Basic iminophosphazenium salt-containing composition, method for producing same, and method for producing polyalkylene glycol using said composition

Abstract

To provide a basic iminophosphazenium salt-containing composition that enables a basic iminophosphazenium salt, which has a promising utility as an organic base, to be stored stably for a long time even at high or low temperatures, a method for producing the same and a method for producing a polyalkylene glycol using the composition.SOLUTION: A basic iminophosphazenium salt-containing composition contains (i) a basic iminophosphazenium salt having a specific structure: 20-50 wt.%, (ii) water: 9-30 wt.%, (iii) a protic organic solvent with a solubility parameter of 10-13 (cal / cm3)1 / 2: 20-71 wt.%, and (iv) alkali metal ions or alkaline-earth metal ions: 10-1000 ppm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an iminophosphazenium salt-containing composition useful as an organic base, a method for producing the same, and a method for producing a polyalkylene glycol using the composition. [Background technology]

[0002] Basic iminophosphazenium salts are known as useful organic bases. Patent Document 1 proposes their use as catalysts for the alkylation of secondary amines, the alkylation of phenylacetonitrile, and the Dazen reaction, which is the condensation reaction of aldehydes with α-haloesters to produce α,β-epoxy esters.

[0003] Furthermore, Patent Document 2 proposes a catalyst solution for producing polyalkylene glycol, which comprises a basic iminophosphazenium salt solution that enables the basic iminophosphazenium salt to be stably stored for a long period of time, and a method for producing polyalkylene glycol using the same. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] German Patent Application Publication No. 102006010034 [Patent Document 2] Patent No. 5609354 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the basic iminophosphazenium salt obtained by the method proposed in Patent Document 1 is unstable, and if stored in a solid state, decomposition progresses over time, making it difficult to store after synthesis, and therefore has problems as an industrial catalyst for polyalkylene glycols.

[0006] Although the basic iminophosphazenium salt solution obtained by the method proposed in Patent Document 2 has storage stability at room temperature, it has problems with storage stability at high temperatures (50°C or higher) expected for summer storage. Furthermore, Patent Document 2 does not contain any disclosure that refers to the concentration of alkali metal ions or alkaline earth metal ions in the basic iminophosphazenium salt solution. Furthermore, the basic iminophosphazenium salt solution obtained by the method described in Patent Document 2 has a high alkali metal ion or alkaline earth metal ion concentration of 5,000 to 50,000 ppm. Therefore, when stored at high temperatures (50°C or higher) expected for summer storage, coloration due to alkali metal ions or alkaline earth metal ions is observed. When stored at low temperatures (0°C or lower) expected for winter storage, precipitates due to alkali metal ions or alkaline earth metal ions are formed, adversely affecting handling when used as an organic base.

[0007] The present invention has been made in view of the above background, and an object of the present invention is to provide a basic iminophosphazenium salt-containing composition that enables a basic iminophosphazenium salt, which is expected to be useful as an organic base, to be stably stored for a long period of time even at high and low temperatures, a method for producing the same, and a method for producing a polyalkylene glycol using the composition. [Means for solving the problem]

[0008] The embodiments of the present invention are [1] to [5] shown below. [1] A basic iminophosphazenium salt-containing composition comprising the following (i) to (iv): (i) A basic iminophosphazenium salt represented by the following general formula (1): 20 to 50 wt%

[0009] [ka]

[0010] (In the above general formula (1), R1 and R 2 Each of R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 1 and R 2 may be bonded to each other to form a ring structure, or R 1 Comrades or R 2 They may be bonded to each other to form a ring structure. - represents a hydroxy anion, a hydrogen carbonate anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, or an alkylcarboxy anion having 2 to 5 carbon atoms. (ii) Water: 9~30wt% (iii) Solubility parameter is 10-13 (cal / cm 3 ) 1 / 2 Protic organic solvent: 20-71 wt% (iv) Alkali metal ions or alkaline earth metal ions: 10 to 1000 ppm [2] Solubility parameter is 10-13 (cal / cm 3 ) 1 / 2 The basic iminophosphazenium salt-containing composition according to [1], wherein the protic organic solvent is selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol. [3] The basic iminophosphazenium salt-containing composition according to [1] or [2], wherein the purity of the basic iminophosphazenium salt decreases by 3% or less after storage at 50°C for 180 days. [4] A method for producing the basic iminophosphazenium salt-containing composition according to any one of [1] to [3], which comprises at least the following steps (1) to (4): Step (1): A halogenated iminophosphazenium salt represented by the following general formula (2) and a compound having a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 preparing a solution containing a halogenated iminophosphazenium salt containing a protic organic solvent in which

[0011] [ka]

[0012] (In the above general formula (2), R 1 and R 2 represents R in the general formula (1). 1 and R 2 It has the same definition as A - represents a chlorine anion or a bromine anion. Step (2): A step of adding an alkali metal compound or an alkaline earth metal compound to the solution obtained in Step (1) to ion-exchange the halogenated iminophosphazenium salt with a basic iminophosphazenium salt. Step (3): A step of filtering the reaction solution obtained in Step (2) to remove the by-product alkali metal halide salt or alkaline earth metal halide salt. Step (4): A step of adding water to the filtrate obtained in step (3), and then removing the lower phase by a separation operation to obtain a basic iminophosphazenium salt-containing composition. [5] A method for producing a polyalkylene glycol, comprising contacting the basic iminophosphazenium salt-containing composition according to any one of [1] to [3] with an active hydrogen-containing compound, removing the solvent and by-product water, and then adding an alkylene oxide to carry out ring-opening polymerization of the alkylene oxide. [Effects of the Invention]

[0013] One aspect of the present invention provides a basic iminophosphazenium salt-containing composition that enables stable storage of a basic iminophosphazenium salt, which is useful as an organic base, for long periods of time even at high and low temperatures. Another aspect of the present invention provides a method for producing the basic iminophosphazenium salt-containing composition. Yet another aspect of the present invention provides a method for producing a polyalkylene glycol using the basic iminophosphazenium salt-containing composition. The resulting polyalkylene glycol is expected to be used as a variety of resin materials, such as polyurethane raw materials, polyester raw materials, surfactant raw materials, and lubricant raw materials, and is therefore of extremely high industrial value. DETAILED DESCRIPTION OF THE INVENTION

[0014] Exemplary embodiments for carrying out the present invention are described in detail below. <Composition containing basic iminophosphazenium salt> A basic iminophosphazenium salt-containing composition according to one embodiment of the present invention comprises the following (i) to (iv): (i) A basic iminophosphazenium salt represented by the following general formula (1): 20 to 50 wt%

[0015] [ka]

[0016] (In the above general formula (1), R 1 and R 2 Each of R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 1 and R 2 may be bonded to each other to form a ring structure, or R 1 Comrades or R 2 They may be bonded to each other to form a ring structure. - represents a hydroxy anion, a hydrogen carbonate anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, or an alkylcarboxy anion having 2 to 5 carbon atoms. (ii) Water: 9~30wt% (iii) Solubility parameter is 10-13 (cal / cm 3 ) 1 / 2 Protic organic solvent: 20-71 wt% (iv) Alkali metal ions or alkaline earth metal ions: 10 to 1000 ppm The basic iminophosphazenium salt may be any salt as long as it falls within the category of iminophosphazenium salts represented by the above formula (1).

[0017] In formula (1), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 1 and R 2 and a ring structure in which they are bonded to each other, or R1 Friends or R 2 They may be bonded to each other to form a ring structure.

[0018] Examples of hydrocarbon groups having 1 to 20 carbon atoms include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclobutyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a phenyl group, a heptyl group, a cycloheptyl group, an octyl group, a cyclooctyl group, a nonyl group, a cyclononyl group, a decyl group, a cyclodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and a nonadecyl group.

[0019] R 1 and R 2 Examples of the ring structure in which the and are bonded to each other include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, and an isoindolyl group.

[0020] R 1 Friends or R 2 Examples of ring structures in which two R 1 Or two R's 2 are each independently one group selected from alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group, and one alkylene group and the other alkylene group are bonded to each other to form a ring structure.

[0021] Among these, R is a basic iminophosphazenium salt-containing composition that exhibits particularly strong basicity and has excellent storage stability. 1 and R 2 are each independently preferably a methyl group, an ethyl group, or an isopropyl group. 1 and R 2 is preferably a methyl group.

[0022] In formula (1), X -represents a hydroxy anion, a hydrogen carbonate anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, or an alkyl carboxy anion having 2 to 5 carbon atoms. Examples of the alkoxy anion having 1 to 4 carbon atoms include a methoxy anion, an ethoxy anion, an n-propoxy anion, an isopropoxy anion, an n-butoxy anion, an isobutoxy anion, and a t-butoxy anion. Examples of the alkyl carboxy anion having 2 to 5 carbon atoms include an acetoxy anion, an ethyl carboxy anion, an n-propyl carboxy anion, an isopropyl carboxy anion, an n-butyl carboxy anion, an isobutyl carboxy anion, and a t-butyl carboxy anion.

[0023] Among these, X - As the anion, a hydroxy anion and a hydrogen carbonate anion are preferred, as they exhibit particularly strong basicity and result in a basic iminophosphazenium salt-containing composition with excellent storage stability.

[0024] Specific examples of the basic iminophosphazenium salt represented by formula (1) include tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydroxide, tetrakis(1,1,3 ,3-tetra(n-butyl)guanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydroxide, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidine-2-imino)phosphonium hydroxide, tetrakis(1,3-diethylimidazolidine-2-imino)phosphonium hydroxide; tetrakis(1,1,3,3- Tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraethylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-propyl)guanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetraisopropylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetra(n-butyl)guanidino)phosphonium Examples of suitable iminophosphazenium salts include tetrakis(1,1,3,3-tetraphenylguanidino)phosphonium hydrogen carbonate, tetrakis(1,1,3,3-tetrabenzylguanidino)phosphonium hydrogen carbonate, tetrakis(1,3-dimethylimidazolidine-2-imino)phosphonium hydrogen carbonate, and tetrakis(1,3-diethylimidazolidine-2-imino)phosphonium hydrogen carbonate. Among these, tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide and tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydrogen carbonate are preferred because they exhibit particularly strong basicity and result in a basic iminophosphazenium salt-containing composition with excellent storage stability.

[0025] The content of the basic iminophosphazenium salt in the basic iminophosphazenium salt-containing composition according to this embodiment is 20 to 50 wt%, preferably 20 to 42 wt%. If the content of the basic iminophosphazenium salt is less than 20 wt%, when used as an organic base catalyst for producing polyalkylene glycol, it takes a long time to remove the solvent and water, and if the solvent and water cannot be sufficiently removed, the catalytic activity is not exhibited, which is undesirable. On the other hand, if the content of the basic iminophosphazenium salt is more than 50 wt%, the storage stability of the basic iminophosphazenium salt is reduced, which is undesirable.

[0026] There is no limitation on the type of water in the basic iminophosphazenium salt-containing composition according to this embodiment, and examples thereof include ultrapure water, distilled water, ion-exchanged water, and tap water.

[0027] The water content is 9 to 30 wt%, preferably 13 to 30 wt%, and more preferably 13 to 28 wt%. If the water content is less than 9 wt%, the storage stability of the basic iminophosphazenium salt decreases, which is undesirable. On the other hand, if the water content is more than 30 wt%, it takes a long time to remove the water when used as an organic base catalyst for producing polyalkylene glycol, and if the water cannot be sufficiently removed, the catalytic activity will not be expressed, which is undesirable.

[0028] The basic iminophosphazenium salt-containing composition according to this embodiment has a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 The protic organic solvent contains 20 to 71 wt % of a protic organic solvent having a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 Any suitable material may be used, and preferably, the viscosity is 10.5 to 12.5 (cal / cm 3 ) 1 / 2 , more preferably 11 to 12 (cal / cm 3 ) 1 / 2 Here, aprotic solvents or solvents with a solubility parameter of 10 (cal / cm3 ) 1 / 2 If the protic organic solvent has a solubility parameter of less than 13 (cal / cm), the storage stability of the basic iminophosphazenium salt constituting the basic iminophosphazenium salt-containing composition will decrease, which is not preferred. 3 ) 1 / 2 A larger protic organic solvent is not preferred because it increases the concentration of halogenated iminophosphazenium salt in the basic iminophosphazenium salt-containing composition or increases the concentration of alkali metal ions or alkaline earth metal ions in the basic iminophosphazenium salt-containing composition.

[0029] Solubility parameter is 10-13 (cal / cm 3 ) 1 / 2 A specific example of a protic organic solvent is ethanol (EtOH) (solubility parameter 12.7 (cal / cm 3 ) 1 / 2 ), n-propanol (solubility parameter 11.9 (cal / cm 3 ) 1 / 2 ), isopropanol (IPA) (solubility parameter 11.5 (cal / cm 3 ) 1 / 2 ), n-butanol (solubility parameter 11.4 (cal / cm 3 ) 1 / 2 ), isobutanol (solubility parameter 10.5 (cal / cm 3 ) 1 / 2 ), t-butanol (solubility parameter 10.6 (cal / cm 3 ) 1 / 2 ) and other monoalcohols; diethylene glycol (solubility parameter 12.1 (cal / cm 3 ) 1 / 2 ), triethylene glycol (solubility parameter 10.7 (cal / cm 3 ) 1 / 2 ), propylene glycol (solubility parameter 12.6 (cal / cm 3 ) 1 / 2 ), 1,3-butanediol (solubility parameter 11.6 (cal / cm 3 ) 1 / 2), 1,4-butanediol (solubility parameter 12.1 (cal / cm 3 ) 1 / 2 ), 2,3-butanediol (solubility parameter 11.1 (cal / cm 3 ) 1 / 2 ) and other polyhydric alcohols; ethylene glycol monomethyl ether (solubility parameter 11.4 (cal / cm 3 ) 1 / 2 ), ethylene glycol monoethyl ether (solubility parameter 10.5 (cal / cm 3 ) 1 / 2 ), ethylene glycol monobenzyl ether (solubility parameter 10.9 (cal / cm 3 ) 1 / 2 ), ethylene glycol monophenyl ether (solubility parameter 11.5 (cal / cm 3 ) 1 / 2 ) and other polyhydric alcohol derivatives; formic acid (solubility parameter 12.1 (cal / cm 3 ) 1 / 2 ), acetic acid (solubility parameter 10.1 (cal / cm 3 ) 1 / 2 ) and other fatty acids; ethylenediamine (solubility parameter 12.3 (cal / cm 3 ) 1 / 2 ), aniline (solubility parameter 10.3 (cal / cm 3 ) 1 / 2 ) and other nitrogen-containing compounds. These solvents may be mixed solvents of two or more kinds. Among these, monoalcohols having 2 to 4 carbon atoms such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol are preferred, as they are easily available and provide a basic iminophosphazenium salt-containing composition that is particularly excellent in storage stability, and n-propanol, isopropanol, and n-butanol are more preferred.

[0030] The content of the protic organic solvent is 20 to 71 wt%. If the content of the protic organic solvent is less than 20 wt%, the storage stability of the basic iminophosphazenium salt decreases, which is undesirable. On the other hand, if the content of the protic organic solvent is more than 71 wt%, when used as an organic base catalyst for producing polyalkylene glycol, it takes a long time to remove the solvent, and if the solvent cannot be sufficiently removed, catalytic activity is not exhibited, which is undesirable.

[0031] The basic iminophosphazenium salt-containing composition according to this embodiment contains 10 to 1000 ppm of alkali metal ions or alkaline earth metal ions, such as lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, magnesium ions, calcium ions, strontium ions, and barium ions.

[0032] The content of alkali metal ions or alkaline earth metal ions is preferably 10 to 1000 ppm, more preferably 20 to 800 ppm, and even more preferably 50 to 500 ppm. If the content is less than 10 ppm, the pH of the basic iminophosphazenium salt-containing composition decreases when stored at high temperatures, resulting in a decrease in catalytic activity when used as a catalyst for producing polyalkylene glycol. On the other hand, if the content of alkali metal ions or alkaline earth metal ions is more than 1000 ppm, coloration due to the alkali metal ions or alkaline earth metal ions is observed when the basic iminophosphazenium salt-containing composition is stored at high temperatures, and the resulting polyalkylene glycol also becomes colored when used as a catalyst for producing polyalkylene glycol. This is also undesirable. Furthermore, if the content of alkali metal ions or alkaline earth metal ions is more than 1000 ppm, when the basic iminophosphazenium salt-containing composition is stored at low temperatures, precipitates derived from the alkali metal ions or alkaline earth metal ions are formed, which undesirably adversely affects handling, such as making weighing and transfer difficult when used as an organic base.

[0033] The basic iminophosphazenium salt-containing composition according to this embodiment may contain other components as long as the effects of the present invention are not impaired.

[0034] In the basic iminophosphazenium salt-containing composition according to this embodiment, the content of the halogenated iminophosphazenium salt represented by the following formula (2) is not particularly limited, but is preferably 5 wt% or less, more preferably 3 wt% or less, and even more preferably 2 wt% or less. If the content of the halogenated iminophosphazenium salt exceeds 5 wt%, the catalytic activity decreases when used as a catalyst for producing polyalkylene glycol, which is not preferred.

[0035] [ka]

[0036] (In the above general formula (2), R 1 and R 2 represents R in the general formula (1). 1 and R 2 It has the same definition as A - represents a chlorine anion or a bromine anion. The basic iminophosphazenium salt-containing composition according to this embodiment preferably does not lose purity when stored at high temperatures for a long period of time. Specifically, it is preferable that the purity of the basic iminophosphazenium salt loses 3% or less after storage at 50°C for 180 days. In this case, the purity of the basic iminophosphazenium salt is measured by 1 The purity decrease was measured by H-NMR, and the decrease in purity was calculated from the absolute decrease in purity from the purity immediately after production. That is, the decrease in purity (%) of the basic iminophosphazenium salt was calculated using the following formula.

[0037] Purity loss of basic iminophosphazenium salt (%) = (Purity immediately after production) - (Purity after storage at 50°C for 180 days) The basic iminophosphazenium salt-containing composition according to this embodiment preferably does not decrease in pH when stored at high temperatures for a long period of time. Specifically, it is preferable that the pH decrease of the basic iminophosphazenium salt-containing composition after storage at 50°C for 180 days is 1.0 or less. In this case, the pH decrease can be calculated from the absolute pH value decreased from the pH immediately after production. That is, the pH decrease of the basic iminophosphazenium salt was calculated using the following formula.

[0038] pH reduction of basic iminophosphazenium salts = (pH immediately after production) - (pH after storage at 50°C for 180 days) The basic iminophosphazenium salt-containing composition of the present invention preferably does not show coloration when stored at high temperatures for a long period of time. Specifically, it is preferable that the coloration after storage at 50°C for 180 days remains unchanged compared to before storage at 50°C for 180 days.

[0039] The basic iminophosphazenium salt-containing composition of the present invention has excellent long-term storage stability at low temperatures, specifically, it is preferable that no precipitates are observed after storage at 0°C for 180 days. <Method for producing a basic iminophosphazenium salt-containing composition> A method for producing a basic iminophosphazenium salt-containing composition according to one embodiment of the present invention includes at least the following steps (1) to (4). Step (1): A halogenated iminophosphazenium salt represented by the following general formula (2) and a compound having a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 preparing a solution containing a halogenated iminophosphazenium salt containing a protic organic solvent in which

[0040] [ka]

[0041] (In the above general formula (2), R 1 and R 2represents R in the general formula (1). 1 and R 2 It has the same definition as A - represents a chlorine anion or a bromine anion. Step (2): A step of adding an alkali metal compound or an alkaline earth metal compound to the solution obtained in Step (1) to ion-exchange the halogenated iminophosphazenium salt with a basic iminophosphazenium salt. Step (3): A step of filtering the reaction solution obtained in Step (2) to remove the by-product alkali metal halide salt or alkaline earth metal halide salt. Step (4): A step of adding water to the filtrate obtained in step (3), and then removing the lower phase by a separation operation to obtain a basic iminophosphazenium salt-containing composition.

[0042] The step (1) is carried out by reacting a halogenated iminophosphazenium salt represented by the general formula (2) with a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 Any method may be used as long as it is possible to prepare a solution containing a halogenated iminophosphazenium salt containing a protic organic solvent represented by the formula (I), and an example of such a method includes the following steps (1-1) to (1-3):

[0043] Step (1-1): A step of reacting a phosphorus pentahalide represented by the following general formula (3) with a guanidine derivative represented by the following general formula (4) in a non-aqueous solvent under an inert gas atmosphere to produce a halogenated iminophosphazenium salt represented by the general formula (2).

[0044] [ka]

[0045] (In the above general formula (3), Y represents a chlorine atom or a bromine atom.)

[0046] [ka]

[0047] (In the above general formula (4), R 1 and R 2 represents R in the general formula (1). 1 and R 2 This is the same definition as Step (1-2): After Step (1-1), an aqueous medium is added to the obtained reaction liquid to carry out oil-water separation, a halogenated solvent is further added to the obtained aqueous phase to carry out oil-water separation, and the reaction product is made into a halogenated solvent extract solution.

[0048] Step (1-3): After step (1-2), the halogenated solvent of the halogenated solvent extract solution obtained is dissolved in a solvent having a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 and forming a solution by substituting the protic organic solvent with the protic organic solvent.

[0049] In the above step (1-1), the stoichiometric ratio of the phosphorus pentahalide to the guanidine derivative is 1 mole of the phosphorus pentahalide to 4 moles of the guanidine derivative, and it is preferably 4 moles or more, particularly preferably 6 to 20 moles, and more preferably in the range of 8 to 12 moles, since this allows the reaction to proceed more efficiently.

[0050] In the above step (1-1), the amount of the non-aqueous solvent can be appropriately selected depending on the reaction system. Among them, the amount is preferably 0.1 to 80 liters, particularly 0.5 to 40 liters, and more preferably 1 to 20 liters, per mol of phosphorus pentahalide, because this allows for a more efficient reaction.

[0051] In the above step (1-1), the reaction temperature when reacting the phosphorus pentahalide with the guanidine derivative may be any temperature as long as the reaction proceeds, and can be, for example, −50° C. to 180° C., but a range of −30 to 150° C. is preferred to enable a more efficient reaction. Furthermore, it is preferable to carry out the reaction at a temperature of 20° C. or less in the early stage of the reaction and to raise the reaction temperature to 80° C. or higher in the later stage of the reaction, in order to control the heat generation in the early stage of the reaction and compensate for the decrease in reactivity in the later stage of the reaction.

[0052] The halogenated iminophosphazenium salt in the above step (1-1) may be any salt as long as it falls within the category of halogenated iminophosphazenium salts represented by the above formula (2). 1 and R 2 is the R listed in the above formula (1). 1 and R 2 The same as A - represents a chloride anion or a bromide anion.

[0053] In the above step (1-2), the aqueous medium may be any so long as it is called an aqueous medium, and examples thereof include ultrapure water, ion-exchanged water, distilled water, industrial water, tap water, drinking water, etc. The amount of the aqueous medium used may be any amount that can dissolve the halogenated iminophosphazenium salt represented by the above formula (2), and is, for example, in the range of 0.1 to 3 liters, preferably 0.2 to 1 liter, per liter of the water-insoluble solvent.

[0054] In the above step (1-2), examples of the halogenated solvent include dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane. Among these, dichloromethane or chloroform is preferred because of the ease of subsequent solvent removal. The amount of the halogenated solvent used is preferably 5 to 500 parts by weight, and particularly preferably 10 to 200 parts by weight, per 100 parts by weight of the aqueous medium.

[0055] In the above step (1-3), the solubility parameter is 10 to 13 (cal / cm 3 ) 1 / 2 Examples of the protic organic solvent include the same protic organic solvents as those explained in the basic iminophosphazenium salt-containing composition.

[0056] In the above step (1-3), the solvent substitution may be carried out by any method as long as it is possible to perform solvent substitution. For example, after removing the halogenated solvent from the halogenated solvent extract solution obtained in step (1-2) by a method such as distillation, a solution having a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 a method of solvent substitution by adding a protic organic solvent having a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 and then removing the halogenated solvent by a method such as distillation to effect solvent substitution.

[0057] In the above step (1-3), the conditions for distillation removal of the halogenated solvent are as follows: the halogenated solvent to be used has a solubility parameter of 10 to 13 (cal / cm 3 ) 1 / 2 For example, dichloromethane is used as the halogenated solvent, and the solvent parameter is 10 to 13 (cal / cm 3 ) 1 / 2When isopropanol is used as the protic organic solvent, dichloromethane and isopropanol can be removed at normal pressure in the range of 80 to 100° C. so that the solution concentration is in the range of 25 to 70% by weight.

[0058] The alkali metal compound or alkaline earth metal compound in the above step (2) may be any compound that can ion-exchange a halogenated iminophosphazenium salt into a basic iminophosphazenium salt, and examples thereof include hydroxides of alkali metals or alkaline earth metals, alkoxides of alkali metals or alkaline earth metals, alkali metal salts or alkaline earth metal salts of carboxylic acids, and hydrogen carbonates of alkali metals or alkaline earth metals.

[0059] Specific examples of alkali metal or alkaline earth metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.

[0060] Specific examples of alkali metal or alkaline earth metal alkoxides include alkali metal or alkaline earth metal methoxides, ethoxides, n-propoxides, isopropoxides, n-butoxides, isobutoxides, t-butoxides, n-pentyl oxides, n-hexyl oxides, n-octyl oxides, n-nonyl oxides, n-decyl oxides, phenoxides, 2-methylphenoxides, 3-methylphenoxides, 4-methylphenoxides, benzyl oxides, ethylene glycooxides, diethylene glycooxides, 1,2-dihydropropoxides, polyalkylene glycooxides having a number average molecular weight of 200 to 20,000, and the like.

[0061] Examples of alkali metal salts or alkaline earth metal salts of carboxylic acids include formates (carboxylates), acetates (methylcarboxylates), propionates (ethylcarboxylates), butyrates (n-propylcarboxylates), isobutyrates (isopropylcarboxylates), valerates (n-butylcarboxylates), isovalerates (isobutylcarboxylates), and pivalates (t-butylcarboxylates) of alkali metals or alkaline earth metals.

[0062] Examples of the hydrogen carbonate of an alkali metal or alkaline earth metal include sodium hydrogen carbonate and potassium hydrogen carbonate.

[0063] Among these, hydroxides of alkali metal compounds or alkaline earth metal compounds are preferred, and sodium hydroxide and potassium hydroxide are particularly preferred, because they are easily available and allow efficient ion exchange from a halogenated iminophosphazenium salt to a basic iminophosphazenium salt.

[0064] The amount of alkali metal compound or alkaline earth metal compound used can be appropriately selected, and is preferably 0.9 to 1.5 mol, more preferably 1.0 to 1.2 mol, and even more preferably 1.1 to 1.2 mol, per 1 mol of halogenated iminophosphazenium salt, since this allows for efficient production of a basic iminophosphazenium salt.

[0065] In the above step (2), the reaction temperature for carrying out the ion exchange reaction can be appropriately selected, and is preferably in the range of 25 to 100°C, and particularly preferably in the range of 40 to 80°C.

[0066] In the above step (3), the filtration conditions may be any method that allows removal of by-product alkali metal halide salts or alkaline earth metal halide salts, and the filtration may be performed under pressure or under reduced pressure. The filtration temperature may be, for example, 0 to 80°C, with 10 to 60°C being particularly preferred since it allows efficient removal of by-product alkali metal halide salts or alkaline earth metal halide salts.

[0067] In the above step (4), water is added to the filtrate obtained in step (3), and then the lower phase is removed by a separation operation to obtain a basic iminophosphazenium salt-containing composition. If step (4) is not performed, the alkali metal ion or alkaline earth metal ion concentration in the obtained basic iminophosphazenium salt-containing composition will be high, which is undesirable.

[0068] The amount of water added in the above step (4) is preferably 9 to 30 wt%, more preferably 13 to 30 wt%, and even more preferably 13 to 28 wt%. Adding less than 9 wt% of water is undesirable because the storage stability of the resulting basic iminophosphazenium salt-containing composition decreases. Adding more than 30 wt% of water is undesirable because two-phase separation does not occur after adding water, making it impossible to remove the lower phase. If the lower phase cannot be removed, the alkali metal ion or alkaline earth metal ion concentration in the basic iminophosphazenium salt-containing composition increases, which is undesirable. <Method of producing polyalkylene glycol> In one aspect of the present invention, a method for producing polyalkylene glycol comprises contacting the basic iminophosphazenium salt-containing composition with an active hydrogen-containing compound, removing the solvent and by-product water, adding alkylene oxide, and carrying out ring-opening polymerization of the alkylene oxide.

[0069] Examples of the active hydrogen-containing compound include hydroxy compounds, amine compounds, carboxylic acid compounds, phenol compounds, and thiol compounds. More specifically, examples include hydroxy compounds such as water, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, and glucose; amine compounds such as ethylenediamine, N,N'-dimethylethylenediamine, piperidine, and piperazine; carboxylic acid compounds such as benzoic acid and adipic acid; phenol compounds such as 2-naphthol and bisphenol; and thiol compounds such as ethanedithiol and butanedithiol. It is also possible to use polyether polyols having hydroxyl groups, such as polypropylene glycol and polypropylene glycol glycerin ether, and in this case, there are no particular limitations on the molecular weight of the polyether polyol, and among these, polyether polyols having a molecular weight of 200 to 3000, which have low viscosity and excellent fluidity, are preferred. These active hydrogen-containing compounds may be used alone or in combination.

[0070] Examples of methods for removing the solvent and by-product water contained in the basic iminophosphazenium salt-containing composition include methods for removing the solvent and by-product water under reduced pressure, and the degree of reduced pressure in this case can be, for example, 50 kPa or less, preferably 10 kPa or less, and particularly preferably 5 kPa or less. Furthermore, examples of temperature conditions in this case include a temperature range of 30 to 130°C, preferably a range of 40 to 100°C. Furthermore, examples of time for this case include 4 to 6 hours.

[0071] Examples of the alkylene oxide include alkylene oxides having 2 to 20 carbon atoms, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, butadiene monoxide, pentene oxide, styrene oxide, and cyclohexene oxide. Among these, ethylene oxide and propylene oxide are preferred because of their easy availability and high industrial value. The alkylene oxides may be used alone or in combination of two or more. When two or more alkylene oxides are used in combination, for example, a first alkylene oxide may be reacted first, followed by a second alkylene oxide, or two or more alkylene oxides may be reacted simultaneously.

[0072] The polyalkylene glycol obtained by the above-mentioned method for producing polyalkylene glycol can be a polyalkylene glycol having a different hydroxyl value, and there is no particular limitation on the hydroxyl value of the obtained polyalkylene glycol. Among them, a hydroxyl value in the range of 5 to 500 mgKOH / g is preferable, and a hydroxyl value in the range of 10 to 170 mgKOH / g is particularly preferable.

[0073] The above polyalkylene glycols are useful as raw materials for polyurethanes, polyesters, surfactants, lubricants, etc. In particular, by reacting them with various isocyanate compounds, they are expected to be used in rigid foams used in insulation materials, flexible foams used in automobile seats and cushions, bedding, adhesives, paints, sealants, thermosetting elastomers, and thermoplastic elastomers. [Example]

[0074] The present invention will be described below with reference to examples, but the present invention is not limited to these examples in any way.

[0075] The evaluation and measurement methods used in the examples and comparative examples are shown below. (1) Content of basic iminophosphazenium salt in basic iminophosphazenium salt-containing composition (unit: wt%) HPLC analysis was performed using a high performance liquid chromatography (HPLC) apparatus (8020 manufactured by Tosoh Corporation) under the following conditions: column: L-column2ODS (particle diameter: 5 μm, φ: 4.6 mm, L: 250 mm), developing solvent: methanol / water / trifluoroacetic anhydride=150 ml / 850 ml / 1 ml, sample concentration: 250 μg / g, sample injection amount: 5 μl, UV wavelength: 230 nm, flow rate: 1 ml / min, and the content of basic iminophosphazenium salt in the basic iminophosphazenium salt-containing composition was measured. (2) Water content in the basic iminophosphazenium salt-containing composition (unit: wt%) The water content in the basic iminophosphazenium salt-containing composition was measured using a Karl Fischer moisture meter (Model CA-05, manufactured by Mitsubishi Chemical) and Aquamicron CXU and Aquamicron AX as measurement solutions. (3) The solubility parameter in the composition containing the basic iminophosphazenium salt is 10 to 13 (cal / cm 3 ) 1 / 2 The content of protic organic solvent (unit: wt%) The content of the basic iminophosphazenium salt and the water content in the basic iminophosphazenium salt were used to calculate the content according to the following formula. The solubility parameter in the basic iminophosphazenium salt-containing composition is 10 to 13 (cal / cm 3 ) 1 / 2 The content of the protic organic solvent is equal to or greater than 100=(the content of the basic iminophosphazenium salt in the composition)−(the content of water in the composition). (4) Concentration of alkali metal ions or alkaline earth metal ions in the basic iminophosphazenium salt-containing composition (unit: ppm) The concentrations of alkali metal ions or alkaline earth metal ions in the basic iminophosphazenium salt-containing compositions were calculated by inductively coupled plasma atomic emission spectroscopy (ICP-AES) using a PerkinElmer Optima 8300. When measuring the concentration of potassium ions as alkali metal ions or alkaline earth metal ions, the measurement was performed at a wavelength of 766.490 nm. (5) Purity of basic iminophosphazenium salt in basic iminophosphazenium salt-containing composition (unit: %) A nuclear magnetic resonance (NMR) spectrometer (JEOL, product name: JNM-ECZ400S / LI) was used, and heavy water was used as the heavy solvent. 1 H-NMR was measured. The purity of the basic iminophosphazenium salt was calculated from the ratio of the area of ​​the peak at 2.85 ppm to the area of ​​the peaks in the range of 2.60 to 3.10 ppm. (6) pH of the composition containing basic iminophosphazenium salt (unit: no) The pH of the basic iminophosphazenium salt-containing composition was measured using a pH meter (PH72 pH / ORP meter manufactured by YOKOGAWA Corporation). (7) Coloration of a composition containing a basic iminophosphazenium salt at high temperatures The appearance of the basic iminophosphazenium salt-containing composition was visually observed after storage for 180 days at 50°C. When compared to before storage at 50°C for 180 days, compositions showing no change in color were marked with an ⊚, compositions showing almost no change with an ◯, and compositions showing a darker color with an ×. (8) Precipitation of a composition containing a basic iminophosphazenium salt at low temperatures The appearance of the basic iminophosphazenium salt-containing composition was visually observed after storage at 0° C. for 180 days. The composition in which no precipitate was observed on the bottom of the storage container was marked with a double circle, the composition in which almost no precipitate was observed was marked with a circle, and the composition in which precipitate was observed was marked with an x. (9) Hydroxyl value of polyalkylene glycol (unit: mgKOH / g) Calculation was performed according to the method described in JIS K-1557-1.

[0076] Example 1 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of isopropanol (IPA) was added. The temperature was then raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R 2 is a methyl group, A - An isopropanol solution of iminophosphazenium salt (wherein the anion corresponds to chloride) was obtained.

[0077] The obtained isopropanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. The temperature was then cooled to 25°C, and the precipitated by-product salt was removed by filtration. 95 g of water was added to the obtained filtrate, and the mixture was allowed to stand until it separated into two phases. The lower phase was then removed to obtain the basic iminophosphazenium salt (R in the above formula (1) 1 is a methyl group, R 2 is a methyl group, X -A basic iminophosphazenium salt-containing composition A (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition A was 23 wt%, the water content was 9 wt%, the isopropanol content was 68 wt%, and the potassium ion concentration was 800 ppm.

[0078] After storing this basic iminophosphazenium salt-containing composition A under an environment of 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 1.5%, the pH decreased by 0.1, and almost no change in color was observed (rating: ◯), indicating high storage stability at high temperatures.Furthermore, after storing basic iminophosphazenium salt-containing composition A under an environment of 0°C for 180 days, almost no change in appearance was observed (rating: ◯), indicating high storage stability at low temperatures.

[0079] Then, 5.5 g of basic iminophosphazenium salt composition A (basic iminophosphazenium salt content 1.3 g) after being placed under an environment of 50 ° C for 180 days and 100 g of polypropylene triol with a molecular weight of 600 were added to a 2-liter autoclave equipped with a stirring blade, and the solvent and by-product water were removed at an internal temperature of 80 ° C and a reduced pressure of 0.5 kPa for 6 hours. Subsequently, while maintaining an internal temperature of 90 ° C and a pressure of 0.3 MPa or less, 946 g of propylene oxide was intermittently supplied to carry out a polymerization reaction of propylene oxide, and then unreacted propylene oxide was removed under a reduced pressure of 0.5 kPa. Furthermore, while maintaining an internal temperature of 130 ° C and a pressure of 0.3 MPa or less, 173 g of ethylene oxide was intermittently supplied to carry out a polymerization reaction of ethylene oxide, and then unreacted ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain polyalkylene glycol (1206 g). The resulting polyalkylene glycol was colorless and had a hydroxyl value of 24 mgKOH / g.

[0080] Example 2 In the production of a composition containing a basic iminophosphazenium salt, the same procedure as in Example 1 was carried out, except that the amount of water added to the filtrate after ion exchange and filtration was changed from 95 g to 140 g. 1 is a methyl group, R 2 is a methyl group, X - A basic iminophosphazenium salt-containing composition B (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition B was 22 wt%, the water content was 13 wt%, the isopropanol content was 65 wt%, and the potassium ion concentration was 500 ppm.

[0081] After storing this basic iminophosphazenium salt-containing composition B in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 0.8%, the pH decreased by 0.2, and no change in color was observed (rating: ◎), indicating high storage stability at high temperatures.Furthermore, after storing basic iminophosphazenium salt-containing composition B in an environment at 0°C for 180 days, there was no change in appearance (rating: ◎), indicating high storage stability at low temperatures.

[0082] Then, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 5.8 g of basic iminophosphazenium salt-containing composition B (basic iminophosphazenium salt content 1.3 g) after being left in an environment at 50°C for 180 days was used. Polymerization proceeded efficiently, and polyalkylene glycol (1206 g) was obtained. The obtained polyalkylene glycol was colorless and had a hydroxyl value of 24 mg KOH / g.

[0083] Example 3 In the production of a composition containing a basic iminophosphazenium salt, the same procedure as in Example 1 was carried out, except that the amount of water added to the filtrate after ion exchange and filtration was changed from 95 g to 190 g. 1 is a methyl group, R 2 is a methyl group, X -A basic iminophosphazenium salt-containing composition C (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition C was 21 wt%, the water content was 17 wt%, the isopropanol content was 62 wt%, and the potassium ion concentration was 140 ppm.

[0084] After storing this basic iminophosphazenium salt-containing composition C under an environment of 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 0.3%, the pH decreased by 0.2, and no change in color was observed (rating: ◎), indicating high storage stability at high temperatures.Furthermore, after storing basic iminophosphazenium salt-containing composition C under an environment of 0°C for 180 days, there was no change in appearance (rating: ◎), indicating high storage stability at low temperatures.

[0085] Then, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 6.1 g of basic iminophosphazenium salt-containing composition C (basic iminophosphazenium salt content 1.3 g) after being left in an environment at 50 ° C for 180 days was used. Polymerization proceeded efficiently, and polyalkylene glycol (1206 g) was obtained. The obtained polyalkylene glycol was colorless and had a hydroxyl value of 24 mg KOH / g.

[0086] Example 4 In the production of a composition containing a basic iminophosphazenium salt, the same procedure as in Example 1 was carried out, except that the amount of water added to the filtrate after ion exchange and filtration was changed from 95 g to 240 g. 1 is a methyl group, R 2 is a methyl group, X - A basic iminophosphazenium salt-containing composition D (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content of the obtained basic iminophosphazenium salt-containing composition D was 20 wt%, the water content was 20 wt%, the isopropanol content was 60 wt%, and the potassium ion concentration was 80 ppm.

[0087] After storing this basic iminophosphazenium salt-containing composition D in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 0.1%, the pH decreased by 0.2, and no change in color was observed (rating: ◎), indicating high storage stability at high temperatures.Furthermore, after storing basic iminophosphazenium salt-containing composition D in an environment at 0°C for 180 days, there was no change in appearance (rating: ◎), indicating high storage stability at low temperatures.

[0088] Then, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 6.4 g of basic iminophosphazenium salt-containing composition D (basic iminophosphazenium salt content 1.3 g) after being left in an environment at 50 ° C for 180 days was used. Polymerization proceeded efficiently, and polyalkylene glycol (1206 g) was obtained. The obtained polyalkylene glycol was colorless and had a hydroxyl value of 24 mg KOH / g.

[0089] Example 5 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of isopropanol was added. After that, the temperature was raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R2 is a methyl group, A - An isopropanol solution of iminophosphazenium salt (wherein the anion corresponds to chloride) was obtained.

[0090] The obtained isopropanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. The temperature was then cooled to 25°C, and the precipitated by-product salt was removed by filtration. The obtained filtrate was concentrated to 430 g, and 180 g of water was added. The mixture was allowed to stand until two phases separated, and the lower phase was removed to obtain the basic iminophosphazenium salt (R in the above formula (1) 1 is a methyl group, R 2 is a methyl group, X - A basic iminophosphazenium salt-containing composition E (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition E was 36 wt%, the water content was 28 wt%, the isopropanol content was 36 wt%, and the potassium ion concentration was 50 ppm.

[0091] After storing this basic iminophosphazenium salt-containing composition E in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 0.8%, the pH decreased by 0.2, and no change in color was observed (rating: ◎), indicating high storage stability at high temperatures.Furthermore, after storing basic iminophosphazenium salt-containing composition E in an environment at 0°C for 180 days, there was no change in appearance (rating: ◎), indicating high storage stability at low temperatures.

[0092] Then, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 3.6 g of basic iminophosphazenium salt-containing composition E (basic iminophosphazenium salt content: 1.3 g) after being left in an environment at 50°C for 180 days was used. Polymerization proceeded efficiently, and polyalkylene glycol (1200 g) was obtained. The obtained polyalkylene glycol was colorless and had a hydroxyl value of 24 mg KOH / g.

[0093] Example 6 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of isopropanol was added. After that, the temperature was raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R 2 is a methyl group, A - An isopropanol solution of iminophosphazenium salt (wherein the anion corresponds to chloride) was obtained.

[0094] The obtained isopropanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. The temperature was then cooled to 25°C, and the precipitated by-product salt was removed by filtration. The obtained filtrate was concentrated to 360 g, and 170 g of water was added. The mixture was allowed to stand until two phases separated, and the lower phase was removed to obtain the basic iminophosphazenium salt (R in the above formula (1) 1 is a methyl group, R 2 is a methyl group, X -A basic iminophosphazenium salt-containing composition F (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition F was 42 wt%, the water content was 30 wt%, the isopropanol content was 28 wt%, and the potassium ion concentration was 20 ppm.

[0095] After storing this basic iminophosphazenium salt-containing composition F under an environment of 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 1.5%, the pH decreased by 0.4, and no change in color was observed (rating: ◎), indicating high storage stability at high temperatures.Furthermore, after storing basic iminophosphazenium salt-containing composition F under an environment of 0°C for 180 days, there was no change in appearance (rating: ◎), indicating high storage stability at low temperatures.

[0096] Then, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 3.1 g of basic iminophosphazenium salt-containing composition F (basic iminophosphazenium salt content: 1.3 g) after being left in an environment at 50°C for 180 days was used. Polymerization proceeded efficiently, and polyalkylene glycol (1160 g) was obtained. The obtained polyalkylene glycol was colorless and had a hydroxyl value of 25 mg KOH / g.

[0097] Example 7 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of isopropanol was added. After that, the temperature was raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R 2 is a methyl group, A - An isopropanol solution of iminophosphazenium salt (wherein the anion corresponds to chloride) was obtained.

[0098] The obtained isopropanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. The temperature was then cooled to 25°C, and the precipitated by-product salt was removed by filtration. The obtained filtrate was concentrated to 310 g, and 140 g of water was added. The mixture was allowed to stand until two phases separated, and the lower phase was removed to obtain the basic iminophosphazenium salt (R in the above formula (1) 1 is a methyl group, R 2 is a methyl group, X -A basic iminophosphazenium salt-containing composition G (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition G was 50 wt %, the water content was 29 wt %, the isopropanol content was 21 wt %, and the potassium ion concentration was 10 ppm.

[0099] After storing this basic iminophosphazenium salt-containing composition G under an environment of 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 1.9%, the pH decreased by 0.6, and no change in color was observed (rating: ◎), indicating high storage stability at high temperatures.Furthermore, after storing basic iminophosphazenium salt-containing composition G under an environment of 0°C for 180 days, there was no change in appearance (rating: ◎), indicating high storage stability at low temperatures.

[0100] Then, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 2.6 g of basic iminophosphazenium salt-containing composition G (basic iminophosphazenium salt content: 1.3 g) after being left in an environment at 50°C for 180 days was used. Polymerization proceeded efficiently, and polyalkylene glycol (1150 g) was obtained. The obtained polyalkylene glycol was colorless and had a hydroxyl value of 25 mg KOH / g.

[0101] Example 8 The same procedure as in Example 1 was carried out to prepare a basic iminophosphazenium salt-containing composition, except that ethanol (EtOH) was used instead of isopropanol. 1 is a methyl group, R 2 is a methyl group, X - A basic iminophosphazenium salt-containing composition H (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition H was 23 wt%, the water content was 9 wt%, the ethanol content was 68 wt%, and the potassium ion concentration was 1000 ppm.

[0102] After storing this basic iminophosphazenium salt-containing composition H in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 1.1%, the pH decreased by 0.1, and almost no change in color was observed (rating: ◯), indicating high storage stability at high temperatures.Furthermore, after storing basic iminophosphazenium salt-containing composition H in an environment at 0°C for 180 days, almost no change in appearance was observed (rating: ◯), indicating high storage stability at low temperatures.

[0103] Then, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 5.5 g of basic iminophosphazenium salt-containing composition H (basic iminophosphazenium salt content 1.3 g) after being left in an environment at 50 ° C for 180 days was used. Polymerization proceeded efficiently, and polyalkylene glycol (1160 g) was obtained. The obtained polyalkylene glycol was colorless and had a hydroxyl value of 25 mg KOH / g.

[0104] Comparative Example 1 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of isopropanol was added. After that, the temperature was raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R2 is a methyl group, A - An isopropanol solution of iminophosphazenium salt (wherein the anion corresponds to chloride) was obtained.

[0105] The obtained isopropanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per 1 mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. Thereafter, the temperature was cooled to 25°C, and the precipitated by-product salt was removed by filtration. The obtained filtrate was concentrated to 720 g, and 15 g of water was added, but no separation into two phases was observed. The obtained basic iminophosphazenium salt (R in the above formula (1)) 1 is a methyl group, R 2 is a methyl group, X - The basic iminophosphazenium salt content in composition I (iminophosphazenium salt corresponding to hydroxy anion) was 29 wt %, the water content was 2 wt %, the isopropanol content was 69 wt %, and the potassium ion concentration was 6000 ppm.

[0106] After storing this basic iminophosphazenium salt-containing composition I in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 30%, the pH decreased by 1.5, and the coloration became darker than before storing at 50°C for 180 days (evaluation: x), and storage stability at high temperatures could not be maintained. Furthermore, after storing basic iminophosphazenium salt-containing composition I in an environment at 0°C for 180 days, precipitation was observed (evaluation: x), and storage stability at low temperatures could not be maintained.

[0107] Then, except for using 4.5 g of basic iminophosphazenium salt-containing composition I (basic iminophosphazenium salt content before purity reduction: 1.3 g) that had been left in an environment at 50°C for 180 days, polyalkylene glycol was synthesized in the same manner as in Example 1. As a result, the catalyst did not exhibit activity, and the ring-opening polymerization reaction did not proceed.

[0108] Comparative Example 2 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of isopropanol was added. After that, the temperature was raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R 2 is a methyl group, A - An isopropanol solution of iminophosphazenium salt (wherein the anion corresponds to chloride) was obtained.

[0109] The obtained isopropanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. Thereafter, the temperature was cooled to 25°C, and the precipitated by-product salt was removed by filtration. 190 g of water was added to the obtained filtrate. Note that no separation operation was performed after adding water. The obtained basic iminophosphazenium salt (R in the above formula (1) 1 is a methyl group, R 2 is a methyl group, X -The basic iminophosphazenium salt content in composition J (iminophosphazenium salt corresponding to hydroxy anion) was 21 wt %, the water content was 18 wt %, the isopropanol content was 61 wt %, and the potassium ion concentration was 6000 ppm.

[0110] After storing this basic iminophosphazenium salt-containing composition J in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 0.2% and the pH decreased by 0.2, but the coloration became darker (evaluation: ×) compared to before storing at 50°C for 180 days, and storage stability at high temperatures could not be maintained. Furthermore, after storing basic iminophosphazenium salt-containing composition J in an environment at 0°C for 180 days, precipitation was observed (evaluation: ×), and storage stability at low temperatures could not be maintained.

[0111] Then, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 6.2 g of basic iminophosphazenium salt-containing composition J (basic iminophosphazenium salt content: 1.3 g) after being left in an environment at 50°C for 180 days was used. As a result, polyalkylene glycol (1100 g) was obtained. The recovery rate of polyalkylene glycol was low at 90%, and the hydroxyl value was high at 27 mg KOH / g. In addition, the obtained polyalkylene glycol was colored, which had an adverse effect when used as a urethane raw material.

[0112] Furthermore, polyalkylene glycol was synthesized in the same manner as in Example 1, except that 6.2 g of basic iminophosphazenium salt-containing composition J (basic iminophosphazenium salt content: 1.3 g) that had been left in an environment at 0°C for 180 days was used. As a result, polyalkylene glycol (1100 g) was obtained. The recovery rate of polyalkylene glycol was low at 90%, and the hydroxyl value was high at 27 mg KOH / g. Furthermore, the obtained polyalkylene glycol contained a large amount of potassium residue, so it was cloudy, making it difficult to control the reaction when used as a urethane raw material.

[0113] Comparative Example 3 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of isopropanol was added. After that, the temperature was raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R 2 is a methyl group, A - An isopropanol solution of iminophosphazenium salt (wherein the anion corresponds to chloride) was obtained.

[0114] The obtained isopropanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. Thereafter, the temperature was cooled to 25°C, and the precipitated by-product salt was removed by filtration. The obtained filtrate was concentrated to 540 g, and 350 g of water was added, but no separation into two phases was observed. The obtained basic iminophosphazenium salt (R in the above formula (1)) 1 is a methyl group, R 2 is a methyl group, X -The basic iminophosphazenium salt content in composition K (iminophosphazenium salt corresponding to hydroxy anion) was 24 wt %, the water content was 39 wt %, the isopropanol content was 37 wt %, and the potassium ion concentration was 5000 ppm.

[0115] After storing this basic iminophosphazenium salt-containing composition K in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 0.1% and the pH decreased by 0.1, but the color became darker (evaluation: ×) compared to before storing at 50°C for 180 days, and storage stability at high temperatures could not be maintained. Furthermore, after storing basic iminophosphazenium salt-containing composition K in an environment at 0°C for 180 days, precipitates were confirmed (evaluation: ×), and storage stability at low temperatures could not be maintained.

[0116] Then, except for using 5.4 g of basic iminophosphazenium salt-containing composition K (basic iminophosphazenium salt content: 1.3 g) that had been left in an environment at 50°C for 180 days, the synthesis of polyalkylene glycol was investigated in the same manner as in Example 1. However, when the internal temperature was set to 80°C and the solvent and by-product water were removed under a reduced pressure of 0.2 kPa for 6 hours, the solvent and by-product water could not be sufficiently removed, so the catalyst did not exhibit activity and the ring-opening polymerization reaction did not proceed.

[0117] Comparative Example 4 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of isopropanol was added. After that, the temperature was raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R 2 is a methyl group, A - An isopropanol solution of iminophosphazenium salt (wherein the anion corresponds to chloride) was obtained.

[0118] The obtained isopropanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. The temperature was then cooled to 25°C, and the precipitated by-product salt was removed by filtration. The obtained filtrate was concentrated to 310 g, and 35 g of water was added. The mixture was allowed to stand until two phases separated, and the lower phase was removed to obtain the basic iminophosphazenium salt (R in the above formula (1) 1 is a methyl group, R 2 is a methyl group, X -A basic iminophosphazenium salt-containing composition L (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition L was 64 wt%, the water content was 9 wt%, the isopropanol content was 27 wt%, and the potassium ion concentration was 5 ppm.

[0119] After storing this basic iminophosphazenium salt-containing composition L under an environment of 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 20%, the pH decreased by 1.4, and storage stability at high temperatures was not maintained. Furthermore, there was no change in the appearance of basic iminophosphazenium salt-containing composition L under an environment of 0°C for 180 days.

[0120] Then, except for using 2.1 g of the basic iminophosphazenium salt-containing composition L (basic iminophosphazenium salt content before purity reduction: 1.3 g) that had been left in an environment at 50°C for 180 days, the synthesis of polyalkylene glycol was investigated in the same manner as in Example 1. As a result, the catalyst did not exhibit activity, and the ring-opening polymerization reaction did not proceed.

[0121] Comparative Example 5 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was concentrated to obtain a halogenated iminophosphazenium salt (R in the above formula (2) 1 is a methyl group, R 2 is a methyl group, A - An iminophosphazenium salt (R corresponds to chloride anion) was obtained as a white solid. 2.2 g of the obtained halogenated iminophosphazenium salt was dissolved in ion-exchanged water to prepare a 0.01 mol / L solution. This solution was passed through a column (diameter 30 mm, height 600 mm) packed with 100 ml of hydroxyl group-type anion exchange resin (Amberlite IRA4100H, manufactured by Organo Corporation) at room temperature at a flow rate of 200 ml / h, and 150 ml of ion-exchanged water was passed through at the same flow rate. The effluent was concentrated to obtain a basic iminophosphazenium salt. 0.9 g of water and 6 g of isopropanol were added to the obtained basic iminophosphazenium salt, and the basic iminophosphazenium salt (R in the above formula (1)) was obtained. 1 is a methyl group, R 2 is a methyl group, X - A basic iminophosphazenium salt-containing composition M (in which the hydroxy anion corresponds to the basic iminophosphazenium salt) was obtained. The basic iminophosphazenium salt content in the obtained basic iminophosphazenium salt-containing composition M was 23 wt%, the water content was 10 wt%, the isopropanol content was 67 wt%, and the potassium ion concentration was 0 ppm.

[0122] After storing this basic iminophosphazenium salt-containing composition M in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 1.1% and the pH decreased by 2.1, indicating that the composition could not maintain storage stability at high temperatures. Furthermore, there was no change in the appearance of the basic iminophosphazenium salt-containing composition M after storing it in an environment at 0°C for 180 days.

[0123] Then, except for using 5.7 g of the basic iminophosphazenium salt-containing composition M (basic iminophosphazenium salt content: 1.3 g) that had been left in an environment at 50°C for 180 days, the synthesis of polyalkylene glycol was investigated in the same manner as in Example 1. As a result, the catalyst did not exhibit activity, and the ring-opening polymerization reaction did not proceed.

[0124] Comparative Example 6 A 2-liter, four-necked flask equipped with a stirring blade was placed under a nitrogen atmosphere. 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added and stirred at 20°C. While continuing to stir, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours. The mixture was then heated to 100°C, and 107 g (0.92 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 1 hour. The resulting white slurry solution was stirred at 100°C for 14 hours, then cooled to 80°C. 250 ml of ion-exchanged water was added and stirred for 30 minutes. When stirring was stopped, all of the slurry dissolved, yielding a two-phase solution. The resulting two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the resulting aqueous phase, and oil-water separation was performed. The dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water. The obtained dichloromethane solution was transferred to a 2-liter four-neck flask equipped with a stirring blade, and 900 g of methanol (MeOH) was added. The temperature was then raised to 80 to 100°C under normal pressure, and the dichloromethane was removed to obtain a halogenated iminophosphazenium salt (R in the above formula (2)). 1 is a methyl group, R 2 is a methyl group, A -A methanol solution of iminophosphazenium salt (where the solubility parameter of methanol is 14.5 (cal / cm 3 ) 1 / 2 is.

[0125] The obtained methanol solution of the halogenated iminophosphazenium salt was allowed to cool to an internal temperature of 60°C while stirring, and then 31 g (0.47 mol, 1.1 mol per 1 mol of the halogenated iminophosphazenium salt) of 85 mass% potassium hydroxide was added and stirred at 60°C for 2 hours. Thereafter, the temperature was cooled to 25°C, and the precipitated by-product salt was removed by filtration. 95 g of water was added to the obtained filtrate, but no separation into two phases was observed. The obtained basic iminophosphazenium salt (R in the above formula (1)) 1 is a methyl group, R 2 is a methyl group, X - The basic iminophosphazenium salt content in composition N (iminophosphazenium salt in which the hydroxy anion is equivalent to hydroxy anion) was 23 wt %, the water content was 10 wt %, the methanol (MeOH) content was 67 wt %, and the potassium ion concentration was 15,000 ppm.

[0126] After storing this basic iminophosphazenium salt-containing composition N in an environment at 50°C for 180 days, the purity of the basic iminophosphazenium salt decreased by 0.1% and the pH decreased by 0.1, but the color became darker (evaluation: ×) compared to before storing at 50°C for 180 days, and storage stability at high temperatures could not be maintained. Furthermore, after storing basic iminophosphazenium salt-containing composition N in an environment at 0°C for 180 days, precipitation was observed (evaluation: ×), and storage stability at low temperatures could not be maintained.

[0127] Then, the same procedure as in Example 1 was carried out, except that 6.2 g of basic iminophosphazenium salt-containing composition N (basic iminophosphazenium salt content: 1.3 g) after being left in an environment at 50°C for 180 days was used, to obtain polyalkylene glycol (1100 g). The recovery rate of polyalkylene glycol was low at 90%, and the hydroxyl value was high at 27 mg KOH / g. Furthermore, the obtained polyalkylene glycol was colored, which had an adverse effect when used as a urethane raw material.

[0128] Furthermore, the same procedure as in Example 1 was carried out, except that 5.7 g of basic iminophosphazenium salt-containing composition N (basic iminophosphazenium salt content: 1.3 g) after being left in an environment at 0°C for 180 days was used, to obtain polyalkylene glycol (1000 g). The recovery rate of polyalkylene glycol was low at 82%, and the hydroxyl value was high at 29 mg KOH / g. Furthermore, because the obtained polyalkylene glycol contained a large amount of potassium residue, it was cloudy, making it difficult to control the reaction when used as a urethane raw material. [Industrial Applicability]

[0129] The basic iminophosphazenium salt-containing composition according to one embodiment of the present invention is useful as an organic base catalyst, such as a catalyst for producing polyalkylene glycols. The resulting polyalkylene glycols are useful as raw materials for polyurethanes, polyesters, surfactants, lubricants, etc. In particular, by reacting them with various isocyanate compounds, they are expected to be used in rigid foams used in insulation, flexible foams used in automotive seat cushions and bedding, adhesives, paints, sealants, thermosetting elastomers, and thermoplastic elastomers.

[0130] [Table 1]

[0131] [Table 2]

Claims

1. A basic iminophosphazenium salt-containing composition comprising the following (i) to (iv): (i) A basic iminophosphazenium salt represented by the following general formula (1): 20 to 50 wt % 【Chemical 1】 (In the above general formula (1), R １ and R ２ Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. １ and R ２ may be bonded to each other to form a ring structure, or R １ Comrades or R ２ They may be bonded to each other to form a ring structure. － represents a hydroxy anion, a hydrogen carbonate anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, or an alkylcarboxy anion having 2 to 5 carbon atoms. (ii) Water: 9-30wt% (iii) Solubility parameter is 10 to 13 (cal / cm ３ ) １／２ protic organic solvent: 20 to 71 wt % (iv) Alkali metal ions or alkaline earth metal ions: 10 to 1000 ppm

2. Solubility parameter is 10 to 13 (cal / cm ３ ) １／２ 2. The basic iminophosphazenium salt-containing composition according to claim 1, wherein the protic organic solvent represented by the formula (I) is a protic organic solvent selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol.

3. 3. The basic iminophosphazenium salt-containing composition according to claim 1, wherein the purity of the basic iminophosphazenium salt decreases by 3% or less after storage at 50°C for 180 days.

4. A method for producing the basic iminophosphazenium salt-containing composition according to any one of claims 1 to 3, comprising at least the following steps (1) to (4): Step (1): A halogenated iminophosphazenium salt represented by the following general formula (2) and a solubility parameter of 10 to 13 (cal / cm ３ ) １／２ preparing a solution containing a halogenated iminophosphazenium salt containing a protic organic solvent in which 【Chemistry 2】 (In the above general formula (2), R １ and R ２ represents R in the general formula (1). １ and R ２ It has the same definition as A － represents a chlorine anion or a bromine anion. Step (2): A step of adding an alkali metal compound or an alkaline earth metal compound to the solution obtained in Step (1) to ion-exchange the halogenated iminophosphazenium salt into a basic iminophosphazenium salt. Step (3): A step of filtering the reaction solution obtained in step (2) to remove the by-product alkali metal halide salt or alkaline earth metal halide salt. Step (4): A step of adding water to the filtrate obtained in step (3), and then removing the lower phase by a separation operation to obtain a composition containing a basic iminophosphazenium salt.

5. A method for producing a polyalkylene glycol, comprising contacting the basic iminophosphazenium salt-containing composition according to any one of claims 1 to 3 with an active hydrogen-containing compound, removing the solvent and by-product water, and then adding an alkylene oxide to carry out ring-opening polymerization of the alkylene oxide.

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