JP2012057030A - Method for producing polyalkylene glycol monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyalkylene glycol monomer, in which formation of by-products such as a bifunctional monomer is very slight.SOLUTION: Glycidyl (meth)acrylate and a specific monoalkoxypolyalkylene glycol are brought into an etherification reaction in a feed molar ratio of glycidyl (meth)acrylate/monoalkoxypolyalkylene glycol=0.8/1 to 1.2/1 to produce the objective polyalkylene glycol monomer.

Description

  The present invention relates to a method for producing a polyalkylene glycol monomer, a method for producing a polyalkylene glycol polymer, and a dispersant containing the polyalkylene glycol polymer obtained by the production method.

  Polyalkylene glycol compounds are used as raw material monomers for polyalkylene glycol polymers, and polyalkylene glycol polymers are used in a variety of applications such as dispersants, thickeners, detergent builders, and scale inhibitors. Has been.

  As a polyalkylene glycol polymer, a polymer using methacrylic acid or acrylic acid and a polyalkylene glycol ester monomer obtained by esterification of polyalkylene glycol is known (Patent Document 1). Since the esterification reaction is an equilibrium reaction, it is advantageous in terms of promoting the reaction to use an excess of either unsaturated carboxylic acid such as methacrylic acid or acrylic acid and polyalkylene glycol. Specifically, the unsaturated carboxylic acid is used in excess relative to the polyalkylene glycol, and the excess unsaturated carboxylic acid is distilled off after completion of the esterification reaction, or the remaining unsaturated carboxylic acid is used in the next step. The raw material for coalescence production is performed. In Examples of Patent Document 1, 2.1 to 8.8 mol of polyalkylene glycol is used per 1 mol of unsaturated carboxylic acid.

  The polyalkylene glycol ester monomer can be produced, for example, by etherifying glycidyl (meth) acrylate and monoalkoxy polyalkylene glycol. Moreover, in producing a polycarboxylic acid polymer, it is known to use a sorbitol / ethylene oxide adduct monomer (sorbitol EO adduct macromer) obtained by reacting a sorbitol ethylene oxide adduct with glycidyl methacrylate. (Patent Document 2).

In addition, a method for producing an unsaturated (poly) alkylene glycol ether monomer by adding an alkylene oxide to an unsaturated alcohol under specific conditions is known (Patent Document 3).

Japanese Patent Laid-Open No. 11-60302 JP 2004-2175 A JP 2009-46655 A

  When the polyalkylene glycol ester monomer is produced by etherification of glycidyl (meth) acrylate and monoalkoxy polyalkylene glycol, depending on the reaction conditions, bifunctionality such as having two unsaturated bonds Monomer is formed as a by-product. When a mixture containing a large amount of the bifunctional monomer is used for the polymerization, the polymer forms a cross-linked structure and causes an increase in viscosity or gelation. Therefore, the bifunctional in the polyalkylene glycol ester monomer is used. It is desirable that the amount of functional monomer is small.

  An object of the present invention is to provide a method for producing a polyalkylene glycol monomer that produces very little by-products such as a bifunctional monomer.

  In the present invention, glycidyl (meth) acrylate and a monoalkoxy polyalkylene glycol represented by the following general formula (ii) are converted into glycidyl (meth) acrylate / monoalkoxy polyalkylene glycol = 0.8 / 1 to 1.2 /. The present invention relates to a method for producing a polyalkylene glycol monomer (hereinafter referred to as Method 1) which is etherified at a charge molar ratio of 1.

[Wherein, A represents an alkylene group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group having 1 to 18 carbon atoms, and n represents an average added mole number of AO, which is a number of 1 to 500. ]

In the present invention, glycidyl (meth) acrylate and monoalkoxypolyalkylene glycol represented by the following general formula (ii) are glycidyl (meth) acrylate / monoalkoxypolyalkylene glycol = 0.8 / 1 to 1. By carrying out the etherification reaction at a charged molar ratio of 2/1,
A polyalkylene glycol monomer (ib) represented by the following general formula (ib) and a polyalkylene glycol monomer (ic) represented by the following general formula (ic): The weight ratio of the monomer (ib) to the monomer (ic) is 0.1 ((ic) / [(ib) + (ic))]. Producing a polyalkylene glycol monomer composition which is:
The present invention relates to a method for producing a polyalkylene glycol monomer composition (hereinafter referred to as method 1 ′).

[Wherein, A represents an alkylene group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group having 1 to 18 carbon atoms, and n represents an average added mole number of AO, which is a number of 1 to 500. ]

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, n is a number having 1 to 500, and A is an alkylene group having 2 to 18 carbon atoms. ]

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, n is a number having 1 to 500, and A is an alkylene group having 2 to 18 carbon atoms. ]

In the present invention, glycidyl (meth) acrylate and monoalkoxypolyalkylene glycol represented by the following general formula (ii) are glycidyl (meth) acrylate / monoalkoxypolyalkylene glycol = 0.8 / 1 to 1. A step (A) of producing a polyalkylene glycol monomer composition by an etherification reaction at a charged molar ratio of 2/1;
A step (B) for producing a polyalkylene glycol polymer by copolymerizing the polyalkylene glycol monomer composition obtained in the step (A) and an unsaturated carboxylic acid monomer;
The present invention relates to a method for producing a polyalkylene glycol polymer having the following (hereinafter referred to as method 2).

[Wherein, A represents an alkylene group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group having 1 to 18 carbon atoms, and n represents an average added mole number of AO, which is a number of 1 to 500. ]

  The present invention also relates to a dispersant comprising a polyalkylene glycol polymer obtained by the production method of the present invention.

  Moreover, this invention relates to the manufacturing method of the hydraulic composition which mixes the dispersing agent of the said invention, hydraulic powder, and water.

  According to the present invention, there is provided a method for producing a polyalkylene glycol monomer composition that produces very little by-products such as bifunctional monomers. The polyalkylene glycol polymer obtained by copolymerizing the polyalkylene glycol monomer composition and the unsaturated carboxylic acid monomer produced according to the present invention does not increase in viscosity or gel, The performance as a dispersing agent etc. is exhibited appropriately.

<Method for Producing Polyalkylene Glycol Monomer (Method 1)>
In the present invention, glycidyl (meth) acrylate and a specific monoalkoxy polyalkylene glycol are glycidyl (meth) acrylate / monoalkoxy polyalkylene glycol = 0.8 / 1 to 1.2 / 1, preferably 0.9 / The etherification reaction is carried out at a charged molar ratio in the range of 1 to 1.1 / 1, more preferably 0.95 / 1 to 1.05 / 1. By carrying out the etherification reaction at a charged molar ratio within this range, a polyalkylene glycol-based monomer that produces very little by-products such as a bifunctional monomer can be produced. If the charged molar ratio is less than 0.8, the yield of the etherified product obtained decreases, and if it exceeds 1.2, the amount of by-products such as bifunctional monomers increases. Here, glycidyl (meth) acrylate means glycidyl acrylate and / or glycidyl methacrylate. The molecular weight of the monoalkoxy polyalkylene glycol is determined from the hydroxyl value.

  The monoalkoxypolyalkylene glycol used in Method 1 is a compound represented by the following general formula (ii).

[Wherein, A represents an alkylene group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group having 1 to 18 carbon atoms, and n represents an average added mole number of AO, which is a number of 1 to 500. ]

  A polyalkylene glycol monomer represented by the following general formula (i) [hereinafter, a glycidyl (meth) acrylate and a monoalkoxy polyalkylene glycol represented by the above general formula (ii) are etherified. Monomer (i)] is obtained.

[Wherein R ¹ is a hydrogen atom or a methyl group, ^one of B ¹ and B ² is a hydrogen atom, and the other is the following general formula (ii-a)

(A is an alkylene group having 2 to 18 carbon atoms, R ² is a hydrocarbon group having 1 to 18 carbon atoms, and n is an average added mole number of AO, which is a number of 1 to 500.) It is. ]

In General Formula (i), B ¹ and B ² are groups represented by one of hydrogen atom and the other of General Formula (ii-a). In the general formula (ii) or the general formula (ii-a), n is an average added mole number of AO, and is 1 to 500 from the viewpoint of the dispersion performance of the polymer powder using the monomer (i). It is a number, preferably a number from 2 to 300, more preferably a number from 5 to 150, more preferably a number from 5 to 75. A is a C2-C18 alkylene group, Preferably it is C2-C8, More preferably, it is a C2-C4 alkylene group. R ¹ is a hydrogen atom or a methyl group, preferably a methyl group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and a carbon atom having 1 to 4 carbon atoms. A hydrogen group is more preferable. The hydrocarbon group is preferably an alkyl group.

  When the glycidyl (meth) acrylate and the monoalkoxypolyalkylene glycol represented by the general formula (ii) are subjected to an etherification reaction, the production method of the present invention uses the monomer (i), which is the target product, A composition containing a product, a polyalkylene glycol monomer represented by the following general formula (ia) [hereinafter referred to as a monomer (ia)], A polyalkylene glycol monomer composition in which the weight ratio of i) to the monomer (ia) is 0.1 or less in terms of (ia) / [(i) + (ia)]. Obtainable.

[Wherein R ¹ is a hydrogen atom or a methyl group, and B ³ and B ⁴ are each represented by the following general formula (ii-a)

(A is an alkylene group having 2 to 18 carbon atoms, R ² is a hydrocarbon group having 1 to 18 carbon atoms, and n is an average added mole number of AO, which is a number of 1 to 500.) And the other is the following general formula (ii-b)

(R ¹ is a hydrogen atom or a methyl group). ]

<Method for Producing Polyalkylene Glycol Monomer Composition (Method 1 ′)>
Furthermore, in the present invention, by subjecting glycidyl (meth) acrylate and the monoalkoxypolyalkylene glycol represented by the above general formula (ii) to an etherification reaction at the above-mentioned specific charged molar ratio, A monomer (ib) represented by the formula (ib) and a polyalkylene glycol monomer (ic) represented by the following general formula (ic) as a by-product [ Hereinafter referred to as monomer (ic)], and the weight ratio of monomer (ib) to monomer (ic) is (ic). It is possible to obtain a polyalkylene glycol monomer composition that is 0.1 or less in / [(ib) + (ic)] (Method 1 ′). The preferred embodiment in Method 1 ′ is the same as Method 1.

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, n is a number having 1 to 500, and A is an alkylene group having 2 to 18 carbon atoms. ]

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, n is a number having 1 to 500, and A is an alkylene group having 2 to 18 carbon atoms. ]

  The monomer (ia) and the monomer (ic) are bifunctional monomers, and when a monomer composition containing a large amount thereof is used for polymerization, the polymer forms a crosslinked structure. However, although it is thought to cause an increase in viscosity or gelation, in the production method of the present invention, the amount of monomer (ia) or monomer (ic) produced is extremely low. In the present invention, the content of the monomer (i), monomer (ia), monomer (ib), and monomer (ic) in the reaction product is high speed. It can isolate | separate by a liquid chromatography, each solvent can be evaporated, and it can obtain | require by measuring the weight.

  In the etherification reaction of Method 1 and Method 1 ', a solvent can be used. Since the effective amount can be increased and the productivity is excellent, the reaction may be carried out in bulk without using a solvent. A solvent may be previously charged in a reaction vessel, and glycidyl (meth) acrylate and monoalkoxypolyalkylene glycol may be dropped into the reaction vessel. A monoalkoxy polyalkylene glycol may be previously charged in a reaction vessel and glycidyl (meth) acrylate may be dropped. Glycidyl (meth) acrylate may be previously charged in a reaction vessel, and monoalkoxy polyalkylene glycol may be dropped. You may charge all to a reaction container collectively. From the viewpoint of temperature control of reaction, quality, and prevention of runaway, a method in which a monoalkoxypolyalkylene glycol is previously charged in a reaction vessel and glycidyl (meth) acrylate is dropped is preferable.

  Moreover, glycidyl (meth) acrylate may be diluted with a solvent or may be used as it is without being diluted.

  When using a solvent, the thing which does not have a hydroxyl group, an amino group, a carboxyl group, a thiol group, etc. which react with glycidyl (meth) acrylate is preferable. Specifically, toluene, hexane, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like are preferable, but alcohol, water, lower alcohol, and glycol solvents can also be used.

  In Method 1 and Method 1 ', a base catalyst or an acid catalyst may be used to accelerate the reaction. Examples of the base catalyst include tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, and N-methylmorpholine, and alkali metal salts such as potassium carbonate, sodium hydroxide, and potassium hydroxide. N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine and potassium carbonate are preferred. The catalyst is preferably in a molar ratio of 0.1 to 200, more preferably 1 to 100, still more preferably 3 to 75, and most preferably 5 to 50 with respect to the monoalkoxypolyalkylene glycol. Further, in order to accelerate the reaction, a metal compound such as dioctylic acid tin may be used in combination with the base catalyst.

  As an acid catalyst, p-toluenesulfonic acid, m-xylenesulfonic acid, alkylbenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, boron trifluoride, boron trifluoride complex, boron trifluoride diethyl ether complex, aluminum trial Examples include coloxide, titanium tetraalkoxide, tin chloride, and the like. Among them, boron trifluoride diethyl ether complex and trifluoromethanesulfonic acid are preferable. The catalyst has a molar ratio [catalyst / glycidyl (meth) acrylate] of preferably 0.01 to 50, more preferably 0.1 to 40, still more preferably 0.5 to 30 with respect to glycidyl (meth) acrylate. 1 to 20 is most preferable. The acid may be used in the form of a hydrate or an aqueous solution.

  The catalyst may be charged into the reaction vessel together with the raw materials. The catalyst may be introduced into the reaction vessel during the reaction. The catalyst may be dropped together with the raw material. After completion of the reaction, the catalyst may be neutralized. After completion of the reaction, the catalyst may be removed.

  The catalyst can be used with or without neutralization. When neutralizing, either complete neutralization or partial neutralization may be used. The degree of neutralization is preferably 0 to 1.0, more preferably 0 to 0.5, and still more preferably 0 to 0.1.

  The reaction temperature in Method 1 and Method 1 'is preferably 0 to 200 ° C, more preferably 25 to 150 ° C, and still more preferably 50 to 100 ° C.

  In Method 1 and Method 1 ', a polymerization inhibitor may be added from the viewpoint of suppressing the reaction of unsaturated bond of glycidyl (meth) acrylate during the etherification reaction. The polymerization inhibitor may be previously charged into the reaction vessel before the etherification reaction, or may be introduced into the reaction vessel during the reaction. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine and the like.

  The etherification reaction in the method 1 and the method 1 'can be performed in an oxidizing gas atmosphere such as air or an inert gas atmosphere such as nitrogen. Air is preferable from the viewpoint of preventing polymerization. The target gas can be introduced by atmosphere and / or bubbling.

  The end point of the ether reaction can be confirmed by an analysis method using a peak derived from an epoxy group by a nuclear magnetic resonance (NMR) method. The time when the peak is no longer detected is preferably the end of the reaction.

  In method 1 and method 1 ′, depending on the purpose of use, when the purpose is a raw material for producing the polymer according to method 2, unreacted glycidyl (meth) acrylate remains in the obtained reaction product. You may do it. The remaining glycidyl (meth) acrylate may be hydrolyzed to give glycerin (meth) acrylate. The glycidyl (meth) acrylate and glycerin (meth) acrylate remaining together with the compound (i) may be used as a copolymerization component when the polymer according to the method 2 is produced. Unreacted monoalkoxypolyalkylene glycol may remain. When removing the remaining raw material, distillation by distillation or solvent extraction can be used.

  The obtained monomer (i) can be stored as it is in a storage tank or a suitable container. Depending on the melting point of the monomer (i), it may be stored in a solid state, or may be heated and melted. The solution may be diluted with a solvent such as water. From the viewpoint of being stored at room temperature and ease of handling, it is preferable to store it in a solution, especially an aqueous solution. Monomer (i) can be used as a constituent monomer of the polymer according to Method 2.

<Method for producing polyalkylene glycol polymer (Method 2)>
In the method 2 of the present invention, a glycidyl (meth) acrylate and a specific monoalkoxypolyalkylene glycol are charged and subjected to an etherification reaction in a molar ratio range of 0.8 / 1 to 1.2 / 1 to form a polyalkylene glycol single unit. Step (A) for producing a monomer composition, and a polyalkylene glycol polymer obtained by copolymerizing the polyalkylene glycol monomer composition obtained in step (A) and an unsaturated carboxylic acid monomer. A process (B) for producing a polyalkylene glycol-based polymer. Step (A) may be Method 1 or Method 1 ′.

  The polyalkylene glycol polymer produced by Method 2 is a polyalkylene glycol polymer containing a structural unit represented by the following general formula (Ia) and a structural unit represented by the following general formula (Ib) Is mentioned.

[Wherein R ¹ is a hydrogen atom or a methyl group, ^one of B ¹ and B ² is a hydrogen atom, and the other is the following general formula (II)

(A is an alkylene group having 2 to 18 carbon atoms, R ² is a hydrocarbon group having 1 to 18 carbon atoms, and n is an average added mole number of AO, which is a number of 1 to 500.) It is. ]

[Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom, a methyl group, COOH or COOM ¹ , R ⁵ is a hydrogen atom, a methyl group, OH, COOH, COOM, CH ₂ COOH or CH ₂ COOM ¹ , M and M ¹ each represent a hydrogen atom, a metal atom, an ammonium group or an organic ammonium group. ]

  The monomer serving as the structural unit of the general formula (Ib) is a carboxylic acid having an unsaturated group, and a monovalent or divalent carboxylic acid having one unsaturated group is preferable. Specific examples include monomers such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, α-hydroxyacrylic acid, itaconic acid, citraconic acid, and crotonic acid. Among these, acrylic acid and methacrylic acid are preferable.

  A preferred proportion of the structural unit (Ia) in the polyalkylene glycol polymer produced by the method 2 is 1 to 99 mol%, more preferably 5 to 95 mol%, and further 10 to 90 from the viewpoint of hydraulic powder dispersibility. Mol%, and further 20 to 80 mol%. Further, the preferred proportion of the structural unit (Ib) in the polymer is 99 to 1 mol%, more preferably 95 to 5 mol%, and further 90 to 10 mol%, more preferably 80 from the viewpoint of the dispersibility of the hydraulic powder. ~ 20 mol%. In the step (B), the charged molar ratio of the polyalkylene glycol monomer obtained in the step (A), that is, the monomer (i) and the unsaturated carboxylic acid monomer, is obtained in the step (A). The polyalkylene glycol monomer / unsaturated carboxylic acid monomer thus obtained is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and even more preferably 20/80 to 80/20.

The following are mentioned as a monomer for obtaining the other structural unit which the polyalkylene glycol type polymer manufactured by the method 2 can contain.
(1) Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylic acid Lauryl, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanedi (Meth) acrylate, methoxypolyethyleneglycol mono (meth) acrylate, methoxy {polyethyleneglycol (poly) propyleneglycol} mono (meth) acrylate, ethoxypolyethyleneglycolmono (meth) a (Meth) acrylates such as relate, ethoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, propoxypolyethylene glycol mono (meth) acrylate, etc. (2) methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, vinyl acetate Unsaturated alcohols such as allyl acetate, allyl alcohol, methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether (3) vinyl sulfonate, (meta ) Allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxy Unsaturated sulfonic acids such as butyl sulfonate, (meth) acrylamide methyl sulfonic acid, (meth) acrylamide ethyl sulfonic acid, 2-methylpropane sulfonic acid (meth) acrylamide and styrene sulfonic acid, and monovalent metal salts thereof; (4) Unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate (5) Phosphate ester monomers such as 2-hydroxyethyl (meth) acrylate, croton Acid 2-hydroxy Examples thereof include monomers obtained by phosphorylating ethyl, 2-hydroxyethyl α-hydroxyacrylate, etc. with phosphorylating agents such as diphosphorus pentoxide, phosphoric acid, polyphosphoric acid, tripolyphosphoric acid, phosphorous trichloride, phosphorous oxychloride. Specific examples include phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester, phosphoric acid mono (2-hydroxyethyl) acrylic acid ester, and phosphoric acid mono (2-hydroxyethyl) crotonic acid ester. Among these, phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester and phosphoric acid mono (2-hydroxyethyl) acrylic acid ester are preferable. Further, di (2-hydroxyethyl) methacrylic acid ester, di (2-hydroxyethyl) acrylic acid phosphate, di (2-hydroxyethyl) crotonic acid phosphate and the like can be mentioned. Among these, di (2-hydroxyethyl) methacrylic acid ester and di (2-hydroxyethyl) acrylic acid phosphate are preferable.

  The preferable weight average molecular weight of the polyalkylene glycol polymer produced by the method 2 is 10,000 to 200,000, further 20,000 to 150,000, and more preferably 30,000 to 100,000. In addition, since the polyalkylene glycol monomer composition obtained in the step (A) has a low content of bifunctional monomer, the polyalkylene glycol polymer has a low content of cross-linked structure and a narrow molecular weight distribution. Coalescence is obtained. The weight average molecular weight (Mw) relative to the number average molecular weight (Mn), which is an index of the distribution of molecular weight, that is, (Mw / Mn) is preferably 1.0 to 1.5 from the viewpoint of performance as a dispersant. -1.4 is more preferable, and 1.2-1.4 is still more preferable. A weight average molecular weight and a number average molecular weight are measured by the method described in an Example.

  In the step (B), a polymerization initiator can be used for copolymerization of the polyalkylene glycol monomer and the unsaturated carboxylic acid monomer. Examples of the polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azobis-2-methylpropionamidine hydrochloride, 4,4′-azobis-4-cyanovaleric acid, azoisobutyrate Azo compounds such as rhonitrile, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, Examples thereof include peroxides such as cumene hydroperoxide, peracetic acid, and di-t-butyl peroxide. Decomposition accelerators include sodium bisulfite, sodium sulfite, potassium bisulfite, potassium sulfite, ammonium bisulfite, ammonium sulfite, moor salt, sodium pyrobisulfite, sodium formaldehyde sulfoxylate, ascorbic acid, phosphite and hyposulfite. Reducing agents such as phosphates; amine compounds such as ethylenediamine, sodium ethylenediaminetetraacetate, and glycine can also be used in combination. It is preferable to use a polymerization initiator in the ratio of 0.1-20 mol%, 0.5-15 mol%, and 0.75-10 mol% with respect to the sum total of all the monomers. Two or more polymerization initiators may be used in combination.

  A chain transfer agent can be used for the copolymerization of the polyalkylene glycol monomer and the unsaturated carboxylic acid monomer. Chain transfer agents include mercaptoethanol, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, butanethiol, octanethiol, decanethiol, dodecanethiol, thiophenol, Thiol chain transfer agents such as octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-mercaptoethanesulfonic acid; secondary alcohols such as isopropanol; Acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite); sulfurous acid, hydrogen sulfite, dithionite, metabisulfite and salts thereof (sodium sulfite, sodium hydrogen sulfite) , Sodium dithionite); carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, halides such as bromotrichloroethane; and the like. The chain transfer agent is preferably used in a proportion of 0.1 to 20 mol%, 1 to 10 mol%, and 2.5 to 7.5 mol% with respect to the total of all monomers.

  In addition, when the polyalkylene glycol monomer and the unsaturated carboxylic acid monomer are copolymerized, a polymerization inhibitor can be used from the viewpoint of suppressing polymerization. Polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,6-di-t-butylphenol and other phenols; amines such as phenothiazine and methylene blue; copper salts such as copper dibutyldithiocarbamate, other nitro compounds, nitroso compounds , N-oxyl compounds and the like. The polymerization inhibitor is preferably used in a proportion of 0.005 to 0.5 wt%, 0.01 to 0.3 wt%, 0.15 to 0.1 wt% with respect to the polyalkylene glycol monomer. . The polymerization inhibitor may be added to the raw material in advance. Further, it may be charged in advance before the etherification reaction, or may be charged during or after the reaction.

  For the copolymerization of the polyalkylene glycol monomer and the unsaturated carboxylic acid monomer, a pH adjuster such as phosphoric acid, a chelating agent, an antifoaming agent and the like can be used as necessary.

  Examples of the copolymerization method include solution polymerization and bulk polymerization using a monomer component and a polymerization initiator.

  In the copolymerization of the polyalkylene glycol monomer and the unsaturated carboxylic acid monomer, the reaction temperature can be 25 to 100 ° C, further 40 to 90 ° C, and further 60 to 80 ° C. The completion of the polymerization reaction can be confirmed by quantifying the remaining monomer using high performance liquid chromatography or nuclear magnetic resonance (NMR) method. After completion of the reaction, a polyalkylene glycol polymer can be obtained by neutralization and concentration adjustment as necessary.

  The polyalkylene glycol polymer obtained by the production method of the present invention can be used for various uses such as a dispersant, a thickener, a detergent builder, and a scale inhibitor.

  The polyalkylene glycol polymer obtained by the production method of the present invention has an adsorbing group based on carboxylic acid and a steric repulsion group based on polyalkylene glycol. Useful. It can be used for inorganic powder or organic powder, and can be used more suitably for inorganic powder. Especially, it can use more suitably for the hydraulic powder which has a physical property hardened | cured by a hydration reaction at the point with little inhibition to the hydration reaction of hydraulic powder. Examples thereof include hydraulic powder cement and gypsum such as ordinary Portland cement, medium heat cement, early strong cement, ultra early strong cement, high belite-containing cement, blast furnace cement, fly ash cement, alumina cement, and silica fume cement. In addition, a filler can also be used as the inorganic powder, and examples thereof include calcium carbonate, fly ash, blast furnace slag, silica fume, bentonite, and clay (natural minerals mainly containing hydrous aluminum silicate: kaolinite, halosite, etc.). . These powders may be used alone or in combination. That is, the polyalkylene glycol polymer obtained by the production method of the present invention is suitable as a dispersant for hydraulic powder.

  According to the present invention, the polyalkylene glycol polymer (that is, the dispersant according to the present invention) obtained by the production method of the present invention, the hydraulic powder, and water are mixed to form a hydraulic material containing these. A composition is provided. Examples of the hydraulic composition include mortar, concrete, and grout. The hydraulic composition can contain cement, water, fine aggregate, coarse aggregate, filler such as calcium carbonate, and the like. Moreover, what added fine powders, such as fly ash, blast furnace slag, a silica fume, and limestone, may be used. In such a hydraulic composition, the polyalkylene glycol polymer obtained by the production method of the present invention is 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight with respect to 100 parts by weight of the hydraulic powder. Further, 0.1 to 5 parts by weight can be used.

  The hydraulic composition containing the polyalkylene glycol polymer obtained by the production method of the present invention has a water / hydraulic powder ratio [weight percentage (%) of water and hydraulic powder in slurry, usually W Although abbreviated as / P, when the powder is cement, it is abbreviated as W / C. ] Can exhibit the effect of dispersion performance and low viscosity. That is, in the polyalkylene glycol polymer obtained by the production method of the present invention, W / P (%) is preferably 10 to 60%, more preferably 10 to 45%, more preferably 10 to 30 by weight ratio. %, More preferably 10 to 20%, and still more preferably 10 to 15%, an excellent effect can be exhibited with dispersibility and low viscosity.

Example 1 and Comparative Example 1
In a glass reaction vessel (four-necked flask) with a stirrer, 264.6 g of monomethoxypolyethylene glycol (average added mole number of ethylene oxide 23) and 7.0 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., reagent) The temperature was raised to 105 ° C. while stirring and stirring under air. Thereafter, 36.0 g of glycidyl methacrylate (manufactured by Dow Chemical Co., hereinafter referred to as GMA) was dropped over 4 hours. Thereafter, aging was carried out at 105 ° C. for 1.5 hours. After completion of aging, the mixture was neutralized with acetic acid and diluted with water to obtain an aqueous compound solution having a solid content of 65% by weight and a purity of 84.0%. This aqueous compound solution was designated as Monomer Composition 1. In the same manner, but changing the molar ratio of GMA and monomethoxypolyethylene glycol, monomer compositions 2 to 4 and monomer composition 5 (comparative example) were produced.

  The obtained monomer compositions 1 to 5 were subjected to high-performance liquid chromatography to separate the peaks, and the structure was confirmed by a nuclear magnetic resonance (NMR) method. It was found to be a reaction product containing b) and monomer (ic). Table 1 shows the molar ratio at the time of producing each monomer composition, and the weight ratio of the monomer (ib) to the monomer (ic). The weight ratio was determined by evaporating the solvent from the fraction obtained from each peak and measuring the weight.

Example 2 and Comparative Example 2
115.0 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. Monomer composition 1 [Methoxypolyethylene glycol monoglycidyl methacrylate (average addition mole number of ethylene oxide 23, purity 84.0%) aqueous solution (65 wt% solid content)] 250.0 g and methacrylic acid 29.7 g were mixed. The dissolved monomer solution, 3-mercaptopropionic acid aqueous solution [3-mercaptopropionic acid (Sigma Aldrich Japan Co., Ltd., reagent) 1.95 g dissolved in 27.0 g of water], ammonium persulfate aqueous solution ( I) [Ammonium persulfate (manufactured by Wako Pure Chemical Industries, Ltd., reagent) 1.05 g dissolved in 45.0 g of water] was started dropwise at the same time and dropped over 1.5 hours each. . After aging at 80 ° C. for 1.0 hour, an aqueous ammonium persulfate solution (II) [0.52 g of ammonium persulfate dissolved in 15.0 g of water] was added, followed by further aging for 2 hours. After completion of aging, the solution was neutralized with a 20% by weight aqueous sodium hydroxide solution to obtain a copolymer aqueous solution. This copolymer was designated as copolymer 1. In the same manner, except that the monomer composition 1 is replaced with the monomer composition 2 to 4 or the monomer composition 5 (comparative example) or methoxypolyethylene glycol (average added mole number of ethylene oxide 23) methacrylate (comparative example) ) Were used to produce Copolymers 2 to 4 and Copolymers 5 and 6 (Comparative Example).

The weight average molecular weight Mw and the number average molecular weight Mn of the obtained copolymer were measured by gel permeation chromatography (GPC) method under the following conditions. The results are shown in Table 2.
GPC molecular weight measurement condition use column: TSK guard column PWxl manufactured by Tosoh Corporation
TSKgel G4000PWxl + G2500PWxl
Eluent: 0.2 mol / L phosphate buffer (manufactured by Shinyo Chemical Co., Ltd.) / Acetonitrile for high performance liquid chromatograph (manufactured by Wako Pure Chemical Industries, Ltd.) = 9/1 (vol%)
Flow rate: 1.0mL / min.
Column temperature: 40 ° C
Detection: RI
Injection volume: 10 μL (0.5 wt% aqueous solution)
Standard substance: polyethylene oxide, weight average molecular weight (Mw) 875000, 540000, 235000, 145000, 107000, 24000
Calibration curve order: Tertiary device: HLC-8320GPC (manufactured by Tosoh Corporation)
Software: EcoSEC-WS (manufactured by Tosoh Corporation)

* Although it does not correspond to the polyalkylene glycol monomer mixture in the present invention, it is described in this column for easy comparison.
** Examples 2-1 to 2-4 and Comparative Example 2-1 are molar ratios of the polyalkylene glycol monomer and the unsaturated carboxylic acid monomer in the monomer compositions 1 to 5 is there.
*** Weight average molecular weight (Mw) / Number average molecular weight (Mn)

<Mortar test>
The mortar flow of the mortar prepared using the copolymers 1 to 6 obtained in Example 2 was measured. The mortar formulation was as shown in Table 3. The amount of copolymer added relative to 100 parts by weight of cement was as shown in Table 4. Under the above conditions, fine aggregate and cement were put into a mortar mixer and kneaded for 15 seconds, and then water containing 0.05 g of a fatty acid ester antifoaming agent and any of copolymers 1 to 6 was added. And kneaded for another 10 minutes to produce a mortar. Mortar flow was measured immediately after mortar production (0 minutes), 15 minutes, 30 minutes, 60 minutes and 90 minutes. The flow test was measured according to JIS R5201. In addition, the drop motion described in JIS R 5201 is not performed. Those having a large flow with a smaller addition amount are excellent in dispersibility, and those having a small change in fluidity with time are excellent in fluid retention.

The compounding components in Table 3 are as follows.
W: Tap water in Wakayama City C: Ordinary Portland cement, Taiheiyo Cement Co., Ltd., density 3.16 g / cm ³
S: Fine aggregate, Joyosan sand density 2.55g / cm ³

  In the table, the addition amount is parts by weight with respect to 100 parts by weight of cement.

  As shown in Table 4, in Examples 2-1 to 2-4 using the copolymers 1 to 4, a mortar flow of 202 to 208 mm was obtained immediately after the preparation with the same addition amount. It turns out that it is excellent in the fluidity | liquidity provision effect with respect to mortar compared with the copolymer 5 which is a polymer. Moreover, in Examples 2-1 to 2-4 using the copolymers 1 to 4, a comparative copolymer using methoxypolyethylene glycol (ethylene oxide average addition mole number 23) methacrylate as the polyalkylene glycol monomer. It can be seen that the fluidity-imparting effect is equal to or greater than that of the copolymer 6 (conventional product).

Claims (5)

A glycidyl (meth) acrylate and a monoalkoxy polyalkylene glycol represented by the following general formula (ii) are charged in a molar amount of glycidyl (meth) acrylate / monoalkoxy polyalkylene glycol = 0.8 / 1 to 1.2 / 1. A method for producing a polyalkylene glycol monomer that undergoes an etherification reaction at a ratio.

[Wherein, A represents an alkylene group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group having 1 to 18 carbon atoms, and n represents an average added mole number of AO, which is a number of 1 to 500. ] A glycidyl (meth) acrylate and a monoalkoxy polyalkylene glycol represented by the following general formula (ii) are charged in a molar amount of glycidyl (meth) acrylate / monoalkoxy polyalkylene glycol = 0.8 / 1 to 1.2 / 1. By etherification reaction at a ratio
A polyalkylene glycol monomer (ib) represented by the following general formula (ib) and a polyalkylene glycol monomer (ic) represented by the following general formula (ic): The weight ratio of the monomer (ib) to the monomer (ic) is 0.1 ((ic) / [(ib) + (ic))]. Producing a polyalkylene glycol monomer composition which is:
A method for producing a polyalkylene glycol monomer composition.

[Wherein, A represents an alkylene group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group having 1 to 18 carbon atoms, and n represents an average added mole number of AO, which is a number of 1 to 500. ]

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, n is a number having 1 to 500, and A is an alkylene group having 2 to 18 carbon atoms. ]

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, n is a number having 1 to 500, and A is an alkylene group having 2 to 18 carbon atoms. ] A glycidyl (meth) acrylate and a monoalkoxy polyalkylene glycol represented by the following general formula (ii) are charged in a molar amount of glycidyl (meth) acrylate / monoalkoxy polyalkylene glycol = 0.8 / 1 to 1.2 / 1. A step (A) of producing a polyalkylene glycol monomer composition by etherification reaction in a ratio;
A step (B) for producing a polyalkylene glycol polymer by copolymerizing the polyalkylene glycol monomer composition obtained in the step (A) and an unsaturated carboxylic acid monomer;
A process for producing a polyalkylene glycol polymer having

[Wherein, A represents an alkylene group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group having 1 to 18 carbon atoms, and n represents an average added mole number of AO, which is a number of 1 to 500. ]   A dispersant comprising a polyalkylene glycol polymer obtained by the production method according to claim 3.   The manufacturing method of the hydraulic composition which mixes the dispersing agent of Claim 4, hydraulic powder, and water.