JP2011132179A - Aqueous solution of catalyst comprising iminophosphazenium salt, and method of producing polyalkylene glycol using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of storing/stabilizing an alkaline iminophosphazenium salt, an aqueous solution of a catalyst comprising an alkaline iminophosphazenium salt that can easily be handled and is excellent in storage stability, and a method of producing a polyalkylene glycol using the same. <P>SOLUTION: An alkaline iminophosphazenium salt represented by formula (1) is used in a form of an aqueous solution. In the formula, R<SB>1</SB>and R<SB>2</SB>each independently represent a hydrogen atom or a 1-20C hydrocarbon group, provided that R<SB>1</SB>and R<SB>2</SB>may bind to each other to form a ring, or R<SB>1</SB>themselves or R<SB>2</SB>themselves may bind to each other to form a ring; and X<SP>-</SP>represents a hydroxy anion, a 1-4C alkoxy anion, a 1-4C carboxy anion or the like. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a storage stabilization method for a basic iminophosphazenium salt, a basic iminophosphazenium salt-containing catalyst aqueous solution excellent in storage stability, a method for producing the same, and a method for producing a polyalkylene glycol using the same. Is.

  Basic iminophosphazenium salts are known as useful organic bases and include, for example, α, β- by alkylation of secondary amines, alkylation of phenylacetonitrile, condensation reactions of aldehydes with α-haloesters. Use as a catalyst for an epoxy ester production reaction (dadane reaction) has been proposed (see, for example, Patent Document 1).

  In Patent Document 1, this basic iminophosphazenium salt is produced by synthesizing a neutral iminophosphazenium salt and then ion-exchanged to the basic phosphazenium salt. As an ion exchange method, a neutral iminophosphazenium salt having tetrafluoroborate ion as a counter anion and potassium hydroxide are reacted in a mixed solvent of methanol and diethyl ether, and the resulting basic iminophos is obtained. A method of removing the solvent from the fazenium salt solution under reduced pressure is employed. Finally, the iminophosphazenium salt is obtained as a solid.

  However, the basic iminophosphazenium salt synthesized according to the method described in the same document is unstable and has a problem of decomposing with the passage of time if stored in a solid state.

  On the other hand, a basic phosphazenium salt is known to be an industrially useful compound in the same manner as the basic iminophosphazenium salt in terms of its nucleophilic properties and basicity (for example, Patent Document 2). reference).

  This basic phosphazenium salt can be produced by synthesizing a neutral phosphazenium salt and then ion-exchanged into a basic phosphazenium salt by treatment with an ion exchange resin or a basic compound (for example, Patent Document 3, 4). In the method described in Patent Document 3, a basic phosphazenium salt is isolated as a solid, and polymerization of propylene oxide is performed using the salt as a catalyst. In the method described in Patent Document 4, a phosphazenium salt composed of a hydroxy anion and an alkoxy anion is efficiently converted into a phosphazenium salt of a hydroxy anion by adding equimolar or more water to the filtrate of the reaction solution. Although the basic phosphazenium salt itself is still isolated as a solid.

  Further, it is known that this basic phosphazenium salt can be used as a catalyst for producing polyalkylene glycol (for example, see Patent Document 5). In the method described in Patent Document 5, the basic phosphazenium salt obtained as a solid is used as an aqueous solution in the reaction system, but there is no description referring to the storage stability of the basic phosphazenium salt.

  Thus, in these patent documents relating to basic phosphazenium salts, there is no problem with respect to the storage stability of the isolated basic phosphazenium salts, and no investigation is made on it.

German Patent Application Publication No. 102006010034 Japanese Patent No. 3497004 JP 2001-31689 A JP 2001-89487 A JP 2000-38443 A

  The present invention has been made in view of the above-described background art, and its purpose is to provide a storage stabilization method for a basic iminophosphazenium salt, a basic iminophosphatase that is easy to handle and excellent in storage stability. It is an object to provide a catalyst aqueous solution containing a zenium salt and a method for producing a polyalkylene glycol using the same.

  As a result of intensive studies to solve the above problems, the inventors of the present invention can stably store the basic iminophosphazenium salt for a long period of time by using the aqueous solution, and the basic iminophosphazenium salt-containing aqueous solution. Has been found to be particularly suitable for use as a catalyst for producing a polyalkylene glycol, and the present invention has been completed.

  That is, the present invention is a storage and stabilization method for a basic iminophosphazenium salt, a basic iminophosphazenium salt-containing catalyst aqueous solution, and a method for producing a polyalkylene glycol using the same as described below.

  [1] The following general formula (1)

［上記一般式（１）中、Ｒ_１及びＲ_２は、各々独立して、水素原子又は炭素数１〜２０の炭化水素基を表す。なお、Ｒ_１とＲ_２が互いに結合して環構造を形成していても良いし、Ｒ_１同士又はＲ_２同士が互いに結合して環構造を形成していても良い。Ｘ⁻は、ヒドロキシアニオン、炭素数１〜４のアルコキシアニオン、カルボキシアニオン、炭素数２〜５のアルキルカルボキシアニオン、又は炭酸水素アニオンを表す。］
で示される塩基性イミノホスファゼニウム塩を水溶液とすることを特徴とする塩基性イミノホスファゼニウム塩の保存安定化方法。

[In General Formula (1), R ₁ and R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Incidentally, the R ₁ and R ₂ may be bonded to form a ring structure, R ₁ s or R ₂ together may form a ring structure together. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. ]
A method for preserving and stabilizing a basic iminophosphazenium salt, characterized in that an aqueous solution of the basic iminophosphazenium salt represented by formula (1) is used.

  [2] The following general formula (3)

［上記一般式（３）中、Ｒ_１及びＲ_２は、上記一般式（１）中のＲ_１及びＲ_２と同じ定義である。］
で示されるイミノホスファゼニウム塩を、塩基性化合物又はイオン交換樹脂を用いてイオン交換し、得られた上記一般式（１）で示される塩基性イミノホスファゼニウム塩の有機溶媒溶液を、有機溶媒から水へ溶媒置換することを特徴とする上記［１］に記載の塩基性イミノホスファゼニウム塩の保存安定化方法。

[In the general formula (3), R ₁ and R ₂ have the same definitions as R ₁ and R ₂ in the general formula (1). ]
Is ion-exchanged using a basic compound or an ion exchange resin, and an organic solvent solution of the basic iminophosphazenium salt represented by the above general formula (1) is obtained. The method for preservation and stabilization of a basic iminophosphazenium salt according to the above [1], wherein the solvent is substituted from an organic solvent to water.

  [3] The following general formula (1)

［上記一般式（１）中、Ｒ_１及びＲ_２は、各々独立して、水素原子又は炭素数１〜２０の炭化水素基を表す。なお、Ｒ_１とＲ_２が互いに結合して環構造を形成していても良いし、Ｒ_１同士又はＲ_２同士が互いに結合して環構造を形成していても良い。Ｘ⁻は、ヒドロキシアニオン、炭素数１〜４のアルコキシアニオン、カルボキシアニオン、炭素数２〜５のアルキルカルボキシアニオン、又は炭酸水素アニオンを表す。］
で示される塩基性イミノホスファゼニウム塩を含有することを特徴とする触媒水溶液。

[In General Formula (1), R ₁ and R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Incidentally, the R ₁ and R ₂ may be bonded to form a ring structure, R ₁ s or R ₂ together may form a ring structure together. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. ]
A catalytic aqueous solution comprising a basic iminophosphazenium salt represented by the formula:

  [4] The following general formula (3)

［上記一般式（３）中、Ｒ_１及びＲ_２は、上記一般式（１）中のＲ_１及びＲ_２と同じ定義である。］
で示されるイミノホスファゼニウム塩を、塩基性化合物又はイオン交換樹脂を用いてイオン交換し、得られた上記一般式（１）で示される塩基性イミノホスファゼニウム塩の有機溶媒溶液を、有機溶媒から水へ溶媒置換することを特徴とする上記［３］に記載の触媒水溶液の製造方法。

[In the general formula (3), R ₁ and R ₂ have the same definitions as R ₁ and R ₂ in the general formula (1). ]
Is ion-exchanged using a basic compound or an ion exchange resin, and an organic solvent solution of the basic iminophosphazenium salt represented by the above general formula (1) is obtained. The method for producing an aqueous catalyst solution according to the above [3], wherein the solvent is replaced from an organic solvent to water.

  [5] A polyalkylene obtained by adding the catalyst aqueous solution according to the above [3] to an active hydrogen-containing compound, performing dehydration under reduced pressure, and then adding alkylene oxide to perform ring-opening polymerization reaction of alkylene oxide. A method for producing glycol.

  [6] The production method according to the above [5], wherein the ring-opening polymerization reaction of the alkylene oxide is carried out at a reaction pressure of 0.05 to 1.0 MPa and a reaction temperature of 40 to 130 ° C.

  According to the present invention, a basic iminophosphazenium salt can be stably stored for a long period of time. Further, since the aqueous catalyst solution can be used as it is as a catalyst for producing polyalkylene glycol, the operation for producing polyalkylene glycol is simplified.

^{1 is} a ¹ H-NMR spectrum of a basic iminophosphazenium salt-containing aqueous solution (B). ^{1 is} a ¹ H-NMR spectrum of a basic iminophosphazenium salt (G).

  The present invention is described in detail below.

  First, a storage and stabilization method for the basic iminophosphazenium salt represented by the general formula (1) and a catalyst comprising an aqueous solution of the basic iminophosphazenium salt will be described.

In the present invention, R ₁ and R ₂ of the iminophosphazenium salt represented by the general formula (1) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In the general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Incidentally, the R ₁ and R ₂ may be bonded to form a ring structure, R ₁ s or R ₂ together may form a ring structure together.

  Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, and t-butyl group. , Cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, decyl group, Examples thereof include 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.

Examples of the case where R ₁ and R ₂ are bonded to each other to form a ring structure include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, and an isoindolyl group.

In addition, when R ₁ or R ₂ are bonded to each other to form a ring structure, for example, one substituent is an alkylene group such as an ethylene group, a propylene group, or a butylene group, and the other Examples include a case where a substituent is bonded to each other to form a ring structure.

Among these hydrocarbon groups, as R ₁ and R ₂ , a methyl group, an ethyl group, and an isopropyl group are preferable because guanidines as raw materials are easily available.

In the present invention, X ⁻ of the iminophosphazenium salt represented by the general formula (1) is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or Represents a bicarbonate anion.

  Here, as a C1-C4 alkoxy anion, a methoxy anion, an ethoxy anion, n-propoxy anion, an isopropoxy anion, n-butoxy anion, isobutoxy anion, t-butoxy anion etc. are mentioned, for example.

  Examples of the alkylcarboxy 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. Can be mentioned.

Among these, a hydroxy anion is preferable as X ⁻ from the viewpoint that the iminophosphazenium salt represented by the general formula (1) has a strong basicity.

  In the present invention, the basic iminophosphazenium salt represented by the general formula (1) may be produced by any method. For example, phosphorus pentachloride and the following general formula (2)

［上記一般式（２）中、Ｒ_１及びＲ_２は、上記一般式（１）中のＲ_１及びＲ_２と同じ定義である。］
で示されるグアニジン類を反応させ、下記一般式（３）

[In the general formula (2), R ₁ and R ₂ have the same definitions as R ₁ and R ₂ in the general formula (1). ]
Is reacted with a guanidine represented by the following general formula (3):

［上記一般式（３）中、Ｒ_１及びＲ_２は、上記一般式（１）中のＲ_１及びＲ_２と同じ定義である。］
で示されるイミノホスファゼニウム塩を合成し、これを、塩基性化合物又はイオン交換樹脂を用いてイオン交換する方法により合成することができる。

[In the general formula (3), R ₁ and R ₂ have the same definitions as R ₁ and R ₂ in the general formula (1). ]
Can be synthesized by a method of ion exchange using a basic compound or an ion exchange resin.

  As a method for ion-exchange of an iminophosphazenium salt represented by the above general formula (3) to an iminophosphazenium salt represented by the above general formula (1) using a basic compound, for example, the above general formula Examples include a method in which the iminophosphazenium salt represented by (3) is treated with a basic compound in an organic solvent and ion-exchanged to the iminophosphazenium salt represented by the general formula (1).

  Here, examples of the basic compound include alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal alkoxides, carboxylic acid alkali metal salts or alkaline earth metal salts, alkali metals or alkalis. Examples include earth metal hydrogencarbonate.

  Specific examples of the alkali metal or alkaline earth metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide; magnesium hydroxide, calcium hydroxide, strontium hydroxide. And barium hydroxide.

  Examples of the alkali metal or alkaline earth metal alkoxide include, for example, alkali metal or alkaline earth metal methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, t-butoxide, and the like. be able to.

  Examples of the alkali metal salt or alkaline earth metal salt of carboxylic acid include, for example, alkali metal or alkaline earth metal formate (carboxyde), acetate (methylcarboxylate), propionate (ethylcarboxylate). , Butyrate (n-propylcarboxyl), isobutyrate (isopropylcarboxyl), valerate (n-butylcarboxyl), isovalerate (isobutylcarboxyl), pivalate (t-butylcarboxyl) And the like.

  Among these, from the viewpoint of easy availability and strong basicity, the basic compound is preferably an alkali metal or alkaline earth metal hydroxide, particularly preferably sodium hydroxide or potassium hydroxide.

  Moreover, as an organic solvent at the time of ion-exchange using a basic compound, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, neopentanol, Examples of the alcohol include n-hexanol, n-heptanol, n-octanol, n-nonanol, and n-decanol. Among these, ethanol, n-propanol, isopropanol, and t-butanol are preferable because the reaction rate of the target ion exchange reaction is high and the solvent substitution into an aqueous solution is easy.

  The aqueous catalyst solution of the present invention can be obtained by replacing the organic solvent solution of the iminophosphazenium salt represented by the above general formula (1) thus obtained from an organic solvent with water.

In addition, as a method of ion-exchanging the iminophosphazenium salt represented by the general formula (3) to the iminophosphazenium salt represented by the general formula (1) using an ion exchange resin, for example, The iminophosphazenium salt represented by the general formula (3) is dissolved in water or a mixed solvent of water and an organic solvent compatible with water, and then treated with a hydroxyl group-type anion exchange resin. The method of ion-exchange to the iminophosphazenium salt whose X < ^- > is a hydroxy group in Formula (1) is mentioned.

  When the iminophosphazenium salt represented by the general formula (1) thus obtained is an organic solvent solution, it is replaced with an aqueous solution, and when it is an aqueous solution, it is concentrated or diluted to a predetermined concentration. Thus, the aqueous catalyst solution of the present invention can be obtained.

  In the present invention, the method for replacing the organic solvent solution of the iminophosphazenium salt represented by the above general formula (1) with an aqueous solution is not particularly limited. For example, the entire amount of the organic solvent is removed under reduced pressure. After that, water can be added to make an aqueous solution. Moreover, after adding water before removing an organic solvent, an organic solvent can also be removed and it can also be set as aqueous solution.

  Of the two methods described above, a method using a basic compound is more preferable because it is inexpensive and easily available and the amount of solvent used during ion exchange is small.

  The purity of the iminophosphazenium salt represented by the general formula (1) in the catalyst aqueous solution of the present invention is usually 85% by weight or more, preferably 90% by weight or more, particularly preferably 95% by weight or more. is there. If the purity is less than 85% by weight, the basicity of the iminophosphazenium salt is lowered, and the catalytic activity when used as a base catalyst may be lowered.

  The concentration of the iminophosphazenium salt represented by the general formula (1) in the catalyst aqueous solution of the present invention is usually 1 to 99% by weight, preferably 20 to 80% by weight, based on the whole catalyst aqueous solution. is there. When the concentration of the iminophosphazenium salt represented by the general formula (1) is less than 1% by weight, the dehydration operation when used as a base catalyst may take a long time. On the other hand, when the concentration of the iminophosphazenium salt represented by the general formula (1) exceeds 99% by weight, the viscosity increases and transfer becomes difficult, and the general formula (1) indicates There is a possibility that the decomposition reaction of the iminophosphazenium salt proceeds and the purity is lowered.

  The aqueous catalyst solution of the present invention can be used as a base catalyst for various organic reactions and polymer reactions (see, for example, Patent Document 1). For example, the organic reaction can be used for epoxide ring-opening reaction, halogenated aromatic compound halogen substitution reaction, alkoxylation reaction, and the like. The polymer reaction can be used for alkylene oxide ring-opening polymerization reaction, lactam ring-opening polymerization reaction, methyl methacrylate polymerization reaction, and the like.

  In addition, since the aqueous catalyst solution of the present invention can suppress the decomposition of the iminophosphazenium salt and can maintain high catalytic activity even after long-term storage, there is no particular limitation on the period until preparation and use for the above reaction. Absent. For example, a product immediately after preparation may be used, or a product after 100 days or more may be used.

  Next, the manufacturing method of the polyalkylene glycol using the catalyst aqueous solution of this invention is demonstrated.

  The method for producing the polyalkylene glycol of the present invention comprises adding the aqueous catalyst solution of the present invention to an active hydrogen-containing compound, subjecting it to dehydration under reduced pressure, and then adding alkylene oxide to perform a ring-opening polymerization reaction of the alkylene oxide. Features.

  In the present invention, the active hydrogen-containing compound is not particularly limited as long as it is a compound having an active hydrogen group in the molecule. For example, hydroxy compounds, amine compounds, carboxylic acid compounds, phenol compounds, thiol compounds Etc.

  More specifically, as the active hydrogen-containing compound, water, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, Hydroxy compounds such as glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose; amine compounds such as ethylenediamine, N, N′-dimethylethylenediamine, piperidine, piperazine; benzoic acid, adipic acid, etc. Carboxylic acid compounds of the above; phenol compounds such as 2-naphthol and bisphenol; thiol compounds such as ethanedithiol and butanedithiol. These can be appropriately selected according to the application.

  Moreover, it is also possible to use the polyether polyol which has a hydroxyl group as an active hydrogen containing compound, For example, polypropylene glycol, polypropylene glycol glycerol ether, etc. can be mentioned. Although there is no restriction | limiting in particular in the molecular weight of the polyether polyol used in this case, Since it is low viscosity and excellent in fluidity | liquidity, the polyether polyol of molecular weight 200-3000 is preferable.

  These active hydrogen-containing compounds may be used alone or in combination of several kinds.

In the method for producing a polyalkylene glycol of the present invention, the amount of the catalyst aqueous solution of the present invention used is usually the amount of the iminophosphazenium salt represented by the above general formula (1) with respect to 1 mol of the active hydrogen-containing compound. The range is 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, preferably 5 × 10 ^{−3 to} 5 × 10 ⁻² mol. If it is less than 1 × 10 ⁻⁴ mol, the catalytic activity becomes insufficient, and it may take a long time for the polymerization reaction. On the other hand, when it exceeds 1 × 10 ⁻¹ mol, the polymerization heat generated by the reaction increases, and it may be difficult to control the temperature in the reaction system.

  In the method for producing polyalkylene glycol of the present invention, the method for the dehydration treatment under reduced pressure is not particularly limited, but a known method using a water flow pump, a vacuum pump, a roots type exhaust blower or the like can be applied.

  In the method for producing a polyalkylene glycol of the present invention, the degree of reduced pressure during the dehydration treatment is not particularly limited, but is usually 50 kPa or less, preferably 10 kPa or less, and more preferably 5 kPa or less. If the degree of vacuum is higher than 50 kPa, the dehydration process may take a long time.

  In the method for producing the polyalkylene glycol of the present invention, the temperature at which the dehydration treatment is performed is not particularly limited, but is usually in the range of 30 to 130 ° C, preferably 40 to 100 ° C. If it is less than 30 degreeC, there exists a possibility that dehydration may require a long time. On the other hand, when it exceeds 130 ° C., the decomposition reaction of the iminophosphazenium salt represented by the general formula (1) proceeds, and there is a possibility that the purity thereof is lowered.

  In the method for producing a polyalkylene glycol of the present invention, the time for the vacuum dehydration treatment is not particularly limited, but is usually 10 minutes or longer, preferably 30 minutes or longer. If it is shorter than 10 minutes, dehydration becomes insufficient, which may adversely affect the polymerization reaction.

  In the method for producing a polyalkylene glycol of the present invention, the alkylene oxide used in the ring-opening polymerization reaction is not particularly limited, and examples thereof include alkylene oxides having 2 to 20 carbon atoms. Specific examples of the alkylene oxide having 2 to 20 carbon atoms include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, butadiene monooxide, pentene oxide, styrene oxide, and cyclohexene oxide. Can be mentioned. Of these, ethylene oxide and propylene oxide, which are easily available and have high industrial value, are preferable.

  In the method for producing a polyalkylene glycol of the present invention, alkylene oxides may be used alone or in combination of two or more. When two or more types are used in combination, for example, the first alkylene oxide may be reacted and then the second alkylene oxide may be reacted, or two or more alkylene oxides may be reacted simultaneously. . Moreover, the alkylene oxide to be used may be added all at once or sequentially.

  In the method for producing a polyalkylene glycol of the present invention, the pressure during the ring-opening polymerization reaction is not particularly limited, but is usually in the range of 0.05 to 1.0 MPa, preferably 0.1 to 0.6 MPa. It is. If it is less than 0.05 MPa, the catalytic activity is lowered, and there is a possibility that a long time is required for the polymerization reaction. On the other hand, when it exceeds 1.0 MPa, there is a possibility that a side reaction proceeds during the polymerization reaction.

  In the method for producing a polyalkylene glycol of the present invention, the temperature for carrying out the ring-opening polymerization reaction is usually 40 to 130 ° C, preferably 60 to 130 ° C. If it is less than 40 degreeC, there exists a possibility that catalyst activity may fall and a polymerization reaction may require a long time. On the other hand, when it exceeds 130 ° C., the decomposition reaction of the produced polyalkylene glycol may proceed.

  Polyalkylene glycols having different hydroxyl groups can be produced by the method for producing polyalkylene glycols of the present invention. Although there is no restriction | limiting in particular in the hydroxyl value of polyalkylene glycol, Preferably it is 5-500 mgKOH / g, More preferably, it is the range of 10-170 mgKOH / g.

  The polyalkylene glycol obtained by the method for producing polyalkylene glycol of the present invention is useful for polyurethane raw materials, polyester raw materials, surfactant raw materials, lubricant raw materials and the like. In particular, by reacting with various isocyanate compounds, rigid foam used for heat insulating materials, etc., flexible foam used for automobile seats / cushions, bedding, etc., adhesives, paints, sealing materials, thermosetting elastomers, heat Development to plastic elastomer is expected.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example does not restrict | limit this invention at all. First, an analysis method for an aqueous catalyst solution and polyalkylene glycol obtained by the present invention will be described.

(1) Purity of basic iminophosphazenium salt (unit:%).
Using a nuclear magnetic resonance (NMR) spectrum measuring apparatus (manufactured by JEOL Ltd., product name: GSX270WB), ¹ H-NMR was measured using heavy water as a heavy solvent. The purity of the basic iminophosphazenium salt was calculated from the ratio of the peak area of 2.85 ppm to the peak area in the range of 2.60 to 3.10 ppm.

(2) Concentration of aqueous solution containing basic iminophosphazenium salt (unit:% by weight).
Using a trace total nitrogen analyzer (product name: TN-100, manufactured by Mitsubishi Chemical Corporation) under the conditions of heater temperature T1: 600 ° C, T2: 800 ° C, gas flow rate O2: 500 ml / min, O3: 200 ml / min, The nitrogen concentration of the basic iminophosphazenium salt-containing aqueous solution was measured. From this nitrogen concentration, the concentration of the basic iminophosphazenium salt in the aqueous solution was calculated.

(3) Hydroxyl value of polyalkylene glycol (unit: mgKOH / g)
According to the method described in JIS K-1557, the hydroxyl value of polyalkylene glycol was calculated.

Synthesis Example 1 Synthesis of chloride body of iminophosphazenium salt.
A 200 ml four-necked flask equipped with a stirring blade was put in a nitrogen atmosphere, 2.3 g (11 mmol) of phosphorus pentachloride and 23 ml of toluene were added, and the mixture was stirred at -20 ° C. While maintaining the inside of the flask at −20 ° C., 13 g (110 mmol) of tetramethylguanidine was added dropwise, and stirring was continued at −20 ° C. for 1 hour. Furthermore, it heated up at 110 degreeC and stirred for 15 hours. The resulting white suspension was filtered to obtain a white solid as a filtrate. This white solid was dissolved in acetone and filtered to obtain a colorless transparent filtrate. The obtained filtrate was concentrated to obtain a crude product of the target iminophosphazenium chloride as a white solid. The obtained crude product was subjected to liquid separation extraction with chloroform and water. The chloroform phase was concentrated to obtain 5.1 g (9.7 mmol; yield 88%) of the target iminophosphazenium chloride as a white solid.

Example 1 Stability evaluation of aqueous solution (A) containing basic iminophosphazenium salt.
To a 300 ml Schlenk flask equipped with a magnetic rotator, 21 g (40 mmol) of iminophosphazenium chloride was added, and the atmosphere in the flask was changed to a nitrogen atmosphere. Potassium hydroxide 2.2g (40mmol) and ethanol 80ml were added there, and it stirred at room temperature for 1 hour. The suspension containing the white solid obtained after completion of the reaction was filtered under reduced pressure using a funnel with filter paper. An ethanol solution of the desired basic iminophosphazenium salt was obtained on the filtrate side, and potassium chloride as a by-product salt was obtained on the filtrate side. To the obtained ethanol solution of the basic iminophosphazenium salt, 80 ml of ion-exchanged water was added, the solvent was removed under reduced pressure, and the mixture was concentrated to 40 ml. Further, 80 ml of ion exchange water was added, the solvent was removed under reduced pressure, and the mixture was concentrated to 40 ml. Let the obtained aqueous solution be basic iminophosphazenium salt containing aqueous solution (A). As a result of analyzing the basic iminophosphazenium salt-containing aqueous solution (A), the purity was 99.6% and the aqueous solution concentration was 50% by weight.

Example 2 Stability evaluation of aqueous solution (B) containing basic iminophosphazenium salt.
A basic iminophosphazenium salt-containing aqueous solution was prepared in the same manner as in Example 1. This aqueous solution 10 days after synthesis is designated as a basic iminophosphazenium salt-containing aqueous solution (B). As a result of analyzing the basic iminophosphazenium salt-containing aqueous solution (B), the purity was 99.2% and the aqueous solution concentration was 50% by weight. The ¹ H-NMR spectrum of this basic iminophosphazenium salt-containing aqueous solution (B) is shown in FIG.

Example 3 Stability evaluation of aqueous solution (C) containing basic iminophosphazenium salt.
A basic iminophosphazenium salt-containing aqueous solution was prepared in the same manner as in Example 1. This aqueous solution 100 days after synthesis is designated as a basic iminophosphazenium salt-containing aqueous solution (C). As a result of analyzing the basic iminophosphazenium salt-containing aqueous solution (C), the purity was 98.4% and the aqueous solution concentration was 50% by weight.

Example 4 Stability evaluation of aqueous solution (D) containing basic iminophosphazenium salt.
In Example 1, a basic iminophosphazenium salt-containing aqueous solution was synthesized in the same manner except that the amount of the finally obtained aqueous solution was changed from 40 ml to 100 ml. This aqueous solution 10 days after the synthesis is designated as a basic iminophosphazenium salt-containing aqueous solution (D). As a result of analyzing the basic iminophosphazenium salt-containing aqueous solution (D), the purity was 99.4% and the aqueous solution concentration was 20% by weight.

Example 5 Stability evaluation of aqueous solution (E) containing basic iminophosphazenium salt.
In Example 1, a basic iminophosphazenium salt-containing aqueous solution was synthesized by the same method except that the amount of the aqueous solution finally obtained was changed from 40 ml to 25 ml. This aqueous solution 10 days after synthesis is designated as a basic iminophosphazenium salt-containing aqueous solution (E). As a result of analyzing the basic iminophosphazenium salt-containing aqueous solution (E), the purity was 98.8% and the aqueous solution concentration was 80% by weight.

Reference Example 1 Stability evaluation of basic iminophosphazenium salt (F).
To a 300 ml Schlenk flask equipped with a magnetic rotator, 21 g (40 mmol) of iminophosphazenium chloride was added, and the atmosphere in the flask was changed to a nitrogen atmosphere. Potassium hydroxide 2.2g (40mmol) and ethanol 80ml were added there, and it stirred at room temperature for 1 hour. The suspension containing the white solid obtained after completion of the reaction was filtered under reduced pressure using a funnel with filter paper. An ethanol solution of the desired basic iminophosphazenium salt was obtained on the filtrate side, and potassium chloride as a by-product salt was obtained as a filtrate. The solvent removal of the ethanol solution of the obtained basic iminophosphazenium salt was performed under reduced pressure. Let the obtained basic iminophosphazenium salt be a basic iminophosphazenium salt (F). As a result of analyzing this basic iminophosphazenium salt (F), the purity was 99.5%.

Comparative Example 1 Stability evaluation of basic iminophosphazenium salt (G).
A basic iminophosphazenium salt was synthesized in the same manner as in Reference Example 1. This basic iminophosphazenium salt one day after the synthesis is defined as a basic iminophosphazenium salt (G). As a result of analyzing this basic iminophosphazenium salt (G), the purity was 11.6%. The ¹ H-NMR spectrum of this basic iminophosphazenium salt (G) is shown in FIG.

  The results of Examples 1 to 5, Reference Example 1 and Comparative Example 1 are also shown in Table 1.

実施例６．
攪拌翼を付した２．０Ｌのオートクレーブに、実施例１で調製した塩基性イミノホスファゼニウム塩含有水溶液（Ａ）４．０ｇ（４．０ｍｍｏｌ）と３官能のポリアルキレングリコール（三洋化成工業社製、製品名：サンニックスＧＰ−１０００、水酸基価１６０ｍｇＫＯＨ／ｇ）１７５ｇ（１７５ｍｍｏｌ）を加え、オートクレーブ内を窒素雰囲気とした。内温を８０℃とし、０．２ｋＰａの減圧下で脱水処理を行った後、内温を９０℃とし、プロピレンオキシド８８０ｇを反応圧力０．３ＭＰａ以下を保つように間欠的に供給しながら、内温８８〜９１℃の範囲で８時間反応させた。次いで、０．２ｋＰａの減圧下で残留プロピレンオキシドの除去を行った後、エチレンオキシド２１０ｇを反応圧力０．４ＭＰａ以下を保つように間欠的に供給しながら、内温８８〜９１℃の範囲で６時間反応させた。０．２ｋＰａの減圧下で残留エチレンオキシドの除去を行い、無色無臭のポリアルキレングリコール１１９０ｇを得た。得られたポリアルキレングリコールの水酸基価は２３．９ｍｇＫＯＨ／ｇであった。

Example 6
To a 2.0 L autoclave equipped with a stirring blade, 4.0 g (4.0 mmol) of the basic iminophosphazenium salt-containing aqueous solution (A) prepared in Example 1 and trifunctional polyalkylene glycol (Sanyo Chemical Industries) 175 g (175 mmol) of product made by company, product name: Sanniks GP-1000, hydroxyl value 160 mgKOH / g) was added, and the inside of the autoclave was made into nitrogen atmosphere. The internal temperature was set to 80 ° C., and dehydration was performed under a reduced pressure of 0.2 kPa, then the internal temperature was set to 90 ° C., and 880 g of propylene oxide was intermittently supplied so as to keep the reaction pressure at 0.3 MPa or less The reaction was carried out at a temperature in the range of 88 to 91 ° C. for 8 hours. Next, after removing residual propylene oxide under a reduced pressure of 0.2 kPa, while supplying 210 g of ethylene oxide intermittently so as to maintain a reaction pressure of 0.4 MPa or less, the internal temperature ranges from 88 to 91 ° C. for 6 hours. Reacted. Residual ethylene oxide was removed under reduced pressure of 0.2 kPa to obtain 1190 g of colorless and odorless polyalkylene glycol. The obtained polyalkylene glycol had a hydroxyl value of 23.9 mgKOH / g.

Example 7
The same method as in Example 6 was used except that the basic iminophosphazenium salt-containing aqueous solution (B) prepared in Example 2 was used instead of the basic iminophosphazenium salt-containing aqueous solution (A). Thus, polyalkylene glycol was synthesized. As a result, 1230 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 23.4 mgKOH / g.

Example 8 FIG.
In the same manner as in Example 6, except that the basic iminophosphazenium salt-containing aqueous solution (C) prepared in Example 3 was used instead of the basic iminophosphazenium salt-containing aqueous solution (A). Thus, polyalkylene glycol was synthesized. As a result, 1240 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 23.1 mgKOH / g.

Example 9
The same method as in Example 6 was used except that the basic iminophosphazenium salt-containing aqueous solution (D) prepared in Example 4 was used instead of the basic iminophosphazenium salt-containing aqueous solution (A). Thus, polyalkylene glycol was synthesized. As a result, 1220 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 23.5 mgKOH / g.

Example 10
The same method as in Example 6 was used, except that the basic iminophosphazenium salt-containing aqueous solution (E) prepared in Example 5 was used instead of the basic iminophosphazenium salt-containing aqueous solution (A). Thus, polyalkylene glycol was synthesized. As a result, 1200 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 23.6 mgKOH / g.

Reference Example 2
To a 2.0 L autoclave with a stirring blade, 2.0 g (4.0 mmol) of the basic iminophosphazenium salt (F) synthesized in Reference Example 1 and a trifunctional polyalkylene glycol (manufactured by Sanyo Chemical Industries) , Product name: Sanniks GP-1000, hydroxyl value 160 mgKOH / g) 175 g (175 mmol) was added, and the inside of the autoclave was made a nitrogen atmosphere. The internal temperature was set to 80 ° C., and dehydration was performed under a reduced pressure of 0.2 kPa, then the internal temperature was set to 90 ° C., and 880 g of propylene oxide was intermittently supplied so as to keep the reaction pressure at 0.3 MPa or less The reaction was carried out at a temperature in the range of 88 to 91 ° C. for 8 hours. Next, after removing residual propylene oxide under a reduced pressure of 0.2 kPa, while supplying 210 g of ethylene oxide intermittently so as to maintain a reaction pressure of 0.4 MPa or less, the internal temperature ranges from 88 to 91 ° C. for 6 hours. Reacted. Residual ethylene oxide was removed under a reduced pressure of 0.2 kPa to obtain 1200 g of colorless and odorless polyalkylene glycol. The obtained polyalkylene glycol had a hydroxyl value of 23.8 mgKOH / g.

Comparative Example 2
In the same manner as in Reference Example 2, except that the basic iminophosphazenium salt-containing aqueous solution (F) prepared in Comparative Example 1 was used instead of the basic iminophosphazenium salt-containing aqueous solution (F), Polyalkylene glycol was synthesized. As a result, 180 g of brown polyalkylene glycol having an amine odor was obtained. The obtained polyalkylene glycol has a hydroxyl value of 150 mgKOH / g, and a trifunctional polyalkylene glycol used as an initiator (manufactured by Sanyo Chemical Industries, product name: Sannix GP-1000, hydroxyl value 160 mgKOH / g) Since they almost coincide, it can be said that the target polymerization reaction has not progressed.

  The results of Examples 5 to 10 and Reference Example 2 are also shown in Table 2.

Claims (6)

The following general formula (1)

[In General Formula (1), R ₁ and R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Incidentally, the R ₁ and R ₂ may be bonded to form a ring structure, R ₁ s or R ₂ together may form a ring structure together. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. ]
A method for preserving and stabilizing a basic iminophosphazenium salt, characterized in that an aqueous solution of the basic iminophosphazenium salt represented by formula (1) is used. The following general formula (3)

[In the general formula (3), R ₁ and R ₂ have the same definitions as R ₁ and R ₂ in the general formula (1). ]
Is ion-exchanged using a basic compound or an ion exchange resin, and an organic solvent solution of the basic iminophosphazenium salt represented by the above general formula (1) is obtained. The method for stabilizing and storing a basic iminophosphazenium salt according to claim 1, wherein the solvent is substituted from an organic solvent to water. The following general formula (1)

[In General Formula (1), R ₁ and R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Incidentally, the R ₁ and R ₂ may be bonded to form a ring structure, R ₁ s or R ₂ together may form a ring structure together. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. ]
A catalytic aqueous solution comprising a basic iminophosphazenium salt represented by the formula: The following general formula (3)

[In the general formula (3), R ₁ and R ₂ have the same definitions as R ₁ and R ₂ in the general formula (1). ]
Is ion-exchanged using a basic compound or an ion exchange resin, and an organic solvent solution of the basic iminophosphazenium salt represented by the above general formula (1) is obtained. The method for producing an aqueous catalyst solution according to claim 3, wherein the solvent is replaced from an organic solvent to water. A method for producing a polyalkylene glycol, comprising: adding the catalyst aqueous solution according to claim 3 to an active hydrogen-containing compound; performing dehydration under reduced pressure; and then adding an alkylene oxide to perform a ring-opening polymerization reaction of the alkylene oxide. . 6. The production method according to claim 5, wherein the ring-opening polymerization reaction of the alkylene oxide is carried out at a reaction pressure of 0.05 to 1.0 MPa and a reaction temperature of 40 to 130 ° C.

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