JPH08245657A - Bis(1,1,3,3-tetramethylbutyl)phosphinic acid compound, its production and extractant - Google Patents

Abstract

PURPOSE: To provide a new compound useful as an extractant for metal existing in an aqueous solution and capable of extracting and separating especially cobalt and nickel from an aqueous solution in high selectivity. CONSTITUTION: This compound is expressed by formula I (X<1> and X<2> are each O or S), e.g. bis(1,1,3,3-tetramethylbutyl)phosphinic acid. The compound can be produced by reacting phosphine with a trimethylpentene (preferably diisobutylene) in the presence of an alkanesulfonic acid of formula R-SO3 H (R is a 1-4C alkyl) (e.g. methanesulfonic acid) and an organic solvent (preferably toluene, etc.) preferably at 60-80 deg.C for 2-10hr and reacting the resultant di(1,1,3,3- tetramethylbutyl)phosphine of formula II with an oxidizing agent (preferably hydrogen peroxide) or sulfur.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound, a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound and a method for producing the same, and particularly to selectively separate rare metals such as cobalt. The present invention relates to a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound useful as a solvent extractant, a method for producing the same, and an extractant.

[0002]

2. Description of the Related Art It has been conventionally known that dialkylphosphinic acid compounds derived from dialkylphosphine are useful for separating nickel, cobalt, chromium, copper and lead by solvent extraction. (JP-A-57-731
42, JP 57-73143, and JP 6
(JP-A-1-44139, JP-A-1-315384, JP-A-6-264156)

However, the above publication does not disclose the bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound according to the present invention.

As the phosphinic acid compound, bis (2,4,4-trimethylpentyl) phosphinic acid represented by the following formula (5) and a method for producing the same have been disclosed. (U.S. Pat. No. 4,374,780)

[0005]

[Chemical 9]

The method for producing dialkylphosphinic acid specified in this patent uses a radical catalyst to form phosphine and diisobutylene (70% 2,4,4-trimethylpentene-1, 2,4,4-trimethyl). A mixture of 30% pentene-2) to produce a dialkylphosphine, and then the product is reacted with an oxidizing agent to produce a dialkylphosphinic acid.

However, the radical addition reaction in the reaction between the above phosphine and diisobutylene has no reaction selectivity, and generally a mixture of mono-, di-, and tri-alkylphosphines is produced. Therefore, it is difficult to selectively increase the production ratio of dialkylphosphine. Therefore, the yield of dialkylphosphinic acid derived from dialkylphosphine in the above reaction is poor.

[0008]

In view of the above facts, the present inventors have conducted earnest research on a phosphinic acid compound useful as a metal extractant for cobalt and the like, and as a result, bis () which is a novel dialkylphosphinic acid compound. 1, 1,
The present invention has been completed by confirming that a 3,3-tetramethylbutyl) phosphinic acid compound, a method for producing the same, and its usefulness as a metal extractant.

[0009]

Means for Solving the Problems That is, the present invention provides the following general formula (1):

[0010]

[Chemical 10] (In the formula, X ¹ and X ² represent an oxygen atom or a sulfur atom.
However, X ¹ and X ² may be the same or different. ) Is a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound.

In the present invention, phosphine and trimethylpentene are used as catalysts in the following general formula (2).

[0012]

Embedded image R—SO ₃ H (2) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
Is reacted with an alkanesulfonic acid represented by the formula (3) below in the presence of an organic solvent.

[0013]

[Chemical 12] Di (1,1,3,3-tetramethylbutyl) represented by
After generating phosphine, the following general formula (1) is characterized in that the di (1,1,3,3-tetramethylbutyl) phosphine is reacted with an oxidizing agent or sulfur.

[0014]

[Chemical 13] (In the formula, X ¹ and X ² represent an oxygen atom or a sulfur atom.
However, X ¹ and X ² may be the same or different. The present invention provides a method for producing a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound represented by

Further, in the present invention, phosphine and trimethylpentene are used as catalysts in the following general formula (2).

[0016]

Embedded image R—SO ₃ H (2) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
Is reacted with an alkanesulfonic acid represented by the formula (3) below in the presence of an organic solvent.

[0017]

[Chemical 15] Di (1,1,3,3-tetramethylbutyl) represented by
After generating phosphine, the di (1,1,3,3-tetramethylbutyl) phosphine is reacted with an oxidizing agent or sulfur to give a compound represented by the following general formula (4):

[0018]

Embedded image (In the formula, X ¹ and X ² represent an oxygen atom or a sulfur atom.), Bis (1,1,3,3-tetramethylbutyl) phosphine oxide or sulfide is produced, and then the bis (1 , 1,3,3-Tetramethylbutyl) phosphine oxide or sulfide and an oxidizing agent or sulfur are reacted with the following general formula (1):

[0019]

[Chemical 17] (In the formula, X ¹ and X ² represent an oxygen atom or a sulfur atom.
However, X ¹ and X ² may be the same or different. The present invention provides a method for producing a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound represented by

The present invention also provides the above-mentioned screws (1, 1,
The present invention provides a metal extractant comprising a 3,3-tetramethylbutyl) phosphinic acid compound.

The present invention also provides the above-mentioned bis (1, 1,
An organic solvent containing an extractant consisting of a 3,3-tetramethylbutyl) phosphinic acid compound is contact-mixed with an aqueous solution containing cobalt and nickel, and cobalt is extracted from the aqueous solution into an organic solvent phase for separation. The present invention provides a method for extracting a metal.

The present invention will be described in detail below. The bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound represented by the above formula (1) of the present invention is
3,3-tetramethylbutyl) phosphinic acid, bis (1,1,3,3-tetramethylbutyl) monothiophosphinic acid, and bis (1,1,3,3-tetramethylbutyl) dithiophosphinic acid.

The method for producing the bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound of the present invention includes the following methods and. As a first reaction, phosphine and trimethylpentene are reacted with alkanesulfonic acid as a catalyst in the presence of an organic solvent to produce di (1,1,3,3-tetramethylbutyl) phosphine. Then, as a second reaction, the product di (1,1,3,3-tetramethylbutyl) phosphine is reacted with an oxidizing agent or sulfur to produce bis (1,1,3,3-tetramethylbutyl) phosphine. It is a method of obtaining an acid compound.

In the above production method, the second reaction is represented by the general formula as follows.

[0025]

Embedded image (In the formula, R ¹ represents a 1,1,3,3-tetramethylbutyl group.)

In the first reaction, phosphine and trimethylpentene are reacted with alkylsulfonic acid as a catalyst in the presence of an organic solvent to give di (1,1,1).
3,3-Tetramethylbutyl) phosphine is produced.

The second reaction is then carried out in the following two steps. First, as a first step of the second reaction, bis (1,1,3,3) is obtained by reacting the product di (1,1,3,3-tetramethylbutyl) phosphine with an oxidizing agent or sulfur. 3-Tetramethylbutyl) phosphine oxide or sulfide is produced. Next, as the second step of the second reaction, the bis (1,1,3,3
-Tetramethylbutyl) phosphine oxide or sulfide is reacted with an oxidant or sulfur to give bis (1,
This is a method for obtaining a 1,3,3-tetramethylbutyl) phosphinic acid compound.

In the above second reaction, bis (1,
When 1,3,3-tetramethylbutyl) phosphine oxide or sulfide is reacted with sulfur, it is preferable to carry out the reaction in the presence of an amine because the reaction yield is high.

In the above production method, there are specifically three reaction routes in the second reaction. That is, the reaction is represented by the following general formula.

[0030]

[Chemical 19] (In the formula, R ¹ means the same as above)

In the first reaction of the present invention, the raw material phosphine (PH ₃ ) may be obtained by any production method. For example, crude phosphine produced as a by-product in the production of sodium hypophosphite is dehydrated, dearsine, phosphine gas obtained by purifying dehydrogenated neighboring compounds, high-pressure compressed phosphine gas, liquefied phosphine, etc. It is not particularly limited to.

The trimethylpentene which is another raw material in the first reaction of the present invention is not particularly limited as long as it is industrially available, but for example, 2,4,4-trimethylpentene-1; 2,4,4- Trimethylpentene-2; diisobutylene (2,4,4-trimethylpentene-1 (A)
And 2,4,4-trimethylpentene-2 (B)) are preferred. Particularly, diisobutylene is industrially preferable because it is inexpensive, but its isomer ratio (mixing ratio of 2,4,4-trimethylpentene-1 (A) and 2,4,4-trimethylpentene-2 (B)) Varies depending on the manufacturer, for example, (A) :( B) = 75: 25%, 75:
22%, 70: 30%, etc., but the mixing ratio is not particularly limited in the present invention.

The alkanesulfonic acid used as a catalyst in the first reaction of the present invention is represented by the following general formula (2)

[0034]

Embedded image R—SO ₃ H (2) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)

It is preferable to use a lower alkane sulfonic acid having 1 to 4 carbon atoms represented by, for example, methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid and the like. These may be one kind or a mixture of two or more kinds, and may be anhydrous or an aqueous solution.

The first reaction of the present invention is carried out in the presence of an organic solvent, and as the organic solvent used in the present invention, a saturated hydrocarbon which is industrially easily available is suitable, for example, n-pentane, n- Hexane, isohexane, n-pentane, n-
Octane, n-isooctane, n-decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, petroleum naphtha, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene and the like are preferable, and toluene, benzene and n-hexane are preferable. Etc.

The reaction may be carried out in the presence of an organic solvent, and may be a system of an organic solvent alone or a mixture of an organic solvent and water. This water may be mixed when water is used as a diluent solvent for the catalyst, or may be mixed at an arbitrary ratio.

The oxidizing agent used in the second reaction of the present invention includes hydrogen peroxide, peroxides such as benzoyl peroxide, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, NO, N ₂ O ₄ , N ₂ O and the like. Nitrogen oxides, chlorine, etc. may be mentioned, but hydrogen peroxide is industrially advantageous.

Similarly, the amine used in the second reaction of the present invention is N, N-dimethylbenzylamine, benzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n. -Propylamine,
Tree n-propylamine, isopropylamine, n-
Butylamine, isobutylamine, sec-butylamine, tert-butylamine, cyclohexylamine,
Examples include α-phenyletylamine, β-phenyletylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine.

In the first reaction of the present invention, the reaction conditions for reacting phosphine and trimethylpentene in the presence of alkanesulfonic acid as a catalyst and an organic solvent are as follows.
In order to prevent acid corrosion, a device equipped with a Teflon inner cylinder is suitable. The molar ratio of phosphine to trimethylpentene is 1: 2 to 1: 5 mol, preferably 1: 2 to 2.
A ratio of 1: 3 is suitable. The reaction temperature is room temperature to 100
C., preferably 60 to 80.degree. C., and the reaction time is generally 1 to 24 hours, preferably 2 to 10 hours.

The raw materials are charged in the order of an organic solvent, trimethylpentene, and phosphine in order to prevent self-polymerization of trimethylpentene after the inside of the reaction vessel is sufficiently replaced with an inert gas such as nitrogen or helium. It is desirable to press-fit the catalyst after raising the temperature to.

After completion of the reaction, after cooling to room temperature, the unreacted phosphine gas is replaced with an inert gas. Generate di (1,
When water is used as the solvent for diluting the catalyst, 1,3,3-tetramethylbutyl) phosphine is partially released into the organic solvent, but most of the product is alkane of the catalyst in the lower aqueous layer. It forms a phosphonium salt with sulfonic acid. Also,
When anhydrous alkanesulfonic acid is used as the catalyst, all the products form phosphonium salts with alkanesulfonic acid.

The two organic layers and the aqueous layer are separated by a conventional method. When di (1,1,3,3-tetramethylbutyl) phosphine is isolated from the product, di (1,1,1,3) is added to the organic phase by neutralizing with an alkaline aqueous solution.
The 3,3-tetramethylbutyl) phosphine is transferred. Further, by distilling this organic phase under reduced pressure, highly pure di (1,1,3,3-tetramethylbutyl) phosphine containing almost no isomer can be obtained.

Regarding the second reaction to be carried out next, the reactions A to E will be described. The reaction A is a reaction of the di (1,1,3,3-tetramethylbutyl) phosphine obtained in the first reaction with an oxidizing agent. The reaction is carried out when di (1,1,3,3-tetramethylbutyl) phosphine is isolated and purified by the above reaction and when di (1,1,3,3) is separated in the aqueous layer after the reaction is completed to separate the organic layer. The operation is different from the case where 3-tetramethylbutyl) phosphine and alkylsulfonic acid form a phosphonium salt.

That is, when di (1,1,3,3-tetramethylbutyl) phosphine is isolated and purified, the oxidation reaction proceeds in the same manner as in Reaction A, simply by adding an oxidizing agent. It is possible to obtain bis (1,1,3,3-tetramethylbutyl) phosphinic acid which is a substance.

When di (1,1,3,3-tetramethylbutyl) phosphine and alkanesulfonic acid form a phosphonium salt in the reaction solution obtained in the first reaction, three methods are available. There is.

In the first method, as in the reaction A, a predetermined amount of an oxidizing agent is added to the reaction solution to obtain bis (1,1,3,3-).
Tetramethylbutyl) phosphinic acid is generated and separated from alkylsulfonic acid.

In the second method, as in the reaction B, half of the required amount of the oxidizing agent is added to the reaction solution to prepare di (1,1,3,3-).
After producing tetramethylbutyl) phosphine oxide, bis (1,1,3,3
3-tetramethylbutyl) phosphinic acid. At this time, the alkanesulfonic acid is preferably separated when the phosphine oxide is produced, and can be distilled and purified at the same time.

In the third method, first, an alkali is added to the reaction solution to separate alkanesulfonic acid into a metal salt and then separated, and then an oxidant is added and reacted as in Reaction A to produce bis (1,2).
1,3,3-tetramethylbutyl) phosphinic acid.

In the above method, the method of obtaining bis (1,1,3,3-tetramethylbutyl) phosphinic acid of higher purity is the second method in which the phosphine oxide obtained during the reaction is purified by distillation. Is particularly preferable. The reason for this is that it cannot be purified by distillation after it is made into a dialkylphosphinic acid.

In any of the above methods, the di (1,
The reaction between 1,3,3-tetramethylbutyl) phosphine and an oxidizing agent is carried out by mixing di (1,1,3,3-tetramethylbutyl) phosphine with or without a solvent in a solvent such as water or acetic acid. By using an oxidizing agent such as hydrogen oxide to oxidize, bis (1,
1,3,3-Tetramethylbutyl) phosphinic acid can be obtained.

The amount of oxidizing agent used is di (1,1,3,3-).
2 to 1 mol of tetramethylbutyl) phosphine
It is 2.2 mol, preferably 2.1 to 2.15 mol.
The reaction temperature is room temperature to 100 ° C, preferably 50 to 100 ° C.
° C. Since the oxidation reaction is an exothermic reaction, it is desirable to control the dropping rate so that the temperature does not rise suddenly.

Reaction C is the di (1,2) obtained in the first reaction.
A reaction solution containing 1,3,3-tetramethylbutyl) phosphine was added with a predetermined amount of an oxidizing agent to prepare di (1,1,3,3).
-Tetramethylbutyl) phosphine oxide is formed, and then bis (1,1,1,
3,3-tetramethylbutyl) monothiophosphinic acid. When reacting with sulfur, it is more preferable to react in the presence of an amine.

The amount of the oxidizing agent used is di (1,1,3,3-).
1 to 1 mol of tetramethylbutyl) phosphine
The amount is 1.2 mol, preferably 1.1 to 1.15 mol.
The reaction temperature is the same as in the reactions A and B above. The amount of sulfur used is 1 to 1.2 with respect to 1 mol of di (1,1,3,3-tetramethylbutyl) phosphine oxide.
The molar amount is preferably 1.0 to 1.05 mol. Similarly, the amount of amine used is 1 to 1.2 mol, preferably 1.0 to
It is 1.05. The reaction temperature is room temperature to 100 ° C, preferably 30 to 50 ° C.

Reaction D is the di (1,2) obtained in the first reaction.
To a reaction liquid containing 1,3,3-tetramethylbutyl) phosphine, a predetermined amount of sulfur was added to di (1,1,3,3-).
Tetramethylbutyl) phosphine sulfide is produced, and sulfur is further added and reacted to react with bis (1,1,3,3-
This is a method for producing tetramethylbutyl) dithiophosphinic acid. The amine is preferably added in the reaction of phosphine sulfide to dithiophosphinic acid.

The amount of sulfur used is 2 to 1 mol of di (1,1,3,3-tetramethylbutyl) phosphine.
It is 2.2 mol, preferably 2.0 to 2.1 mol. The amount of amine used is 1.0 to 1 mol of di (1,1,3,3-tetramethylbutyl) phosphine sulfide.
The amount is 1.2 mol, preferably 1.0 to 1.05 mol.
The reaction temperature is room temperature to 100 ° C, preferably 30 to 50 ° C
Is.

Next, the reaction E is a method in which the di (1,1,3,3-tetramethylbutyl) phosphine obtained in the first reaction is directly reacted with sulfur. In the reaction, a predetermined amount of sulfur was added to a reaction liquid containing di (1,1,3,3-tetramethylbutyl) phosphine obtained in the first reaction, and bis (1,1,3,3) was directly added. 3-tetramethylbutyl)
This is a method for producing dithiophosphinic acid. This time,
It is more preferable to react in the presence of an amine.

The amount of sulfur used is 2 to 1 mol of di (1,1,3,3-tetramethylbutyl) phosphine.
It is 2.2 mol, preferably 2.0 to 2.1 mol. The amount of amine used is 1.0 to 1.2 moles per 1 mole of di (1,1,3,3-tetramethylbutyl) phosphine,
It is preferably 1.0 to 1.05 mol. The reaction temperature is
Room temperature to 100 ° C, preferably 30 to 50 ° C.

Next, the bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound of the present invention is useful as an extractant for metals contained in an aqueous solution. Examples of the metal to be extracted include precious metal elements such as cobalt, nickel, zirconium, hafnium, gallium, vanadium and molybdenum, and rare earth metal elements such as yttrium, samarium and neodymium. Of these, it is particularly suitable for separating cobalt and nickel.

As a method of extracting the metal contained in the aqueous solution, for example, extraction of cobalt or nickel is carried out by using an organic compound containing an extracting agent composed of a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound. It is carried out by contact-mixing the solvent with an aqueous solution containing cobalt and nickel, extracting cobalt from the aqueous solution into an organic solvent phase, retaining nickel in the aqueous phase, and separating cobalt and nickel. The organic solvent phase containing cobalt is back-extracted into the aqueous phase of the aqueous solution by contacting it with an aqueous solution containing a mineral acid to recover cobalt from the aqueous phase.

The concentration of the extractant contained in the organic solvent varies depending on the metal ion concentration, the phase ratio of the organic solvent phase and the aqueous phase, etc., but is usually 3 to 70% by weight, preferably 5 to 40% by weight. The pH during extraction is 5 to 9, preferably 6
~ 8 is desirable.

Organic solvents used for extraction include aliphatic hydrocarbons such as hexane, heptane and normal paraffin, naphthenic hydrocarbons such as 1-naphthenic acid and 2-naphthenic acid, and aromatic hydrocarbons such as kerosene and xylene. Etc. are used.

[0063]

The reaction mechanism in the production method according to the present invention is that in the reaction between phosphine and trimethylpentene, the proton of the alkanesulfonic acid of the catalyst is added to the unsaturated bond of the olefin (trimethylpentene), and the following formula (6) ) Is formed, and this cation causes an electrophilic addition reaction to the unpaired electron pair of phosphine.

[0064]

[Chemical 21]

Therefore, trimethylpentene as a raw material, for example, isomers of diisobutylene 2,4,4-trimethylpentene-1 and 2,4,4-trimethylpentene 2
Both produce a carbonium cation represented by the same formula (6), and therefore dialkylphosphine [di (1,1,3,3-tetramethylbutyl) containing almost no isomer is used.
Phosphine] can be obtained. Furthermore, the dialkylphosphinic acid can be easily obtained with an oxidizing agent.

This means that the olefin mixture as a raw material can be used as it is, so that it is not necessary to use a single compound which has been separated and purified as a raw material, and the reaction may be stopped in the middle of the reaction or the charging ratio may be excessive. Since no special reaction operation is required, a highly pure dialkylphosphinic acid compound containing almost no isomer can be produced at low cost.

[0067]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

Example 1 An autoclave having a capacity of 1.5 L (liter) equipped with a Teflon inner cylinder was sufficiently replaced with nitrogen, and diisobutylene (2,4,4-trimethylpentene-1 was 75%;
Mixture of 25% 4,4-trimethylpentene-2) 2
24.4 g (2.0 mol) and n-hexane 300 ml were charged, and 34.0 g (1.0 mol) of phosphine was introduced from a cylinder. The temperature was raised to 80 ° C and methanesulfonic acid 19 was added.
2.2 g (2.0 mol) of 50% aqueous solution at a temperature of 80
While maintaining at 0 ° C., the mixture was added by a press-fitting pump over 3 hours.
Further, it was aged at 80 ° C. for 2 hours. Internal pressure is 15.0 kg
/ Cm ² to 5.5 kg / cm ² . Cool to room temperature, gradually blow residual phosphine to the exclusion facility,
The system was replaced with nitrogen three times.

The reaction solution was placed under a nitrogen atmosphere in a condenser,
The mixture was transferred to a 3 L four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, and 320 g (2.0 mol) of a 25% aqueous sodium hydroxide solution was added dropwise while keeping the temperature at 30 ° C or lower.
The hexane layer was separated, washed with a 10% aqueous sodium carbonate solution, dehydrated with anhydrous sodium sulfate, and left standing overnight.

After removing sodium sulfate, n-hexane was further distilled off with an evaporator. The colorless transparent liquid thus obtained was distilled under reduced pressure to separate a fraction of 114 to 116 ° C./1.8 mmHg to give 121.7 g of the colorless transparent liquid.
I got

According to GC-MASS, di (1,1,3,
It was confirmed to be 3-tetramethylbutyl) phosphine. The purity by gas chromatography is 9
6.8%, 1.1% structural isomers, yield 4
It was 5.7%.

[0072] GC-MASS: m / z = 258 "M" ^{+ 1 H-NMR: (CDC1} 3, δ) 1.00 (s, 1
8H), 1.37 (d, 12H, J = 11.4Hz),
1.63 (d, 4H, J = 9.0 Hz) FT-IR; (liquid film method, cm ^-1 ) 2940 (CH stretching), 2260 (PH stretching), 1465 (t-butyl asymmetric variation). Angle), 1360 (t-butyl symmetrical bending angle), 12
00 (t-butyl skeleton vibration), 1120 (P-C expansion and contraction), 800 (C-P-C bending angle)

In a 1 L four-necked flask equipped with a condenser, thermometer, stirrer and dropping funnel, di (1,1,3,3-tetramethylbutyl) phosphine 106. Charge 6 g (0.40 mol) and 300 ml of acetic acid, and add 30% hydrogen peroxide 9 at 60 ° C.
5.2 g (0.84 mol) was added dropwise and further aged at 100 ° C. for 2 hours. After cooling, acetic acid was distilled off with an evaporator to obtain 112.2 g of a white solid. This solid was converted to FA
When analyzed by B-MASS, bis (1, 1, 3, 3
-Tetramethylbutyl) phosphinic acid was confirmed. The melting point is 101 to 102 ° C., and the titration purity is 98.
At 5%, the yield was 95.3%.

[0074] FAB-MASS: m / z = 291 "M + H" ^{+ 1 H-NMR: (CDC1} 3, δ) 1.03 (s, 1
8H), 1.40 (d, 12H, J = 16.8Hz),
1.77 (d, 4H, J = 8.4 Hz), 9.94
(S, 1H) FT-IR; (KBr, cm ^-1 ) 2950 (CH stretching), 1470 (t-butyl asymmetric bending), 1360.
(T-butyl symmetrical bending angle), 1145 (P = O expansion / contraction), 9
25 (P-O-H expansion and contraction), 800 (C-P-C bending angle)

Example 2 An autoclave having a capacity of 1.5 L equipped with a Teflon inner cylinder was sufficiently replaced with nitrogen, and diisobutylene (75% 2,4,4-trimethylpentene-1, 2,4,4-) was used. A mixture of 25% trimethylpentene-2) 224.4 g (2.
0 mol) and 300 ml of n-hexane were charged, and 34 g (1.0 mol) of phosphine was introduced from a cylinder. 80 ° C
The temperature was raised to 50 ° C., and a 50% aqueous solution of 192.2 g (2.0 mol) of methanesulfonic acid was added to the mixture while maintaining the temperature at 80 ° C.
It was added with a press-fitting pump over time. 2 at 80 ° C
Aged for hours. The internal pressure is from 15.0 kg / cm ² to 5.
It was reduced to 5 kg / cm ² . After cooling to room temperature, residual phosphine was gradually blown into an exclusion facility, and the system was replaced with nitrogen three times.

The reaction solution was separated with a separating funnel under a nitrogen atmosphere to obtain 541.2 g of a slightly yellow transparent aqueous solution. FAB
-When analyzed by MASS etc., it was found that di (1,1,3,3-
It has been found that tetramethylbutyl) phosphine forms a stable phosphonium salt with methanesulfonic acid. Nonaqueous titration of this aqueous solution with an acetic anhydride solution of perchloric acid revealed a concentration of 37.6% and a yield of 57.5%.

In a 1 L four-necked flask equipped with a condenser, a thermometer, a stirrer and a dropping funnel, 470.9 g of the reaction solution obtained in the above reaction [di (1,1,3,3-tetramethylbutyl) phosphine 0 .50 mol], 30%
Liquid temperature of 60% hydrogen peroxide 120.2g (1.06mol)
The mixture was added dropwise so that the temperature was maintained at ˜70 ° C., and further aged at 100 ° C. for 2 hours. The reaction solution was separated into two layers, and the product was released from the aqueous methanesulfonic acid solution.

The reaction solution was extracted and separated with 300 ml of n-hexane, washed with a 5% aqueous solution of sodium carbonate, dehydrated with anhydrous sodium sulfate, and allowed to stand overnight. Concentration of the separated aqueous solution with an evaporator gave a purity of 95.
167.8 g of 1% methanesulfonic acid was obtained. Recovery rate 9
It could be regenerated at 5.4% and this regenerated methanesulfonic acid could be reused in the first reaction.

From the hexane solution, sodium sulfate was filtered off, and hexane was distilled off with an evaporator to obtain 140.9 g of a white solid. It was confirmed to be bis (1,1,3-3 tetramethylbutyl) phosphinic acid by FAB-MASS analysis. (Titration purity 96.5
%, Yield 93.6%)

Example 3 An autoclave having a capacity of 1.5 L equipped with an inner tube made of Teflon was sufficiently replaced with nitrogen, and diisobutylene (75% 2,4,4-trimethylpentene-1, 2,4,4-trimethyl) was added. Pentene-2 25% mixture) 224.4 g (2.
0 mol) and 300 ml of n-hexane were charged, and 34 g (1.0 mol) of phosphine was introduced from a cylinder. 80 ° C
The temperature was raised to 50 ° C., and a 50% aqueous solution of 192.2 g (2.0 mol) of methanesulfonic acid was added to the mixture while maintaining the temperature at 80 ° C.
It was added with a press-fitting pump over time. 2 at 80 ° C
Aged for hours. The internal pressure is from 15.0 kg / cm ² to 5.
It was reduced to 5 kg / cm ² . After cooling to room temperature, residual phosphine was gradually blown into an exclusion facility, and the system was replaced with nitrogen three times.

The reaction solution was separated with a separatory funnel under a nitrogen atmosphere to obtain 541.2 g of a slightly yellow transparent aqueous solution. FA
When analyzed by B-MASS and the like, it was found that di (1,1,3,3
-Tetramethylbutyl) phosphine was found to form a stable phosphonium salt with methanesulfonic acid. Nonaqueous titration of this aqueous solution with an acetic anhydride solution of perchloric acid revealed a concentration of 37.6% and a yield of 57.5%.

In a 1 L four-necked flask equipped with a condenser, a thermometer, a stirrer and a dropping funnel, 470.9 g of the reaction solution obtained in the above reaction [di (1,1,3,3-tetramethylbutyl) phosphine 0 .50 mol], 30%
Liquid temperature of hydrogen peroxide 60.1g (0.53mol) is 60 ~
The mixture was added dropwise so as to maintain the temperature at 70 ° C, and further aged at 100 ° C for 2 hours. The reaction solution was separated into two layers, and the product was released in the upper layer.

The upper layer was separated, and n-hexane 300 was added.
The lower layer methanesulfonic acid aqueous solution was extracted with ml, and combined with the free upper layer. Subsequently, it was washed with a 5% sodium carbonate aqueous solution, dehydrated with anhydrous sodium sulfate, and allowed to stand for a day and night.

When sodium sulfate was filtered off and hexane was distilled off with an evaporator, a colorless transparent viscous liquid 13 was obtained.
2.7 g was obtained. Distilled under reduced pressure, 152-154 ° C /
By collecting a fraction of 3.5 mmHg, 114.8 g of a colorless transparent viscous liquid was obtained. It was confirmed to be di (1,1,3,3-tetramethylbutyl) phosphine oxide by analysis with GC-MASS. (Purity 9
(8.1%, yield 82.2%)

[0085] GC-MASS; m / z = 274 [M] + 1 H-NMR; (CDC1 3, δ) 1.06 (s, 18
H), 1.41 (dd, 12H, J = 17.4, 3.6)
Hz), 1.80 (dd, 4H, J = 7.8, 2.4H)
z), 5.81 (d, 1H, J = 425.1 Hz) FT-IR; (liquid film method, cm ^-1 ) 2950 (C-H stretching), 2260 (P-H stretching), 1475 (t-). Butyl asymmetrical bending), 1362 (t-butyl symmetrical bending), 11
70 (P = O expansion / contraction), 1130 (PC expansion / contraction), 800
(C-P-C bending angle)

In a 1 L four-necked flask equipped with a condenser, a thermometer, a stirrer and a dropping funnel, 97.8 g of di (1,1,3,3-tetramethylbutyl) phosphine oxide obtained in the above reaction (0. 35 mol), acetic acid 300 m
1 was charged, and 41.9 g (0.37 mol) of 30% hydrogen peroxide was added dropwise so as to maintain the liquid temperature at 60 to 70 ° C., and further aged at 100 ° C. for 2 hours. Acetic acid was distilled off with an evaporator to obtain 94.5 g of a white solid. FAB-MASS
Was confirmed to be bis (1,1,3,3-tetramethylbutyl) phosphinic acid. (Titration purity 99.1%, Yield 92.3%)

Example 4 1 equipped with a condenser, thermometer, stirrer and dropping funnel
In a L four-necked flask, the di (1,1,1) obtained in Example 3 was added.
3,3-tetramethylbutyl) phosphine oxide 9
7.8 g (0.35 mol), toluene 300 ml, and sulfur 11.2 g (0.35 mol) were charged, and N, N-dimethylbenzylamine 47.3 g (0.
35 mol) was added dropwise. The sulfur decreased as the solution was added dropwise, and the mixture was aged at 60 ° C. for 2 hours. After cooling, the amine was removed by extracting with a hydrochloric acid aqueous solution, washed with pure water, and dehydrated with anhydrous sodium sulfate.

Toluene was distilled off with an evaporator to obtain 108.2 g of a white solid. FAB-MA
When analyzed by SS, it was confirmed to be bis (1,1,3,3-tetramethylbutyl) monothiophosphinic acid. The melting point is 121 to 122 ° C., and the titration purity is 97.
At 9%, the yield was 98.8%.

[0089] FAB-MASS; m / z = 307 [M + H] + 1 H-NMR; (CDC1 3, δ) 1.05 (s, 1
8H), 1.49 (dd, 12H, J = 18.0, 1.
2 Hz), 1.88 (dd, 4H, J = 9.0, 0.6
Hz) FT-IR; (KBr, cm ^-1 ) 2950 (CH stretching), 1475 (t-butyl asymmetric bending), 1368.
(T-butyl symmetric bending), 1240 (t-butyl skeleton vibration), 1125 (P-C stretching), 910 (P-O-H stretching), 800 (C-P-C bending), 678 (C -PS
Deflection), 620 (P = S expansion and contraction), 535 (P-S-H expansion and contraction)

Example 5 In a 1 L four-necked flask equipped with a condenser, a thermometer and a stirrer, 106.6 g (0.40 mol) of di (1,1,3,3-tetramethylbutyl) phosphine under a nitrogen atmosphere. Then, 300 ml of toluene and 12.8 g (0.4 mol) of sulfur were charged, and the mixture was stirred at room temperature. The liquid temperature rose to 35 ° C, and the mixture was aged at 60 ° C for 2 hours. After cooling, it was confirmed that unreacted sulfur did not precipitate in the lower part. Toluene was distilled off with an evaporator to give a white solid 120.
3 g were obtained. When this solid was analyzed by FAB-MASS, it was confirmed to be di (1,1,3,3-tetramethylbutyl) phosphine sulfide. Melting point is 7
At 9 to 80 ° C., the titration purity is 95.1%, and the yield is 98.5.
%Met.

[0091] FAB-MASS; m / z = 291 [M + H] + 1 H-NMR; (CDC1 3, δ) 1.06 (s, 1
8H), 1.50 (d, 12H, J = 18.6Hz),
1.95 (dd, 4H, J = 16.8, 6.3 Hz),
5.90 (d, 1H, 382.6 Hz) FT-IR; (KBr, cm ^-1 ) 2970 (CH stretching), 2310 (PH stretching), 1480 (t-butyl asymmetric bending), 1370. (T-Bubutyl symmetric bending), 1
245 (t-butyl skeleton vibration), 1125 (P-C expansion and contraction), 800 (C-P-C bending angle), 680 (C-P-S)
Deflection), 632 (P = S expansion / contraction)

1 equipped with condenser, thermometer and stirrer
In an L four-necked flask, 91.6 g of di (1,1,3,3-tetramethylbutyl) phosphine sulfide (0.30
Mol), 300 ml of toluene, and 9.6 g (0.3 mol) of sulfur were charged, and 40.6 g (0.3 mol) of N, N-dimethylbenzylamine was added dropwise while stirring at room temperature. The sulfur decreased as the solution was added dropwise, and the mixture was aged at 60 ° C. for 2 hours. After cooling, the amine was removed by extracting with a hydrochloric acid aqueous solution, washed with pure water, and dehydrated with anhydrous sodium sulfate.

Toluene was distilled off with an evaporator to obtain 100.5 g of a white solid. FAB-MA
When analyzed by SS, it was confirmed to be bis (1,1,3,3-tetramethylbutyl) dithiophosphinic acid. Melting point: 42-43 ° C, titration purity: 95.6%
And the yield was 99.5%.

[0094] FAB-MASS; m / z = 323 [M + H] + 1 H-NMR; (CDC1 3, δ) 1.05 (s, 1
8H), 1.58 (d, 12H, J = 20.4Hz),
1.92 (d, 4H, J = 9.6 Hz) FT-IR; (KBr, cm ^-1 ) 2975 (CH stretching), 1480 (t-butyl asymmetric bending), 1370.
(T-butyl symmetric bending), 1240 (t-butyl skeleton vibration), 1120 (P-C stretching), 795 (C-P-C bending), 670 (C-P-S bending), 620 ( P = S expansion / contraction), 530 (P-S-H expansion / contraction)

Example 6 In a 1 L four-necked flask equipped with a condenser, a thermometer and a stirrer, 106.6 g (0.40 mol) of di (1,1,3,3-tetramethylbutyl) phosphine was added under a nitrogen atmosphere. ), 300 ml of toluene, and 25.6 g (0.8 mol) of sulfur were charged, and 54.1 g (0.4 mol) of N, N-dimethylbenzylamine was added dropwise while stirring. The sulfur decreased as the solution was added dropwise, and the mixture was aged at 60 ° C. for 2 hours. After cooling, the amine was removed by extracting with a hydrochloric acid aqueous solution, the toluene layer was washed with pure water, and dehydrated with anhydrous sodium sulfate.

Toluene was distilled off with an evaporator to obtain 130.4 g of a white solid. FAB-MA
When analyzed by SS, it was confirmed to be bis (1,1,3,3-tetramethylbutyl) dithiophosphinic acid. The titration purity was 98.6%, and the yield was 99.8%.

Example 7 Extraction of Cobalt by Solvent Extraction Method 20% by weight of bis (1,1,3,3-tetramethylbutyl) phosphinic acid (titration purity 98.5%) was added, and phosphorus was added to prevent emulsion. An extractant solution (O) was prepared by dissolving acid tri-n-butyl ester in xylene so as to be 10% by volume. In addition, cobalt (II) was added to 10.1 g / l and nickel (II) was added to 10 g / l.
A solution to be extracted (A) was prepared by dissolving cobalt sulfate and nickel sulfate in pure water so that the concentration became 0.5 g / l.
A sodium hydroxide aqueous solution was used for the adjustment to a predetermined pH.

50 ml of each solution was placed in an Erlenmeyer flask (A / O = 1), and it was kept at 50 ° C. with a constant temperature shaker.
Contacted for 10 minutes. After liquid separation into an organic solvent (xylene) phase and an aqueous phase, cobalt (II) and nickel (II) in the organic solvent phase were analyzed to obtain the extraction rate and selectivity of each metal. Table 1 shows the results.

[0099]

[Table 1]

[0100]

[Equation 1]

[0101]

The bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound according to the present invention is a novel compound which is useful as a metal extractant. Further, according to the production method of the present invention, a mixed olefin such as diisobutylene is used as it is, and bis (1,2) of the above target compound is used.
Since a 1,3,3-tetramethylbutyl) phosphinic acid compound can be produced with high purity, it is expected as a very industrially advantageous synthetic method.

Further, the bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound of the present invention is useful as an extractant for metals contained in an aqueous solution, and particularly when contained in an aqueous solution. It is possible to extract and separate the existing cobalt and nickel with high selectivity.

Claims (8)

[Claims] 1. The following general formula (1): (In the formula, X ¹ and X ² represent an oxygen atom or a sulfur atom.
However, X ¹ and X ² may be the same or different. ) The bis (1,1,3,3- tetramethyl butyl) phosphinic acid compound represented by these. 2. A phosphine and trimethylpentene,
As a catalyst, the following general formula (2): R-SO ₃ H (2) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
The alkanesulfonic acid represented by the formula (3) is reacted in the presence of an organic solvent to give the following formula (3): Di (1,1,3,3-tetramethylbutyl) represented by
After the phosphine is formed, the di (1,1,3,3-tetramethylbutyl) phosphine is reacted with an oxidizing agent or sulfur, and the following general formula (1): (In the formula, X ¹ and X ² represent an oxygen atom or a sulfur atom.
However, X ¹ and X ² may be the same or different. ) The method for producing a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound represented by 3. The method for producing a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound according to claim 2, wherein the trimethylpentene is diisobutylene. 4. A phosphine and trimethylpentene,
As a catalyst, the following general formula (2): R-SO ₃ H (2) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
The alkanesulfonic acid represented by the formula (3) is reacted in the presence of an organic solvent to give the following formula (3): Di (1,1,3,3-tetramethylbutyl) represented by
After the phosphine is formed, the di (1,1,3,3-tetramethylbutyl) phosphine is reacted with an oxidizing agent or sulfur to give a compound represented by the following general formula (4): (In the formula, X ¹ represents an oxygen atom or a sulfur atom.), Bis (1,1,3,3-tetramethylbutyl) phosphine oxide or sulfide is formed, and then the bis (1,1,1, 3,3-tetramethylbutyl) phosphine oxide or sulfide is reacted with an oxidizing agent or sulfur, and the following general formula (1): (In the formula, X ¹ and X ² represent an oxygen atom or a sulfur atom.
However, X ¹ and X ² may be the same or different. ) The method for producing a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound represented by 5. The bis (1,1,3,3-) according to claim 4, wherein the bis (1,1,3,3-tetramethylbutyl) phosphine oxide or sulfide is reacted with sulfur in the presence of an amine. Method for producing tetramethylbutyl) phosphinic acid compound. 6. The method for producing a bis (1,1,3,3-tetramethylbutyl) phosphinic acid compound according to claim 4, wherein the trimethylpentene is diisobutylene. 7. The screw (1,1,3,3-) according to claim 1.
A metal extractant composed of a tetramethylbutyl) phosphinic acid compound. 8. The screw (1,1,3,3-) according to claim 1.
An organic solvent containing an extractant consisting of a tetramethylbutyl) phosphinic acid compound is contact-mixed with an aqueous solution containing cobalt and nickel, and cobalt is extracted from the aqueous solution into an organic solvent phase to separate the metal. Extraction method.