JP5609354B2 - Catalyst solution for producing polyalkylene glycol and method for producing polyalkylene glycol using the same - Google Patents

Description

  The present invention relates to a catalyst solution for producing a polyalkylene glycol comprising a basic iminophosphazenium salt solution useful as an organic base and capable of stably storing a basic iminophosphazenium salt for a long period of time, and the polyalkylene thereof The present invention relates to a method for producing a polyalkylene glycol using a catalyst solution for glycol production.

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

  This basic iminophosphazenium salt is obtained by reacting a neutral iminophosphazenium salt having tetrafluoroborate ion as a counter anion with potassium hydroxide in a mixed solvent of methanol and diethyl ether. The basic iminophosphazenium salt solution can be produced by removing the solvent under reduced pressure, and finally the basic iminophosphazenium salt is obtained as a solid.

  On the other hand, a basic phosphazenium salt is a compound that is expected to be industrially useful in the same manner as the basic iminophosphazenium salt in terms of its nucleophilic properties and basicity. For example, a catalyst for producing a polyalkylene glycol (See, for example, Patent Document 2). The basic phosphazenium salt can be isolated as a solid by treating the neutral phosphazenium salt with an ion exchange resin or a basic compound and then removing the solvent (see, for example, Patent Documents 3 and 4). ).

  It has been proposed that the isolated phosphazenium salt be used in the production of polyalkylene glycol in the solid state or as an aqueous solution (see, for example, Patent Document 5).

German Patent Application Publication No. 102006010034 (Claims) Japanese Patent No. 3497004 (Claims) JP 2001-031689 A (Claims) JP 2001-089487 A (Claims) JP 2000-038443 A (Claims)

  However, the basic iminophosphazenium salt obtained by the method proposed in Patent Document 1 is unstable, and if stored in a solid state, the decomposition proceeds with the passage of time. It was difficult to keep it, and it had a problem as an industrial catalyst for polyalkylene glycol. In addition, in any of Patent Documents 2 to 4, there is no description referring to the storage stability of the basic phosphazenium salt as well as the basic iminophosphazenium salt.

  And in an industrial process, since importance is attached to efficiency, the preparation of a raw material is common sense, and what is inferior in storage stability becomes remarkably difficult to apply to an industrial process. At present, no investigation has been made on the storage stability of the basic iminophosphazenium salt and the basic phosphazenium salt solution.

  The present invention has been made in view of such a background, and an object of the present invention is to stably store a basic iminophosphazenium salt expected to be useful as an organic base for a long period of time. An object of the present invention is to provide a polyalkylene glycol production catalyst solution comprising a basic iminophosphazenium salt solution, and a polyalkylene glycol production method using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a solution obtained by dissolving a basic iminophosphazenium salt in a solvent containing a specific solvent is excellent as a catalyst solution for producing polyalkylene glycol. As a result, the present invention has been completed.

That is, the present invention contains at least one type of protic organic solvent having a solubility parameter of 10 (cal / cm ³ ) ^1/2 or more of a basic iminophosphazenium salt represented by the following general formula (1). The present invention relates to a polyalkylene glycol production catalyst solution dissolved in a solvent to be produced and a polyalkylene glycol production method using the polyalkylene glycol production catalyst solution.

（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２〜４のアルキルカルボキシアニオン、または炭酸水素アニオンを表す。）
以下に本発明を詳細に説明する。

(In the general formula (1), R ₁ and R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R ₁ and R ₂ are bonded to each other to form a ring structure. R ₁ or R ₂ may be bonded to each other to form a ring structure, and X ⁻ is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, carbon. Represents an alkylcarboxy anion having 2 to 4 or a hydrogen carbonate anion.)
The present invention is described in detail below.

The catalyst solution for the production of polyalkylene glycol of the present invention is a protic organic solvent in which the basic iminophosphazenium salt represented by the general formula (1) is a solubility parameter of 10 (cal / cm ³ ) ^1/2 or more. It is a solution formed by dissolving in a solvent containing at least one kind.

  The basic iminophosphazenium salt constituting the polyalkylene glycol production catalyst solution of the present invention is a basic iminophosphazenium salt represented by the above general formula (1).

Here, 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. 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 And cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and nonadecyl group.

Examples of the ring structure in which R ₁ and R ₂ are bonded to each other include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, and an isoindolyl group, and a ring structure in which R ₁ or R ₂ are bonded to each other. Examples of the structure include a structure in which one substituent is an alkylene group such as an ethylene group, a propylene group, or a butylene group, and is bonded to the other substituent to form a ring structure.

And since basic iminophosphazenium salt which shows especially strong organic basicity and is suitable as a catalyst solution for polyalkylene glycol production can be easily obtained, R ₁ and R ₂ are methyl group, ethyl group, An isopropyl group is preferred.

X ⁻ in the general formula (1) 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. Here, 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 2-5 alkylcarboxy anion 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, a t-butyl carboxy anion, and the like.

Then, in particular, an organic strong base, suitable basic imino phospha X since the zero salt polyalkylene glycol producing catalyst solution ^- as is preferably a hydroxy anion.

  The basic iminophosphazenium salt represented by the general formula (1) in the present invention can be obtained by any method as long as the basic iminophosphazenium salt can be obtained. Examples thereof include a method in which an iminophosphazenium salt represented by the following general formula (2) is ion exchanged using a basic compound or an ion exchange resin.

（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。Ａ⁻は、塩素アニオン、臭素アニオン、よう素アニオンを表す。）
そして、塩基性化合物を用いて上記一般式（２）で示されるイミノホスファゼニウム塩を上記一般式（１）で示される塩基性イミノホスファゼニウム塩へイオン交換する方法としては、例えば上記一般式（２）で示されるイミノホスファゼニウム塩を有機溶媒中、塩基性化合物で処理し、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へイオン交換する方法が挙げられる。ここで、塩基性化合物としては、例えばアルカリ金属又はアルカリ土類金属の水酸化物、アルカリ金属又はアルカリ土類金属のアルコキシド、カルボン酸のアルカリ金属塩又はアルカリ土類金属塩、アルカリ金属又はアルカリ土類金属の炭酸水素化物等を挙げることができ、その中でも、入手が容易で塩基性が強くイオン交換が容易に進行することから、アルカリ金属またはアルカリ土類金属の水酸化物が好ましく、水酸化ナトリウム、水酸化カリウムが特に好ましい。有機溶媒としては、例えばメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｔ−ブタノール、ｎ−ペンタノール、ネオペンタノール、ｎ−ヘキサノール、ｎ−ヘプタノール、ｎ−オクタノール、ｎ−ノナノール、ｎ−デカノール等のアルコールを挙げることができ、その中でも、目的とするイオン交換反応の反応率が高くなることから、エタノール、ｎ−プロパノール、イソプロパノール、ｔ−ブタノールが好ましい。

(In the general formula (2), _{R 1} and _{R 2} are the same definition as _{R 1} and _{R 2} in the general formula (1) .A ^- represents a chloride anion, a bromine anion, iodine anion .)
And as a method of ion-exchanging the iminophosphazenium salt represented by the general formula (2) to the basic iminophosphazenium salt represented by the general formula (1) using a basic compound, for example, A method in which an iminophosphazenium salt represented by the general formula (2) is treated with a basic compound in an organic solvent and ion-exchanged to the basic iminophosphazenium salt represented by the general formula (1). Can be mentioned. Here, examples of the basic compound include alkali metal or alkaline earth metal hydroxide, alkali metal or alkaline earth metal alkoxide, alkali metal salt or alkaline earth metal salt of carboxylic acid, alkali metal or alkaline earth. Among them, alkali metal or alkaline earth metal hydroxides are preferred because they are easily available, have strong basicity, and facilitate ion exchange. Sodium and potassium hydroxide are particularly preferred. Examples of the organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, neopentanol, n-hexanol, n-heptanol, n-octanol, n- Examples of the alcohol include nonanol and n-decanol. Among them, ethanol, n-propanol, isopropanol, and t-butanol are preferable because the reaction rate of the target ion exchange reaction is increased.

In addition, as a method for ion-exchanging the iminophosphazenium salt represented by the general formula (2) to the basic iminophosphazenium salt represented by the general formula (1) using an ion exchange resin, for example, The iminophosphazenium salt represented by the general formula (2) 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. Examples thereof include a method of ion-exchange to a basic iminophosphazenium salt in which X ⁻ in formula (1) is a hydroxy anion.

  Examples of the method for producing the iminophosphazenium salt represented by the general formula (2) include a method of reacting phosphorus pentachloride 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。）
本発明のポリアルキレングリコール製造用触媒溶液を構成する溶媒は、溶解度パラメータ１０（ｃａｌ／ｃｍ^３）^１／２以上であるプロトン性有機溶媒を少なくとも１種類以上含有する溶媒である。ここで、非プロトン性溶媒、又は、溶解度パラメータ１０（ｃａｌ／ｃｍ^３）^１／２未満のプロトン性有機溶媒のみからなる溶媒である場合、ポリアルキレングリコール製造用触媒溶液を構成する塩基性イミノホスファゼニウム塩の保存安定性が低下し、ポリアルキレングリコール製造用触媒としての使用に課題を有するものとなる。

(In the general formula (3), R ₁ and R ₂ have the same definition as R ₁ and R ₂ in the general formula (1).)
The solvent constituting the polyalkylene glycol production catalyst solution of the present invention is a solvent containing at least one protic organic solvent having a solubility parameter of 10 (cal / cm ³ ) ^1/2 or more. Here, in the case of an aprotic solvent or a solvent consisting only of a protic organic solvent having a solubility parameter of less than 10 (cal / cm ³ ) ^1/2, basic iminophos constituting the catalyst solution for producing polyalkylene glycol. The storage stability of the fazenium salt is lowered, and there is a problem in use as a catalyst for producing a polyalkylene glycol.

Examples of the protic organic solvent having a solubility parameter of 10 (cal / cm ³ ) ^1/2 or more include methanol (solubility parameter 14.5 (cal / cm ³ ) ^1/2 ), ethanol (solubility parameter 12.7 ( cal / cm ³ ) ^1/2 ), n-propanol (solubility parameter 11.9 (cal / cm ³ ) ^1/2 ), isopropanol (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 ) ^Monoalcohol such as ^1/2 ); ethylene glycol (solubility parameter 14.6 (cal / cm ³ ) ^{1 / 2} ), 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 ), glycerin (solubility parameter 16.5 (cal / cm ³ ) ^1/2 ), etc. Esters, ethylene glycol monomethyl ether (solubility parameter ^{11.4 (cal / cm 3) 1/2} ), ethylene glycidyl Over 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 Polyhydric alcohol derivatives such as parameter 11.5 (cal / cm ³ ) ^1/2 ); formic acid (solubility parameter 12.1 (cal / cm ³ ) ^1/2 ), acetic acid (solubility parameter 10.1 (cal / cm ³ ) Fatty acids such as ^1/2 ); ethylenediamine (solubility parameter 12.3 (cal / cm ³ ) ^1/2 ), aniline (solubility parameter 10.3 (cal / cm ³ ) ^1/2 ), acetonitrile (solubility parameter) And nitrogen-containing compounds such as 11.9 (cal / cm ³ ) ^1/2 ). Among them, since it becomes a catalyst solution for polyalkylene glycol production that is easy to obtain and remove the solvent and particularly excellent in storage stability, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t- Monoalcohols having 1 to 4 carbon atoms such as butanol; acetonitrile is preferred. Or a 2 or more types of mixed solvent may be sufficient.

As a method for producing a catalyst solution for producing polyalkylene glycol of the present invention, for example, a basic iminophosphazenium salt represented by the above general formula (1) has a solubility parameter of 10 (cal / cm ³ ) ^1/2 or more. A method of dissolving in a solvent containing at least one protic organic solvent can be mentioned, and more specifically, ion exchange of the iminophosphazenium salt represented by the general formula (2) was obtained. After removing the solvent used in the ion exchange from the basic iminophosphazenium salt solution represented by the general formula (1), the protonicity having a solubility parameter of 10 (cal / cm ³ ) ^1/2 or more Method of adding a solvent containing at least one organic solvent; solubility parameter 10 (c) in a basic iminophosphazenium salt solution after ion exchange After a l / cm ³⁾ a protic organic solvent is ^1/2 or more and adding a solvent containing at least one type, a method to remove only solvent used during the ion exchange; and the like can be given.

The protic organic solvent is the solubility parameter 10 (cal ^/ cm ^{3) 1/2} or more in the present invention and a solvent containing at least one or more, solubility parameter 10 (cal ^/ cm ^{3) 1/2} or more in a protic Any solvent may be used as long as it contains an organic solvent, and it may be a mixed solvent with an aprotic or solvent having a solubility parameter of less than 10 (cal / cm ³ ) ^1/2 . Among them, a solvent containing 40% by weight or more of a protic organic solvent having a solubility parameter of 10 (cal / cm ³ ) ^½ or more because the catalyst solution for producing polyalkylene glycol is particularly excellent in stability. It is preferable that the solvent is a solvent containing 50% by weight or more of a protic organic solvent having a solubility parameter of 10 (cal / cm ³ ) ^1/2 or more, and particularly a solubility parameter of 10 (cal / cm ³ ) ^{1/2. A} solvent composed only of ^two or more protic organic solvents is preferred.

  The catalyst solution for producing the polyalkylene glycol of the present invention may have any concentration as long as it can take the form of a solution. Among them, the catalyst solution for producing polyalkylene glycol is excellent in stability. The concentration of the basic iminophosphazenium salt in the solution is preferably 1 to 99% by weight, more preferably 20 to 80% by weight.

The catalyst solution for producing polyalkylene glycol of the present invention is prepared by dissolving the basic iminophosphazenium salt represented by the general formula (1) in a solvent and preparing the solution, and after 10 days have elapsed, The residual ratio of the basic iminophosphazenium salt is preferably 90% or more. At this time, the residual ratio of the basic iminophosphazenium salt was measured by ¹ H-NMR measurement of a catalyst solution for producing polyalkylene glycol after 10 days and a peak integrated value of 2.84 to 2.88 ppm. (Peak derived from basic iminophosphazenium salt) /2.80 to 3.00 ppm peak integrated value (peak derived from basic iminophosphazenium salt and decomposition product) × 100 it can.

  There is no particular limitation on the atmosphere when producing and storing the catalyst solution for producing the polyalkylene glycol of the present invention, and it may be, for example, under an inert gas atmosphere such as nitrogen or argon, or under air, and among them, Since it becomes the catalyst solution for polyalkylene glycol manufacture excellent in storage stability, it is preferable that it is in inert gas atmosphere, such as nitrogen and argon.

  The catalyst solution for the production of polyalkylene glycol of the present invention can be used for the production of polyalkylene glycol. For example, the catalyst solution for the production of polyalkylene glycol of the present invention and the active hydrogen-containing compound Examples include a method of preparing a polymerization initiator by contacting, removing a solvent and by-product water, and then adding alkylene oxide to perform ring-opening polymerization of the alkylene oxide.

  Examples of the active hydrogen-containing compound in preparing the polymerization initiator include a hydroxy compound, an amine compound, a carboxylic acid compound, a phenol compound, a thiol compound, and more specifically, 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, shoe Hydroxyl compounds such as claw and glucose; amine compounds such as ethylenediamine, N, N′-dimethylethylenediamine, piperidine and piperazine; carboxylic acid compounds such as benzoic acid and adipic acid; 2-naphthol and bisphenol And the like ethanedithiol, thiol compounds such as butane dithiol; phenolic compounds. Further, it is also possible to use a polyether polyol having a hydroxyl group, and examples thereof include polypropylene glycol and polypropylene glycol glycerin ether. The molecular weight of the polyether polyol at this time is not particularly limited, and among them, the viscosity is low. A polyether polyol having a molecular weight of 200 to 3,000 which is excellent in fluidity is preferred. These active hydrogen-containing compounds may be used alone or in combination of several kinds.

The ratio of the catalyst solution for producing the polyalkylene glycol and the active hydrogen compound in preparing the polymerization initiator is arbitrary, and among them, the polyalkylene glycol can be efficiently produced. Therefore, the active hydrogen-containing compound 1 The range in which the basic iminophosphazenium salt in the catalyst solution for producing polyalkylene glycol is 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, preferably 5 × 10 ^{−3 to} 5 × 10, relative to mol. It is preferably used in the range of ⁻² mol.

  Examples of the method for removing water and by-product water produced when preparing the polymerization initiator and the solvent contained in the catalyst solution for producing polyalkylene glycol include a method for removing the solvent and by-product water under reduced pressure. In this case, the degree of reduced pressure is, for example, 50 kPa or less, preferably 10 kPa or less, particularly preferably 5 kPa or less. Moreover, as temperature conditions in that case, the temperature range of 30-130 degreeC, for example, Preferably the range of 40-100 degreeC can be mentioned.

  Examples of the alkylene oxide include alkylene oxides having 2 to 20 carbon atoms, and specific examples include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, butadiene mono Examples thereof include oxide, pentene oxide, styrene oxide, and cyclohexene oxide. Among these, ethylene oxide and propylene oxide are preferable because they are easily available and have high industrial value. An alkylene oxide 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.

  The pressure during the ring-opening polymerization of the alkylene oxide is, for example, in the range of 0.05 to 1.0 MPa, and preferably in the range of 0.1 to 0.6 MPa. Moreover, reaction temperature is the range of 40-130 degreeC, for example, Preferably it is the range of 60-130 degreeC.

  The polyalkylene glycol obtained using the catalyst solution for production of polyalkylene glycol of the present invention can be a polyalkylene glycol having a different hydroxyl value, and the hydroxyl value of the resulting polyalkylene glycol is not particularly limited. Especially, the range of 5-500 mgKOH / g is preferable, and it is especially preferable that it is the range of 10-170 mgKOH / g.

  The polyalkylene glycol obtained by 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.

  The present invention relates to a catalyst solution for producing a polyalkylene glycol comprising a basic iminophosphazenium salt solution useful as an organic base and capable of stably storing a basic iminophosphazenium salt for a long period of time, and the polyalkylene thereof The present invention relates to a method for producing a polyalkylene glycol using a catalyst solution for glycol production, and it is possible to provide polyalkylene glycol expected as various resin materials, and its industrial value is extremely high.

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

-Measurement of residual ratio of basic iminophosphazenium salt (unit: integral%)-
Using a nuclear magnetic resonance (NMR) spectrum measurement apparatus (manufactured by JEOL Ltd., (product name) GSX270WB), ¹ H-NMR was measured using heavy water as a heavy solvent. 2. Basic iminophosphazenium salt depending on the ratio of the integrated value (referred to as b) of the peak at 2.84 to 2.88 ppm in the integrated value (referred to as a) to the peak in the range of 2.80 to 3.00 ppm. The residual ratio of was calculated. That is, the residual ratio of the basic iminophosphazenium salt was calculated by the following formula.
Residual rate of basic iminophosphazenium salt (integral%) = (b / a) × 100
-Measurement of concentration (unit: wt%) of basic iminophosphazenium salt solution-
Using a trace total nitrogen analyzer (Mitsubishi Chemical, (trade name) TN-100), conditions of heater temperature T1: 600 ° C., T2: 800 ° C., gas flow rate O ₂ : 500 ml / min, O ₃ : 200 ml / min Then, the nitrogen concentration (referred to as “c”) of the basic iminophosphazenium salt solution was measured. From this nitrogen concentration, the concentration of the basic iminophosphazenium salt in the aqueous solution was calculated. That is, the concentration of the basic iminophosphazenium salt solution was calculated by the following formula.
Concentration (wt%) of basic iminophosphazenium salt solution = c / 0.33
-Measurement of hydroxyl value of polyalkylene glycol (unit: mgKOH / g)-
It was calculated by the method described in JIS K-1557.

-Measurement of molecular weight of polyalkylene glycol (unit: g / mol)-
From the calculated hydroxyl value of polyalkylene glycol (denoted as d), the molecular weight of polyalkylene glycol was calculated according to the following formula.
Molecular weight of polyalkylene glycol (unit: g / mol) = (1 / ((d / 56.1) / initiator functional group number)) × 1000
-Measurement of ethylene oxide content (unit: wt%) of polyalkylene glycol-
Using a nuclear magnetic resonance (NMR) spectrometer (manufactured by JEOL Ltd., (product name) GSX270WB), ¹ H-NMR of polyalkylene glycol was measured using heavy chloroform as a heavy solvent. Integral value of peak in the range of 0.80 to 1.50 ppm (peak of propylene oxide chain in polyalkylene glycol) and peak in the range of 3.20 to 3.90 ppm (propylene oxide chain and ethylene oxide in polyalkylene glycol) The ethylene oxide content of the polyalkylene glycol was calculated from the integral value of the chain peak).

Synthesis Example 1 (Synthesis of a chloride object 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 is concentrated, and 5.1 g (9.7 mmol; yield 88%) of the target iminophosphazenium salt is obtained. R ₁ in the general formula (2) is a methyl group, R ₂ is a methyl group, A ⁽ Iminophosphazenium salt in which-corresponds to a chlorine anion) was obtained as a white solid.

Synthesis Example 2 (Synthesis of basic iminophosphazenium salt)
To a 300 ml Schlenk flask equipped with a magnetic rotator, 21 g (40 mmol) of the chloride of iminophosphazenium salt obtained in Synthesis Example 1 was added, and the atmosphere in the flask was changed to a nitrogen atmosphere. Potassium hydroxide 2.2g (40mmol) and isopropanol 80ml were added there, and it stirred at room temperature for 3 hours. The suspension containing the white solid obtained after completion of the reaction was filtered under reduced pressure using a funnel with filter paper. An isopropanol 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.

The obtained isopropanol solution of the basic iminophosphazenium salt was concentrated under reduced pressure, and the basic iminophosphazenium salt (wherein R ₁ in the general formula (1) is a methyl group, R ₂ is a methyl group, and X ⁻ is Basic iminophosphazenium salt corresponding to hydroxy anion) was obtained. As a result of analyzing the purity of the basic iminophosphazenium salt, the purity was 99% or more.

Example 1
To a 100 ml Schlenk flask equipped with a magnetic rotor, 2.0 g (4.0 mmol) of the basic iminophosphazenium salt obtained in Synthesis Example 2 was added, and the atmosphere in the flask was changed to a nitrogen atmosphere. Thereto, 2.0 g (27 mmol) of t-butanol was added to obtain a basic iminophosphazenium salt-t-butanol solution to obtain a catalyst solution A for production of polyalkylene glycol.

The residual ratio of the basic iminophosphazenium salt after leaving this catalyst solution A for polyalkylene glycol production for 10 days was measured by ¹ H-NMR to be 92%.

  Then, in a 2 liter autoclave equipped with a stirring blade, 4.0 g of a catalyst solution A (50% by weight) for producing polyalkylene glycol after 10 days, and a trifunctional polyalkylene glycol (Sanyo Chemical Industries) as an activated hydrogen compound (Product name) Sannicks GP-1000; hydroxyl value 160 mgKOH / g) 175 g (175 mmol) was added to prepare a polymerization initiator. At that time, the inside of the autoclave was set to a nitrogen atmosphere, 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. Thereafter, 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, and the ring-opening polymerization reaction was performed in the range of the internal temperature of 88 to 92 ° C. for 8 hours. Subsequently, 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 92 ° C. for 6 hours. A ring-opening polymerization reaction was performed. Then, residual ethylene oxide was removed under a reduced pressure of 0.2 kPa to obtain 1250 g of colorless and odorless polyalkylene glycol. The obtained polyalkylene glycol had a hydroxyl value of 23.8 mgKOH / g, a molecular weight calculated from the hydroxyl value of 7100 g / mol, and an ethylene oxide content of 17% by weight. Details are shown in Table 1.

Example 2
To a 100 ml Schlenk flask with a magnetic rotor, 8.3 g (4.0 mmol) of an isopropanol solution of the basic iminophosphazenium salt obtained after filtration in Synthesis Example 2 was added, and the atmosphere in the flask was changed to a nitrogen atmosphere. . Distill off isopropanol under reduced pressure to concentrate and prepare a basic iminophosphazenium salt-isopropanol solution containing 2.0 g of basic iminophosphazenium salt and 2.0 g (33 mmol) of isopropanol. Then, a catalyst solution B for producing polyalkylene glycol was obtained.

The residual ratio of the basic iminophosphazenium salt after leaving this catalyst solution B for polyalkylene glycol production for 10 days was measured by ¹ H-NMR to be 96%.

  And polyalkylene glycol was manufactured by the method similar to Example 1 except having used 4.0 g of catalyst solution B for polyalkylene glycol manufacture (50 weight%) which passed 10 days. As a result, 1230 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 24.1 mgKOH / g, a molecular weight calculated from the hydroxyl value of 7000 g / mol, and an ethylene oxide content of 17% by weight. Details are shown in Table 1.

Example 3
A catalyst solution C for producing polyalkylene glycol was synthesized in the same manner as in Example 1 except that 2.0 g (49 mmol) of acetonitrile was used instead of 2.0 g (27 mmol) of t-butanol. When this solution was allowed to stand for 10 days, the residual ratio of the basic iminophosphazenium salt was measured by ¹ H-NMR to be 98%.

  Then, polyalkylene glycol was produced in the same manner as in Example 1, except that 4.0 g of catalyst solution C (50% by weight) for producing polyalkylene glycol after 10 days was used. As a result, 1300 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 23.7 mgKOH / g, a molecular weight calculated from the hydroxyl value of 7100 g / mol, and an ethylene oxide content of 17% by weight. Details are shown in Table 1.

Example 4
A polyalkylene was prepared in the same manner as in Example 1 except that a mixed solvent of 2.0 g (25 mmol) of dimethyl sulfoxide and 2.0 g (44 mmol) of ethanol was used instead of 2.0 g (27 mmol) of t-butanol. Catalyst solution D for glycol production was synthesized. The residual ratio of the basic iminophosphazenium salt after leaving this solution for 10 days was measured by ¹ H-NMR to be 97%.

  And polyalkylene glycol was manufactured by the method similar to Example 1 except having used 4.0 g of catalyst solutions D (50 weight%) for polyalkylene glycol manufacture which passed for 10 days. As a result, 1280 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 24.2 mgKOH / g, a molecular weight calculated from the hydroxyl value of 7000 g / mol, and an ethylene oxide content of 17% by weight. Details are shown in Table 1.

Example 5
A catalyst solution E for producing polyalkylene glycol was synthesized in the same manner as in Example 1 except that 2.0 g (44 mmol) of ethanol was used instead of 2.0 g (27 mmol) of t-butanol. The residual ratio of the basic iminophosphazenium salt after leaving this solution for 10 days was measured by ¹ H-NMR to be 95%.

  Then, polyalkylene glycol was produced in the same manner as in Example 1 except that 4.0 g of catalyst solution E for producing polyalkylene glycol (50% by weight) after 10 days was used. As a result, 1230 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 24.8 mgKOH / g, a molecular weight calculated from the hydroxyl value of 6800 g / mol, and an ethylene oxide content of 17% by weight. Details are shown in Table 1.

Example 6
A catalyst solution F for producing polyalkylene glycol was synthesized in the same manner as in Example 1 except that 2.0 g (44 mmol) of ethanol was used instead of 2.0 g (27 mmol) of t-butanol. Exposed to. The residual ratio of the basic iminophosphazenium salt after leaving this solution for 10 days was measured by ¹ H-NMR to be 95%.

  Then, polyalkylene glycol was produced in the same manner as in Example 1 except that 4.0 g of catalyst solution F (50% by weight) for producing polyalkylene glycol after 10 days was used. As a result, 1240 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 24.5 mgKOH / g, a molecular weight calculated from the hydroxyl value of 6900 g / mol, and an ethylene oxide content of 17% by weight. Details are shown in Table 1.

Example 7
A catalyst solution G for producing polyalkylene glycol was synthesized in the same manner as in Example 1 except that 2.0 g (63 mmol) of methanol was used instead of 2.0 g (27 mmol) of t-butanol. When this solution was allowed to stand for 10 days, the residual ratio of the basic iminophosphazenium salt was measured by ¹ H-NMR to be 98%.

  And polyalkylene glycol was synthesize | combined by the method similar to Example 1 except having used 4.0 g of catalyst solutions G (50 weight%) for polyalkylene glycol manufacture which passed for 10 days. As a result, 1260 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 24.0 mgKOH / g, a molecular weight calculated from the hydroxyl value of 7000 g / mol, and an ethylene oxide content of 17% by weight. Details are shown in Table 1.

Example 8
Polyalkylene glycol was synthesized in the same manner as in Example 2 except that 925 g of propylene oxide and 165 g of ethylene oxide were used. As a result, 1250 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 23.8 mgKOH / g, a molecular weight calculated from the hydroxyl value of 7000 g / mol, and an ethylene oxide content of 13% by weight. Details are shown in Table 2.

Example 9
Polyalkylene glycol was synthesized in the same manner as in Example 2 except that 970 g of propylene oxide and 120 g of ethylene oxide were used. As a result, 1230 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 24.7 mgKOH / g, a molecular weight calculated from the hydroxyl value of 6800 g / mol, and an ethylene oxide content of 10% by weight. Details are shown in Table 2.

Example 10
Polyalkylene glycol was synthesized in the same manner as in Example 2 except that 1015 g of propylene oxide and 75 g of ethylene oxide were used. As a result, 1220 g of colorless and odorless polyalkylene glycol was obtained. The obtained polyalkylene glycol had a hydroxyl value of 24.8 mgKOH / g, a molecular weight calculated from the hydroxyl value of 6800 g / mol, and an ethylene oxide content of 6% by weight. Details are shown in Table 2.

比較例１
磁気回転子を付した１００ｍｌのシュレンクフラスコに、合成例２で得られた塩基性イミノホスファゼニウム塩２．０ｇ（４．０ｍｍｏｌ）を加え、フラスコ内を窒素雰囲気とした。そこへ、テトラヒドロフラン２．０ｇ（２８ｍｍｏｌ）を加え、塩基性イミノホスファゼニウム塩−テトラヒドロフラン溶液Ｈとした。この溶液を１０日間放置した後の塩基性イミノホスファゼニウム塩の残存率を^１Ｈ−ＮＭＲにより測定したところ２１％であった。

Comparative Example 1
To a 100 ml Schlenk flask equipped with a magnetic rotor, 2.0 g (4.0 mmol) of the basic iminophosphazenium salt obtained in Synthesis Example 2 was added, and the atmosphere in the flask was changed to a nitrogen atmosphere. Thereto was added 2.0 g (28 mmol) of tetrahydrofuran to obtain a basic iminophosphazenium salt-tetrahydrofuran solution H. When this solution was allowed to stand for 10 days, the residual ratio of the basic iminophosphazenium salt was measured by ¹ H-NMR to be 21%.

  Then, polyalkylene glycol was synthesized in the same manner as in Example 1 except that 4.0 g of basic iminophosphazenium salt-tetrahydrofuran solution H (50% by weight) after 10 days was used. . As a result, 190 g of brown polyalkylene glycol having an amine odor was obtained. The obtained polyalkylene glycol had a hydroxyl value of 158 mgKOH / g and a molecular weight calculated from the hydroxyl value of 1100 g / mol (the molecular weight of the trifunctional polyalkylene glycol used as the active hydrogen compound was 1000 g / mol). The ring polymerization reaction hardly progressed. Details are shown in Table 3.

Comparative Example 2
A basic iminophosphazenium salt-pyridine solution I was synthesized in the same manner as in Comparative Example 1 except that 2.0 g (25 mmol) of pyridine was used instead of 2.0 g (28 mmol) of tetrahydrofuran. The residual ratio of the basic iminophosphazenium salt after this solution was allowed to stand for 10 days was 28% as measured by ¹ H-NMR.

  Then, polyalkylene glycol was synthesized in the same manner as in Example 1 except that 4.0 g of basic iminophosphazenium salt-pyridine solution I (50 wt%) after 10 days was used. . As a result, 230 g of brown polyalkylene glycol having an amine odor was obtained. The obtained polyalkylene glycol had a hydroxyl value of 134 mgKOH / g, a molecular weight calculated from the hydroxyl value of 1300 g / mol (the molecular weight of the trifunctional polyalkylene glycol used as the active hydrogen compound was 1000 g / mol), The ring polymerization reaction hardly progressed. Details are shown in Table 3.

Comparative Example 3
A basic iminophosphazenium salt-dimethyl sulfoxide solution J was synthesized in the same manner as in Comparative Example 1, except that 2.0 g (25 mmol) of dimethyl sulfoxide was used instead of 2.0 g (28 mmol) of tetrahydrofuran. did. After the solution was allowed to stand for 10 days, the residual ratio of the basic iminophosphazenium salt was measured by ¹ H-NMR to be 31%.

  Then, polyalkylene glycol was synthesized in the same manner as in Example 1 except that 4.0 g of basic iminophosphazenium salt-dimethyl sulfoxide solution J (50% by weight) after 10 days was used. It was. As a result, 240 g of brown polyalkylene glycol having an amine odor was obtained. The obtained polyalkylene glycol had a hydroxyl value of 121 mgKOH / g and a molecular weight calculated from the hydroxyl value of 1400 g / mol (the molecular weight of the trifunctional polyalkylene glycol used as the active hydrogen compound was 1000 g / mol). The ring polymerization reaction hardly progressed. Details are shown in Table 3.

Comparative Example 4
To a 100 ml Schlenk flask equipped with a magnetic rotor, 2.0 g (4.0 mmol) of the basic iminophosphazenium salt obtained in Synthesis Example 2 was added, and the atmosphere in the flask was changed to a nitrogen atmosphere. When the residual ratio of the basic iminophosphazenium salt after standing for 10 days was measured by ¹ H-NMR, it was 28%.

  And polyalkylene glycol was synthesize | combined by the method similar to Example 1 except having used obtained basic iminophosphazenium salt K2.0g. As a result, 220 g of brown polyalkylene glycol having an amine odor was obtained. The obtained polyalkylene glycol has a hydroxyl value of 130 mgKOH / g and a molecular weight calculated from the hydroxyl value of 1300 g / mol (the molecular weight of the trifunctional polyalkylene glycol used as the active hydrogen compound is 1000 g / mol). The ring polymerization reaction hardly progressed. Details are shown in Table 3.

  The polyalkylene glycol obtained from the catalyst solution for producing polyalkylene glycol is expected to be useful as a polyurethane raw material, a polyester raw material, a surfactant raw material, a lubricant raw material and the like.

Claims (7)

From a solvent containing at least one protic organic solvent having a basic iminophosphazenium salt represented by the following general formula (1) of 20 to 80 wt% and a solubility parameter of 10 (cal / cm ³ ) ^1/2 or more. A solution for storing a catalyst for producing a polyalkylene glycol characterized by comprising:

(In the general formula (1), R ₁ and R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R ₁ and R ₂ are bonded to each other to form a ring structure. And R ₁ or R ₂ may be bonded to each other to form a ring structure, and X ⁻ represents a hydroxy anion or a hydrogen carbonate anion.) The basic iminophosphazenium salt represented by the above general formula (1) can be obtained by ion exchange of the iminophosphazenium salt represented by the following general formula (2) with a basic compound or an ion exchange resin. The solution for preserving the polyalkylene glycol production catalyst according to claim 1, which is a basic iminophosphazenium salt.

(In the general formula (2), _{R 1} and _{R 2} are the same definition as _{R 1} and _{R 2} in the general formula (1) .A ^- represents a chlorine anion, bromine anion, iodine anion. ) A protic organic solvent having a solubility parameter of 10 (cal / cm ³ ) ^½ or more is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, and acetonitrile. The solution for preserving the polyalkylene glycol production catalyst according to claim 1, wherein the solution is a protic organic solvent. After contacting the solution for storing the polyalkylene glycol production catalyst according to any one of claims 1 to 3 with an active hydrogen-containing compound to prepare a polymerization initiator and removing the solvent and by-product water A method for producing a polyalkylene glycol, comprising adding an alkylene oxide and carrying out ring-opening polymerization. The method for producing a polyalkylene glycol according to claim 4, wherein the active hydrogen compound is a polyether polyol. 6. The method for producing a polyalkylene glycol according to claim 4, wherein the alkylene oxide is ethylene oxide and / or propylene oxide. The method for producing a polyalkylene glycol according to any one of claims 4 to 6, wherein the ring-opening polymerization is carried out under conditions of a reaction pressure of 0.05 to 1 MPa and a reaction temperature of 40 to 130 ° C.