JP2008115371A - Unsaturated monomer, copolymer and dispersant and cement admixture using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an unsaturated monomer expectable of improving dispersing effects by steric repulsion without deteriorating polymerization reactivity, to provide a copolymer obtained by polymerizing a monomer component containing the unsaturated monomer and to provide a dispersant and a cement admixture comprising the copolymer. <P>SOLUTION: The unsaturated monomer is an unsaturated monomer having an ethylenically unsaturated bond and an amino group. In the unsaturated monomer, one amino group is present per one molecule and two polyalkylene glycol chains are bound to the nitrogen atom of the amino group. For example, the unsaturated monomer is represented by formula (1). The copolymer prepared by polymerizing the monomer component containing the unsaturated monomer is useful as a dispersant for various kinds of powder and a cement admixture. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an unsaturated monomer, a copolymer, a dispersant and a cement admixture using the unsaturated monomer, and more particularly, an unsaturated monomer and a monomer component containing the unsaturated monomer. The present invention relates to a copolymer obtained by polymerization, a dispersant containing the copolymer, and a cement admixture.

  A polymer having a carboxyl group and a polyalkylene glycol chain in the molecule can be used, for example, due to the steric repulsion of the polyalkylene glycol chain in addition to the adsorption effect of the carboxyl group. It is useful for such as. A polymer having a carboxyl group and a polyalkylene glycol chain in the molecule is generally obtained by copolymerizing an unsaturated monomer having a polyalkylene glycol chain and an unsaturated carboxylic acid monomer. It is done.

  Conventionally, as an unsaturated monomer having a polyalkylene glycol chain, for example, a monomer obtained by adding a polyalkylene glycol chain with an ester bond to an unsaturated carboxylic acid such as (meth) acrylic acid or maleic acid ( For example, refer to Patent Document 1), and a polyalkylene glycol chain is added to an unsaturated alcohol such as (meth) allyl alcohol, (3-methyl) -3-buten-1-ol, hydroxyalkyl vinyl ether by an ether bond. Monomers (see, for example, Patent Documents 2 and 3) obtained by the above method are known.

  However, since all of these unsaturated monomers have only one polyalkylene glycol chain in the molecule, the polymer obtained by copolymerization with the unsaturated carboxylic acid monomer is based on the molecular weight. Since the ratio of the number of polyalkylene glycol chains is small, the dispersion performance is limited to some extent. Therefore, in order to improve the dispersion performance, it is considered to develop an unsaturated monomer having two or more polyalkylene glycol chains in the molecule.

  Therefore, for example, Patent Document 4 discloses that after polyamidene polyamine is amidated with dibasic acid such as adipic acid and acrylic acid or methacrylic acid, 0 to 4 mol of ethylene oxide with respect to the amino group of the starting polyalkylene polyamine. And unsaturated monomers to which propylene oxide is added are disclosed. This unsaturated monomer has, for example, 7 polyalkylene glycol chains in the molecule when diethylenetriamine is used as the polyalkylene polyamine, but the average added mole of oxyethylene groups in each polyalkylene glycol chain. Since the number is at most 4 mol, the dispersion effect due to steric repulsion is considered to be small.

Patent Document 5 discloses an unsaturated monomer in which an unsaturated group is introduced by esterifying a compound obtained by adding an alkylene oxide to a polyalkyleneimine with, for example, an unsaturated carboxylic acid. This unsaturated monomer is prepared using, for example, a compound obtained by adding ethylene oxide with an average addition mole number of 3 to a polyalkyleneimine having a weight average molecular weight of 600, and has a number of polyalkylene glycol chains in the molecule. Since the average addition mole number of oxyethylene groups in each polyalkylene glycol chain is 3 moles, the dispersion effect due to steric repulsion is considered to be small.
JP-A-9-86990 JP-A-6-271347 JP-A-10-236858 JP 7-33496 A JP 2003-128738 A

  In this way, if the number of polyalkylene glycol chains per molecule is increased, the molecule itself becomes large. Therefore, in order not to reduce the polymerization reactivity due to steric hindrance or the like, the average of oxyalkylene groups in the polyalkylene glycol chain The number of added moles cannot be increased.

  Under the circumstances described above, the problem to be solved by the present invention is not to increase the number of polyalkylene glycol chains contained in the molecule, but to reduce the number of polyalkylene glycol chains per molecule to two, Unsaturated monomer that can be expected to improve the dispersion effect due to steric repulsion without reducing polymerization reactivity by increasing the average number of moles of oxyalkylene group in the polyalkylene glycol chain, and this unsaturated monomer It is another object of the present invention to provide a copolymer obtained by polymerizing a monomer component containing, and a dispersant and a cement admixture containing the copolymer.

  As a result of various studies, the present inventors have found that the use of an unsaturated monomer obtained by adding 2 moles of a polyalkylene glycol chain to methallylamine improves the dispersion effect due to steric repulsion without reducing the polymerization reactivity. As a result, the present invention has been completed.

That is, the present invention relates to an unsaturated monomer having an ethylenically unsaturated bond and an amino group, wherein one amino group is present per molecule, and two polyalkylenes are present at the nitrogen atom of the amino group. Provided is an unsaturated monomer having a glycol chain attached thereto.
Examples of the unsaturated monomer of the present invention include the following formula (1):

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁴ represents an alkylene group having 1 to 20 carbon atoms, a carbonyl group, or Represents an aryl group having 6 to 20 carbon atoms, and A ¹ O and A ² O each independently represent one or more oxyalkylene groups having 2 or more carbon atoms, and in the case of 2 or more blocks Or m and n are the average number of added moles of the oxyalkylene group, and each independently represents an integer of 0 to 300, but (m + n) / 2 = 1 to 300 are satisfied, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms]
Indicated by
Among the unsaturated monomers represented by the above formula (1), for example, the following formula (2):

[Wherein R ⁷ represents hydrogen or a methyl group, R ⁸ represents an alkylene group having 1 to 4 carbon atoms, and A ¹ O, A ² O, m, n, R ⁵ and R ⁶ represent the above formula (1 Is equivalent to
The unsaturated monomer shown by these is preferable.

  The present invention also provides a copolymer obtained by polymerizing a monomer component containing the unsaturated monomer as described above. Here, the monomer component is, for example, the following formula (3):

^Wherein, R ^{9, R 10,} and ^{R 11} are, independently of one another, a hydrogen atom, a group (wherein, _{- (CH} 2) represented by a methyl group or a group represented by the formula ^{_{:-( CH 2) z COOM 2 z}} COOM ² represents —COOM ¹ or other — (CH ₂ ) _z COOM ² and may form a cyclic acid anhydride structure), z represents an integer of 0 to 2, M ¹ and M ² Independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium base, an organic amine base, or a hydrocarbon group having 1 to 20 carbon atoms]
A carboxyl group-containing unsaturated monomer represented by the formula:

  Furthermore, the present invention provides a dispersant characterized by containing the above-mentioned copolymer and a cement admixture characterized by containing the above-mentioned copolymer.

  According to the present invention, it is possible to obtain an unsaturated monomer having an improved dispersion effect due to steric repulsion as compared with a conventional unsaturated monomer having a polyalkylene glycol chain without reducing polymerization reactivity. Since the copolymer obtained by polymerizing the monomer component containing the unsaturated monomer is excellent in dispersion performance, various powder dispersants such as cement admixtures and organic / inorganic pigment dispersants are used. Useful for.

≪Unsaturated monomer≫
The unsaturated monomer of the present invention is an unsaturated monomer having an ethylenically unsaturated bond and an amino group, and one amino group is present per molecule, and 2 amino acids are present in the nitrogen atom of the amino group. It is characterized in that one polyalkylene glycol chain is bonded. Here, the ethylenically unsaturated bond means a double bond between carbon and carbon atoms, specifically, vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, crotyl. A double bond contained in an alkenyl group such as a group, an isocrotyl group, and a methallyl group. In other words, these substituents are bonded to the nitrogen atom of the amino group.
Examples of the unsaturated monomer of the present invention include the following formula (1):

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁴ represents an alkylene group having 1 to 20 carbon atoms, a carbonyl group, or Represents an aryl group having 6 to 20 carbon atoms, and A ¹ O and A ² O each independently represent one or more oxyalkylene groups having 2 or more carbon atoms, and in the case of 2 or more blocks Or m and n are the average number of added moles of the oxyalkylene group, and each independently represents an integer of 0 to 300, but (m + n) / 2 = 1 to 300 are satisfied, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms]
Indicated by
Among the unsaturated monomers represented by the above formula (1), for example, the following formula (2):

[Wherein R ⁷ represents hydrogen or a methyl group, R ⁸ represents an alkylene group having 1 to 4 carbon atoms, and A ¹ O, A ² O, m, n, R ⁵ and R ⁶ represent the above formula (1 Is equivalent to
Is preferably an unsaturated monomer represented by the following formula (4):

[Wherein, A ¹ O, A ² O, m, n, R ⁵ and R ⁶ are the same as those in the above formula (1)]
An unsaturated monomer derived from allylamine represented by the following formula (5):

[Wherein, A ¹ O, A ² O, m, n, R ⁵ and R ⁶ are the same as those in the above formula (1)]
And an unsaturated monomer derived from methallylamine represented by the following formula (6):

[Wherein, A ¹ O, A ² O, m, n, R ⁵ and R ⁶ are the same as those in the above formula (1)]
An unsaturated monomer derived from isoprenylamine is more preferred.

In the above formula (1) to formula (2) and formula (4) to formula (6), the portion represented by (A ¹ O) _m or (A ² O) _n is a polyalkylene glycol chain. Here, the oxyalkylene group represented by A ¹ O or A ² O needs to have higher hydrophilicity from the viewpoint of effectively dispersing particles when the copolymer is used as a dispersant. It is preferably mainly an oxyethylene group having 2 carbon atoms. The proportion of oxyethylene groups having 2 carbon atoms in the polyalkylene glycol chain composed of m or n oxyalkylene groups is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. Especially preferably, it is 80 mol% or more.

  In the above formula (1) to formula (2) and formula (4) to formula (6), m and n are the average number of added moles of the oxyalkylene group, and each independently represents an integer of 0 to 300. However, in practice, not only the average for the molecular population but also the average value for the two polyalkylene glycol chains can be obtained for each molecule. Therefore, in the present invention, m and n do not become 0 at the same time, so it is defined that (m + n) / 2 = 1 to 300 is satisfied.

In the above formula (1) to formula (2) and formula (4) to formula (6), examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵ or R ⁶ include, for example, 1 to 20 carbon atoms. Aliphatic alkyl groups, alicyclic alkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and the like. The substituent represented by R ⁵ or R ⁶ is preferably a hydrophilic group from the viewpoint of dispersibility, specifically, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
The unsaturated monomer represented by the above formula (1) is, for example, the following formula (7):

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁴ represents an alkylene group having 1 to 20 carbon atoms, a carbonyl group, or Represents an aryl group having 6 to 20 carbon atoms]
After adding a polyalkylene glycol chain to the nitrogen atom of the unsaturated amine compound represented by formula (1), and then introducing substituents R ⁵ and R ⁶ at the terminal of the polyalkylene glycol chain.

  However, in general, the unsaturated amine compound represented by the above formula (7) has a high risk, so this production method is not recommended. Therefore, as a safer production method, the unsaturated monomer represented by the above formula (1) is represented by the following formula (8):

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁴ represents an alkylene group having 1 to 20 carbon atoms, a carbonyl group, or Represents an aryl group having 6 to 20 carbon atoms, and X represents a halogen atom]
Is reacted with diethanolamine to give the following formula (9):

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁴ represents an alkylene group having 1 to 20 carbon atoms, a carbonyl group, or Represents an aryl group having 6 to 20 carbon atoms]
Is obtained by adding a polyalkylene glycol chain to the hydroxyl group of this intermediate, and then introducing substituents R ⁵ and R ⁶ into the terminal of the polyalkylene glycol chain. In this case, since diethanolamine is used, the first oxyalkylene group bonded to the nitrogen atom of the unsaturated monomer represented by the above formula (1) becomes an oxyethylene group. If an oxypropylene group is to be introduced, dipropanolamine may be used instead of diethanolamine.

  In addition, in the unsaturated monomer represented by the above formula (1), in order to add two different polyalkylene glycol chains to the nitrogen atom of the amino group, one of the intermediates represented by the above formula (9) is used. After protecting the hydroxyl group, a polyalkylene glycol chain may be added to the other hydroxyl group, and then after deprotecting one of the hydroxyl groups, a different polyalkylene glycol chain may be added to the hydroxyl group. Examples of the protecting group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group, t-butyldiphenylsilyl group, and the like. The conditions for protection and deprotection may be any conventionally known conditions and are not particularly limited.

  Furthermore, in the unsaturated monomer represented by the above formula (1), when there are two or more oxyalkylene groups constituting the polyalkylene glycol chain, these oxyalkylene groups are introduced in a block or random manner. In this case, two or more oxyalkylene groups may be sequentially added to the hydroxyl group of the intermediate represented by the above formula (9) in a block form or a random form. Alternatively, a polyalkylene glycol in which two or more oxyalkylene groups are linked in a block shape or a random shape in advance may be prepared and added to the intermediate hydroxyl group represented by the above formula (9).

  The reaction of the unsaturated halide represented by the above formula (8) with diethanolamine or dipropanolamine can be carried out, for example, in a solvent such as tetrahydrofuran in the presence of a base such as sodium carbonate with stirring. The use amount of the unsaturated halide represented by the above formula (8) and diethanolamine or dipropanolamine is a molar ratio, preferably 1/10 to 10/1, more preferably 1/6 to 6/1, Preferably it exists in the range of 1/3-3/1. The reaction temperature is not particularly limited, but is 0 ° C. to the reflux temperature of the solvent, and the reflux temperature of the solvent is preferable from the viewpoint of the reaction rate. The reaction time is preferably in the range of 1 to 48 hours, more preferably 2 to 24 hours, still more preferably 2 to 12 hours. The reaction pressure may be normal pressure, reduced pressure or increased pressure, but is usually normal pressure.

After completion of the reaction, the precipitated sodium salt such as sodium chloride and the remaining base such as sodium carbonate are removed by filtration, and the obtained filtrate is distilled under reduced pressure or atmospheric pressure to remain in the residue represented by the above formula (8). When a solvent such as saturated halide or tetrahydrofuran is distilled off, an intermediate represented by the above formula (9), which is the target product, is obtained. The end point of the reaction can be confirmed by, for example, a peak derived from diethanolamine or dipropanolamine in the ¹ H-NMR spectrum of the reaction solution.

In order to introduce the substituents R ⁵ and R ⁶ to the terminal of the polyalkylene glycol chain in the intermediate thus obtained, a conventionally known Williamson synthesis method may be employed. More specifically, a base is allowed to act on the intermediate represented by the above formula (9) so that the end of the polyalkylene glycol chain is an alkoxide, and the alkyl halide, alkenyl halide, halogenated corresponding to the substituents R ⁵ and R ⁶ are used. An organic halide such as alkynyl and aryl halide is reacted.

The reaction of the intermediate represented by the above formula (9) and the organic halide corresponding to the substituents R ⁵ and R ⁶ is, for example, stirred in a solvent such as tetrahydrofuran in the presence of a base such as sodium hydride. Can be done. The amount of the intermediate represented by the above formula (9) and the halide corresponding to the substituents R ⁵ and R ⁶ is molar ratio, preferably 1/10 to 10/1, more preferably 1/6 to It is in the range of 6/1, more preferably 1/3 to 3/1. The reaction temperature is not particularly limited, but is 0 ° C. to the reflux temperature of the solvent, and the reflux temperature of the solvent is preferable from the viewpoint of the reaction rate. The reaction time is preferably in the range of 1 to 48 hours, more preferably 2 to 24 hours, still more preferably 2 to 12 hours. The reaction pressure may be normal pressure, reduced pressure or increased pressure, but is usually normal pressure.

After completion of the reaction, the sodium salt such as sodium halide which precipitates is removed by filtration, and the obtained filtrate is distilled under reduced pressure or atmospheric pressure to distill off the remaining organic halide or tetrahydrofuran and other solvents to produce the desired product. An unsaturated monomer represented by the above formula (1) is obtained. Incidentally, the end point of the reaction can be confirmed by the peak of the hydroxyl group from that present at the end of the polyalkylene glycol chain in the ^{1 H-NMR} spectrum of the reaction solution.

When the substituents R ⁵ and R ⁶ are not the same, after protecting the terminal of one polyalkylene glycol chain, for example, the substituent R ⁵ is introduced into the terminal of the other polyalkylene glycol chain, After deprotecting one terminal of the polyalkylene glycol chain, a substituent R ⁶ may be introduced to this terminal. Examples of the protecting group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group, t-butyldiphenylsilyl group, and the like. The protection and deprotection conditions may be any conventionally known method and are not particularly limited.

≪Copolymer≫
The copolymer of the present invention is obtained by polymerizing a monomer component containing an unsaturated monomer represented by the above formula (1) (hereinafter sometimes referred to as “monomer (a)”). It is done. Here, the monomer (a) is preferably in the form of, for example, hydrochloride. The monomer component is preferably the following formula (3):

^Wherein, R ^{9, R 10,} and ^{R 11} are, independently of one another, a hydrogen atom, a group (wherein, _{- (CH} 2) represented by a methyl group or a group represented by the formula ^{_{:-( CH 2) z COOM 2 z}} COOM ² represents —COOM ¹ or other — (CH ₂ ) _z COOM ² and may form a cyclic acid anhydride structure), z represents an integer of 0 to 2, M ¹ and M ² Independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium base, an organic amine base, or a hydrocarbon group having 1 to 20 carbon atoms]
And a carboxyl group-containing unsaturated monomer (hereinafter sometimes referred to as “monomer (b)”).

  Examples of the monomer (b) include acrylic acid, methacrylic acid, crotonic acid, and (meth) acrylic acid type such as monovalent metal salt, divalent metal salt, quaternary ammonium salt, and organic amine salt. Monomers; maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and monovalent unsaturated dicarboxylic acid-based monovalent metal salts, divalent metal salts, quaternary ammonium salts, organic amine salts, etc. And the like. These monomers (b) may be used alone or in combination of two or more. Among these monomers (b), acrylic acid, methacrylic acid, and salts thereof are preferable from the viewpoint of polymerizability, and acrylic acid and salts thereof are more preferable.

  The monomer component is a monomer (a) and / or another monomer copolymerizable with the monomer (b) (hereinafter sometimes referred to as “monomer (c)”). You may contain.

  Examples of the monomer (c) include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and monovalent metal salts, divalent metal salts, quaternary ammonium salts, and organic amine salts thereof. An unsaturated dicarboxylic acid monomer; half esters and diesters of the unsaturated dicarboxylic acid monomer and an alcohol having 1 to 30 carbon atoms; the unsaturated dicarboxylic acid monomer and 1 carbon atom. Half amides and diamides with -30 amines; alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine and the unsaturated dicarboxylic acid monomer Half-esters and diesters of said unsaturated dicarboxylic acid monomers and glycols having 2 to 18 carbon atoms or of these glycols Half ester and diester with polyalkylene glycol having 2 to 500 moles added; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, Esters of unsaturated monocarboxylic acids such as propyl crotonate and alcohols having 1 to 30 carbon atoms; alkoxy obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to alcohol having 1 to 30 carbon atoms ( Esters of poly) alkylene glycol and unsaturated monocarboxylic acids such as (meth) acrylic acid; (poly) ethylene glycol monomethacrylate, (poly) propylene glycol monomethacrylate, (poly) butylene glycol monomethacrylate, etc. 1-500 mole adducts of alkylene oxides of 2-18 carbon atoms to unsaturated monocarboxylic acids such as (meth) acrylic acid; addition of maleamic acid and glycols of 2-18 carbon atoms or these glycols Half amides with polyalkylene glycols having 2 to 500 moles; triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly ) (Poly) alkylene glycol di (meth) acrylates such as propylene glycol di (meth) acrylate; hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate Bifunctional (meth) acrylates such as; (poly) alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxy Sulfobenzoate, 4- (meth) acryloxybutyl sulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylic And unsaturated sulfonic acids such as styrene sulfonic acid, and monovalent metal salts, divalent metal salts, quaternary ammonium salts and organic amine salts thereof; unsaturated monocarboxylic acids such as methyl (meth) acrylamide and carbon Amides with amines having 1 to 30 atoms; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene; 1,4-butanediol mono (meth) acrylate, 1,5-pentane Alkanediol mono (meth) acrylates such as diol mono (meth) acrylate and 1,6-hexanediol mono (meth) acrylate; butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3 -Dienes such as butadiene; (meth) acrylamide, (meth) acrylalkylamide, Unsaturated amides such as N-methylol (meth) acrylamide and N, N-dimethyl (meth) acrylamide; Unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile; Unsaturation such as vinyl acetate and vinyl propionate Esters: aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine, etc. Unsaturated amines; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; dimethylaminoethyl (meth) acrylate and the like Unsaturated Compounds; vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether; polydimethylsiloxanepropylaminomaleamic acid, Polydimethylsiloxane aminopropylamino maleamic acid, polydimethylsiloxane-bis- (propylamino maleamic acid), polydimethylsiloxane-bis- (dipropylamino maleamic acid), polydimethylsiloxane- (1-propyl-3- Acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl) Siloxane derivatives such as (propyl-3-acrylate) and polydimethylsiloxane-bis- (1-propyl-3-methacrylate). These monomers (c) may be used alone or in combination of two or more. Among these monomers (c), unsaturated such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate Esters of monocarboxylic acids and alcohols having 1 to 30 carbon atoms; alkoxy (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to alcohols having 1 to 30 carbon atoms and (meta ) Esters with unsaturated monocarboxylic acids such as acrylic acid; Unsaturated such as (meth) acrylic acid, such as (poly) ethylene glycol monomethacrylate, (poly) propylene glycol monomethacrylate, (poly) butylene glycol monomethacrylate To monocarboxylic acids 1-500 mole adducts of alkylene oxide having 2 to 18 carbon atoms; and the like are preferable.

  The polymerization reaction can be performed by a conventionally known method such as solution polymerization or bulk polymerization. The solution polymerization can be performed either batchwise or continuously. Usable solvents include water; lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, n-hexane and cyclohexane; esters such as ethyl acetate Ketones such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; and the like. These solvents may be used alone or in combination of two or more. Of these solvents, it is preferable to use at least one selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms because of the solubility of the raw material monomers and the resulting copolymer. It is more preferable to use water as a solvent because the solvent removal step can be omitted.

  In the production of the copolymer, it is preferable to use a chain transfer agent in the polymerization reaction. By using a chain transfer agent, a copolymer exhibiting excellent performance as a dispersant can be effectively obtained. If a chain transfer agent is used in the polymerization reaction, the molecular weight of the resulting copolymer can be easily adjusted. In particular, it is effective to use a chain transfer agent when the polymerization reaction is performed at a high concentration of 30% by mass or more based on the total amount of raw materials used during polymerization.

  The chain transfer agent is not particularly limited as long as the molecular weight of the copolymer can be adjusted. Specifically, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3- Thiol compounds such as mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan, butylthioglycolate; carbon tetrachloride, methylene chloride Halides such as bromoform and bromotrichloroethane; secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogensulfite , Dithionite, meta Lower oxides and salts of sulfurous acid and its salts (sodium sulfite, potassium sulfite, sodium bisulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) Can be used.

  Furthermore, a monomer having a high chain transfer property can also be used as a chain transfer agent. Examples of such monomers include α, β-unsaturated dicarboxylic acid compounds such as maleic acid, fumaric acid, citraconic acid, and derivatives thereof, and salts thereof (more specifically, examples of derivatives include For example, half esters with alcohols having 1 to 30 carbon atoms; half amides with amines having 1 to 30 carbon atoms; half amides or half esters with amino alcohols having 1 to 30 carbon atoms; Half-esters with compound (x) to which 1 to 300 moles of alkylene oxide of 2 to 18 on average is added; Half-amides with compound aminated at one terminal hydroxyl group of compound (x); Half esters of -18 glycols or polyalkylene glycols with an average addition mole number of these glycols of 2 to 300; charcoal Examples thereof include, for example, monovalent metal salts, divalent glycols having a prime number of 2 to 18 or half amides of polyalkylene glycol having an average addition mole number of 2 to 300 of these glycols and maleamic acid. Metal salts, ammonium salts, organic amine salts, etc.); allyl compounds such as allyl alcohol and allyl sulfonic acid (salt), and addition of alkylene oxides having an average addition mole number of 2 to 300 and 2 to 18 carbon atoms Methallyl compounds such as methallyl alcohol and methallyl sulfonic acid (salt), and alkylene oxide adducts having an average addition mole number of 2 to 300 and 2 to 18 carbon atoms.

  In addition, said chain transfer agent may be used individually or may use 2 or more types together.

  It is preferable that the chain transfer agent is always present in the reaction system during the polymerization reaction. In particular, when a thiol chain transfer agent or a lower oxide and a salt thereof are used as the chain transfer agent, the chain transfer agent is continuously added by dropping or the like without adding the chain transfer agent all at once, It is effective to add over time. If the concentration of the chain transfer agent relative to the monomer is extremely different between the initial and second half of the reaction, and the chain transfer agent is insufficient in the second half of the reaction, the molecular weight of the copolymer becomes extremely large, and the performance as a dispersant is increased. descend.

  When supplying the chain transfer agent into the reaction system, it is preferable to supply the chain transfer agent in a line different from the acidic raw material such as the monomer (b) or peroxide. When using lower oxides and salts thereof, it is effective to supply them on a line different from the acidic raw material. For example, when a thiol chain transfer agent is supplied in the same line as the monomer (b), the chain transfer agent acts on the monomer (b) as a reaction initiator to cause partial polymerization, resulting in a homopolymer. Is likely to occur, and the performance as a dispersant is reduced. In addition, when the lower oxide and its salt are supplied in the same line as the peroxide, the lower oxide and its salt react with the peroxide, and the activity is lost before the peroxide acts as a reaction initiator. It will end up.

  As the polymerization initiator, a normal radical polymerization initiator can be used. Examples of radical polymerization initiators used in aqueous solution polymerization include peroxides such as persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; and the like as azo initiators. Azoamidine compounds such as 2,2′-azobis-2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, 2-carbamoyl Azoisobutyronitrile; and the like are used.

  In addition, as a radical polymerization initiator in the case of performing solution polymerization or bulk polymerization using lower alcohols, aromatic or aliphatic hydrocarbons, esters, ketones or the like as solvents, for example, peroxides, benzoyl peroxide , Lauroyl peroxide, sodium peroxide, t-butyl hydroperoxide, cumene hydroperoxide and the like are used, and azobisisobutyronitrile and the like are used as the azo initiator. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above radical polymerization initiators. The bulk polymerization is performed within a temperature range of 50 to 200 ° C.

  In the polymerization reaction, it is preferable to start the polymerization with a redox polymerization initiator in which the peroxide and the reducing agent are used in combination.

The reducing agent is not particularly limited as long as it is a general reducing agent. For example, iron (II), tin (II), titanium (III), chromium, and the like represented by mole salts. (II), salts of metals in a low valence state such as V (II), Cu (II); amine compounds such as monoethanolamine, diethanolamine, triethanolamine, hydroxylamine, hydroxylamine hydrochloride, hydrazine and the like include groups such as - sodium dithionite, sodium formaldehyde sulfoxylate, in addition, such as sodium hydroxy methane sulfinate _{dihydrate, -SH, -SO 2 H, -NHNH} 2, -COCH (OH); salt Organic compounds and salts thereof; alkalis such as sodium sulfite, sodium bisulfite, metabisulfite Metal sulfites, lower oxides and salts thereof such as hypophosphorous acid, sodium hypophosphite, sodium hydrosulfite, sodium hyponitrite; invert sugars such as D-fructose and D-glucose; thiourea, thiourea dioxide, etc. Thiourea compounds; L-ascorbic acid (salt), L-ascorbic acid ester, erythorbic acid (salt), erythorbic acid ester; and the like.

  Specific examples of the combination of the peroxide and the reducing agent include, for example, a combination of benzoyl peroxide and an amine, and a combination of cumene hydroperoxide and a metal compound such as iron (II) or Cu (II). . In particular, a combination of a water-soluble peroxide and a reducing agent is preferable. For example, a combination of hydrogen peroxide and L-ascorbic acid, a combination of hydrogen peroxide and erythorbic acid, and a combination of hydrogen peroxide and molle salt. A combination of sodium persulfate and sodium bisulfite is particularly preferred. A particularly preferred combination is a combination of hydrogen peroxide and L-ascorbic acid.

  The amount of peroxide used is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 0.5 mol% or more, based on the total amount of monomer components. Further, it is preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less, and further preferably 5 mol% or less. If the amount of peroxide used is less than 0.01 mol%, the amount of unreacted monomer may increase. On the other hand, when the amount of peroxide used exceeds 30 mol%, a polycarboxylic acid having a large number of oligomer parts may be obtained.

  The amount of the reducing agent used is preferably 0.1 mol% or more, more preferably 1 mol% or more, still more preferably 5 mol% or more, still more preferably 10 mol% or more, more preferably with respect to the peroxide. It is 25 mol% or more, more preferably 50 mol% or more, preferably 500 mol% or less, more preferably 300 mol% or less, still more preferably 200 mol% or less, still more preferably 100 mol% or less. When the amount of the reducing agent used is less than 0.1 mol%, active radicals are not sufficiently generated, and the amount of unreacted monomers may increase. On the other hand, when the amount of the reducing agent used exceeds 500 mol%, the reducing agent remaining without reacting with hydrogen peroxide may increase.

  In the polymerization reaction, it is preferable that at least one of the peroxide and the reducing agent is always present in the reaction system. Specifically, the peroxide and the reducing agent need not be added all at once. For example, they may be added over a long period of time, for example, by dropping them continuously or by adding them separately. When the peroxide and reducing agent are simultaneously added at once, the peroxide and reducing agent react rapidly, and immediately after the addition, reaction control becomes difficult due to a large amount of reaction heat. Since the radical concentration rapidly decreases, a large amount of unreacted monomer remains. Furthermore, since the radical concentration with respect to the monomer is extremely different between the initial stage and the latter half of the reaction, the molecular weight distribution becomes extremely large and the performance as a dispersant is lowered. In addition, it is preferable that the time from the introduction of one to the start of the other is within 5 hours, more preferably within 3 hours, and particularly preferably within 1 hour.

  In the polymerization reaction, in order to obtain high reactivity of the monomer, the half-life of the radical polymerization initiator is preferably 0.5 to 500 hours, more preferably 1 to 300 hours, still more preferably 3 to 150. For example, when persulfate is used as an initiator, the temperature of the polymerization reaction is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and still more preferably 45. ℃ or higher, more preferably 50 ℃ or higher, preferably 120 ℃ or lower, more preferably 100 ℃ or lower, more preferably 95 ℃ or lower, more preferably 90 ℃ or lower, more preferably 85 ℃ or lower, and further preferably. Is 80 ° C. or lower. Moreover, when hydrogen peroxide and L-ascorbic acid (salt) are used as an initiator, the temperature of the polymerization reaction is preferably 30 ° C or higher, more preferably 40 ° C or higher, more preferably 45 ° C or higher, Preferably it is 50 degreeC or more, Preferably it is 100 degrees C or less, More preferably, it is 95 degrees C or less, More preferably, it is 90 degrees C or less, More preferably, it is 85 degrees C or less, More preferably, it is 80 degrees C or less. The time for the polymerization reaction is suitably in the range of 0.5 to 20 hours, preferably 0.5 to 15 hours, more preferably 1 to 10 hours, and even more preferably 2 to 8 hours. . If the time for the polymerization reaction is too long or too short from this range, it is not preferable because the polymerization rate is lowered and the productivity is lowered.

  The amount of all monomers used in the polymerization reaction is 20 to 95% by mass, preferably 30 to 93% by mass, more preferably 40 to 90% by mass, based on the total amount of raw materials. If the amount is too much or too little than this range, the polymerization rate and productivity are lowered, which is not preferable.

  The ratio of each monomer used when synthesizing the copolymer of the present invention is not particularly limited as long as the monomer (a) and the monomer (b) are essential. The range of monomer (a) / monomer (b) / monomer (c) = 1 to 99/1 to 99/0 to 70 (mass%) is appropriate. ) / Monomer (b) / monomer (c) = preferably within the range of 50 to 99/1 to 50/0 to 49 (mass%), monomer (a) / monomer (b) / Monomer (c) = more preferably within the range of 55 to 98/2 to 45/0 to 40 (mass%), monomer (a) / monomer (b) / monomer (c) = More preferably within the range of 60 to 97/3 to 40/0 to 30 (mass%). However, the total amount of the monomer (a), the monomer (b) and the monomer (c) is 100% by mass. The weight average molecular weight of the copolymer is preferably 5,000 or more, more preferably 10,000 or more, and still more preferably, in terms of polyethylene glycol by gel permeation chromatography (hereinafter sometimes referred to as “GPC”). 15,000 or more, more preferably 20,000 or more, preferably 300,000 or less, more preferably 200,000 or less, still more preferably 150,000 or less, still more preferably 100,000 or less, further preferably Is 80,000 or less, more preferably 70,000 or less. By selecting the weight ratio of these monomers and the range of the weight average molecular weight, a copolymer for a dispersant exhibiting higher dispersion performance can be obtained.

≪Dispersant≫
The dispersant of the present invention is characterized by containing a copolymer as described above. Since the dispersant of the present invention is excellent in dispersion performance, various powder dispersants such as cement admixtures, organic / inorganic pigment dispersants, scale inhibitors, detergent builders, used paper recycling deinking agents, chelates It is useful as a dispersant, a dispersant for various dyes, an agrochemical dispersant, a detergent for fine cotton, a dispersant for coal, and the like. Here, the cement admixture will be described in detail.

<Cement admixture>
The blending amount of the copolymer component in the cement admixture of the present invention may be appropriately adjusted according to the desired dispersion performance, and is not particularly limited. It is 50 mass% or more with respect to the total mass of an agent, Preferably it is 60 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more.

  If necessary, the cement admixture of the present invention may contain a polycarboxylic acid polymer in addition to the copolymer component. At that time, the blending amount is a ratio of copolymer component / polycarboxylic acid polymer (unit: mass%), preferably 90/10 to 10/90, more preferably 80/20 to 20/80, The ratio is preferably 70/30 to 30/70, particularly preferably 60/40 to 40/60.

  In addition, the cement admixture of the present invention includes an antifoaming agent (such as (poly) oxyethylene (poly) oxypropylene adduct or diethylene glycol heptyl ether) or a polyalkyleneimine (such as ethyleneimine or propyleneimine) as required A polyalkyleneimine alkylene oxide adduct such as can be blended.

  Specific examples of usable antifoaming agents include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxy Polyoxyalkylene alkyl ethers such as ethylene polyoxypropylene 2-ethylhexyl ether and oxyethyleneoxypropylene adducts of higher alcohols having 12 to 14 carbon atoms; polyoxy such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether Alkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as ru-1-butyn-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate Polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan trioleate; polyoxyalkylene alkyls such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenyl ether sulfate ( Aryl) ether sulfates; polyoxys such as polyoxyethylene stearyl phosphates Alkylene phosphates; polyoxypropylene polyoxyethylene laurylamine (propylene oxide 1-20 mol adduct, ethylene oxide 1-20 mol adduct, etc.), cured beef tallow amine (alkylene oxide 1 Polyoxyalkylene alkylamines such as 20 mol adduct, ethylene oxide 1-20 mol adduct, etc .; polyoxyalkylene amide; and the like. These antifoaming agents may be used alone or in combination of two or more. The antifoaming agent may be added before polymerization is started, during polymerization, or after polymerization. Further, the blending amount of the antifoaming agent is preferably 0.0001% by mass or more and 20% by mass or less, more preferably 0.001% by mass or more and 10% by mass or less with respect to the total mass of the copolymer component. is there. If the blending amount of the antifoaming agent is less than 0.0001% by mass, the defoaming effect may not be sufficiently exhibited. On the contrary, if the blending amount of the antifoaming agent exceeds 20% by mass, the effect of defoaming is substantially saturated, and the defoaming agent is used more than necessary, which increases the production cost. There is.

  The cement admixture of the present invention can be used in combination with a conventionally known cement admixture, and a plurality of conventionally known cement admixtures can also be used in combination. The conventionally known cement admixture used in combination is preferably a conventionally known polycarboxylic acid admixture and a sulfonic acid admixture having a sulfonic acid group in the molecule. When these conventionally known cement admixtures are used in combination, a cement admixture that exhibits stable dispersion performance regardless of the brand or lot number of the cement is obtained.

  The sulfonic acid-based admixture is an admixture that exhibits dispersibility to cement due to electrostatic repulsion mainly caused by sulfonic acid groups, and various conventionally known sulfonic acid-based admixtures can be used. A compound having an aromatic group therein is preferred. Specifically, for example, polyalkylaryl sulfonate system such as naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate; melamine formalin resin sulfone such as melamine sulfonic acid formaldehyde condensate Acid salts; aromatic aminosulfonates such as aminoarylsulfonic acid-phenol-formaldehyde condensates; lignin sulfonates such as lignin sulfonates and modified lignin sulfonates; various types such as polystyrene sulfonates Examples include sulfonic acid-based admixtures. For concrete with a high water / cement ratio, lignin sulfonate-based admixtures are preferably used, whereas for concrete with a moderate water / cement ratio where higher dispersion performance is required, Admixtures such as polyalkylaryl sulfonate, melamine formalin sulfonate, aromatic amino sulfonate, and polystyrene sulfonate are preferably used. In addition, the sulfonic acid type admixture having a sulfonic acid group in the molecule may be used alone or in combination of two or more.

  The cement admixture of the present invention can be used in combination with an oxycarboxylic acid compound in addition to the sulfonic acid admixture described above. By containing the oxycarboxylic acid-based compound, higher dispersion retention performance can be exhibited even in a high-temperature environment. As the oxycarboxylic acid-based compound, an oxycarboxylic acid having 4 to 10 carbon atoms or a salt thereof is preferable. Specifically, for example, gluconic acid, glucoheptonic acid, arabonic acid, malic acid, citric acid, and sodium thereof, Examples thereof include inorganic or organic salts such as potassium, calcium, magnesium, ammonium, triethanolamine and the like. These oxycarboxylic acid compounds may be used alone or in combination of two or more. Of these oxycarboxylic acid compounds, gluconic acid or a salt thereof is particularly suitable. In particular, in the case of poor blend concrete, a lignin sulfonate-based admixture is used as a sulfonic acid-based admixture having a sulfonic acid group in the molecule, and gluconic acid or a salt thereof is used as an oxycarboxylic acid-based compound. It is preferable.

  When the cement admixture of the present invention and the sulfonic acid admixture are used in combination, the blending ratio of the cement admixture of the present invention and the sulfonic acid admixture (that is, the cement admixture of the present invention / sulfonic acid in terms of solid content) System admixture (unit: mass%) is preferably 1 to 99/99 to 1, more preferably 5 to 95/95 to 5, still more preferably 10 to 90/90 to 10, particularly preferably 20 to 80 /. 80-20. When the cement admixture of the present invention and the oxycarboxylic acid compound are used in combination, the blending ratio of the cement admixture of the present invention and the oxycarboxylic acid compound (that is, the cement admixture of the present invention in terms of solid content / The oxycarboxylic acid compound (unit:% by mass) is preferably 1 to 99/99 to 1, more preferably 5 to 95/95 to 5, still more preferably 10 to 90/90 to 10, particularly preferably 20 to. 80 / 80-20. Further, when the three components of the cement admixture of the present invention, the sulfonic acid group admixture having a sulfonic acid group in the molecule, and the oxycarboxylic acid compound are used in combination, the cement admixture of the present invention has a sulfonic acid group in the molecule. Mixing ratio of sulfonic acid-based admixture and oxycarboxylic acid-based compound (that is, cement admixture of the present invention in terms of solid content / sulfonic acid-based admixture having sulfonic acid group in molecule / oxycarboxylic acid-based compound: unit Is preferably 1 to 98/1 to 98/1 to 98, more preferably 5 to 90/5 to 90/5 to 90, still more preferably 10 to 90/5 to 85/5 to 85, Most preferably, it is 20-80 / 10-70 / 10-70.

  Moreover, you may use the cement admixture of this invention together with a conventionally well-known cement additive (material) which is illustrated to following (1)-(11) as needed.

  (1) Water-soluble polymer substance: unsaturated carboxylic acid polymer such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), sodium salt of acrylic acid / maleic acid copolymer; methylcellulose Nonionic cellulose ethers such as ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxypropyl cellulose; alkylated or hydroxyalkylated derivatives of polysaccharides such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose A hydrophobic substituent in which some or all of the hydrogen atoms of the hydroxy group have a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure; A polysaccharide derivative substituted with an ionic hydrophilic substituent having an acid group or a salt thereof as a partial structure; yeast glucan, xanthan gum, β-1,3 glucans (both linear and branched chains may be used, For example, polysaccharides produced by microbial fermentation such as curdlan, paramylon, pachyman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; gelatin; A copolymer of acrylic acid having an amino group and a quaternary compound thereof;

  (2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.

  (3) Curing retarders other than oxycarboxylic acid compounds: monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugar, oligosaccharides such as disaccharide and trisaccharide, or dextrin Oligosaccharides or polysaccharides such as dextran, sugars such as molasses containing them; sugar alcohols such as sorbitol; magnesium fluorosilicate; phosphoric acid and its salts or boric acid esters; aminocarboxylic acid and its salts; Protein; Humic acid; Tannic acid; Phenol; Polyhydric alcohol such as glycerol; Aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephos Phosphate) and alkali metal salts thereof, phosphonic acids and derivatives thereof such as alkaline earth metal salts; and.

  (4) Early strengthening agents / accelerators: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate;

  (5) Antifoaming agents other than oxyalkylene-based: mineral oil-based antifoaming agents such as coconut oil and liquid paraffin; fat and oil-based antifoaming agents such as animal and vegetable oils, sesame oil, castor oil, and these alkylene oxide adducts; oleic acid, stearic acid Fatty acid type antifoaming agents such as these alkylene oxide adducts; Fatty acid ester type antifoaming agents such as glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, natural wax; octyl alcohol, hexadecyl Alcohol defoamers such as alcohol, acetylene alcohol and glycols; Amide defoamers such as acrylate polyamines; Phosphate ester defoamers such as tributyl phosphate and sodium octyl phosphate; Aluminum stearate, calcium oleate, etc. Metal soap base defoaming agents; dimethylsilicone oils, silicone pastes, silicone emulsions, organic modified polysiloxanes (polyorganosiloxanes such as dimethylpolysiloxane), silicone anti-foaming agent such as fluorosilicone oils; like.

  (6) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether , Polyoxyethylene alkyl (phenyl) ether sulfate or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate, and the like.

  (7) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and those having 6 to 30 carbon atoms in the molecule such as abiethyl alcohol Intramolecular such as alicyclic monohydric alcohol, monodecyl mercaptan having 6 to 30 carbon atoms in the molecule such as dodecyl mercaptan, etc. Intramolecular such as alkylphenol having 6 to 30 carbon atoms in the molecule such as nonylphenol, dodecylamine 10 mol or more of an alkylene oxide such as ethylene oxide and propylene oxide was added to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as an amine having 6 to 30 carbon atoms, lauric acid or stearic acid. Polyalkylene oxide derivatives; alkyl or alkoxy groups Alkyl diphenyl ether sulfonates, which may have as a group, two phenyl groups having a sulfone group ether-bonded; various anionic surfactants; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride Agents; various nonionic surfactants; various amphoteric surfactants;

(8) Waterproofing agent: fatty acid (salt), fatty acid ester, fats and oils, silicone, paraffin, asphalt, wax and the like.
(9) Rust preventive: nitrite, phosphate, zinc oxide and the like.
(10) Crack reducing agent: polyoxyalkyl ether and the like.
(11) Expansion material: Ettlingite, coal, etc.

  Other conventionally known cement additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, rust preventives, colorants, anti-corrosion agents. Examples include mold agents. These conventionally known cement additives (materials) may be used alone or in combination of two or more.

  In the cement composition, the following (1) to (4) may be mentioned as particularly preferred embodiments for components other than cement and water.

  (1) A combination comprising two components of the cement admixture of the present invention and an oxyalkylene antifoaming agent. Examples of the oxyalkylene antifoaming agent include polyoxyalkylenes, polyoxyalkylene alkyl ethers, polyoxyalkylene acetylene ethers, and polyoxyalkylene alkylamines. Of these oxyalkylene antifoaming agents, polyoxyalkylene alkylamines are particularly preferred. The amount of the oxyalkylene antifoaming agent is preferably 0.01% by mass or more and 20% by mass or less with respect to the total mass of the copolymer component contained in the cement admixture of the present invention.

  (2) A combination comprising two components of the cement admixture of the present invention and a material separation reducing agent as essential. Examples of the material separation reducing agent include various thickeners such as nonionic cellulose ethers, a hydrophobic substituent composed of a hydrocarbon chain having 4 to 30 carbon atoms as a partial structure, and an alkylene oxide having 2 to 18 carbon atoms. Examples thereof include compounds having a polyoxyalkylene chain added in an average addition mole number of 2 to 300. These material separation reducing agents may be used alone or in combination of two or more. The blending ratio (unit: mass%) of the cement admixture of the present invention and the material separation reducing agent is preferably 10/90 to 99.99 / 0.01, more preferably 50/50 to 99.9 / 0. .1. The cement composition of this combination is suitable as a high fluidity concrete, a self-filling concrete, and a self-leveling material.

  (3) A combination comprising two components of the cement admixture of the present invention and an accelerator. Examples of the accelerator include soluble calcium salts such as calcium chloride, calcium nitrite, and calcium nitrate; chlorides such as iron chloride and magnesium chloride; thiosulfate; formate salts such as formic acid and calcium formate; . These accelerators may be used alone or in combination of two or more. The blending ratio (unit: mass%) of the cement admixture of the present invention is preferably 10/90 to 99.9 / 0.1, more preferably 20/80 to 99/1.

  (4) A combination comprising three components of the cement admixture of the present invention, an oxyalkylene antifoaming agent and an AE agent. Examples of the oxyalkylene antifoaming agent include polyoxyalkylenes, polyoxyalkylene alkyl ethers, polyoxyalkylene acetylene ethers, polyoxyalkylene alkylamines and the like. These oxyalkylene antifoaming agents may be used alone or in combination of two or more. Of these oxyalkylene antifoaming agents, polyoxyalkylene alkylamines are particularly preferred. The amount of the oxyalkylene antifoaming agent is preferably 0.01% by mass or more and 20% by mass or less with respect to the total mass of the copolymer component contained in the cement admixture of the present invention. On the other hand, the blending amount of the AE agent is preferably 0.001% by mass or more and 2% by mass or less with respect to the mass of the cement.

  The cement admixture of the present invention may be used in the form of an aqueous solution, or may be dried after neutralization with a divalent metal hydroxide such as calcium or magnesium after the reaction to form a polyvalent metal salt. , Supported on inorganic powder such as silica-based fine powder and dried, or dried and solidified into a thin film on a support using a drum-type drying device, disk-type drying device or belt-type drying device, and then pulverized Alternatively, it may be used after being powdered by drying and solidifying with a spray dryer. Also, the powdered cement admixture of the present invention is blended in advance with a water-free cement composition such as cement powder or dry mortar, and used as a premix product for plastering, floor finishing, grout, etc. Alternatively, it may be blended when the cement composition is kneaded.

  The cement admixture of the present invention can be used for various hydraulic materials, that is, cement compositions such as cement and gypsum and other hydraulic materials. Specific examples of a hydraulic composition containing such a hydraulic material, water, and the cement admixture of the present invention, and further containing fine aggregate (such as sand) and coarse aggregate (such as crushed stone) as necessary. Examples thereof include cement paste, mortar, concrete, and plaster.

  Among the hydraulic compositions, a cement composition that uses cement as the hydraulic material is the most common, and the cement composition contains the cement admixture of the present invention, cement, and water as essential components. Such a cement composition is one of the preferred embodiments of the present invention.

  The cement used in the cement composition is not particularly limited, and specific examples include, for example, Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate resistance, and respective low alkalis). Shape), various mixed cements (blast furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement , Oil well cement, low exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace cement, high content belite cement), ultra-high strength cement, cement-based solidified material, eco-cement (city waste incineration ash, sewage sludge) Cement produced from one or more types of incinerated ash) And the like. Furthermore, fine powder such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder, or gypsum may be added to the cement composition. Aggregates include gravel, crushed stone, granulated slag, recycled aggregate, etc., as well as silica, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromia, magnesia Refractory aggregates such as can be used.

In the above cement composition, unit water per Part 1 m ^3, the cement usage and water / cement ratio (mass ratio), unit water is preferably 100 kg / ^{m 3} or more, 185 kg / ^{m 3} or less, more preferably 120kg / M ³ or more and 175 kg / m ³ or less, and the amount of cement used is preferably 200 kg / m ³ or more and 800 kg / m ³ or less, more preferably 250 kg / m ³ or more and 800 kg / m ³ or less, The cement ratio (mass ratio) is preferably 0.1 or more and 0.7 or less, more preferably 0.2 or more and 0.65 or less, and it can be used widely from poor blending to rich blending. The cement admixture of the present invention has a high water reduction rate region, that is, water / cement having a water / cement ratio (mass ratio) of 0.15 or more and 0.5 or less (preferably 0.15 or more and 0.4 or less). It can also be used in a low ratio region, and is effective for both high-strength concrete having a large unit cement amount and a small water / cement ratio and poorly blended concrete having a unit cement amount of 300 kg / m ³ or less.

  In the above cement composition, the blending amount of the cement admixture of the present invention is preferably 0 with respect to the mass of the cement in terms of solid content, for example, when used for mortar or concrete using hydraulic cement. 0.01% by mass or more and 10.0% by mass or less, more preferably 0.02% by mass or more and 5.0% by mass or less, further preferably 0.05% by mass or more and 3.0% by mass or less, particularly preferably. It is 0.1 mass% or more and 2.0 mass% or less. Such a blending amount brings various preferable effects such as a reduction in unit water amount, an increase in strength, and an improvement in durability. When the blending amount of the cement admixture of the present invention is less than 0.01% by mass, the dispersion performance may not be fully exhibited. Conversely, if the blending amount of the cement admixture of the present invention exceeds 10.0% by mass, the effect of improving dispersibility is substantially saturated, and the cement admixture of the present invention is used more than necessary. As a result, the manufacturing cost may increase.

  The cement composition has high dispersibility and dispersion retention performance even in a high water reduction rate region, and exhibits sufficient initial dispersibility and viscosity reduction even at low temperatures, and has excellent workability. To ready-mixed concrete, concrete for concrete secondary products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, etc. Is required to have high fluidity such as high-fluidity concrete (slump value of 25 cm or more, slump flow value of 50 cm or more and 70 cm or less), self-filling concrete, self-leveling material, etc. Mortar or concrete It is also effective.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. It is also possible to implement, and they are all included in the technical scope of the present invention. In the following production examples, unless otherwise specified, “%” means mass%, excluding the yield.

First, a method for measuring a reaction solution at the time of producing an unsaturated monomer and a ¹ H-NMR spectrum of the obtained unsaturated monomer will be described.

<Measurement of ¹ H-NMR spectrum>
^{The 1} H-NMR spectrum was measured at a temperature of 25 ° C. with respect to a solution obtained by dissolving the sample in the solvent CDCl ₃ using a Varian 400 MHz-NMR measuring apparatus.

  Next, production examples of unsaturated monomers will be described.

≪Production Example 1≫
In this production example, from diethanolamine and methallyl chloride, the following formula (10):

で示されるＮ，Ｎ−ビス（２−ヒドロキシエチル）メタリルアミンを合成した。

N, N-bis (2-hydroxyethyl) methallylamine represented by the following formula was synthesized.

210.2 g (2.0 mol) of diethanolamine, 452.75 g (5.0 mol) of methallyl chloride and 212 g (2.0 mol) of sodium carbonate were mixed in 300 g of tetrahydrofuran and stirred. The tetrahydrofuran was refluxed by heating on an oil bath at 70 ° C. with stirring. After reacting for 7 hours under reflux, heating of the reaction solution was stopped and the mixture was allowed to cool to room temperature. The precipitated sodium chloride and the remaining sodium carbonate were removed by filtration, and then the filtrate obtained was distilled under reduced pressure to distill off the remaining methallyl chloride and tetrahydrofuran, whereby the target products N, N 318 g of bis (2-hydroxyethyl) methallylamine was obtained. The end point of the reaction was confirmed by a peak derived from diethanolamine in the ¹ H-NMR spectrum of the reaction solution. The yield was 100%.

The ¹ H-NMR spectrum of the obtained N, N-bis (2-hydroxyethyl) methallylamine is shown in FIG.

≪Production Example 2≫
In this production example, by adding an oxyethylene group with an average addition mole number of 10 to the hydroxyl group of N, N-bis (2-hydroxyethyl) methallylamine represented by the above formula (10), the following formula (11):

で示されるメタリルアミン−ジポリエチレングリコール（オキシエチレン基の平均付加モル数１１）を合成した。

The methallylamine-dipolyethylene glycol represented by (average number of moles of oxyethylene group added 11) was synthesized.

A SUS autoclave reaction vessel equipped with a thermometer, stirrer, raw material introduction tube and nitrogen introduction tube was charged with 110 g of N, N-bis (2-hydroxyethyl) methallylamine synthesized in Production Example 1 and 0.36 g of sodium hydroxide. Then, nitrogen gas was introduced into the reaction vessel to sufficiently substitute the nitrogen. Next, while stirring, a pipe equipped with a glass trap was connected from the top of the reaction vessel, and the inside of the reaction vessel was depressurized to 3.99 × 10 ⁴ Pa (300 Torr) using a vacuum pump. Then, it heated up to 105 degreeC and spin-dry | dehydrated at the same temperature for 2 hours, cooling a glass trap with an ethanol-dry ice bath. Next, after introducing nitrogen gas into the reaction vessel and sufficiently purging with nitrogen, the temperature was raised to 150 ° C., and 609 g of ethylene oxide was added over 3 hours. Next, the mixture was further aged at the same temperature for 1 hour to obtain 719 g of methallylamine-dipolyethylene glycol (average added mole number of oxyethylene group 11) having a hydroxyl value of 108 mg · KOH / g.

≪Production Example 3≫
In this production example, by adding an oxyethylene group at an average addition mole number of 40 to the terminal hydroxyl group of methallylamine-dipolyethylene glycol (average addition mole number of oxyethylene group of 11) represented by the above formula (11), the following formula (12):

で示されるメタリルアミン−ジポリエチレングリコール（オキシエチレン基の平均付加モル数５１）を合成した。

A methallylamine-dipolyethylene glycol represented by the formula (average added mole number of oxyethylene group 51) was synthesized.

In a SUS autoclave reaction vessel equipped with a thermometer, a stirrer, a raw material introduction tube and a nitrogen introduction tube, 684 g of methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group added 11) synthesized in Production Example 2, sodium hydroxide 1 .16 g was charged, and nitrogen gas was introduced into the reaction vessel to sufficiently substitute nitrogen. Next, while stirring, a pipe equipped with a glass trap was connected from the top of the reaction vessel, and the inside of the reaction vessel was decompressed to 6.65 × 10 ³ Pa (50 Torr) using a vacuum pump. Then, it heated up to 105 degreeC and spin-dry | dehydrated at the same temperature for 1 hour, cooling a glass trap with an ethanol-dry ice bath. Next, nitrogen gas was introduced into the reaction vessel and sufficiently substituted with nitrogen, and then the temperature was raised to 150 ° C., and 2,316 g of ethylene oxide was added over 4 hours. Next, the mixture was further aged at the same temperature for 1 hour to obtain 3,000 g of methallylamine-dipolyethylene glycol having a hydroxyl value of 26.7 mg · KOH / g (average added mole number of oxyethylene group 51).

FIG. 2 shows the ¹ H-spectrum of the resulting methallylamine-dipolyethylene glycol (average added mole number of oxyethylene group 51).

  Next, the manufacture example of the copolymer obtained by superposing | polymerizing the monomer component containing the unsaturated polymer obtained by said manufacture example is demonstrated. In addition, the weight average molecular weight of the obtained copolymer was measured on condition of the following using gel permeation chromatography (GPC).

<GPC measurement conditions>
The GPC measurement conditions are as follows.
Column used: TSK guard column SWXL manufactured by Tosoh Corporation
TSKgel G4000SWXL,
TSKgel G3000SWXL,
Concatenated TSKgel G2000SWXL in this order Eluent: Dissolved 115.6 g of sodium acetate trihydrate in a solution of 6,001 g of acetonitrile and 10,999 g of water, and further adjusted to pH 6.0 with acetic acid used.
Sample: A copolymer aqueous solution dissolved in the above eluent so that the copolymer concentration is 0.5%. Sample injection amount: 100 μL
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Detector: Empower Software manufactured by Japan Waters
Standard material for preparing calibration curve: polyethylene glycol [peak top molecular weight (Mp) 272,500, 219,300, 107,000, 50,000, 24,000, 11,840, 6,450, 4,250, 1, 470]
Calibration curve: Prepared by a cubic equation based on the Mp value and elution time of the above polyethylene glycol.

Example 1
In this Example, copolymer 1 was obtained by polymerizing methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group 51) and acrylic acid using ammonium persulfate as a polymerization initiator.

  80% aqueous solution of methallylamine-dipolyethylene glycol (average added mole number of oxyethylene group 51) synthesized in Production Example 3 in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser. 255.89 g, acrylic acid 0.37 g, and ion-exchanged water 54.47 g were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. 48.76% acrylic acid aqueous solution 30.59 g for 3 hours, 3-mercaptopropionic acid 0.278 g and water 39.72 g mixed monomer aqueous solution 3.5 hours, 6.67% ammonium persulfate aqueous solution 18.67 g Was dropped into the reaction vessel over 3.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for an additional hour to complete the polymerization reaction, whereby a copolymer 1 was obtained. The weight average molecular weight of the obtained copolymer 1 was 52,000.

<< Example 2 >>
In this example, 2,2-azobis (2-methylpropionamide) dihydrochloride was used as a polymerization initiator to polymerize methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group added 51) and acrylic acid. Thus, a copolymer 2 was obtained.

  80% aqueous solution of methallylamine-dipolyethylene glycol (average added mole number of oxyethylene group 51) synthesized in Production Example 3 in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser. 255.89 g, acrylic acid 0.37 g, and ion-exchanged water 54.47 g were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. A monomer aqueous solution in which 28.01 g of 53.25% acrylic acid aqueous solution was mixed for 3 hours, 0.278 g of 3-mercaptopropionic acid and 39.72 g of water was mixed for 3.5 hours, 6.67% 2,2-azobis ( 21.26 g of 2-methylpropionamide) dihydrochloride aqueous solution was dropped into the reaction vessel over 3.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for an additional hour to complete the polymerization reaction, whereby a copolymer 2 was obtained. The weight average molecular weight of the obtained copolymer 2 was 49,000.

Example 3
In this example, sodium peroxodisulfate was used as a polymerization initiator to polymerize methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group added 11) and acrylic acid to obtain a copolymer 3.

  80% aqueous solution of methallylamine-dipolyethyleneglycol (average added mole number of oxyethylene group 11) synthesized in Production Example 2 in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser. 161.982 g, acrylic acid 0.293 g, and ion-exchanged water 83.596 g were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 80 ° C. under a nitrogen atmosphere. A monomer aqueous solution prepared by mixing 84.13 g of 68.62% acrylic acid aqueous solution for 3 hours, 1.054 g of 3-mercaptopropionic acid and 38.946 g of water for 3.5 hours, 4.73% sodium peroxodisulfate aqueous solution 30 0.000 g was dropped into the reaction vessel over 3.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for an additional hour to complete the polymerization reaction, whereby a copolymer 3 was obtained. The weight average molecular weight of the obtained copolymer 3 was 53,000.

Example 4
In this example, 2,2-azobis (2-methylpropionamide) dihydrochloride was used as a polymerization initiator to polymerize methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group added 51) and acrylic acid. Thus, a copolymer 4 was obtained.

  80% aqueous solution of methallylamine-dipolyethylene glycol (average added mole number of oxyethylene group 51) synthesized in Production Example 3 in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser. 255.89 g, 0.37 g of acrylic acid, 54.47 g of ion-exchanged water, and 0.9 g of hydrochloric acid were charged, and the reaction vessel was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. A monomer aqueous solution in which 28.01 g of 53.25% acrylic acid aqueous solution was mixed for 3 hours, 0.278 g of 3-mercaptopropionic acid and 39.72 g of water was mixed for 3.5 hours, 6.67% 2,2-azobis ( 21.26 g of 2-methylpropionamide) dihydrochloride aqueous solution was dropped into the reaction vessel over 3.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, whereby a copolymer 4 was obtained. The weight average molecular weight of the obtained copolymer 4 was 50,000.

Example 5
In this example, 2,2-azobis (2-methylpropionamide) dihydrochloride was used as a polymerization initiator to polymerize methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group added 51) and acrylic acid. Thus, a copolymer 5 was obtained.

  80% aqueous solution of methallylamine-dipolyethylene glycol (average added mole number of oxyethylene group 51) synthesized in Production Example 3 in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser. 255.89 g, 0.37 g of acrylic acid, 54.47 g of ion-exchanged water, and 1.8 g of hydrochloric acid were charged, and the reaction vessel was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. A monomer aqueous solution in which 28.01 g of 53.25% acrylic acid aqueous solution was mixed for 3 hours, 0.278 g of 3-mercaptopropionic acid and 39.72 g of water was mixed for 3.5 hours, 6.67% 2,2-azobis ( 21.26 g of 2-methylpropionamide) dihydrochloride aqueous solution was dropped into the reaction vessel over 3.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for an additional hour to complete the polymerization reaction, whereby a copolymer 5 was obtained. The weight average molecular weight of the obtained copolymer 5 was 50,000.

Example 6
In this example, 2,2-azobis (2-methylpropionamide) dihydrochloride is used as a polymerization initiator to polymerize methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group added 51) and methyl acrylate. Thus, a copolymer 6 was obtained.

  80% aqueous solution of methallylamine-dipolyethylene glycol (average added mole number of oxyethylene group 51) synthesized in Production Example 3 in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser. 206.595 g, methyl acrylate 0.356 g, and ion-exchanged water 98.681 g were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. A monomer aqueous solution in which 14.368 g of methyl acrylate was mixed for 3 hours, 0.224 g of 3-mercaptopropionic acid and 39.78 g of water was mixed for 3.5 hours, 2.51% 2,2-azobis (2-methylpropion Amide) 40.00 g of dihydrochloride aqueous solution was dropped into the reaction vessel over 3.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, whereby a copolymer 6 was obtained. The weight average molecular weight of the obtained copolymer 6 was 46,000.

Example 7
In this example, 2,2-azobis (2-methylpropionamide) dihydrochloride was used as a polymerization initiator to polymerize methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group added 51) and maleic acid. Thus, a copolymer 7 was obtained.

  80% aqueous solution of methallylamine-dipolyethylene glycol (average added mole number of oxyethylene group 51) synthesized in Production Example 3 in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser. 200.85 g, maleic acid 0.476 g, and ion-exchanged water 99.83 g were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. A monomer aqueous solution in which 18.852 g of maleic acid was mixed for 3 hours, 0.218 g of 3-mercaptopropionic acid and 39.78 g of water was mixed for 3.5 hours, 2.78% 2,2-azobis (2-methylpropionamide) ) 40.00 g of dihydrochloride aqueous solution was dropped into the reaction vessel over 3.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for an additional hour to complete the polymerization reaction, whereby a copolymer 7 was obtained. The weight average molecular weight of the obtained copolymer 7 was 46,500.

  Next, the performance evaluation of the cement admixture containing the copolymer obtained in the above example will be described. In addition, the comparative cement admixture was prepared as follows.

≪Preparation of comparative cement admixture≫
Add ethylene oxide to the hydroxyl group of 3-methyl-3-buten-1-ol (isoprenol) in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser (average of oxyethylene groups) 969 g of the added mole number 50), 1.75 g of acrylic acid, and 500 g of ion-exchanged water were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 58 ° C. under a nitrogen atmosphere. With the inside of the reaction vessel maintained at 58 ° C., 76.23 g of 2% aqueous hydrogen peroxide solution was added. An acrylic acid aqueous solution consisting of 129.25 g of acrylic acid and 123.69 g of ion-exchanged water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 195.65 g of ion-exchanged water. An aqueous solution in which 1.97 g of acid and 2.38 g of 3-mercaptopropionic acid were dissolved was added dropwise over 3.5 hours. Then, after maintaining the temperature at 58 ° C. for 1 hour, the polymerization reaction was terminated. Thereafter, the acidic reaction solution was neutralized to pH 6 using an aqueous sodium hydroxide solution at a temperature lower than the polymerization reaction temperature to obtain a comparative cement admixture comprising an aqueous copolymer solution having a weight average molecular weight of 59,000.

<Mortar test>
(Solid content measurement)
The copolymer used for the performance test was measured for non-volatile content by the following procedure, and the concentration was calculated using the non-volatile content as a cement admixture.

  About 0.5 g of an aqueous cement admixture solution was weighed into an aluminum cup, and about 1 g of ion-exchanged water was added to spread it uniformly. This was dried at 130 ° C. for 1 hour in a nitrogen atmosphere, and the nonvolatile content was measured from the mass difference before and after drying.

(Preparation of cement admixture)
A predetermined amount of the copolymer aqueous solution is weighed, and 10% by mass of the antifoaming agent MA404 (manufactured by Pozzolith Co., Ltd.) is added to the polymer, and ion-exchanged water is added to make 270 g, which is sufficiently homogeneously dissolved. It was. Copolymers 1, 2, 4 and 5 were used in the mortar test. The cement admixture containing copolymer 1 was cement admixture 1, and the cement admixture containing copolymer 2 was cement. The cement admixture containing the admixture 2 and the copolymer 4 is referred to as a cement admixture 4, and the cement admixture containing the copolymer 5 is referred to as a cement admixture 5.

(Contains mortar)
The mortar formulation was C / S / W = 900 / 1,350 / 270 (g). However,
C: Ordinary Portland cement (manufactured by Taiheiyo Cement)
S: ISO standard sand (made by Cement Association)
W: Cement admixture.

(Mortar experimental environment)
The experimental environment was a temperature of 20 ° C. ± 1 ° C. and a relative humidity of 60% ± 10%.

(Measurement of flow value)
900 g of the cement and 270 g of the cement admixture were kneaded at a low speed from 30 seconds using a Hobart mortar mixer (model No. N-50: manufactured by Hobart), and then 1,350 g of the ISO sand was added to the cement paste over 30 seconds. Next, after kneading at high speed for 30 seconds, the rotation was stopped and the mortar on the wall of the kettle was scraped off over 15 seconds. The mixture was further left for 75 seconds and then kneaded at high speed for 60 seconds to prepare a mortar.

  Half of the prepared mortar was packed into a flow cone (JIS standard) placed on a horizontal table and pierced 15 times using a stick. In addition, the mortar was filled to the full extent of the flow cone, and pierced 15 times with a stick. Thereafter, the flow cone filled with mortar was gently lifted vertically, the major axis (mm) and minor axis (mm) of the mortar spread on the table were measured, and the average value was taken as the mortar flow value.

(Measurement of mortar air volume)
About 200 mL of mortar was packed in a glass measuring cylinder having a capacity of 500 mL and pierced with a round bar having a diameter of 8 mm, and then the container was vibrated to remove coarse bubbles. Furthermore, after adding about 200 mL of mortar and extracting bubbles in the same manner, the volume and mass were measured, and the amount of air was calculated from the mass and the density of each material.

(Mortar test results)
Tables 1 and 2 show the results of mortar tests performed using the cement admixture containing the polymer of the present invention and the comparative cement admixture. Table 1 shows the results when the addition amount is constant, and Table 2 shows the results when the addition amount is adjusted so that the flow value becomes substantially constant.

  As is apparent from Table 1, the cement admixture containing the copolymers 1, 2, 4 and 5 of the present invention exhibits a higher flow value at the same addition amount than the comparative cement admixture. Further, as is apparent from Table 2, the cement admixture containing the copolymers 1, 2, 4 and 5 of the present invention has an additive amount for obtaining the same flow value as compared with the comparative cement admixture. It can be reduced by 4 to 6%.

  Thus, the unsaturated monomer of the present invention has an improved dispersion effect due to steric repulsion as compared with the conventional unsaturated monomer having a polyalkylene glycol chain, and contains the unsaturated monomer of the present invention. It can be seen that the copolymer obtained by polymerizing the monomer component is excellent in dispersion performance as, for example, a cement dispersant.

  The unsaturated monomer of the present invention improves the dispersion effect due to steric repulsion as compared with the conventional unsaturated monomer having a polyalkylene glycol chain without lowering the polymerization reactivity. Copolymers obtained by polymerizing monomer components containing saturated monomers are useful as dispersants for various powders, for example, cement admixtures and organic / inorganic pigment dispersants. Thus, the unsaturated monomer, copolymer and dispersant using the same according to the present invention greatly contribute to the civil engineering / architectural field and the paint field.

2 is a chart showing a ¹ H-NMR spectrum of N, N-bis (2-hydroxyethyl) methallylamine obtained in Production Example 1. FIG. 6 is a chart showing a ¹ H-NMR spectrum of methallylamine-dipolyethylene glycol (average number of moles of oxyethylene group added 51) obtained in Production Example 3.

Claims (7)

  An unsaturated monomer having an ethylenically unsaturated bond and an amino group, wherein one amino group is present per molecule, and two polyalkylene glycol chains are bonded to the nitrogen atom of the amino group. An unsaturated monomer characterized by Following formula (1):

[Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁴ represents an alkylene group having 1 to 20 carbon atoms, a carbonyl group, or Represents an aryl group having 6 to 20 carbon atoms, and A ¹ O and A ² O each independently represent one or more oxyalkylene groups having 2 or more carbon atoms, and in the case of 2 or more blocks Or m and n are the average number of added moles of the oxyalkylene group, and each independently represents an integer of 0 to 300, but (m + n) / 2 = 1 to 300 are satisfied, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms]
The unsaturated monomer of Claim 1 shown by these. Following formula (2):

[Wherein R ⁷ represents hydrogen or a methyl group, R ⁸ represents an alkylene group having 1 to 4 carbon atoms, and A ¹ O, A ² O, m, n, R ⁵ and R ⁶ represent the above formula (1 Is equivalent to
The unsaturated monomer of Claim 2 shown by these.   A copolymer obtained by polymerizing a monomer component containing the unsaturated monomer according to any one of claims 1 to 3. The monomer component is represented by the following formula (3):

^Wherein, R ^{9, R 10,} and ^{R 11} are, independently of one another, a hydrogen atom, a group (wherein, _{- (CH} 2) represented by a methyl group or a group represented by the formula ^{_{:-( CH 2) z COOM 2 z}} COOM ² represents —COOM ¹ or other — (CH ₂ ) _z COOM ² and may form a cyclic acid anhydride structure), z represents an integer of 0 to 2, M ¹ and M ² Independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium base, an organic amine base, or a hydrocarbon group having 1 to 20 carbon atoms]
The copolymer of Claim 4 containing the carboxyl group-containing unsaturated monomer shown by these.   A dispersing agent comprising the copolymer according to claim 4 or 5.   A cement admixture comprising the copolymer according to claim 4 or 5.

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