JPS634919B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to the production of glycidyl quaternary ammonium salts, in which a glycidyl compound is synthesized by dehydrohalogenation from an epihalohydrin addition compound using an electrodialysis method. , relates to a novel electrodialysis synthesis method that allows the synthesis reaction to be carried out efficiently.

[Conventional technology]

Glycidyl quaternary ammonium salt is widely used as a cationizing agent for various compounds such as starch, cellulose, and polyamines, and is an extremely important compound in industry.
It is produced by reacting an aqueous solution of a grade amine hydrohalide with an epihalohydrin such as epichlorohydrin to obtain an epihalohydrin adduct, and adding an alkali such as sodium hydroxide to this to perform ring closure. However, when ring-closing with an alkali in this manner, a halogen salt is always produced as a by-product from the alkali metal and the halogen derived from epihalohydrin. Since the removal of halogen salts generally involves many disadvantages, the present inventors previously proposed a method for synthesizing glycidyl quaternary ammonium salts using electrodialysis without producing halogen salts as by-products. (Special Application No. 59-187713).

A method using this electrodialysis method is to perform apparent dehydrohalogenation by electrodialysis from an addition reaction product of a tertiary amine hydrohalide or a polyamine hydrohalide and epihalohydrin to form a glycidyl quaternary ammonium salt. This is the way to obtain. More specifically, using an electrodialysis tank configured with an anion exchange membrane, tertiary amine hydrohalide and epihalohydrin are added to a compartment (organic chamber) in the dialysis tank by a known method. supplying an epihalohydrin adduct obtained by reacting with
On the other hand, in this method, an alkali is supplied to the cathode side (alkali chamber) of the compartment and the ring is closed by passing a direct current to the cathode side (alkali chamber) to obtain a glycidyl quaternary ammonium salt. In other words, OH ^- moves from the alkali chamber through an anion exchange membrane and reacts with the epihalohydrin adduct in the organic chamber to form an oxirane ring, while halogen ions from the organic chamber are electrically transferred to the alkali chamber. . In this way, halogen salts are produced in the alkali chamber without producing halogen salts as by-products in the epihalohydrin adduct system. Furthermore, a high reaction rate of around 80% can be maintained for the production of glycidyl compounds relative to epihalohydrin adducts. As described above, although this method is an excellent reaction method with a high reaction rate and no by-product of halogen salts, it has the following drawbacks.

[Problem that the invention seeks to solve]

One of these is that in the late reaction stage, the alkali concentration in the alkali chamber becomes diluted, and on the other hand, the amount of halogen salt increases, so in the late reaction stage, the halogen ions that have migrated from the organic matter chamber along with OH ^- transfer are returned to the organic matter chamber on the anode side. This is because the reaction efficiency decreases. To prevent this, it is necessary to supply more than the required amount of alkali to the alkali chamber. In such a case, excess alkali will remain at the end of the reaction and must be disposed of as is, leading to an increase in manufacturing costs.

Secondly, since the organic matter chamber and the alkali chamber are adjacent to each other with an anion exchange membrane in between, some of the halogen ions that have migrated from the organic matter chamber pass through the alkali chamber and return to the organic matter chamber on the anode side. As a result, the applied current is not efficiently consumed for ion movement, reducing current efficiency and increasing manufacturing costs. The electrodialysis method using an anion exchange membrane has such drawbacks, and the inventors of the present invention have conducted intensive studies to further improve this problem.
We have completed a new electrodialysis reaction method that has high current efficiency and can react with the same amount of alkali supplied or with a slight excess amount.

[Means for solving problems]

That is, the present invention provides a method for producing a glycidyl compound by dehydrohalogenation from an addition reaction product of a tertiary amine hydrohalide or a polyamine hydrohalide and epihalohydrin. Using an electrodialysis tank with one cation exchange membrane placed on each of the cathode and anode sides, the epihalohydrin addition reaction product is placed in a chamber (organic chamber) sandwiched between the two anion exchange membranes of the electrodialysis tank. an electrolyte solvent is present in a chamber on the anode side adjacent to the organic substance chamber, an alkaline solution is present in a chamber on the cathode side adjacent to the organic substance chamber, and a direct current is applied to perform electrodialysis. A method for producing a glycidyl quaternary ammonium salt is provided.

FIG. 1 schematically shows one example of such an electrodialyzer, which will be explained in more detail with reference to the drawings. As shown in the figure, a cation exchange membrane 3 is arranged on the cathode side and the anode side of two anion exchange membranes 4, respectively, and a large number of sets are set. An epihalohydrin adduct obtained by reacting a tertiary amine hydrohalide and epihalohydrin by a known method is supplied to an organic substance chamber sandwiched between two ion exchange membranes, while the adjacent anode side An electrolyte solution is supplied to the chamber (electrolyte chamber), and an alkaline solution is supplied to the chamber on the cathode side (alkali chamber). By applying a direct current, the OH ^- ions of alkali (MOH) attempt to migrate to the organic matter chamber through the anion exchange membrane. Also, alkali metal ions (M ⁺ ) tend to migrate to the electrolyte chamber. The OH ^- ion transferred to the organic matter chamber reacts with the epihalohydrin adduct present in the organic matter chamber to form an oxirane ring. Taking the epichlorohydrin adduct of tertiary amine hydrochloride as an example, the following reaction takes place.

The Cl ^- generated here passes through the anion exchange membrane and moves to the electrolyte chamber on the anode side. Metal ions from the alkali chamber and halogen ions (Cl ^- in the above equation) from the organic chamber migrate into the electrolyte chamber.
Metal ions are blocked by the anion exchange membrane, and halogen ions are blocked by the cation exchange membrane and cannot move to other chambers, and as a result, halogen salts are formed in this electrolyte chamber. Therefore, the transferred halogen ions do not pass through and return to the original organic substance, which is the case with electrodialyzers composed of anion exchange membranes, and the applied current is efficiently used for ion transfer. be done. On the other hand, only alkali is consumed from the alkali chamber, and no halogen salt is formed within the alkali chamber. Therefore, the above-mentioned drawbacks are eliminated, and the reaction can be carried out efficiently with the amount of alkali equal to or slightly in excess of the amount of alkali required for the reaction. In this way, in this method, the epihalohydrin adduct is apparently dehydrohalogenated and ring-closed in the organic matter chamber, and the generated halogen ion is transferred, so that the desired result is achieved without the by-product of a halogen salt. While the glycidyl quaternary ammonium salt can be obtained with high purity, the alkali can be consumed efficiently and the reaction can be completed with high current efficiency since there is no loss of ion movement. Furthermore, in this method, continuous operation is also possible by sequentially adding the consumed alkali and sequentially extracting the electrolyte solution produced in the electrolyte chamber.

The glycidyl quaternary ammonium salt targeted by the present invention is obtained by using a tertiary amine hydrohalide as a starting material, adding epihalohydrin thereto by a known method, and then ring-closing it by electrodialysis. The hydrocarbon group of the raw material amine hydrohalide has 1 to 22 carbon atoms, and can be linear, branched, or cyclic. For example, the raw material tertiary amines include trimethylamine, triethylamine, tri-n-butylamine, tri-n-propylamine, and tri-n-propylamine.
n-hexylamine, dimethylmonoethylamine, dimethylmono-n-butylamine, dimethylcyclohexylamine, dimethylmonoisopropylamine, dimethylmono-n-octylamine,
Dimethylmono-n-laurylamine, methylethyl-n-propylamine, methylethyl-n-butylamine, N-methylpiperidine, N-ethylpiperazine, dimethylbenzylamine, etc. are used.

Further, as the hydrohalide salt, any of hydrochloride, hydrobromide, hydroiodide, and hydrofluoride can be used. Note that some tertiary amine hydrohalides are difficult to dissolve in water at high concentrations, so it is preferable to dissolve them in a mixed solution of water and a good solvent such as ethanol, and then supply this to electrodialysis. .

Further, the lower polyamine hydrohalide salt can be represented by the following general formulas () to ().

In the formula, R ₁ , R ₂ , R ₃ , R ₄ : Either a methyl group or an ethyl group, l=1-8 m=1-3 n=1-3
z=1 to 5 x=represents either Cl ^- , Br ^- , I ^- or F ^- .

Further, examples of epihalohydrin that can be used in the present invention include epichlorohydrin, epibromohydrin, epifluorohydrin, and epiiodohydrin.

The alkali to be present in the alkali chamber of the electrodialysis tank may be any compound that dissolves well in water and exhibits alkalinity, and the type thereof is not particularly limited. For example, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. , barium hydroxide,
Ammonium hydroxide, sodium aluminate, potassium aluminate, a mixture of aluminum hydroxide and ammonium hydroxide, or a mixture thereof can be used.

Electrodialysis can be performed by making an aqueous solution of these alkaline substances exist in the alkaline chamber, but if the concentration of epihalohydrin adducts present in the organic chamber is high, water will move to the organic chamber, and at the end of electrodialysis, the target will not be reached. The concentration of substances may decrease. Furthermore, when the concentration of water becomes high, glycidyl quaternary ammonium salt may be hydrolyzed and the yield may decrease.

In order to prevent this, it is preferable to use a highly concentrated alkaline aqueous solution as the alkaline solution present in the alkali chamber, or to have a mixed solution of an organic solvent and alkali, or a mixed solution of an organic solvent, an alkali, and water. When using a highly concentrated alkaline aqueous solution, its concentration depends on the concentration of the epihalohydrin adduct supplied to the organic matter chamber, but is generally preferably 1 to 50%, more preferably 3 to 30%.
It is. In addition, when using an organic solvent, it is preferable that the organic solvent that can be used be one that is water-soluble and whose solvent or aqueous solution dissolves an alkali, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, etc. , i-
Lower aliphatic monoalcohols such as propyl alcohol and butyl alcohol, or glycerin,
Lower polyhydric alcohols such as ethylene glycol and propylene glycol, dioxane, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, etc. can be used.

In addition, as the electrolyte to be present in the electrolyte chamber, any substance, whether inorganic or organic, can be used as long as it ionizes in solution and does not damage the ion exchange membrane, but there are no particular restrictions on its type and structure. Examples include sodium chloride, potassium chloride, ammonium chloride, sodium sulfate, potassium sulfate, ammonium sulfate, sodium phosphate, sodium nitrate, potassium nitrate,
Sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium formate, potassium formate, or a mixture thereof can be used. An aqueous solution can generally be used as the electrolyte solution, but as with the alkaline solution mentioned above, if the concentration of epihalohydrin adducts in the organic chamber is high, water may migrate to the organic chamber, resulting in a decrease in the concentration of the target product and a decrease in yield. There is. Therefore, in the case of electrolyte solutions as well as alkaline solutions, in order to prevent this phenomenon, it is necessary to have a highly concentrated electrolyte aqueous solution present or
Preferably, a mixed solution of an organic solvent, water and electrolyte is present. It is preferable to supply the aqueous electrolyte solution so that the concentration thereof is equal to or lower than the saturation solubility of the electrolyte used at the end of the reaction. Generally used concentration is 1~
It is preferably 50%, more preferably 3 to 30%.

In addition, when using an organic solvent, it is preferable that the organic solvent that can be used is one that is water-soluble and whose aqueous solution dissolves the electrolyte, and the type thereof is not particularly limited, but for example, it can be used for the above-mentioned alkaline solution. A solvent or the like is preferred.

In this way, the alkaline chamber is supplied with an aqueous alkali solution, or a mixture of an organic solvent and an alkali, or a mixture of an organic solvent, water, and an alkali, and similarly, an aqueous electrolyte solution or an organic solvent and water is supplied into the electrolyte chamber. Electrodialysis is performed by supplying a mixture of glycidyl and electrolyte, but if these organic solvents or water move to the organic matter chamber and lower the concentration of glycidyl quaternary ammonium salt, it may be necessary to perform operations such as distillation. These organic solvents or water may be removed.

The current density applied in electrodialysis is preferably equal to or less than the critical current density of the substance supplied to electrodialysis. The limiting current density varies greatly depending on the type of dialysis machine, type of solution, concentration of the solution, method of flowing the solution, etc., but generally the current density given is 0.1~
It is about 10 amperes/ ^dm2 .

As described above, the present invention is based on glycidyl quaternary
When producing a high-purity glycidyl quaternary ammonium salt, electrodialysis is used to produce a high-purity glycidyl quaternary ammonium salt without producing a halogen salt as a by-product in the glycidyl quaternary ammonium compound system, and to reduce the consumption of alkali. This is a new reaction method that can efficiently consume current.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 45% by weight aqueous solution of trimethylamine hydrochloride 2000
Add 872g of epichlorohydrin to g and raise the temperature to 80℃.
The mixture was reacted with stirring for 4 hours while maintaining the temperature at 100% by weight to obtain 2872 g of a 62% by weight aqueous solution of epichlorohydrin adduct of trimethylamine hydrochloride. On the other hand 1
An electrodialysis tank was prepared in which 12 anion exchange membranes and 9 cation exchange membranes each having a size of 0.021 m ² were set as shown in FIG. (6 organic matter chambers, 6 alkali chambers
(6 electrolyte chambers, 4 electrode chambers) In FIG. 1, 1 is an anode, 2 is a cathode, 3 is a cation exchange membrane, and 4 is an anion exchange membrane.

2 kg of the 62% by weight trimethylamine hydrochloride epichlorohydrin adduct aqueous solution obtained as described above was circulated with a pump to the chamber (organic chamber) sandwiched between the anion exchange membranes of the electrodialysis tank set as described above. did. On the other hand, add 1.7 kg of 20% by weight sodium hydroxide aqueous solution to the cathode side chamber of the organic matter chamber.
2 kg of a 10% by weight aqueous sodium chloride solution was circulated and fed to each chamber on the anode side. Therefore, the amount of alkali supplied was 1.3 times the theoretical amount of alkali. Further, 2 kg of a 10% by weight aqueous sodium sulfate solution was circulated in the same manner as the polar liquid.

After circulating each liquid, the current density is 6 amperes/d.
m ² , electrodialysis was performed with an initial voltage of 13 volts and a constant current value. When electricity was applied for 150 minutes, a glycidyl quaternary ammonium salt aqueous solution having the following composition was obtained.

Glycidyltrimethylammonium chloride
42.5% by weight Trimethylamine hydrochloride epichlorohydrin adduct (unreacted product) 4% by weight 2,3 dihydroxypropyltrimethylammonium chloride 5% by weight Water 45.5% by weight Sodium chloride 0.1% by weight or less Others 3% by weight Trimethylamine hydrochloride epichlorohydrin in this reaction The yield of glycidyltrimethylammonium chloride based on the adduct was 85%, and the current efficiency was 88%.

Comparative Example 1 A 62% by weight aqueous trimethylamine hydrochloride epichlorohydrin adduct aqueous solution obtained in the same manner as in Example 1 was reacted using an electrodialysis tank comprised of an anion exchange membrane as shown in FIG. The electrodialysis tank was an anion exchange membrane 16 with the same area as in Example 1.
In FIG. 2, 1 is an anode, 2 is a cathode, 3 is a cation exchange membrane, and 4 is an anion exchange membrane. 2 kg of the above trimethylamine hydrochloride epichlorohydrin adduct aqueous solution was circulated into the compartment of the electrodialysis tank, and 2.6 kg of a 20% by weight sodium hydroxide aqueous solution was circulated into the compartment on the cathode side of the compartment. . The alkali supply is therefore twice the theoretical requirement. Also as polar liquid
2 kg of a 10% by weight aqueous sodium sulfate solution was circulated. (8 organic matter chambers, 9 alkali chambers, 4 polar chambers)
room).

After feeding each solution, electrodialysis was performed at a current density of 6 amperes/dm ² and an initial voltage of 14 volts while keeping the current value constant. After 270 minutes of energization, a glycidyl quaternary ammonium salt aqueous solution having the following composition was obtained.

Glycidyltrimethylammonium chloride
40% by weight Trimethylamine hydrochloride epichlorohydrin adduct (unreacted product) 6% by weight 2,3-dihydroxypropyltrimethylammonium chloride 5% by weight Water 46% by weight Sodium chloride 0.1% by weight or less Others 3% by weight Glycidyltrimethylammonium in this reaction The yield of chloride to trimethylamine hydrochloride epichlorohydrin adduct was 80%, and the current efficiency was 35%.

In the same way, electrodialysis was performed using 5 times the theoretical amount of alkali, that is, 6.6 kg, and other conditions were exactly the same as in the above method.
% yield of glycidyltrimethylammonium chloride. The current efficiency at this time is
It was 78%. As described above, in this method, a high current efficiency can be maintained by increasing the amount of alkali used, but the loss of alkali is large, and on the other hand, if an attempt is made to reduce the loss of alkali, the loss of current becomes large.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an apparatus used in an example of the present invention, and FIG. 2 is a schematic diagram of an apparatus used in a comparative example. 1... Anode, 2... Cathode, 3... Cation exchange membrane (indicated by C in the figure), 4... Anion exchange membrane (indicated by A in the figure).

Claims (1)

[Claims] 1. When producing a glycidyl compound from an addition reaction product of a tertiary amine hydrohalide or a polyamine hydrohalide and epihalohydrin using an electrodialysis method, the cathode side of two adjacent anion exchange membranes is used. An electrodialysis tank is composed of one cation exchange membrane on the anode side and one cation exchange membrane on the anode side, and the epihalohydrin addition reaction product is present in a chamber sandwiched between two anion exchange membranes. A method for producing a glycidyl quaternary ammonium salt, which comprises carrying out electrodialysis in the presence of an electrolyte solution in a chamber on the anode side and an alkaline solution in a chamber on the cathode side adjacent to the chamber.