JP2001031689A - Production of phosphazenium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phosphazenium salt comprising a phosphazenium cation and an organic anion in high yield by adding a specific amount of a basic hydroxy compound to a solution including the phosphazenium cation and a salt of an inorganic anion. SOLUTION: To a solution comprising a phosphazenium cation of formula I (a-d is 0-3; R is a 1-10C hydrocarbon; r is 1-3; Tr- is an inorganic anion of r valence), an inorganic anionic salt and an organic solvent that dissolves the inorganic anionic salt, are added a solution comprising 0.86-1.6 equivalent amount, based on the above-stated inorganic anion salt, of a basic hydroxy compound and an organic solvent dissolving the basic hydroxy compound. Then, the content of the phosphazenium salt of formula I in the reaction products is controlled to <15 wt.% to obtain the objective phosphazenium salt of formula II (Q- is a hydroxy anion, alkoxy anion), for example, tetrakis[tris(dimethylamino)phosphoranylidenamino]phsphonium hydroxide or the like}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a phosphazenium salt. Specifically, the present invention relates to a method for producing a phosphazenium salt composed of an organic anion in which a phosphazenium salt composed of an inorganic anion is anion-exchanged with a basic hydroxide.

[0002]

2. Description of the Related Art A phosphazenium salt comprising an organic anion is used for producing a polyoxyalkylene polyol.
JP-A-10-77289 discloses that the compound is useful as an alkylene oxide polymerization catalyst. Further, the publication discloses that as a method for producing a phosphazenium salt comprising an organic anion such as a hydroxy anion or an alkoxy anion, a phosphazenium salt comprising an inorganic anion such as chloride may be used, for example, a hydroxide or alkoxide of an alkali metal or an alkaline earth metal. And a method using an ion exchange resin (page 21, column 40, lines 8 to 19).

[0003] However, this publication does not disclose any detailed production conditions and the composition of the obtained phosphazenium salt in the method of treating with a hydroxide or alkoxide of an alkali metal or alkaline earth metal. .

Further, as a method for producing phosphazenium hydroxide which is a phosphazenium salt comprising an organic anion, a method using an ion exchange resin is exemplified. Phosphazenium chloride which is a precursor of phosphazenium hydroxide, for example, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride (JP-A-10-77289,
Page 28, column 53, described in Comparative Example 1).
Since the compound hardly dissolves in water, it is formed because it is necessary to dilute the concentration of the compound in a solution when dissolved in water and a mixed solvent with an organic solvent compatible with water. The concentration of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide is also reduced, and a concentration step is required. Therefore, when the production scale is increased, the production time of the phosphazenium salt becomes longer.

[0005] Further, when an ion exchange resin is packed in a column and used, an operation of exchanging ion exchange groups in the ion exchange resin into hydroxyl groups is required, so that a simple and efficient phosphazenium salt can be obtained. A manufacturing method was desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a phosphazenium salt comprising an inorganic anion in a simple and convenient manner.
An object of the present invention is to provide a method for efficiently producing a phosphazenium salt comprising a high-purity organic anion.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, in a method for producing a phosphazenium salt composed of a phosphazenium cation and an organic anion, a phosphazenium salt was prepared. It has been found that the above-mentioned problem can be solved by adding a solution containing a specific amount of a basic hydroxide to a solution containing a salt of a lithium cation and an inorganic anion, and the method of the present invention has been completed.
That is, the present invention provides a compound represented by the following chemical formula (1):

[0008]

Embedded image

[A, b, c and d in the chemical formula (1)]
Is an integer of 0 to 3 that is not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine to form a ring structure. Q ^- represents a hydroxy anion or an alkoxy anion] in a method for producing a phosphazenium salt comprising an organic anion and a phosphazenium cation represented by the following chemical formula (2):

[0010]

Embedded image

[A, b, c and d in the chemical formula (2)]
Is an integer of 0 to 3 that is not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine to form a ring structure. r is an integer of 1 to 3,
Represents the number of phosphazenium cations, and T ^r- is the valence r
The salt of a phosphazenium cation and an inorganic anion represented by, and a solution containing an organic solvent that dissolves the salt of the inorganic anion, the salt of the inorganic anion, the basic After adding a solution containing 0.86 to 1.6 equivalents of a hydroxide and an organic solvent that dissolves the basic hydroxide, the reaction product contains a phosphazenium salt represented by the chemical formula (2). A method for producing a phosphazenium salt, wherein the amount is controlled to less than 15% by weight.

At this time, 0.91 to 1.3 equivalents of a basic hydroxide are added to the salt of the phosphazenium cation represented by the chemical formula (2) and the inorganic anion, and The above production method in which the content of the phosphazenium salt represented by the chemical formula (2) is controlled to less than 10% by weight is preferable. Further, as the Q in the chemical formula (1), hydroxy anion, or phosphazenium salt of alkoxy anion having 1 to 4 carbon atoms are preferred, the formula (2) with respect to T ^r- in the, T is in chloride, r is 1 It is preferred that

According to the present invention, it is possible to provide a simple, efficient, and highly pure method for producing a phosphazenium salt without a complicated operation such as an ion exchange resin method. Therefore, the phosphazenium salt obtained by the production method of the present invention is a very useful compound that can be used not only for organic reactions but also for polymer reactions. In particular, it is useful as a catalyst for addition polymerization of an alkylene oxide to an active hydrogen compound.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel method for producing a phosphazenium salt composed of an organic anion from a phosphazenium salt composed of an inorganic anion. First, chemical formula (1) will be described. The phosphazenium salt represented by the chemical formula (1) is the same as the compound described in JP-A-10-77289 (corresponding to the chemical formula (7) described in the publication).

In the present invention, in the chemical formula (1), a,
b, c, and d are integers from 0 to 3 that are not all 0 at the same time. Preferably, regardless of the order of a, b, c and d, (1,1,1,1), (0,1,1,1), (0,1,1)
(0,1,1), (0,0,0,1), and most preferably (1,1,1,1), (0,1,1).
1, 1, 1).

R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine to form a ring structure. R is methyl,
Ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-
Methyl-1-butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl, 1,
1-dimethyl-3,3-dimethylbutyl (tert-octyl), nonyl, decyl, phenyl, 4-toluyl,
Examples thereof include an aliphatic or aromatic hydrocarbon group such as benzyl, 1-phenylethyl, or 2-phenylethyl. Of these, methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl,
An aliphatic hydrocarbon group having 1 to 10 carbon atoms such as tert-octyl is preferred. Most preferred is a methyl group or an ethyl group.

Furthermore, Q of an organic anion ^- is a hydroxy anion or alkoxy anion. The alkoxy anion is preferably an aliphatic compound having 1 to 4 carbon atoms, and is derived from, for example, aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol. The alkoxy anion is preferably methoxy, ethoxy, or n-propoxy, and most preferably methoxy or ethoxy.

Q ^- is in the form of a hydroxy anion or an alkoxy anion, and the abundance ratio of these anions is not particularly limited. Selecting a form ^- Q in the reaction system to apply the phosphazenium salt. Although it depends on the composition of the organic solvent used when producing the phosphazenium salt, the molar ratio of the hydroxy anion to the alkoxy anion is from 99.99 / 0.01 to 0.01 / 99.
99.

Examples of the compound represented by the chemical formula (1) include tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide,
Tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium methoxide, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium ethoxide, tetrakis [tri (pyrrolidin-1-yl) phospho [Ranylideneamino] phosphonium tert-butoxide and the like. Preferably, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide,
Tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium methoxide and tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium ethoxide.

Next, the phosphazenium salt of the formula (2), which is a precursor of the phosphazenium salt of the formula (1), will be described. As with the chemical formula (1), the phosphazenium salt of the chemical formula (2) is also disclosed in JP-A-10-77289.
The compound is the same as that described in the publication (corresponding to the chemical formula (5) in the publication). The production method is the same as the method described in JP-A-10-77289 (page 13, column 24, line 12 to page 14, column 26, line 27).
Further, a, b, c, d, and R in the chemical formula (2) are the same as those described in the description of the chemical formula (1).

[0021] r in the formula (2) is an integer of 1 to 3, represents the number of phosphazenium cations, T ^r- is
It shows an inorganic anion having a valence of r. As the inorganic anion,
For example, bromine, chlorine, fluorine, iodine, boric acid, tetrafluoroboric acid, hydrocyanic acid, thiocyanic acid, hydrofluoric acid, hydrochloric acid, or hydrohalic acid such as oxalic acid, nitric acid, sulfuric acid, phosphoric acid , Phosphorous acid, hexafluorophosphoric acid, carbonic acid, hexafluoroantimonic acid, hexafluorothallic acid and perchloric acid. HSO ₄ ⁻ , HC are used as inorganic anions.
O ₃ ^- also there. Among these inorganic anions, bromine, chlorine, sulfuric acid, phosphoric acid, phosphorous acid, carbonate ions are preferred,
Further, chlorine, phosphoric acid, phosphorous acid and carbonate ions are most preferred.

In order to obtain the phosphazenium salt of an organic anion, the phosphazenium salt of an inorganic anion is dissolved in an organic solvent, and 0.86 to 1.6 equivalents of basic water are added to the phosphazenium salt of the inorganic anion. Add the oxide solution.

As the organic solvent for dissolving the phosphazenium salt of the inorganic anion, those which do not cause a chemical change even when the phosphazenium salt and the basic compound are added are preferable. Such organic solvents include, for example, pentane, hexane, cyclohexane, heptane,
Saturated aliphatic hydrocarbons such as octane, nonane and decane; benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-propylbenzene, cumene, 1,2,3-trimethylbenzene, ,
2,4-trimethylbenzene, mesitylene, tetralin, butylbenzene, p-cymene, cyclohexylbenzene, 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 1,2-diisopropylbenzene, 1,3 -Diisopropylbenzene,
Examples thereof include alkyl-substituted aromatic hydrocarbons such as 1,4-diisopropylbenzene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, and dodecylbenzene.

Further, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, o-dibromobenzene, m-dichlorobenzene
Dibromobenzene, 1-bromo-2-chlorobenzene,
Halogenated aromatic hydrocarbons such as 1-bromo-3-chlorobenzene, 1-chloronaphthalene or 1-bromonaphthalene, 2-chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, 2-bromotoluene, 3-bromotoluene, Bromotoluene, 2,4-dichlorotoluene, 3,4-dichlorotoluene, 1-chloro-2-ethylbenzene, 1
-Chloro-4-ethylbenzene, 1-bromo-2-ethylbenzene, 1-bromo-4-ethylbenzene, 1-chloro-4-isopropylbenzene, 1-bromo-4-isopropylbenzene, mesityl chloride, 2-chloro-
Examples include halogenated alkyl-substituted aromatic hydrocarbons such as o-xylene or 4-chloro-o-xylene.

Further, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, anisole, o-dimethoxybenzene, ethylphenyl ether, butylphenyl ether and o-diethoxybenzene And carbon tetrachloride, chloroform, dichloromethane, 1,1,2-
Chlorinated aliphatic hydrocarbons such as trichlorethylene or tetrachloroethylene are exemplified. In addition, any solvent may be used as long as it does not inhibit the reaction of the present invention.

Of these, preferred are the aforementioned saturated aliphatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, and
Halogenated aromatic hydrocarbons, and organic solvents such as the above-mentioned halogenated alkyl-substituted aromatic hydrocarbons and ethers. More preferred are organic solvents such as saturated aliphatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, halogenated aromatic hydrocarbons and ethers.

These organic solvents capable of dissolving the phosphazenium salt of an inorganic anion may be used alone or in combination. The amount of the organic solvent used for dissolving the phosphazenium salt of the inorganic anion is not particularly limited, but is usually 0.5 to 1 part by weight of the phosphazenium salt.
500 parts by weight. Preferably, it is 1 to 100 parts by weight, more preferably 1.5 to 20 parts by weight. The solution containing the phosphazenium salt of the inorganic anion is a solution in which the separated phosphazenium salt is once dissolved in the above-described organic solvent, and a partially insoluble phosphazenium salt may coexist.

In the present invention, a basic hydroxide is dissolved in an organic solvent in order to remove a phosphazenium salt of an inorganic anion and a water-soluble impurity contained in a solution in which the phosphazenium salt is dissolved in the organic solvent. In some cases, washing with water is performed before contact with the solution. The washing with water may be any method as long as the solution containing the phosphazenium salt and water are sufficiently contacted. Usually, a method of removing the aqueous phase after the organic phase and the aqueous phase are separated after washing with water is preferably used. When water is mixed in the organic phase, the water can be distilled off under reduced pressure or atmospheric pressure.

The amount of water in the washing is not particularly limited, but is usually 0.05 to 5 parts by weight based on 1 part by weight of a solution containing a phosphazenium salt of an inorganic anion.
Depending on the amount of water, the solution can be washed several times. As a preferred method, 0.05 to 1 part by weight of water is used for 1 to 5 parts by weight of the solution every time.
Wash twice. The temperature during this operation and the washing time are not particularly limited, but are usually 10 to 80 ° C, preferably 15 to 40 ° C, more preferably 17 to 35 ° C, and the washing time is Within 3 hours, preferably 0.01 to
1 hour, more preferably 0.05 to 0.5 hour.
The water content in the solution after the water washing operation is preferably reduced as much as possible in order to improve the purity of the target organic anion phosphazenium salt.

Next, the phosphazenium salt of the inorganic anion and the basic hydroxide added to the solution containing the phosphazenium salt in the method of the present invention will be described. Examples of the basic hydroxide used in the present invention include lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, alkali metal hydroxides such as cesium hydroxide, and, for example, magnesium hydroxide, Alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, barium hydroxide and the like. Further, ammonium hydroxide salts such as tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide and trimethylbenzylammonium hydroxide can be used.

Of these basic hydroxides, preferred are alkali metal hydroxides and alkaline earth metal hydroxides. More preferred are alkali metal hydroxides, and particularly preferred are sodium hydroxide, potassium hydroxide and cesium hydroxide. These basic hydroxides may be used alone or in combination.

From the viewpoint of the purity of the phosphazenium salt of the desired organic anion, the amount of the basic hydroxide to be used is 0.86 to 0.85 based on the phosphazenium salt of the inorganic anion.
1.6 equivalents, preferably 0.91 to
1.3 equivalents, more preferably 0.95 to 1.2 equivalents. When the use amount of the basic hydroxide is less than 0.86 equivalent, the residual amount of the phosphazenium salt of the inorganic anion in the reaction product becomes 15% by weight or more. When the residual amount of the phosphazenium salt of the inorganic anion is 15% by weight or more, the activity per unit weight of the phosphazenium salt when the phosphazenium salt of the organic anion, which is the target substance, is used as a catalyst for an organic reaction or a polymer reaction. Is significantly reduced. In the present invention, the reaction product refers to a compound present in the reaction system after reacting a phosphazenium salt of an inorganic anion with a basic hydroxide. In order to maintain the activity per unit weight of the phosphazenium salt, the phosphazenium salt of the inorganic anion in the reaction product is controlled to less than 15% by weight, preferably less than 10% by weight, more preferably less than 5% by weight. .

On the other hand, if the amount of the basic hydroxide used exceeds 1.6 equivalents relative to the phosphazenium salt of the inorganic anion, the concentration of the basic hydroxide in all the reaction products increases. Depending on the reaction system, the basic hydroxide is
Since the catalytic effect of the phosphazenium salt of the organic anion is reduced, the amount of the basic hydroxide used must be controlled to 1.6 equivalents or less.

To efficiently contact the solution containing the phosphazenium salt of the inorganic anion with the basic hydroxide, an organic solvent that dissolves the basic hydroxide is used. Such organic solvents include, for example, methanol, ethanol, n-propanol, iso-propanol, n-propanol.
Examples thereof include aliphatic alcohols such as butanol, sec-butanol, tert-butanol, propylene glycol, ethylene glycol, diethylene glycol, and glycerin; nitriles such as acetonitrile; and ethers such as tetrahydrofuran.

Of these organic solvents, preferred are
Aliphatic alcohols, particularly preferred are methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, ter
It is an aliphatic alcohol having 1 to 4 carbon atoms such as t-butanol, ethylene glycol, propylene glycol, diethylene glycol, and glycerin. These organic solvents may be used alone or in combination. The amount of these solvents is not particularly limited as long as the basic hydroxide can be sufficiently dissolved, but is usually 0.01 to 5 parts by weight based on 1 part by weight of a solution containing a phosphazenium salt of an inorganic anion. . Preferably, it is 0.05 to 3 parts by weight,
More preferably, it is 0.05 to 2 parts by weight.

As a method of adding a solution containing a basic hydroxide to a solution containing a phosphazenium salt of an inorganic anion, a solution containing a basic hydroxide is charged at once into the above solution containing a phosphazenium salt. Or a method of dropping a solution containing a basic hydroxide. A dropping method is preferably used because of easy control of the reaction temperature.

The reaction conditions after adding the solution containing the basic hydroxide to the solution containing the phosphazenium salt of the inorganic anion are not particularly limited, but the reaction temperature is usually 5 to 180 ° C. , Preferably 10 to 50 ° C, more preferably 15 to 45 ° C. The reaction pressure may be either atmospheric pressure or under pressure. When a pressure reaction is performed, 0.8 MPaG or less, preferably 0.5 MPa
G or less, more preferably 0.4 MPaG or less.
The reaction time is 0.2-3 hours, preferably 0.3-2.
5 hours, more preferably 0.3 to 1 hour.

As described above, by bringing the phosphazenium salt of the inorganic anion into contact with the basic hydroxide, the inorganic anion and the hydroxide ion are exchanged, and the phosphazenium salt of the organic anion and the basic hydroxide are exchanged. In which the hydroxyl group of the compound has been replaced by an inorganic anion.

The starting material, a phosphazenium salt of an inorganic anion, and the target material, a phosphazenium salt of an organic anion, can be obtained by the following steps:
Although it is dissolved in a mixed solvent of an organic solvent in which a basic hydroxide is dissolved (hereinafter, abbreviated as a reaction solution), the generated inorganic salt is hardly soluble in the reaction solution. Usually, the formed inorganic salt is removed by a filtration operation. Excessive basic hydroxide can also be filtered off after the organic solvent dissolving the basic hydroxide is distilled off from the reaction solution and precipitated as a solid.

When water is present in the reaction solution, the water dissolves the phosphazenium salt of the inorganic anion and the inorganic salt formed from the basic hydroxide, and thus the inorganic salt is separated from the reaction solution by filtration. Becomes difficult. Therefore, it is preferable to reduce the water content in the organic solvent in which the basic hydroxide is dissolved as much as possible. Furthermore, it is preferable to reduce as much as possible the water content in the reaction solution of the solution containing the phosphazenium salt of the inorganic anion and the solution containing the basic hydroxide.

The solution containing the phosphazenium salt of the organic anion thus obtained can be distilled to remove the organic solvent to obtain a solution of the phosphazenium salt at an arbitrary concentration. If necessary, the dried product can be subjected to a refining operation such as recrystallization. The phosphazenium salt obtained by the production method of the present invention is a very useful compound that can be used not only for organic reactions but also for polymer reactions.

[0042]

EXAMPLES Examples of the present invention will be shown below to clarify aspects of the present invention. First, the compounds used will be described.

(A) Phosphazenium salt of inorganic anion In the chemical formula (2), (a, b, c, d) = (1,
1,1,1), wherein R is a methyl group, r = 1, T = C
l phosphazenium salt of Cl ⁻ (chloride ion) (tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride} [(Me
₂ N) ₃ P = N] ₄ P ⁺ Cl ⁻ ｝ (manufactured by Fluka), hereinafter abbreviated as P5Cl).

(B) Organic solvent dissolving phosphazenium salt of inorganic anion Toluene (special grade reagent, Wako Pure Chemical Industries, Ltd.) was used. Before the reaction, a molecular sieve (manufactured by Union Showa KK, model: 4AXH-5) was added to toluene in an amount of 10% by weight, mixed, and allowed to stand for 24 hours to remove water. Karl Fischer measurement (Measuring device: Hiranuma Sangyo Co., Ltd.,
Format: The water content in toluene determined by AQUACOUNTER AQV-7) was 57 ppm.

(C) Basic hydroxide: Sodium hydroxide (special grade reagent, Wako Pure Chemical Industries, Ltd.) was used. Hereinafter, it is abbreviated as NaOH. (D) Organic solvent dissolving basic hydroxide Methanol (Katayama Chemical Co., Ltd. reagent, special grade, dehydrated) was used. Karl Fischer measurement (same device as in (b))
Was found to be 138 ppm. Hereinafter, it is abbreviated as MeOH.

By using the above compound, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me ₂ N) ₃ P =
N] ₄ P ⁺ OH ^-, hereinafter abbreviated as P5OH}, and tetrakis [tris (dimethylamino) phosphoranylideneamino Rani isopropylidene amino] phosphonium methoxide {[(Me ₂ N) ₃
[P = N] ₄ P ⁺ OMe ⁻ , which is hereinafter referred to as P5OMe. At the time of analysis, a sample was used in which an organic solvent in which P5Cl was dissolved and an organic solvent in which NaOH was dissolved were distilled off from the reaction solution at 60 ° C. and 665 Pa. The method for analyzing each component in the reaction product is described below.

(1) Concentration of phosphazenium salt of inorganic anion (P5Cl) (unit: wt%) The chlorine ion concentration (unit: ppm) in the reaction product was determined, and the obtained value was determined as the atomic weight of chlorine (unit: g / mol). ) And then multiplying by the molecular weight of P5Cl (unit: g / mol) to calculate the P5Cl concentration in the reaction product. Hereinafter, a method for measuring the chloride ion concentration in the reaction product will be described.

After weighing about 60 mg of a sample on a quartz board,
In an electric furnace, heated to 900 ° C. in an argon / oxygen mixed gas, the mixed gas was absorbed in an aqueous solution of hydrogen peroxide having a concentration of 1 vol%, and ultrapure water (MILLIPORE, small-sized pure water production apparatus, model: MILL) A solution adjusted to a volume of 10 ml with -Q Labo (water adjusted to a specific resistance of 17 MΩ-cm) is used as a test solution. Then, ion chromatography of the test solution (manufactured by Dionex, model: DX-300)
The analysis is performed to determine the chloride ion concentration in the reaction product.
The separation column uses IonPacAS12A (manufactured by Dionex), and uses a 2.7 mM aqueous sodium carbonate solution and a 0.3 mM aqueous sodium hydrogen carbonate solution as eluents.

(2) Concentration of phosphazenium salts of organic anions (P5OH and P5OMe) (unit:% by weight) A sample of P5OH was synthesized and measured using the analytical method described below to obtain the reaction product. The phosphazenium salt of the organic anion in the product was identified and quantified. First, a production example of P5OH and an analysis method thereof will be described.

31.02 g of P5Cl (manufactured by Fluka)
(40 mmol) was dissolved in 200 ml of a 50% by weight methanol-water mixed solvent to prepare a 0.2 mol / l solution. This solution was distributed at room temperature through a column (diameter 20 mm, height 450 mm) packed with 140 ml of an anion exchange resin (trade name: Levatit MP500, manufactured by Bayer Corp.) exchanged into a hydroxyl group type at a rate of 140 ml / h. did. Subsequently, 450 ml of a 50% by weight methanol-water mixed solvent was flowed at the same speed. After the effluent was concentrated, it was dried at 80 ° C. and 665 Pa to obtain a solid. This solid was dissolved in a mixed solvent of tetrahydrofuran and diethyl ether at a volume ratio of 1:15 and then recrystallized to obtain 28.76 g of a colorless compound. The yield was 95%.

³¹ P-NMR of tri-n-butyl phosphate as an internal standard compound in a deuterated dimethyl sulfoxide solution (nuclear magnetic resonance apparatus manufactured by JEOL Ltd.)
Has a chemical shift of −33.3 (quintuple, 1P) ppm,
7.7 (doublet, 4P) ppm, assigned as the central phosphorus atom in the tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium cation and the four surrounding phosphorus atoms . The chemical shift of ¹ H-NMR using tetramethylsilane as an internal standard was 2.6 ppm, which was attributed to the methyl group in the tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium cation, Due to coupling with an atom, it is observed as a double line. Elemental analysis value (% by weight) was C: 38.28, H: 9.82, N: 29.4.
3, P: 19.94 (theoretical value, C: 38.09, H:
9.72, N: 29.61, P: 20.46). The above is the analysis method of P5OH.

Regarding the analysis method of P5OMe,
^The tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium cation was measured by ³¹ P-NMR, and the methyl group of the methoxyanion group was further measured by ¹ H-NMR using tetramethylsilane as an internal standard. (3.2 ppm). Then, P5
The following analysis is performed to measure the P5OMe concentration in a mixture of OH and P5OMe.

The reaction product is previously dissolved in tetrahydrofuran dehydrated with metallic sodium, and 5% by weight of ultrapure water is added to the reaction product, whereby the released methanol is subjected to gas chromatography (Shimadzu). Quantitative measurement is performed using a model (GC-14A, manufactured by Seisakusho Co., Ltd.).
By dividing the methanol concentration (unit: wt%) by its molecular weight and then multiplying by the molecular weight of P5OMe,
The P5OMe concentration (unit:% by weight) is calculated. Further, the reaction product, a phosphoric acid tri -n- butyl as an internal standard compound, was dissolved in deuterated dimethyl sulfoxide, ³¹ P
-NMR (nuclear magnetic resonance apparatus manufactured by JEOL Ltd.) is measured to determine the concentration (unit: mol) of the tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium structure. Then, from the value,
The number of moles of P5OH was determined by subtracting the number of moles obtained by dividing the P5Cl and P5OMe concentrations by the molecular weight of each component,
By multiplying the value by the molecular weight of P5OH, the concentration (unit: wt%) of P5OH in the reaction product is determined.
The concentration of the phosphazenium salt of the organic anion in the examples is the sum of the concentrations of P5OH and P5OMe. The composition of the reaction product was determined by the method described in detail above.
The components other than (1) and (2) were confirmed to be compounds derived from NaOH by ion chromatography measurement of the reaction product.

Further, in order to compare the catalytic performance of the phosphazenium salts obtained in Examples and Comparative Examples, a polymerization test of propylene oxide using the compounds was carried out. The catalytic performance of the phosphazenium salt was examined by measuring the reaction rate of propylene oxide, the hydroxyl value and the total unsaturation of the obtained polyoxyalkylene polyol.

(3) Propylene oxide conversion (unit:%) Propylene oxide was polymerized using a 2 L autoclave. Using glycerin as a polymerization initiator, a certain amount of propylene oxide was charged under the conditions of a polymerization temperature of 120 ° C. and a maximum reaction pressure of 0.45 MPaG. The propylene oxide from the reaction was collected. The amount of the collected propylene oxide (b, unit; g) was subtracted from the amount of the charged propylene oxide (a, unit; g), and the resulting value was divided by the amount of the charged propylene oxide (a). 1
By multiplying by 00, the reaction rate of propylene oxide is calculated.

(4) Hydroxyl value of polyoxyalkylene polyol (hereinafter abbreviated as OHV, unit: mgKOH /
g) and the total degree of unsaturation (hereinafter abbreviated as C = C, unit: meq./g) It is determined by the method described in JIS K-1557.

EXAMPLE 1 P5Cl was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a condenser, and a dropping funnel under a nitrogen atmosphere of phosphazenium salt A.
Was added thereto, and toluene (81.9 g) was added to adjust the P5Cl concentration to 17% by weight. While stirring at 25 ° C., a 4.8% by weight methanol solution of sodium hydroxide (sodium hydroxide 19.53 mmol, 0.9 equivalent to P5Cl) was added dropwise to this solution over 15 minutes. After stirring at 25 to 27 ° C for 30 minutes, the temperature was raised to 80 ° C, and the mixture was further stirred for 3 hours.
A white suspension was obtained. This suspension was filtered under reduced pressure using a 0.45 μm Teflon membrane filter. 60
The obtained filtrate was concentrated and dried at 399 Pa at 399 Pa to obtain a white solid. As a result of analyzing the white solid by the method described above, the concentration of the phosphazenium salt of the organic anion was 88.3% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 11.5% by weight.

Example 2 The procedure was the same as in Example 1, except that the amount of sodium hydroxide used was increased to 1.0 equivalent relative to the phosphazenium salt BP5Cl.
As a result of analyzing the obtained white solid, the concentration of the phosphazenium salt of the organic anion was 98.4% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.52% by weight.

Example 3 The procedure was the same as in Example 1, except that the amount of sodium hydroxide used was increased to 1.2 equivalents relative to the phosphazenium salt CP5Cl.
As a result of analyzing the obtained white solid, the concentration of the phosphazenium salt of the organic anion was 97.0% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.51% by weight.

Comparative Example 1 The procedure was the same as that of Example 1, except that the amount of sodium hydroxide used was reduced to 0.7 equivalent relative to the phosphazenium salt DP5Cl.
As a result of analyzing the obtained white solid, the concentration of the phosphazenium salt of the organic anion was 68.4% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 31.5% by weight.

Comparative Example 2 The procedure was the same as in Example 1 except that the amount of sodium hydroxide used was increased to 2.0 equivalents relative to the phosphazenium salt EP5Cl.
As a result of analyzing the obtained white solid, the concentration of the phosphazenium salt of the organic anion was 91.8% by weight, and the concentration of the phosphazenium salt of the inorganic anion was 1.42% by weight.

The results of the above Examples and Comparative Examples are summarized in [Table 1].

[0063]

[Table 1]

<Consideration of Experimental Results> A basic hydroxide (N) for a phosphazenium salt (P5Cl) of an inorganic anion was used.
Examples 1 to 3 in which the usage of aOH) is within the scope of the present invention
, The P5Cl concentration in the reaction product is 5% by weight or less. However, when the amount of NaOH used was lower than the range of the present invention (Comparative Example 1), the P5Cl concentration was 31.5% by weight.
And the concentration of the phosphazenium salt of the organic anion decreases. On the other hand, when the amount of NaOH used exceeds the upper limit of the present invention (Comparative Example 2), the P5Cl concentration is 15% by weight or less, and the concentration of the phosphazenium salt of the organic anion is 9%.
The value is as high as 1.8% by weight, and the concentration of a compound derived from sodium other than the phosphazenium compound is as high as 6.78% by weight.

In order to compare the catalytic performance of the phosphazenium salts obtained in Examples 1 to 3 and Comparative Examples 1 and 2, polymerization of propylene oxide was carried out using the compound as a catalyst.

Evaluation Test 1 100 parts by weight of glycerin and 7.75 parts by weight of phosphazenium salt A were added to a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a vacuum line, and nitrogen was introduced. Decompression treatment was performed at 105 ° C. and 1.33 kPa or less for 4 hours. Thereafter, the pressure was increased to atmospheric pressure with nitrogen, and 37.8 g of the content of the flask was charged into a 2.2 L autoclave. After the inside of the autoclave was replaced with nitrogen, the temperature was increased to 120 ° C. under nitrogen pressure. Next, after adjusting the pressure to 6.65 kPa, 1600 g of propylene oxide was charged while keeping the internal temperature constant. After reacting at a polymerization temperature of 120 ° C. for 300 minutes, propylene oxide in the reaction system was distilled off under reduced pressure, and the collected amount was measured. The conversion of propylene oxide was 95.7%.

Next, after adjusting the internal temperature to 80 ° C., 5% by weight of ion-exchanged water and an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.) were added to the polyoxyalkylene polyol containing the phosphazenium salt. , Product name: KW-700S
EL) was added at 1% by weight, and the mixture was stirred and mixed at the same temperature for 3 hours. Thereafter, while the internal temperature was raised to 105 ° C. and the pressure was gradually reduced, finally, a vacuum dehydration treatment was performed for 3 hours at 105 ° C. and 1.33 kPa or less. By performing filtration under reduced pressure using a filter paper having a retention particle size of 1 μm,
The polyoxyalkylene polyol was recovered. The OHV of the obtained polyoxyalkylene polyol is 4
2.8 mgKOH / g, and C = C is 0.033me
q. / G.

Evaluation test 2 Polymerization of propylene oxide was carried out in the same manner as in Evaluation test 1 except that phosphazenium salt B was used.
The polyoxyalkylene polyol was recovered. The conversion of propylene oxide is 97.2%, and the OHV of the polyoxyalkylene polyol is 41.6 mgKOH /
g, C = C is 0.032 meq. / G.

Comparative Evaluation Test 1 Polymerization of propylene oxide was carried out in the same manner as in Evaluation Test 1, except that phosphazenium salt D was used.
The polyoxyalkylene polyol was recovered. The conversion of propylene oxide is 42.5%, and the OHV of the polyoxyalkylene polyol is 89.2 mg KOH.
/ G, C = C is 0.017 meq. / G.

Comparative Evaluation Test 2 Propylene oxide was polymerized in the same manner as in Evaluation Test 1 except that phosphazenium salt E was used.
The polyoxyalkylene polyol was recovered. The conversion of propylene oxide is 93.1%, and the OHV of the polyoxyalkylene polyol is 45.2 mgKOH /
g, C = C is 0.043 meq. / G.

The results of the evaluation tests 1 and 2 and the comparative evaluation tests 1 and 2 are summarized in [Table 2].

[0072]

[Table 2]

<Consideration of Evaluation Test> In the evaluation tests 1 and 2 in which a phosphazenium salt having a P5Cl concentration of 15% by weight or less, which is a phosphazenium salt of an inorganic anion, was used as a polymerization catalyst for propylene oxide, the reaction rate of propylene oxide was high. , OHV is 41 to 43 mgKOH /
g level. Moreover, the total degree of unsaturation (C = C) generated by the side reaction of propylene oxide is 0.032 to
0.033 meq. / G is almost constant. On the other hand, in Comparative Evaluation Test 1 using a phosphazenium salt having a P5Cl concentration outside the range of the present invention, it can be seen that the reaction rate of propylene oxide was low and that polymerization of propylene oxide did not proceed. In Comparative Evaluation Test 2 in which a compound containing a large amount of components other than the phosphazenium compound was used as a catalyst, the reaction rate of propylene oxide was lower than those in Evaluation Tests 1 and 2, and the total unsaturation of polyol (C = The value of C) was also high, which indicates that the catalytic performance of the phosphazenium salt was reduced. Therefore, the phosphazenium salt produced by the method of the present invention exhibits excellent catalytic performance in a polymer reaction.

[0074]

According to the method of the present invention, a simple, efficient and highly pure phosphazenium salt can be produced without a complicated operation such as an ion exchange resin method. Therefore, the phosphazenium salt obtained by the production method of the present invention is a very useful compound that can be used not only for organic reactions but also for polymer reactions.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shinsuke Matsumoto 2-1-1 Tango-dori, Minami-ku, Nagoya City, Aichi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Yasunobu Hara 134 Higashihata, Otacho, Tokai City, Aichi Prefecture (72) Inventor Yama ▲ Saki ▼ Fumio 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi, Japan Mitsui Chemicals, Inc. (72) Inventor Saku Izugawa 2-1-1, Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Chemicals, Inc. F Term (reference) 4H050 AA02 BB11 BB12 BB14 BB15 BB21 BB25 BC10 BC31 BC37 BE10 BE11 WA19

Claims (6)

[Claims] [Chemical formula 1] [Chemical formula 1] (A, b, c and d in the chemical formula (1) are each an integer of 0 to 3 which are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, in some cases two R on the same nitrogen atom to form a ring structure bonded .Q ^- the phosphazenium salt comprising a hydroxy anion, phosphate represented by the alkoxy represents an anion) file peptidase cation and an organic anion In a method for producing a compound represented by the formula (2): (A, b, c and d in the chemical formula (2) are each an integer of 0 to 3 that are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms. , .r, sometimes form two R are bonded to the ring structure on the same nitrogen atom, an integer of 1 to 3, represents the number of phosphazenium cations, T ^r- is A salt of a phosphazenium cation and an inorganic anion represented by a valence r), and a solution containing an organic solvent that dissolves the salt of the inorganic anion. After adding a solution containing 0.86 to 1.6 equivalents of a basic hydroxide and an organic solvent that dissolves the basic hydroxide, the phosphazenium represented by the chemical formula (2) in the reaction product is added. Phosphazenium characterized in that the content of salt is controlled to less than 15% by weight Method for producing salt. 2. The method for producing a phosphazenium salt according to claim 1, wherein Q in the chemical formula (1) is a hydroxy anion or an alkoxy anion having 1 to 4 carbon atoms. 3. The method for producing a phosphazenium salt according to claim 1, wherein 0.91 to 1.3 equivalents of a basic hydroxide are added to the phosphazenium salt represented by the chemical formula (2). 4. The method for producing a phosphazenium salt according to claim 1, wherein T of T ^{r− in} the chemical formula (2) is chloride and r = 1. 5. The method for producing a phosphazenium salt according to claim 1, wherein the content of the phosphazenium salt represented by the chemical formula (2) is controlled to less than 10% by weight. 6. The reaction temperature according to claim 1, wherein the reaction temperature is 5 to 180 ° C.
A method for producing the phosphazenium salt described above.