JP2002187913A - Polyvinylimidazoline hydroxycarboxylate and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyvinylimidazoline hydroxycarboxylate which has heat resistance and no halogen, and accordingly is applicable as a water-soluble polymer to various uses, particularly very useful in the field of electronic materials. SOLUTION: The polyvinylimidazoline hydroxycarboxylate is obtained by reacting a nitrile group-containing polymer with a polyamine in the presence of a hydroxycarboxylic acid and/or a hydroxycarboxylic acid salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyvinyl imidazoline hydroxycarboxylate and a method for producing the same. Polyvinylimidazoline hydroxycarboxylate is a compound useful as a water-soluble polymer.

[0002]

2. Description of the Related Art A conventionally known salt of polyvinylimidazoline is obtained by first reacting acrylonitrile with a polyamine in the presence of sulfur to produce polyvinylimidazoline hydrogen sulfide, and then adding an acid thereto to obtain a desired salt. It was manufactured (see Japanese Patent Publication No. Sho 42-6271). It is extremely difficult to completely change the hydrogen sulfide salt of polyvinylimidazoline to another salt, and the salts that can be derived by this method are limited to hydrochloride, sulfate, and p-toluenesulfonate. Met. Also, a method for producing polyvinyl imidazoline hydrochloride by reacting acrylonitrile and polyamine in the presence of salt ammonium (Japanese Patent Application Laid-Open No. 10-25920)
No. 9) is also known, but it has been difficult to derive another salt because the hydrochloride is very stable.

[0003] As described above, no example of synthesizing and isolating a hydroxycarboxylic acid salt of polyvinylimidazoline has been known so far.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has unexpectedly added polyvinyl imidazoline hydroxy by adding hydroxycarboxylic acid and / or hydroxycarboxylate as a catalyst. The present inventors have found a novel fact that a carboxylate can be produced at once, and that a polyvinylimidazoline hydroxycarboxylate can be isolated in a stable form, thereby completing the present invention.

That is, the present invention provides a polyvinylimidazoline hydroxycarboxylate comprising reacting a polyamine with a polyvinylimidazoline hydroxycarboxylate and a polymer containing a nitrile group in the presence of the hydroxycarboxylic acid and / or the hydroxycarboxylate. This is a method for producing a carboxylate.

Hereinafter, the present invention will be described in more detail.

[0007] The polyvinyl imidazoline hydroxycarboxylate of the present invention specifically has the following general formula (1):

[0008]

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(Where n is an integer of 2 or more, R ¹ , R ² ,
R ³ and R ⁴ each independently represent hydrogen or an alkyl group having 1 to 12 carbon atoms. ) And the following general formula (2)

[0010]

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(Wherein R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydroxyl group, a carboxyl group, hydrogen, an alkyl group having 1 to 5 carbon atoms, The carboxyl group shall contain at least one each.) Or the following general formula (3)

[0012]

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(Wherein m is 1 to 5, R ¹⁴ and R ¹⁵
Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group. ) Is a salt consisting of a hydroxycarboxylic acid.

Specific examples of the hydroxycarboxylic acid represented by the general formula (2) used in the present invention include salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, , 4
-Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,
Examples include 3,4-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, and 3,4,5-trihydroxybenzoic acid.

Specific examples of the hydroxycarboxylic acid represented by the general formula (3) include glycolic acid, lactic acid,
Examples thereof include 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, and tartaric acid.

The polyvinylimidazoline hydroxycarboxylate of the present invention is produced by reacting a polymer containing a nitrile group with a polyamine in the presence of a hydroxycarboxylic acid.

As the nitrile group-containing polymer used in the production method of the present invention, a homopolymer of acrylonitrile or methacrylonitrile may be used, or a copolymer may be used. Examples of monomers copolymerizable with acrylonitrile and methacrylonitrile include vinyl chloride, vinyl bromide, vinyl halides such as vinyl fluoride, vinylidene halides such as vinylidene chloride,
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride and salts thereof, (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, methyl vinyl ketone, Unsaturated ketones such as methyl isopropenyl ketone, vinyl esters such as vinyl acetate and vinyl benzoate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, (meth) acrylamide and alkyl-substituted products thereof,
Unsaturated sulfonic acids such as vinylsulfonic acid, (meth) allylsulfonic acid, p-styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, (meth) acryloyloxyethylsulfonic acid and salts thereof, styrene, α Bases such as styrene such as methylstyrene and chlorostyrene and alkyl- or halogen-substituted products thereof, allyl alcohol and esters or ethers thereof, vinylpyridine, vinylpyrimidine, vinylpyrrolidone, vinylimidazole, dimethylaminoethyl methacrylate, and vinylbenzyldimethylamine; Vinyl compounds and the like.

The hydroxycarboxylic acid and / or hydroxycarboxylate used in the production method of the present invention acts as a catalyst. Hydroxycarboxylates are
Hydroxycarboxylates of ammonia and / or amines can be used. The amine is not particularly limited, for example, aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, alicyclic amines such as piperidine, pyrrolidine, cyclohexylamine, and aromatic amines such as pyridine and aniline , Ethylenediamine, diethylenetriamine,
And polyamines such as propanediamine.

As the raw material polyamine used in the production method of the present invention, 1,2-diamine is exemplified.
The 1,2-diamine is specifically represented by the following general formula (4).

H ₂ NCHR ⁵ CHR ⁶ NHR ⁷ (4) (wherein R ⁵ , R ⁶ and R ⁷ are each independently hydrogen, aliphatic,
Means one or more selected from the group consisting of araliphatic and aromatic groups) As the 1,2-diamine, specifically, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, Ethylene amines such as aminoethylene piperazine,
Diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, cyclohexylethylenediamine, benzylethylenediamine, phenylethylenediamine, methoxyphenylethylenediamine, dimethylphenylethylenediamine, tolylethylenediamine, N-cyclohexylethylenediamine, N- Benzylethylenediamine, N-phenylethylenediamine, N-methoxyphenylethylenediamine, N-dimethylphenylethylenediamine, N-tolylethylenediamine, N-methylethylenediamine, N
-Ethylethylenediamine, N-isobutylethylenediamine, N-phenylethylenediamine, N- (2-aminoethyl) ethylenediamine, and the like.

The order of addition of the hydroxycarboxylic acid and / or hydroxycarboxylate, the polymer containing a nitrile group and the polyamine used in the production method of the present invention is not particularly limited, but the hydroxycarboxylate and the polyamine are contacted. Care must be taken to react violently to As a solvent to be used at this time, it is not preferable to use a solvent that decomposes imidazoline such as water.

In the production method of the present invention, the hydroxycarboxylic acid and / or hydroxycarboxylate is equivalent to the nitrile group of the nitrile group-containing polymer, and the polyamine and the nitrile group-containing polymer are chemically equivalent or The reaction can be performed with one excess.

In the production method of the present invention, the reaction temperature is
Usually performed in the range of 60 to 200 ° C.,
More preferably, it is carried out at a temperature of 0 ° C. Although the reaction can be carried out at a temperature higher than 200 ° C., the molecular chain of the acrylonitrile or methacrylonitrile polymer as a raw material may be cut off. If the reaction temperature is lower than 60 ° C., the reaction rate becomes extremely slow, and the amount of the catalyst needs to be increased, which is not economical.

The production method of the present invention is usually carried out in a liquid phase.

In the production method of the present invention, the reaction may be carried out at normal pressure or under pressure, as long as the raw materials are kept in a liquid, solution or suspension state. In this reaction, since ammonia is generated during the reaction, the pressure increases in the case of a pressurized reaction, but this ammonia can be removed during the reaction or can be removed after the reaction is completed. . When the reaction temperature exceeds the boiling point of the raw materials, a method of performing the reaction under pressure, providing a condenser, or supplying the raw materials little by little can be employed.

In the production method of the present invention, a solvent may or may not be used. As the solvent, use of a solvent that decomposes imidazoline such as water is not preferred, but any solvent can be used without particular limitation as long as it is inert to the reaction conditions.

The production method of the present invention may be carried out by a continuous reaction, a batch reaction, or a semi-batch reaction. In addition, the reaction can be carried out using a fixed bed or a suspension bed.

The polyvinylimidazoline hydroxycarboxylate of the present invention has excellent heat resistance and can be used for a wide range of applications as a halogen-free water-soluble polymer. For example, semiconductor manufacturing, electrolyte, ionic conductor,
It can be used as an antistatic agent, a polymer flocculant, a bactericide, a thickener, a paint additive, an anticorrosive, a surfactant and the like.

[0029]

The present invention provides a polyvinyl imidazoline hydroxycarboxylate. The polyvinyl imidazoline hydroxycarboxylate of the present invention is excellent in heat resistance and does not contain halogen, so that it is applicable to a wide range of uses as a water-soluble polymer, and is particularly useful for electronic materials.

[0030]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 A 200 mL four-necked flask was charged with 5.0 g of polyacrylonitrile (average molecular weight: 86000) and 13.01 g of p-hydroxybenzoic acid, and the mixture was stirred under nitrogen and stirred, and 35.0 g of ethylenediamine was added to the flask. And the temperature was raised. After heating at 110 ° C. for 4 hours, it was cooled and crystallized with 200 ml of tetrahydrofuran. When this was dried, 14.4 g of a white polyvinylimidazoline p-hydroxybenzoate powder was obtained.

¹ H-NMR data polyvinyl imidazoline: (δ 1.5 to 2.0 ppm,
m) (δ 2.2 to 2.3 ppm, m) (δ 3.4 to 3.9 ppm, m) p-hydroxybenzoic acid: (δ 6.8 ppm, m) (δ 7.9 ppm, m) IR data imidazoline ring: 1603 cm ^-1 .

Example 2 5.0 g of polyacrylonitrile (average molecular weight: 86000), 20 g of n-propanol and 13.01 g of p-hydroxybenzoic acid were added to a 200 mL four-necked flask, and the mixture was stirred under nitrogen and stirred. 20g
Was placed in a flask and the temperature was raised. After heating at 110 ° C. for 10 hours, this was cooled and tetrahydrofuran 200
Crystallization was performed in ml. When this was dried, 14.0 g of a white polyvinyl imidazoline p-hydroxybenzoate powder was obtained.

Example 3 5.0 g of polyacrylonitrile (average molecular weight: 86,000) and salicylic acid 1 were placed in a 200 mL four-necked flask.
After adding 3.01 g and stirring with nitrogen replacement, 35.0 g of ethylenediamine was placed in a flask and the temperature was raised. After heating at 110 ° C. for 4 hours, it was cooled and crystallized with 200 ml of tetrahydrofuran. When this was dried, 19.5 g of white polyvinyl imidazoline salicylate powder was obtained.

¹ H-NMR data Polyvinyl imidazoline: (δ 1.5 to 2.0 ppm,
m) (δ 2.2 to 2.3 ppm, m) (δ 3.4 to 3.9 ppm, m) Salicylic acid: (δ 6.8 ppm, m) (δ 7.3 ppm, m) (δ 7.8 ppm, m) IR data imidazoline Ring: 1603 cm ^-1 .

Example 4 To a 200 mL four-necked flask were added 5.0 g of polyacrylonitrile (average molecular weight: 86,000) and 0.45 g of methanesulfonic acid, and the mixture was purged with nitrogen and stirred. Then, 35.0 g of ethylenediamine was put into the flask. The heating was started. After heating at 110 ° C. for 24 hours, it was cooled and crystallized with 200 ml of tetrahydrofuran. After drying, 4.74 g was weighed and dissolved in 20 g of methanol. A solution obtained by dissolving 3.57 g of glycolic acid in 10 g of methanol was added dropwise thereto, and the mixture was stirred at 60 ° C. for 3 hours. The methanol was removed to obtain 7.9 g of a white polyvinylimidazoline rulicholate powder.

¹ H-NMR data Polyvinyl imidazoline: (δ 1.5 to 2.0 ppm,
m) (δ 2.2 to 2.3 ppm, m) (δ 3.4 to 3.9 ppm, m) Glycolic acid: (δ 3.9 ppm, s) IR data Imidazoline ring: 1603 cm ^-1 .

Claims (9)

[Claims] 1. Polyvinyl imidazoline hydroxycarboxylate. 2. Polyvinyl imidazoline is represented by the following general formula (1): Wherein n is an integer of 2 or more, and R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen or an alkyl group having 1 to 12 carbon atoms. The polyvinyl imidazoline hydroxycarboxylate according to claim 1, characterized in that: 3. Hydroxycarboxylic acid is represented by the following general formula (2): (Wherein, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydroxyl group, a carboxyl group, hydrogen, an alkyl group having 1 to 5 carbon atoms, and At least one each.) Or the following general formula (3): (In the formula, m is 1 to 5, and R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group.) 3. The compound according to claim 1 or 2, wherein
Polyvinyl imidazoline hydroxycarboxylate described in 1. 4. The method according to claim 1, wherein a polymer containing a nitrile group is reacted with a polyamine in the presence of a hydroxycarboxylic acid and / or a hydroxycarboxylic acid salt.
A method for producing a polyvinyl imidazoline hydroxycarboxylate according to any one of claims 1 to 3. 5. The method according to claim 4, wherein the polymer containing a nitrile group is a homopolymer or a copolymer of acrylonitrile or methacrylonitrile. 6. The method according to claim 4, wherein the polyamine is 1,2-diamine. 7. A 1,2-diamine represented by the following general formula (4)
The method according to claim 6, wherein the compound is represented by the formula: H ₂ NCHR ⁵ CHR ⁶ NHR ⁷ (4) (wherein R ⁵ , R ⁶ and R ⁷ are each independently hydrogen, aliphatic,
An araliphatic or aromatic group is meant, which may contain functional groups. ) 8. The method according to claim 4, wherein the reaction temperature is in a range of 60 ° C. to 200 ° C. 9. The method according to claim 4, wherein the reaction is carried out in a liquid phase.