JPH0291089A - Production of quaternary phosphonium hydroxide - Google Patents

Abstract

PURPOSE:To industrially and readily obtain the title phosphonium useful for catalyst, etc., in high purity and yield by regenerating an ion exchange resin in raising stream of alkali regeneration liquid and bringing an aqueous solution of phosphonium into contact with the above-mentioned resin in descending stream. CONSTITUTION:An aqueous solution of alkali is passed in raising stream from the lower part of column packing a strongly basic anion exchange resin through the column and brought into contact with the ion exchange resin to regenerate the above-mentioned resin to OH type resin and the regenerated ion exchange resin is washed by feeding pure water to the column in raising stream and further in descending stream and then an aqueous solution of quaternary phosphonium compound expressed by formula I(R1-R4 are 1-18C alkyl, aryl or aralkyl or at least one kind of group thereof; X is anion) is fed to the column in descending stream to recover an aqueous solution of the aimed phosphonium compound from the lower part and further pure water is fed to the column in descending stream to push out the residual aimed phosphonium.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing quaternary phosphonium hydroxide. Furthermore, polymerization catalysts useful in the production of polysiloxanes (UK Patent No. 794,119 published by Mei A) and quaternary phosphonium salts for electrolytes in electrolytic capacitors (Japanese Patent Application Laid-Open No. 62-272,5
12, JP-A No. 62-272,513) Furthermore, it can be used as a raw material for curing catalysts for epoxy resins with excellent electrical properties, which are widely used for sealing and impregnating electronic components such as semiconductor devices and electronic equipment. The present invention relates to a method for producing useful high-purity phosphonium hydroxide by an ion exchange method.

<Prior art and problems> As a method for producing quaternary phosphonium hydroxide, there is a method to obtain quaternary phosphonium hydroxide by reacting tetra-n-butylphosphonium iodide with silver oxide in an aqueous solution (UK approved method). 794,119 Mei 111] (n-C4119) 4 1+1/2AQO+1/2H2
0→(n-C4H9)J POtl to 18gl.

However, since silver oxide is expensive in this method, the production cost is high and it is not an industrially desirable method.

G, H, 08OLAPOFF and L, HAI
ER(ORGANICPH0SPHOI(US COM
POUND)ltlLEY-INTER3CIENCE
, a Division of John Will
ey & 5ons, lnc, Vol, 2. 201
Page, 1972, states that quaternary phosphonium salts can be ion-exchanged using ion-exchange resins.

However, as described in Pronation, when ionizing using an ion exchange resin, it is necessary to dilute the acondensation of the stock solution, which has the drawback of requiring a long time for exchange. .

In addition, in order to overcome this point, in JP-A-62-212,397, quaternary phosphonium halide is brought into contact with a strongly basic anion exchange resin (OH type) in a relatively high concentration region to undergo ion exchange. A method for obtaining quaternary phosphonium hydroxides is described. However, in the case of this method, as described in the example, ion exchange is not completely performed (yield 66.4-90.8%), so the raw material quaternary phosphonium is mixed into the effluent. Contamination with halide is unavoidable.

Therefore, it is necessary to remove it using an organic solvent such as a halogenated hydrocarbon.

Furthermore, even if the raw material is removed using a solvent in this way, it is difficult to completely recover it from the effluent, and analysis of the halogen in the effluent reveals several hundred to several thousand I)I
)l is included.

<Means for Solving the Problem> As mentioned above, none of the conventional methods yields highly pure quaternary phosphonium hydroxide or is completely unsuitable for industrial use.

As a result of intensive and detailed research in view of the above-mentioned problems, the authors researched improvements to the manufacturing method based on the ion exchange method, which is considered particularly industrially effective, and found that unexpectedly high purity and high yields were obtained. discovered a method for producing quaternary phosphonium hydroxide and completed the present invention.

In other words, the present invention uses a column filled with a strongly basic ion exchange resin, and uses a column packed with a strongly basic ion exchange resin to produce -maximum (1) R3 (wherein R1, R2, R3, and R4 are the same or different 1 to 18 alkyl groups). Base.

represents an aryl group, an aralkyl group, or one in which at least one group thereof is substituted with a hydroxyl group or an alkoxy group, X represents an anion;
) by anion-exchanging the quaternary phosphonium compound represented by -maximum (2) (wherein R1, R2, R3, and R4 are each as defined above) In a method for producing quaternary phosphonium, an alkaline regenerating solution is passed upward from the bottom of the column to regenerate it into an OH form, and then an aqueous solution of a quaternary phosphonium compound is passed down to the regenerated ion exchange resin. The present invention relates to a method for producing high-purity phosphonium hydroxide, which comprises contacting the same with phosphonium hydroxide. First, the quaternary phosphonium compound which is the raw material to be ion-exchanged in Mokkomei is represented by the above formula (1).

As specific examples, R1-R4 in the formula are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
Alkyl groups such as octyl.

Aryl groups such as phenyl, tolyl, xylyl.

An aralkyl group such as benzyl or phenityl, or a group in which one of these groups is replaced with a hydroxy group or an alkoxy group, and X is fluorine.

Halogen ions of chlorine, bromine or iodine, formic acid.

Carboxyl ions such as acetic acid and oxalic acid, fi! ! Examples include acids, ions such as dimethyl or diethyl 18, nitrate ions, phosphate ions, organic phosphoric acids such as methyl or dimethyl phosphate, ethyl or diethyl phosphate, or hydroxyl group anions. Next, regarding strong basic ion exchange resins, for example, Avanlite ERA-400, Amberlite IRA401. Select a desired resin, such as Amberlite IRA900, and prepare a column packed with it.

There are no particular restrictions on the material that makes up the column, but since it creates an alkaline atmosphere during ion exchange,
Any material may be used as long as it is alkali-resistant so that impurities are not eluted at that time. Further, the shape of the column is not particularly limited, and may be a normal cylindrical shape.

In the present invention, the column prepared in this manner is subjected to ion exchange using the method described above, and it is particularly preferable to carry out ion exchange using the following five operations as one cycle to obtain high-purity water. Produce phosphonium oxide.

■ A predetermined amount of alkaline aqueous solution is supplied from the bottom of the column in an upward flow (Step 7: it is brought into contact with the ion exchange resin and the resin is regenerated into an OH type. (Upward flow regeneration) ■ Next, pure water is supplied in an upward flow as in [1] The remaining alkali is extruded and washed.

(Upward flow cleaning) Next, pure water is supplied downstream from the upper part of the column, and cleaning is continued until substantially no alkali flows out from the lower outlet. (Downflow washing) ■Next, the raw material quaternary phosphonium compound aqueous solution is supplied from the top of the washing column in a downward flow in the same manner as in ■, and the corresponding ion-exchanged aqueous solution of quaternary phosphonium hydroxide is supplied from the bottom of the column. get. (Generation of downward flow) (2) Next, pure water is caused to flow downward in the same manner as in [4] to push out the quaternary phosphonium hydroxide remaining in the column and complete the ion exchange. (Downflow washing) This is produced by ion exchange with the above operations ① to ③ as one cycle, but as described above in the present invention, the alkaline regenerating liquid is supplied to the ion exchange column as an upward liquid for regeneration. The most fundamentally important point is (■) that the aqueous solution of the quaternary phosphonium compound, which is the raw material, is allowed to flow downward (■).

Therefore, a method different from the present invention, such as a method in which the alkaline regenerating liquid and the quaternary phosphonium compound aqueous solution are passed together in a downward flow, a method in which both are passed in an upward flow, or a method in which the alkali In either method, such as by passing the regenerating liquid in a downward flow for regeneration and passing the quaternary phosphonium compound aqueous solution in an upward flow for ion exchange, ion exchange is performed, but not completely, and the corresponding anions are is mixed into the quaternary phosphonium hydroxide product, making it impossible to obtain a highly pure product.

First, to explain the regeneration conditions in operation (2), the alkaline aqueous solution used for regeneration may be a caustic alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.

Further, the concentration and flow rate are not particularly limited, but in most cases, the total amount rate of 1 to 10% by weight aqueous solution to the resin, that is, 5V=O.

5 to 6 Hr-1 is suitable. The reason for this is that the S V
If it is supplied in an upward flow with a force larger than la, the filled resin will become fluidized, which is undesirable.On the other hand, if it is too slow, a pulsating flow will occur and the regeneration will be uneven, so it is preferable that 5V=0 .5 to 4 Hr-1 is good.

In addition, in the regeneration of ion exchange resin with alkali, the amount used is 2 to 20 times the nominal total exchange capacity of the resin, preferably 3 to 5 @ of alkali, and the ion exchange resin is sufficiently regenerated into an OH type. It is important to keep

Next, upward flow cleaning (operation ■) and downward flow cleaning (operation ■)
In step 2, the flow rate is similar to that of the alkali upflow regeneration (operation ①), but especially in the downflow backwashing in step ②, it is necessary to sufficiently wash the alkali ions to a virtually negligible concentration. . Naturally, if this cleaning is insufficient, it will cause alkali metals to be mixed into the ion-exchanged product.

Next, in step (2), the quaternary phosphonium compound supplied in a downward flow is generally used as an aqueous solution, but may contain an organic solvent having affinity for water, such as a lower alcohol or acetone.

However, since the blue-white color of the ion exchange resin may be shortened, it is preferable to use as little as possible. The concentration of the quaternary phosphonium compound is not particularly limited, but is often in the range of 2 to 50% by weight, preferably 5 to 30% by weight.

Also, the descending flow rate is 5V = 0.5 to 68r for the filled resin.
A range of is appropriate.

Generally, the total ion exchange capacity of an ion exchange resin decreases as the number of times it is used increases.

For example, when using a new strongly basic ion exchange resin, the total ion exchange capacity decreases rapidly, especially during the first cycle.
It remains approximately constant at 40-60% of the nominal total ion exchange capacity of the resin.

Therefore, in the present invention, it is extremely important that the amount of raw material quaternary phosphonium compound to be treated is less than or equal to the total ion exchange capacity of the ion exchange resin.

If a raw material exceeding the exchange capacity is passed through the column, unexchanged raw material naturally flows out from the outlet of the column.

In this way, when unexchanged phosphonium compounds flow out from the outlet, in other words, an ion exchange resin that has experienced breakthrough, its ion exchange ability rapidly decreases, and even if the ion exchange resin is regenerated using an excessive amount of alkaline aqueous solution, Even if the exchange is performed, the exchange is not completed completely, and the resulting quaternary phosphonium hydroxide aqueous solution is contaminated with several tens to hundreds of ppra of the corresponding anion, resulting in a significant decrease in purity.

Therefore, ion exchange! Ij! It is necessary to fully understand the exchange capacity of the resin in advance and pay close attention to passing the raw material solution with less than that capacity.

Thus, according to the method of the present invention, the aqueous solution of quaternary phosphonium hydroxide produced contains not only anions derived from the raw materials but also almost no other anions, and moreover, almost no anions of high purity are contained. Obtained quantitatively.

<Examples> The method of the present Komei will be specifically explained below using Examples and Comparative Examples.

Example 1 Amberlite IRA-401 fully swollen in water
(CI type: Organo Co., Ltd. product) 180 yen was packed into a column with an inner diameter of 25 mm. 5wt% caustic soda aqueous solution 672! ?
(840 mmol) from the bottom of the column at 5V=1. O
The resin was supplied in an upward flow at a flow rate of 100 hr" to regenerate the resin into an OH type.

Next, apply deionized water to the regenerant in the same direction and at the same speed for about 1 hour.
After extrusion by flowing 80 ae, deionized water was further flowed downward from the top of the column at a flow rate of S = 1, oHr-', and this was continued until the Na concentration in the water flowing out from the bottom of the column became negligible. (<0.05ppm).

Then 5 wt% of tetraethylphosphonium bromide 218! ? (57.7 mmol) at 5V=1.0H
The column was supplied in a downward flow from the top of the column at a flow rate of r-1, and deionized water was then flowed out in the same direction and at the same speed to obtain 410 g of the main fraction.

As a result of analyzing this solution, as shown below, a high-strength tetraethylphosphonium hydroxide aqueous solution with extremely low halogen and metal content and a concentration of 0.137 mol/Kg was obtained with a yield of 97.
% of high purity.

Further, when compared with the results of repeating the same operation as above 10 times, a yield of 96.8% was obtained as shown in Table 1.

Table 1 The analysis results were as shown in Table 2.

Table 2 Example 2 Ion exchange was carried out under the same conditions as in Example 1 except that Amberlite IRA-900 was used as the ion exchange resin. As a result, 396 g of an aqueous tetraethylphosphonium hydroxide solution with a concentration of 0.14 mol/Kg was obtained. Ta. This corresponds to a yield of 96.1% based on the feedstock.

Example 3 In a 300 d four-eye flask under nitrogen atmosphere, 20.8 y (1 fluorimole) of triethylphosphine was mixed with 120 y of toluene.
rd, and add diethyl sulfur 132% while stirring at room temperature.
6h (211 mmol) was added dropwise. 8vF at 50℃
After the reaction was heated for a while, toluene was distilled off under reduced pressure.
1.2 g (151 mmol) of tetraethylphosphonium ethyl sulfate was obtained (yield 86.0%). 16 of these
．． 3y (60.0 mmol) was dissolved in 160 g of deionized water and ion exchanged under the same conditions as in Example 1.
Contains almost no ethyl sulfate ion (<0.2ppl
) High purity aqueous solution of tetraethylphosphonium hydroxide 3
10 g was obtained (concentration 0.189 mol/Ky).

Table 3 Example 4 Ion exchange resin Amberlite IRA400 with an inner diameter of 25
A column of AA was filled with 150 ml of 140.
Example 1 except that 0 g (82.5 mmol) was used.
As a result of ion exchange using the same procedure as above, the main fraction was 0.
30 mol/Kfi of tetrabutylphosphonium hydroxide 2
65.44? was obtained (yield 96.5%). The analysis results of the obtained product are as shown in Table 3.

Comparative Example 1 Amberlite IRA-400 sufficiently swollen in water
, 150+te was packed into a column with an inner diameter of 25M. 5W
A 1% aqueous solution of caustic soda 672 (840 mmol) was passed downward from the top of the column at a flow rate of 5 V = 1.0 Hr-1 to regenerate the resin into the OH form, followed by deionized water in the same direction and at the same rate. The column was washed until no sodium ions were detected in the eluate from the bottom of the column. (<
0. 140° Og (82.5 mmol) of a 20% by weight aqueous solution of tetrabutylphosphonium bromide (O5ppm) was added from the top of the column at a flow rate of 5 V = 1.0 Hr-1.
By passing deionized water in the same direction and at the same flow rate, 275 g of the main fraction of an aqueous solution containing 0.277 mol/h of tetrabutylphosphonium hydroxide was obtained (yield: 9
2.5%). Analysis of this aqueous solution revealed that it contained 2090 ppm of Br ions.

This is 27! After extracting M twice with dichloromethane, trace amounts of dichloromethane remaining in the aqueous solution were distilled off under reduced pressure to obtain 213 g of an aqueous solution.

As a result of analyzing this aqueous phase, Br ions were found to be 1055 ppp.
n, the concentration of tetrabutylphosphonium hydroxide is O,'
It was 2650 mol/Ky (loss due to extraction 25.8%).

As is clear from the above results, when an alkali regenerant and an aqueous solution of a quaternary phosphonium salt are passed through the column in a downward flow, ions are not completely exchanged and anions are mixed into the product, and it is difficult to recover and remove them. incomplete.

Comparative Example 2 Amberlite IRA400, 180ae was packed in a column with an inner diameter of 25 mm in the same manner as in Example 1.

820 g (1025 mmol) of a 5 wt % aqueous solution of caustic soda was supplied from the top of the column in a downward flow at a flow rate of V) sV = 1.0 Hr-1 to regenerate the resin to 0-1 type.

Subsequently, approximately 180 g of deionized water was forced out in the same direction and at the same flow rate, and further washing of deionized water was continued from the bottom of the column at a flow rate of 5 V = 1.0 t er-1. This was done until the concentration of Na+ ions in the wash water flowing out from the top became negligible to <0.05 ppl.

Next, 210.4 g (60.5 mmol) of a 6.54 wt% tetraethylphosphonium bromide aqueous solution was added at 5 V.
The column was passed upwardly from the bottom of the column at a flow rate of -1,OHr'', and then washed with deionized water in the same direction and at the same rate to obtain 442 main fractions.

As a result of analyzing this main fraction, the concentration of tetraethylphosphonium hydroxide obtained was 129 mmol/Kg (yield 9
4.6%>Br-11i degree was 136 ppn.

As described above, contrary to the method of the present invention, even if the stock solution is passed in an upward flow for ion exchange through an ion exchange column that has been alkali regenerated in a downward flow, the ion exchange is not complete and anions are mixed into the product. The purity of the product was poor.

According to the method of the present invention, quaternary phosphonium hydroxide can be produced collectively and easily with high purity and high yield, regardless of the aqueous solution of the quaternary phosphonium compound as a raw material. can do.

The quaternary phosphonium obtained by the method according to the present invention can be effectively used as a raw material for various known catalysts or special electrolytes.

Claims (3)

[Claims] (1) Using a column filled with a strong basic anion exchange resin, the general formula (1) ▲Mathematical formula, chemical formula, table, etc.▼(1) (In the formula, R1, R2, R3, and R4 are each The same or different alkyl groups and aryl groups having 1 to 18 carbon atoms,
By ion-exchanging a quaternary phosphonium compound represented by an aralkyl group, or one in which at least one group thereof is substituted with a hydroxy group or an alkoxy group, and X represents an anion, General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1, R2, R3, and R4 each have the same meaning as above) In the method for producing quaternary phosphonium hydroxide, The ion exchange resin is regenerated into (OH type) by passing an alkaline regeneration liquid in an upward flow, and then the aqueous solution of the quaternary phosphonium compound is brought into contact with the ion exchange resin (OH type) in a downward flow. A method for producing quaternary phosphonium hydroxide. (2) In the method for producing quaternary phosphonium hydroxide according to claim 1, [1] an aqueous alkaline solution is passed through the column in an upward flow from the bottom of the column to contact with an ion exchange resin to regenerate the resin into an OH type; [2] Then, as in [1], pure water is supplied in an upward flow to wash away the residual alkali. [3] Next, pure water is supplied in a downward flow from the upper part of the column until the alkali is substantially removed from the bottom outlet. [4] Next, similarly to [3], supply the quaternary phosphonium compound aqueous solution in a downward flow and recover the quaternary phosphonium hydroxide aqueous solution from the lower part; 5] Next, as in [4], pure water is supplied in a downward flow, and the remaining quaternary phosphonium hydroxide is extruded to complete the ion exchange, which is one cycle of ion exchange. Method for producing quaternary phosphonium. (3) A method for producing quaternary phosphonium hydroxide, wherein the quaternary phosphonium according to claim 1 or 2 is an aqueous solution of tetraethylphosphonium bromide or tetraethylphosphonium ethyl sulfate.