JP2002003456A - Betaine-type monomer, method for producing the same and polymer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a betaine-type monomer useful as a surfactant, a germicide, an antistatic agent, a soft-finishing agent, a rust proof agent, a resin modifier or the like, and further to provide a method for producing the monomer, and a polymer containing the betaine-type monomer. SOLUTION: This method for producing the betaine-type monomer is characterized in that a β-alanine derivative represented by general formula (1) (wherein, R1 and R2 are each independently a 1-8C linear or branched alkylene group or a 1-8C linear or branched hydroxyalkylene group, or form a cyclic group by binding directly or through at least one element selected from O, S and N to each other; and R3 is hydrogen, a methyl group or a hydroxymethyl group) is reacted with a mono-oxirane compound represented by general formula (2) (wherein, R4 is an organic group having one polymerizable carbon-carbon double bond; and R5 is hydrogen or a methyl group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing a betaine-type monomer, which comprises reacting a β-alanine derivative with a monooxirane compound having one polymerizable carbon-carbon double bond. And a polymer containing a betaine monomer having a specific structure as a repeating unit.

[0002]

BACKGROUND ART A betaine compound is a compound having a cation portion and an anion portion in one molecule, and has recently attracted attention as an amphoteric activator due to its structural characteristics. Such amphoteric surfactants are extremely excellent in hard water resistance, have various excellent properties such as extremely low toxicity, surfactants, bactericides, antistatic agents, softening agents,
It is suitably used for applications such as rust inhibitors.

[0003] Many polymerizable monomers having a betaine-type functional group are already known and have been synthesized by several techniques. For example, JP-A-8-27225 discloses a method of synthesizing a carboxybetaine type monomer by reacting a tertiary amine type monomer with a monohaloalkylcarboxylic acid. However, in the reaction between the tertiary amine type monomer and the monohaloalkyl carboxylic acid, highly corrosive and highly toxic hydrogen halide is generated, so that a reactor having corrosion resistance and an exclusion facility are required. Further, in the reaction between the tertiary amine type monomer and the monohaloalkyl carboxylate, a metal halide salt which is an inorganic salt is generated, so that a step of removing the inorganic salt is required. The polymer disclosed in this publication containing a carboxybetaine-type monomer as a repeating unit absorbs an aqueous electrolyte solution, and thus can be used as an absorbent for an aqueous electrolyte solution. However, a polymer containing such a carboxybetaine-type monomer as a repeating unit also imparts various properties other than water absorbability, and, in order to broaden the use thereof, further research on related compounds. There was room. Japanese Patent Publication No. 55-33783 discloses a method of synthesizing a carboxybetaine type monomer by reacting a tertiary amine type monomer with a cyclic ester such as propiolactone. In the case of a reaction between a tertiary amine type monomer and a cyclic ester such as propiolactone, in order to synthesize a carboxybetaine type monomer similar to the carboxybetaine type monomer of the present invention, β is used as a cyclic ester. -It is necessary to use propiolactone, but β-propiolactone is not an industrial product and is expensive, so that it has no utility for industrial use. The polymer disclosed in this publication containing a carboxybetaine-type monomer as a repeating unit is a thermosetting resin having water resistance and chemical resistance, and thus can be used for paints and the like. However, a polymer containing such a carboxybetaine-type monomer as a repeating unit also has various similarities in order to impart various properties other than water resistance and chemical resistance, and to thereby broaden the application. There was room to study compounds.

[0004] The reaction between amino acids and monooxirane compounds is already known. For example, Chiba University Research Report, 1974, Vol. 26, No. 49, 117-123
On the page, a copolymer of glycidyl methacrylate and methyl methacrylate, glycine, N-methyl glycine,
Reactants with amino acids such as N-phenylglycine, alanine and N-acetylglycine have been described,
Also, US Pat. No. 3,200,142 describes a reaction product of N-phenylglycine sodium salt and glycidyl methacrylate or glycidyl acrylate, but none of the obtained compounds is betaine.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, has excellent biodegradability, and has a surfactant, a bactericide, an antistatic agent, a softening agent, a rust inhibitor, and a resin. Betaine type monomer having a specific method and a method for producing a novel betaine type monomer useful as a modifier, an intermediate raw material,
Still another object is to provide a polymer containing a betaine-type monomer having a specific structure as a repeating unit.

[0006]

According to the present invention, there is provided the following general formula (1):

[0007]

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(Wherein, R ₁ and R ₂ each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkyl group having 1 to 8 carbon atoms) Or a cyclic group in which both are bonded directly to each other or via at least one element selected from O, S, and N;
R ₃ is hydrogen, a methyl group or a hydroxymethyl group. And a β-alanine derivative represented by the following general formula (2):

[0009]

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(Wherein R ₄ represents an organic group having one polymerizable carbon-carbon double bond, and R ₅ represents hydrogen or a methyl group). And a method for producing a betaine-type monomer.

[0011] The present invention also relates to a monooxirane compound,
The following general formula (3)

[0012]

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(Wherein, R ₅ is the same as above; R ₆ is hydrogen or a methyl group; A is an ester group, an amide group, an ether group, a sulfide group, a substituted or unsubstituted phenylene group, and Represents any one selected from a bond, and m and n are each independently an integer of 0 to 5).
A method for producing a betaine-type monomer, which is a monooxirane compound having one heavy bond.

The present invention also provides the following general formula (4):

[0015]

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(Wherein, R ₁ , R ₂ , R ₃ , R ₅ , R
₆ , m and n are the same as above. B represents any one selected from an ether group, a sulfide group, and a direct bond. )).

The present invention also provides the following general formula (5):

[0018]

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(Where R ₇ , R ₈ , R ₃ , R ₅ , R
₆ , m and n are the same as above. D represents any one selected from an ester group, an amide group, and a substituted or unsubstituted phenylene group. )). The present invention also provides the following general formula (6):

[0020]

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(Where R _{1 ,} R ₂ , R ₃ , R ₅ ,
R ₆ , A, m and n are the same as above. 1) to 100% by mole of the repeating unit (X) represented by ()) and 0 to 99% by mole of the repeating unit (V) derived from another vinyl monomer (provided that the components (X) and (V) The sum is 100 mol%.), And the polymer does not contain a repeating unit derived from a crosslinkable monomer.

The present invention also provides the following general formula (7):

[0023]

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(Where R _{1 ,} R ₂ , R ₃ , R ₅ ,
R ₆ , B, m and n are the same as above. ), The repeating unit (V) derived from another vinyl monomer is 0 to 99 mol% (provided that the components (Y) and (V) The sum is 100 mol%.)

The present invention further provides the following general formula (8):

[0026]

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(Where R ₇ , R ₈ , R ₃ , R ₅ , R
₆ , D, m and n are the same as above. ), The repeating unit (V) derived from another vinyl monomer is 1 to 100 mol%, and the repeating unit (V) is 0 to 99 mol% (provided that the components (Z) and (V) are The sum is 100 mol%.)

Hereinafter, the present invention will be described in detail. The method for producing a betaine-type monomer of the present invention is achieved by reacting a β-alanine derivative represented by the above general formula (1) with a monooxirane compound represented by the above general formula (2). You. In the present specification, the above step is referred to as a monooxirane compound addition step.

The β-alanine derivative represented by the general formula (1) used in the step of adding the monooxirane compound is not particularly limited, and examples thereof include (meth) acrylic acid,
2 for acrylic acids such as 2-hydroxymethylacrylic acid
A compound which is easily synthesized by adding a secondary amine can be used. The method for producing a betaine-type monomer of the present invention may include a step of synthesizing the β-alanine derivative represented by the general formula (1). In this specification, the above step is referred to as a β-alanine derivative synthesis step.

The secondary amine is not particularly limited.
For example, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-n-pentylamine, methylethylamine, dihexylamine, dioctylamine, ethyleneimine, pyrrolidine, piperidine,
Hexamethyleneimine, morpholine, piperazine, N-
Examples thereof include linear, branched or cyclic secondary alkylamines such as methylpiperazine, diethanolamine and N- (2-hydroxyethyl) propylamine. These may be used alone or in combination of two or more.

In the step of synthesizing the β-alanine derivative, the method of mixing the acrylic acid and the secondary amine is not particularly limited. For example, in order to suppress heat generation due to mixing and to facilitate temperature control. Preferably, one of them is charged in a reaction vessel, and the other is added continuously or sequentially. That is, the acrylic acid is charged in the reaction vessel, the secondary amine may be added continuously or sequentially, or the secondary amine may be charged in the reaction vessel, and the acrylic acid may be added continuously or sequentially. .

In the step of synthesizing the β-alanine derivative, the reaction can be carried out without a solvent, but a solvent may be used if necessary. A catalyst is not particularly required, but a catalyst may be used for the purpose of accelerating the reaction and suppressing side reactions.

The solvent is not particularly limited as long as it does not react with the starting acid or amine and does not inhibit the reaction. Examples thereof include aliphatic hydrocarbons such as hexane and octane; cyclohexane and the like. Alicyclic saturated hydrocarbons such as: cycloaliphatic unsaturated hydrocarbons such as cyclohexene; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; methyl acetate;
Esters such as ethyl acetate; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as diethyl ether and dioxane; alcohols and water such as methanol and ethanol; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide. A nitrile such as acetonitrile; These may be used alone or in combination of two or more.

The catalyst is not particularly restricted but includes, for example, bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methylate, lithium methylate, sodium ethylate, tertiary amine compounds and quaternary ammonium compounds. Catalysts and the like. These may be used alone or in combination of two or more.

In the step of synthesizing the β-alanine derivative, a polymerization inhibitor may be used to prevent polymerization of acrylic acids. The polymerization inhibitor to be used is not particularly limited, and examples thereof include phenol-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone and benzoquinone, and sulfur such as dilauryl-3,3'-thiodipropionate, 2-mercaptobenzimidazole and phenothiazine. And a phosphorus-based polymerization inhibitor such as tris (isodecyl) phosphite and diphenylisodecylphosphite. These may be used alone or in combination of two or more.

The reaction temperature in the step of synthesizing the β-alanine derivative is not particularly limited, and is preferably, for example, a temperature range not higher than the boiling point of the acid or amine used as a raw material. More preferably, the temperature is 0 to 250 ° C. from the viewpoint of easy control of the reaction temperature. More preferably, the temperature is from 20 to 150 ° C., since a side reaction due to excessive heating can be suppressed and the β-alanine derivative can be obtained with high selectivity. Further, the reaction pressure is not particularly limited, for example,
It is preferable to carry out at 10 atm or less.

The process for producing the betaine-type monomer of the present invention comprises:
By including the above-mentioned monooxirane compound addition step, the following general formula (9):

[0038]

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(Wherein, R ₁ and R ₂ each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkyl group having 1 to 8 carbon atoms) Or a cyclic group in which both are bonded directly to each other or via at least one element selected from O, S, and N;
R ₃ represents hydrogen or a methyl group or a hydroxymethyl group, R ₄ represents an organic group having one polymerizable carbon-carbon double bond, and R ₅ represents a hydrogen or methyl group. ) Can be efficiently produced in high yield.

The monooxirane compound represented by the general formula (2) used in the step of adding the monooxirane compound is not particularly limited, and may be any monooxirane compound having one polymerizable carbon-carbon double bond.

In the general formula (2), the organic group having one polymerizable carbon-carbon double bond for R ₄ is not particularly limited, but may be a linear or branched alkyl group having 2 to 10 carbon atoms, Examples thereof include a linear or branched alkyl group having an ether bond and / or a sulfide bond and having 2 to 10 carbon atoms, a hydrocarbon group having a (meth) acryloyloxy group, and a hydrocarbon group having a (meth) acrylamide group. Can be Specifically, for example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, methallyl group, (meth) acryloyloxymethyl group, (meth) acrylamidomethyl group, Examples include a vinylphenyl group, an allyloxymethyl group, a 2-butenyloxymethyl group, a vinyloxymethyl group, and a 1-methylallyloxymethyl group.

In the step of adding a monooxirane compound, in order to obtain a betaine type monomer having good polymerizability, the monooxirane compound represented by the general formula (2) is represented by the general formula (3). It is preferably a monooxirane compound having one carbon-carbon double bond at its terminal. The monooxirane compound having one carbon-carbon double bond at the terminal represented by the general formula (3) is not particularly limited,
For example, glycidyl (meth) acrylate, N-glycidyl (meth) acrylamide, allyl glycidyl ether, methallyl glycidyl ether, vinyl glycidyl ether, epoxybutene, 1-epoxy-4-pentene, isoprene epoxide, divinylbenzene monoxide, glycidylvinyl Sulfides and the like can be mentioned. Among these, glycidyl methacrylate, allyl glycidyl ether, epoxybutene and the like are exemplified as monooxirane compounds having one carbon-carbon double bond at a terminal which is industrially highly useful. These may be used alone or in combination of two or more.

In the step of adding the monooxirane compound, the method of mixing the β-alanine derivative and the monooxirane compound is not particularly limited. For example, considering the reactivity of the monooxirane compound and the like, It is preferred to determine the method of mixing with the oxirane compound. Usually, it is preferable to charge a β-alanine derivative in a reaction vessel and continuously or sequentially add a monooxirane compound. However, depending on reaction conditions, the β-alanine derivative and the monooxirane compound may be mixed at once.

In the step of adding the monooxirane compound, the reaction is preferably performed in an inert gas atmosphere because the monooxirane compound has explosive properties. The inert gas is not particularly limited, for example,
Examples thereof include nitrogen, helium, and neon, and usually, nitrogen gas is used.

In the step of adding the monooxirane compound, when the reaction is carried out under a pressurized condition, the reaction vessel may be preliminarily pressurized with the inert gas in order to avoid an explosion range of the monooxirane compound. preferable.
The state of pressurization by the inert gas is preferably determined in consideration of the reactivity and reaction temperature of the monooxirane compound used, and the pressure resistance of the reaction vessel used. Also,
The reaction pressure is not particularly limited, and is, for example, 10 atm.
It is preferable to perform the following.

The monooxirane compound addition step can be carried out without a solvent, but a solvent may be used if necessary. A catalyst is not particularly required, but a catalyst may be used for the purpose of accelerating the reaction or suppressing a side reaction.

The solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include the same solvents as those described above. These may be used alone,
Two or more kinds may be used in combination.

The above-mentioned catalyst is not particularly restricted but includes, for example, the above-mentioned basic catalysts; acid catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid and zeolite. These may be used alone or in combination of two or more.

In the step of adding the monooxirane compound, a polymerization inhibitor may be used in consideration of the polymerizability of the monooxirane compound used. The polymerization inhibitor to be used is not particularly limited, and includes, for example, those similar to the above-mentioned polymerization inhibitors. These may be used alone or in combination of two or more.

The reaction temperature in the step of adding the monooxirane compound is not particularly limited. For example, it is preferably 0 to 200 ° C. from the viewpoint of easy control of the reaction temperature. More preferably, it is 20-150 degreeC from a viewpoint of suppression of a side reaction.

The betaine type monomer of the present invention is represented by the above general formula (4).

In the general formula (4), the linear or branched alkyl group having 1 to 8 carbon atoms in R ₁ and R ₂ is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, isobutyl group,
Examples thereof include a pentyl group, a hexyl group, a cyclohexyl group, and an octyl group. The straight-chain or branched hydroxyalkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a 2-hydroxyethyl group and a 3-hydroxypropyl group. Group, 2-hydroxypropyl group, and 3-hydroxybutylene group, and when both are bonded to each other directly or via at least one element selected from the group consisting of O, S, and N, Is not particularly limited, and examples thereof include a tetramethylene group, a pentamethylene group, a hexamethylene group, an ethyleneoxyethylene group, and an ethyleneiminoethylene group.

The betaine type monomer of the present invention is represented by the above general formula (5). In the general formula (5), the linear or branched alkyl group having 3 to 8 carbon atoms in R ₇ and R ₈ is not particularly limited, and examples thereof include a propyl group, an isopropyl group, a butyl group, an isobutyl group, Pentyl group, hexyl group, cyclohexyl group, octyl group,
The straight-chain or branched hydroxyalkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 3-hydroxybutylene group. And
The group in which both are bonded to each other directly or via at least one element selected from the group consisting of O, S and N is not particularly limited, and examples thereof include a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples include a methylene group, an ethyleneoxyethylene group, and an ethyleneiminoethylene group.

The general formulas (4) and (5) of the present invention
In represented by betaine monomers, COO is N ⁺ and anion portion is a cation portion in a molecule ^- and a binding specific alkyl group or hydroxyalkyl group or the like in the N ⁺ In addition, it is a betaine-type monomer having a specific structure with a hydroxyl group, and has excellent biodegradability, surfactants, bactericides, antistatic agents, softening agents, rust inhibitors, resin modifiers It is useful as a raw material for intermediates such as

The polymer of the present invention contains 1 to 100 mol% of the repeating unit (X) represented by the above general formula (6) and 0 to 99% of the repeating unit (V) derived from another vinyl monomer.
Mol% (however, the sum of the components (X) and (V) is 100
Mol%. ) Is a polymer that does not contain a repeating unit derived from a crosslinkable monomer. Preferably, the polymer is composed of 5 to 95 mol% of the repeating unit (X) and 5 to 95 mol% of the repeating unit (V), and more preferably 10 to 90 mol% of the repeating unit (X). It is a polymer comprising 10 to 90 mol% of the repeating unit (V). In the above general formula (6), R ₁ , R ₂ , R ₃ , R ₅ , R ₆ ,
m, n and A are the same as above. The polymer of the present invention comprises the repeating unit (Y) represented by the general formula (7) as 1 to 1
A polymer containing 0 mol% and 0 to 99 mol% of the repeating unit (V) derived from another vinyl monomer (however, the sum of the components (Y) and (V) is 100 mol%). is there. Preferably, it is a polymer comprising 5 to 95 mol% of the repeating unit (Y) and 5 to 95 mol% of the repeating unit (V).
It is a polymer comprising 0 to 90 mol% and 10 to 90 mol% of the repeating unit (V). In the above general formula (7),
R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , m, n and B are the same as above.

In the polymer of the present invention, 1 to 100 mol% of the repeating unit (Z) represented by the above general formula (8) and 0 to 99% of the repeating unit (V) derived from other vinyl monomer units are used.
Mol% (provided that the sum of the components (Z) and (V) is 100
Mol%. ). Preferably, the repeating unit (Z) is 5 to 95 mol% and the repeating unit (V)
Is a polymer composed of 5 to 95 mol%, more preferably a polymer composed of 10 to 90 mol% of the repeating unit (Z) and 10 to 90 mol% of the repeating unit (V). In the above general formula (8), R ₇ , R ₈ , R ₃ , R ₅ , R ₆ ,
m, n, and D are the same as above.

The vinyl monomer for obtaining the repeating unit (V) derived from a vinyl monomer used in the present invention includes a polymerizable carbon-carbon double bond per vinyl monomer unit. It is not particularly limited as long as it is a monomer having one and is a monomer copolymerizable with the betaine-type monomer of the present invention. Examples thereof include (meth) acrylic acid,
(Meth) acrylates such as sodium (meth) acrylate, (meth) acrylates such as methyl (meth) acrylate, (meth) acrylamide and its derivatives, styrene and its derivatives, vinyl esters such as vinyl acetate , Maleic acid and its esters, (meth) acrylonitrile, vinyl ethers such as vinyl methyl ether, vinyl ketones such as vinyl methyl ketone, N-vinyl lactams such as N-vinyl pyrrolidone, N-vinyl oxazolidone, 2-vinyl oxazoline And the like. Vinyl oxazolines such as vinyl ethylene carbonate, vinyl carbonates such as vinyl ethylene carbonate, vinyl pyridines such as 2-vinyl pyridine, allyl ethers such as allyl phenyl ether, and vinyl sulfides such as vinyl ethyl sulfide. The vinyl monomer is appropriately selected according to the desired properties of the polymer, and may be used alone or in combination of two or more. Also, unit (X) and unit (V)
The molar ratio of the unit (Y) to the unit (V) and the molar ratio of the unit (Z) to the unit (V) are determined according to the properties of the desired polymer. It is appropriately selected from the range.

The molecular weight of the polymer of the present invention is not particularly limited, and is generally 500 to 1000 in number average molecular weight.
000. The molecular weight can be adjusted by the amount of the polymerization initiator used, the monomer concentration in the solvent used, the use of a chain transfer agent, and the like.

The polymer in the present invention can be obtained by (co) polymerization of a betaine-type monomer and another vinyl monomer, but the (co) polymerization mode is not particularly limited, and the radical polymerization is carried out. Conventional methods such as cation polymerization and anion polymerization can be used as appropriate.

Examples of the polymerization initiator used for radical polymerization include azo-based initiators such as azobis (isobutyronitrile), organic peroxides such as benzoyl peroxide, and inorganic peroxides such as potassium persulfate. Examples of the polymerization initiator used for cationic polymerization include, for example, acids such as perchloric acid and trichloroacetic acid, and Friedel-Crafts catalysts such as trifluoroborane etherate.
Examples of the polymerization initiator used for anionic polymerization include bases such as sodium methylate. The use amount of these polymerization initiators is not particularly limited, either, but is preferably 0.1 to 10% by weight based on all monomers.

The solvent used in the (co) polymerization is not particularly limited as long as it does not react with the monomer or the like and does not inhibit the (co) polymerization.
Aliphatic hydrocarbons such as octane; alicyclic saturated hydrocarbons such as cyclohexane; alicyclic unsaturated hydrocarbons such as cyclohexene; aromatic hydrocarbons such as benzene, toluene and xylene; acetone and methyl ethyl ketone Ketones; esters such as methyl acetate and ethyl acetate; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as diethyl ether dioxane; methanol;
Alcohols such as ethanol; water; amides such as dimethylformamide; sulfoxides such as dimethylsulfoxide; nitriles such as acetonitrile.
These may be used alone or in combination of two or more.

The temperature of the (co) polymerization is not particularly limited and may be appropriately selected according to the (co) polymerization mode, but is usually in the range of -50 to 200 ° C.

The present invention also includes a polymer having a betaine-type functional group introduced into the polymer by a polymer reaction with the polymer. That is, a polymer having a betaine-type functional group introduced can also be obtained by a polymer reaction between a polymer having an oxirane ring in the side chain of the polymer and a β-alanine derivative.

A polymer containing the above general formula (6) as a repeating unit and containing no crosslinkable monomer, a polymer containing the above general formula (7) as a repeating unit, formula (8) polymer containing as a repeating unit is, COO in the repeating unit is N ⁺ and anion portion is a cation portion ^- and a specific alkyl or hydroxyalkyl group the N ⁺ Etc. are combined, and
It is a polymer having a specific betaine structure having a hydroxyl group, and has excellent biodegradability and is useful as a surfactant, a bactericide, an antistatic agent, a softening agent, a rust inhibitor, a resin modifier, and the like.

[0065]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

<Reference Example 1> Synthesis of N, N-diethyl-β-alanine 10 equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
50 g of diethylamine in a 0 ml four-necked flask
(0.6837 mol), and while maintaining the temperature inside the system at 30 ° C. or lower with stirring in an ice water bath, acrylic acid 4
9.3 g (0.6840 mol) and phenothiazine 0.0
The mixture with 5 g was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was heated in an oil bath at 80 ° C. and reacted for 4 hours. After the reaction was completed, acrylic acid and diethylamine were quantified by gas chromatography. The conversion of acrylic acid was 95%, and the conversion of diethylamine was 95%.
94.3 g of N, N-diethyl-β-alanine (yield 95
%).

Reference Example 2 N, N-di-n-butyl-
Synthesis of β-alanine 30 equipped with stirrer, condenser, thermometer and dropping funnel
In a 0 ml four-necked flask, di-n-butylamine 10 was added.
0g (0.7738 mol) was charged, and 55.7 g (0.7730 mol) of acrylic acid and 0.1% of phenothiazine were added while maintaining the temperature inside the system at 30 ° C. or less while stirring in an ice water bath.
The mixture with 0.6 g was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was heated in an oil bath at 80 ° C. and reacted for 4 hours. After completion of the reaction, when acrylic acid and di-n-butylamine were quantified by gas chromatography, the conversion of acrylic acid was 98% and the conversion of di-n-butylamine was 98%.
%, N, N-di-n-butyl-β-alanine 15
2.5 g (98% yield) were obtained.

Example 1 3- (N, N-diethyl-
Synthesis of N- (2-hydroxy-3-methacryloyloxy) propyl) ammoniopropanoate (betaine type monomer 1) In a 200 ml four-necked flask equipped with a stirrer, a condenser, and a thermometer, <Reference Example 1> N, N-diethyl-β obtained in>
-30 g (0.2066 mol) of alanine, polymerizable carbon-
As a monooxirane compound having one carbon double bond, 29.44 g of glycidyl methacrylate (0.2071)
Mol), 0.03 g of phenothiazine as a polymerization inhibitor and 30 g of toluene as a solvent were charged at room temperature.
The inside of the one-necked flask was replaced with nitrogen gas for 10 minutes. Thereafter, the mixture was reacted for 6 hours with stirring while heating in an oil bath at 80 ° C. After the obtained reaction solution was cooled to room temperature, the reaction solution was transferred to a 500 ml eggplant-shaped flask, and toluene was distilled off with a rotary evaporator to obtain the betaine-type monomer 1 of the present invention, 3- (N, N-diethyl-N- (2-hydroxy-3-methacryloyloxy)
About 57.6 g (yield: 96.9%) of propyl) ammoniopropanoate was obtained.

FIG. 1 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine-type monomer 1 and FIG. 2 shows the infrared absorption spectrum.

Referring to FIG. 1, a peak derived from the methine group of the glycidyl methacrylate group of glycidyl methacrylate is observed at 5.2 to 5.4 ppm. The peak of the methine group (3.2-3.3 ppm) is about 2.
It was shifted to a low magnetic field side of 0 ppm. Also, 2.8pp
m, a peak derived from the methylene group of N, N-diethyl-β-alanine (methylene group at the β-position to the carboxyl group) is observed, and this peak is observed when N, N is not reacted.
The peak of the methylene group of N-diethyl-β-alanine (methylene group at the β-position to the carboxyl group) (3.0 pp)
m) was shifted to the higher magnetic field side by 0.2 ppm. Referring to FIG. 2, it can be seen that around 810 cm ^−1, around 945 cm ⁻¹ ,
-CH ₂ -NH- newly formed around 170 cm ^-1 ,
-CH ₂ -OH-derived absorption was observed, and 3400 to 350
At 0 cm ^-1 , stretching vibration absorption of OH groups was observed,
450cm in the vicinity ^-1 (COO) ^- is the stretching vibration absorption is observed.

From these results, it was confirmed that betaine type monomer 1 represented by the following formula (10) was obtained.

[0072]

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Example 2 Synthesis of 3- (N, N-di-n-butyl-N- (2-hydroxy-3-methacryloyloxy) propyl) ammoniopropanoate (betaine type monomer 2) Stirrer In a 200 ml four-necked flask equipped with a cooling tube and a thermometer, 30 g (0.1490 mol) of N, N-di-n-butyl-β-alanine obtained in Reference Example 2 and polymerizable carbon As a monooxirane compound having one carbon double bond, glycidyl methacrylate 21.2 g (0.14
91 mol), and phenothiazine 0.03 as a polymerization inhibitor.
g and 30 g of toluene as a solvent were charged, and the inside of the four-necked flask was replaced with nitrogen gas for 10 minutes at room temperature. Thereafter, the mixture was reacted for 6 hours with stirring while heating in an oil bath at 80 ° C. After cooling the obtained reaction solution to room temperature, the reaction solution was transferred to a 500 ml eggplant flask, and toluene was distilled off with a rotary evaporator to obtain
The betaine type monomer 2 of the present invention, about 4- (N, N-di-n-butyl-N- (2-hydroxy-3-methacryloyloxy) propyl) ammoniopropanoate, is about 4%.
9 g (yield: 95.7%) was obtained.

The ¹ H-nuclear magnetic resonance spectrum of the obtained betaine type monomer 2 is shown in FIG. 3, and the infrared absorption spectrum is shown in FIG.

Referring to FIG. 3, a peak derived from the methine group of the glycidyl methacrylate group of glycidyl methacrylate was observed at 5.1 to 5.3 ppm. The peak of the methine group (3.2-3.3 ppm) is about 2.
It was shifted to a low magnetic field side of 0 ppm. Also, 2.8pp
m, a peak derived from the methylene group of N, N-di-n-butyl-β-alanine (methylene group at the β-position to the carboxyl group) is observed, and this peak is observed when N, N is not reacted. The peak was shifted to a higher magnetic field side by 0.3 ppm than the peak (3.1 ppm) of the methylene group of N-di-n-butyl-β-alanine (methylene group at the β-position to the carboxyl group). Turning to FIG. 4, 810 cm around ^-1, 940c
-CH newly generated around m ^{-1 and} around 1170 cm ^-1
₂ -NH -, - absorption from CH ₂ -OH was observed, 340
The 0～3500Cm ^-1 observed stretching vibration absorption of OH group, also in the vicinity of 1450cm ^-1 (COO) ^- it is the stretching vibration absorption is observed.

From these results, it was confirmed that the betaine type monomer 2 represented by the following formula (11) was obtained.

[0077]

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Example 3 Synthesis of 3- (N, N-di-n-butyl-N- (2-hydroxy-3-allyloxy) propyl) ammoniopropanoate (betaine type monomer 3) In a 100 ml four-necked flask equipped with a cooling tube and a thermometer, 30 g (0.1490 mol) of N, N-di-n-butyl-β-alanine obtained in <Reference Example 2>, polymerizable carbon-carbon As a monooxirane compound having one double bond, 17.0 g (0.14 g) of allyl glycidyl ether was used.
90 mol), phenothiazine 0.02 as a polymerization inhibitor
g and 30 g of toluene as a solvent were charged, and the inside of the four-necked flask was replaced with nitrogen gas for 10 minutes at room temperature. Thereafter, the mixture was reacted for 6 hours with stirring while heating in an oil bath at 100 ° C. After cooling the obtained reaction solution to room temperature, the reaction solution was transferred to a 300 ml eggplant flask, and toluene was distilled off with a rotary evaporator to give 3- (N, N
About 46 g of di-n-butyl-N- (2-hydroxy-3-allyloxy) propyl) ammoniopropanoate
(Yield: 97.9%) was obtained.

FIG. 5 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine type monomer 3, and FIG. 6 shows the infrared absorption spectrum.

Referring to FIG. 5, a peak derived from the methine group of the glycidyl group of the allyl glycidyl ether was observed at 3.7 to 3.9 ppm, and this peak was observed when the glycidyl ether of the allyl glycidyl ether was not reacted. Methine group peak (3.2 ppm) about 0.5-0.
7 ppm was shifted to the lower magnetic field side. Also, 2.8pp
m, a peak derived from the methylene group of N, N-di-n-butyl-β-alanine (methylene group at the β-position to the carboxyl group) is observed, and this peak is observed when N, N is not reacted. The peak was shifted to a higher magnetic field side by 0.3 ppm than the peak (3.1 ppm) of the methylene group of N-di-n-butyl-β-alanine (methylene group at the β-position to the carboxyl group). Referring to FIG. 6, 800cm around ^-1, 930c
At around m ^-1, around 1100 cm ^{-1 and} around 1200 cm ^-1 , absorptions derived from newly generated -CH ₂ -NH- and -CH ₂ -OH are seen, and at 3400 to 3500 cm ^-1 , the stretching vibration absorption of OH groups is absorbed. And stretching vibration absorption of (COO) ⁻ is observed around 1450 cm ⁻¹ .

From these results, it was confirmed that the betaine type monomer 3 represented by the following formula (12) was obtained.

[0082]

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Example 4 Synthesis of 3- (N, N-di-n-butyl-N- (2-hydroxy) -3-butenyl) ammoniopropanoate (betaine type monomer 4) Stirrer, cooling In a 100 ml four-necked flask equipped with a tube and a thermometer, 30 g (0.1490 mol) of N, N-di-n-butyl-β-alanine obtained in Reference Example 2 and polymerizable carbon-carbon 2 As a monooxirane compound having one heavy bond, 10.45 g of 1-epoxy-3-butene (0.1
491 mol), and phenothiazine 0.0 as a polymerization inhibitor.
1 g and 30 g of toluene as a solvent were charged, and the inside of the four-necked flask was replaced with nitrogen gas at room temperature for 10 minutes. Thereafter, the mixture was reacted for 6 hours with stirring while heating in an oil bath at 100 ° C. After the obtained reaction solution was cooled to room temperature, the reaction solution was transferred to a 300 ml eggplant flask, and toluene was distilled off with a rotary evaporator to obtain the betaine-type monomer 4 of the present invention, 3- (N, N
-Di-n-butyl-N- (2-hydroxy) -3-butenyl was obtained in an amount of about 39.2 g (yield: 96.9%).

FIG. 7 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine type monomer 4 and FIG. 8 shows the infrared absorption spectrum.

FIG. 7 shows that 1 to 4.0-4.2 ppm
-A peak derived from the methine group of the epoxy group of epoxy-3-butene is observed, and this peak is the peak of the methine group of the epoxy group of 1-epoxy-3-butene which is observed in the case of no reaction (3.3). 0.7p than -3.4 ppm)
pm low magnetic field. Also, a peak derived from the methylene group of N, N-di-n-butyl-β-alanine (methylene group at the β-position to the carboxyl group) was observed at 2.8 ppm. 0.3 ppm higher than the peak (3.1 ppm) of the methylene group of N, N-di-n-butyl-β-alanine (3.1 ppm with respect to the carboxyl group). . Looking at FIG. 8, the vicinity of 810 cm ⁻¹ and 930 c
m around ^-1, 1080 cm around ^-1, -CH ₂ -NH newly generated in the vicinity of 1200cm ^-1 -, - CH ₂ -OH absorption derived is observed, the stretching vibration absorption of the OH groups to 3400～3500Cm ^-1 Was observed, and (CO) was observed around 1450 cm ^-1.
O) ^- is stretching vibration absorption seen.

From these results, it was confirmed that the betaine type monomer 4 represented by the following formula (13) was obtained.

[0087]

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Example 5 Synthesis of 3- (N, N-diethyl-N- (2-hydroxy-3-allyloxy) propyl) ammoniopropanoate (betaine type monomer 5) Stirrer, cooling tube and temperature The N, N-diethyl-β obtained in Reference Example 1 was placed in a 100 ml four-necked flask equipped with a
-30 g (0.2066 mol) of alanine, polymerizable carbon-
23.58 g of allyl glycidyl ether (0.2066) as a monooxirane compound having one carbon double bond
Mol), 0.02 g of phenothiazine as a polymerization inhibitor and 30 g of toluene as a solvent were charged at room temperature.
The inside of the one-necked flask was replaced with nitrogen gas for 10 minutes. Thereafter, the mixture was reacted for 6 hours with stirring while heating in an oil bath at 100 ° C. After cooling the obtained reaction solution to room temperature,
The reaction solution was transferred to a 300 ml eggplant-shaped flask, and toluene was distilled off by a rotary evaporator to give 3- (N, N-diethyl-N- (2-hydroxy-3) which is betaine-type monomer 5 of the present invention. About 51.4 g of (allyloxy) propyl) ammoniopropanoate (yield: 9
5.9%).

The ¹ H-nuclear magnetic resonance spectrum of the obtained betaine-type monomer 5 is shown in FIG. 9, and the infrared absorption spectrum is shown in FIG.

Referring to FIG. 9, a peak derived from the methine group of the glycidyl group of the allyl glycidyl ether is observed at 3.7 to 3.9 ppm, and this peak is observed when the glycidyl ether of the allyl glycidyl ether is not reacted. Methine group peak (3.2 ppm) about 0.5-0.
7 ppm was shifted to the lower magnetic field side. Also, 2.8pp
m, a peak derived from the methylene group of N, N-diethyl-β-alanine (methylene group at the β-position to the carboxyl group) is observed, and this peak is observed when N, N is not reacted.
The peak (3.1 pp) of the methylene group of N-diethyl-β-alanine (methylene group at the position β with respect to the carboxyl group)
m) was shifted to the higher magnetic field side by 0.3 ppm. Looking at FIG. 10, it can be seen that around 800 cm ^−1, around 930 cm ⁻¹ ,
1110cm around ^-1, -CH ₂ -NH newly generated in the vicinity of 1200 cm ^-1 -, - absorption from CH ₂ -OH was observed, the 3400～3500Cm ^-1 observed stretching vibration absorption of OH group, also , Around 1450cm ^-1 (COO)
^- stretching vibration absorption of it can be seen. From these, it was confirmed that the betaine type monomer 3 represented by the following formula (14) was obtained.

[0091]

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<Polymerization Example 1> Synthesis of 3- (N, N-diethyl-N- (2-hydroxy-3-methacryloxy) propyl) ammoniopropanoate-acrylamide copolymer (polymer 1) Stirrer, cooling 10 with tube, thermometer and dropping funnel
In a 0 ml four-necked flask, 20 g of isopropyl alcohol was charged as a solvent, and the 3-
(N, N-di-n-butyl-N- (2-hydroxy-3
-Methacryloxy) propyl) ammoniopropanoate (betaine type monomer 2) (15 g, 0.04368 mol), and acrylamide 9.3 g (0.
1309 mol), a monomer mixture solution comprising 0.5 g (0.00471 mol) of 3-mercaptopropionic acid as a chain transfer agent and 15 g of isopropyl alcohol;
As a polymerization initiator, a polymerization initiator solution composed of 0.7 g of dimethyl 2,2′-azobis (isobutyrate), which is an azo polymerization initiator, and 5 g of isopropyl alcohol was charged into separate dropping funnels. At room temperature, the inside of the four-necked flask and the inside of the dropping funnel were purged with nitrogen gas for 10 minutes.

After the completion of the nitrogen gas replacement, the internal temperature was raised until the isopropyl alcohol was heated to reflux using an oil bath at 110 ° C. After the internal temperature became constant, both the monomer mixture solution and the polymerization initiator solution were continuously dropped over 40 minutes, and after the completion of the dropping, the reaction was aged for 2 hours.

After the completion of the reaction, the internal temperature was cooled to around room temperature to obtain a pale yellow transparent reaction solution. This reaction solution was sequentially added to 1000 ml of toluene to precipitate a polymer, which was dried under reduced pressure at 80 ° C. for 5 hours. As a result, 21 g of a light brown flaky polymer was obtained (polymerization yield: 84.7%).
was gotten. The number average molecular weight of the obtained polymer is 2200
(In terms of polystyrene). Further, the obtained polymer was soluble in water and methanol.

The nitrogen content in the obtained polymer is 0.04
95, the result that the oxygen content was 0.0902 was obtained from the elemental analysis. Therefore, the copolymerization ratio between the betaine type monomer 2 and the acrylamide was approximately equal to the betaine type monomer 2 / acrylamide = 1/3 ( (Molar ratio).

The infrared absorption spectrum of the obtained polymer was
As shown in FIG. FIG. 11 shows that the betaine-type monomer 2
Coming -CH_Two-NH-, -CH_Two-OH absorption is 940
cm ^-1Near 1060cm^-1Near 1200cm^-1Attached
Closely visible, absorption of stretching vibration of OH group is 3400cm^-1Attached
Seen nearby and 1450cm^-1Nearby (COO) ^-
Since the absorption of stretching vibration of
It was confirmed that in-type monomer 2 was contained.

<Polymerization Example 2> Synthesis of 3- (N, N-diethyl-N- (2-hydroxy-3-methacryloxy) propyl) ammoniopropanoate / n-docosanyl methacrylate copolymer (Polymer 2) 10) equipped with stirrer, cooling tube, thermometer and dropping funnel
30 g of toluene as a solvent in a 0 ml four-necked flask
And the 3- (N, N-di-) obtained in <Example 2> was prepared.
10 g (0.02912 mol) of n-butyl-N- (2-hydroxy-3-methacryloxy) propyl) ammoniopropanoate (betaine type monomer 2) and 23 g (0.029 mol) of n-docosanyl methacrylate as a comonomer
5828 mol) and 20 g of toluene, and a polymerization initiator solution consisting of 0.7 g of 2,2′-azobisisobutyronitrile, which is an azo polymerization initiator, as a polymerization initiator and 5 g of toluene, respectively. Charged into separate dropping funnel. At room temperature, the inside of the four-necked flask and the inside of the dropping funnel were purged with nitrogen gas for 10 minutes.

After the completion of the nitrogen gas replacement, the temperature in the flask was raised using an oil bath at 80 ° C. After the internal temperature became constant, both the monomer mixture solution and the polymerization initiator solution were continuously dropped over 1.5 hours, and after the completion of the dropping, the reaction was aged for 3 hours.

After completion of the reaction, the internal temperature was cooled to around room temperature to obtain a light brown transparent reaction solution. The reaction solution was sequentially added to 1000 ml of ethanol to precipitate a polymer, which was dried under reduced pressure at 80 ° C. for 5 hours. As a result, 24.8 g of a light brown waxy polymer was obtained (polymerization yield: 75.
2%). The number average molecular weight of the obtained polymer is 4
500 (in terms of polystyrene). Further, the obtained polymer was soluble in tetrahydrofuran and N, N-dimethylformamide.

The nitrogen content in the obtained polymer is 0.01
19. Since the result that the oxygen content was 0.1285 was obtained by the elemental analysis, the copolymerization ratio between the betaine-type monomer 2 and n-docosanyl methacrylate was approximately equal to the betaine-type monomer 2 / n- Docosanil methacrylate = 1/2
(Molar ratio).

FIG. 12 shows the infrared absorption spectrum of the obtained polymer. Turning to FIG. 12, betaine monomer 2 from the -CH ₂ -NH -, - absorption of CH ₂ -OH is 940c
m around ^-1, 1070 cm around ^-1, observed at about 1170Cm ^-1, stretching vibration absorption of OH group 3400~3500c
m- ¹ and (COO) around 1460cm- ^1
Since absorption of stretching vibration of-was observed, it was confirmed that betaine type monomer 2 was contained in the polymer.

<Polymerization Example 3> Synthesis of 3- (N, N-di-n-butyl-N- (2-hydroxy-3-allyloxy) propyl) ammoniopropanoate / acrylamide copolymer (Polymer 3) 10 equipped with stirrer, cooling tube, thermometer and dropping funnel
In a 0 ml four-necked flask, 20 g of isopropyl alcohol was charged as a solvent, and the mixture of 3-isopropyl alcohol obtained in <Example 3> was obtained.
(N, N-di-n-butyl-N- (2-hydroxy-3
-Allyloxy) propyl) ammoniopropanoate (betaine type monomer 3) 10 g (0.03170 mol), and 6.8 g of acrylamide (0.
09568 mol), 15 g of isopropyl alcohol and 3 g of water, 0.5 g of dimethyl 2,2′-azobis (isobutyrate), which is an azo polymerization initiator, and 5 g of isopropyl alcohol as polymerization initiators
Was charged into separate dropping funnels. At room temperature, the inside of the four-necked flask and the inside of the dropping funnel were purged with nitrogen gas for 10 minutes.

After the completion of the nitrogen gas replacement, the temperature in the flask was increased using an oil bath at 100 ° C. until the isopropyl alcohol was heated to reflux. After the internal temperature became constant, both the monomer mixed solution and the polymerization initiator solution were continuously dropped over 1 hour. The reaction solution in the flask became turbid during the dropping of the monomer mixture solution and the polymerization initiator solution, and became a pale yellow suspension. After completion of the dropwise addition, the reaction was aged for 2 hours.

After the completion of the reaction, the internal temperature was cooled down to around room temperature to obtain a pale yellow suspension. When the reaction solution was allowed to stand for a while, it was separated into a yellow-white polymer and a light brown transparent solution. Thereafter, the polymer was separated by filtration. Since this polymer was soluble in water, it was dissolved in water, and then sequentially added to 500 ml of isopropyl alcohol to precipitate a polymer. The polymer was dried at 80 ° C. for 5 hours under reduced pressure to obtain yellow-white flakes. Polymer 10.8g
(Polymerization yield: 64.3%) was obtained. The number average molecular weight of the obtained polymer was 1,700 (in terms of polyethylene oxide). Moreover, the obtained polymer was soluble in water.

The nitrogen content in the obtained polymer was 0.13.
Since the elemental analysis yielded a result of 85 and an oxygen content of 0.2185, the copolymerization ratio of betaine-type monomer 3 to acrylamide was approximately 1/3 (betaine-type monomer 3 / acrylamide = 1 / ( (Molar ratio).

FIG. 13 shows the infrared absorption spectrum of the obtained polymer. Turning to FIG. 13, betaine monomer 3 derived from -CH ₂ -NH -, - absorption of CH ₂ -OH is 940c
It is found near m ^-1 , 1120 cm ^-1 and 1200 cm ^-1 , and the absorption of stretching vibration of OH group is 3400 to 3500 cm ^-1
And the absorption of stretching vibration of (COO) ⁻ was observed at around 1450 cm ⁻¹ , confirming that betaine type monomer 3 was contained in the polymer.

[Brief description of the drawings]

FIG. 1 shows the betaine-type monomer 1 obtained in Example 1.
¹ shows a ¹ H-nuclear magnetic resonance spectrum.

FIG. 2 shows an infrared absorption spectrum of betaine-type monomer 1 obtained in Example 1.

FIG. 3 shows the betaine-type monomer 2 obtained in Example 2.
¹ shows a ¹ H-nuclear magnetic resonance spectrum.

4 shows an infrared absorption spectrum of betaine type monomer 2 obtained in Example 2. FIG.

FIG. 5 shows the results of the betaine-type monomer 3 obtained in Example 3.
¹ shows a ¹ H-nuclear magnetic resonance spectrum.

6 shows an infrared absorption spectrum of betaine type monomer 3 obtained in Example 3. FIG.

FIG. 7 shows the relationship between the betaine-type monomer 4 obtained in Example 4
¹ shows a ¹ H-nuclear magnetic resonance spectrum.

8 shows an infrared absorption spectrum of betaine type monomer 4 obtained in Example 4. FIG.

FIG. 9 shows ^{one of} the betaine-type monomers obtained in Example 5.
1 shows an H-nuclear magnetic resonance spectrum.

FIG. 10 shows an infrared absorption spectrum of the betaine-type monomer obtained in Example 5.

FIG. 11 shows an infrared absorption spectrum of Polymer 1 obtained in Polymerization Example 1.

FIG. 12 shows an infrared absorption spectrum of Polymer 2 obtained in Polymerization Example 2.

FIG. 13 shows an infrared absorption spectrum of Polymer 3 obtained in Polymerization Example 3.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 20/60 C08F 20/60 26/02 26/02 28/02 28/02 F-term (Reference) 4H006 AA02 AC52 BN10 BS10 BT12 BU30 4J100 AB01Q AB07P AE03Q AE09P AE18P AE26P AF10Q AG02Q AH01Q AJ02Q AJ09Q AK08Q AL03Q AL08P AL78Q AL79Q AM01Q AM14Q AM21P AN02P AN03P AN04P BA01P AQAP AQA BAQA

Claims (7)

[Claims] 1. The following general formula (1): (Wherein, R ₁ and R ₂ are each independently
A straight-chain or branched alkyl group having 1 to 8 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 1 to 8 carbon atoms, or both directly or O, S, and At least one selected from N
A cyclic group bonded through a certain element, and R ₃ is hydrogen or a methyl group or a hydroxymethyl group. And a β-alanine derivative represented by the following general formula (2): (However, in the formula, R ₄ represents one polymerizable carbon-carbon double bond.
R ₅ represents hydrogen or a methyl group. A method for producing a betaine-type monomer, characterized by reacting with a monooxirane compound represented by the formula: 2. A monooxirane compound represented by the following general formula (3): (Wherein, in the formula, R ₅ and R ₆ are each independently hydrogen or a methyl group, and A is an ester group, an amide group, an ether group, a sulfide group, a substituted or unsubstituted phenylene group, and a direct bond. A monooxirane compound having one polymerizable carbon-carbon double bond at a terminal represented by the following formula: The method for producing a betaine-type monomer according to claim 1, characterized in that: 3. The following general formula (4): (Wherein, R ₁ and R ₂ are each independently
A straight-chain or branched alkyl group having 1 to 8 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 1 to 8 carbon atoms, or both directly or O, S, and At least one selected from N
A cyclic group bonded through a certain element, R ₃ is hydrogen or a methyl group or a hydroxymethyl group, and R ₅ and R ₆ are each independently a hydrogen or a methyl group. B represents any one selected from an ether group, a sulfide group, and a direct bond, and m and n are each independently an integer of 0 to 5. A betaine-type monomer represented by). 4. The following general formula (5): (Wherein, R ₇ and R ₈ are each independently
A straight-chain or branched alkyl group having 3 to 8 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 1 to 8 carbon atoms, or both are directly each other or O, S, and At least one selected from N
A cyclic group bonded through a certain element, R ₃ is hydrogen or a methyl group or a hydroxymethyl group, and R ₅ and R ₆ are each independently a hydrogen or a methyl group. D represents any one selected from an ester group, an amide group and a substituted or unsubstituted phenylene group, and m and n each independently represent an integer of 0 to 5. A betaine-type monomer represented by). 5. The following general formula (6): (Wherein, R ₁ and R ₂ are each independently
A straight-chain or branched alkyl group having 1 to 8 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 1 to 8 carbon atoms, or both directly or O, S, and At least one selected from N
A cyclic group bonded through a certain element, R ₃ is hydrogen or a methyl group or a hydroxymethyl group, and R ₅ and R ₆ are each independently a hydrogen or a methyl group. A represents any one selected from an ester group, an amide group, a substituted or unsubstituted phenylene group, an ether group, a sulfide group and a direct bond, and m and n each independently represent an integer of 0 to 5 is there. )) And 1 to 100 mol% of the repeating unit (V) derived from another vinyl monomer (0 to 99 mol%)
The sum of the components (X) and (V) is 100 mol%. )
A polymer containing no repeating unit derived from a crosslinkable monomer. 6. The following general formula (7): (Wherein, R ₁ and R ₂ are each independently
A straight-chain or branched alkyl group having 1 to 8 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 1 to 8 carbon atoms, or both directly or O, S, and At least one selected from N
A cyclic group bonded through a certain element, R ₃ is hydrogen or a methyl group or a hydroxymethyl group, and R ₅ and R ₆ are each independently a hydrogen or a methyl group. B represents any one selected from an ether group, a sulfide group and a direct bond, and m and n are each independently an integer of 0 to 5. ) Repeating unit (Y)
And the repeating unit (V) derived from another vinyl monomer is 0 to 99 mol% (however, the sum of the components (Y) and (V) is 100 mol%). Polymer. 7. The following general formula (8): (Wherein, R ₇ and R ₈ are each independently
A straight-chain or branched alkyl group having 3 to 8 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 1 to 8 carbon atoms, or both are directly each other or O, S, and At least one selected from N
A cyclic group bonded through a certain element, R ₃ is hydrogen or a methyl group or a hydroxymethyl group, and R ₅ and R ₆ are each independently a hydrogen or a methyl group. D represents any one selected from an ester group, an amide group and a substituted or unsubstituted phenylene group, and m and n each independently represent an integer of 0 to 5. ), The repeating unit (V) derived from another vinyl monomer is 1 to 100 mol%, and the repeating unit (V) is 0 to 99 mol% (provided that the components (Z) and (V) are The sum is 100 mol%).