JP2016037560A - Method for producing polyalkylene glycol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing polyalkylene glycol which makes it possible to efficiently produce polyalkylene glycol with high activity, a narrow molecular weight distribution, and stable physical properties.SOLUTION: A method for producing polyalkylene glycol performs ring opening polymerization of alkylene oxide in the presence of a specific iminophosphazenium salt, an active hydrogen-containing compound having two or more active hydrogen atoms, and hydrotalcite.SELECTED DRAWING: None

Description

  The present invention relates to a process for producing a polyalkylene glycol, and in particular, ring-opening polymerization of alkylene oxide in the presence of a specific iminophosphazenium salt, an active hydrogen-containing compound having two or more active hydrogens, and hydrotalcite. The present invention relates to a novel method for producing a polyalkylene glycol that can efficiently produce a polyalkylene glycol having high activity, a narrow molecular weight distribution, and stable physical properties.

  A method for producing a polyalkylene glycol by ring-opening polymerization of an alkylene oxide is generally known. Examples of the catalyst used at that time include alkali metal salts such as alkali metal hydroxides and alkaline earth metal hydroxides. Many reports have been made on alkaline earth metal salts, double metal cyanide (DMC) catalysts, phosphazene catalysts, and the like. In recent years, it has been reported that iminophosphazenium salts can be used as a catalyst for producing polyalkylene glycol (see, for example, Patent Document 1). It has also been reported that hydrotalcite serves as a production catalyst for polyalkylene glycol (see, for example, Patent Document 2 and Non-Patent Document 1).

2010-150514 gazette (Refer to a claim.) US Pat. No. 4,962,237 (refer to the claims)

JOURNAL OF CATALYSIS 130, 354-358 (1991)

  However, in the method proposed in Patent Document 1, the reaction activity when producing polyalkylene glycol is low. In addition, if the method of increasing the reaction temperature is selected in order to increase the reaction activity, the amount of monool compound having an allyl terminal due to side reaction increases, and the resulting polyalkylene glycol has a low purity. When glycol is used as a raw material for polyurethane, the obtained polyurethane has a problem that the physical properties such as mechanical properties and curability are low.

  In addition, in the methods proposed in Patent Document 2 and Non-Patent Document 1, the resulting polyalkylene glycol has a molecular weight as low as about 5000, it is difficult to produce a high molecular weight polyalkylene glycol, and the molecular weight distribution is wide. Even if it is polyalkylene glycol of the same molecular weight, it had the subject that it was difficult to manufacture polyalkylene glycol which has the stable physical property, such as a viscosity fluctuate | varied large.

  There has been a demand for a method for efficiently producing highly active and stable polyalkylene glycol.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that ring opening of alkylene oxide in the presence of a specific iminophosphazenium salt, an active hydrogen-containing compound having two or more active hydrogens, and hydrotalcite. By conducting polymerization, a novel polyalkylene glycol production method capable of efficiently producing a polyalkylene glycol having high activity, a narrow molecular weight distribution, and stable physical properties has been found, and the present invention has been completed. It was.

  That is, the present invention performs ring-opening polymerization of alkylene oxide in the presence of an iminophosphazenium salt represented by the following general formula (1), an active hydrogen-containing compound having two or more active hydrogens, and a hydrotilesite. The present invention relates to a process for producing a polyalkylene glycol characterized by the following.

（１）
（式中、Ｒ_１，Ｒ_２は各々独立して炭素数１〜１０のアルキル基、無置換の若しくは置換基を有する炭素数６〜１０のフェニル基又はアルキルフェニル基を表し、Ｒ_１とＲ_２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。Ｙ^ｎ−は、活性水素含有化合物中のｎ個のプロトンが脱離した活性水素含有化合物のアニオンを表し、ｎは２以上の整数を表す。）
以下に、本発明を詳細に説明する。

(1)
Wherein R ₁ and R ₂ each independently represents an alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted phenyl group having 6 to 10 carbon atoms or an alkylphenyl group, and R ₁ and R 2 ₂ or R ₂ may be bonded to each other to form a ring structure, where Y ⁿ⁻ represents an anion of the active hydrogen-containing compound from which n protons in the active hydrogen-containing compound are eliminated, and n is Represents an integer of 2 or more.)
The present invention is described in detail below.

  The method for producing a polyalkylene glycol of the present invention comprises the step of opening an alkylene oxide in the presence of an iminophosphazenium salt represented by the general formula (1), an active hydrogen-containing compound having two or more active hydrogens, and a hydrotilesite. This is a method for producing a polyalkylene glycol which undergoes ring polymerization.

In this case, the iminophosphazenium salt may be any salt as long as it belongs to the category represented by the general formula (1), and R ₁ and R ₂ each independently represent 1 to 1 carbon atoms. 10 alkyl group, unsubstituted or substituted phenyl group having 6 to 10 carbon atoms or alkylphenyl group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group , Sec-butyl group, tert-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 2-methyl-1-butyl group, isopentyl group, tert-pentyl group, 3- Methyl-2-butyl group, neopentyl group, n-hexyl group, 4-methyl-2-pentyl group, cyclopentyl group, cyclohexyl group, 1-heptyl group, 3-heptyl group, 1-octyl 2-octyl group, 2-ethyl-1-hexyl group, 1,1-dimethyl-3,3-dimethylbutyl group, nonyl group, decyl group, phenyl group, 4-toluyl group, benzyl group, 1-phenylethyl And aliphatic or aromatic hydrocarbon groups such as 2-phenylethyl group, among which methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, tert-pentyl group, 1, C1-C10 aliphatic hydrocarbon groups, such as 1-dimethyl-3,3-dimethylbutyl group, are preferable, and a methyl group is more preferable. R ₁ and R ₂ , or R ₂ may be bonded to each other to form a ring structure. Examples of such substituents include dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, Methylene group and the like, and since it is easy to synthesize and a strongly basic iminophosphazenium hydrogen carbonate is obtained, when R ₁ and R ₂ are bonded to each other to form a ring structure, tetramethylene Group is preferred, and when R ₂ is bonded to each other to form a ring structure, a dimethylene group is preferred.

Y ⁿ⁻ represents an anion of the active hydrogen-containing compound from which n protons in the active hydrogen-containing compound have been eliminated, and n represents an integer of 2 or more. The active hydrogen-containing compound for deriving Y ^n- may be the same as the active hydrogen-containing compound having two or more active hydrogens present in the production of the polyalkylene glycol. Examples thereof include hydroxy compounds, amine compounds, carboxylic acid compounds, phenol compounds, thiol compounds, and more specifically, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butane. Hydroxy compounds such as diol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, etc .; ethylenediamine, N, N′-dimethyl Ethylenediamine, amine compounds such as piperazine; carboxylic acid compounds such as adipic acid; phenol compounds such as bisphenol; ethanedithiol, can be exemplified thiol compounds such as butane dithiol. 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 as a mixture of several kinds.

As a method for producing the imino phosphazenium salt, a compound represented by general formula (3) basic imino phospha active hydrogen-containing compound having active hydrogen least two of inducing ^n- Ze salt and Y represented by The method of preparing by heat-processing under reduced pressure can be mentioned.

（３）
（式中、Ｒ_１，Ｒ_２は上記一般式（１）におけるＲ_１，Ｒ_２と同じ官能基を表す。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。）
そして、該塩基性イミノホスファゼニウム塩は、例えば特開２０１３−１１２６４６号公報、特開２０１４−１１８３５３号公報等に記載の方法により製造することができる。ここで、Ｒ_１，Ｒ_２としては、上記したものと同様のものを例示することができる。また、該塩基性イミノホスファゼニウム塩の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であり、炭素数１〜４のアルコキシアニオンとしては、例えばメトキシアニオン、エトキシアニオン、ｎ−プロポキシアニオン、イソプロポキシアニオン、ｎ−ブトキシアニオン、イソブトキシアニオン、ｔ−ブトキシアニオン等が挙げられ、炭素数２〜５のアルキルカルボキシアニオンとしては、例えばアセトキシアニオン、エチルカルボキシアニオン、ｎ−プロピルカルボキシアニオン、イソプロピルカルボキシアニオン、ｎ−ブチルカルボキシアニオン、イソブチルカルボキシアニオン、ｔ−ブチルカルボキシアニオン等が挙げられる。そして、中でも、該塩基性イミノホスファゼニウム塩の塩基性が強いものとなることから、Ｘ⁻としては、ヒドロキシアニオンまたは炭酸水素アニオンが好ましい。

(3)
(In the formula, R ₁ and R ₂ represent the same functional groups as R ₁ and R ₂ in the general formula (1). X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, and a carbon number. Represents 2 to 5 alkylcarboxy anions or hydrogencarbonate anions.)
And this basic iminophosphazenium salt can be manufactured by the method as described in Unexamined-Japanese-Patent No. 2013-112646, Unexamined-Japanese-Patent No. 2014-118353, etc., for example. Here, examples of R ₁ and R ₂ are the same as those described above. Further, X ⁻ of the basic iminophosphazenium salt 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 a hydrogen carbonate anion, Examples of the alkoxy anion having 1 to 4 include a methoxy anion, an ethoxy anion, an n-propoxy anion, an isopropoxy anion, an n-butoxy anion, an isobutoxy anion, a t-butoxy anion, and the like. Examples of the carboxy 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, and a t-butyl carboxy anion. It is. Then, among them, since it becomes strong basic said basic imino phosphazenium salt, X ^- as a hydroxy anion or bicarbonate anions are preferred.

  Furthermore, specific examples of the basic iminophosphazenium salt 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-dimethyl Louisimidazolidine-2-imino) phosphonium hydroxide, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydroxide, 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 hydrogen carbonate, 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, tetrakis (1,3-dimethylimidazolidine- 2-imino) phosphonium hydrogen carbonate and the like, and since the basic iminophosphazenium salt has strong basicity, tetrakis (1,1,3,3-tetramethylguanidino) phosphazenium hydroxide Tetrakis (1,1,3,3-tetramethylguanidino) phosphazenium hydrogen carbonate is preferable.

The mixing ratio of the basic iminophosphazenium salt and the active hydrogen-containing compound having two or more active hydrogens when preparing the iminophosphazenium salt is arbitrary, and among these, the iminophosphazenium salt Can be efficiently produced from the iminophosphazenium salt, the active hydrogen-containing compound having two or more surplus active hydrogens, and the hydrotalcite described later. Therefore, the range in which the basic iminophosphazenium salt is 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol with respect to 1 mol of the active hydrogen-containing compound having two or more active hydrogens, preferably 5 × It is preferably used in the range of 10 ⁻³ to 1 × 10 ⁻¹ mol.

  In preparing the iminophosphazenium salt, examples of a method for removing water and by-product water in the active hydrogen-containing compound having two or more active hydrogens include a method of removing water under reduced pressure. In this case, the degree of reduced pressure can be, for example, 50 kPa or less, preferably 10 kPa or less, and 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, As reaction time in that case, it is 0.5-10 hours, for example, Preferably Can be in the range of 1 to 5 hours. In preparing the iminophosphazenium salt, a mixture of the basic iminophosphazenium salt and an active hydrogen-containing compound having two or more active hydrogens in the presence of hydrotalcite described later. The iminophosphazenium salt, which is a salt of an iminophosphazenium cation and a divalent or higher active hydrogen-containing compound anion, may be prepared.

  In the production method of the polyalkylene glycol of the present invention, by using the iminophosphazenium salt, the active hydrogen compound having two or more active hydrogens, and hydrotalcite, the production method is highly active and excellent in efficiency. In this case, the hydrotalcite may be anything as long as it belongs to the category called hydrotalcite, and a commercially available product may be used as it is, and among them, higher activity. Is a hydrotalcite calcined in a temperature range of 300 to 900 ° C., and preferably hydrotalcite calcined in a temperature range of 400 to 800 ° C. More preferred. The firing method at that time is arbitrary, and for example, it can be carried out using a muffle furnace or a tubular furnace under an air atmosphere or an inert gas atmosphere such as nitrogen. There is no restriction | limiting in particular in baking time, For example, it is the range of 1-10 hours, Preferably it is the range of 2-6 hours.

Moreover, since it becomes a manufacturing method of polyalkylene glycol which shows especially high activity, it is preferable that it is a hydrotalcite shown by following General formula (2).
(Mg _1-x Al _x (OH) ₂ ) ^{x +} (CO _{3x / 2} · mH ₂ O) ^x− (2)
(In the formula, x and m satisfy the conditions of 0 <x ≦ 0.33 and 0 <m ≦ 1.0.)
Furthermore, the hydrotalcite may contain other metals and anions as long as the polymerization activity is not impaired. Examples of other metals include divalent metals such as manganese, iron, cobalt, nickel, copper, and zinc. Examples thereof include trivalent metals such as chromium, iron, cobalt, and indium. As the anion, for example, _WO ⁴ _2-, ^{MoO 4} _2-, can be exemplified _VO ^{4 3-,} and the like.

Then, specific examples of the hydrotalcite, for example _{Mg 6 · A1 2 · (OH} ) 16 · CO 3 · 4H 2 O, Mg 4.5 · A1 2 · (OH) 13 · CO 3 · 3.5H 2 Those having a composition such as O may be mentioned. These hydrotalcites are naturally occurring minerals or synthetically obtained compounds. In these natural and synthetic hydrotalcites, the Mg ²⁺ / Al ³⁺ ratio is in the range of 1-8, and the OH ⁻ / CO ₃ ²⁻ ratio is in the range of 10-20.

  The amount of hydrotalcite used in the present invention is arbitrary, and among these, it becomes a production method having a high polymerization activity, and the treatment after the reaction is facilitated. It is preferably from 05 to 10% by weight, particularly preferably from 0.1 to 5% by weight.

  The method for producing a polyalkylene glycol of the present invention comprises ring-opening polymerization of alkylene oxide in the presence of the iminophosphazenium salt, an active hydrogen-containing compound having two or more active hydrogens, and hydrotalcite. The timing of adding hydrotalcite at that time is arbitrary. For example, an active hydrogen-containing compound having two or more basic iminophosphazenium salts and active hydrogen is heat-treated under reduced pressure, and an iminophosphazenium salt is obtained. A hydrotalcite, a basic iminophosphazenium salt, an active hydrogen-containing compound having two or more active hydrogens, and a hydrotalcite, and the imino in the presence of hydrotalcite A method for preparing a phosphazenium salt can be mentioned. Among them, since it becomes a method for producing a polyalkylene glycol exhibiting higher activity, the basic iminophosphazenium salt and two or more active hydrogens. After the active hydrogen-containing compound and hydrotalcite are mixed at the same time, heat treatment is performed under reduced pressure, Methods of preparing the imino phosphazenium salt standing under is preferable.

  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 40-150 degreeC, for example, Preferably it is the range of 60-130 degreeC.

  In the method for producing polyalkylene glycol of the present invention, steps such as purification and recovery of polyalkylene glycol can be optionally added, and the catalyst components used in production are removed from polyalkylene glycol. For example, the catalyst component can be removed by a method of contacting the solid acid with the solid acid to cause the solid acid to be adsorbed and then separating the solid acid.

  The polyalkylene glycol obtained by the present invention can be a polyalkylene glycol having a different hydroxyl value, and the hydroxyl value of the obtained polyalkylene glycol is not particularly limited, and among them, the range of 5 to 100 mgKOH / g. Particularly preferred is a range of 10 to 70 mg KOH / g. Moreover, molecular weight distribution is the range of 1.01-1.2, Preferably it is the range of 1.02-1.1.

  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.

  According to the method of the present invention, an alkylene oxide is subjected to ring-opening polymerization in the presence of an iminophosphazenium salt, an active hydrogen-containing compound having two or more active hydrogens, and hydrotalcite, thereby achieving high activity and molecular weight distribution. Is very useful industrially since it is possible to efficiently produce a polyalkylene glycol having a narrow and stable physical property.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these at all. In the following synthesis examples and examples, NMR spectra, GC-MS, ion chromatography, and gel permeation chromatography (GPC) were measured as follows.

~ NMR spectrum measurement (iminophosphazenium salt purity measurement) ~
A nuclear magnetic resonance spectrometer (trade name: GSX270WB) manufactured by JEOL Ltd. was used, and the organic phase was analyzed using tetramethylsilane (TMS) as an internal standard and deuterated chloroform as a heavy solvent. For the analysis of the aqueous phase, measurement was performed using heavy water as a heavy solvent.

~ Measurement of GC-MS ~
Measurement was performed using FAB + as an ionization mode using a gas chromatography-mass spectrometer (trade name: JMS-700, manufactured by JEOL Ltd.).

~ Ion chromatography measurement (Ion exchange rate measurement) ~
Column (trade name; TSKgel IC-Anion-PW _XL ) manufactured by Tosoh Corporation, an anion standard solution (manufactured by Tosoh Corporation) as the eluent, and conductivity detector (trade name, manufactured by Tosoh Corporation) CM-8200) was used to measure the chlorine or bromine ion concentration in a 1% by weight solution of iminophosphazenium halide at 35 ° C. and a flow rate of 1.0 ml / min.

-GPC measurement (measurement of molecular weight distribution)-
Using gel permeation chromatography (GPC) (trade name: HLC8020GPC, manufactured by Tosoh Corporation), the value was measured as a standard polystyrene conversion value from an elution curve measured at 40 ° C. using tetrahydrofuran as a solvent.

~ Measurement of hydroxyl value and total unsaturation ~
It measured according to the measuring method of JISK1557.

-Calculation method of activity (g / mol.min)-
Alkylene oxide amount: A (g) (total product weight- (active hydrogen-containing compound amount + basic iminophosphazenium salt + hydrotalcite amount)), catalyst amount: B (mol), reaction time: C ( Time), the activity was calculated as A / (B × C × 60).

  The active hydrogen-containing compounds and hydrotalcites having two or more active hydrogens used in Examples and Comparative Examples are shown below.

-Active hydrogen-containing compound having two or more active hydrogens-
A glycerin-type polypropylene glycol having a molecular weight of 250 (three active hydrogens) (hereinafter referred to as polyol A).
A glycerin-type polypropylene glycol having a molecular weight of 1000 (3 active hydrogens) (hereinafter referred to as polyol B).
Propylene glycol polypropylene glycol having a molecular weight of 400 (2 active hydrogens) (hereinafter referred to as polyol C).

~ Hydrotalcite _{(composition: Mg 6 A1 2 (OH)} 16 CO 3 · 4H 2 O) ~
Commercial product (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter referred to as hydrotalcite A).
Hydrotalcite A fired at 400 ° C. under a nitrogen stream (hereinafter referred to as hydrotalcite B).
Hydrotalcite A fired at 800 ° C. under a nitrogen stream (hereinafter referred to as hydrotalcite C).

Synthesis example 1
According to Example 3 of JP2013-112646A, a concentration of 40.1% by weight of tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide, which is a basic iminophosphazenium salt, was obtained. A propanol solution was obtained. The ion exchange rate by ion chromatography was 99.3%, and the yield of tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide was 92.0%.

The product was identified by ¹ H-NMR and GC-MS.

¹ H-NMR (heavy solvent: D ₂ O):
Chemical shift: 2.92 ppm (methyl group derived from phosphazenium salt).

GC-MS (FAB +) measurement results:
m / z = 487 (corresponding to the molecular weight of tetrakis (1,1,3,3-tetramethylguanidino) phosphonium cation).

Synthesis example 2
According to Example 1 of Unexamined-Japanese-Patent No. 2014-118353, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydrogen carbonate was obtained. The resulting tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydrogen carbonate was identified by ¹ H-NMR, GC-MS, and ion chromatography.

¹ H-NMR (heavy solvent: D ₂ O, internal standard: tetramethylsilane):
Chemical shift: 2.87 ppm (methyl group derived from phosphazenium salt).

GC-MS (FAB +) measurement results:
m / z = 487 (corresponding to the molecular weight of tetrakis (1,1,3,3-tetramethylguanidino) phosphonium cation).

  As a result of measuring by ion chromatography, the ion exchange rate for hydrogen carbonate ions was 99.5%.

Example 1
40.1% by weight of tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide obtained in Synthesis Example 1 as a basic iminophosphazenium salt (in formula (3), R ₁ , R ₂ is a methyl group, and X ⁻ is a hydroxy anion.) 0.5 g (0.4 mmol) of the solution, 5.0 g (20 mmol) of polyol A and 1.0 g of hydrotalcite A, a thermocouple, a pressure gauge, The glass autoclave having an actual volume of 200 ml equipped with a stirrer and an alkylene oxide introduction tube was charged. Thereafter, the inside of the reactor was replaced with dry nitrogen, the temperature was raised to 80 ° C., and heat treatment was performed for 3 hours under a reduced pressure of 0.5 kPa, and iminophosphazenium salt (Y ⁿ⁻ An anion from which three protons were eliminated), a mixture of polyol A and hydrotalcite A was prepared.

  After the heat treatment, the preparation is returned to normal pressure with nitrogen, heated to 90 ° C., and propylene oxide is intermittently supplied into the reactor at 90 ° C. so as to keep the reaction pressure at 0.3 MPa or less. The reaction was performed for 4 hours. After the supply of propylene oxide was completed, the reaction was continued at 90 ° C. for 1.5 hours until there was no decrease in pressure. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the contents were cooled to room temperature and returned to normal pressure.

  115.2 g of colorless and odorless polyoxypropylene triol was obtained. The catalytic activity was 835 g / mol · min. The obtained polyoxypropylene triol had a hydroxyl value of 29.2 mgKOH / g, a total unsaturation of 0.017 meq / g, and a molecular weight distribution (Mw / Mn) determined by GPC of 1.04.

Comparative Example 1
Except for using no hydrotalcite A, subjected to heat treatment in the same manner as in Example 1, imino phosphazenium salt (Y ^n-protons in the polyol A is released three de-anion) and Polyol A A mixture was prepared.

  After the heat treatment, the preparation is returned to normal pressure with nitrogen, heated to 90 ° C., and propylene oxide is intermittently supplied into the reactor so as to keep the reaction pressure at 0.3 MPa or less for 4 hours at 90 ° C. Reacted. After the supply of propylene oxide was completed, the reaction was continued at 90 ° C. for 1.5 hours until there was no decrease in pressure. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the contents were cooled to room temperature and returned to normal pressure.

  36.8 g of colorless and odorless polyoxypropylene triol was obtained. The catalytic activity was 241 g / mol · min. The obtained polyoxypropylene triol had a hydroxyl value of 91.5 mgKOH / g, a total unsaturation of 0.019 meq / g, and a molecular weight distribution (Mw / Mn) determined by GPC of 1.06. Compared with Example 1, the activity was greatly reduced.

Example 2
In place of 5 g (20 mmol) of polyol A, 8.7 g (8.7 mmol) of polyol B and 40% by weight of tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide instead of 0.5 g (0.4 mmol) 0.25 g (0.2 mmol) except that used in example 1 and subjected to heat treatment in the same manner, imino phosphazenium salt ^{(Y n-protons} in the polyol B releases three de-anion), the A mixture of polyol B and hydrotalcite A was prepared.

  After the heat treatment, the temperature was raised to 90 ° C., and propylene oxide was reacted in the temperature range of 88 to 92 ° C. for 5 hours while being intermittently supplied into the reactor so as to maintain a reaction pressure of 0.3 MPa or less. After the supply of propylene oxide was completed, the reaction was continued at 90 ° C. for 2 hours until there was no pressure decrease. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the pressure was returned to normal pressure with nitrogen, and the contents were cooled to room temperature.

  81 g of colorless and odorless polyoxypropylene triol was obtained. The catalytic activity was 848 g / mol · min. The obtained polyoxypropylene triol had a hydroxyl value of 18.1 mgKOH / g, a total degree of unsaturation of 0.026 meq / g, and a molecular weight distribution (Mw / Mn) of 1.04.

Example 3
Except that instead of polyol A5g (20mmol) was used polyol C8g (20mmol) performs the same heat treatment as in Example 1, imino phosphazenium salt ^{(Y n-protons} in the polyol C are two desorption An anion), polyol C and hydrotalcite A were prepared.

  After the heat treatment, the preparation is returned to normal pressure with nitrogen, heated to 90 ° C., and propylene oxide is intermittently supplied into the reactor so as to keep the reaction pressure at 0.3 MPa or less for 4 hours at 90 ° C. Reacted. After the supply of propylene oxide was completed, the reaction was continued at 90 ° C. for 2 hours until there was no pressure decrease. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the contents were cooled to room temperature and returned to normal pressure.

  125.2 g of colorless and odorless polyoxypropylene was obtained. The catalytic activity was 807 g / mol · min. The obtained polyoxypropylene had a hydroxyl value of 18.1 mgKOH / g, a total unsaturation of 0.019 meq / g, and a molecular weight distribution (Mw / Mn) determined by GPC of 1.04.

Example 4
Except for using hydrotalcite B1g instead of hydrotalcite A1g is subjected to heat treatment in the same manner as in Example 2, imino phosphazenium salt (Y ^n-protons in the polyol B releases three de A mixture of anion), polyol B and hydrotalcite B was prepared.

  After the heat treatment, the temperature was raised to 90 ° C., and propylene oxide was reacted in the temperature range of 88 to 92 ° C. for 4 hours while intermittently supplying the reactor with a reaction pressure of 0.3 MPa or less. After the supply of propylene oxide was completed, the reaction was continued at 90 ° C. for 1.5 hours until there was no decrease in pressure. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the pressure was returned to normal pressure with nitrogen, and the contents were cooled to room temperature.

  67 g of colorless and odorless polyoxypropylene triol was obtained. The catalyst activity was 868 g / mol · min. The obtained polyoxypropylene triol had a hydroxyl value of 22.2 mgKOH / g, a total unsaturation degree of 0.022 meq / g, and a molecular weight distribution (Mw / Mn) of 1.04.

Example 5
Except for using hydrotalcite C1g instead of hydrotalcite A1g, heat treatment is performed in the same heat treatment as in Example 2, imino phosphazenium salt (Y ^n-protons in the polyol B is three A mixture of desorbed anions), polyol B and hydrotalcite C was prepared.

  After the heat treatment, the temperature was raised to 90 ° C., and propylene oxide was reacted in the temperature range of 88 to 92 ° C. for 4 hours while intermittently supplying the reactor with a reaction pressure of 0.3 MPa or less. After the supply of propylene oxide was completed, the reaction was continued at 90 ° C. for 2 hours until there was no pressure decrease. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the pressure was returned to normal pressure with nitrogen, and the contents were cooled to room temperature.

  69 g of colorless and odorless polyoxypropylene triol was obtained. The catalytic activity was 821 g / mol · min. The obtained polyoxypropylene triol had a hydroxyl value of 21.6 mgKOH / g, a total degree of unsaturation of 0.027 meq / g, and a molecular weight distribution (Mw / Mn) of 1.04.

Example 6
Tetrakis (1,1,3,3-tetramethylguanidino) phosphonium obtained in Synthesis Example 2 instead of 0.25 g (0.2 mmol) of tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide Except that 0.11 g (0.2 mmol) of hydrogen carbonate was used, heat treatment was carried out in the same manner as in Example 2, and an iminophosphazenium salt (Y ^n- was anion from which three protons in polyol B were eliminated). ), A mixture of polyol B and hydrotalcite A was prepared.

  After the heat treatment, the temperature was raised to 90 ° C., and propylene oxide was reacted in the temperature range of 88 to 92 ° C. for 4 hours while intermittently supplying the reactor with a reaction pressure of 0.3 MPa or less. After the supply of propylene oxide was completed, the reaction was continued at 90 ° C. for 2 hours until there was no pressure decrease. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the pressure was returned to normal pressure with nitrogen, and the contents were cooled to room temperature.

  62 g of colorless and odorless polyoxypropylene triol was obtained. The catalytic activity was 724 g / mol · min. The obtained polyoxypropylene triol had a hydroxyl value of 24.0 mgKOH / g, a total degree of unsaturation of 0.024 meq / g, and a molecular weight distribution (Mw / Mn) of 1.04.

Example 7
Heat treatment was carried out in the same manner as in Example 2 to prepare a mixture of iminophosphazenium salt (Y ⁿ⁻ is an anion from which three protons in polyol B were eliminated), polyol B and hydrotalcite B.

  After the heat treatment, the temperature was raised to 90 ° C., and 46 g of propylene oxide was reacted in the temperature range of 88 to 92 ° C. for 5 hours while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. Subsequently, residual propylene oxide was removed under reduced pressure at 90 ° C. over 1 hour. After removing propylene oxide, the temperature was raised to 110 ° C., and 12 g of ethylene oxide was supplied at 110 ° C. so that the reaction pressure was 0.4 MPa (gauge) or less. After feeding ethylene oxide, aging was performed at the same temperature for 1 hour. After aging, ethylene oxide was removed under reduced pressure, and then returned to normal pressure with nitrogen, and the contents were cooled to room temperature.

  63 g of colorless and odorless polyalkylene oxide was obtained. The activity of propylene oxide addition was 730 g / mol · min. The resulting polyalkylene oxide has an ethylene oxide content of 15.1% by weight, a hydroxyl value of 22 mg KOH / g, a total unsaturation of 0.024 meq / g, and a molecular weight distribution (Mw / Mn) of 1. .04.

Example 8
Except for using hydrotalcite A5g instead of hydrotalcite A1g, heat treatment is performed in the same manner as in Example 1, imino phosphazenium salt (Y ^n-protons in the polyol A is released three de-anion ), A mixture of polyol A and hydrotalcite A was prepared.

  After the heat treatment, the preparation is returned to normal pressure with nitrogen, heated to 90 ° C., and propylene oxide is intermittently supplied into the reactor so as to keep the reaction pressure at 0.3 MPa or less for 4 hours at 90 ° C. Reacted. After the supply of propylene oxide was completed, the reaction was continued at 90 ° C. for 1.5 hours until there was no decrease in pressure. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the contents were cooled to room temperature and returned to normal pressure.

  116.2 g of colorless and odorless polyoxypropylene triol was obtained. The catalytic activity was 805 g / mol · min. The obtained polyoxypropylene triol had a hydroxyl value of 30.3 mgKOH / g, a total unsaturation of 0.017 meq / g, and a molecular weight distribution (Mw / Mn) determined by GPC of 1.03.

Comparative Example 2
The same procedure as in Example 1 was performed, except that 0.5 g (0.4 mmol) of 40 wt% tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide solution was not used. A mixture of hydrotalcite A was prepared.

  After the heat treatment, the temperature was raised to 90 ° C., and propylene oxide was reacted in the temperature range of 88 to 92 ° C. for 5 hours while being intermittently supplied into the reactor so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, the pressure was reduced to 0.5 kPa, and unreacted propylene oxide was removed at 90 ° C. for 1 hour. Thereafter, the pressure was returned to normal pressure with nitrogen, and the contents were cooled to room temperature.

  39 g of colorless and odorless polyoxypropylene was obtained. The amount of polyoxypropylene obtained was greatly reduced to 39 g, and the activity was lowered. The obtained polyoxypropylene has a hydroxyl value of 78.3 mgKOH / g, a total unsaturation of 0.020 meq / g, and a molecular weight distribution (Mw / Mn) of 2.15, indicating a wide distribution. It was.

  The polyalkylene glycol obtained by the production method 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.

Claims (5)

A polyalkylene comprising ring-opening polymerization of alkylene oxide in the presence of an iminophosphazenium salt represented by the following general formula (1), an active hydrogen-containing compound having two or more active hydrogens, and a hydrotilesite A method for producing glycol.

(1)
Wherein R ₁ and R ₂ each independently represents an alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted phenyl group having 6 to 10 carbon atoms or an alkylphenyl group, and R ₁ and R 2 ₂ or R ₂ may be bonded to each other to form a ring structure, where Y ⁿ⁻ represents an anion of the active hydrogen-containing compound from which n protons in the active hydrogen-containing compound are eliminated, and n is Represents an integer of 2 or more.) _2. The production of polyalkylene glycol according to claim 1, wherein the iminophosphazenium salt represented by the general formula (1) is an iminophosphazenium salt having a methyl group in both R ₁ and R _2. Method. The method for producing a polyalkylene glycol according to claim 1 or 2, wherein the hydrotalcite is hydrotalcite that has been calcined in a temperature range of 300 to 900 ° C. The method for producing a polyalkylene glycol according to any one of claims 1 to 3, wherein the hydrotalcite is a hydrotalcite represented by the following general formula (2).
(Mg _1-x Al _x (OH) ₂ ) ^{x +} (CO _{3x / 2} · mH ₂ O) ^x− (2)
(In the formula, x and m satisfy the conditions of 0 <x ≦ 0.33 and 0 <m ≦ 1.0.) A basic iminophosphazenium salt represented by the following general formula (3), an active hydrogen-containing compound having two or more active hydrogens, and hydrotalcite are heat-treated under reduced pressure, and then ring-opening polymerization of alkylene oxide is performed. The manufacturing method of the polyalkylene glycol in any one of Claims 1-4 characterized by the above-mentioned.

(3)
(In the formula, R ₁ and R ₂ represent the same functional groups as R ₁ and R ₂ in the general formula (1). X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, carbon. Represents an alkylcarboxy anion of number 2 to 5, or a hydrogen carbonate anion.)