JP2000239323A - Amino polymer compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound composition excellent solubility and stability, useful especially as a polymer additive by making the compound include an end group composed of an aromatic group-containing constituent unit as at least one end group and an amino group, etc., at the side chain of a repeating unit. SOLUTION: This compound comprises an end group composed of an aromatic group-containing constituent unit as at least one end group and one or more of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt at the side chain of a repeating unit. The compound contains preferably a repeating unit of the formula (R1 and R2 are each a 1-3C or bonded to form 3-6C oxygen-containing ring; R3 is H or the like; p is 1-5), etc. The compound is obtained by a preferable production method for (co)polymerizing a monomer containing a radical-polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent containing one or more aromatic groups in the molecule with a polymerization initiator containing a carboxy group, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel amino polymer compound and a method for producing the same.

[0002]

2. Description of the Related Art Amino high molecular compounds are widely used in fiber and paper treatment agents, cosmetics, water treatment agents, and the like. Many of these compounds exhibit high cationicity, and therefore have high tens of thousands to several millions. It has a molecular weight. However, these conventional amino polymer compounds may be restricted when used as various additives. That is, for example, in a composition that needs to have a low viscosity due to a high molecular weight, the amount added is limited due to an increase in viscosity. Further, it is difficult to dissolve in a solvent, and it is difficult to prepare a high concentration. Relatively low molecular weight products are commercially available among polyethyleneimines as amino polymer compounds, but primary amino groups,
Since it has a secondary amino group, there is a problem in its stability when used in combination with another composition which can react with them. Accordingly, there is a need for an amino polymer compound that solves these problems.

[0003]

An object of the present invention is to provide an amino polymer compound which is excellent in solubility and stability and is useful as various additives, especially as a polymer additive, and a method for producing the same.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned conventional problems. As a result, at least one terminal group of a polymer is composed of a structural unit having an aromatic group. It has been found that conventional problems can be solved by using an amino polymer compound having at least one of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt as a side group of the repeating unit. Further, the present inventors, in a method for producing an amino polymer compound,
Method of (co) polymerizing a monomer having a radical polymerizable ethylenically unsaturated group and an amino group in the presence of a specific chain transfer agent and / or with a specific polymerization initiator, terminal reactivity of a reactive polymer A tertiary ammonium salt in a desired ratio (including 100%) by reacting an acid with a tertiary amino group of a polymer obtained by these methods by using a group to introduce a desired terminal group structure; And a method for introducing a quaternary ammonium salt in a desired ratio (including 100%) by reacting a quaternizing agent with the quaternary agent, and completed the present invention. The present invention relates to amino polymer compounds represented by the following (1) to (22) and a method for producing the same.

(1) At least one terminal group is composed of a structural unit having an aromatic group, and at least one of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt is added to a side group of the repeating unit. An amino polymer compound comprising: (2) The following general formula (1)

Embedded image (Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 3 carbon atoms, or R ¹ and R ² may form a ring containing an oxygen atom having 3 to 6 carbon atoms. , R ³ represents a hydrogen atom or a methyl group, and p represents an integer of 1 to 5.)
A repeating unit represented by the following general formula (2)

Embedded image (Wherein, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, or R ⁴ and R ⁵ may form a ring containing an oxygen atom having 3 to 6 carbon atoms. , R ⁶ represents a hydrogen atom or a methyl group, q represents an integer of 1 to 5. X represents a halogen, R ¹¹ COO, NO ₃ , R ¹² OSO.
₃ or BF ₄ , wherein R ¹¹ and R ¹² each represent an alkyl group having 1 to 6 carbon atoms. ) Or the following general formula (3)

Embedded image (Wherein, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 3 carbon atoms, or R ⁷ and R ⁸ may form a ring containing an oxygen atom having 3 to 6 carbon atoms. , R ⁹ is an alkyl group having 1 to 22 carbon atoms, a fluorine-substituted alkyl group, an aralkyl group, or the following general formula (4)-(R ¹³ -Y) _s -R ¹⁴ (4) (where R ¹³ is a substituent Y represents -CONH-, -NHCO-, -NHCOO-, -OCON
H-, -NHCOS-, -SCONH-, -NHCONH-, -S-,
Represents either -O- or -CO-. Also, R
¹⁴ represents a carboxyl group, a hydroxyl group, a sulfonic acid group or an alkyl group having 1 to 22 carbon atoms which may have a salt thereof, a fluorine-substituted alkyl group or an aralkyl group,
s represents an integer of 1 to 5. R ¹⁰ represents a hydrogen atom or a methyl group. R represents an integer of 1 to 5, and X has the same meaning as described above. Also, R ⁷ , R
⁸ and R ⁹ may be the same or different. The amino polymer compound according to the above (1), wherein the amino polymer compound has at least one kind of a repeating unit represented by the formula (1), and at least one terminal group is a constituent unit having an aromatic group.

(3) The repeating unit is (1) to (3)
The amino polymer compound according to the above (1) or (2), wherein the repeating unit is represented by the following formula, and the composition ratio of each repeating unit is in the range of 0 to 100%. (4) The amino polymer compound according to any one of the above (1) to (3), wherein the molecular weight of the terminal group comprising the structural unit having an aromatic group is 500 or less. (5) The amino polymer compound according to any one of (1) to (4) above, wherein the number average molecular weight is 1,000 to 10,000. (6) The amino polymer compound according to any one of the above (1) to (5), wherein the pH of the aqueous solution of the amino polymer compound is 9 to 11.

(7) In the presence of a chain transfer agent having at least one aromatic group in a molecule, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is reacted with a polymerization initiator ( A method for producing an amino polymer compound, which is characterized in that it is copolymerized). (8) A method for producing an amino polymer compound, which comprises (co) polymerizing a monomer having a radically polymerizable ethylenically unsaturated group and an amino group with a polymerization initiator having an aromatic group. (9) In the presence of a chain transfer agent having at least one aromatic group in a molecule, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is converted into a polymerization initiator having an aromatic group. A method for producing an amino polymer compound, comprising: (10) reacting a reactive polymer having a reactive group on at least one of the terminal groups and having an amino group on a side group of the repeating unit with a compound having at least one aromatic group in the molecule; A method for producing an amino polymer compound, comprising introducing an aromatic group into a terminal.

(11) A monomer having a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent in which the reactive polymer has at least one reactive group in the molecule. The method for producing an amino polymer compound according to the above (10), which is a polymer obtained by (co) polymerization with a polymerization initiator. (12) The reactive polymer is a polymer obtained by (co) polymerizing a monomer having a radical polymerizable ethylenically unsaturated group and an amino group with a polymerization initiator having a reactive group. The method for producing the amino polymer compound according to (10). (13) The above (7), wherein the chain transfer agent having at least one aromatic group in the molecule is benzyl mercaptan or 2,4-diphenyl-4-methyl-1-pentene.
Or the method for producing an amino polymer compound according to (9). (14) The method for producing an amino polymer compound according to the above (8) or (9), wherein the polymerization initiator having an aromatic group is 1,1′-azobis (1-acetoxy-1-phenylethane).

(15) The above (7), (8), (9), (1) wherein the amino group of the monomer is a tertiary amino group, a tertiary ammonium salt and / or a quaternary ammonium salt.
The method for producing an amino polymer compound according to 1) or (12). (16) The above (7), (8), (9), or (1) wherein the monomer is N, N-dialkylaminoalkyl (meth) acrylamide, a salt thereof and / or a quaternary salt thereof.
1) The method for producing an amino polymer compound according to (12) or (15). (17) The tertiary amino group of the amino polymer compound according to any one of the above (7) to (16) is reacted with an acid to convert a part or all of the acid to a tertiary ammonium salt. For producing an amino polymer compound. (18) The method for producing an amino polymer compound according to the above (17), wherein the acid is an organic acid or an inorganic acid having 1 to 6 carbon atoms.

(19) A tertiary amino group and a quaternary amino group of the amino polymer compound according to any one of the above (7) to (16)
A method for producing an amino polymer compound, comprising reacting a grading agent and converting a part or all of the compound into a quaternary ammonium salt. (20) The method for producing an amino polymer compound according to the above (19), wherein the quaternizing agent is an alkyl halide having 1 to 22 carbon atoms, a halogenated fluorine-substituted alkyl, an aralkyl halide, or a sulfate. (21) The tertiary amino group of the amino polymer compound according to any one of the above (7) to (16) is reacted simultaneously or separately with an acid and a quaternizing agent to form one of the tertiary amino groups. A method for producing an amino polymer compound, wherein part or all of the compound is converted into a tertiary ammonium salt and a quaternary ammonium salt. (22) The above wherein the acid is an organic or inorganic acid having 1 to 6 carbon atoms and the quaternizing agent is an alkyl halide having 1 to 22 carbon atoms, a halogenated fluorinated alkyl, an aralkyl halide, or a sulfate. 21. The method for producing an amino polymer compound according to 21).

That is, the present invention is an amino polymer compound having excellent solubility and stability and useful as various additives, particularly as a polymer additive, and a method for producing the same.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the amino polymer compound of the present invention will be described. The amino polymer compound of the present invention,
Amino polymer compound having at least one terminal group comprising a structural unit having an aromatic group and having at least one of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt as a side group of the repeating unit Is not particularly limited as long as it has a tertiary amino group in the side group of the repeating unit.

Embedded image (Wherein, R ¹ , R ² , R ³ and p each have the same meaning as described above), and when the repeating unit has a tertiary ammonium salt in a side group, the following general formula: (2),

Embedded image (Wherein R ⁴ , R ⁵ , R ⁶ , q and X each have the same meaning as described above), and when the repeating unit has a quaternary ammonium salt in the side group, The following general formula (3)

Embedded image (Wherein, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , r and X each have the same meaning as described above). An amino polymer compound comprising a structural unit having a terminal group having an aromatic group is preferred. The above (1)
The repeating unit of (1) to (3) has at least one kind, and the composition ratio of each repeating unit can be in the range of 0 to 100%, and the structures of the repeating units may be different in the same molecule. However, they may have the same structure. Further, these may be random copolymerization or block polymerization.

Further, for the purpose of adjusting the cationic strength, other repeating units may be contained. Specific examples of the other repeating units include the following repeating units (5) to (10). Is shown. However, wherein R ¹⁵ represents a hydrogen atom or a methyl group, represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms R ^{1 6} are each independently.

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[0014]

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Embedded image These may be random copolymers or block copolymers.

The terminal group consisting of the structural unit having an aromatic group is not particularly limited. Examples of the aromatic group include a substituted or unsubstituted phenyl group or a naphthyl group,
Preferably, a structural unit having a substituted or unsubstituted phenyl group is preferred. The unit molecular weight is preferably 500 or less, and specifically, the following (11) to (2)
The structural unit shown in 2) is exemplified.

[0016]

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[0017]

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[0018]

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The amino polymer compound preferably has a number average molecular weight (hereinafter abbreviated as Mn) of 1,000 to 10,000. Here, Mn indicates a value determined by gel permeation chromatography (hereinafter abbreviated as GPC). The method of measuring the hydrogen ion concentration index (pH) is not particularly limited, but a method of measuring the pH using a commercially available pH measuring device is simple. A pH measuring device using a glass electrode pH meter is often used. The measurement is usually performed with an aqueous solution at normal pressure and 25 ° C.

Next, the method for producing the amino polymer compound of the present invention will be described. The method for producing the amino polymer compound of the present invention includes the following two methods (A) and (B). First, the method (A) is a method of (co) polymerizing a monomer having a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a specific chain transfer agent and / or with a specific polymerization initiator. The above monomer has an amino group having at least one of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt. At this time, when it is desired to introduce a tertiary amino group, a tertiary ammonium salt or a quaternary ammonium salt into the side group of the repeating unit of the amino polymer compound, a radical polymerizable ethylenically unsaturated group and It is only necessary to copolymerize a monomer having an amino group with a desired composition ratio.

In the method (A), a combination of a chain transfer agent and a polymerization initiator is used to form (A-1), (A-2) and (A-3).
And three methods. That is, in the method (A-1), a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is polymerized in the presence of a chain transfer agent having at least one aromatic group in the molecule. Initiator (co)
The method (A-2) is a method of (co) polymerizing a monomer having a radically polymerizable ethylenically unsaturated group and an amino group with a polymerization initiator having an aromatic group. In addition, the method (A-3) includes a method of preparing a monomer having a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent having at least one aromatic group in a molecule. And (co) polymerization with a polymerization initiator having an aromatic group.

The method (B) is a method of introducing a desired terminal group structure using a terminal reactive group of a reactive polymer having an amino group in a side group of a repeating unit. Is a combination of terminal reactive groups (B-1) and (B-
There are two methods 2). That is, (B-1)
The method comprises a reactive polymer having one end group consisting of a constituent unit having a reactive group and having an amino group in a side group of the repeating unit, and a compound having at least one aromatic group in the molecule. In the method (B-2), a reactive polymer comprising a structural unit having a reactive group at both terminal groups and having an amino group in a side group of the repeating unit, and an aromatic group are used. This is a method of reacting a compound having at least one compound in a molecule.

The reactive polymer used in the methods (B-1) and (B-2) is not particularly limited, but can be obtained, for example, by the following method. First, the reactive polymer shown in the production method (B-1) includes two of (B-1-1) and (B-1-2).
It can be synthesized by the following methods. In the method (B-1-1), a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is added to a monomer having an amino group in the presence of a chain transfer agent having at least one reactive group in a molecule. (Co) polymerization method,
The method (B-1-2) is a method of (co) polymerizing a monomer having a radically polymerizable ethylenically unsaturated group and an amino group with a polymerization initiator having at least one reactive group in a molecule. How to

Next, the reactive polymer shown in the production method (B-2) can be synthesized by the method (B-2-1). That is, in the method (B-2-1), a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is prepared in the presence of a chain transfer agent having at least one reactive group in a molecule. ,
This is a method of (co) polymerizing with a polymerization initiator having a reactive group.

Here, (B-1-1), (B-1-
The monomers used in the methods 2) and (B-2-1) have an amino group having at least one of a tertiary amino group, a tertiary ammonium salt and a quaternary ammonium salt. At this time, when it is desired to introduce a tertiary amino group, a tertiary ammonium salt or a quaternary ammonium salt into the side group of the repeating unit of the reactive polymer, a radical polymerizable ethylenically unsaturated group and It is only necessary to copolymerize a monomer having an amino group with a desired composition ratio.

The tertiary ammonium salt and / or quaternary ammonium salt can be introduced into the polymer by the following method (C). That is, the method of (C)
A method in which a tertiary amino group is introduced into the side group of the repeating unit by the method (A) or (B) to add an acid to convert the tertiary amino group into a tertiary ammonium salt, and / or A method of reacting a tertiary amino group with a quaternizing agent to form a quaternary ammonium salt, wherein the tertiary amino group can be reacted simultaneously with or separately from the acid and the quaternizing agent. Tertiary ammonium salts and / or quaternary ammonium salts
The ratio of the quaternary ammonium salt can be adjusted by the addition amount of the acid and the quaternizing agent, respectively.

Further, (A-1), (A-2), (A-
3), (B-1-1), (B-1-2), (B-2-
When a polymer is obtained by each method of 1), another monomer having a radically polymerizable ethylenically unsaturated group may be copolymerized for the purpose of adjusting cationic strength and the like.

Hereinafter, each of the manufacturing methods will be described in more detail. First, a monomer having a radical polymerizable ethylenically unsaturated group and a tertiary amino group is represented by the following general formula (2)
3)

Embedded image It is represented by Here, R ³ has the same meaning as described above,
It is particularly preferable that both ¹ and R ² are a methyl group having 1 carbon atom and p is 3.

Next, a monomer having a radical polymerizable ethylenically unsaturated group and a tertiary ammonium salt is represented by the following general formula (24)

Embedded image It is represented by Here, R ⁶ and X represent the same meaning as described above, and it is particularly preferable that both R ⁴ and R ⁵ are a methyl group having 1 carbon atom and q is 3.

The monomer having a radically polymerizable ethylenically unsaturated group and a quaternary ammonium salt is represented by the following general formula (25)

Embedded image It is represented by Here, R ⁹ , R ¹⁰ and X have the same meaning as described above, and R ⁷ and R ⁸ are both a methyl group having 1 carbon atom, r
Is particularly preferably 3.

As the monomers (23) to (25), the same compound may be used, or a plurality of types may be used in a mixture at an arbitrary ratio. In the method based on the copolymerization of the method (A), the ratio of the monomers (23) to (25) depends on the polymerization reactivity of the monomers. It must be prepared so that the composition ratio can be obtained in the desired ratio. However, when the method (A) and the method (C) are combined, the tertiary amino group of the repeating unit side group of the amino polymer compound is adjusted by adjusting the addition amount of the acid and / or the quaternizing agent. The ratio of groups, tertiary ammonium salts and quaternary ammonium salts can be adjusted.

The chain transfer agent having at least one aromatic group in the molecule is not particularly limited as long as it has the characteristic group. Examples of the aromatic group include a substituted or unsubstituted phenyl group or a naphthyl group, and a compound having a substituted or unsubstituted phenyl group is preferable. For example, benzyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene and the like can be mentioned.
These chain transfer agents can be used alone or in combination of two or more kinds at an arbitrary ratio.

The polymerization initiator having an aromatic group is not particularly limited as long as it has the characteristic group. Examples of the aromatic group include a substituted or unsubstituted phenyl group and a naphthyl group, and a structural unit having a substituted or unsubstituted phenyl group is preferable. For example, 1,
1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-
(Hydroxyphenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N-
(2-phenylmethyl) -propionamidine] dihydrochloride and the like. These polymerization initiators can be used alone or in combination of two or more at an arbitrary ratio.

As the polymerization initiator used in the production method (A-1), a compound containing no aromatic group can be used as long as it is used as a general radical polymerization reaction initiator. 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-
Azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1
-Cyano-1-methylethyl) azo] formamide,
2,2′-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride,
2'-azobis [N- (2-hydroxyethyl) -2-
Methylpropionamidine] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2-
(2-imidazolin-2-yl) propane] dihydrochloride,
2,2′-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (3 4,
5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-
Yl) propane] dihydrochloride, 2,2'-azobis {2-
[1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane｝ dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane],
2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N-
[1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2′-azobis {2-methyl-N-
(2-hydroxyethyl) -propionamide {, 2,
2′-azobis (2-methylpropionamide) dihydrate, 2,2′-azobis (2,4,4-trimethylpentane), dimethyl 2,2′-azobis (2-methylpropionate), , 4'-Azobis (4-cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl) propionnitrile], 2,2'-azobis [N-
(2-carboxyethyl) -2-methylpropionamidine] and the like, and these can be used alone or in combination of two or more.

In the production method (A-2), the polymerization may be carried out in the presence of a chain transfer agent for the purpose of controlling the molecular weight.
As the chain transfer agent used at this time, a compound containing no aromatic group can be used as long as it is used as a molecular weight regulator for general radical polymerization. For example, thioglycerol, 2-mercapto Ethanol, t
-Butyl mercaptan, dimethylaminoethyl mercaptan and its hydrochloride, cyclohexyl mercaptan,
Thioglycolic acid, 3-mercaptopropionic acid, esters thereof and the like can be mentioned. These chain transfer agents can be used alone or in combination of two or more.

The reaction used in the polymer reaction shown in the production methods (B-1) and (B-2) is not particularly limited, but a reaction between a hydroxyl group and an isocyanate group, a reaction between a hydroxyl group and an epoxy group, A preferred example is a reaction between a secondary amino group and a carboxyl group. The reaction between a hydroxyl group and an isocyanate group is particularly preferred because the reaction is easy. At this time, examples of the terminal reactive group of the reactive polymer include a hydroxyl group, a primary amino group, a secondary amino group, and a carboxyl group.

For these polymer reactions, conditions suitable for each reaction can be freely selected from conventionally known methods. It is preferable to carry out the reaction in a solution for reasons such as simplicity of the reaction operation and smoother reaction. A reaction solvent which is substantially inert to the raw materials during the reaction and which can dissolve or disperse these raw materials can be appropriately selected from conventionally known ones. For example, ethyl acetate,
Esters such as butyl acetate and amyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane;
-Dimethylformamide, N-methylformamide,
Amides such as N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, pyrrolidones such as 1-methyl-2-pyrrolidone, 2-pyrrolidone, ε-caprolactam, benzene , Toluene, aromatic hydrocarbons such as xylene, n-pentane, n-hexane, aliphatic hydrocarbons such as cyclohexane, dichloromethane, chloroform,
And halogenated hydrocarbons such as carbon tetrachloride.
These solvents may be used as a mixture of two or more kinds at an arbitrary ratio.

The reactive group of the compound having at least one aromatic group in the molecule shown in the production methods (B-1) and (B-2) depends on the reactive group of the reactive polymer reacting therewith. To be elected. When the reactive group on the polymer side is a hydroxyl group, examples thereof include an isocyanate group. Examples of the compound include benzyl isocyanate. The reactive group on the polymer side is a primary amino group or a secondary amino group. In such a case, an isocyanate group or an epoxy group can be used, and examples of the compound include benzyl isocyanate and 1,2-epoxy-3-phenoxypropane. When the reactive group on the polymer side is a carboxyl group, the first group is used. And a benzylamine.

The chain transfer agent having at least one reactive group in the molecule is not particularly limited as long as it has reactivity such as a hydroxyl group, a primary amino group and a carboxyl group and can be used as a chain transfer agent. For example, thioglycerol,
2-mercaptoethanol, thioglycolic acid, 3-mercaptopropionic acid, and the like.

The polymerization initiator having at least one reactive group in the molecule is not particularly limited as long as it has reactivity such as a hydroxyl group, a primary amino group and a carboxyl group and can be used as a polymerization initiator. For example, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis [N-
(2-carboxyethyl) -2-methylpropionamidine], 2,2′-azobis {2-methyl-N- [1,
1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- (2-hydroxybutyl) -propionamide}, 2,2′-azobis {2- Methyl-N- (2-hydroxyethyl) -propionamide {2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2, 2 '
-Azobis (2-methylpropionamidine) dihydrochloride and the like.

The other monomer having a radically polymerizable ethylenically unsaturated group is not particularly limited as long as it can be copolymerized with the aforementioned monomer having a radically polymerizable ethylenically unsaturated group and an amino group. Specifically, the following (26)-
The monomer represented by (31) is exemplified. However, R ¹⁵
And R ¹⁶ have the same meaning as described above.

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[0042]

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Embedded image These monomers (26) to (31) may use the same compound or may mix and use a plurality of kinds at an arbitrary ratio.

In the above method (C), an organic acid or an inorganic acid is used as an acid used to convert a tertiary amino group into a tertiary ammonium salt. As the organic acid, for example,
Acetic acid, propionic acid, lactic acid and the like can be mentioned, and inorganic acids include, for example, hydrochloric acid, sulfuric acid, nitric acid and the like. Known conditions can be used for the reaction, and these acids may be used as a mixture of two or more kinds at an arbitrary ratio.

In the method (C), the quaternary amino group used for converting a tertiary amino group into a quaternary ammonium salt is used.
As the grading agent, alkyl halides having 1 to 22 carbon atoms, halogenated fluorine-substituted alkyls, aralkyl halides, sulfates, sodium chloroacetate, propane sultone, and the like can be used. Can be.

Examples of the alkyl halide include methyl chloride, 1-chloropropane, 1-chlorooctane,
1-chlorododecane and the like. Examples of the halogenated fluorine-substituted alkyl include 2- (perfluorobutyl) ethyl iodide, 1H, 1H, 5H-octafluoropentyl iodide and the like. Examples of the aralkyl halide include benzyl chloride and 3-phenylpropyl chloride. Examples of the sulfate include dimethyl sulfate and diethyl sulfate. These quaternizing agents may use the same compound, or may mix and use a plurality of kinds at an arbitrary ratio. In the case where quaternizing agents react with each other, they may be reacted in multiple stages without mixing.

Production methods (A-1), (A-2), (A-
3), (B-1-1), (B-1-2), (B-2-
The polymerization method of the polymer shown in 1) can be carried out by a known radical polymerization method. That is, polymerization is carried out by blending a monomer selected under the conditions described above, a polymerization initiator and, if necessary, a chain transfer agent.

The amount of the polymerization initiator to be added is determined by the polymerizability of the monomer, the amount of the chain transfer agent, and the molecular weight of the polymer. preferable. Further, for the purpose of lowering the concentration of the reaction residue and the like, the same or different polymerization initiators may be additionally added during the reaction.

The reaction can be carried out at normal pressure. In addition, since the reaction is a radical reaction, the reaction is preferably performed in an inert atmosphere (for example, nitrogen, argon, or the like). The reaction temperature is not particularly limited, but may be any temperature at which the polymerization initiator is decomposed, and is usually preferably in the range of 40 to 180 ° C., and may be a method in which the temperature is increased stepwise from a low temperature to a high temperature. When the reaction temperature is lower than 40 ° C., a long time is required for the reaction. When the reaction temperature is higher than 180 ° C., the solvent which can be used is limited. Although the reaction time is not particularly limited, it can be usually performed in the range of 1 to 36 hours.

The polymerization reaction is preferably carried out in a solution for reasons such as simplicity of operation and smoother reaction. The polymerization solvent is substantially inert to the raw materials during the polymerization reaction, and those capable of dissolving or dispersing these raw materials can be appropriately selected from conventionally known ones and used. In addition to the solvents that can be used, methanol, ethanol, isopropanol, butanol,
Alcohols such as 1,2,6-hexanetriol, glycerin, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, butylene glycol, trimethylene glycol, triethylene glycol, hexylene glycol, diethylene glycol, Glycols such as dipropylene glycol and polyethylene glycol, 2-methoxyethanol, 2-
Ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-propoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, 1-methoxy-2-propanol,
Glycol ethers such as 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, water and the like are exemplified. These solvents may be used as a mixture of two or more kinds at an arbitrary ratio. However, the production methods (B-1) and (B-
When the reactive polymer used in 2) is synthesized, when a solvent that inhibits the subsequent polymer reaction is used for the polymerization, the solvent may be replaced with a solvent that does not inhibit the polymer reaction after the polymerization. If there are no factors that hinder the polymerization, it is possible to carry out the polymerization reaction in a solvent that does not inhibit the polymer reaction, and it is possible to carry out the polymer reaction as it is after the polymerization reaction without solvent replacement, so that it is a simple production method Is preferred.

The mixing ratio of the solvent is not particularly limited, and an appropriate ratio may be selected depending on the viscosity and solubility of the obtained polymer and raw materials. Usually 1 to 95
It is about 30% by weight, but preferably 30 to 85% by weight from the viewpoint of the operability of the reaction and the ease of handling during purification of the product.

The method for adjusting the molecular weight is not particularly limited, but a method for adjusting the amount of the polymerization initiator or the amount of the chain transfer agent can be used. It is advisable to add a large amount to lower the molecular weight, and to add a small amount to increase the molecular weight. The addition amount of the chain transfer agent is determined by the polymerizability of the raw material monomers, the molecular weight of the polymer, and the addition amount of the polymerization initiator.
Usually, the range of 0.1 to 60% by weight based on the monomer is preferable. The obtained polymer can be purified by a known method such as solvent evaporation, column chromatography, reprecipitation, or dialysis, if necessary. Depending on the use of the additive, it may be used as a reaction solvent mixture, or may be used after concentration or dilution to adjust the concentration.

[0052]

The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited to these Examples. Example 1 15.0 g of N, N-dimethylaminopropylacrylamide was placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
2,4-diphenyl-4-methyl-1-pentene was added to 0.1.
After charging 57 g and 20.0 g of n-butyl acetate, 20.0 g of n-butyl acetate in which 0.44 g of dimethyl 2,2′-azobis (2-methylpropionate) was dissolved was added, and the mixture was stirred under a nitrogen atmosphere. The temperature was raised to 95 ° C. for 4 hours, and the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 57 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 13.0 g.
Was obtained. As a result of GPC measurement of the product, it was confirmed that the weight average molecular weight was 9400 and the number average molecular weight was 5100 in terms of polyethylene glycol. Also, ¹³ C
From the analysis results of -NMR and ¹ H-NMR, it was found that the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was about 2.1: 100. Also,
This solid is dissolved in purified water, and p
When H was measured, it was 10.4.

Example 2 The reaction and purification were carried out in the same manner as in Example 1 except that the amount of 2,4-diphenyl-4-methyl-1-pentene was changed to 1.13 g. The yield after drying was 12.2 g. As a result of GPC measurement of the product, the weight average molecular weight was 4 in terms of polyethylene glycol.
It was confirmed that the number average molecular weight was 600 and the number average molecular weight was 2700. From the results of ¹³ C-NMR and ¹ H-NMR analysis, it was found that the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was about 4.1: 100. Further, this solid content is dissolved in purified water, and 40 w
When the pH of the t% aqueous solution was measured, it was 10.4.

Example 3 15.0 g of N, N-dimethylaminopropyl methacrylamide and 2,4-diphenyl-4 were placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. -Methyl-1-
After charging 0.83 g of pentene and 20.0 g of n-butyl acetate, 20.0 g of n-butyl acetate in which 0.41 g of dimethyl 2,2′-azobis (2-methylpropionate) was dissolved was added, and nitrogen was added. The temperature was raised while stirring under an atmosphere, and the temperature was maintained at 80 ° C. for 4 hours, and then the temperature was raised to 95 ° C., and the reaction was continued for 2 hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 12.9 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 7000 and the number average molecular weight was 40 in terms of polyethylene glycol.
00 was confirmed. In addition, ¹³ C-NMR and ¹ H
-NMR analysis results show that aromatic ring (benzene ring) and N, N
The ratio of -dimethylaminopropylamide structure is about 3.
It turned out to be 0: 100. This solid was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured to be 10.3.

Example 4 15.0 g of N, N-dimethylaminopropylacrylamide and 2,4-diphenyl-4-N were placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. After charging 1.13 g of methyl-1-pentene and 20.0 g of n-butyl acetate, 1,1′-azobis (cyclohexane-1-yl) was added.
After adding 20.0 g of n-butyl acetate in which 1.79 g of (carbonitrile) was dissolved, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C. for 4 hours.
The reaction was continued for hours. After cooling to room temperature, about 57 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 13.1 g of a solid. As a result of GPC measurement of the product, it was confirmed that the weight average molecular weight was 4900 and the number average molecular weight was 2600 in terms of polyethylene glycol. In addition, ¹³ C-NMR and
^{From the} result of ¹ H-NMR analysis, the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was about 4.1: 100. Further, when this solid was dissolved in purified water and the pH of a 40 wt% aqueous solution was measured,
10.5.

Example 5 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product of Example 4, 10.0 g of methyl ethyl ketone and 10.0 g of methanol. Was dissolved in a mixed solution of The solution is stirred while benzyl chloride 1.6
2 g was gradually added, and the temperature was raised to 80 ° C. and reacted for 8 hours.
It was cooled to room temperature to obtain about 27 g of a pale yellow transparent solution. The solvent was distilled off under reduced pressure, dissolved in methanol, and reprecipitated repeatedly with a methanol-acetone system, and the precipitate was dried.
0 g of solid was obtained. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 5000 and the number average molecular weight was 2700 in terms of polyethylene glycol. Also, ¹³ C-NM
From the analysis results of R and ¹ H-NMR, the ratio of the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure and dimethylbenzylaminopropylamide chloride structure excluding those derived from benzyl chloride was about 4.1: 61: It turned out to be 39. Further, this solid content is dissolved in purified water,
When the pH of the 0 wt% aqueous solution was measured, it was 10.3.

Example 6 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product of Example 4, and dissolved in 15.0 g of methyl ethyl ketone. While stirring this solution, 2.5 g of 1-chlorododecane was gradually added, and
C. and allowed to react for 8 hours.
g of a pale yellow clear solution was obtained. The solvent was distilled off under reduced pressure, dissolved in acetone, and reprecipitated repeatedly with an acetone-hexane system, and the precipitate was dried to obtain 4.2 g of a solid content. GP
As a result of the C measurement, it was confirmed that the weight average molecular weight was 5000 and the number average molecular weight was 2600 in terms of polyethylene glycol. From the analysis results of ¹³ C-NMR and ¹ H-NMR, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure and dodecyldimethylaminopropylamide structure was about 4.1: 85: 15. It turned out to be. This solid was dissolved in purified water, and the pH of a 40 wt% aqueous solution was measured.
It was 3.

(Example 7) In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 2,4-diphenyl-4-methyl-4-acrylamide were added. After charging 1.20 g of methyl-1-pentene and 70.0 g of methanol, 1.65 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] was added, and the mixture was added with a nitrogen atmosphere. The temperature was raised while stirring under the
After keeping for a time, it was cooled to room temperature. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 13.7 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 5900 in terms of polyethylene glycol,
It was confirmed that the number average molecular weight was 2,200. Also,
^{From the} results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was about 5.0: 100. The solid content was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured to be 10.6.

Example 8 14.0 g of N, N-dimethylaminopropylacrylamide and 75 wt% of trimethylaminopropylacrylamide chloride were placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 1.3 g of an aqueous solution, 0.90 g of 2,4-diphenyl-4-methyl-1-pentene, N, N-
After 20.0 g of dimethylformamide was charged, 20.0 g of N, N-dimethylformamide in which 1.09 g of dimethyl-2,2'-azobis (2-methylpropionate) was dissolved, and the mixture was stirred under a nitrogen atmosphere. The temperature was raised to 95 ° C. for 4 hours, and then the temperature was raised to 95 ° C., and the reaction was continued for another 2 hours. After cooling to room temperature, about 57 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 12.3 g of a solid. As a result of the GPC measurement,
The weight average molecular weight is 420 in terms of polyethylene glycol.
0, it was confirmed that the number average molecular weight was 2,800. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of the aromatic ring (benzene ring), the N, N-dimethylaminopropylamide structure to the trimethylaminopropylamide chloride structure was about 4.1: 93: 7. It turned out to be zero. This solid was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured to be 10.3.

Example 9 12.7 g of N, N-dimethylaminopropylacrylamide and 75 wt% of trimethylaminopropylacrylamide chloride were placed in a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 1.30 g of aqueous solution, 1.35 g of acryloylmorpholine, 0.11 g of 2,4-diphenyl-4-methyl-1-pentene, 1,3-dimethyl-2
-After charging 20.0 g of imidazolidinone, dimethyl 2,2'-azobis (2-methylpropionate)
After adding 20.0 g of 1,3-dimethyl-2-imidazolidinone in which 1.00 g was dissolved, the temperature was increased while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C. for 4 hours, and then the temperature was increased to 95 ° C. The reaction was continued for another 2 hours. After cooling to room temperature, about 56g
Was obtained as a pale yellow clear solution. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 12.0 g of a solid. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 6700 and the number average molecular weight was 3800 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure, trimethylaminopropylamide chloride structure to morpholino group was about 4.0: 86. : 5.0:
It turned out to be 9.0. This solid was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured to be 10.2.

Example 10 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 14.0 g of N, N-dimethylaminopropylacrylamide and 75 wt% of trimethylaminopropylacrylamide chloride. 1.3 g of aqueous solution, 0.40 g of benzyl mercaptan, and 2 g of N, N-dimethylformamide
After charging 0.0 g, 20.0 g of N, N-dimethylformamide in which 1.79 g of 1,1′-azobis (cyclohexane-1-carbonitrile) was dissolved, and the mixture was heated while stirring under a nitrogen atmosphere. After maintaining at 80 ° C. for 4 hours, the temperature was raised to 95 ° C. and the reaction was further performed for 2 hours. After cooling to room temperature, about 57 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in methyl ethyl ketone, and reprecipitation was repeated with a methyl ethyl ketone-hexane system, and the precipitate was dried to obtain 13.0 g of a solid. As a result of GPC measurement, the weight average molecular weight was 6500 and the number average molecular weight was 3000 in terms of polyethylene glycol.
Was confirmed. In addition, ¹³ C-NMR and ¹ H-N
According to the result of MR analysis, the ratio of the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure and trimethylaminopropylamide chloride structure was about 3.5: 93: 7.0.
It turned out to be. Further, this solid was dissolved in purified water, and the pH of a 40 wt% aqueous solution was measured.
0.3.

Example 11 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 0.41 g of 2-mercaptoethanol were placed. ,
After charging 60.0 g of n-butyl acetate, 1,1′-
Azobis (1-acetoxy-1-phenylethane) 2.
And added with stirring under a nitrogen atmosphere.
After maintaining at 0 ° C. for 4 hours, the temperature was raised to 95 ° C. and the reaction was further performed for 2 hours. After cooling to room temperature, about 56 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 12.1 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 7000 and the number average molecular weight was 3000 in terms of polyethylene glycol. In addition, ¹³ C-NMR and ¹ H-NM
From the analysis results of R, the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was 4.1: 100.
Met. Also, this solid content was dissolved in purified water,
When the pH of the wt% aqueous solution was measured, it was 10.6.

Example 12 15.0 g of N, N-dimethylaminopropylacrylamide and 0.40 g of cyclohexylmercaptan were placed in a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser.
g, 60.0 g of n-butyl acetate, and
2.00 g of 1'-azobis (1-acetoxy-1-phenylethane) was added, and the mixture was heated with stirring under a nitrogen atmosphere, kept at 80 ° C. for 4 hours, and then heated to 95 ° C. for another 2 hours. Reacted. After cooling to room temperature, about 77 g of a pale yellow solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 12.5 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 6000 and the number average molecular weight was 250 in terms of polyethylene glycol.
It was confirmed to be 0. In addition, ¹³ C-NMR and ¹ H-
From the results of NMR analysis, the aromatic ring (benzene ring) and N, N-
The ratio of the dimethylaminopropylamide structure is about 4.3:
It was 100. The solid content was dissolved in purified water, and the pH of a 40 wt% aqueous solution was measured.
Met.

Example 13 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product of Example 12, and 10.0 g of methyl ethyl ketone and 10.0 g of methanol were added. Was dissolved in a mixed solution of While stirring this solution, 1.80 g of methyl iodide was gradually added thereto, and the temperature was raised to 40 ° C. and reacted for 8 hours. After cooling to room temperature, about 26 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the residue was dissolved in methanol, reprecipitation was repeated with a methanol-acetone system, and the precipitate was dried to obtain 5.1 g of a solid content. As a result of the GPC measurement,
The weight average molecular weight is 630 in terms of polyethylene glycol.
0, the number average molecular weight was confirmed to be 2,700. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure and trimethylaminopropylamide iodide structure was about 4.3: 61: 39. It turned out to be. This solid was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured to be 10.4.

Example 14 A 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 14.0 g of N, N-dimethylaminopropylacrylamide and 75 wt% of trimethylaminopropylacrylamide chloride. After charging 1.3 g of an aqueous solution, 0.40 g of cyclohexyl mercaptan and 60.0 g of N, N-dimethylformamide, 1,1′-azobis (1-
(2.00 g of acetoxy-1-phenylethane) was added thereto and dissolved by stirring. The temperature is increased by 80 with stirring under a nitrogen atmosphere.
After keeping the temperature at 95 ° C for 4 hours, the temperature was raised to 95 ° C, and the reaction was carried out for another 2 hours. After cooling to room temperature, about 77 g of a pale yellow solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 12.8 g of a solid content. G
As a result of PC measurement, it was confirmed that the weight average molecular weight was 6100 and the number average molecular weight was 2500 in terms of polyethylene glycol. From the analysis results of ¹³ C-NMR and ¹ H-NMR, the ratio of the aromatic ring (benzene ring), the N, N-dimethylaminopropylamide structure and the trimethylaminopropylamide structure was about 4.3: 94: 6. I found it. Also, this solid content was dissolved in purified water,
The pH of the wt% aqueous solution was measured and found to be 10.5.

Example 15 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 2,4-diphenyl-4-methyl-4-acrylamide were added. After charging 1.13 g of methyl-1-pentene and 20.0 g of n-butyl acetate, 1,1′-azobis (1-acetoxy-1-
After adding 40.0 g of n-butyl acetate in which 2.02 g of (phenylethane) was dissolved, the temperature was raised while stirring under a nitrogen atmosphere and kept at 80 ° C. for 4 hours, and then raised to 95 ° C. for another 2 hours. Reacted. After cooling to room temperature, about 76 g of a pale yellow transparent solution was obtained. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 13.5 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 5800 and the number average molecular weight was 25 in terms of polyethylene glycol.
00 was confirmed. In addition, ¹³ C-NMR and ¹ H
-NMR analysis results show that aromatic ring (benzene ring) and N, N
-Ratio of dimethylaminopropylamide structure is 7.9:
It turned out to be 100. This solid was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured to be 10.6.

Example 16 A 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 5.0 g of the product of Example 15 and dissolved in 15.0 g of methyl ethyl ketone. While stirring this solution, 2.5 g of 1-chlorododecane was gradually added, and
The temperature was raised to ° C. and the reaction was performed for 8 hours. After cooling to room temperature, about 2
2 g of a pale yellow clear solution were obtained. The solvent was distilled off under reduced pressure, dissolved in acetone, and reprecipitated repeatedly with an acetone-hexane system, and the precipitate was dried to obtain 4.5 g of a solid content. G
As a result of PC measurement, it was confirmed that the weight average molecular weight was 5,800 and the number average molecular weight was 2,600 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of the aromatic ring (benzene ring), N, N-dimethylaminopropylamide structure and dodecyldimethylaminopropylamide structure was about 7.9: 84: 16. It turned out to be. The solid content was dissolved in purified water, and the pH of a 40 wt% aqueous solution was measured.
Met.

Example 17 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 2,4-diphenyl-4-methyl-4-acrylamide were added. After charging 1.20 g of methyl-1-pentene and 70.0 g of methanol, 1.65 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] was added, and the mixture was added with a nitrogen atmosphere. The temperature is raised while stirring under the reflux temperature.
After keeping for 2 hours, it was cooled to room temperature. The solvent was distilled off under reduced pressure, 40 g of methyl ethyl ketone was added, the solvent was distilled off again, and the remaining highly viscous liquid was washed with 40 g of methyl ethyl ketone.
Was dissolved. To this solution was added benzyl isocyanate 2.4.
0 g was gradually added, and after the whole amount was added, the temperature was raised and maintained at 80 ° C. for 6 hours, and then cooled to room temperature to obtain about 60 g of a yellow transparent solution. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 14.5 g of a solid content. G
As a result of PC measurement, it was confirmed that the weight average molecular weight was 6000 and the number average molecular weight was 2100 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analysis, the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was about 3.2: 100. Also, this solid content was dissolved in purified water, and 40 wt.
% Of the aqueous solution was 10.6.

Example 18 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide, 0.40 g of cyclohexylmercaptan,
After charging 70.0 g of methanol, 1.65 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] was added, and the mixture was heated to reflux while stirring under a nitrogen atmosphere. After maintaining at the temperature for 12 hours, it was cooled to room temperature. The solvent was distilled off under reduced pressure, 40 g of methyl ethyl ketone was added, the solvent was again distilled off, and the remaining highly viscous liquid was dissolved in 40 g of methyl ethyl ketone. 1.8 g of 1,2-epoxy-3-phenoxypropane was added to this solution.
Was gradually added, and after the whole amount was added, the temperature was raised and maintained at 80 ° C. for 6 hours, and then cooled to room temperature to obtain about 60 g of a yellow transparent solution.
The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and re-precipitation was repeated with acetone-hexane,
The precipitate was dried to give 13.2 g of solids. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 6,300 and the number average molecular weight was 2,700 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analysis, it was found that the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was about 4.3: 100. Further, this solid content is dissolved in purified water,
When the pH of the 0 wt% aqueous solution was measured, it was 10.6.

Example 19 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 0.41 g of 2-mercaptoethanol were placed. ,
After charging 60.0 g of n-butyl acetate, 1,1′-
Azobis (1-acetoxy-1-phenylethane) 2.
And added with stirring under a nitrogen atmosphere.
After maintaining at 0 ° C. for 4 hours, the temperature was raised to 95 ° C. and the reaction was further performed for 2 hours. After cooling to room temperature, 2.40 g of benzyl isocyanate was gradually added to this solution, and after the whole amount was added, the temperature was raised and maintained at 80 ° C. for 6 hours, followed by cooling to room temperature to obtain about 79 g of a yellow transparent solution. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 13.0 g of a solid content. As a result of GPC measurement, the weight average molecular weight was 7200 and the number average molecular weight was 3 in terms of polyethylene glycol.
000. Also, ¹³ C-NMR and ¹
From the results of H-NMR analysis, the aromatic ring (benzene ring) and N,
The ratio of the N-dimethylaminopropylamide structure is about 7.
It turned out to be 7: 100. This solid was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured to be 10.6.

Example 20 In a 100 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide and 0.41 g of 2-mercaptoethanol were placed. ,
After charging 20.0 g of n-butyl acetate, dimethyl
2,2′-azobis (2-methylpropionate) 1.
After adding 20.0 g of n-butyl acetate in which 30 g was dissolved, the temperature was raised while stirring under a nitrogen atmosphere, and the temperature was maintained at 80 ° C. for 4 hours. Then, the temperature was raised to 95 ° C., and the reaction was further continued for 2 hours. After cooling to room temperature, benzyl isocyanate was added to the solution.
40 g was gradually added, and after the whole amount was added, the temperature was raised and maintained at 80 ° C. for 6 hours, followed by cooling to room temperature to obtain about 60 g of a yellow transparent solution. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 13.4 g of a solid content. G
As a result of PC measurement, it was confirmed that the weight average molecular weight was 7100 and the number average molecular weight was 3000 in terms of polyethylene glycol. From the results of ¹³ C-NMR and ¹ H-NMR analyses, it was found that the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was about 3.6: 100. This solid was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured.
Met.

Example 21 In a 200 ml flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 15.0 g of N, N-dimethylaminopropylacrylamide, 0.41 g of 2-mercaptoethanol, After charging 70.0 g of methanol, 1.65 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] was added, and the mixture was heated to reflux while stirring under a nitrogen atmosphere. After maintaining at the temperature for 12 hours, it was cooled to room temperature. The solvent was distilled off under reduced pressure, 40 g of methyl ethyl ketone was added, the solvent was again distilled off, and the remaining highly viscous liquid was dissolved in 40 g of methyl ethyl ketone. To this solution, 2.40 g of benzyl isocyanate was gradually added, and after the whole amount was added, the temperature was raised and maintained at 80 ° C. for 6 hours, followed by cooling to room temperature to obtain about 60 g of a yellow transparent solution. The solvent was distilled off under reduced pressure, the remaining highly viscous liquid was dissolved in acetone, and reprecipitation was repeated with an acetone-hexane system, and the precipitate was dried to obtain 14.3 g of a solid content. As a result of GPC measurement, it was confirmed that the weight average molecular weight was 6500 and the number average molecular weight was 3000 in terms of polyethylene glycol. Also, ¹³
From the results of C-NMR and ¹ H-NMR analysis, it was found that the ratio of the aromatic ring (benzene ring) to the N, N-dimethylaminopropylamide structure was about 6.1: 100. This solid was dissolved in purified water, and the pH of the 40 wt% aqueous solution was measured to be 10.6.

(Effects) To 95 parts by weight of the solvents shown in Table 1, 5 parts by weight of the compounds obtained in Examples 1 to 21 were added, and the mixture was stirred at room temperature for 1 hour, and the solubility was evaluated by visual observation. did. As a comparative example, Sunfix 555 (a polyamine-based water-soluble cation resin manufactured by Sanyo Chemical Industries, Ltd.) was added in an amount of 5 parts by weight for each of 95 parts by weight of a solvent, and the solubility was similarly evaluated.

[0074]

[Table 1]

(Results) The compound of the present invention had high solubility in general-purpose organic solvents and water, but the compound of the comparative example had low solubility.

[0076]

The amino polymer compound of the present invention is a novel amino group-containing polymer, having excellent solubility and stability, cosmetics, surface treatment agents such as antistatic treatment, paper processing agents, and water treatment agents. It is useful as various additives such as adhesives and the like. In addition, the production method of the present invention makes it possible to produce the amino polymer compound easily in a short time with good yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Takahashi 1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture Inside Showa Denko KK Research Institute (72) Inventor Yoshisumi Nakamura 1-chome Onodai, Midori-ku, Chiba City, Chiba Prefecture No. 1-1 Inside Showa Denko KK (72) Inventor Naoko Ito 1-1-1, Onodai, Midori-ku, Chiba-shi, Chiba Prefecture Inside Showa Denko KK-institute (72) Inventor Toshio Koshikawa Chiba-shi, Chiba 1-1-1, Onodai-ku, Showa Denko KK Research Institute F-term (reference) 4J011 NA17 NB04 4J015 AA01 AA08 EA05 4J100 AM19Q AM21P AM21Q AN04Q AQ06Q AQ08Q BA02Q BA11Q BA12Q BA31P BA32P CA01 HC04 HC03 HC04 H52 HC52

Claims (22)

[Claims] 1. A method according to claim 1, wherein at least one of the terminal groups comprises a structural unit having an aromatic group, and
An amino polymer compound having at least one of a quaternary amino group, a tertiary ammonium salt and a quaternary ammonium salt. 2. The following general formula (1): (Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 3 carbon atoms, or R ¹ and R ² may form a ring containing an oxygen atom having 3 to 6 carbon atoms. , R ³ represents a hydrogen atom or a methyl group, and p represents an integer of 1 to 5.)
A repeating unit represented by the following general formula (2): (Wherein, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, or R ⁴ and R ⁵ may form a ring containing an oxygen atom having 3 to 6 carbon atoms. , R ⁶ represents a hydrogen atom or a methyl group, q represents an integer of 1 to 5. X represents a halogen, R ¹¹ COO, NO ₃ , R ¹² OSO.
₃ or BF ₄ , wherein R ¹¹ and R ¹² each represent an alkyl group having 1 to 6 carbon atoms. ) Or the following general formula (3): (Wherein, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 3 carbon atoms, or R ⁷ and R ⁸ may form a ring containing an oxygen atom having 3 to 6 carbon atoms. , R ⁹ is an alkyl group having 1 to 22 carbon atoms, a fluorine-substituted alkyl group, an aralkyl group, or the following general formula (4)-(R ¹³ -Y) _s -R ¹⁴ (4) (where R ¹³ is a substituent Y represents -CONH-, -NHCO-, -NHCOO-, -OCON
H-, -NHCOS-, -SCONH-, -NHCONH-, -S-,
Represents either -O- or -CO-. Also, R
¹⁴ represents a carboxyl group, a hydroxyl group, an alkyl group having 1 to 22 carbon atoms which may have a sulfonic acid group or a salt thereof, a fluorine-substituted alkyl group or an aralkyl group,
s represents an integer of 1 to 5. R ¹⁰ represents a hydrogen atom or a methyl group. R represents an integer of 1 to 5, and X represents the same meaning as described above. R ⁷ , R
⁸ and R ⁹ may be the same or different. 2. The amino polymer compound according to claim 1, wherein the amino polymer compound has at least one terminal group comprising a structural unit having an aromatic group. 3. The amino polymer compound according to claim 1, wherein the repeating unit is a repeating unit of the above (1) to (3), and the composition ratio of each repeating unit is in the range of 0 to 100%. . 4. The amino polymer compound according to claim 1, wherein the molecular weight of the terminal group comprising a structural unit having an aromatic group is 500 or less. 5. The amino polymer compound according to claim 1, which has a number average molecular weight of 1,000 to 10,000. 6. An aqueous solution of an amino polymer compound having a pH of 9
The amino polymer compound according to any one of claims 1 to 5, wherein 7. In the presence of a chain transfer agent having at least one aromatic group in a molecule, a monomer having a radically polymerizable ethylenically unsaturated group and an amino group is co-polymerized with a polymerization initiator. A) a method for producing an amino polymer compound, characterized by polymerizing; 8. A process for producing an amino polymer compound, comprising (co) polymerizing a monomer having a radically polymerizable ethylenically unsaturated group and an amino group with a polymerization initiator having an aromatic group. . 9. A monomer having a radically polymerizable ethylenically unsaturated group and an amino group is polymerized in the presence of a chain transfer agent having at least one aromatic group in a molecule. A method for producing an amino polymer compound, which comprises (co) polymerizing with an initiator. 10. A reaction between a reactive polymer having a reactive group on at least one of the terminal groups and having an amino group on a side group of the repeating unit and a compound having at least one aromatic group in the molecule. And introducing an aromatic group into the terminal. 11. A monomer having a radically polymerizable ethylenically unsaturated group and an amino group in the presence of a chain transfer agent in which the reactive polymer has at least one reactive group in the molecule, The method for producing an amino polymer compound according to claim 10, which is a polymer obtained by (co) polymerization with a polymerization initiator. 12. A polymer obtained by (co) polymerizing a monomer having a radically polymerizable ethylenically unsaturated group and an amino group with a polymerization initiator having a reactive group. A method for producing the amino polymer compound according to claim 10. 13. The amino group according to claim 7, wherein the chain transfer agent having at least one aromatic group in the molecule is benzyl mercaptan or 2,4-diphenyl-4-methyl-1-pentene. A method for producing a molecular compound. 14. A polymerization initiator having an aromatic group,
The method for producing an amino polymer compound according to claim 8 or 9, which is 1'-azobis (1-acetoxy-1-phenylethane). 15. The amino acid according to claim 7, wherein the amino group of the monomer is a tertiary amino group, a tertiary ammonium salt and / or a quaternary ammonium salt. A method for producing a molecular compound. 16. The method according to claim 7, wherein the monomer is N, N-dialkylaminoalkyl (meth) acrylamide, a salt thereof and / or a quaternary salt thereof.
Or a method for producing an amino polymer compound according to item 15. 17. A reaction between the tertiary amino group of the amino polymer compound according to claim 7 and an acid,
A method for producing an amino polymer compound, wherein a part or all of the compound is converted into a tertiary ammonium salt. 18. The process according to claim 17, wherein the acid is an organic or inorganic acid having 1 to 6 carbon atoms. 19. A tertiary amino group of the amino polymer compound according to claim 7 and a quaternizing agent, and a part or the whole thereof is converted to a quaternary ammonium salt. A method for producing an amino polymer compound, comprising: 20. The method according to claim 19, wherein the quaternizing agent is an alkyl halide having 1 to 22 carbon atoms, a halogenated fluorinated alkyl, an aralkyl halide, or a sulfate. 21. A part of the tertiary amino group by reacting the tertiary amino group of the amino polymer compound according to claim 7 simultaneously or separately with an acid and a quaternizing agent. Alternatively, a method for producing an amino polymer compound, which comprises converting all of the compound into a tertiary ammonium salt and a quaternary ammonium salt. 22. The acid is an organic or inorganic acid having 1 to 6 carbon atoms, and the quaternizing agent is an alkyl halide having 1 to 22 carbon atoms, a halogenated fluorinated alkyl, an aralkyl halide or a sulfate. A method for producing the amino polymer compound according to claim 21.