JP2001172332A - Novel polymer and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a specific water-soluble polymer having trapping force to a hardness component, for example, calcium ion and also having trapping force to heavy metalsly using a characteristic extremely excellent in dispersibility to inorganic particles, to provide its manufacturing method, and to obtain a component comprising the polymer, for example, a treating agent for fiber, a bleaching assistant for wood pulp, a stabilizer for hydrogen peroxide, a dispersant for inorganic pigments, a scale inhibitor and a detergent composition. SOLUTION: This polymer is obtained by reacting a primary or secondary amine or ammonia with epoxy butenes, and has a structure derived from a monomer containing a carbon-carbon double bond, hydroxyl group and amino group, and has a weight-average molecular weight of 500 to 200,000 and is represented by general formula (1) wherein R1 and R2 are independently each hydrogen or an organic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymer having a hydroxyl group and an amino group in a side chain, a method for producing the polymer, and a composition containing the polymer. This composition is, for example, a fiber treatment agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment dispersant, a scale inhibitor, and a detergent composition.

[0002]

BACKGROUND OF THE INVENTION In a wide variety of fields, very different polymers are used in very different applications. For example, a polycarboxylic acid-based polymer represented by an acrylic acid homopolymer, a maleic acid homopolymer, or an acrylic acid / maleic acid copolymer has an ability to capture a hardness component such as calcium ions and an inorganic particle. It is known that the dispersing action is extremely excellent, and taking advantage of these features, for example, fiber treatment agents, wood pulp bleaching aids, hydrogen peroxide stabilizers, inorganic pigment dispersants, scale inhibitors, detergent compositions It is used for various purposes such as objects.

[0003] Although these polycarboxylic acid-based polymers have the above-mentioned characteristics, their ability to capture heavy metals is inadequate, and at present, they are not always sufficient for the above-mentioned applications. It is known that organic chelating agents such as ethylenediaminetetraacetate, nitrilotriacetate, or organic phosphonic acid chelating agents are relatively high in terms of the capturing power for heavy metals. However, the effect on the above-mentioned application is extremely insufficient because the capturing power for the hardness component such as calcium ions is insufficient and the dispersing action on the inorganic particles is completely insufficient.

[0004] Therefore, for the above-mentioned applications, an agent having a sufficiently high scavenging power for heavy metals and an extremely excellent scavenging power for hardness components such as calcium ions and a dispersing action for inorganic particles, ie, calcium ions, etc. There is an urgent need for the development of a polymer that utilizes the characteristics of being extremely excellent in the ability to capture hard components and the action of dispersing inorganic particles, and has the ability to capture heavy metals.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present inventors solve the above-mentioned problem, that is, the problem of developing a polymer having specific characteristics which can exert its effects for various specific applications. To this end, the inventors considered the importance of the structure design of the polymer, particularly the structural design of the side chain portion for imparting various functions according to the purpose, and conducted intensive studies. As a result, they have found that a specific polymer having a hydroxyl group and an amino group in a side chain and a method for producing the same are very useful.

Accordingly, an object of the present invention is to provide a specific water-soluble heavy powder which has a characteristic of being extremely excellent in capturing a hard component such as calcium ions and a dispersing action on inorganic particles and also has a capturing power for heavy metals. Including coalescing, for various specific applications, a polymer having specific characteristics to exert its effects, and a method for producing the same and a composition containing the polymer, for example,
An object of the present invention is to provide a fiber treatment agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment dispersant, a scale inhibitor, and a detergent composition.

[0007]

Means for Solving the Problems In order to solve the above problems, the present invention provides the following configurations.

A simple compound containing a carbon-carbon double bond, a hydroxyl group and an amino group, obtained by reacting a primary or secondary amine or ammonia with an epoxybutene represented by the following general formula (1): 1 to 100 mol% of the structure derived from the monomer
It has a range of weight average molecular weight of 500 to 200,000
A water-soluble polymer .

[0009]

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Here, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or an organic group.

Preferably, in the above general formula (1),
³ , ⁴ when R ¹ , R ² , R ³ and R ⁴ are all hydrogen
- epoxy-1-Buten'n, primary or secondary amine or carbon obtained by reacting ammonia - carbon double bond and a hydroxyl group and structure derived from monomers containing an amino group 1
Weight average molecular weight in the range of
A water-soluble polymer having a molecular weight of 0 to 200,000, and more preferably water having a structural unit represented by the following general formula (2) in a range of 1 to 100 mol%.
It is a soluble polymer .

[0012]

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Here, R ⁵ and R ⁶ are each independently hydrogen or an organic group.

A single compound containing a carbon-carbon double bond, a hydroxyl group and an amino group, which is obtained by reacting a primary or secondary amine or ammonia with the epoxybutene represented by the general formula (1). A method for producing a polymer, comprising a step of polymerizing a monomer. Preferred is a method for producing a water-soluble polymer.

Preferably, in the above general formula (1),
³ , ⁴ when R ¹ , R ² , R ³ and R ⁴ are all hydrogen
-A monomer containing a carbon-carbon double bond, a hydroxyl group and an amino group obtained by reacting a primary or secondary amine or ammonia with epoxy-1-butene; This is a method for producing a polymer, comprising a step of polymerizing a monomer represented by the general formula (3). Preferred is a method for producing a water-soluble polymer.

[0016]

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Here, R ⁵ and R ⁶ are each independently hydrogen or an organic group. And a polymer obtained by the production method described above. Preferably, it is a water-soluble polymer obtained by the production method described above.

A fiber treating agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment dispersant, a scale inhibitor comprising the above-mentioned polymer or a polymer obtained by the above-mentioned production method. , Detergent compositions.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a polymer having a specific structure in a side chain, a method for producing the polymer, and a composition containing the polymer according to the present invention will be described in detail.

[Water-soluble polymer] The water-soluble polymer having a specific structure in the side chain of the present invention will be described below in order.

(Structural Unit) The structural unit of the water-soluble polymer of the present invention is obtained by reacting an epoxybutene represented by the above general formula (1) with a primary or secondary amine or ammonia. 1 to 10 structural units based on a structure derived from a monomer containing a carbon-carbon double bond, a hydroxyl group and an amino group
It has 0 mol% . Preferably, the general formula (1)
Wherein a carbon-carbon double bond obtained by reacting a primary or secondary amine or ammonia with epoxybutene wherein R ¹ , R ² , R ³ and R ⁴ are all hydrogen, a hydroxyl group and an amino group And a structural unit based on a structure derived from a monomer containing a group, and has a structural unit represented by the general formula (2) as one form of the polymer.

Further, the polymer of the present invention is used for applications such as a fiber treating agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment dispersant, a scale inhibitor, and a detergent composition. In some cases, preferably, in the general formula (2), R ⁵ and R ⁶ are not hydrogen at the same time, and independently of each other, an organic group having a hydrogen carboxylic acid group or a salt of these acid groups. . An organic group having a sulfonic acid group or a salt of these acid groups. It is a water-soluble polymer having a structural unit that is any one of an organic group having a hydroxyl group and an organic group having an amino group.

Here, the organic group includes, for example, an alkenyl group, an alkynyl group and an aromatic group. Also,
Here, the salt of the acid group is not particularly limited, for example, alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, monoethanolamine, triethanolamine and the like. Organic amine salts.

Since these polymers have various functional groups in addition to hydroxyl groups and amino groups in the side chains via a specific structure, the polymers have an ability to capture hardness components such as calcium ions and to disperse inorganic particles. It is very excellent and has a heavy metal capturing power, which is very preferable for the above-mentioned applications. Hereinafter, in the present invention, this preferable water-soluble polymer is referred to as “polymer A”.

Further, the water-soluble compounds of the present invention for the above uses
When a polymer is used, most preferably, in the general formula (2), R ⁵ and R ⁶ are not hydrogen at the same time, and independently of one another, hydrogen or any of the substituents shown below Is a compound.

[0026]

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Here, X ^{1 to} X ⁷ independently of each other,
Hydrogen or an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or an organic amine salt. R ⁷ and R ⁸ are not simultaneously hydrogen, but are each independently hydrogen or an organic group.

In the above, alkali metals include, for example, sodium, potassium, lithium and the like, alkaline earth metals include calcium, magnesium and the like, and organic amines include monoethanolamine and triethanolamine. And the like.

Specifically, these polymers are, for example, polymers having the following structural units, and those having a salt type structure are salts thereof. In the following equation:
The structures of the substituents R ⁵ and R ⁶ in the general formula (2) are more specifically shown.

Here, the “salt” in the present invention refers to
Examples thereof include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, and organic amine salts such as monoethanolamine and triethanolamine. These may be used alone or as a mixture of two or more. Further, preferred are alkali metal salts such as sodium and potassium, and particularly preferred are sodium salts. Hereinafter, in the present invention, these are simply described as "salts" only.

In the general formula (2), R ⁵ and R ⁶ are R ⁵ =
CH ₂ COOX ¹ , R ⁶ = CH ₂ COOX ¹ . More specifically, this is the case where R ⁵ and R ⁶ are the substituents shown below.

[0032]

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Similarly, in the general formula (2), R ⁵ and R ⁶
Is a substituent shown below.

Embedded image Similarly, in the general formula (2), R ⁵ and R ⁶ are the substituents shown below.

[0034]

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Here, R ⁶ may have the following structure.

[0036]

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However, the structure of X ⁴ and X ^{5 is} the structure defined above.

Similarly, in the general formula (2), R ⁵ and R ⁶
Is a substituent shown below.

[0039]

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In the above formula, R ⁶ may have the following structure.

[0041]

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However, the structures of X ⁶ and X ⁷ are the structures defined above.

Similarly, in the general formula (2), R ⁵ and R ⁶
Is a substituent shown below.

[0044]

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In the above formula (2), R ⁶ is C
It may be H ₂ CH ₂ SO ₃ X ³ . Here, X ³ is the structure defined above.

Similarly, in the general formula (2), R ⁵ and R ⁶
Is a substituent shown below.

[0047]

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In the above equation (2),R ⁶ Is shown below
Where R is ⁷And R⁸At the same time
They do not become hydrogen, but independently of each other.
It is a machine base.

Embedded image (Structural Unit Amount) The water-soluble polymer of the present invention, preferably a water-soluble polymer having a structural unit represented by the general formula (2)
Although it is a polymer , the amount of the structural unit derived from the above-mentioned general formula (2) possessed by these water-soluble polymers is not particularly limited, and may be appropriately set according to the purpose.
100 mol%, more preferably 5 to 80 mol
%, More preferably 10 to 60 mol%, and most preferably 10 to 40 mol%. The remaining structural units are structural units derived from the monomer (b) described later.

The water-soluble polymer of the present invention, preferably a water-soluble polymer having the structural unit of the above general formula (2),
The structural unit amount derived from the above general formula (2) is 1 mol
If it is less than%, the effect of exhibiting a specific characteristic function for various specific applications, which is the object of the present invention, may not be sufficient, which is not preferable. In particular, a water-soluble polymer having a structural unit represented by the general formula (2) of less than 1 mol% is used, for example, as a fiber treatment agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment dispersant, When used for a scale inhibitor or a detergent composition, there is a possibility that a sufficient effect on the heavy metal trapping force may not be obtained, which is not preferable.

For the above-mentioned applications, the amount of the structural unit derived from the general formula (2) of the water-soluble polymer of the present invention is determined based on the structural unit derived from the general formula (2) of the polymer A. When the amount is within the range of 1 to 100 mol%, the heavy metal trapping force increases as the amount of the structural unit increases, but the trapping force for calcium ions per unit weight tends to decrease. Therefore, by setting the structural unit amount to 5 to 80 mol%, more preferably 10 to 60 mol%, and still more preferably 10 to 40 mol%, in addition to a sufficient heavy metal trapping force, a trapping force for a hardness component such as calcium ions. The performance is well-balanced, which is very preferable. Hereinafter, a preferred embodiment of the water-soluble polymer of the present invention is referred to as polymer A.

(Weight average molecular weight) Water solubility in the present invention
The weight average molecular weight of the polymer is not particularly limited, depending on the purpose of use of the water-soluble polymer, may be suitably set, but is preferably 500 to 200,000, more preferably at 2,000 to 50,000 , And most preferably 3,000 to 15,000.

When the water-soluble polymer , preferably polymer A, is used in, for example, a fiber treatment agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment dispersant, a scale inhibitor, and a detergent composition. If the weight average molecular weight is less than 500, the heavy metal trapping power and calcium ion trapping power required for the use are not sufficient, and if the weight average molecular weight exceeds 200,000, the dispersing action on inorganic particles is remarkable. It is not preferable because it becomes worse.

The weight average molecular weight of the water-soluble polymer , preferably polymer A, is 500 to 2,000
Within the range of 00, the higher the weight-average molecular weight is, the more the heavy metal trapping force and the trapping force for calcium ions are improved, but the dispersing action on inorganic particles tends to be reduced. Therefore, by setting the weight average molecular weight preferably to 2,000 to 50,000, and most preferably to 3,000 to 15,000, the above performance can be exhibited very preferably in a well-balanced manner.

[Method for producing polymer] Water-soluble polymerization of the present invention
The body can be manufactured, for example, by the following manufacturing method. After homopolymerizing the epoxybutene represented by the general formula (1) or copolymerizing it with a monoethylenically unsaturated monomer copolymerizable with the epoxybutene, a primary or secondary amine or A method for producing the polymer of the present invention, comprising a step of reacting ammonia. Monomers containing a carbon-carbon double bond, a hydroxyl group and an amino group, obtained by reacting an epoxybutene represented by the general formula (1) with a primary or secondary amine or ammonia Hereinafter, the monomer (a) will be referred to as a monoethylenically unsaturated monomer that can be homopolymerized or copolymerized with the monomer (a) (hereinafter referred to as a monomer (b)). ) To obtain the polymer of the present invention.

Of these, the polymer can be easily designed, and the water-soluble polymer of the present invention can be used, for example, as a fiber treatment agent, wood pulp bleaching aid, hydrogen peroxide stabilizer, inorganic pigment dispersant. When used for an anti-scale agent, a detergent composition, etc., these applications are usually carried out in an aqueous system, and therefore, preferably, they can be easily produced in an aqueous solvent.
In the above method, a solvent must be selected from the viewpoint of the solubility of epoxybutene and the like, and in the case of copolymerization using the solvent, the monomer to be copolymerized may need to be limited.

Hereinafter, in the present invention, the above-mentioned production method, that is, a carbon-containing compound obtained by reacting an epoxybutene represented by the general formula (1) with a primary or secondary amine or ammonia is used. Monomer (a) containing a carbon double bond, a hydroxyl group and an amino group alone or copolymerized with monoethylenically unsaturated monomer (b) copolymerizable with monomer (a) About the manufacturing method characterized by including the step of
Details will be described. This method of producing a polymer is one of the preferable methods for obtaining, for example, a water-soluble polymer having a specific structure which is a preferred embodiment of the present invention. Further, a water-soluble polymer obtained by the above-described polymerization method is also one of the preferable embodiments in the present invention.

(Monomer (a)) The monomer (a) used in the production of the water-soluble polymer of the present invention is obtained by adding a first or second monomer to the epoxybutene represented by the general formula (1). A monomer containing a carbon-carbon double bond, a hydroxyl group and an amino group, which is obtained by reacting an amine or ammonia. Preferably, in the general formula (1), a carbon obtained by reacting a primary or secondary amine or ammonia with epoxybutene in which R ¹ , R ² , R ³ and R ⁴ are all hydrogen. −
It is a monomer having a carbon double bond, a hydroxyl group and an amino group, and is a compound represented by the general formula (3) as one form of the monomer. Furthermore, for example, when the polymer of the present invention is used for applications such as a fiber treatment agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment dispersant, a scale inhibitor, and a detergent composition, In the general formula (3), R ⁵ and R ⁶ are not hydrogen at the same time, and each independently represents a hydrogen carboxylic acid group or a salt of these acid groups. An organic group having a sulfonic acid group or a salt of these acid groups. It is preferable to produce a polymer using a monomer having at least one substituent of any one of an organic group having a hydroxyl group and an organic group having an amino group. Here, the organic group includes, for example, an alkenyl group, an alkynyl group and an aromatic group.

The salt of the acid group is not particularly limited, but examples thereof include alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, monoethanolamine, and the like. Organic amine salts such as triethanolamine are exemplified.

(Hereinafter, the more preferable monomer (a) in the above general formula (3) will be referred to as monomer (aa).) In addition to the hydroxyl group and the amino group, these monomers (aa) Furthermore, because it has various functional groups of a specific structure, a polymer,
In other words, when the above-mentioned polymer of the present invention (hereinafter sometimes referred to as polymer A) is used, it is very excellent in capturing power for hardness components such as calcium ions, dispersing action for inorganic particles, and capturing power for heavy metals. Is very preferable.

When used for the above applications, most preferably, R ⁵ , R ^5
6 is not to be hydrogen at the same time, but to produce a polymer using, as a monomer, hydrogen or a compound which is one of the following substituents independently of each other.

[0061]

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Here, X ^{1 to} X ⁷ independently of each other,
Hydrogen or an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or an organic amine salt. R ⁷ and R ⁸ are
They are not hydrogen at the same time and are independently hydrogen or organic groups.

In the above, alkali metals include, for example, sodium, potassium, lithium and the like, alkaline earth metals include calcium, magnesium and the like, and organic amines include monoethanolamine and triethanolamine. And the like.

Specifically, these monomers (a) are, for example, the following compounds, and those having a salt type structure are salts thereof. In the following formulas, the structures of the substituents R ⁵ and R ⁶ in the general formula (3) are more specifically shown.

In the general formula (3), R ⁵ and R ⁶ are the substituents shown below.

[0066]

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In the above structure, R ₅ and R ₆ are CH ₂ C
It may have a structure of OOX ^2. However, the structure of X ^{2 is} the structure defined above.

In the general formula (3), R ⁵ and R ⁶ are the substituents shown below.

[0069]

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In the general formula (3), R ⁵ and R ⁶ are the substituents shown below.

Embedded image However, R6 may have a structure represented by the following formula.

[0071]

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However, X ⁴ and X ⁵ are the structures defined above.

In the general formula (3), R ⁵ and R ⁶ are the substituents shown below.

[0074]

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However, R6 may be represented by the following formula.

[0076]

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Further, in the general formula (3), R ⁵ and R ⁶
Is a substituent shown below.

[0078]

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Further, R6 may have a structure represented by the following formula.

[0080]

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Here, X ³ is the structure defined above.

[0082]

In the general formula (3), R ⁵ and R ⁶ are the substituents shown below.

Further, R ⁶ may have a structure represented by the following formula. However, R ⁷ and R ⁸ are not simultaneously hydrogen and are each independently hydrogen or an organic group.

[0084]

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The method of using these monomers (a) is as follows:
They may be used alone or as a mixture of two or more.

Further, the method of adding the monomer (a) is not particularly limited, and the entire amount is initially charged,
Either the whole amount may be dripped, or a part may be initially charged and partly dripped. In consideration of the addition ratio of the monomer (a), the polymerizability of the monomer (b) described later, etc., it may be appropriately set as needed.

The method for producing the monomer (a) is not particularly limited, but is preferably
For example, in an aqueous solvent, particularly preferably in water, under stirring,
The primary or secondary amine or ammonia is preferably
% By weight, more preferably 80% by weight or more, most preferably the whole amount is initially charged.
It can be produced by dropping 0% by weight or more, more preferably 80% by weight or more, most preferably the whole amount, and reacting.

At that time, the reaction temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower. If it exceeds 50 ° C., epoxybutene may react with water in an aqueous solvent, which is not preferable. The pH in the reaction system is generally preferably 7 or more, more preferably 8 or more, more preferably 1 or more, because the higher the pH, the higher the reactivity of the epoxide ring-opening reaction with an amino group.
0 or more. If the pH is less than 7, the reactivity may be significantly deteriorated. The pH adjuster is not particularly limited and may be appropriately used as needed. Further, the solid content concentration is not particularly limited, but is preferably 10% by weight or more, and more preferably 20% by weight or more. If it is less than 10% by weight, productivity is extremely low, which is not preferable.

The reaction pressure may be any of normal pressure (atmospheric pressure), pressurization and decompression. Although a catalyst is basically unnecessary,
If necessary, any substance that does not adversely affect the reaction may be appropriately used. Further, in order to improve the solubility of the primary or secondary amine or ammonia used, another aqueous organic solvent may be appropriately added in an amount of 30% by weight or less. Specifically, one or two or more of lower alcohols such as methanol, ethanol, and isopropyl alcohol; amides such as dimethylformamide; ethers such as diethyl ether and dioxane; .

(Monomer (b)) The monoethylenically unsaturated monomer (b) used in the production of the water-soluble polymer of the present invention is not particularly limited, and may be selected depending on the intended polymer. May be appropriately set, preferably a water-soluble monomer
However, if the resulting polymer does not impair the water solubility
A hydrophobic monomer may be used.

The hydrophobic monomer is not particularly restricted but includes, for example, olefin monomers such as ethylene and propylene, styrene monomers such as styrene and p-methoxystyrene, ethyl vinyl ether and isobutyl vinyl ether. Vinyl ether monomers, acrylate monomers such as ethyl acrylate and butyl acrylate, methacrylate monomers such as ethyl methacrylate and butyl methacrylate, and hydrophobic monoethylene having other esters And unsaturated monomers.

The water-soluble monoethylenically unsaturated monomer is not particularly limited, and examples thereof include a monocarboxylic acid monomer, a dicarboxylic acid monomer and a sulfonic acid group. Monomer, a monomer having a hydroxyl group, and other monomers.

Specifically, preferably, the monocarboxylic acid monomer includes acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, and the like, and salts thereof.

Examples of the dicarboxylic acid monomer include maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid and the like, and salts thereof, and those having an anhydride.

Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 3-allyloxy-2-hydroxypropane sulfonic acid, and 2-acrylamido-2-methylpropane. Sulfonic acid, sulfoethyl acrylate,
Examples include sulfoethyl methacrylate, 2-hydroxy-3-butenesulfonic acid, and the like, and salts thereof.

Examples of the monomer having a hydroxyl group include 3-methyl-2-buten-1-ol (prenol), 2-methyl-3-buten-2-ol (isoprene alcohol), and 3-methyl-3-butene. -1-ol (isoprenol), hydroxyethyl acrylate, hydroxyethyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol methacrylate and the like.

Examples of other monomers include 2-vinylpyrrolidone.

The method of using these monomers (b) is as follows:
They may be used alone or as a mixture of two or more.

In particular, the polymers of the present invention are used for applications such as fiber treatment agents, wood pulp bleaching aids, hydrogen peroxide stabilizers, inorganic pigment dispersants, scale inhibitors, detergent compositions and the like. In some cases, the monomer (b) is preferably the above-mentioned water-soluble monomer.

Also in this case, the hydrophobic monomer is very excellent in the effect of the polymer of the present invention, that is, the ability to capture hardness components such as calcium ions and the effect of dispersing inorganic particles, depending on the application. It may be added within a range that does not impair the combined effect of capturing heavy metals, but is preferably added in an amount of less than 5 mol% of all monomers (including the monomer (a), the same applies hereinafter). Most preferably, no addition is made. When the hydrophobic monomer is added in an amount of 5 mol% or more, the water solubility of the obtained polymer is impaired, and the above-described effects may be significantly deteriorated. Absent.

For the above-mentioned applications, it is particularly preferable to use acrylic acid, methacrylic acid, maleic acid, allylsulfonic acid, methallylsulfonic acid, 3-allyloxy-2 among the exemplified monomers (b). -Hydroxypropanesulfonic acid, and those having salts and anhydrides thereof, are the anhydrides and 2-vinylpyrrolidone.

Further, the method of adding the monomer (b) is not particularly limited, and any of initial charge, total drop, partial initial charge and partial drop may be used. In view of the addition ratio of the monomer (b), the polymerizability, etc., or the copolymerizability with the monomer (a), it may be appropriately set as necessary.

(Addition ratio of monomer) The addition ratio of the monomer used in the production of the water-soluble polymer of the present invention is monomer (a) / monomer (b) in molar ratio. = 1-100 / 0-99, preferably 5-80 / 20-95, most preferably 10-40
/ 90-60, a total of 100 mol%. As described above, the content of the monomer (a) is most preferably 10 to 40 mol%.

(Polymerization method) The polymerization method in the production of the water-soluble polymer of the present invention is not particularly limited, and may be appropriately set according to the desired water-soluble polymer .

For example, any of continuous polymerization, semi-continuous polymerization, and batch polymerization may be used, and any of stirring polymerization and standing polymerization may be used. Further, any of solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization may be used. , Uniform polymerization and heterogeneous polymerization may be used. Further, the solution polymerization may be any of aqueous solution polymerization and solvent solution polymerization.

Further, any of radical polymerization, anionic polymerization and cationic polymerization may be used.

In particular, the water-soluble polymer of the present invention is
When used for applications such as fiber treatment agents, wood pulp bleaching aids, hydrogen peroxide stabilizers, inorganic pigment dispersants, scale inhibitors, detergent compositions, etc., in aqueous solvents, uniform solution stirring radical polymerization is used. preferable. For these uses, it is preferable to use the monomer (aa) as the monomer (a). However, when polymerizing the monomer (aa), the monomer (aa) is subjected to uniform solution stirring radical polymerization in an aqueous solvent. Is preferred.

In the following, preferred water-soluble compounds for use in the present invention, for example, fiber treatment agents, wood pulp bleaching aids, hydrogen peroxide stabilizers, inorganic pigment dispersants, scale inhibitors, detergent compositions and the like . A method for producing a polymer , that is, a polymer A, that is, a method for polymerizing using these preferable monomers (aa) will be described in detail.

<Solvent> The solvent used in the process for producing the polymer A of the present invention is an aqueous solvent, preferably 80% by weight or more of water, and most preferably water. In addition, an organic solvent may be appropriately added as needed in order to improve the solubility of the monomers and the initiator used for the polymerization within a range that does not adversely affect the polymerization and the obtained water-soluble polymer.

Examples of the organic solvent 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, diethyl ether and dioxane; And dimethylformaldehyde. These may be used alone or as a mixture of two or more.

<Polymerization Initiator> The radical polymerization initiator in the method for producing the polymer A of the present invention is not particularly limited, and may be appropriately set. In some cases, a polyvalent metal ion may be used as a chain transfer agent or a decomposition accelerator for the initiator.

Examples of the radical polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, 2,2′-azobis (2-amidinopropane) hydrochloride, and 4,4′-azobis- Azo compounds such as 4-cyanovaleric acid, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t Organic peroxides such as -butyl peroxide and cumene hydroperoxide; and hydrogen peroxide.

These polymerization initiators may be used alone or, if necessary, in combination of two or more. Among the examples, particularly preferred are persulfate, hydrogen peroxide and a combination thereof.

The amount of the initiator used is not particularly limited, and may be appropriately set as necessary in consideration of the polymerizability of the monomer used, the molecular weight of the target polymer, and the like. Preferably, the amount used is a total of 1 monomer.
It is 2 g to 10 g per mol. If the amount is less than 2 g, the residual amount of the monomer may greatly increase, and if it exceeds 10 g, the resulting polymer may have a low net content, which is not preferable.

Further, the method of adding these initiators is not particularly limited in view of the decomposability, but it is preferable to add 50% by weight or more of the total amount of the initiator substantially continuously by dropping. It is particularly preferable to drop 80% by weight or more. Also, the dropping time is not particularly limited and may be set as appropriate. When two or more kinds are used in combination, it is also possible to appropriately set the dropping in parallel, the dropping of one after completion of dropping, or the dropping of the other after a lapse of a certain time after the start of dropping of one. In addition,
For example, in the case of an initiator having a relatively slow decomposition such as hydrogen peroxide, the dropping is preferably completed at least 10 minutes earlier than the time at which the dropping of the monomer is completed. If the dropping is not completed earlier than 10 minutes, depending on the polymerization conditions, the initiator is not completely decomposed by the time the polymerization is completed, the effect as the initiator is not obtained, and the initiator is wasted. It is not preferable because the thermal stability of the obtained polymer may be adversely affected.

When there is no risk of adversely affecting the polymerization system, it is not particularly necessary to terminate the dropwise addition as early as 10 minutes or more. In addition, in the case of an initiator such as persulfate which is relatively quick to decompose, it is preferable to set the dropping end time within 30 minutes from the end of the monomer dropping to the end of the dropping. As a result, an effect can be found in which the amount of monomers remaining in the obtained polymer can be significantly reduced. In addition, before the end of the monomer dropping, even if the dropping is completed, the polymerization is not particularly adversely affected, and may be appropriately set according to the remaining amount of the monomer in the obtained polymer. .

If necessary, a chain transfer agent may be used together with the polymer as a molecular weight regulator within a range that does not adversely affect the polymerization. Specific examples include, but are not limited to, sulfites, bisulfites, hypophosphites, and the like. These may be used alone or in combination of two or more. The amount used and the method of addition are not particularly limited, and may be appropriately set according to the case.

Further, if necessary, a polyvalent metal ion may be used in combination as a decomposition accelerator of the radical polymerization initiator. Specific examples of effective polyvalent metal ions that can be used include, for example, Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Cu
²⁺ , Cu ⁺ , Ni2 ⁺ , Co2 ⁺ , Co3 ⁺ , V2 ⁺ , ^{V3 +} , V
O ^{2+ and the} like. These may be used alone,
More than one species may be used in combination. The amount used and the method of addition are not particularly limited, and may be set as appropriate according to the case.
The supply form of the polyvalent metal ion is not particularly limited, and any metal compound or metal may be used as long as it can be ionized and present in the polymerization system. .

<Other Conditions> Other conditions in the method for producing the polymer A of the present invention will be described sequentially. The pH at the time of the polymerization is not particularly limited, and may be appropriately set in view of the polymerizability of the monomer used. The pH adjuster is also not particularly limited, and sodium hydroxide or the like may be used, if necessary, and the final pH may be appropriately set to a desired pH after the polymerization, if necessary. Good.

The temperature at the time of the polymerization is not particularly limited, but the polymerization is preferably carried out at 80 ° C. or higher, and most preferably at a boiling point. When the temperature is lower than 80 ° C., the decomposition efficiency of the polymerization initiator may be deteriorated, and the residual amount of the monomer in the obtained polymer may be increased. In addition,
It is very preferable to carry out the polymerization at a boiling point because the temperature control becomes very easy, the reproducibility of the polymerization is very good, and the obtained polymer is very stable in quality.

The concentration at the time of polymerization is not particularly limited, and may be appropriately set in consideration of the solubility of the monomer, the viscosity of the obtained polymer, and the like. Further, the pressure during polymerization is not particularly limited, and may be any of pressurization, normal pressure (atmospheric pressure), and reduced pressure.

[Use of Polymer] The use of a water-soluble polymer, which is another object of the present invention, will be described. The use of the water-soluble polymer of the present invention is, in view of the characteristics of these water-soluble polymers , in view of the characteristics of these water-soluble polymers , depending on the purpose, depending on the purpose, in various fields and various applications. Can be appropriately set and used, and is not particularly limited.

Hereinafter, a fiber treating agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment, which is particularly useful in the water-soluble polymer of the present invention, preferably the polymer A, is useful. The dispersant, the scale inhibitor, and the detergent composition will each be specifically described.

In the compositions of the present invention to be described hereinafter, for example, a conventionally known acrylic acid homopolymer, maleic acid homopolymer, or acrylic acid / maleic acid used in these compositions. A polymer represented by a polycarboxylic acid polymer such as a copolymer may be used in combination with the polymer of the present invention, preferably the polymer A, as long as the effects of the composition of the present invention are not impaired. .

(Fiber treatment agent) The fiber treatment agent according to the present invention, which comprises the polymer, preferably polymer A, is at least selected from the group consisting of dyes, peroxides and surfactants. One comprises the polymer of the present invention, preferably polymer A. Further, the present fiber treatment agent may be liquid or solid, and when in liquid form, preferably in aqueous solution form, but the active ingredient concentration is not particularly limited,
What is necessary is just to set suitably according to the use. The fiber treating agent can be used in the steps of refining, dyeing, bleaching, and soaping in fiber treatment. Dyes, peroxides and surfactants include those commonly used in fiber treatments. The ratio of the polymer of the present invention, preferably polymer A, to at least one selected from the group consisting of dyes, peroxides and surfactants is, for example, the whiteness of the fiber, uneven color, and the degree of dyeing In order to improve
At least one selected from the group consisting of a dye, a peroxide and a surfactant is added to 1 part by weight of the polymer.
It is blended in a ratio of 1 to 100 parts by weight. The fibers for which the fiber treating agent of the present invention can be used are not particularly limited. For example, cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, and semi-synthetic fibers such as human silk. Fibers and their fabrics and blends. When applying the fiber treating agent of the present invention to the refining step, it is preferable to mix the water-soluble polymer of the present invention, an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the polymer, a peroxide, and a silicate-based agent such as sodium silicate as a decomposition inhibitor of an alkaline bleaching agent.

(Wood Pulp Bleaching Aid) The wood pulp bleaching aid characterized by comprising the polymer of the present invention, preferably polymer A, is blended with the polymer of the present invention, preferably polymer A. Have been. As long as the effects of the invention are not hindered, another water-soluble polymer or the like may be blended. For example, a polycarboxylic acid polymer such as a polyacrylate, a poly-α-hydroxyacrylate, and the like.

Preferably, the polymer component in the wood pulp bleaching aid comprises the polymer of the present invention. If necessary, as other compounding agents, aminocarboxylates, silicates, sulfites, condensed phosphates such as tripolyphosphate, alkaline earth metal compounds such as magnesium and calcium, aluminum compounds and the like may be used. . The blending amount of the polymer A of the present invention in the wood pulp bleaching aid is preferably 1 to 100% by weight. More preferably,
10-100% by weight.

The wood pulp bleaching aid of the present invention may be in the form of a liquid,
It may be solid or liquid, and preferably in the form of an aqueous solution, but the concentration of the active ingredient is not particularly limited, and may be appropriately set according to the use.

The wood pulp which can be suitably bleached includes mechanical pulp, chemical mechanical pulp, deinked pulp,
Soda pulp, kraft pulp and the like can be mentioned.

The amount of the wood pulp bleaching aid used is not particularly limited, but is preferably 0.02 to 1% by weight of the active ingredient based on the dry pulp. Use of less than 0.02% by weight is not preferred because bleachability may decrease.
Also, if it is used in an amount exceeding 1% by weight, the effect of addition is no longer observed, and it is only economically disadvantageous. The amount of the active ingredient can be appropriately adjusted so that a predetermined bleaching effect is obtained and workability is improved.

(Hydrogen peroxide stabilizing agent) The hydrogen peroxide stabilizing agent comprising the polymer of the present invention, preferably polymer A, is a polymer of the present invention, preferably polymer A Consists of As the polymer component in the hydrogen peroxide stabilizer, other water-soluble polymers, as long as the effect is not affected,
For example, polycarboxylic acid polymers such as polyacrylates,
A poly α-hydroxy acrylate or the like may be blended. The amount of the polymer A of the present invention in the hydrogen peroxide stabilizer of the present invention is not particularly limited, but is, for example, 1 to 100% by weight. More preferably, it is 5 to 100% by weight.
If necessary, aminocarboxylates and silicates may be used as other compounding agents.

The hydrogen peroxide stabilizer of the present invention may be in the form of a liquid,
It may be solid or liquid, and preferably in the form of an aqueous solution, but the concentration of the active ingredient is not particularly limited, and may be appropriately set according to the use.

The amount of the hydrogen peroxide stabilizer of the present invention is not particularly limited, but usually, for example, the amount of the polymer is 0.01 to 2% by weight based on 35% aqueous hydrogen peroxide. % Is preferable. When the amount of the polymer used is 0.0
If the amount is less than 1% by weight, a sufficient effect of stabilizing hydrogen peroxide cannot be obtained, and hydrogen peroxide may be decomposed during transporting, storing, or using the hydrogen peroxide solution. This is not only undesirable because it is extremely dangerous, such as not only wasting hydrogen but also generating a large amount of oxygen. If it is used in an amount of 2% by weight or more, the effect of addition is no longer observed, and it is economically disadvantageous, which is not preferable. (Inorganic pigment dispersant) An inorganic pigment dispersant characterized by being blended with the water-soluble polymer of the present invention (polymer A of the present invention) comprises the water-soluble polymer of the present invention. If necessary, as long as the effect of the inorganic pigment dispersant of the present invention is not hindered, as the other compounding agents, use a polymerized phosphoric acid and its salt, phosphonic acid and its salt, polyvinyl alcohol and other water-soluble polymers. May be. The content of the polymer A of the present invention in the scale inhibitor of the present invention is not particularly limited, but is preferably, for example, 1 to 100% by weight. More preferably, it is 5 to 100% by weight.

The inorganic pigment dispersant of the present invention may be either liquid or solid. When it is liquid, it is preferably in the form of an aqueous solution, but the concentration of the active ingredient is not particularly limited. Just set it. In either case,
This dispersant exhibits good performance as a dispersant for inorganic pigments of heavy or light calcium carbonate and clay used for paper coating. For example, by adding a small amount of the inorganic pigment dispersant of the present invention to an inorganic pigment and dispersing the same in water, it has a low viscosity and high fluidity, and the aging stability of the performance thereof is high. Highly concentrated inorganic pigment slurries such as concentrated calcium carbonate slurries can be produced. The amount of the inorganic pigment dispersant used in the present invention is as follows.
The active ingredient is preferably 0.05 to 2.0 parts by weight with respect to 00 parts by weight. If the amount of the active ingredient is less than 0.05 part, a sufficient dispersing effect cannot be obtained, and if it exceeds 2.0 parts by weight, the effect corresponding to the added amount can no longer be obtained, and it is economically disadvantageous. It is not preferable because there is a possibility of becoming.

(Scale Inhibitor) The scale inhibitor which comprises the polymer of the present invention, preferably polymer A, comprises the polymer of the present invention, preferably polymer A, and if necessary. In addition, a composition containing a polymerized phosphate, a phosphonate, an anticorrosive, a slime control agent, and a chelating agent as other compounding agents can be used.
The amount of the polymer A of the present invention in the scale inhibitor of the present invention is preferably 1 to 100% by weight. More preferably 5-
100% by weight.

The scale inhibitor of the present invention may be in the form of a liquid or a solid. When it is in the form of a liquid, it is preferably in the form of an aqueous solution. Just do it.

In any case, it is useful for preventing scale in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentration vessel, and the like.

(Detergent Composition) The detergent composition according to the present invention, which comprises the polymer, preferably the polymer A, comprises the polymer, preferably the polymer A, in an amount of the entire detergent composition. 1 to 20% by weight, and the amount of the surfactant is preferably 5 to 70% by weight of the entire detergent composition,
In some cases, the enzyme may be added in a range of 5% by weight or less. If the amount of the polymer is less than 1% by weight, the effect of addition does not appear, and if it exceeds 20% by weight, the effect of the addition no longer leads to improvement in detergency and may be economically disadvantageous. On the other hand, if the amount of the surfactant, which is the main component of the detergent composition, is out of the above range, the balance with other components may be lost and the detergency of the detergent composition may be adversely affected. When the enzyme is blended, it contributes to the improvement of the detergency, but if it exceeds 5% by weight, the effect of the addition is no longer exhibited, which is economically disadvantageous and is not preferred. As the surfactant, at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and a cationic surfactant can be used. Examples of the anionic surfactant include, but are not particularly limited to, alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfone Examples thereof include acid salts, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylate salts, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters and salts thereof. The nonionic surfactant is not particularly limited, but includes, for example, polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycooxide, Fatty acid glycerin monoester, alkylamine oxide and the like can be mentioned. The amphoteric surfactant is not particularly limited, but includes, for example, a carboxy-type or sulfobetaine-type amphoteric surfactant, and the cationic surfactant is not particularly limited. Ammonium salts and the like can be mentioned.

[0139] As the enzyme to be incorporated in the detergent composition of the present invention, protease, lipase, cellulase and the like can be used. Particularly, protease, alkaline lipase and alkaline cellulase having high activity in an alkaline washing solution are preferable. Furthermore, if necessary, the detergent composition of the present invention may contain a known alkali builder, chelate builder, anti-redeposition agent, soil release agent, color transfer inhibitor, softener, fluorescent agent, bleaching agent, bleaching aid. Ingredients commonly used in detergent compositions such as fragrances and the like may be blended. Further, zeolite may be blended. Silicates, carbonates, sulfates and the like can be used as the alkali builder.
As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), D
TPA (diethylenetriaminepentaacetic acid), citric acid and the like can be used as needed.

[0140]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. “%” Indicates “% by weight”.

Reference Example First, a method for synthesizing the monomer (a) used in the present example will be described as a reference example.

Reference Example 1 As the monomer (a), an epoxybutene-L-aspartic acid derivative monomer (hereinafter referred to as
It is described as "monomer (a1)". ) Was synthesized.

Specifically, 358 g of ion-exchanged water and a 48% aqueous sodium hydroxide solution 33 were placed in a 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer.
3 g were charged, and 266 g of L-aspartic acid was added.
Thereafter, 140 g of epoxybutene was gradually added dropwise with stirring while keeping the liquid temperature at 40 ° C. or lower. After dropping, 40 ° C
For 1 hour to obtain a 45% aqueous solution of the monomer (a1). In addition, water is removed from the aqueous solution, and the monomer (a
1) was isolated. For the monomer (a1), ¹ H-NM
The results of the R measurement were as follows. ¹ H-NMR (D ₂ O): δ 2.22 to 2.46 (4
H), δ 3.35 (2H), δ 5.18 (2H), δ
5.63 (1H) From the above results, the structure of the monomer (a1) is represented by the general formula
In (3) , it was found that the following structure was applicable.

[0144]

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Reference Example 2 As a monomer (a), an epoxybutene-iminodiacetic acid derivative monomer (hereinafter, referred to as “monomer (a2)”) was synthesized.

That is, in the same manner as in Reference Example 1, 358 g of ion-exchanged water and 333 g of a 48% aqueous sodium hydroxide solution were charged into a 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer. 266 g of acetic acid
Was added. Thereafter, 140 g of epoxybutene was gradually added dropwise with stirring while keeping the liquid temperature at 40 ° C. or lower. After completion of the dropwise addition, the mixture was reacted at 40 ° C. for 1 hour,
% Aqueous solution was obtained. Further, water was removed from the aqueous solution to isolate the monomer (a2). The result of ¹ H-NMR measurement of the monomer (a2) was as follows. ¹ H-NMR (D ₂ O): δ 3.15 (6H), δ 3.4
6 (1H), δ5.12 (2H), δ5.63 (1H) From the above results, the structure of the monomer (a2) is represented by the general formula
In (3) , R ⁵ is CH ₂ COONa, and R ⁶ is CH ₂ COONa.
It turned out that this was the case for ONa.

(Reference Example 3) As the monomer (a), an epoxybutene-diethanolamine derivative monomer (hereinafter referred to as
It is described as “monomer (a3)”. ) Was synthesized.

That is, as in Reference Example 1, 163 g of ion-exchanged water was charged into a 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer, and 53 g of diethanolamine was added. Then, while stirring, the liquid temperature was reduced to 40.
35 g of epoxy butene was gradually dropped while keeping the temperature at not more than ° C. After completion of the dropwise addition, the mixture was reacted at 40 ° C. for 1 hour to obtain a 35% aqueous solution of the monomer (a3). Further, water was removed from the aqueous solution to isolate the monomer (a3). The result of ¹ H-NMR measurement of the monomer (a3) was as follows. ¹ H-NMR (D ₂ O): δ2.59 (6H), δ3.5
2 (5H), δ5.14 (2H), δ5.65 (1H) From the above results, the structure of the monomer (a3) is represented by the general formula
In (3) , R ⁵ is CH ₂ CH ₂ OH, and R ⁶ is CH ₂ CH ₂
It became clear that this was the case for OH.

Reference Example 4 As the monomer (a), a 2-epoxybutene-ethylenediamine derivative monomer (hereinafter, referred to as
It is described as "monomer (a4)". ) Was synthesized.

That is, 371 g of ion-exchanged water was charged into a 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer, and 60 g of ethylenediamine was added. Thereafter, 140 g of epoxybutene was gradually added dropwise with stirring while keeping the liquid temperature at 40 ° C. or lower. After the completion of the dropwise addition, the reaction was carried out at 40 ° C. for 1 hour, and 35% of the monomer (a4)
An aqueous solution was obtained. Also, removing water from this aqueous solution,
Monomer (a4) was isolated. For the monomer (a4),
^{The result of 1} H-NMR measurement was as follows. ¹ H-NMR (D ₂ O): δ 2.50 (8H), δ 3.3
8 (2H), δ5.09 (4H), δ5.60 (2H) From the above results, the structure of the monomer (a4) is represented by the general formula
In (3) , it was found that the structure corresponds to the following structure.

[0151]

Embedded image

Hereinafter, polymerization was carried out using the monomers (a1) to (a4) obtained in Reference Examples 1 to 4.

(Example 1) Example 1 is an example of the production of the polymer of the present invention. The weight average molecular weight (hereinafter referred to as “Mw”) was measured as follows.

<Method for Mw Measurement> Measured by GPC (gel permeation chromatography). The measurement conditions are as follows.・ Column: G-3000PWXL (manufactured by Tosoh) ・ Mobile phase: disodium hydrogen phosphate dodecahydrate 34.5
g and sodium dihydrogen phosphate dihydrate 46.2 g (all are special grade reagents, and all reagents used in the following measurement use special grades)
To a total weight of 5000 g by adding pure water to
Aqueous solution filtered with a micron membrane filter ・ Detector; UV 214 nm (Waters model 481 type) ・ Pump; L-7110 (Hitachi) ・ Flow rate: 0.5 ml / min ・ Temperature; 35 ° C. ・ Calibration curve: Polyacryl Sodium acid standard sample (manufactured by Sowa Kagaku) (Example 1-1) Monomer (a1) as monomer (a)
Using acrylic acid as the monomer (b), (a) /
(B) Polymer 1-1 having a ratio of 25/75 (mol ratio) was produced. That is, a capacity of 2.5 with a reflux condenser and a stirrer
In a 1 liter SUS separable flask, add the monomer (a
220 g of a 45% aqueous solution of 1) and 48 g of pure water are charged,
Under stirring, the temperature was raised to the boiling point. Then, while maintaining the reflux state under stirring, 108 g of an 80% aqueous solution of acrylic acid was added to 22.4 g of 35% aqueous hydrogen peroxide over 120 minutes.
Over a period of 50 minutes, and 32 g of a 25% aqueous sodium persulfate solution were dropped substantially continuously at a uniform rate from separate nozzles over a period of 80 minutes after the completion of the dropping of the hydrogen peroxide solution. After the completion of all the dropwise additions, the reaction solution was kept at the boiling point for 30 minutes to complete the polymerization reaction.

After completion of the reaction, 75 g of a 48% aqueous sodium hydroxide solution was added dropwise to neutralize 85% to obtain a yellow-brown transparent polymer 1-1 aqueous solution having a solid content of 42.3%. Water was removed from the aqueous solution to obtain a brown powder of polymer 1-1.

The resulting brown powder was analyzed by ¹ H-NMR.
As a result of the measurement, the signal derived from the carbon-carbon double bond disappeared in the polymer 1-1, and the signal derived from the monomer (a1) other than the signal derived from the double bond. It was found that monomer (a1) had been introduced into polymer 1-1. As described above, it was confirmed that the water-soluble polymer 1-1 was synthesized.

As a result of the measurement, Mw of the polymer 1-1 was 6,700.

(Examples 1-2 to 1-5) As in Example 1-1, monomer (a1) was used as monomer (a), and acrylic acid was used as monomer (b). M as shown in Table 1
ol ratio of polymers 1-2 to 1-5 were produced.

That is, in the same manner as in Example 1-1, polymerization was carried out at the initial charge amount, the drop amount, the drop time, and the aging time as summarized in Table 1, and the aqueous solution of the polymers 1-2 to 1-5 was obtained. Obtained. As a result of performing ¹ H-NMR measurement in the same manner as in Example 1-1,
It was confirmed that a polymer was synthesized in each case, and Mw was 8500, 7900,
6400, 3800.

Examples 1-6 to 1-9 Using the monomer (a2) as the monomer (a) and acrylic acid as the monomer (b), the molar ratios were as shown in Table 2. Polymers 1-6 to
1-9 were prepared.

That is, in the same manner as in Example 1-1, polymerization was carried out with the initial charge amount, the drop amount, the drop time, and the aging time as summarized in Table 2, and the aqueous solution of the polymers 1-6 to 1-9 was obtained. Obtained.

As a result of ¹ H-NMR measurement, it was confirmed that a polymer was successfully synthesized in each case.
Are 5200, 2500 and 790, respectively, as a result of the measurement.
0, 3000.

Example 1-10 Using monomer (a3) as monomer (a) and acrylic acid as monomer (b), (a) / (b) = 20/80 ( (mol ratio) of polymer 1-10.

That is, in the same manner as in Example 1-1, a 2.5% SUS separable flask equipped with a reflux condenser and a stirrer was charged with a 35% aqueous solution of the monomer (a3).
0 g was added, and the temperature was raised to the boiling point under stirring. Then, while maintaining the reflux state under stirring, 144 g of an 80% aqueous solution of acrylic acid was added for 120 minutes, and 100 g of a 35% aqueous solution of the monomer (a3) was added for 70 minutes to obtain 35% hydrogen peroxide. 40 g of water for 70 minutes, 16 g of pure water
0%, 25% sodium persulfate aqueous solution 2
4 g over 60 minutes after the end of the dropping of the hydrogen peroxide solution,
Each was dropped substantially continuously at a uniform rate from a separate nozzle. After completion of all the dropwise additions, the reaction solution was
The polymerization reaction was completed by maintaining the boiling point for one minute.

After the completion of the reaction, 113 g of a 48% aqueous sodium hydroxide solution was added dropwise to neutralize 85%, and the solid content was 30.9%.
A 7% aqueous solution of polymer 1-10 was obtained. Water was removed from the aqueous solution to obtain a brown powder of polymer 1-10.

About the obtained brown powder, Example 1-1
As a result of ¹ H-NMR measurement, the monomer (a
It became clear that 3) was introduced into the polymer 1-10. As described above, it was confirmed that the water-soluble polymer 1-10 was synthesized. As a result of the measurement, Mw of the polymer 1-1 was 3,500.

(Example 1-11) Using monomer (a2) as monomer (a) and sodium maleate as monomer (b), (a) / (b) = 30/70 (Mol
(Ratio) of polymer 1-11.

That is, 165 g of a 45% aqueous solution of the monomer (a2) and maleic anhydride 6 were placed in a 2.5-liter SUS separable flask equipped with a reflux condenser and a stirrer.
9 g, 0.02 g of Mohr's salt and 58 g of a 48% aqueous sodium hydroxide solution were added, and the mixture was heated to the boiling point with stirring. Next, 86 g of 35% aqueous hydrogen peroxide was dropped substantially continuously at a uniform rate over 120 minutes while maintaining the reflux state under stirring. After the completion of the dropwise addition, the reaction solution was kept at the boiling point for 30 minutes to complete the polymerization.

After completion, a 48% aqueous sodium hydroxide solution 3
3 g was added dropwise to neutralize 85% to obtain a yellow-brown transparent aqueous solution of polymer 1-11 having a solid content of 44.7%. The water was removed from the aqueous solution to obtain a brown powder. The obtained brown powder was subjected to ¹ H-NMR measurement in the same manner as in Example 1-1, and as a result, it was found that the monomer (a2) had been introduced into the polymer 1-11. Also, as a result of the measurement, M
w900.

(Example 1-12) Using monomer (a4) as monomer (a) and sodium maleate as monomer (b), (a) / (b) = 20/80 (Mol
(Ratio) of polymer 1-12.

That is, in the same manner as in Example 1-11, a 2.5-liter SUS having a reflux condenser and a stirrer was used.
60 g of a 35% aqueous solution of monomer (a4), 118 g of maleic anhydride, 0.03 mol salt
g, 157 g of pure water, and 100 g of a 48% aqueous sodium hydroxide solution, and the mixture was heated to the boiling point with stirring. Then, under stirring, 129 g of 35% hydrogen peroxide solution was dropped substantially continuously at a uniform rate over 130 minutes while maintaining the reflux state. After the completion of the dropwise addition, the reaction solution was kept at the boiling point for 30 minutes to complete the polymerization. After the completion of the polymerization, a polymer 1-12 adjusted to a degree of neutralization of 85% was obtained. As a result of the measurement, Mw was 8000. Examples 1-1 to 1-
Table 1 collectively shows production examples of No. 5.

[0172]

[Table 1]

Examples of the production of Examples 1-6 to 1-9 are shown in Table 2 below.
Are shown together.

[0174]

[Table 2]

The abbreviations in the table are described as follows: 48% NaOH aq... 48% sodium hydroxide aqueous solution 80% Aa aq. % Acrylic acid aqueous solution 35% H ₂ O ₂ aq... 35% hydrogen peroxide aqueous solution 25% NaPSaq... 25% sodium persulfate aqueous solution.

As described above, the polymer of the present invention was obtained.
Further, it has been clarified that the polymer of the present invention can be easily and quantitatively obtained by the production method of the present invention.

(Comparative Reference Example 1) Here, the comparative polymer used in Example 2, ie, a conventional polymer such as a detergent builder,
Acrylic acid homopolymer and maleic acid, which are polycarboxylic acid polymers that are very effective as fiber treatment agents, etc.
An acrylic acid copolymer was synthesized.

Comparative Reference Example 1-13 A conventionally known sodium salt of an acrylic acid homopolymer was synthesized by a conventionally known method. That is, basically, in the same manner as in Example 1-1, first, 557 g of pure water was charged as an initial charge, and the temperature was raised to the boiling point under stirring. Then, while maintaining the reflux state under stirring, an 80% aqueous solution of acrylic acid 360 is used.
g of 483 g of a 48% aqueous sodium hydroxide solution over the same 180 minutes, and 53 g of a 15% aqueous sodium persulfate solution over a period of 180 minutes.
Over a period of 0 minutes, a further 600 g of pure water was dripped substantially continuously at a uniform rate from each of the nozzles over a period of 190 minutes. Further, the polymerization was completed by maintaining the boiling point reflux state for 30 minutes after the completion of all the dropwise additions.

After completion of the polymerization, pH and concentration were adjusted.
A comparative polymer 1-13 having a pH of 7.5 and a solid content of 45% was obtained. As a result of the measurement, Mw was 5000.

Comparative Reference Example 1-14 A conventionally known maleic acid / acrylic acid copolymer sodium salt (40/60 by mol ratio) was synthesized by a conventionally known method. That is,
Basically, in the same manner as in Example 1-1, first, 111 g of pure water and 196 g of maleic anhydride are charged as initial charges, and then, with stirring, 48% sodium 333
g, and then the temperature was raised to the boiling point. Then, 270 g of an 80% aqueous solution of acrylic acid was added to the mixture over a period of 120 minutes from the start of polymerization while maintaining the reflux state under stirring.
70% aqueous hydrogen peroxide over 50 minutes and 50% aqueous 15% sodium persulfate 5 g
Over a period of 80 minutes from 0 minute to 130 minutes, 178 g of pure water was also substantially continuously supplied from separate nozzles over a period of 80 minutes from 50 minutes to 130 minutes after the start of polymerization. It was dropped at a uniform rate. Further, the polymerization was completed by maintaining the boiling point reflux state for 30 minutes after the completion of all the dropwise additions.

After completion of the polymerization, pH and concentration were adjusted.
A comparative polymer 1-14 having a pH of 7.5 and a solid content of 45% was obtained. As a result of the measurement, Mw was 10,000.

(Example 2) In Example 2, a hydrogen peroxide stabilizer and a fiber treatment characterized in that the polymer obtained by the present invention contains the polymer which is another object of the present invention. In order to perform evaluation as an agent, the stabilizing ability of hydrogen peroxide was measured by the following method.

<Hydrogen peroxide stabilizing ability> A pinhole was made in a pig inside 250 ml of polyvin. 10 g of a 2.5% polymer aqueous solution was prepared. 100 g of a mixed aqueous solution of heavy metal ions of 0.225% Mohr salt, 0.0142% manganese sulfate, and 0.0039% copper sulfate was prepared. A 0.1% aqueous solution of magnesium sulfate was prepared. 48% sodium hydroxide and 35% hydrogen peroxide were prepared. Next, it was added to 250 ml polyvin in the following order. (I) Heavy metal ion mixed aqueous solution 1 ml (ii) 2.5% polymer aqueous solution 4 ml (iii) Pure water 80 g (iv) 0.1% magnesium sulfate aqueous solution 10 ml (v) 48% hydroxide Sodium: 2 ml (vi) 35% hydrogen peroxide solution: 3 ml After standing in a constant temperature bath at 50 ° C for 2 hours, the concentration of hydrogen peroxide in the solution was measured by a redox titration method. This value was defined as the hydrogen peroxide stabilizing ability.

(Examples 2-1 to 2-12) Example 1-1
About the polymers 1-1 to 1-12 obtained in 1-12, the hydrogen peroxide stabilizing ability was measured according to the above procedure. The results are shown in Table 3.

(Comparative Examples 2-13, 2-14) Similarly, conventionally known polymers 2-13, 2-1 obtained in Comparative Reference Examples.
For No. 4, the ability to stabilize hydrogen peroxide was measured according to the above procedure. The results are also shown in Table 3.

[0186]

[Table 3]

As is clear from Table 3, the copolymer of the present invention has an extremely high hydrogen peroxide stabilization as compared with a conventionally known polycarboxylic acid-based polymer which is effective as a fiber treatment agent and the like. Has ability. Therefore, these polymers of the present invention,
For example, it can be suitably used as a hydrogen peroxide stabilizer, a fiber treatment agent and the like.

[0188]

According to the present invention, the polymer has a specific water-soluble property which has an excellent ability to scavenge hardness components such as calcium ions and a dispersing action to inorganic particles, and has a scavenging ability to heavy metals. It is a polymer having specific characteristics, which exerts its effects for various specific applications including a hydrophilic polymer.

The polymer according to the present invention is a monomer having a carbon-carbon double bond, a hydroxyl group and an amino group, obtained by reacting an epoxybutene with a primary or secondary amine or ammonia. It can be easily produced by polymerizing the body.

Further, the polymer of the present invention, taking advantage of the characteristics of the polymer, includes, for example, a fiber treatment agent, a wood pulp bleaching aid, a hydrogen peroxide stabilizer, an inorganic pigment dispersant, a scale inhibitor, and a detergent composition. It can be suitably used as a product.

 ──────────────────────────────────────────────────続 き Continuing on the front page F-term (reference) 4H003 BA12 DA01 EA21 EB28 EB30 ED02 EE04 FA44 4J100 AA02Q AA03Q AB02Q AB07Q AE02Q AE04Q AJ01R AJ02R AJ08R AJ09R AK31R AK32R AL03Q CA02P01 BA01 BA03 BA01 BA01 JA15 JA57 4L033 AB01 AC15 CA19

Claims (7)

[Claims] An epoxybutene represented by the following general formula (1) having a carbon-carbon double bond, a hydroxyl group and an amino group obtained by reacting a primary or secondary amine or ammonia. A water-soluble polymer having a structure derived from a monomer in the range of 1 to 100 mol% and a weight average molecular weight of 500 to 200,000. Embedded image Here, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or an organic group. 2. A method structural unit represented by the following general formula (2) 1
-100 mol%, and the weight average molecular weight is 50
0 to 200,000 water-soluble polymer . Embedded image Here, R ⁵ and R ⁶ are each independently hydrogen or an organic group. 3. The compound according to claim 2, wherein R ⁵ and R ^{6 in the} general formula (2) are not hydrogen at the same time and are independently of each other a hydrogen carboxylic acid group or an acid thereof. An organic group having a salt of the group. An organic group having a sulfonic acid group or a salt of these acid groups. The water-soluble polymer according to claim 2, wherein the substituent is any one of an organic group having a hydroxyl group and an organic group having an amino group. 4. An epoxybutene represented by the following general formula (1) containing a carbon-carbon double bond, a hydroxyl group and an amino group obtained by reacting a primary or secondary amine or ammonia. A method for producing a polymer, comprising a step of polymerizing a monomer. Embedded image Here, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or an organic group. 5. The method for producing a polymer according to claim 4, wherein the monomer is a compound represented by the following general formula (3). Embedded image Here, R ⁵ and R ⁶ are each independently hydrogen or an organic group. 6. A hydrogen peroxide stabilizer comprising the polymer according to claim 1. 7. A fiber treating agent comprising the polymer according to claim 1.