each component was 30 ° C.) (preparation of a mixed solution) and allowed to stand at 25 ° C. for 36 hours, and ammonium persulfate. Two of 7.8 g dissolved in 44 g of water were added dropwise over 1.5 hours. At that time, the temperature of the mixed solution was maintained at 25 ° C. until it was introduced into the reaction system. After aging for 1 hour, a solution prepared by dissolving 3.1 g of ammonium persulfate in 18 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 33.0 g of a 32% aqueous sodium hydroxide solution to obtain a phosphate ester polymer. In the reaction product, the content of unreacted monomer 2 and monomer 3 was 1.6 mol% with respect to the total amount of monomers 2 and 3 charged.

  The examples and comparative examples described above are polymer Nos. With the charged raw materials shown in Table 1 below. This corresponds to the production of A-1 to A-5. Table 2 summarizes the weight average molecular weights (Mw) of the phosphate ester polymers when a plurality of examples and comparative examples are performed.

表中の記号は以下のものである。
・ＭＥＰＥＧ−Ｅ：ω−メトキシポリエチレングリコールモノメタクリレート
・ＨＥＭＡ−ＭＰＥ：リン酸モノ−〔（２−ヒドロキシエチル）メタクリル酸〕エステル
・ＨＥＭＡ−ＤＰＥ：リン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステル

The symbols in the table are as follows.
MEPEG-E: ω-methoxypolyethylene glycol monomethacrylate HEMA-MPE: phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester HEMA-DPE: phosphoric acid di-[(2-hydroxyethyl) methacrylic acid 〕ester

(note)
The polymerization reaction in Table 2 was carried out by changing the days without continuously performing the first to third times, and different raw materials were used for each monomer lot. In addition, in the polymerization method in Table 2, “initiator solution dropping” means that the reaction was started by dropping the polymerization initiator aqueous solution, and “mixed solution dropping” was the start of the reaction by dropping the mixed solution. Means you have gone. In addition, “uniformly transparent” in appearance means that it is below the cloud point before the start of the reaction.

<Test example>
Using the phosphate ester polymer obtained by the above production method, a test was conducted on the mortar having the composition shown in Table 3. The results are shown in Table 4. Evaluation was performed by the following methods for dispersibility and viscosity.
(1) Mortar combination

The materials used in Table 3 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 premixed after 200 seconds of air kneading 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) Fluidity 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 ( The fluidity was evaluated based on the weight% of the effective amount of cement with respect to cement (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.

(3-2) Viscosity A recorder is connected to the torque tester shown in FIG. 1, and a torque of 200 mm in mortar flow 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 Examples 1 and 2, the molecular weight variation was small, and the resulting dispersion effect (required addition amount) and viscosity reduction effect (mortar viscosity) were similar in performance with good reproducibility.

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 (5)

A mixture containing the monomer 1 represented by the following general formula (1), the monomer 2 represented by the following general formula (2), and the monomer 3 represented by the following general formula (3) A method for producing a phosphate ester polymer using a solution,
The mixed solution is obtained by mixing the monomers 1 to 3 at a temperature of 10 to 50 ° C.,
Polymerization begins within 72 hours after mixing of monomers 1-3,
In addition, the temperature of the mixed solution is maintained in the range of 10 to 50 ° C. until the polymerization is started.
A method for producing a phosphate ester polymer.

[Wherein R ¹ and R ² are each 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 average added 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 method for producing a phosphate ester polymer according to claim 1, wherein a solution containing a chain transfer agent is used for the reaction while maintaining the temperature of the solution in the range of 10 to 50 ° C until the polymerization is started.   The content of unreacted monomer 2 and monomer 3 in the reaction product is 5 mol% or less with respect to the total amount of monomers 2 and 3 charged. The manufacturing method as described. A mixture containing the monomer 1 represented by the following general formula (1), the monomer 2 represented by the following general formula (2), and the monomer 3 represented by the following general formula (3) A method for producing a dispersant for a hydraulic composition using a solution,
The mixed solution is obtained by mixing the monomers 1 to 3 at a temperature of 10 to 50 ° C.,
Polymerization begins within 72 hours after mixing of monomers 1-3,
In addition, the temperature of the mixed solution is maintained in the range of 10 to 50 ° C. until the polymerization is started.
The manufacturing method of the dispersing agent for hydraulic compositions.

[Wherein R ¹ and R ² are each 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 average added 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 hydraulic composition containing hydraulic powder, water, and a dispersant for hydraulic composition obtained by the production method according to claim 4.

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