JP2002121220A - Polyvinylimidazoline methanesulfonate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyvinylimidazoline methanesulfonate having excellent heat resistance, and not containing a halogen. SOLUTION: A nitrile group-containing polymer is reacted with a polyamine in the presence of methanesulfonic acid and/or a methanesufonate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyvinyl imidazoline methanesulfonate and a method for producing the same. Polyvinylimidazoline methanesulfonate is a compound useful as a water-soluble polymer.

[0002]

2. Description of the Related Art A salt of polyvinylimidazoline is produced, for example, by 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. (See Japanese Patent Publication No. 42-6271).

[0003] A method of producing polyvinyl imidazoline hydrochloride by reacting acrylonitrile with a polyamine in the presence of salt salt is also known (JP-A-10-25920).
No. 9).

[0004]

However, it is extremely difficult to completely change the hydrogen sulfide salt of polyvinylimidazoline to another salt, and it is said that the method can be derived by the method described in JP-B-42-6271. Salt, hydrochloride,
It was limited to sulfates and p-toluenesulfonates.

[0005] The hydrochloride obtained by the method described in JP-A-10-259209 is extremely stable, and it has been difficult to induce it to other salts.

As described above, it is difficult to synthesize methanesulfonate of polyvinylimidazoline by the conventional method, and there has been no actual isolation.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a methanesulfonic acid salt of polyvinylimidazoline.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have surprisingly added polyvinyl imidazoline methane by adding methanesulfonic acid and / or methanesulfonate as a catalyst. The present inventors have found a novel fact that a sulfonate can be produced at once, and that polyvinyl imidazoline methanesulfonate can be isolated in a stable form, thereby completing the present invention.

That is, the present invention relates to polyvinyl imidazoline methanesulfonate, and methanesulfonic acid and / or methanesulfonic acid.
Alternatively, there is provided a method for producing a polyvinylimidazoline methanesulfonate, which comprises reacting a polymer containing a nitrile group with a polyamine in the presence of a methanesulfonate.

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

The polyvinylimidazoline methanesulfonate of the present invention has the following general formula (1)

[0012]

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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. ) Is a methanesulfonic acid salt of polyvinylimidazoline.

The polyvinylimidazoline methanesulfonate of the present invention is produced by reacting a polymer having a nitrile group with a polyamine in the presence of a methanesulfonate.

The nitrile group-containing polymer used in the production method of the present invention may be a homopolymer of acrylonitrile or methacrylonitrile, or a copolymer of acrylonitrile or methacrylonitrile with another monomer. Polymers can also be used. Acrylonitrile, monomers that can be copolymerized with 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 catalyst used in the production method of the present invention is methanesulfonic acid and / or methanesulfonic acid salt. As the methanesulfonate, ammonia and / or
Alternatively, an amine methanesulfonate can be used. The amine is not particularly limited, for example, aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine, alicyclic amines such as piperidine, pyrrolidine and cyclohexylamine, and aromatic amines such as pyridine and aniline And polyamines such as ethylenediamine, diethylenetriamine and propanediamine.

As the raw material polyamine used in the production method of the present invention, the following general formula (2) H ₂ NCHR ⁵ CHR ⁶ NHR ⁷ (2) (wherein R ⁵ , R ⁶ and R ⁷ are each independently Hydrogen, aliphatic,
(Which means an araliphatic or aromatic group, 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-methoxyphenyl Ethylenediamine, N-dimethylphenyl Ethylenediamine, N- tolyl ethylenediamine, N- methyl ethylenediamine,
N-ethylethylenediamine, N-isobutylethylenediamine, N-phenylethylenediamine, N- (2-
Aminoethyl) ethylenediamine and the like.

The order of addition of the methanesulfonic acid and / or methanesulfonic acid salt, the polymer containing a nitrile group and the polyamine used in the production method of the present invention is not particularly limited, but the methanesulfonic acid salt is contacted with the polyamine. Care must be taken to react violently to At this time, methanesulfonic acid may be added dropwise or may be diluted with a solvent before use. 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.

In the production method of the present invention, methanesulfonic acid and / or methanesulfonate is preferably reacted in an equivalent amount with a nitrile group of a polymer having a nitrile group. It is preferable that the polymer containing the polyamine and the nitrile group is reacted in a chemical equivalent or one of the 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 material, a method of performing the reaction under pressure, providing a condenser, or supplying the raw material little by little can be employed.

In the production method of the present invention, a solvent may or may not be used. It is not preferable to use a solvent that decomposes imidazoline such as water, 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 methanesulfonate of the present invention is excellent in heat resistance and can be used for a wide range of applications as a halogen-free water-soluble polymer. For example, semiconductor manufacturing, electrolytes, ion conductors, antistatic agents, polymer flocculants, bactericides, thickeners, paint additives,
It can be used as an anticorrosive, a surfactant and the like.

[0026]

The present invention provides a polyvinylimidazoline methanesulfonate having excellent heat resistance and containing no halogen. The polyvinylimidazoline methanesulfonate of the present invention is applicable to a wide range of uses such as electronic materials. It is industrially very significant.

[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 53.1 g of polyacrylonitrile (average molecular weight: 86000) and 40 parts of ethylenediamine were placed in a 1 L four-necked flask.
After 0 g was added and the mixture was stirred with replacement with nitrogen, 96.1 g of methanesulfonic acid was gradually added to the flask, and the temperature was raised. After heating at 115 ° C. for 4 hours, it was cooled and washed three times with 400 ml of tetrahydrofuran. The obtained viscous yellow solution was taken out and dried to obtain 175 g of a white polyvinylimidazoline methanesulfonate.

¹ H-NMR data Polyvinylimidazoline: (δ 1.8 to 2.2 ppm,
m) (δ2.5 to 3.0 ppm, m) (δ3.8 to 4.2 ppm, m) Methanesulfonic acid: (δ3.0 ppm, s) IR data Imidazoline ring: 1610 cm ^-1 Methanesulfonic acid: 1200 to 1200 1240 cm ^-1 Example 2 53.1 g of polyacrylonitrile (average molecular weight: 86000) and 50 g of n-propanol were placed in a ¹ L four-necked flask.
And 300 g of ethylenediamine, followed by nitrogen replacement and stirring, and 96.1 g of methanesulfonic acid was added to 50 g of n.
-The solution dissolved in propanol was gradually put into the flask, and the temperature was raised. After heating at 100 ° C. for 10 hours, it was cooled and washed three times with 400 ml of tetrahydrofuran. The obtained viscous yellow solution was taken out and dried to obtain 177 g of a pale yellow polyvinylimidazoline methanesulfonate powder.

Claims (9)

[Claims] 1. Polyvinyl imidazoline methanesulfonate. 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 polyvinylimidazoline methanesulfonate according to claim 1, characterized in that: 3. The polyvinylimidazoline methanesulfone according to claim 1, wherein the polyamine is reacted with a polymer containing a nitrile group in the presence of methanesulfonic acid and / or a methanesulfonic acid salt. Method for producing acid salt. 4. The polymer containing a nitrile group is a homogeneous polymer of acrylonitrile or methacrylonitrile,
Or a copolymer of acrylonitrile or methacrylonitrile and another monomer.
The production method described in 1. 5. The method according to claim 3, wherein the polyamine is 1,2-diamine. 6. A polyamine represented by the following general formula (2): H ₂ NCHR ⁵ CHR ⁶ NHR ⁷ (2) (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. The method according to any one of claims 3 to 5, which is a compound represented by the formula: 7. The method according to claim 3, wherein the methanesulfonate is a methanesulfonate of ammonia and / or amine. 8. The method according to claim 3, wherein the reaction temperature is in a range of 60 ° C. to 200 ° C. 9. The production method according to claim 3, wherein the reaction is carried out in a liquid phase.