JP2011072851A - Scale inhibitor containing amino group-containing copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water treatment agent which has an excellent capacity of inhibiting scale of calcium phosphate. <P>SOLUTION: The water treatment agent contains an amino group-containing copolymer which has a structural unit (n) derived from one or more monomers (N) selected from amino group-containing monomers having an amino group substituted by one or more groups selected from 6-20C aryl, 4-20C alkyl, and 1-8C hydroxyalkyl, and a structural unit (b) derived from a carboxyl group-containing monomer (B) at a predetermined ratio as essential constitutional units. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a water treatment agent containing an amino group-containing copolymer. Specifically, the present invention relates to a scale inhibitor containing an amino group-containing copolymer.

In cooling water systems, boiler water systems, seawater desalination equipment, pulp dissolving kettles, black liquor concentration kettles, etc., deposits (scales) such as calcium carbonate, calcium phosphate, zinc hydroxide, magnesium silicate adhere to the inner wall. Various obstacles may occur during operation, such as reduced thermal efficiency and local corrosion.
In particular, when a pipe using iron is used in an aqueous system, it is necessary to use a large amount of a phosphoric acid compound, a zinc salt, or the like as a corrosion inhibitor. In that case, generation of a scale composed of calcium phosphate becomes a problem.
For example, in Patent Document 1, a copolymer produced by a method in which an amino group-containing monomer synthesized from iminodiacetic acid and allyl glycidyl ether is polymerized with acrylic acid or the like can be used as a water treatment agent. It is disclosed. However, the polymer disclosed in Patent Document 1 has room to improve the scale prevention performance (scale prevention ability) for calcium phosphate scales.

Special table 2008-523162

As described above, despite the fact that various polymers have been reported in the past, there is a demand for a polymer that exhibits a better calcium phosphate scale-inhibiting ability when used in water treatment applications. It is a fact.
Then, an object of this invention is to provide the water treatment agent containing the polymer with the favorable scale prevention ability of calcium phosphate when used for water treatment.

As a result of intensive studies on various polymers / copolymers in order to achieve the above-mentioned object, the present inventors have found that a constitutional unit derived from a predetermined amino group-containing monomer and a constitution of a carboxyl group-containing monomer It has been found that a copolymer (amino group-containing copolymer) having a unit introduced at a specific ratio has an excellent ability to prevent scale of calcium phosphate. Based on the above findings, the present invention has been completed.
That is, the present invention is a water treatment agent containing an amino group-containing copolymer,
Derived from one or more monomers (N) selected from amino group-containing monomers represented by the following formulas (N1), (N2), (N3), and (N4) of 1 to 75% by mass Structural unit (n) of
An amino group-containing copolymer having, as an essential constituent unit, a structural unit (b) derived from a carboxyl group-containing monomer (B) in an amount of 25% by mass to 99% by mass;
It is a water treatment agent containing.

In the general formula (N1), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, R ₂ and R ₃ represent a hydrogen atom, Represents an organic group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express.

In the general formula (N2), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ represent a hydrogen atom or Represents an organic group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express.

In the general formula (N3), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ , R ₃ and R ₄ represent Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of R ₂ , R ₃ and R ₄ is an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and 1 to 1 carbon atoms. Represents a hydroxyalkyl group of 8;

In the general formula (N4), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ , R ₃ and R ₄ represent Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of R ₂ , R ₃ and R ₄ is an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and 1 to 1 carbon atoms. Represents a hydroxyalkyl group of 8;

The water treatment agent of the present invention is characterized by containing a specific amino group-containing copolymer (or the polymer composition of the present invention) that exhibits excellent calcium phosphate scale-preventing ability. Therefore, it can be preferably used as a water treatment agent.

Hereinafter, the present invention will be described in detail.

[Water Treatment Agent of the Present Invention]
The water treatment agent of the present invention is characterized by containing a specific amino group-containing copolymer (hereinafter also referred to as the amino group-containing copolymer of the present invention). By including the amino group-containing copolymer of the present invention, the water treatment agent of the present invention exhibits excellent calcium phosphate scale prevention ability. That is, the water treatment agent of the present invention can be usefully used as a scale inhibitor (hereinafter also referred to as the scale inhibitor of the present invention).

(Composition of the water treatment agent of the present invention)
The water treatment agent of the present invention contains an amino group-containing copolymer. That is, the water treatment agent of the present invention may be composed of the amino group-containing copolymer alone or may contain the amino group-containing copolymer and other additives. Arbitrary appropriate additives can be employ | adopted as said other additive. For example, polycarboxylic acid polymers such as phosphorus compounds, polyacrylic acid and / or salts thereof, polymaleic acid and / or salts thereof, acrylic acid copolymers and styrene / maleic acid copolymers; other scales An inhibitor; a slime inhibitor; a chelating agent; an oxygen scavenger; One of the other additives may be used, or two or more may be used in combination. The water treatment agent of the present invention may contain water or another organic solvent.
The water treatment agent of the present invention can be used as a scale inhibitor (scale inhibitor of the present invention). That is, the scale inhibitor of the present invention may contain the above amino group-containing copolymer, and may contain other additives as optional components.

(Method of using the water treatment agent of the present invention)
The water treatment agent of the present invention can be used by adding any appropriate amount to water of water such as cooling water and boiler water. Preferably, the amino group-containing copolymer is added to water in an amount of 0.1 to 100 ppm, more preferably 1 to 50 ppm with respect to water.

  What is necessary is just to add the water treatment agent of this invention as it is, for example to water systems, such as a cooling water system, a boiler water system, a seawater desalination apparatus, a pulp digester, a black liquor concentration tank. Moreover, when adding the water treatment agent of this invention to an aqueous system, you may add a phosphoric acid type compound and / or a zinc salt together. By adding a phosphate compound and / or a zinc salt together, corrosion of iron piping that can be used as an aqueous flow path can be prevented. Examples of the phosphoric acid compound include polymerized phosphoric acid and / or a salt thereof, phosphoric acid and / or a salt thereof, phosphonic acid and / or a salt thereof, and the like. Examples of the zinc salt include zinc nitrate and zinc chloride. Only 1 type may be used for the phosphoric acid type compound and zinc salt which can be added, and 2 or more types may be used together.

(Amino group-containing copolymer)
Hereinafter, the amino group-containing copolymer (the amino group-containing copolymer of the present invention), which is an essential component of the water treatment agent of the present invention, will be described in detail.
<Amino group-containing monomer>
The amino group-containing copolymer of the present invention is one or more monomers selected from amino group-containing monomers represented by the following general formulas (N1), (N2), (N3), and (N4) ( It is essential to have the structural unit (n) derived from N) at a specific ratio.

In the general formula (N1), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ represent a hydrogen atom or Represents an organic group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express.

In the general formula (N2), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ represent a hydrogen atom or Represents an organic group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express.

In the general formula (N3), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ , R ₃ and R ₄ represent Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of R ₂ , R ₃ and R ₄ is an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and 1 to 1 carbon atoms. Represents 8 hydroxyalkyl groups

In the general formula (N4), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ , R ₃ and R ₄ represent Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of R ₂ , R ₃ and R ₄ is an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and 1 to 1 carbon atoms. In the above general formulas (N1) to (N4), the case where R ₁ is a single bond represents a structure in which H ₂ C═C (R ₀ ) —R ₁ —O— ₂ represents C═C (R ₀ ) —O—.

At least one of R ₂ and R ₃ in the general formulas (N1) and (N2), and at least one of R ₂ , R ₃ and R _{4 in} the general formulas (N3) and (N4) has 6 to 20 carbon atoms. An aryl group of 4 to 20 carbon atoms and a hydroxyalkyl group of 1 to 8 carbon atoms, where the aryl group having 6 to 20 carbon atoms is 6 to 20 carbon atoms as a whole, It may be substituted with other organic groups. The alkyl group having 4 to 20 carbon atoms may be substituted with another organic group as long as it has 4 to 20 carbon atoms as a whole, and may be linear, branched, cyclic, or the like. The hydroxyalkyl group having 1 to 8 carbon atoms may be substituted with other organic groups as long as it has 1 to 8 carbon atoms as a whole, and may be linear, branched, cyclic, etc. It may be a secondary alcohol, a secondary alcohol, or a tertiary alcohol.
In the general formulas (N1) and (N2), at least one of R ₂ and R ₃ , and at least one of R ₂ , R ₃ , and R _{4 in} the general formulas (N3) and (N4) has 6 to 20 carbon atoms. By being an aryl group, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms, the ability to prevent scale of calcium phosphate of the amino group-containing copolymer of the present invention is improved. Hereinafter, an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms may be referred to as a substituent A.

In the general formulas (N1) and (N2), it is more preferable that both R ₂ and R ₃ are substituents A because the scale-preventing ability of calcium phosphate tends to be improved. In addition, it is more preferable that two or more of R ₂ , R ₃ , and R _{4 in} the general formulas (N3) and (N4) are a substituent A because the scale-preventing ability of calcium phosphate tends to be improved, It is particularly preferred that all three are unsubstituted alkyl groups.

  If the substituent A in the general formulas (N1), (N2), (N3), and (N4) is a hydroxyalkyl group having 1 to 8 carbon atoms, in addition to the ability to prevent the scale of calcium phosphate, the scale of zinc hydroxide Although the prevention ability tends to be particularly improved, the hydroxyalkyl group preferably has 1 to 4 carbon atoms, and more preferably 2 to 3 carbon atoms.

As a hydroxyalkyl group having 1 to 8 carbon atoms, a hydroxymethyl group (—CH ₂ OH), a 1-hydroxyethyl group (—CH (OH) CH ₃ ), a 2-hydroxyethyl group (—CH ₂ CH ₂ OH), 3-hydroxypropyl group (—CH ₂ CH ₂ CH ₂ OH), 2-methyl-2-hydroxyethyl group (—CH ₂ CH (CH ₃ ) OH), 1-methyl-2-hydroxyethyl group (—CH ( _{CH 3) CH 2 OH))} , 4- hydroxybutyl group _{(-CH 2 CH 2 CH 2 CH} 2 OH), 1- ethyl-2-hydroxyethyl group _{(-CH (C 2 H 5)} CH 2 OH)) 1-hexyl-2-hydroxyethyl group (—CH (C ₆ H ₁₃ ) CH ₂ OH)) and the like.

  When the substituent A in the general formulas (N1), (N2), (N3), and (N4) is an aryl group having 6 to 20 carbon atoms and an alkyl group having 4 to 20 carbon atoms, the ability to prevent scale of calcium phosphate However, since the residual amount of the amino group-containing monomer after polymerization is reduced and the scale prevention ability is improved, the substituent A is an aryl group having 6 to 10 carbon atoms and a carbon number having 4 to 10 carbon atoms. An alkyl group is preferred.

  Specific examples of the aryl group having 6 to 10 carbon atoms and the alkyl group having 4 to 10 carbon atoms in the general formulas (N1), (N2), (N3), and (N4) include a tertiary butyl group and an isobutyl group. N-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, hexadecyl group, phenyl group, naphthyl group, methylphenyl group, benzyl group, A methoxyphenyl group etc. are illustrated.

At least one of R ₂ and R ₃ in the general formulas (N1) and (N2), and at least one of R ₂ , R ₃ and R _{4 in} the general formulas (N3) and (N4) has 6 to 20 carbon atoms. An aryl group, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms, but the other group is a hydrogen atom or an organic group having 1 to 20 carbon atoms. The organic group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, and is an alkyl group, aryl group, alkenyl group, alkoxy group, hydroxyl group, carboxyl group, sulfonic acid group, acyl group, ether. Groups, amide groups, ester groups, ketone groups, etc., as long as they have 1 to 20 carbon atoms as a whole, even if they are unsubstituted organic groups, they may be organic groups substituted with these organic groups. good. If the number of carbon atoms of other groups exceeds 20, it is not preferable because the residual amount of the amino group-containing monomer remaining after the production of the amino group-containing copolymer tends to increase. Since the scale prevention ability of the amino group-containing copolymer tends to be improved, the organic group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

  It is preferable that the monomer (N) does not contain an ester group or an amide group, since the amino group-containing copolymer of the present invention stably exhibits the ability to prevent scale even under alkaline conditions.

In the above general formulas (N1) and (N2), R ₂ and R ₃ may form a cyclic structure to form the substituent A together. In addition, two groups out of R ₂ , R ₃ , and R _{4 in} the general formulas (N3) and (N4) may form a cyclic structure to form the substituent A as a unit. In this case, in order to make the cyclic structure sufficiently stable, the number of carbon atoms of the substituent A in the cyclic structure is preferably 4-20. For example, in the above general formula (N1), the form in which R ₂ and R ₃ are formed into a cyclic structure and integrally form the substituent A is represented by the following general formula (N5).

In the general formula (N5), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₄ has 4 to 20 carbon atoms. Represents an alkylene group or an alkylene ether group; Specifically, a structure in which the cyclic structure formed by N and R ₄ is a piperidine ring or a morpholine ring is exemplified.

The structural unit (n) is a structural unit formed by radical polymerization of the monomer (N). In the above formulas (N1) to (N4), the unsaturated double bond (CH ₂ ═CH— ) Becomes a single bond (—CH ₂ —CH—).

  For example, when the monomer is the monomer (N1), the structural unit (n) derived from the monomer (N) is represented by the following general formula (n1).

In the general formula (n1), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ represent a hydrogen atom or Represents an organic group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express.

  The amino group-containing copolymer of the present invention is a structural unit derived from one or more monomers (N) selected from amino group-containing monomers represented by the general formulas (N1) to (N4) (n ) At a ratio of 1% by mass to 75% by mass with respect to 100% by mass of the structure derived from all monomers. In the present invention, a monomer refers to a compound having an unsaturated double bond (referring to a carbon-carbon double bond). When the structural unit (n) is within the above range, an effect of improving the scale prevention ability of zinc hydroxide in addition to the excellent scale prevention ability of the copolymer and calcium phosphate can be obtained. The ratio of the structural unit (n) to 100% by mass of the structure derived from all monomers is preferably 2% by mass to 70% by mass, more preferably 3% by mass to 60% by mass, and particularly preferably. It is 4 mass% or more and 50 mass% or less, More preferably, it is 5 mass% or more and 40 mass% or less.

  In addition, in this invention, when calculating the mass ratio (mass%) with respect to the structure derived from all the monomers of the structural unit (n) derived from the amino group-containing monomer (N), the primary to tertiary amine salts In the case of a quaternary amine salt, the counter anion is not included in the calculation. When the structural unit (n) derived from the amino group-containing monomer (N) and the structural unit (b) derived from the carboxyl group-containing monomer (B) are applicable, the mass relative to the structure derived from all monomers When calculating a ratio (mass%), it calculates as a structural unit (n) derived from an amino group containing monomer (N). The same calculation is performed when the mass ratio (mass%) of the amino group-containing monomer (N) in the total monomer composition is calculated.

  The amino group-containing monomer (N) is preferably produced by reacting an amino group-containing compound with a glycidyl ether compound selected from (meth) allyl glycidyl ether, vinyl glycidyl ether, and isoprenyl glycidyl ether. preferable. The amino group-containing monomer (N3) and amino group-containing monomer (N4) are quaternized after reacting an amino group-containing compound having a primary or secondary amino group with the glycidyl ether compound. Alternatively, it may be produced by directly reacting a tertiary amine salt (eg, tertiary amine hydrochloride) with the glycidyl ether compound.

<Carboxyl group-containing monomer>
The amino group-containing copolymer of the present invention is required to have the structural unit (b) derived from the carboxyl group-containing monomer (B) at a specific ratio.

  The carboxyl group-containing monomer (B) of the present invention is a monomer containing 1) an unsaturated double bond and 2) a carboxyl group and / or a salt thereof as essential components (provided that the monomer (N) The monomer to which it belongs is excluded from the monomer (B)). Specifically, unsaturated monocarboxylic acids and salts thereof such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and derivatives thereof; itaconic acid, fumaric acid, Examples thereof include unsaturated dicarboxylic acids such as maleic acid and 2-methylene glutaric acid, and salts thereof. In this case, the unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two carboxyl groups in the molecule, such as maleic acid, itaconic acid, citraconic acid, and fumaric acid. In addition, a monovalent metal salt, a divalent metal salt, an ammonium salt, an organic ammonium salt (organic amine salt), or the like thereof, or an anhydride thereof is preferable. The carboxyl group-containing monomer (B) is a half ester of an unsaturated dicarboxylic acid monomer and an alcohol having 1 to 22 carbon atoms, a half amide of an unsaturated dicarboxylic acid and an amine having 1 to 22 carbon atoms, A half ester of an unsaturated dicarboxylic acid monomer and a glycol having 2 to 4 carbon atoms, a half amide of maleamic acid and a glycol having 2 to 4 carbon atoms, or the like may be used.

  The salt of the unsaturated monocarboxylic acid or the salt of the unsaturated dicarboxylic acid is a metal salt, an ammonium salt or an organic amine salt. In this case, the metal salt is a monovalent metal salt of an alkali metal such as sodium salt, lithium salt, potassium salt, rubidium salt or cesium salt; alkaline earth such as magnesium salt, calcium salt, strontium salt or barium salt Metal salts; salts of aluminum, iron, etc. Organic amine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts and other alkanolamine salts; monoethylamine salts, diethylamine salts, triethylamine salts and other alkylamine salts; ethylenediamine salts, triethylenediamine salts and other polyamines And salts of organic amines such as Of these, ammonium salts, sodium salts, and potassium salts are preferable, and sodium salts are more preferable because the resulting copolymer has a high effect of improving the scale prevention ability.

  Among the carboxyl group-containing monomers (B), acrylic acid, acrylic acid salt, maleic acid, maleic acid salt is preferable because it has a high effect of improving the scale preventing ability of the copolymer, and acrylic acid, acrylic acid salt Is more preferable.

  The carboxyl group-containing monomer (B) may be only one type, but may have a structure derived from two or more types. In this case, the amino group-containing copolymer of the present invention has the sum of the structural units (b) derived from all kinds of carboxyl group-containing monomers (B) at a specific ratio.

The structural unit (b) is in a form in which the unsaturated double bond of the monomer (B) is a single bond (for example, when CH ₂ ═CH—, —CH ₂ —CH—).

  In the amino group-containing copolymer of the present invention, the structural unit (b) derived from the carboxyl group-containing monomer (B) is 25% by mass to 99% by mass with respect to 100% by mass of the structure derived from all monomers. It is essential to have a ratio of When the structural unit (b) is within the above range, an excellent effect of improving the scale preventing ability of the copolymer can be obtained. The ratio of the structural unit (b) to 100% by mass of the structure derived from all monomers is preferably 30% by mass to 98% by mass, more preferably 40% by mass to 97% by mass, and particularly preferably. They are 50 mass% or more and 96 mass% or less, More preferably, they are 60 mass% or more and 95 mass% or less.

  When the amino group-containing copolymer of the present invention is used as a scale inhibitor, it has a specific proportion of the structural unit (b), whereby the water solubility of the polymer is improved, and the scale-preventing ability of calcium phosphate and calcium carbonate is improved. Can be achieved.

In addition, in this invention, when calculating the mass ratio (mass%) with respect to the structure derived from all the monomers of the structural unit (b) derived from a carboxyl group-containing monomer (B), it calculates as a corresponding acid conversion. Shall. For example, if the structural unit is —CH ₂ —CH (COONa) — derived from sodium acrylate, the structural unit —CH ₂ —CH (COOH) — derived from acrylic acid, which is the corresponding acid, is represented by a mass ratio (mass% ). Similarly, also when calculating the mass ratio (mass%) with respect to all the monomers of a carboxyl group-containing monomer (B), it shall calculate as a corresponding acid conversion. For example, if it is sodium acrylate, a mass ratio (mass%) is calculated as acrylic acid which is a corresponding acid.

  Furthermore, when calculating the mass ratio (% by mass) of the structural unit derived from the acid group-containing monomer other than the carboxyl group-containing monomer (B) with respect to the structure derived from all monomers, the calculation is performed as the corresponding acid conversion. In the case of calculating the mass ratio (% by mass) of the acid group-containing monomer other than the carboxyl group-containing monomer (B) with respect to all the monomers, it is also calculated as the corresponding acid conversion.

<Other monomers>
The amino group-containing copolymer of the present invention may have a structural unit (e) derived from another monomer (E).
As the other monomer (E) when the amino group-containing copolymer of the present invention contains another monomer (E), it is copolymerizable with the monomer (N) or (B). If it is, it will not specifically limit, It selects suitably by a desired effect. Specifically, the above monomers such as vinyl pyridine, vinyl imidazole, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, aminoethyl methacrylate, diallylamine, diallyldimethylamine, and quaternized products and salts thereof. Amino group-containing monomers other than (N); sulfonic acid monomers such as 3-allyloxy-2-hydroxypropanesulfonic acid, (meth) allylsulfonic acid, isoprenesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, and the like; These salts; N-vinyl monomers such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyloxazolidone; (Meta) a Amide monomers such as rilamide, N, N-dimethylacrylamide, N-isopropylacrylamide; 3- (meth) allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane, 3-allyloxy- A compound in which 6 to 200 mol of ethylene oxide is added to 1,2-dihydroxypropane (3-allyloxy-1,2-di (poly) oxyethylene ether propane, etc.), allyl ether-based monomer such as (meth) allyl alcohol Isoprene-based monomers such as isoprenol; (meth) acrylic acid alkyl ester monomers such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate; hydroxyethyl (meth) Acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxy (Meth) acrylic acid hydroxyalkyl monomers such as methyl ethyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, methoxypolyalkylene glycol (meth) acrylate (Alkylene glycol addition mole number 1 to 300), phenoxy polyalkylene glycol (meth) acrylate (alkylene glycol addition mole number 1 to 300) and other polyalkylene Glycol chain-containing monomer, styrene, indene, vinyl aryl monomers such as vinyl aniline, isobutylene, vinyl acetate, and the like.
Moreover, the said other monomer (E) may be used individually by 1 type, or may be used with the form of a 2 or more types of mixture.

  When the polyalkylene glycol chain-containing monomer as the other monomer (E) is copolymerized, at least one monomer selected from monomers represented by the following general formulas (E1) and (E2) is used. Preferably, it is a monomer. Copolymerization of a polyalkylene glycol chain-containing monomer as the other monomer (E) is advantageous because gel resistance tends to be improved.

In General Formula (E1), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group, or a single bond, and Y ₁ represents an alkylene group having 2 to 20 carbon atoms. X represents a number of ₁ to 300, R ₁ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms,

In General Formula (E2), R ₀ represents a hydrogen atom or a CH ₃ group, R represents a CH ₂ group, a CH ₂ CH ₂ group, or a single bond, and Y ₁ represents an alkylene group having 2 to 20 carbon atoms. X represents a number of ₁ to 300, and R ₁ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.

In the general formula (E1), R is preferably a CH ₂ CH ₂ group, and in (2), R is preferably a CH ₂ group.

In General Formulas (E1) and (E2), Y ₁ represents an alkylene group having 2 to 20 carbon atoms as described above, but Y ₁ is from the viewpoint of the copolymerizability of the resulting amino group-containing copolymer. , Preferably it is a C2-C4 alkylene group, More preferably, it is a C2-C3 alkylene group, More preferably, it is a C2-C2 alkylene group. Y ₁ may be one type of alkylene group or two or more types of alkylene groups.
Specifically, Y ₁ is an ethylene group, an isopropyl group, a butylene group, an octylene group, a phenylethylene group, a diphenylethylene group, or the like. Y ₁ is preferably an ethylene group, an isopropyl group, or a butylene group, more preferably an ethylene group or an isopropyl group, and even more preferably an ethylene group because the precipitation suppression ability of the resulting amino group-containing copolymer is improved. It is a group.
The alkylene group having 2 to 20 carbon atoms may be an alkylene group substituted with an organic group as long as the carbon number is 2 to 20, and the substituent is large in the polymerizability of the ether bond-containing monomer. It can be used as long as it does not have an adverse effect, and examples thereof include an aryl group, an alkoxy group, a ketone group, a hydroxyl group, an amino group, an amide group, and a carboxyl group.
Y ₁ is preferably an alkylene group derived from alkylene oxide. Examples of the alkylene oxide include ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, butadiene monooxide, and styrene oxide.

  As described above, in general formulas (E1) and (E2), X represents a number from 1 to 300, but X is preferably from 10 to 150.

In the general formulas (E1) and (E2), as described above, R ₁ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, but R ₁ is preferably an organic group having 4 to 18 carbon atoms. Is preferable, and an organic group having 6 to 16 carbon atoms is more preferable. R ₁ may contain a functional group such as an amino group, an amide group, a hydroxyl group, an alkoxide group, a sulfonic acid group, a carbonyl group, or a carboxyl group. R ₁ may contain an ether bond, a sulfide bond, an ester bond, or an amide bond. The organic group is preferably an alkyl group, an aryl group, or an alkenyl group.

Preferable R ₁ is specifically an alkyl group of n-butyl group, isobutyl group, octyl group, lauryl group, stearyl group, cyclohexyl group, 2-ethylhexyl group; alkenyl group such as butylene group, octylene group, nonylene group; Examples thereof include aryl groups such as phenyl group, phenethyl group, 2,3- or 2,4-xylyl group, mesityl group, and naphthyl group.

  It is preferable that the monomer (E) does not contain an ester group or an amide group because the amino group-containing copolymer of the present invention stably exhibits the ability to prevent calcium phosphate from scale even under alkaline conditions.

The structural unit (e) derived from the other monomer (E) is in a form in which the unsaturated double bond is a single bond in the monomer (E), that is, the above formula (E1) or (E2). _(e.g., when the _{CH 2 = CH-, -CH 2 -CH-} ). .

The amino group-containing copolymer of the present invention is optional, but if desired, the structural unit (e) derived from the monomer (E) is 0% by mass with respect to 100% by mass of the structure derived from all monomers. % Or more and less than 50% by mass. In the present invention, a monomer refers to a compound having an unsaturated double bond (referring to a carbon-carbon double bond).
In the amino group-containing copolymer of the present invention, the structural units (n), (b), and if necessary, the structural unit (e) may be introduced at a specific ratio as described above. The structural unit may exist in either a block shape or a random shape. Moreover, the weight average molecular weight of the amino group-containing copolymer of the present invention can be appropriately set and is not particularly limited. Specifically, the weight average molecular weight of the amino group-containing copolymer is preferably 2,000 to 200,000, more preferably 3,000 to 100,000, and most preferably 4,000 to 50, 000. When the weight average molecular weight is within the above range, the scale preventing ability tends to be improved. In addition, in this specification, a weight average molecular weight is a measured value by GPC (gel permeation chromatography), and the specific measuring method is computed according to the method described in an Example.

[Amino group-containing copolymer composition of the present invention]
The amino group-containing copolymer composition of the present invention contains the amino group-containing copolymer of the present invention as an essential component, and may contain only the amino group-containing copolymer. Contains one or more selected from agent residues, residual monomers, by-products during polymerization, and moisture. A preferable form of the amino group-containing copolymer composition is a form containing 40 to 60% by mass of the amino group-containing copolymer and 40 to 60% by mass of water.
The amino group-containing copolymer composition of the present invention may be used as it is as a water treatment agent or a scale inhibitor.

[Method for producing amino group-containing copolymer]
The method for producing the amino group-containing copolymer (the amino group-containing copolymer of the present invention) is represented by the following formulas (N1), (N2), (N3), and (N4) of 1% by mass or more and less than 75% by mass. Polymerization is carried out in the presence of a polymerization initiator essentially comprising at least one monomer selected from the amino group-containing monomers represented, and a carboxyl group-containing monomer (B) of 25% by mass or more and less than 99% by mass. This is a method for producing an amino group-containing copolymer.

In the general formula (N1), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ represent a hydrogen atom or Represents an organic group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express.

In the general formula (N2), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ represent a hydrogen atom or Represents an alkyl group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an organic group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express.

In the general formula (N3), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ , R ₃ and R ₄ represent Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of R ₂ , R ₃ and R ₄ is an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and 1 to 1 carbon atoms. Represents a hydroxyalkyl group of 8;

In the general formula (N4), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ , R ₃ and R ₄ represent Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of R ₂ , R ₃ and R ₄ is an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and 1 to 1 carbon atoms. Represents a hydroxyalkyl group of 8;

  As a method for producing the amino group-containing copolymer of the present invention, a monomer component containing an amino group-containing monomer (N) and a carboxyl group-containing monomer (B) as essential components is copolymerized. Although it can manufacture, when copolymerizing a monomer component, you may further copolymerize the said other monomer (E) as needed.

In such a production method, the monomer component may be copolymerized using a polymerization initiator. In addition, the kind and usage-amount of the monomer contained in a monomer component are set suitably so that the structural unit which comprises an amino group containing copolymer may become as mentioned above. That is, the composition ratio of each monomer forming the amino group-containing copolymer is such that the amino group-containing monomer (N) is 1% by mass or more and 75% by mass or less with respect to all monomers, and the carboxyl group. Containing monomer (B) is 25 mass% or more and 99 mass% or less. As described above, when the other monomer (E) copolymerizable with these is further set to 100% by mass when the total of the monomers (N), (B), and (E) is 100% by mass, You may use it in the quantity of 50 mass%.
Preferably, the amino group-containing monomer (N) is 2% by mass or more and less than 70% by mass, the carboxyl group-containing monomer (B) is 30% by mass or more and 98% by mass or less, and more preferably the amino group-containing monomer The monomer (N) is 3% by mass or more and less than 60% by mass, the carboxyl group-containing monomer (B) is 40% by mass or more and 97% by mass or less, and particularly preferably the amino group-containing monomer (N). 4 mass% or more and less than 50 mass%, carboxyl group-containing monomer (B) is 50 mass% or more and 96 mass% or less, and particularly preferably amino group-containing monomer (N) is 5 mass% or more. Less than 40% by mass and the carboxyl group-containing monomer (B) is 60% by mass or more and 95% by mass or less. The total amount of the monomers (N), (B) and (E) is 100% by mass.


<Polymerization initiator>
As the initiator, known ones can be used, for example, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; dimethyl 2,2′-azobis (2-methylpro Pionate), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyric acid) dimethyl, 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-Methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, 2,2′-azobis [2- (2- Imidazoline- 2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 1,1′-azobis (cyclohexane-1-carbohydrate) Suitable are azo compounds such as nitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene hydroperoxide, and the like. Of these polymerization initiators, hydrogen peroxide and persulfate are preferable, and persulfate is most preferable. These polymerization initiators may be used alone or in the form of a mixture of two or more. For example, a combination of hydrogen peroxide and persulfate is a preferred form.

<Chain transfer agent>
In the method for producing an amino group-containing copolymer of the present invention, a chain transfer agent may be used as a molecular weight adjusting agent for the polymer as long as it does not adversely affect the polymerization. Specific examples of the chain transfer agent include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2- Thiol chain transfer agents such as mercaptoethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan, butylthioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; Secondary alcohol; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfite, and salts thereof ( Sodium bisulfite, potassium bisulfite , Sodium dithionite, potassium dithionite, sodium metabisulfite, metabisulfite potassium, etc.) and the like, and the like lower oxides and salts thereof. The chain transfer agent may be used alone or in the form of a mixture of two or more.
The use of a chain transfer agent has the advantage that the amino group-containing copolymer to be produced can be prevented from becoming unnecessarily high in molecular weight, and a low molecular weight amino group-containing copolymer can be produced efficiently. is there. Among these, in the copolymerization reaction according to the present invention, it is preferable to use sulfite or sulfite. Thereby, it becomes possible to introduce a sulfonic acid group quantitatively to the end of the main chain of the (meth) acrylic acid copolymer to be obtained, and to improve the gel resistance. Further, it is preferable to use sulfite or sulfite as a chain transfer agent because the oxidation of amine can be suppressed and the color tone of the resulting amino group-containing copolymer (composition) can be improved.
In the production method of the present invention, as described above, it is preferable to use sulfite and / or sulfite (hereinafter simply referred to as “sulfur (salt)”) as a chain transfer agent. In addition to sulfurous acid (salt), an initiator is used. Furthermore, heavy metal ions may be used in combination as a reaction accelerator.
The sulfurous acid (salt) refers to sulfurous acid or hydrogen sulfite or a salt thereof, and a form in which sulfurous acid / bisulfite is a salt is preferable. When sulfite / bisulfite is a salt, in addition to the examples described above, salts of metal atoms, ammonium or organic ammonium are preferred. Examples of the metal atom include monovalent metal atoms of alkali metals such as lithium, sodium and potassium; divalent metal atoms of alkaline earth metals such as calcium and magnesium; trivalent metal atoms such as aluminum and iron And the like are preferred. As the organic ammonium (organic amine), alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. Further, it may be ammonium. Therefore, examples of the sulfite preferably used in the present invention include sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite and the like, and sodium bisulfite is particularly suitable. The above sulfurous acid (salt) may be used alone or in the form of a mixture of two or more.

<Reaction accelerator>
In the method for producing an amino group-containing copolymer of the present invention, a reaction accelerator may be added for the purpose of reducing the amount of initiator used. Examples of the reaction accelerator include heavy metal ions. In the present invention, the heavy metal ion means a metal having a specific gravity of 4 g / cm ³ or more. As said metal ion, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable. The ionic valence of the heavy metal ions is not particularly limited. For example, when iron is used as the heavy metal, the iron ions in the initiator may be Fe ²⁺ or Fe ³⁺ , and these may be combined. May be.
The heavy metal ions are not particularly limited as long as they are included in the form of ions. However, it is preferable to use a method using a solution in which a heavy metal compound is dissolved because the handleability is excellent. The heavy metal compound used in that case should just contain the heavy metal ion desired to contain in an initiator, and can be determined according to the initiator to be used. When iron is used as the heavy metal ion, the mole salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal compound or the like. Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. In the case of using these heavy metal compounds, since they are water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability. The solvent of the solution obtained by dissolving the heavy metal compound is not limited to water, and does not hinder the polymerization reaction in the production of the hydrophobic group-containing copolymer of the present invention, and is a heavy metal compound. As long as it dissolves.

  The method for adding the heavy metal ions is not particularly limited, but it is preferably added before the completion of the dropwise addition of the monomer, and it is particularly preferable to initially charge the entire amount. Further, the amount used is preferably 100 ppm or less, more preferably 70 ppm or less, still more preferably 50 ppm or less, and particularly preferably 30 ppm or less with respect to the total amount of the reaction solution. If it exceeds 100 ppm, the effect of the addition is no longer seen, and the resulting copolymer is unfavorably colored and cannot be used depending on the application.

  The content of the heavy metal ions is preferably 0.1 to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. If the content of heavy metal ions is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited. On the other hand, when the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting copolymer may be deteriorated. Moreover, when there is much content of heavy metal ion, when using the copolymer which is a product as a scale inhibitor, there exists a possibility of becoming a cause of a scale.

  The time when the polymerization reaction is completed means the time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained. For example, when the polymer polymerized in the polymerization reaction solution is neutralized with an alkali component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range.

  In the method for producing an amino group-containing copolymer of the present invention, in the polymerization, a decomposition catalyst for the polymerization initiator or a reducing compound may be added to the reaction system in addition to the above-described compounds. Examples of the decomposition catalyst for the polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid and the like. Metal salts of inorganic acids; carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid and benzoic acid, their esters and metal salts; heterocyclic amines such as pyridine, indole, imidazole and carbazole and their derivatives It is done. These decomposition catalysts may be used alone or in combination of two or more.

Examples of the reducing compound include organometallic compounds such as ferrocene; iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, manganese naphthenate, and the like, such as iron, copper, nickel, cobalt, and manganese. Inorganic compounds capable of generating metal ions; boron trifluoride ether adducts, potassium permanganate, perchloric acid and other inorganic compounds; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxide, Sulfur-containing compounds such as benzenesulfinic acid and its substitutes, homologues of cyclic sulfinic acid such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid, α -Sodium thiopropionate sulfopropyl es Tercap, mercapto compounds such as α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethyl hydrazine, hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde Aldehydes such as L-ascorbic acid and the like. These reducing compounds may also be used alone or in combination of two or more. A reducing compound such as a mercapto compound may be added as a chain transfer agent.
The combination of the chain transfer agent, the initiator, and the reaction accelerator is not particularly limited, and can be appropriately selected from the above examples. For example, a combination of a chain transfer agent, an initiator, and a reaction accelerator includes sodium bisulfite (SBS) / hydrogen peroxide (H ₂ O ₂ ), sodium bisulfite (SBS) / sodium persulfate (NaPS), and bisulfite. Sodium (SBS) / Fe, Sodium bisulfite (SBS) / Hydrogen peroxide (H ₂ O ₂ ) / Fe, Sodium bisulfite (SBS) / Sodium persulfate (NaPS) / Fe, Sodium bisulfite (SBS) / Over Forms such as sodium sulfate (NaPS) / hydrogen peroxide (H ₂ O ₂ ) and sodium bisulfite (SBS) / oxygen / Fe are preferred. More preferably, sodium persulfate (NaPS) / hydrogen peroxide (H ₂ O ₂ ), sodium persulfate (NaPS) / hydrogen peroxide (H ₂ O ₂ ) / Fe, sodium bisulfite (SBS) / sodium persulfate (NaPS), sodium bisulfite (SBS) / sodium persulfate (NaPS) / Fe, most preferably sodium bisulfite (SBS) / sodium persulfate (NaPS) / Fe, sodium persulfate (NaPS) / peroxidation Hydrogen (H ₂ O ₂ ) / Fe.

<Amount of polymerization initiator used>
The amount of the initiator used is not particularly limited as long as it is an amount capable of initiating copolymerization of the monomers (N) and (B) and, if necessary, other monomers (E). ), (B) and if necessary, it is preferably 15 g or less, more preferably 1 to 12 g, relative to 1 mol of all monomer components comprising the other monomer (E).

  When hydrogen peroxide is used as an initiator, the amount of hydrogen peroxide added is preferably 1.0 to 10.0 g, and 2.0 to 8.0 g with respect to 1 mol of the monomer. Is more preferable. When the added amount of hydrogen peroxide is less than 2.0 g, the polymerization average molecular weight of the resulting copolymer tends to increase. On the other hand, when the added amount exceeds 10.0 g, the effect of hydrogen peroxide cannot be obtained as the added amount increases, and the remaining hydrogen peroxide amount increases.

  When persulfate is used as an initiator, the amount of persulfate added is preferably 1.0 to 5.0 g, and 2.0 to 4.0 g, based on 1 mol of the monomer. Is more preferable. If the amount of persulfate added is too small, the molecular weight of the resulting copolymer tends to increase. On the other hand, if the addition amount is too large, the effect of persulfate cannot be obtained as the addition amount increases, and further, the purity of the resulting copolymer is adversely affected.

  When hydrogen peroxide and persulfate are used together as an initiator, the addition ratio of hydrogen peroxide and persulfate is such that when the weight of hydrogen peroxide is 1 by weight, the weight of persulfate is 0.00. It is preferably 1 to 5.0, and more preferably 0.2 to 2.0. When the weight ratio of persulfate is less than 0.1, the weight average molecular weight of the resulting copolymer tends to be high. On the other hand, if the weight ratio of persulfate exceeds 5.0, the persulfate is wasted in the polymerization reaction system in a state where the effect of lowering the molecular weight due to the addition of persulfate cannot be obtained as much as the addition. It will be.

  As a method for adding hydrogen peroxide, the amount of dripping substantially continuously with respect to the total amount used is preferably 85% by weight or more of the required predetermined amount, particularly preferably 90% by weight or more. Most preferably, is dropped. Hydrogen peroxide is dripped continuously, but the dripping speed may be changed.

The dropwise addition of hydrogen peroxide is preferably started with a delay after the start of dropping of the monomer (excluding the monomer to be initially charged) under the conditions of the polymerization temperature and pH at the time of polymerization described later. Preferably, hydrogen peroxide is dropped after 1 minute or more has passed since the start of dropping of the carboxyl group-containing monomer, more preferably after 3 minutes or more, more preferably after 5 minutes or more, and most preferably after 10 minutes or more. Is to start. By delaying the dropping start time of hydrogen peroxide, it is possible to smooth the initial polymerization start and narrow the molecular weight distribution.
The time for delaying the hydrogen peroxide dropping start time is preferably within 60 minutes, more preferably within 30 minutes after the start of dropping of the monomer.
It is possible to start the dropping of hydrogen peroxide at the same time as the dropping of the monomer, and to charge hydrogen peroxide in advance before the dropping of the monomer. It is preferably 10% or less, more preferably 7% or less, still more preferably 5% or less, and particularly preferably 3% or less.
If hydrogen peroxide exceeding 10% of the required predetermined amount is added by the time when the dropping of the monomer is started, for example, in the case of using persulfate together, the ratio of the concentration of hydrogen peroxide to persulfate increases, and polymerization is performed. May stop. On the other hand, if it starts later than 60 minutes from the start of dropping of the monomer, the chain transfer reaction due to hydrogen peroxide does not occur, so the molecular weight at the initial stage of polymerization increases.

  The hydrogen peroxide dropping end time is preferably completed simultaneously with the monomer dropping end time under the conditions of the polymerization temperature and pH at the time of polymerization described later, and is 10 minutes or more earlier than the monomer dropping end time. It is more preferable to end, and it is particularly preferable to end 30 minutes or more early. In addition, even if it complete | finishes later than the dripping completion time of a monomer, it does not have a bad influence in a polymerization system especially. However, since the added hydrogen peroxide is not completely decomposed by the end of the polymerization, the effect as hydrogen peroxide is not obtained and is wasted, and a large amount of hydrogen peroxide may remain. This is not preferable because it may adversely affect the thermal stability of the obtained copolymer.

  In addition, the persulfate addition method is not particularly limited in view of its decomposability and the like, but the amount dripped substantially continuously with respect to the total use amount is 50% by weight or more of the required predetermined amount. It is particularly preferable that the content is 80% by weight or more, and it is most preferable to add the whole amount dropwise. The persulfate is dripped continuously, but the dripping speed may be changed.

  Although there is no particular limitation on the dropping time, in the case of an initiator that decomposes relatively quickly, such as persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate under the conditions of polymerization temperature and pH at the time of polymerization described later. It is preferable to drop until the monomer dropping end time, more preferably within 30 minutes after the monomer dropping ends, and particularly within 5 to 20 minutes after the monomer dropping. preferable. Thereby, the effect which can reduce the residual amount of the monomer in a copolymer remarkably can be found. It should be noted that, even if the addition of these initiators is completed before the completion of the monomer addition, it does not particularly adversely affect the polymerization, and is set according to the residual amount of monomer in the obtained copolymer. It is good.

  For these initiators that are relatively quick to decompose, the preferred range is described only for the dropping end time, but the dropping start time is not limited at all and may be set as appropriate. For example, in some cases, the dropping of the initiator may be started before the start of dropping of the monomer, or in the case of a combined system in particular, the dropping of one initiator is started and a certain time has elapsed. Then, or after completion, another initiator may be dropped. Any of these may be set as appropriate according to the decomposition rate of the initiator and the reactivity of the monomer.

The concentration of the radical polymerization initiator at the time of addition is not particularly limited, but is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. If the concentration of the initiator is less than 5% by weight, the monomer concentration during the polymerization will be very low as a result. The remaining amount of the body becomes very large. Further, the efficiency and productivity of transportation and the like are lowered, which is not preferable from the economical aspect. On the other hand, if it exceeds 60% by weight, there is a problem in terms of safety and ease of dripping.
In the method of the present invention, the addition amount of the chain transfer agent is not limited as long as the monomer (N), (B) and, if necessary, the other monomer (E) is polymerized satisfactorily, Preferably it is 1-20g with respect to 1 mol of all the monomer components which consist of monomer (N), (B), and another monomer (E) if necessary, More preferably, it is 2-15g is there. If the molecular weight is less than 1 g, the molecular weight may not be controlled. On the other hand, if it exceeds 20 g, a large amount of impurities may be generated and the pure polymer content may be reduced. Especially when sulfite is used. Excess sulfite may be decomposed in the reaction system, and sulfurous acid gas may be generated. Moreover, there is a risk that it may be economically disadvantageous.
As a combination of the initiator and the chain transfer agent, it is most preferable to use one or more persulfates and sulfites. In this case, the mixing ratio of persulfate and sulfite is not particularly limited, but it is preferable to use 0.5 to 5 parts by mass of sulfite with respect to 1 part by mass of persulfate. More preferably, with respect to 1 part by mass of persulfate, the lower limit of sulfite is 1 part by mass, and most preferably 2 parts by mass. Further, the upper limit of the sulfite is more preferably 4 parts by mass, and most preferably 3 parts by mass with respect to 1 part by mass of the persulfate. Here, if the amount of sulfite is less than 0.5 parts by mass, the total amount of the initiator may increase when the molecular weight is lowered. Conversely, if the amount exceeds 5 parts by mass, side reactions increase, resulting in impurities. May increase.
The total amount of the chain transfer agent, initiator, and reaction accelerator used is the total monomer component 1 consisting of the monomers (N) and (B) and, if necessary, other monomers (E). It is preferable that it is 2-20g with respect to a mole. By setting it as such a range, the amino group containing copolymer of this invention can be produced efficiently, and the molecular weight distribution of an amino group containing copolymer can be made into a desired thing. More preferably, it is 4-18g, More preferably, it is 6-15g.
As a method for adding the polymerization initiator and the chain transfer agent to the reaction vessel, a continuous charging method such as dropping or divided charging can be applied. In addition, a chain transfer agent may be introduced alone into the reaction vessel, and is previously confused with each monomer (N), (B), other monomer (E), solvent, etc. constituting the monomer component. You may keep it.

<Polymerization solvent>
In the present invention, the copolymerization of the monomers (N), (B) and, if necessary, other monomers (E) uses water in 50% by mass or more of the solvent used and / or chain It is preferably carried out in the presence of a transfer agent, more preferably 50% by mass or more of the solvent used and water in the presence of a chain transfer agent. At this time, by using water in 50% by mass or more of the solvent to be used, the amount of the organic solvent used for the polymerization can be suppressed, so that there is an advantage that the organic solvent can be easily distilled off after the polymerization is completed.

Therefore, the preferable form of the manufacturing method of this invention is 1 mass% or more and less than 75 mass% of amino group containing monomer (N) of Formula (1), 25 mass% or more of less than 99 mass% of Formula (2). Carboxyl group-containing monomer (B), if necessary, other monomer (E) (however, the total ratio of monomers (N), (B), and (E) is 100% by mass) The present invention relates to a method for producing an amino group-containing copolymer, comprising a step of carrying out a polymerization reaction using water in 50% by mass or more of a solvent to be used and using a chain transfer agent.
The solvent used in the above embodiment is not particularly limited as long as it contains water in a proportion of 50% by mass with respect to the total amount of the solvent used. From the viewpoint of improving the solubility of the monomer used for polymerization in a solvent, an organic solvent may be added as necessary. Even in this case, the content of water in the total mixed solvent is 50% by mass or more. Examples of organic solvents that can be used include lower alcohols such as methanol, ethanol, and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone, and diethyl ketone; ethers such as dimethyl ether and dioxane; and amides such as dimethylformaldehyde. . These solvents may be used alone or in the form of a mixture of two or more. In the present invention, the amount of water is preferably 80% by mass or more, and most preferably water alone (ie, 100% by mass) with respect to the total amount of solvent used. In the case of adding the organic solvent, from the viewpoint of the solubility of the monomer component and the resulting copolymer, one or more selected from the group consisting of water and a lower alcohol having 1 to 4 carbon atoms. It is preferable to use a solvent.
The amount of the solvent such as water used is preferably 40 to 200% by mass with respect to 100% by mass of the monomer component. More preferably, it is 45 mass% or more, More preferably, it is 50 mass% or more. Moreover, More preferably, it is 180 mass% or less, More preferably, it is 150 mass% or less. If the amount of the solvent used is less than 40% by mass, the resulting copolymer may have a high molecular weight. If it exceeds 200% by mass, the concentration of the obtained copolymer will be low, and solvent removal is required. There is a risk. The solvent may be partly or wholly charged in the reaction vessel in the initial stage of polymerization, but a part of the solvent may be added (dropped) into the reaction system during the polymerization reaction, or the monomer. Components, initiators, and the like may be added (dropped) into the reaction system during the polymerization reaction together with these components in a form in which the components and initiator are dissolved in advance.
In the above copolymerization method, monomer components, polymerization initiators, etc. can be added to the reaction vessel by charging all of the monomer components into the reaction vessel and adding the polymerization initiator into the reaction vessel. Method of performing polymerization: charging a part of the monomer component into the reaction vessel, and adding the polymerization initiator and the remaining monomer component continuously or stepwise (preferably continuously) into the reaction vessel. A method in which a polymerization solvent is charged into a reaction vessel and the whole amount of monomer components and a polymerization initiator is added; one of monomers (N), (B), and optionally (E) (For example, a part of the monomer (B)) is charged into a reaction vessel, the polymerization initiator and the remaining monomer components (the remainder of the monomer (B) and the monomer (N), and if necessary) Adding all of the monomers (E) into the reaction vessel (preferably continuously) The method for performing the copolymerization I are preferred. Among such methods, the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), and the dispersibility when used as a scale inhibitor can be improved. It is preferable to carry out the copolymerization by a method in which the monomer component is successively dropped into the reaction vessel.
The copolymerization method can be carried out by commonly used methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization, and is not particularly limited, but solution polymerization is preferred. As described above, the solvent that can be used in this case is preferably a mixed solvent in which 50% by mass of water or water is based on the total solvent. When only water is used, it is preferable in that the solvent removal step can be omitted.
The copolymerization method can be carried out either batchwise or continuously.
In the above copolymerization method, the copolymerization conditions such as the copolymerization temperature are appropriately determined depending on the copolymerization method used, the solvent, and the polymerization initiator, but the copolymerization temperature is usually preferably 0 ° C. or higher. Moreover, it is preferable that it is 150 degrees C or less. More preferably, it is 40 degreeC or more, More preferably, it is 60 degreeC or more, Most preferably, it is 80 degreeC or more. Moreover, More preferably, it is 120 degrees C or less, More preferably, it is 110 degrees C or less. In particular, when sulfurous acid (salt) is used, the copolymerization temperature is usually 60 ° C to 95 ° C, preferably 70 ° C to 95 ° C, and more preferably 80 ° C to 95 ° C. At this time, below 60 ° C,
There is a possibility that a large amount of impurities derived from sulfurous acid (salt) may be generated. On the contrary, when it exceeds 95 ° C., toxic sulfurous acid gas may be released.
The copolymerization temperature need not always be kept substantially constant in the polymerization reaction. For example, the polymerization is started from room temperature, the temperature is increased to a set temperature at an appropriate temperature increase time or rate, and then the set temperature is reached. Depending on the dropping method of the monomer component, the initiator, etc., the temperature may be changed over time (temperature increase or decrease) during the polymerization reaction.

<Polymerization time, polymerization pressure, polymerization pH>
The polymerization time is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and most preferably 90 to 300 minutes. In the present invention, “polymerization time” represents the time during which a monomer is added unless otherwise specified.
The pressure in the reaction system in the copolymerization method may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure, but in terms of the molecular weight of the resulting copolymer, The reaction system is preferably sealed and the reaction is carried out under pressure. Moreover, it is preferable to carry out under a normal pressure (atmospheric pressure) at the point of equipment, such as a pressurization apparatus, a pressure reduction apparatus, a pressure-resistant reaction container, and piping. The atmosphere in the reaction system may be an air atmosphere, but is preferably an inert atmosphere. For example, the inside of the system is preferably replaced with an inert gas such as nitrogen before the start of polymerization.
The pH during the polymerization in the copolymerization is preferably acidic. In particular, when persulfate and bisulfite are used in combination as the initiator, it is preferably carried out under acidic conditions. By carrying out under acidic conditions, the increase in the viscosity of the aqueous solution of the polymerization reaction system can be suppressed, and the copolymer can be produced satisfactorily. In addition, since the polymerization reaction can proceed under high concentration conditions, the production efficiency can be greatly increased, and the final solid content concentration can be high concentration polymerization of 40% or more, and the residual contained A monomer having a total monomer concentration of 30000 ppm or less can be obtained. Furthermore, the polymerizability of the amino group-containing monomer can be improved.
As said acidic condition, it is preferable that pH at 25 degreeC of the reaction solution in superposition | polymerization is 1-6. More preferably, it is 5 or less, More preferably, it is 3 or less. The copolymer obtained by the above copolymerization method can be used as it is as a main component of a scale inhibitor, but may be further neutralized with an alkaline substance if necessary. As the alkaline substance, it is preferable to use inorganic salts such as hydroxides, chlorides and carbonates of monovalent metals and divalent metals; ammonia; organic ammonium (organic amine) and the like.
The neutralization rate at the time of copolymerization can be appropriately changed depending on the initiator. For example, when persulfate and bisulfite are used in combination, the neutralization rate of the monomer is 0 to 0 with respect to the total amount of acid groups of the acid group-containing monomer such as a carboxyl group-containing monomer. It is preferable to carry out the copolymerization of the monomer components at 60 mol%. The neutralization rate of the monomer is represented by mol% of the monomer forming the salt when the total number of moles of the monomer is 100 mol%. If the neutralization rate of the monomer exceeds 60 mol%, the polymerization rate in the copolymerization step does not increase, and the molecular weight of the resulting copolymer may decrease, or the production efficiency may decrease. More preferably, it is 50 mol% or less, more preferably 40 mol% or less, particularly preferably 30 mol% or less, more particularly preferably 20 mol% or less, and most preferably 10 mol%. It is as follows.
When persulfate and hydrogen peroxide are used in combination, 99 mol% or less, preferably 50 to 95 mol% or less, based on the total amount of acid groups of the acid group-containing monomer such as a carboxyl group-containing monomer. It is. If the degree of neutralization is less than 50 mol%, hydrogen peroxide is not sufficiently decomposed and the weight average molecular weight tends to be high. Also, if it exceeds 99 mol%, strong alkaline and corrosive conditions are required, so that the production equipment may be corroded at high temperatures, and furthermore, hydrogen peroxide is decomposed by alkali, so that the addition amount may increase. There is also. The degree of neutralization after the completion of polymerization (that is, after the completion of monomer dropping) is determined by the total amount of the acid amount of the carboxyl group-containing monomer and amino group-containing monomer in order to promote the decomposition of the remaining hydrogen peroxide. On the other hand, it is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more.
Examples of a method for carrying out the copolymerization with the neutralization rate of the monomer being 0 to 60 mol% include, for example, when the monomer is an unsaturated carboxylic acid monomer, all of which are unsaturated acid carboxylic acid When neutralizing monomeric unsaturated carboxylic acid monomers into salt forms such as sodium salts and ammonium salts using alkaline substances A method in which a neutralization rate of 0 to 60 mol% is added to the copolymer is suitable.

[Other uses of copolymer and polymer composition]
As described above, the amino group-containing copolymer (or polymer composition) of the present invention can be usefully used as a water treatment agent and a scale inhibitor (scale inhibitor). The amino group-containing copolymer (or polymer composition) of the present invention can be usefully used as a fiber treatment agent, a dispersant, a thickener, various binders, an emulsifier, a skin care agent, a hair care agent and the like.

<Fiber treatment agent>
The amino group-containing copolymer (or polymer composition) of the present invention can be used as a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the amino group-containing copolymer (or polymer composition) of the present invention.

  The content of the amino group-containing copolymer of the present invention in the fiber treatment agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treatment agent. Further, any appropriate water-soluble polymer may be included as long as the performance and effects are not affected.

  Below, the compounding example of the fiber processing agent which is closer to embodiment is shown. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Examples of dyeing agents, peroxides and surfactants include those usually used for fiber treatment agents.

  The blending ratio of the amino group-containing copolymer of the present invention to at least one selected from the group consisting of a dye, a peroxide, and a surfactant is, for example, the whiteness of the fiber, uneven color, and dyeing tempering degree. For the improvement, at least one selected from the group consisting of a dye, a peroxide and a surfactant is used per 1 part by weight of the amino group-containing copolymer of the present invention in terms of a pure amount of the fiber treatment agent. It is preferable to use the composition mix | blended in the ratio of 0.1-100 weight part as a fiber processing agent.

  Arbitrary appropriate fiber can be employ | adopted as a fiber which can use the said fiber processing agent. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.

When the fiber treatment agent is applied to the refining process, it is preferable to blend the amino group-containing copolymer of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the amino group-containing copolymer of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for the alkaline bleaching agent.
<Inorganic pigment dispersant>
The amino group-containing copolymer (or polymer composition) of the present invention can be used as an inorganic pigment dispersant. In the inorganic pigment dispersant, condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol may be used as other compounding agents as required.

  The content of the amino group-containing copolymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.

  The inorganic pigment dispersant can exhibit good performance as a dispersant for heavy or light calcium carbonate or clay inorganic pigment used in paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, high concentration calcium carbonate having low viscosity and high fluidity and good aging stability of their performance. High concentration inorganic pigment slurries such as slurries can be produced.

  When the inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, and an effect commensurate with the addition amount can be obtained, which can be economically advantageous.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
Moreover, the weight average molecular weight and precipitation inhibitory ability of the polymer were measured in accordance with the following method.

<Method for quantifying monomer N>
Monomer N and the like were quantified by high-speed chromatography under the following conditions.
Measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 10 mmol / L Disodium hydrogen phosphate.12 hydrate aqueous solution (adjusted to pH 7 with phosphoric acid) / acetonitrile = 45/55 (volume ratio)
Flow rate: 1.0 ml / min
Detector: RI, UV (detection wavelength 215 nm).
<Method for quantifying monomer B>
The measurement of the content of the monomer B and the like was performed using liquid chromatography under the following conditions.
Apparatus: L-7000 series detector manufactured by Hitachi, Ltd .: UV detector L-7400 manufactured by Hitachi, Ltd.
Column: Shodex RSpak DE-413 manufactured by Showa Denko Co., Ltd.
Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Mobile phase: 0.1% aqueous phosphoric acid solution.
<Measurement conditions of weight average molecular weight>
Equipment: Hitachi L-7000 series detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 0.5 ml / min.
Calibration curve: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio)
<Analysis of monomers, etc.>
The progress of the reaction in the production of the amine monomer was confirmed by ¹ HNMR and liquid chromatography.
The polymerization was confirmed by quantifying the residual monomer by liquid chromatography.

<Scale inhibition rate of calcium phosphate>
Deionized water, boric acid-sodium borate pH buffer solution, aqueous calcium chloride solution, aqueous polymer solution obtained in Examples and Comparative Examples, and aqueous sodium phosphate solution were added in this order to a 225 ml screw cap bottle, pH = 8 .6, 100 ml of a test solution having a polymer concentration of 6 mg / L in terms of solid content, calcium hardness = 50 mg CaCO 3 / L, phosphate ion = 10 mg PO 43 − / L was prepared. After sealing, it was put in a 60 ° C. hot air dryer. After 40 hours, the test solution was filtered through a filter paper having a pore size of 0.1 μm, and the residual phosphate ion concentration in the filtrate was analyzed. A blank test solution obtained by removing the polymer from the above test solution was prepared as a blank, and the same operation was performed to analyze the residual phosphate ion concentration. The calcium phosphate scale inhibition rate was determined by the following formula.
Calcium phosphate scale inhibition rate = 100 × (R−Q) / (P−Q)
P: Charged phosphate ion concentration (mg / L)
Q: Blank residual phosphate ion concentration (mg / L)
R: Residual phosphate ion concentration (mg / L).

<Synthesis Example 1>
Into a 1-liter glass four-necked flask equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube was charged 315.4 g of diethanolamine, and the liquid temperature was adjusted to 50 ° C. while introducing nitrogen and stirring. . Next, with stirring, 349.3 g of allyl glycidyl ether (hereinafter abbreviated as AGE) was slowly added dropwise over 2 hours. The liquid temperature was maintained at 50 to 60 ° C. After completion of the dropwise addition, the mixture was further aged for 2 hours at a liquid temperature of 60 ° C., and the monomer A (that is, the glycidyl group of AGE added with diethanolamine as the amino group-containing monomer (N) of the present invention). (Mer). Formation of monomer A was confirmed by high performance liquid chromatography and ¹ H-NMR.

<Synthesis Example 2>
A 2 liter glass four-necked flask equipped with a reflux condenser, a stirrer, and a nitrogen inlet tube was charged with 491.0 g of pure water and 258.0 g of di-n-butylamine, introduced with nitrogen, and stirred. The liquid temperature was adjusted to 50 ° C. Next, 232.8 g of AGE was slowly added dropwise over 2 hours while stirring. The liquid temperature was maintained at 50 to 60 ° C. After completion of dropping, the mixture was further aged for 2 hours at a liquid temperature of 60 ° C. After cooling to room temperature, it was transferred to a separatory funnel and allowed to stand to separate into two layers, so the lower aqueous layer was discarded. Further, pure water was added to the upper layer for washing. This was transferred to an eggplant flask, and the water was completely removed with a rotary evaporator, whereby the monomer B (that is, di-n-butylamine was added to the glycidyl group of AGE as the amino group-containing monomer (N) of the present invention). Monomer added) was obtained. Formation of monomer B was confirmed by high performance liquid chromatography and ¹ H-NMR.

<Synthesis Example 3>
Into a 1-liter glass four-necked flask equipped with a reflux condenser, a stirrer, and a nitrogen inlet tube, 234.0 g of Nn-butyl-N-ethanolamine was charged, and nitrogen was introduced and stirred. The liquid temperature was adjusted to 50 ° C. Next, 232.8 g of AGE was slowly added dropwise over 2 hours while stirring. The liquid temperature was maintained at 50 to 60 ° C. After completion of the dropwise addition, the mixture was further aged for 2 hours at a liquid temperature of 60 ° C., and the monomer C (that is, NN-butyl added to the glycidyl group of AGE) as the amino group-containing monomer (N) of the present invention. -N-ethanolamine added monomer). Formation of monomer C was confirmed by high performance liquid chromatography and ¹ H-NMR.

<Synthesis Example 4>
Into a 1-liter glass four-necked flask equipped with a reflux condenser, a stirrer, and a nitrogen inlet tube was charged with 266.0 g of di-2-propanolamine, and the liquid temperature was adjusted while introducing nitrogen and stirring. Adjusted to 50 ° C. Next, 232.8 g of AGE was slowly added dropwise over 2 hours while stirring. The liquid temperature was maintained at 50 to 60 ° C. After completion of the dropwise addition, the mixture was further aged for 2 hours at a liquid temperature of 60 ° C., and the monomer D (that is, glycidyl group of AGE and di-2-propanol) as the amino group-containing monomer (N) of the present invention. A monomer to which an amine was added was obtained. Formation of monomer D was confirmed by high performance liquid chromatography and ¹ H-NMR.

<Synthesis Example 5>
A 2-liter glass four-necked flask equipped with a reflux condenser, a stirrer, and a nitrogen inlet tube was charged with 435.0 g of pure water and 202.0 g of di-n-propylamine, introduced with nitrogen, and The liquid temperature was adjusted to 50 ° C. while stirring. Next, 232.8 g of AGE was slowly added dropwise over 2 hours while stirring. The liquid temperature was maintained at 50 to 60 ° C. After completion of the dropwise addition, the mixture was further aged at a liquid temperature of 60 ° C. for 2 hours. After cooling to room temperature, it was transferred to a separatory funnel and allowed to stand to separate into two layers, so the lower aqueous layer was discarded. Further, pure water was added to the upper layer for washing. This was transferred to an eggplant flask, and the water was completely removed with a rotary evaporator. As a result, the monomer E (that is, di-n-propyl was added to the glycidyl group of AGE as the amino group-containing monomer (N) of the present invention). A monomer to which an amine was added was obtained. Formation of monomer E was confirmed by high performance liquid chromatography and ¹ H-NMR.

<Synthesis Example 6>
Into a 1 liter glass four-necked flask equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube, 153.0 g of pure water and 261.4 g of morpholine were charged, while introducing nitrogen and stirring, The liquid temperature was adjusted to 50 ° C. Next, AGE 349.3 g was slowly added dropwise over 2 hours while stirring. The liquid temperature was maintained at 50 to 60 ° C. After completion of the dropwise addition, the mixture was further aged for 2 hours at a liquid temperature of 60 ° C., and as the amino group-containing monomer (N) of the present invention, monomer F (that is, morpholine added to the glycidyl group of AGE) (Mer). Formation of monomer F was confirmed by high performance liquid chromatography and ¹ H-NMR.

<Synthesis Example 7>
Into a 2-liter glass four-necked flask equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube, 403.0 g of pure water and 170.0 g of piperidine were charged, while introducing nitrogen and stirring, The liquid temperature was adjusted to 50 ° C. Next, 232.8 g of AGE was slowly added dropwise over 2 hours while stirring. The liquid temperature was maintained at 50 to 60 ° C. After completion of dropping, the mixture was further aged for 2 hours at a liquid temperature of 60 ° C. After cooling to room temperature, it was transferred to a separatory funnel and allowed to stand to separate into two layers, so the lower aqueous layer was discarded. Further, pure water was added to the upper layer for washing. This was transferred to an eggplant flask, and the water was completely removed by a rotary evaporator, whereby piperidine was added to the glycidyl group of monomer G (that is, AGE) as the amino group-containing monomer (N) of the present invention. Monomer). Formation of monomer E was confirmed by high performance liquid chromatography and ¹ H-NMR.

<Comparative Synthesis Example 1>
In a 2.5 liter separable flask equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube, 500.0 g of pure water, 399.3 g of iminodiacetic acid (IDA), and a 48% aqueous sodium hydroxide solution (hereinafter referred to as “a”). 480.0 NaOH.) 500.0 g was charged, and the liquid temperature was adjusted to 60 ° C. while stirring. Next, AGE342.4g was slowly dripped over 2 hours, stirring in the reaction system hold | maintained at 60 degreeC. After completion of the dropwise addition, the reaction solution was further aged at 55 ° C. for 1 hour, and a 50% aqueous solution of monomer H (that is, a monomer in which IDA was added to the glycidyl group of AGE) (hereinafter, 50% single amount). Abbreviated as body H.).

<Example 1>
A 1-liter glass separable flask equipped with a reflux condenser and a stirrer was charged with 136.0 g of pure water and heated to 90 ° C. while stirring.
Next, 175.0 g of an 80% aqueous acrylic acid solution (hereinafter abbreviated as 80% AA) and 75.0 g of an 80% aqueous monomer A solution are added to the polymerization reaction system maintained at 90 ° C. while stirring. % Sodium persulfate aqueous solution (hereinafter abbreviated as 15% NaPS) 44.4 g and 35% sodium hydrogen sulfite aqueous solution (hereinafter abbreviated as 35% SBS) 38.0 g were dropped from separate nozzles. . Each dropping time was 180 minutes for 80% AA, 160 minutes for 80% aqueous monomer A solution, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 113.4 g of a 48% aqueous sodium hydroxide solution (hereinafter abbreviated as 48% NaOH) was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. . In this way, an aqueous solution of the polymer (1) was obtained.

<Example 2>
79.5 g of pure water was charged into a 1-liter glass separable flask equipped with a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. while stirring.
Next, 80% AA 108.0 g, 80% monomer A aqueous solution 46.3 g, 15% NaPS 36.5 g and 35% SBS 11.7 g were added to the polymerization reaction system maintained at 90 ° C. while stirring. Each was dropped from separate nozzles. Each dropping time was 180 minutes for 80% AA, 160 minutes for 80% aqueous monomer A solution, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 70.0 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (2) was obtained.

<Example 3>
72.7 g of pure water was charged into a 1-liter glass separable flask equipped with a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. while stirring.
Next, 121.5 g of 80% AA, 30.4 g of 80% monomer A aqueous solution, 39.0 g of 15% NaPS, and 12.5 g of 35% SBS were added to the polymerization reaction system maintained at 90 ° C. while stirring. Each was dropped from separate nozzles. Each dropping time was 180 minutes for 80% AA, 160 minutes for 80% aqueous monomer A solution, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 78.8 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (3) was obtained.

<Example 4>
A 1-liter glass separable flask equipped with a reflux condenser and a stirrer was charged with 150.0 g of pure water and heated to 90 ° C. while stirring.
Next, in a polymerization reaction system maintained at 90 ° C., while stirring, 175.0 g of 80% AA, 60.0 g of monomer B, 43.8 g of 15% NaPS, and 43.8 g of 35% SBS were added to separate nozzles. Then, each was dropped. Each dropping time was 180 minutes for 80% AA, 120 minutes for monomer B, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 113.5 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (4) was obtained.

<Example 5>
76.4 g of pure water was charged into a 1-liter glass separable flask equipped with a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. while stirring.
Next, in a polymerization reaction system maintained at 90 ° C., 80% AA 118.8 g, monomer B 23.8 g, 15% NaPS 37.8 g, and 35% SBS 16.2 g were added to separate nozzles while stirring. Then, each was dropped. Each dropping time was 180 minutes for 80% AA, 120 minutes for monomer B, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 77.0 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (5) was obtained.

<Example 6>
79.5 g of pure water was charged into a 1-liter glass separable flask equipped with a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. while stirring.
Next, in a polymerization reaction system maintained at 90 ° C., 80% AA 108.0 g, 80% monomer C aqueous solution 46.3 g, 15% NaPS 36.3 g, and 35% SBS 11.7 g were stirred. Each was dropped from separate nozzles. Each dropping time was 180 minutes for 80% AA, 150 minutes for 80% monomer C aqueous solution, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 70.0 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (6) was obtained.

<Example 7>
79.5 g of pure water was charged into a 1-liter glass separable flask equipped with a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. while stirring.
Next, in a polymerization reaction system maintained at 90 ° C., 80% AA 108.0 g, 80% monomer D aqueous solution 46.3 g, 15% NaPS 36.0 g, and 35% SBS 11.6 g were stirred. Each was dropped from separate nozzles. Each dropping time was 180 minutes for 80% AA, 150 minutes for 80% aqueous monomer D solution, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 70.0 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (7) was obtained.

<Example 8>
A 1-liter glass separable flask equipped with a reflux condenser and a stirrer was charged with 88.8 g of pure water and heated to 90 ° C. while stirring.
Next, in a polymerization reaction system maintained at 90 ° C., 108.0 g of 80% AA, 37.0 g of monomer E, 37.5 g of 15% NaPS, and 12.1 g of 35% SBS were added to separate nozzles while stirring. Then, each was dropped. Each dropping time was 180 minutes for 80% AA, 120 minutes for monomer E, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 70.0 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (8) was obtained.

<Example 9>
79.5 g of pure water was charged into a 1-liter glass separable flask equipped with a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. while stirring.
Next, in a polymerization reaction system maintained at 90 ° C., 80% AA 108.0 g, 80% monomer F aqueous solution 46.3 g, 15% NaPS 36.9 g, and 35% SBS 11.9 g were stirred. Each was dropped from separate nozzles. Each dropping time was 180 minutes for 80% AA, 160 minutes for 80% monomer F aqueous solution, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 70.0 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (9) was obtained.

<Example 10>
72.2 g of pure water was charged into a 1-liter glass separable flask equipped with a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. while stirring.
Next, in a polymerization reaction system maintained at 90 ° C., 108.0 g of 80% AA, 37.0 g of monomer G, 36.0 g of 15% NaPS and 11.6 g of 35% SBS were added to separate nozzles while stirring. Then, each was dropped. The dropping time was 180 minutes for 80% AA, 120 minutes for monomer G, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 70.0 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the polymer (10) was obtained.

<Comparative Example 1>
A 1-liter glass separable flask equipped with a reflux condenser and a stirrer was charged with 65.8 g of pure water and heated to 90 ° C. while stirring.
Next, 80% AA 90.0 g, 50% monomer H 61.7 g, 15% NaPS 22.5 g, and 35% SBS 19.3 g were separately added to the polymerization reaction system maintained at 90 ° C. while stirring. Each nozzle was dropped from the nozzle. The dropping time was 180 minutes for 80% AA, 120 minutes for 50% monomer H, and 190 minutes for 15% NaPS and 35% SBS. The dropping was performed continuously, and the dropping rate of each component was constant throughout the dropping.
After completion of the dropwise addition, the polymerization reaction liquid was further aged at 90 ° C. for 30 minutes to complete the polymerization. Thereafter, the polymerization reaction liquid was allowed to cool, and 52.1 g of 48% NaOH was gradually added dropwise to the polymerization reaction liquid while stirring to neutralize the polymerization reaction liquid. In this way, an aqueous solution of the comparative polymer (1) was obtained.

<Example 11>
In Example 7, the copolymers (polymers (1) to (10) and comparative polymer (1)) obtained in Examples 1 to 10 and Comparative Example 1 were evaluated for the ability to suppress precipitation according to the above method. I did it. The results are summarized in Table 1.

As is apparent from Table 1, the copolymer of the present invention has a significantly superior ability to prevent the scale of calcium phosphate as compared with the conventional comparative polymer. Therefore, it became clear that the water treatment agent containing the copolymer of the present invention has an excellent scale preventing ability.

Claims (1)

A water treatment agent containing an amino group-containing copolymer,
The amino group-containing copolymer is
Derived from one or more monomers (N) selected from amino group-containing monomers represented by the following formulas (N1), (N2), (N3), and (N4) of 1 to 75% by mass Structural unit (n) of
An amino group-containing copolymer having, as an essential constituent unit, a structural unit (b) derived from a carboxyl group-containing monomer (B) in an amount of 25% by mass to 99% by mass;
A water treatment agent.

In the general formula (N1), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ represent a hydrogen atom or Represents an organic group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express,

In the general formula (N2), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ and R ₃ represent a hydrogen atom or Represents an organic group having 1 to 20 carbon atoms, and at least one of R ₂ and R ₃ represents an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. To express,

In the general formula (N3), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ , R ₃ and R ₄ represent Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of R ₂ , R ₃ and R ₄ is an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and 1 to 1 carbon atoms. Represents a hydroxyalkyl group of 8;

In the general formula (N4), R ₀ represents a hydrogen atom or a CH ₃ group, R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a single bond, and R ₂ , R ₃ and R ₄ represent Represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and at least one of R ₂ , R ₃ and R ₄ is an aryl group having 6 to 20 carbon atoms, an alkyl group having 4 to 20 carbon atoms, and 1 to 1 carbon atoms. Represents a hydroxyalkyl group of 8;