JP2002338623A - Production method for vinylimidazoline copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problems with a conventional production method that counter ions derived from a catalyst are formed and salts are inevitably present and that these salts are stable and the counter ions are hardly removed. SOLUTION: An acrylonitrile-acrylic acid copolymer is reacted with a polyamine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a vinylimidazoline copolymer.

[0002]

2. Description of the Related Art As a method for producing a vinylimidazoline polymer, there is known a method in which an acrylonitrile polymer containing a nitrile group is reacted with a polyamine, and sulfur is used as a catalyst (Japanese Patent Publication No. 42-6271). ).

[0003] A method is also known in which acrylonitrile or an acrylonitrile copolymer is reacted with a polyamine in the presence of a salt salt to produce a vinylimidazoline polymer or a vinylimidazoline copolymer (JP-A-10-259).
209).

[0004]

However, since the produced vinylimidazoline polymer is a basic substance,
The method using sulfur as a catalyst described in JP-B-42-6271 forms a salt with acidic hydrogen sulfide, and it is difficult to remove hydrogen sulfide. Further, Japanese Patent Application Laid-Open No. 10-25920
In the method described in Japanese Patent Publication No. 9 using salt ammonium as a catalyst, it is difficult to completely remove hydrogen chloride since the obtained hydrochloride is extremely stable.

[0005] As described above, in the conventional method, a counter anion derived from the catalyst was formed, and a salt was always present. In addition, since these salts were stable, it was difficult to remove the counter anion.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that acrylonitrile-
By adding a polyamine to an acrylic acid copolymer, a vinylimidazoline copolymer can be produced all at once without adding a new catalyst, and the vinylimidazoline copolymer can be isolated in a stable form. And found the new fact, and completed the present invention.

That is, the present invention is a method for producing a vinylimidazoline copolymer, which comprises reacting an acrylonitrile-acrylic acid copolymer with a polyamine.

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

The vinylimidazoline copolymer of the present invention is produced by reacting an acrylonitrile-acrylic acid copolymer with a polyamine. In the production method of the present invention, a vinylimidazoline copolymer can be produced at once without adding a new catalyst, and the vinylimidazoline copolymer can be isolated in a stable form.

The acrylonitrile-acrylic acid copolymer used in the production method of the present invention has the following general formula (1)

[0011]

Embedded image (R ¹ represents hydrogen or a methyl group; n represents an integer of 2 or more.) And (2)

[0012]

Embedded image (R ² represents hydrogen or a methyl group; R ³ represents hydrogen or an alkyl group having 1 to 4 carbon atoms; m represents an integer of 2 or more).

The structural unit represented by the general formula (2) is not particularly limited as long as it contains a carboxyl group or an ester group. It is considered that a reaction product of these and a polyamine, that is, an amidoamine has a function of accelerating the reaction between the nitrile group and the polyamine.

In the acrylonitrile-acrylic acid copolymer used in the production method of the present invention, the constitutional ratio of the structural units represented by the above general formulas (1) and (2) is not particularly limited. If the amount of the structural unit represented by the general formula (2) is too small, the reaction becomes extremely slow. Therefore, as the composition ratio, the ratio of n to m in the general formulas (1) and (2) is n / m. m = 10000
0.01 is preferred, and n / m = 1000 is particularly preferred.
~ 0.1.

In the present invention, the molecular weight of the acrylonitrile-acrylic acid copolymer is not particularly limited, but preferably one having a weight average molecular weight of 1,000,000 or less can be used.
Those having a weight average molecular weight of about 50,000 or less are commercially available, and can be used.

The acrylonitrile-acrylic acid copolymer used in the production method of the present invention is specifically represented by the following general formula (3)

Embedded image (R ⁴ represents a hydrogen atom or a methyl group) and an acrylonitrile monomer represented by the following general formula (4)

Embedded image (R ⁵ represents hydrogen or a methyl group; R ⁶ represents hydrogen or an alkyl group having 1 to 4 carbon atoms).

Further, the acrylonitrile-acrylic acid copolymer used in the production method of the present invention may be a copolymer of the above-mentioned acrylonitrile monomer and acrylic acid monomer, and other monomers. Examples of such copolymerizable monomers include vinyl halides such as vinyl chloride, vinyl bromide, and vinyl fluoride; vinylidene halides such as vinylidene chloride; unsaturated carboxylic acids such as itaconic acid and maleic anhydride; Unsaturated ketones such as methyl vinyl ketone and methyl isopropenyl ketone,
Vinyl esters such as vinyl acetate and vinyl benzoate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, acrylamide and alkyl-substituted products thereof,
Methacrylamide and its alkyl-substituted products, vinylsulfonic acid, methallylsulfonic acid, allylsulfonic acid, p-
Unsaturated sulfonic acids and unsaturated sulfonic acids such as styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacryloyloxyethylsulfonic acid, and acryloyloxyethylsulfonic acid; styrene;
Alkyl-substituted styrene such as α-methylstyrene, halogen-substituted styrene such as chlorostyrene, allyl alcohols, allyl esters, allyl ethers, vinylpyridine, vinylpyrimidine, vinylimidazole, dimethylaminoethyl methacrylate, vinylbenzyl And basic vinyl compounds such as dimethylamine.

The polyamine used in the production method of the present invention is represented by the following general formula (6): H ₂ NCHR ¹¹ CHR ¹² NHR ¹³ (6) (wherein R ¹¹ , R ¹² and R ¹³ are each independently hydrogen. , Aliphatic, araliphatic or aromatic groups, which may contain a functional group.). As the 1,2-diamine, specifically, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, ethyleneamine such as aminoethylenepiperazine, 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 are exemplified.

In the production method of the present invention, the order of addition of the acrylonitrile-acrylic acid copolymer and polyamine to be used is not particularly limited, and a solvent may be used. As a solvent to be used at this time, 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.

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-acrylic acid copolymer may be broken. Also 60
If the reaction temperature is lower than 0 ° C., the reaction rate becomes extremely slow, which is not preferable.

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, in the case of a pressurized reaction, the pressure increases. However, 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 material, a method of performing the reaction under pressure, providing a condenser, or supplying the raw material little by little can be employed.

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 vinylimidazoline copolymer obtained by the production method of the present invention has the following general formula (5)

Embedded image (Wherein, R ⁷ represents a hydrogen atom or a methyl group. R ⁸ , R
⁹ and R ¹⁰ each independently represent a hydrogen atom or an aliphatic, araliphatic or aromatic group, which may contain a functional group. p represents an integer of 2 or more. )).

Further, the vinylimidazoline copolymer of the present invention does not contain a counter anion, and thus can be easily converted into a desired salt. Specifically, a salt can be easily formed by treating with an acid. The acid may be an organic acid or an inorganic acid. As the organic acid, for example, methanesulfonic acid, trifluoromethanesulfonic acid, p-
Toluenesulfonic acid, glycolic acid, diglycolic acid,
Acetic acid, oxalic acid, phthalic acid, salicylic acid, benzoic acid, p
-Hydroxybenzoic acid and the like; and inorganic acids include hydrochloric acid, hydrofluoric acid, boric acid, sulfuric acid, nitric acid, phosphoric acid and the like. Instead of using an acid, an acid salt thereof, for example, ammonium chloride, ammonium sulfate, sodium acid phosphate or the like can also be used.

The vinylimidazoline copolymer of the present invention comprises
As a water-soluble polymer having excellent heat resistance and containing no counter anion, it can be used for a wide range of applications. For example,
It can be used for semiconductor production, electrolytes, ion conductors, antistatic agents, polymer flocculants, bactericides, thickeners, paint additives, anticorrosives, surfactants and the like.

[0027]

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 An acrylonitrile-acrylic acid copolymer (copolymer composition: acrylonitrile 94) was placed in a 200 mL four-necked flask.
%, Acrylic acid 6%, weight-average molecular weight: 50,000), 10 g of which were replaced with nitrogen, 60 g of ethylenediamine was added, and the temperature was raised. After heating for 9 hours under reflux of ethylenediamine, a clear tan liquid was obtained. This was cooled and added to 400 ml of tetrahydrofuran for crystallization. After filtration and drying, 16 g of a vinylimidazoline copolymer was obtained.

Example 2 An acrylonitrile-methyl methacrylate copolymer (copolymer composition: 94% acrylonitrile, 6% methyl methacrylate, weight average molecular weight:
After adding 10 g of (50,000) and purging with nitrogen, 60 g of ethylenediamine was added and the temperature was raised. After heating for 26 hours under reflux of ethylenediamine, a clear tan liquid was obtained. This was cooled and added to 400 ml of tetrahydrofuran for crystallization. After filtration and drying, 15 g of a vinylimidazoline copolymer was obtained.

Example 3 A 200 mL four-necked flask was charged with an acrylonitrile-acrylic acid copolymer (copolymer composition: acrylonitrile 92
%, Acrylic acid 8%, weight-average molecular weight: 50,000), 10 g of which were replaced by nitrogen, 60 g of ethylenediamine was added, and the temperature was raised. 26 under reflux of ethylenediamine
After heating for an hour, a clear tan liquid was obtained. This was cooled and added to 400 ml of tetrahydrofuran for crystallization. After filtration and drying, 16 g of a vinylimidazoline copolymer was obtained.

Example 4 A 200 mL four-necked flask was charged with an acrylonitrile-acrylic acid copolymer (copolymer composition: acrylonitrile 88
%, Acrylic acid 12%, weight average molecular weight: 50,000) 10 g
Was added and purged with nitrogen, 60 g of ethylenediamine was added, and the temperature was raised. 2 under reflux of ethylenediamine
After heating for 6 hours, a clear tan liquid was obtained. This was cooled and added to 400 ml of tetrahydrofuran for crystallization. After filtration and drying, 15 g of a vinylimidazoline copolymer was obtained.

Example 5 Acrylonitrile-acrylic acid-sodium sulfonic acid copolymer (copolymer composition: acrylonitrile 94%, acrylic acid 5%, sodium sulfonate 1%, weight average molecular weight: 20,000) was placed in a 200 mL four-necked flask. ) After adding 10 g and purging with nitrogen, 60 g of ethylenediamine was added, and the temperature was raised. After heating for 9 hours under reflux of ethylenediamine, a clear tan liquid was obtained. This was cooled and added to 400 ml of tetrahydrofuran for crystallization. This was filtered and dried to obtain 15 g of a copolymer.

Example 6 An acrylonitrile-methacrylic acid-acrylic acid copolymer (copolymer composition: acrylonitrile 94%, methacrylic acid 4%, acrylic acid 2%) was placed in a 200 mL four-necked flask.
After adding 10 g of (weight average molecular weight: 50,000) and purging with nitrogen, 60 g of ethylenediamine was added, and the temperature was raised. After heating for 9 hours under reflux of ethylenediamine, a clear tan liquid was obtained. This was cooled and added to 400 ml of tetrahydrofuran for crystallization. After filtration and drying, 15 g of a vinylimidazoline copolymer was obtained.

[0034]

According to the method of the present invention, a vinylimidazoline copolymer containing no counter anion can be provided. Since the vinylimidazoline copolymer of the present invention has excellent heat resistance and does not contain a counter anion, it can be used for a wide range of uses as a water-soluble polymer. For example, the present invention can be used for semiconductor production, electrolytes, ion conductors, antistatic agents, polymer flocculants, bactericides, thickeners, paint additives, anticorrosives, surfactants, etc. It is extremely significant.

Continuing from the front page (72) Inventor Hiroyuki Yoshimura 3-9-10 F-term, Shinnanyo City Office, Yamaguchi Pref. AM15R AM17R AM19R AM21R AP01R AQ12R AQ19P AQ19R BA31R BA56R BC43R BC73H CA04 CA05 CA31 HA61 HC46 HE05 HE32 JA01 JA15 JA18 JA46

Claims (10)

[Claims] 1. A method for producing a vinylimidazoline copolymer containing no counter anion, comprising reacting an acrylonitrile-acrylic acid copolymer with a polyamine. 2. An acrylonitrile-acrylic acid copolymer represented by the following general formula (1): ## STR1 ## (Wherein R ¹ represents a hydrogen atom or a methyl group; n represents an integer of 2 or more) and the following general formula (2): Wherein R ² represents a hydrogen atom or a methyl group; R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; m represents an integer of 2 or more. Item 1
The production method described in 1. 3. An acrylonitrile-acrylic acid copolymer represented by the following general formula (3): (R ⁴ represents a hydrogen atom or a methyl group.) And an acrylonitrile monomer represented by the following general formula (4): (R ⁵ is .R ⁶ represents a hydrogen or a methyl group represents an alkyl group having 1 to 4 carbon hydrogen or carbon.) In claim 1, characterized in that a copolymer of acrylic acid monomer represented by The manufacturing method as described. 4. An acrylonitrile-acrylic acid copolymer represented by the following general formula (3): (R ⁴ represents a hydrogen atom or a methyl group), an acrylonitrile monomer represented by the following general formula (4): Wherein R ⁵ represents hydrogen or a methyl group; R ⁶ represents hydrogen or an alkyl group having 1 to 4 carbon atoms; vinyl halides, vinylidene halides, and unsaturated carboxylic acids , Acrylates, methacrylates, unsaturated ketones, vinyl esters, vinyl ethers, acrylamide and its alkyl-substituted products, acrylamidoamine, methacrylamide and its alkyl-substituted products, methacrylamidoamine, unsaturated sulfonic acid, styrene And a copolymer of one or more compounds selected from the group consisting of alkyl-substituted styrenes, halogen-substituted styrenes, allyl alcohols, allyl esters, allyl ethers, and basic vinyl compounds. Item 1. The production method according to Item 1. 5. A vinylimidazoline copolymer represented by the following general formula (5): (Wherein, R ⁷ represents a hydrogen atom or a methyl group. R ⁸ , R
⁹ and R ¹⁰ each independently represent a hydrogen atom or an aliphatic, araliphatic or aromatic group, which may contain a functional group. p represents an integer of 2 or more. The method according to any one of claims 1 to 4, wherein the structural unit (1) is included. 6. The method according to claim 1, wherein the polyamine is 1,2-diamine. 7. The polyamine is represented by the following general formula (6): H ₂ NCHR ¹¹ CHR ¹² NHR ¹³ (6) (wherein, R ¹¹ , R ¹² and R ¹³ are each independently hydrogen, aliphatic or araliphatic) Or an aromatic group, which may contain a functional group.) The method according to any one of claims 1 to 5, wherein the compound is a compound represented by the formula: 8. The method according to claim 1, wherein the reaction temperature is in the range of 60 to 200 ° C. 9. The method according to claim 1, wherein the reaction is carried out in a liquid phase. 10. The production method according to claim 1, wherein the reaction is carried out without adding a catalyst.