JPS60258488A - Manufacture of polystyrene bromous quaternary ammonium salt - Google Patents

Abstract

PURPOSE:To manufacture very stable prescribed polystyrene bromous quat. ammonium salt by electrolytically oxidizing polystyrene bromous quat. ammonium salt represented by a specified formula in a liq. medium. CONSTITUTION:Polystyrene bromous quat. ammonium salt represented by formula I is dissolved in water, alcohol or the like to prepare a soln. having about 0.01-2mol/l concn., and the soln. is kept at about 9-2pH. The soln. is electrolytically oxidized as an anolyte at <=about 1.5A/cm<2> current density and about 0-80 deg.C. The polystyrene bromous quat. ammonium salt may be obtd. by quaternizing pyridine groups in a styrene-divinylbenzene-vinylpyridine copolymer. By this method, polystyrene bromous quat. ammonium salt represented by formula IIis obtd. The resulting polystyrene is not degenerated even when allowed to stand in the air for a long period.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to a polystyrene-based quaternary ammonium bromide salt, which is characterized by electrolytically oxidizing a polystyrene-based quaternary ammonium bromide salt in a liquid medium. Regarding manufacturing methods.

Bromite is a valuable chemical used as a desizing agent for textiles and as an oxidizing agent in a variety of organic chemical reactions.

[Conventional technology]

Conventional methods for producing bromite compounds include, for example, a method of passing bromine and chlorine into an alkaline aqueous solution (Japanese Patent Publication No. 39-25
543), a method in which hydrobromide is reacted with hydrogen peroxide, and the like.

[Problem that the invention seeks to solve]

In the conventional manufacturing method described above, the former tends to produce side reactions and has a low yield, and the reaction product is an aqueous solution containing a mixture of chlorides and bromides, so this bath solution itself is usually used as a desizing agent. There is little use for it other than to use it as a gas, and the latter uses expensive hydrogen peroxide.
Furthermore, there is a danger of explosion when producing this, and neither method is preferred.

Moreover, since bromous acid is unstable even in the form of an alkali salt, it usually needs to be stored as a concentrated alkaline aqueous solution, and at present it is used for various purposes as an alkaline aqueous solution.

Originally, although bromite has good suitability as an oxidizing agent in organic chemical reactions, its use is limited due to the instability mentioned above. The development of bromate salts was desired.

[Means for solving problems]

As a result of intensive research into a method for producing stable bromite, the present inventor found that a polystyrene-based quaternary ammonium bromide salt can be easily obtained by electrolytically oxidizing a polystyrene-based quaternary ammonium bromide salt in a liquid. It was discovered that this polystyrene-based quaternary ammonium bromite salt does not deteriorate even when left in the air for a long time and is extremely stable, leading to the completion of the present invention. That is, the present invention is a method for producing a polystyrene-based quaternary bromide ammonium salt represented by: electrolytically oxidizing a polystyrene-based quaternary ammonium bromide salt represented by: in a liquid.

The present invention is represented by the following formula (1).

The present invention also includes a reaction in which a polystyrene-based quaternary ammonium bromide salt is formed in the reaction system, and is further oxidized to a polystyrene-based quaternary ammonium bromite salt by the reaction of formula (1). That is, according to the following formula (It), a polystyrene-based quaternary ammonium bromide salt is formed by an exchange reaction of hydrobromic acid or its salt with a polystyrene-based quaternary ammonium salt in the reaction system, and then the formula (
1) This is a reaction in which oxidation occurs. Formula (n) represents an ion other than bromine, and p represents a cation other than quaternary ammonium.

The polystyrene quaternary ammonium salt referred to in the present invention is
It refers to a polymer in which a quaternary ammonium group is bonded to the main chain or side chain of a polymer whose main component is styrene. For example,
Polystyrene with a benzene ring bound to a quaternary ammonium group via a methylene or alkylene group, a copolymer of a monomer unit consisting of a quaternary ammonium group and another monomer, or a crosslinked copolymer thereof Even if it's a combination (,
For example, a styrene-methacrylic acid-vinylpyridine copolymer, a styrene-syhenylbenzene-vinylpyridine copolymer in which the pyridine group is quaternized, or a benzene ring is quaternized via a methylene group. Examples include a stynone-divinylbenzene copolymer in which a quaternary ammonium group is bonded to the benzene ring via a methylene group.

Generally, commercially available strongly basic anion exchange resins are suitable for use in the purpose of the present invention.

The material may be any material that does not inhibit the production of polystyrene-based quaternary ammonium bromite under electrolytic oxidation conditions (including, but not limited to, hydroxide ions, fluorine, halodane ions such as chlorine, perchlorate ions, and sulfite ions). ion, hydrogen sulfite ion, sulfate ion, hydrogen sulfate ion, etc., and - is preferably an alkali metal or an alkaline earth metal, but is not limited thereto.

The exchange reaction may be carried out in liquid before electrooxidation (
Furthermore, a method in which one salt is present in excess in the electrolytic cell and electrolytically oxidized while adding the other salt, or a method in which both salts are added simultaneously in the electrolytic cell is also adopted.

The liquid used in the present invention is water or an organic solvent containing water, and the organic solvent may be soluble, partially soluble, or sparingly soluble in water (depending on the purpose, each of water and organic solvent may be It may be used alone or as a mixture (and in some cases, a mixture of liquid media forming two phases may also be suitably used. However, the organic solvent used may be oxidized by the generated bromite groups). Usually, water or a homogeneous or heterogeneous mixed medium of water and an organic solvent is used, but organic solvents alone may also be used as a medium (i.e., when the bromide ions are in liquid form). The medium may be selected such that it is liberated in the medium.

Specific examples include water-containing alcohols, ethers, alkoxy alcohols, ketones,
Examples include alkyl hydrocarbons, halodanized hydrocarbons, benzene compounds, and aprotic solvents.

The polystyrene-based quaternary ammonium salt is directly supplied to the reaction system in the form of a slurry, but it is preferable to maintain the ... of the system at 9-2.

The above describes the polystyrene-based quaternary ammonium bromide base and the mixture of hydrobromic acid or its salt and polystyrene-based quaternary ammonium salt that can form a polystyrene-based quaternary ammonium bromide salt in the reaction system. These compositions are fed to the anode cell of the electrolytic cell. On the other hand, the catholyte does not need to be particularly limited, and various solutions that can flow the necessary current in the electrolytic reaction are usually used.

The equipment used for the electrolytic oxidation reaction does not require any special consideration and may be a normal equipment.

Examples of the material of the anode include platinum, lead dioxide, manganese dioxide, carbon-based materials, etc., and the material of the cathode is:
Examples include metal materials such as platinum, iron, lead, copper, etc., or carbon-based materials.

Specific examples of the materials for the anode and cathode are given above, but the material is not limited to these (in addition, the shapes of the anode and cathode should be appropriately determined depending on the shape of the electrolytic cell to be used).
Flat, cylindrical, cylindrical, mesh, etc. shapes are used.

As the diaphragm that separates the anolyte and catholyte, various types of membranes can be used in addition to the clay plate.

The amount of polystyrene quaternary ammonium salt supplied to the anolyte is 0.01 to 2 mol/13. Preferably it is 0.05 to 0.5 mol/no. Moreover, when using a special device, it may be outside this range.

The current may be supplied using either a constant current method or a constant voltage method. The optimum current density should be determined depending on the electrolyte concentration of the anolyte and other factors, but it is usually 1.5 A/cm2 or less, preferably in the range of 0.005 to 0.5 fi-/crn2.

The appropriate temperature range for the electrolytic solution is from 0°C to 80°C.At low temperatures, the reaction rate decreases, and at high temperatures, the yield of polystyrene-based quaternary ammonium bromite salt decreases. It is desirable to adjust within the above range.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to this.

The electrolytic cell used in the example uses a 500 d glass sleeve cylindrical container, in which a cylindrical unglazed diaphragm (45 φ x 150) is placed, the inside of this is used as an anode chamber, and a reticular cylindrical electrode (6 φ x 5) is installed in the anode chamber. , the outer cathode chamber is equipped with a lead plate ("
80 crn2) was installed.

Commercially available polystyrene quaternary ammonium salt O in the anode chamber.
4 g of type H (the ion exchange capacity was 20 mmol when measured with NaCAl) and 100 y of a 2N potassium bromide aqueous solution were supplied, and 100 d of a 2N potassium bromide water bath solution was supplied to the cathode chamber. After that, while stirring the anode chamber with a magnetic stirrer, a current density of 0.5 A/c was applied.
The temperature of the electrolytic solution was maintained at 10°C. After electrolyzing the resin with a current of 1 mole of 4F, the orange-colored resin was separated from the reaction solution by decantation, washed with water, Dry.

Next, this dried product was analyzed with an infrared atomic element meter, and it showed B.
Absorption of r02 (760 m-1) was confirmed.

In addition, this resin was immersed in 100 μg of 1N strength soda, and the bromite group was dissolved in the bath liquid as a sodium salt.The amount of bromite group was determined by iodine titration. 19.6 mmol (yield*98.0%) of the acid salt was produced.

〔Effect of the invention〕

The effects of the present invention are that, although it has been known that bromate can be obtained by electrolyzing hydrobromide, boristine-based bromite, which is at an intermediate stage, can be synthesized by electrolysis. This was completely unknown, but in the present invention, by allowing a polystyrene-based quaternary ammonium salt to coexist in the electrolytic system, it was first possible to successfully bond a °C bromite group to a polystyrene-based quaternary ammonium salt. It is.

Furthermore, the bromite group of the polystyrene-based quaternary ammonium bromite group obtained by the method of the present invention is extremely stable even when left in the air, and after being used in various organic chemical reactions such as oxidation, The polystyrene-based quaternary ammonium group is recovered by any method and used again to prepare a polystyrene-based bromite quaternary ammonium salt, which is an industrially advantageous method.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment May 27, 1985 Commissioner of the Patent Office Manabu Shiga '1. 1. Indication of the case 1985 Patent Application No. 91130 2. Name of the invention Process for producing polystyrene-based quaternary ammonium bromite salt 6. Person making the amendment Relationship to the case Patent applicant address 1 Yurakucho, Chiyoda-ku, Tokyo Claims column and Detailed Description of the Invention column 5 of Specification No. 4-1, contents of amendments 1) The claims on page 1 are corrected as shown in the attached sheet.

2) "Polystyrene-based bromite quaternary ammonium salt" in lines 5-6 of page 4 is corrected to "polystyrene-based bromite quaternary ammonium salt."

Claims: ``A method for producing a polystenone-based quaternary ammonium bromite salt represented by: electrolytically oxidizing a polystenone-based quaternary ammonium salt represented by bromite in a liquid medium.''

Claims (1)

[Scope of Claims] A method for producing a polystyrene-based quaternary bromide ammonium salt represented by: electrolytically oxidizing a polystyrene-based tetraR bromide ammonium salt represented by: in a liquid medium.