JPH10330475A - Production of polyoxyalkylene polyol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polyol by efficiently recovering a phosphazenium compound used as a catalyst by adding at least one kind of neutralizing agent comprising water and an inorganic acid or an organic acid and by further re-utilizing the recovered phosphazenium compound. SOLUTION: (C) An alkylene oxide is subjected to addition polymerization in the presence of (A) a salt of a phosphazenium cation represented by the formula [(a), (b), (c) and (d) are each 0-3; R is a 1-10C hydrocarbon; (r) is 1-3 and represents a number of phosphazenium cation; T<r-> is an inorganic anion having a valence of (r)] with an inorganic anion and (B) an alkali (earth)metal salt of an active hydrogen compound to produce (D) a crude polyoxyalkylene polyol and (E) at least one kind of neutralizing agent selected from water and an inorganic acid or an organic acid is added to the component D to neutralize the phosphazenium compound and the neutralized compound is dehydrated and dried, and the objective polyol is separated from the deposited component A and the component A is recovered and re-utilized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for recovering a polyoxyalkylene polyol polymerization catalyst and a method for producing a polyoxyalkylene polyol. Specifically, the present invention relates to a method for recovering a phosphazenium compound having a specific structure from a polyoxyalkylene polyol used as a polymerization catalyst for a polyoxyalkylene polyol, and a polyalkylene oxide obtained by addition polymerization of an alkylene oxide using the recovered phosphazenium compound as a catalyst. The present invention relates to a method for producing an oxyalkylene polyol. Polyoxyalkylene polyols are widely used as raw materials for polyurethane foams and polyurethane elastomers or as raw materials for surfactants, hydraulic oils, lubricating oils, and synthetic resins other than polyurethane.

[0002]

2. Description of the Related Art Polyoxyalkylene polyols are usually produced on an industrial scale by addition polymerization of an active hydrogen compound with an alkylene oxide in the presence of a potassium hydroxide catalyst. An alkylene oxide is continuously or collectively charged into a reactor charged with a potassium hydroxide catalyst and an active hydrogen compound as a polymerization initiator, and the reaction temperature is 105 to 150.
° C, maximum reaction pressure 5-6 kgf / cm ² (490-58
Under a condition of 8 kPa), the reaction is carried out until a predetermined molecular weight is obtained to obtain a crude polyoxyalkylene polyol. Then, the potassium alcoholate in the crude polyoxyalkylene polyol is neutralized with an acid such as an inorganic acid, dehydrated, dried, and subjected to a post-treatment purification step by filtration of a precipitated potassium salt. Various methods have been conventionally studied to increase the productivity of polyoxyalkylene polyol. In order to increase the reaction rate of the alkylene oxide as a monomer, there are known methods of increasing the alkylene oxide concentration during the reaction, increasing the reaction temperature, and increasing the amount of the catalyst. However, according to such a method, when propylene oxide, which is most widely used as an alkylene oxide, is used, the potassium hydroxide catalyst increases the molecular weight of the polyoxyalkylene polyol and increases the monool having an unsaturated group at the molecular terminal. It is known to produce by-products. This monool causes deterioration of the quality of the produced polyoxyalkylene polyol, and brings about unfavorable results such as deterioration of physical properties of the polyurethane resin. Conventionally, various studies have been made on polymerization catalysts capable of suppressing the production of by-product monols and improving the productivity of polyoxyalkylene polyols. EP 0 763 555 discloses a method using a phosphazene compound or a phosphazenium salt comprising an active hydrogen compound and a phosphazene compound as a polymerization catalyst for alkylene oxide. As a result of investigations by the present inventors, the phosphazene or a phosphazenium salt comprising an active hydrogen compound and a phosphazene compound disclosed in EP 0 765 555 is obtained by polymerizing propylene oxide in comparison with an alkali metal hydroxide such as potassium hydroxide or cesium hydroxide. High activity, USP5
This is a catalyst which is almost equivalent to the by-product monol content of the high molecular weight polypropylene glycol obtained with the double metal cyanide complex catalyst exemplified in P. 144,093, and is also capable of copolymerization with ethylene oxide. I understand. However, EP 0 765 555 does not disclose a method of recovering a phosphazene compound or a phosphazenium salt from a polyalkylene oxide and subjecting them to polymerization of the alkylene oxide again.

[0003]

An object of the present invention is to provide a polyoxyalkylene polyol from a crude polyoxyalkylene polyol obtained by addition polymerization of an alkylene oxide in the presence of a phosphazenium compound having a specific structure and an active hydrogen compound. An object of the present invention is to provide a method for efficiently recovering a phosphazenium compound as a polymerization catalyst, and a method for producing a polyoxyalkylene polyol by reusing the recovered phosphazenium compound.

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that an active hydrogen compound uses a phosphazenium compound having a specific structure as a catalyst,
A crude polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide under specific reaction conditions is used to recover a phosphazenium compound obtained by at least one neutralizing agent consisting of water and an inorganic acid or an organic acid; and An organic solvent was added, and after separation, the aqueous phase was separated and the phosphazenium compound was recovered, and the recovered phosphazenium compound was found to be usable again as a polymerization catalyst for polyoxyalkylene polyol, and the present invention was completed. It led to. That is, the first object of the present invention is to provide (step 1) (step 1a) chemical formula (1)

[0004]

Embedded image (A, b, c and d in the chemical formula (1) are each 0
And a, b, c and d are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations;
^r- represents an inorganic anion having a valence of r. A) a process of producing a crude polyoxyalkylene polyol by addition-polymerizing an alkylene oxide in the presence of a salt of a phosphazenium cation and an inorganic anion represented by the formula) and an alkali metal or alkaline earth metal salt of an active hydrogen compound Or (step 1b) chemical formula (2)

[0005]

Embedded image (In the chemical formula (2), a, b, c and d are integers from 0 to 3, but all of a, b, c and d are not simultaneously 0. R is the same or different carbon number of 1 to 3. It is 10 hydrocarbon groups, and two Rs on the same nitrogen atom may combine with each other to form a ring structure, and Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion. A) a process of producing a crude polyoxyalkylene polyol by addition-polymerizing an alkylene oxide in the presence of a phosphazenium compound and an active hydrogen compound represented by (2), (Step 2) adding water to the crude polyoxyalkylene polyol obtained in Step 1; A neutralization step of adding at least one neutralizing agent selected from inorganic acids or organic acids, (Step 3) the liquid obtained in Step 2 is dehydrated and dried, A step of recovering a phosphazenium salt for separating a zenium salt and a polyoxyalkylene polyol, and (step 4) converting the alkylene oxide in the presence of the phosphazenium salt recovered in step 3 and an alkali metal or alkaline earth metal salt of an active hydrogen compound. A process for producing a polyoxyalkylene polyol, which is characterized by performing addition polymerization.

[0006] A second object of the present invention is to (step 5) adding water or water and an organic solvent to the crude polyoxyalkylene polyol obtained in step 1a of the first present invention.
A step of recovering a phosphazenium salt by separating an aqueous phase and removing water, (step 6) adding an alkylene oxide in the presence of the phosphazenium salt recovered in step 5 and an alkali metal or alkaline earth metal salt of an active hydrogen compound A process for producing a polyoxyalkylene polyol characterized by polymerizing the polyoxyalkylene polyol. The third object of the present invention is to add (step 7) water or water and an organic solvent to the crude polyoxyalkylene polyol obtained in the step 1b of the first present invention, separate the aqueous phase, and separate the aqueous phase. A step of recovering the phosphazenium salt to remove water, and (step 8)
A process for producing a polyoxyalkylene polyol, which comprises subjecting an alkylene oxide to addition polymerization in the presence of the phosphazenium compound and the active hydrogen compound recovered in Step 7. is there. A fourth object of the present invention is to contact the phosphazenium salt obtained in Step 3 of the first present invention as an aqueous solution with an OH type anion exchange resin to thereby obtain the first chemical formula (1) or (1) of the present invention. A method for producing a polyoxyalkylene polyol, which comprises subjecting a phosphazenium hydroxide derived from (2) to addition polymerization of an alkylene oxide in the presence of the phosphazenium hydroxide and an active hydrogen compound. A fifth object of the present invention is to contact the phosphazenium salt obtained in step 5 of the second present invention as an aqueous solution with an OH type anion exchange resin to thereby obtain the chemical formula (1) of the first present invention or A method for producing a polyoxyalkylene polyol, which comprises subjecting a phosphazenium hydroxide derived from (2) to addition polymerization of an alkylene oxide in the presence of the phosphazenium hydroxide and an active hydrogen compound.

A sixth object of the present invention is to react the phosphazenium salt obtained in step 3 of the first present invention with an alkali metal or alkaline earth metal hydroxide, alkoxide, aryloxide or carboxide. And subjecting the alkylene oxide to addition polymerization in the presence of a phosphazenium compound and an active hydrogen compound obtained by the above method. The seventh object of the present invention is obtained by reacting the phosphazenium salt obtained in step 5 of the second present invention with an alkali metal or alkaline earth metal hydroxide, alkoxide, aryloxide or carboxide. Phosphazenium compound and active hydrogen compound,
This is a method for producing a polyoxyalkylene polyol, which comprises addition-polymerizing an alkylene oxide.
Further, an eighth object of the present invention is a method for recovering a phosphazenium salt from a polyoxyalkylene polyol, comprising a first (step 2) neutralization step and a (step 3) recovery step of the present invention. is there. A ninth object of the present invention is to
A method for recovering a phosphazenium salt from a polyoxyalkylene polyol, comprising a second (step 5) recovery step of the present invention. A tenth object of the present invention is to
A method for recovering a phosphazenium salt from a polyoxyalkylene polyol, which comprises a third (step 7) recovery step of the present invention.

[0008]

First, step 1 will be described.
The phosphazenium cation in the phosphazenium compound represented by the chemical formula (1) or (2) in the present invention is represented by an extreme structural formula whose positive charge is localized on a central phosphorus atom. Besides, countless infinite structural formulas are drawn, and the positive charges are actually delocalized as a whole.

In the present invention, a in the phosphazenium cation represented by the chemical formula (1) or (2),
b, c and d are each an integer of 0 to 3. Preferably it is an integer of 0 to 2. However, in each case, not all are simultaneously 0. More preferably, regardless of the order of a, b, c and d, (2,1,1,1), (1,
(1,1,1), (0,1,1,1), (0,0,1,
1) or a number in the combination of (0,0,0,1). More preferably, (1,1,1,1), (0,
1,1,1), (0,0,1,1) or (0,0,
(0, 1).

In the present invention, R in the phosphazenium cation represented by the chemical formulas (1) and (2) is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms. R is, for example, methyl, ethyl, n
-Propyl, isopropyl, allyl, n-butyl, se
c-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1
-Butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-
Methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-
It is selected from aliphatic or aromatic hydrocarbon groups such as octyl, 2-ethyl-1-hexyl, tert-octyl, nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl. Among these, an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl, 1-octyl or tert-octyl is preferable, and a methyl group or ethyl Groups are more preferred.

When two Rs on the same nitrogen atom in the phosphazenium cation combine to form a ring structure, the divalent hydrocarbon group on the nitrogen atom is 4 to 6 A divalent hydrocarbon group having a main chain composed of carbon atoms (the ring is a 5- to 7-membered ring containing a nitrogen atom), preferably, for example, tetramethylene, pentamethylene or hexamethylene; These are those whose main chains are substituted by an alkyl group such as methyl or ethyl. More preferably, it is a tetramethylene or pentamethylene group. Such a ring structure may be employed for all possible nitrogen atoms in the phosphazenium cation, or a part thereof may be employed.

In the present invention, T ^r− in the chemical formula (1) represents an inorganic anion having a valence of r. And r is an integer of 1 to 3. Such inorganic anions include, for example, boric acid, tetrafluoroboric acid, hydrocyanic acid, thiocyanic acid, hydrofluoric acid, hydrohalic acid such as hydrochloric acid or hydriodic acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid Inorganic anions such as acids, hexafluorophosphoric acid, carbonic acid, hexafluoroantimonic acid, hexafluorothallic acid and perchloric acid are included. In addition, H as an inorganic anion
SO ₄ ^-, HCO ₃ ^- in some cases. In some cases, these inorganic anions can be exchanged with each other by an ion exchange reaction. Of these inorganic anions, boric acid,
Anions of inorganic acids such as tetrafluoroboric acid, hydrohalic acid, phosphoric acid, hexafluorophosphoric acid and perchloric acid are preferred, and chlorine anions are more preferred. Regarding the synthesis of the salt of the phosphazenium cation represented by the chemical formula (1) and the inorganic anion of the present invention, the following method is mentioned as a general example. (A) One equivalent and three equivalents of a disubstituted amine (HN
R ₂ ) and 1 equivalent of ammonia, and then treated with a base to give a compound of the formula (3)

[0013]

Embedded image 2,2,2-tris (disubstituted amino) -2λ represented by
Synthesize ⁵ -phosphazene. (B) This phosphazene compound (chemical formula (3)) and bis (disubstituted amino) phosphorochloridate {(R
₂ N) of ₂ P (O) a Cl} are reacted to obtain bis (disubstituted amino) tris (disubstituted amino) phosphoranylideneamino Rani isopropylidene-amino phosphine oxide was chlorinated with phosphorus oxychloride, then reacting this with ammonia After treatment with a base, the compound of formula (4)

[0014]

Embedded image To obtain 2,2,4,4-pentakis (disubstituted amino) -2λ ⁵ , 4λ ⁵ -phosphazene. (C) The phosphazene compound (chemical formula (4)) is used in place of the phosphazene compound (chemical formula 3) used in (b) and reacted by the same operation as in (b) to obtain a compound of formula (5)

[0015]

Embedded image (In the formula, q represents an integer of 0 and 1 to 3. When q is 0, it is a disubstituted amine, when 1 is a compound of formula (3), when 2 is 2, a compound of formula (4) and In the case of 3, the oligophosphazene in which q is 3 among the compounds represented by (c) represents the oligophosphazene obtained in (c). (D) reacting the compounds of formula (5) of different q and / or R sequentially or simultaneously with the same compounds of formula (5) of the same q and R with phosphorus pentachloride in 4 equivalents to obtain the compound of formula (1) r = 1, in) T ^r- = Cl ^- salt with the desired phosphazenium cation and chlorine anion is obtained. When it is desired to obtain a salt of an inorganic anion other than a chloride anion, ion exchange is performed by a usual method, for example, a method of treating with a salt of an alkali metal cation and a desired inorganic anion or a method of using an ion exchange resin. be able to. Thus, a salt of a general phosphazenium cation represented by the chemical formula (1) and an inorganic anion is obtained.

The alkali metal or alkaline earth metal salt of the active hydrogen compound coexisted with the chemical formula (1) is that the active hydrogen of the active hydrogen compound dissociates as a hydrogen ion and is replaced by an alkali metal or alkaline earth metal ion. It is a salt in the form. Active hydrogen compounds that give such salts include alcohols, phenol compounds,
Examples include polyamines and alkanolamines. For example, methanol, ethanol, monohydric alcohols such as butanol, water, ethylene glycol, diethylene glycol,
Propylene glycol, dipropylene glycol, 1,
3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, dihydric alcohols such as 1,4-cyclohexanediol, monoethanolamine, Alkanolamines such as diethanolamine and triethanolamine, polyhydric alcohols such as glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol, glucose, sorbitol, dextrose, fructose, sucrose, methyl glucoside, etc. Saccharides or derivatives thereof, fatty acid amines such as ethylenediamine, di (2-aminoethyl) amine, hexamethylenediamine, and aromatic amines such as toluylenediamine and diphenylmethanediamine , Bisphenol A, bisphenol F, bisphenol S, novolak, resol, phenolic compounds such as resorcinol and the like. These active hydrogen compounds can be used in combination of two or more. Further, an alkylene oxide is added to these active hydrogen compounds by a conventionally known method in an amount of about 2 per equivalent of active hydrogen groups.
A compound obtained by addition polymerization of ８8 mol can also be used.

In order to obtain an alkali metal or alkaline earth metal salt thereof from these active hydrogen compounds, the active hydrogen compound and a metal selected from alkali metals or alkaline earth metals or a basic alkali metal or A usual method of reacting with a compound of an alkaline earth metal is used. Examples of the metal selected from alkali metals or alkaline earth metals include lithium metal, sodium metal, potassium metal, cesium metal, rubidium metal, magnesium metal, calcium metal, strontium metal, and metal barium, and the like. As the alkali metal or alkaline earth metal compound,
Amides of alkali metals or alkaline earth metals such as sodium amide, potassium amide, magnesium amide or barium amide; n-propyl lithium, n-butyl lithium, vinyl lithium, cyclopentadienyl lithium, ethynyl sodium, n- Butyl sodium, phenyl sodium, cyclopentadienyl sodium, ethyl potassium, cyclopentadienyl potassium, phenyl potassium, benzyl potassium, diethyl magnesium, ethyl isopropyl magnesium,
Organic alkalis such as di-n-butylmagnesium, di-tert-butylmagnesium, vinylmagnesium bromide, phenylmagnesium bromide, dicyclopentadienylmagnesium, dimethylcalcium, potassium acetylide, ethylstrontium bromide, and phenylbarium iodide A metal or alkaline earth metal compound, sodium hydride, potassium hydride, a hydride compound of an alkali metal or alkaline earth metal such as calcium hydride, sodium hydroxide, potassium hydroxide,
Lithium hydroxide, rubidium hydroxide, cesium hydroxide,
Magnesium hydroxide, calcium hydroxide, alkali metal or alkaline earth metal hydroxides such as strontium hydroxide or barium hydroxide, lithium carbonate,
Alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate and barium carbonate, and hydrogencarbonate such as potassium hydrogencarbonate, sodium hydrogencarbonate and cesium hydrogencarbonate Salt and the like.

A metal selected from these alkali metals or alkaline earth metals or a compound of a basic alkali metal or alkaline earth metal is selected according to the acidity of the active hydrogen compound. The alkali metal or alkaline earth metal salt of the active hydrogen compound thus obtained acts as a basic alkali metal or alkaline earth metal compound, and the other active hydrogen compound is converted to the alkali metal or alkaline earth metal. In some cases, it can be converted into a salt of a class of metals.

In an active hydrogen compound having a plurality of active hydrogens, all of the active hydrogens are eliminated to form a metal selected from alkali metals or alkaline earth metals or a basic alkali metal or alkaline earth metal. In some cases, the compound leads to an anion, but in some cases, only a part of the compound is eliminated to become an anion. Of these alkali metal or alkaline earth metal salts of active hydrogen compounds, alkali metal salts of active hydrogen compounds are preferred, and the cation of the alkali metal salt of the active hydrogen compound is lithium, sodium, potassium, rubidium or cesium. The cation chosen is more preferred.

The alkylene oxide is subjected to addition polymerization in the presence of a salt of a phosphazenium cation represented by the chemical formula (1) and an inorganic anion and an alkali metal or alkaline earth metal salt of an active hydrogen compound. At this time, a salt of a cation of an alkali metal or an alkaline earth metal and an inorganic anion is by-produced. If the by-product salt inhibits the polymerization reaction, the salt is removed by a method such as filtration prior to the polymerization reaction. You can keep it. Further, a phosphazenium salt of an active hydrogen compound derived from a salt represented by the chemical formula (1) and an alkali metal or alkaline earth metal salt of the active hydrogen compound is previously isolated, and the alkylene oxide is polymerized in the presence of the phosphazenium salt. You can also.

As a method for previously obtaining the phosphazenium salt of the active hydrogen compound, a salt represented by the chemical formula (1) is reacted with an alkali metal or alkaline earth metal salt of the active hydrogen compound. The use ratio of the salt is not particularly limited as long as the desired salt is formed, and there is no particular problem even if any salt is excessive. Usually, the amount of the alkali metal or alkaline earth metal salt of the active hydrogen compound to be used is 0.2 to 5 equivalents, preferably 0 to 1 equivalent of the salt of the phosphazenium cation and the inorganic anion. 0.5 to 3 equivalents, more preferably 0.7 to
It is in the range of 1.5 equivalents.

It is also possible to use a solvent to make the contact between them effective. Any solvent may be used as long as it does not inhibit the reaction. Examples thereof include water, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, n-pentane, n-hexane and cyclohexane. Aliphatic or aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as dichloromethane, chloroform, bromoform, carbon tetrachloride, dichloroethane, orthodichlorobenzene, ethyl acetate, methyl propionate or benzoic acid Esters such as methyl, diethyl ether, tetrahydrofuran,
Ethers such as 1,4-dioxane, ethylene glycol dimethyl ether or triethylene glycol dimethyl ether, nitriles such as acetonitrile or propionitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide or 1,3 Polar aprotic solvents such as -dimethyl-2-imidazolidinone. These solvents are selected depending on the chemical stability of the raw material salt used in the reaction. Preferably, aromatic hydrocarbons such as benzene, toluene or xylene, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane or ethylene glycol dimethyl ether, nitriles such as acetonitrile, N, N -Dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide or 1,3-dimethyl-
Polar aprotic solvents such as 2-imidazolidinone; The solvents may be used alone or in combination of two or more. It is preferable that the raw material salt is dissolved, but it may be in a suspended state. The temperature of this reaction is not uniform depending on the kind, amount and concentration of the salt used, but is usually 150 ° C. or lower, preferably −78 to 80 ° C., more preferably 0 ° C.
~ 50 ° C. The reaction pressure can be reduced, normal pressure or increased pressure, preferably 0.1 to 10 k
gf / cm ² (absolute pressure, the same applies hereinafter to 9.8 to 980 kP
a), more preferably 1 to 3 kgf / cm ² (9
8 to 294 kPa). The reaction time is usually 1
Minutes to 24 hours, preferably 1 minute to 10 hours, more preferably 5 minutes to 6 hours.

When isolating the target phosphazenium salt of the active hydrogen compound from the reaction solution, a conventional method combining conventional means is used. The method is not uniform depending on the type of the target salt, the type and excess ratio of the salt of the two raw materials used, the type and amount of the solvent used, and the like. Usually, the by-product salt of an alkali metal or alkaline earth metal cation and an inorganic anion is precipitated as a solid, so it is used as it is or after a slight concentration, and then subjected to solid-liquid separation by filtration or centrifugation. Then, this is removed, and the liquid is concentrated to dryness to obtain a target salt. If the by-produced salt is still dissolved after concentration, a poor solvent is added as it is or after concentration to precipitate either the by-produced salt or the target salt, or after concentration to dryness, one is extracted. It can be separated by such a method. When the salt of the raw material used in excess is mixed in a large amount with the target salt, the salt can be extracted as it is or after redissolution with another suitable solvent, and separated. Further, if necessary, it can be purified by recrystallization or column chromatography. The desired salt is usually obtained as a high viscosity liquid or solid.

The alkylene oxide is subjected to addition polymerization in the presence of a salt of a phosphazenium cation represented by the chemical formula (1) and an inorganic anion and an alkali metal or alkaline earth metal salt of an active hydrogen compound. At this time,
An active hydrogen compound of the same or different type as the active hydrogen compound constituting the alkali metal or alkaline earth metal salt of the active hydrogen compound or the phosphazenium salt of the active hydrogen compound derived therefrom may be present in the reaction system. When the salt is present, the amount thereof is not particularly limited, but is 1 × 10 ^{−15 to} 5 × 1 with respect to 1 mol of the alkylene oxide.
0 ^-1 mol, preferably in the range of 1 × 10 ^-7 to 1 × 10 ^-1 mol.

In another case of the method for producing the polyoxyalkylene polyol of the present invention, that is, the chemical formula (2)
The case where a polyoxyalkylene polyol is produced by addition-polymerizing an alkylene oxide in the presence of a phosphazenium compound represented by and an active hydrogen compound will be described. Q ⁻ in the phosphazenium compound represented by the chemical formula (2) is a hydroxy anion, an alkoxy anion,
An anion selected from the group consisting of an aryloxy anion and a carboxy anion.

[0026] These Q ^- of, preferably, hydroxy anions, such as methanol, ethanol,
An alkoxy anion derived from an aliphatic alcohol such as n-propanol and isopropanol, for example, an aryloxy anion derived from an aromatic hydroxy compound such as phenol and cresol, and a carboxy derived from formic acid, acetic acid, propionic acid, etc. Is an anion.

Of these, hydroxy anions such as alkoxy anions derived from low boiling alkyl alcohols such as methanol, ethanol and n-propanol, and carboxy anions derived from carboxylic acids such as formic acid and acetic acid are more preferred. More preferred are a hydroxy anion, a methoxy anion, an ethoxy anion and an acetate anion. These phosphazenium compounds may be used alone or as a mixture of two or more.

As a general method for synthesizing the phosphazenium compound represented by the chemical formula (2), first, in the same manner as the method for synthesizing the salt represented by the chemical formula (1), r = 1 in the chemical formula (1) , A phosphazenium chloride wherein T ^r− = Cl ⁻ is synthesized. Then, the phosphazenium chloride is treated with a hydroxide, alkoxide, aryloxide or carboxide of, for example, an alkali metal or an alkaline earth metal, or a method using an ion exchange resin to convert the chloride anion into the desired anion Q. ^-
Can be replaced by Thus, a general phosphazenium compound represented by the chemical formula (2) is obtained.

The active hydrogen compound coexisting with the chemical formula (2) is the same as described in detail above as the active hydrogen compound which gives a salt of an alkali metal or an alkaline earth metal of the active hydrogen compound.

In the method of the present invention in which an alkylene oxide is addition-polymerized in the presence of a phosphazenium compound represented by the chemical formula (2) and an active hydrogen compound, the excess amount of the active hydrogen compound which is usually used in excess remains as it is. In addition, water, alcohol, aromatic hydroxy compound or carboxylic acid is by-produced depending on the type of phosphazenium compound. If necessary, these by-products are removed prior to the addition polymerization reaction of the alkylene oxide. Depending on the physical properties of these by-products, conventional methods such as a method of distilling off by heating or reduced pressure, a method of passing an inert gas, and a method of using an adsorbent are used.

The alkylene oxide to be addition-polymerized to an active hydrogen compound in the presence of a phosphazenium compound includes propylene oxide, ethylene oxide,
2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide,
Epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether and the like can be mentioned. These may be used in combination of two or more. Of these, propylene oxide, 1,2-butylene oxide and ethylene oxide are preferred. Particularly preferred are propylene oxide and ethylene oxide.

In the production of the crude polyoxyalkylene polyol in the present invention, the following conditions need to be selected. That is, the phosphazenium compound represented by the chemical formula (1) or (2) per mol of the active hydrogen compound is 5 × 10 ^{−5 to} 5 mol, preferably 1 × 10 ⁻⁵ mol.
^{-4 to} 5 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 ×
It is in the range of 10 ^-2 mol. When increasing the molecular weight of the polyoxyalkylene polyol, it is preferable to increase the concentration of the phosphazenium compound relative to the active hydrogen compound within the above range. When the amount of the phosphazenium compound represented by the chemical formula (1) or the chemical formula (2) is lower than 5 × 10 ⁻⁵ mol per mol of the active hydrogen compound, the polymerization rate of the alkylene oxide decreases, and Manufacturing time is longer. When the amount of the phosphazenium compound represented by the chemical formula (1) or the formula (2) is more than 5 mol per 1 mol of the active hydrogen compound, the viscosity of the mixture of the active hydrogen compound and the phosphazenium compound increases, and stirring and mixing becomes difficult. Become.

The reaction temperature of the alkylene oxide is in the range of 15 to 130 ° C., preferably 40 to 120 ° C., more preferably 50 to 110 ° C. When the reaction temperature of the alkylene oxide is lower than the above range, the concentration of the phosphazenium compound with respect to the active hydrogen compound is preferably increased within the range described above. A method for supplying an alkylene oxide to an active hydrogen compound catalyzed by a phosphazenium compound charged in a pressure-resistant reactor,
A method in which a required amount of alkylene oxide is partially supplied, or a method in which alkylene oxide is supplied continuously or intermittently is used. In the method of supplying a part of the required amount of alkylene oxide in a lump, a method in which the reaction temperature at the beginning of the alkylene oxide polymerization reaction is set to a lower temperature within the above range and the reaction temperature is gradually increased after charging the alkylene oxide is preferable. . When the reaction temperature is lower than 15 ° C., the polymerization rate of the alkylene oxide decreases, and the production time of the polyoxyalkylene polyol increases. When the reaction temperature exceeds 130 ° C., when propylene oxide is used as the alkylene oxide, the content of by-product monols increases.

The maximum pressure during the reaction of the alkylene oxide is preferably 9 kgf / cm ² (882 kPa, absolute pressure, the same applies hereinafter). Usually, the reaction of alkylene oxide is carried out by a pressure-resistant reactor. The reaction of the alkylene oxide may be started from a reduced pressure state or from an atmospheric pressure state. When starting the reaction from atmospheric pressure,
It is desirable to carry out the reaction in the presence of an inert gas such as nitrogen or helium. Maximum reaction pressure of alkylene oxide is 9k
If it exceeds gf / cm ² (882 kPa), the amount of by-product monol increases. Preferably 7 kg as maximum reaction pressure
f / cm ² (686 kPa), more preferably 5 kgf
/ Cm ² (490 kPa). When propylene oxide is used as the alkylene oxide, the maximum reaction pressure is preferably 5 kgf / cm ² (490 kPa).

In the alkylene oxide addition polymerization reaction, a solvent can be used if necessary. Examples of the solvent to be used include aliphatic hydrocarbons such as pentane, hexane and peptane, ethers such as diethyl ether, tetrahydrofuran and dioxane, and aprotic polar solvents such as dimethyl sulfoxide and N, N-dimethylformamide. And so on. When a solvent is used, a method of collecting and reusing the solvent after the production is desirable in order not to increase the production cost of the polyoxyalkylene polyol.

Next, step 2 will be described. As a method for neutralizing the crude polyoxyalkylene polyol, 40
The reaction is carried out by adding at least one neutralizing agent selected from water, an inorganic acid or an organic acid at a temperature of up to 120 ° C. As the water, city water, ion-exchanged water, distilled water or the like is used according to the purpose. The addition amount is 1 to 40 parts by weight based on 100 parts by weight of the crude polyoxyalkylene polyol. Preferably 1 to 30 parts by weight, more preferably 1.2 parts by weight.
-20 parts by weight.

At this time, an organic solvent inert to the polyoxyalkylene polyol can be used together with water. The organic solvent inert to the polyoxyalkylene polyol includes, among hydrocarbon solvents, toluene, hexanes, pentanes, heptanes, butanes, lower alcohols, cyclohexane, cyclopentane, xylenes and the like. In order to evaporate these organic solvents from the polyoxyalkylene polyol, a method of performing heating and decompression operations may be used. The temperature is 100 ~ 140 ℃ and the degree of decompression is 10mmHg
abs. (1330 Pa) or less.

As the acid for neutralizing the phosphazenium compound, an inorganic acid or an organic acid is used. Examples of the inorganic acid include phosphoric acid, phosphorous acid, hydrochloric acid, sulfuric acid, sulfurous acid, and aqueous solutions thereof. As organic acids, for example, formic acid, oxalic acid, succinic acid, acetic acid, maleic acid,
Examples include phthalic acid, salicylic acid, malic acid and aqueous solutions thereof. Particularly preferably, phosphoric acid, hydrochloric acid, sulfuric acid,
Maleic acid and oxalic acid are preferably used in the form of an aqueous solution. These neutralizing agents can be used alone or in combination of two or more kinds. The amount of the neutralizing agent is 0.5 to 2 to 1 mol per 1 mol of the phosphazenium compound contained in the crude polyoxyalkylene polyol. 5 moles.
Preferably, it is 0.7 to 2.4 mol, more preferably 0.1 mol.
9 to 2.3 mol. The neutralization time is 0.5 to 3 hours, depending on the reaction scale.

After the above-described neutralization treatment, the polyoxyalkylene polyol can be purified using an adsorbent, depending on the purpose. The amount of the adsorbent that adsorbs the acid and alkali components is 0.005 to 1.5 parts by weight based on 100 parts by weight of the crude polyoxyalkylene polyol. Preferably, it is 0.02 to 1.2 parts by weight, more preferably 0.03 to 1.1 parts by weight. As the adsorbent, for example, synthetic magnesium silicate, synthetic aluminum silicate, activated clay, and acid clay are used. Since the treatment with sodium hydroxide is performed in the step of producing the adsorbent, an adsorbent with a small sodium elution content is preferable. Specific adsorbents include Tomix AD-60
0, Tomix AD-700 (manufactured by Tomita Pharmaceutical Co., Ltd.), Kyoward 400, Kyoward 500, Kyoward 600, Kyoward 700 (Kyowa Chemical Industry Co., Ltd.)
It is marketed under various trade names. Further, after neutralization treatment, t-butylhydroxytoluene (B
It is preferable to add an antioxidant such as HT). The antioxidant is crude polyoxyalkylene polyol 100
It is used in an amount of 200 to 5000 ppm based on the weight. Preferably 300 to 4000 ppm, more preferably 350 to
2000 ppm.

Step 3 will be described. After charging the adsorbent, water or water and the organic solvent are distilled off under reduced pressure. 100-140 ° C, 10mmH, depending on reaction scale
gabs. (1330 Pa) for 3 to 12 hours. Thereafter, the phosphazenium salt is recovered from the polyoxyalkylene polyol by a filtration operation, a centrifugation operation, or the like.

However, a small amount of polyoxyalkylene polyol is usually attached to this phosphazenium salt. In order to further enhance the recovery efficiency of the phosphazenium salt, a mixture of water and an organic solvent which is a poor solvent for the phosphazenium salt is added to the phosphazenium salt obtained by separation, and
After stirring and mixing at 0 to 100 ° C., it is preferable to carry out stationary liquid separation. After liquid separation into a polyoxyalkylene polyol phase and a phosphazenium salt aqueous solution phase, the phosphazenium salt aqueous solution phase is separated and concentrated or dehydrated to a desired concentration. In this case, examples of the organic solvent used as the poor solvent for the phosphazenium salt include aliphatic hydrocarbons such as pentane, hexane, octane, and cyclohexane, and ethers such as diethyl ether, dibutyl ether, dipropyl ether, and diisopropyl ether. be able to. Particularly preferred are diethyl ether and hexane.

Further, by mixing and using the polyoxyalkylene polyol phase separated by the above-mentioned method with the crude polyoxyalkylene polyol or the like after polymerization, the loss in the polyoxyalkylene polyol purification step is also reduced.

Step 4 and the subsequent steps 6 and 8 relate to a method for polymerizing a polyoxyalkylene polyol, and these steps are carried out in accordance with the method of step 1 described above.

Subsequently, steps 5 and 7 will be described. A method for recovering a phosphazenium salt by a water washing process will be described. Crude polyoxyalkylene polyol 100
10 to 300 parts by weight of water or a mixture of water and an organic solvent is added to 10 parts by weight of
After mixing and stirring at ° C, the mixture is separated into a polyoxyalkylene polyol phase and an aqueous phosphazenium salt phase. The aqueous phase of the phosphazenium salt is separated and concentrated or dehydrated to a desired concentration. The liquid separation time is 2 to 30 hours. In order to increase the efficiency of recovering the phosphazenium salt from the crude polyoxyalkylene polyol, washing with water is usually performed 2 to 5 times, depending on the separation scale. Further, the crude polyoxyalkylene polyol to be subjected to the water washing treatment is preferably a polyoxyalkylene polyol composed of a monomer other than ethylene oxide which becomes a hydrophilic group. When a crude polyoxyalkylene polyol having a high ethylene oxide content is subjected to a water-washing treatment, the polyoxyalkylene polyol may be in a gel state due to a chemical bond between water and a hydrophilic group comprising an ethylene oxide unit. Recovery efficiency is reduced.

The steps of the fourth and fifth objects of the present invention will be described. The phosphazenium salt recovered by the neutralizing agent described in detail above and the phosphazenium salt recovered by the water washing treatment were adjusted to an aqueous solution, and the phosphazenium hydroxide anion-exchanged with the OH-type anion exchange resin was again used as a polyoxyalkylene polyol. Can be used as a polymerization catalyst. The concentration of the recovered aqueous solution of phosphazenium salt is not particularly limited, but usually about 0.01 to 50% by weight is preferably used. The use of a phosphazenium salt aqueous solution outside this concentration range does not impair the gist of the present invention.

As the anion exchange resin used in the present invention, those having a structure having a quaternary ammonium salt compound in the side chain as an ion exchange group using a styrene-divinylbenzene copolymer as a carrier are preferably used. In addition, both the gel type and the macroporous type can be used in the present invention. This type of ion exchange resin is available from Levatit MP500, M500 and M50.
4. MP600, MP500A (above, manufactured by Bayer), Diaion PA406, PA408, PA
412 (Mitsubishi Chemical Corporation), Amberlite IRA
430, IRA458 and IRA900 (both manufactured by Rohm and Haas Co.). These anion exchange resins are used after a part or all of them are converted to an OH type as a counter anion of a quaternary ammonium cation by a conventionally known method. Alternatively, an anion exchange resin that has already been converted to the OH form can be purchased and used. The operating temperature of the ion exchange resin is
Although not particularly limited, usually, 10 to 120 ° C
Is preferably used.

The aqueous phosphazenium salt solution is ion-exchanged and converted into an aqueous phosphazenium hydroxide solution.
The aqueous solution of phosphazenium hydroxide can be used as it is or after being concentrated to a desired concentration, as a phosphazenium hydroxide catalyst in the polymerization of alkylene oxide. Before the addition polymerization of the alkylene oxide, water is preferably removed from the mixture of the active hydrogen compound and the aqueous solution of phosphazenium hydroxide by a method such as drying under reduced pressure. The conditions for the addition polymerization of the alkylene oxide and the amount of the phosphazenium compound used relative to the active hydrogen compound are preferably the same as those described in detail above. The aqueous solution of phosphazenium hydroxide can be dehydrated and used in the form of the above-mentioned polyoxyalkylene polyol in the form of solid phosphazenium hydroxide. The phosphazenium hydroxide catalyst thus recovered can be used again as a polyoxyalkylene polyol polymerization catalyst, and then recovered again and used repeatedly as a polyoxyalkylene polyol polymerization catalyst.

Next, the sixth and seventh objects of the present invention will be described. The phosphazenium salt recovered by the above-described neutralizing agent and the phosphazenium salt obtained by reacting the phosphazenium salt recovered by the water washing treatment with an alkali metal or alkaline earth metal hydroxide, alkoxide, aryl oxide or carboxide are also included. Again, it can be used as a polymerization catalyst for polyoxyalkylene polyols.

The alkali metal or alkaline earth metal hydroxide, alkoxide, aryl oxide or carboxide is preferably reacted in a range of 0.5 to 1.5 moles with respect to 1 mole of the recovered phosphazenium salt. . More preferably, the alkali metal or alkaline earth metal hydroxide, alkoxide, aryloxide or carboxide is in the range of 0.7 to 1.4 moles per mole of the recovered phosphazenium salt, and most preferably the recovered metal salt is an alkali metal or alkaline earth metal hydroxide. 0.1 mol per 1 mol of the phosphazenium salt.
It is in the range of 8 to 1.2 mol.

The compounds exemplified above as alkali metals or alkaline earth metals and their hydroxides can be used. Examples of the alkoxy anion of the compound used as an alkoxide of an alkali metal or an alkaline earth metal include methanol, ethanol, n-
It is an alkoxy anion derived from aliphatic alcohols such as propanol and isopropanol. The aryloxy anion anion of the compound used as the alkali metal or alkaline earth metal aryl oxide is, for example, an aryloxy anion derived from an aromatic hydroxy compound such as phenol or cresol; Examples of the carboxy anion of the compound used as a compound include a carboxy anion derived from formic acid, acetic acid, propionic acid, and the like. Among these, an alkoxy anion derived from a low-boiling alkyl alcohol such as methanol, ethanol or n-propanol, or a carboxy anion derived from a carboxylic acid such as formic acid or acetic acid is more preferable. More preferred are methoxy anion, ethoxy anion and acetate anion. These alkali metal or alkaline earth metal alkoxides, aryl oxides or carboxides may be used alone or as a mixture of two or more.

It is also possible to use a solvent to effect the contact between the recovered phosphazenium salt and the alkali metal or alkaline earth metal alkoxide, aryloxide or carboxide. Any solvent may be used as long as it does not inhibit the reaction.Examples include water, alcohols such as methanol, ethanol or propanol, ketones such as acetone or methyl ethyl ketone, n-pentane, n-hexane, and the like.
Aliphatic or aromatic hydrocarbons such as cyclohexane, benzene, toluene or xylene, dichloromethane,
Halogenated hydrocarbons such as chloroform, bromoform, carbon tetrachloride, dichloroethane, orthodichlorobenzene, esters such as ethyl acetate, methyl propionate or methyl benzoate, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether Or, ethers such as triethylene glycol dimethyl ether, nitriles such as acetonitrile or propionitrile, and polar aprotic solvents such as N, N-dimethylformamide, dimethylsulfoxide, and sulfolane. These solvents are selected depending on the chemical stability of the raw material salt used in the reaction. Preferably, aromatic hydrocarbons such as benzene, toluene or xylene, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane or ethylene glycol dimethyl ether, nitriles such as acetonitrile, N, N -Dimethylformamide,
Polar aprotic solvents such as dimethyl sulfoxide and sulfolane; The solvents may be used alone or in combination of two or more. It is preferable that the raw material salt is dissolved, but it may be in a suspended state. The temperature of this reaction is not uniform depending on the type, amount and concentration of the salt used, but it is usually 1
50 ° C. or lower, preferably −78 to 80 ° C., more preferably 0 to 50 ° C. The reaction can be carried out under reduced pressure, normal pressure or increased pressure.
1 to 10 kgf / cm ² (absolute pressure, hereinafter 9.8 to 9
80 kPa), more preferably 1-3 kgf / c
m ² (98 to 294 kPa). The reaction time is generally in the range of 1 minute to 24 hours, preferably 1 minute to 10 hours, more preferably 5 minutes to 6 hours. These solvents may be removed and used by a method such as drying under reduced pressure before the alkylene oxide addition polymerization. The conditions for the addition polymerization of the alkylene oxide and the amount of the phosphazenium compound used relative to the active hydrogen compound are preferably the same as those described in detail above. The phosphazenium compound catalyst comprising an alkali metal or alkaline earth metal alkoxide, aryl oxide or carboxide thus recovered is used as a polyoxyalkylene polyol polymerization catalyst, then recovered again and repeatedly used as a polyoxyalkylene polyol polymerization catalyst. can do.

In the production of the polyoxyalkylene polyol in the present invention, a phosphazenium compound which is a polyoxyalkylene polyol polymerization catalyst already used through a recovery step can be used. Furthermore, phosphazenium salts recovered from crude polyoxyalkylene polyols can be used as catalysts to polymerize ring-opening polymerizable monomers other than alkylene oxide, such as lactones, lactams, and siloxanes.

[0053]

EXAMPLES Examples of the present invention will be shown below to clarify aspects of the present invention, but the present invention is not limited to these examples.

The hydroxyl value, the total unsaturation and the viscosity of the polyoxyalkylene polyol of the examples are in accordance with JIS K 1557.
It was determined by the method described. Hydroxyl value (abbreviated as OHV: unit mgKOH / g);
The hydroxyl group terminal of the polyoxyalkylene polyol is esterified with a pyridine solution of phthalic anhydride, and excess phthalic anhydride is titrated with a sodium hydroxide solution (JIS K).
1557). Viscosity (abbreviated as η: unit mPa · s / 25 ° C.); measured value at 25 ° C. using a rotational viscometer (JIS K155)
7). Total unsaturation (abbreviated as C = C: unit meq./g);
The unsaturated bond in the polyoxyalkylene polyol is reacted with mercuric acetate, and liberated acetic acid is titrated with a potassium hydroxide solution.

In the synthesis of the polyoxyalkylene polyol, the following phosphazenium compounds were used as alkylene oxide catalysts. Phosphazenium compound a (hereinafter, abbreviated as P5NMe2Cl.); Fluka Co. tetrakis [tris (dimethylamino) phosphoranylideneamino Rani isopropylidene amino] phosphonium chloride _{{[(Me 2 N) 3} P = N] 4 P + C
l ^-}. In the chemical formula (1), the phosphazenium compound is (1,1,1,1) in the order of a, b, c, and d, where R is a methyl group and r is a chlorine anion having 1 (T = C
l). Phosphazenium compound b (. Hereinafter abbreviated as P5NMe2OH); Fluka Co. tetrakis [tris (dimethylamino) phosphoranylideneamino Rani isopropylidene amino] phosphonium chloride _{{[(Me 2 N) 3} P = N] 4 P + Cl -}
Was prepared into a 2.5% by weight aqueous solution using water (hereinafter, abbreviated as ultrapure water) whose specific resistance was adjusted to 16 MΩ-cm by MILL-QLobo (small ultrapure water device manufactured by Nippon Millipore Limited). . Then, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium was placed in a polycarbonate cylindrical column packed with an ion exchange resin Levatit MP-500 (manufactured by Bayer) whose exchange group was changed to a hydroxyl group with a 1N aqueous sodium hydroxide solution. 2.5% by weight aqueous solution of chloride at 23 ° C., SV
(Space Velocity) 0.5 (1 / hr)
Then, the solution was passed through the column from the bottom at an ascending flow, and ion exchange was performed with tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide. Further, ultrapure water was passed through the column filled with the ion exchange resin, and the phosphazenium compound remaining in the column was recovered. Thereafter, an aqueous solution of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide was heated at 80 ° C. under a reduced pressure of 60 mmHgabs. (798
0 Pa) for 2 hours, further at 80 ° C., 1 mmHga
bs. (133 Pa) for 7 hours under reduced pressure to obtain powdered tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me ₂ N) ₃ P = N] ₄ P ⁺ OH ^- to obtain a}. The yield determined from the weight measurement of the compound after drying was 97.
%Met. The chemical shift of ¹ H-NMR (400 MHz NMR manufactured by JEOL) using tetramethylsilane as an internal standard in deuterated dimethylformamide solution is 2.6 ppm.
(D, J = 9.9 Hz, 72H). Elemental analysis: C 38.28, H 9.82, N 29.43, P
19.94 (theoretical C 38.09, H 9.72,
N 29.61, P 20.46). The phosphazenium compound is represented by a, b, c,
In the order of d, (1,1,1,1), R is a methyl group,
Q ⁻ is a hydroxy anion of OH ⁻ .

Further, potassium hydroxide manufactured by Wako Pure Chemical Industries, Ltd. was used as an alkali metal in order to derive an alkali metal salt of an active hydrogen compound. When using potassium hydroxide, ion-exchanged water was used as a diluent in the form of a 50% by weight aqueous solution. Hereinafter, potassium hydroxide is abbreviated as KOH.

The synthesis results of the polyoxyalkylene polyol will be described below in detail. As a polyoxyalkylene polyol synthesizing apparatus, a pressure-resistant autoclave (manufactured by Nitto Kogaku Co., Ltd.) having a capacity of 2.5 L equipped with a stirrer, a thermometer, a pressure gauge, a nitrogen inlet and an alkylene oxide inlet as a monomer was used. Hereinafter, the synthesis device is abbreviated as an autoclave.

Example 1 Polyoxyalkylene polyol A 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
of a glycerin per mole of 0.0
6 mol of P5NMe2OH and 1 mol of toluene (special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.) were added, nitrogen was introduced through a capillary tube, and 105 ° C., 10 mmHgabs. (1330 Pa)
Thereafter, dehydration under reduced pressure and toluene removal for 4 hours were performed. Thereafter, the contents of the flask were charged into an autoclave, and after purging with nitrogen, the reaction temperature was raised to 80 ° C. from the atmospheric pressure, and the maximum pressure during the reaction was 4.0 kgf / cm ² (392).
kPa), the addition polymerization of propylene oxide was performed until the OHV reached 28.0 mgKOH / g. Subsequently, a gauge pressure of 1.2 kgf / cm ² (219
kPa), and OHV under the conditions of a reaction temperature of 100 ° C. and a maximum pressure during the reaction of 4 kgf / cm ² (392 kPa).
Addition polymerization of ethylene oxide was performed until the amount reached 24.0 mgKOH / g. When the internal pressure of the autoclave is no longer changed, 105 ° C., 5 mmHgabs. (665
Pa) for 30 minutes under reduced pressure to obtain a crude polyoxyalkylene polyol. Crude polyoxyalkylene polyol 100 containing phosphazenium compound
4 parts by weight of ion-exchanged water are added to 1 part by weight, and then 2.1 mol of hydrochloric acid (1% by weight) is added to 1 mol of the phosphazenium compound in the crude polyoxyalkylene polyol.
Of hydrochloric acid solution), and a neutralization reaction was performed at 85 ° C. for 3 hours. After the neutralization reaction, 1000 ppm of t-butylhydroxytoluene (BHT) was added to 100 parts by weight of the crude polyoxyalkylene polyol, and finally 105 ° C., 10 mmH
gabs. (1330 Pa) or less for 4 hours. Then, after reducing the pressure from nitrogen to a reduced pressure to the atmospheric pressure with nitrogen, filtration under reduced pressure is performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to collect the phosphazenium salt (hereinafter abbreviated as collected phosphazenium salt a). went. Fractionated polyoxyalkylene polyol 10
0.3 parts by weight of an adsorbent KW-300 (manufactured by Kyowa Chemical Industry) was added to 0 parts by weight, and the mixture was stirred at 80 ° C. for 4 hours. The adsorbent was filtered through a 5C filter paper manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol.
The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification treatment was 24.1 mgKOH / g, and the total unsaturation (C = C) was 0.019 meq. / G, viscosity (η) 114
It was 0 mPa · s / 25 ° C. 300 parts by weight of ion-exchanged water and 300 parts by weight of diethyl ether (special grade reagent, manufactured by Wako Pure Chemical Industries) were added to 10 parts by weight of the recovered phosphazenium a salt, and the mixture was stirred and then left at 25 ° C. for 12 hours to carry out liquid separation. Thereafter, the aqueous phase was separated, and the temperature was set to 105 ° C.
abs. (1330 Pa) or less, and dehydrated under reduced pressure for 4 hours. Next, a polyoxyalkylene polyol was synthesized using the recovered phosphazenium salt. In a 500 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 0.06 mol of KO per mol of glycerin was added.
H (aqueous solution at 50% by weight) was added, and nitrogen was introduced through a capillary tube at 110 ° C., 10 mmHgabs. (13
Dehydration under reduced pressure was performed under the conditions of 30 Pa) for 4 hours to prepare a potassium salt of glycerin (hereinafter abbreviated as Gly-K). Thereafter, 0.06 mol of the above-mentioned recovered phosphazenium salt was added to 1 mol of glycerin charged to prepare Gly-K, and the mixture was stirred at 50 ° C. for 2 hours with toluene in a nitrogen atmosphere. Vacuum filtration was performed using a 5C filter paper (retained particle size: 1 μm) manufactured by Co., Ltd. Then, at 105 ° C., 10 mmHgabs.
(1330 Pa) Thereafter, toluene was removed under reduced pressure under the conditions of 2 hours, and the compound after the reduced pressure treatment was charged into an autoclave, followed by purging with nitrogen. After the replacement with nitrogen, addition polymerization of propylene oxide and ethylene oxide was performed by the same method as described in detail above, and the phosphazenium compound was removed with hydrochloric acid. The resulting polyoxyalkylene polyol has a hydroxyl value (OHV) of 24.2 mgKOH / g and a total unsaturation (C = C) of 0.020 meq. / G and a viscosity (η) of 1150 mPa · s / 25 ° C., and have almost the same physical properties as the polyoxyalkylene polyol obtained by using the phosphazenium compound before recovery as a catalyst.

Example 2 Polyoxyalkylene polyol D 500 m equipped with a stirrer, nitrogen inlet tube and thermometer
Into a four-necked flask, 0.012 mol of P5NMe2OH and 0.1 mol of toluene were added to 1 mol of dipropylene glycol, and nitrogen was introduced through a capillary tube at 103 ° C. and 10 mmHgabs. (1330 Pa),
Under the conditions of 3 hours, dehydration under reduced pressure and toluene removal were performed. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen. (1330 Pa)
OHV is 1 at a reaction temperature of 80 ° C. and a maximum pressure during the reaction of 4 kgf / cm 2 (392 kPa).
Addition polymerization of propylene oxide was carried out until 8.5 mgKOH / g. When the internal pressure of the autoclave is no longer changed, 105 ° C., 5 mmHgabs. (665
Pa) for 40 minutes to obtain a crude polyoxyalkylene polyol. Crude polyoxyalkylene polyol 100 containing phosphazenium compound
150 parts by weight of ion-exchanged water was added to parts by weight of T.K. K. Homomixer (Model HV-M
The mixture was stirred at room temperature for 1 hour. Then, at 50 ° C, 10
The mixture was allowed to stand for a time, and liquid separation was performed. Thereafter, the aqueous phase was separated, and the crude polyoxyalkylene polyol 10 was further charged.
100 parts by weight of ion-exchanged water was added to 0 parts by weight, and the above operation was repeated twice. 105 ° C., 10 mmHg of water-containing polyoxyalkylene polyol
abs. (1330 Pa) for 1 hour, and then 700 ppm of BHT as an antioxidant was added to 100 parts by weight of the crude polyoxyalkylene polyol, and 105 ° C., 5 mmHgabs. (665P
a) Decompression treatment was performed for 3 hours. Collect the separated aqueous phase,
105 ° C., 5 mmHgabs. (665 Pa) The phosphazenium compound was recovered by performing a reduced pressure treatment for 5 hours under the following conditions (hereinafter, abbreviated as a recovered phosphazenium salt b). The hydroxyl value (OHV) of the polyoxyalkylene polyol after the phosphazenium compound removal operation is 18 .8
mgKOH / g, total unsaturation (C = C) 0.025me
q. / G, viscosity (η) was 1200 mPa · s / 25 ° C. Using the recovered phosphazenium salt b, synthesis of a polyoxyalkylene polyol and removal of the phosphazenium compound were carried out under the same conditions as described above. The resulting polyoxyalkylene polyol had a hydroxyl value (OHV) of 18.7 mgKOH / g and a total degree of unsaturation (C = C) of 0.027 meq. / G, viscosity (η) 125
It is 0 mPa · s / 25 ° C., and has almost the same physical properties as the polyoxyalkylene polyol obtained by using the phosphazenium compound before recovery as a catalyst.

Example 3 Polyoxyalkylene polyol C The recovered phosphazenium salt a obtained in Example 1 was prepared into a 2.5% by weight aqueous solution using ultrapure water. Then 1N
The exchange group is changed to hydroxyl group (OH) by aqueous sodium hydroxide solution.
A 2.5% by weight aqueous solution of the recovered phosphazenium salt was placed in a polycarbonate cylindrical column packed with a shaped ion exchange resin Levatit MP-500 (manufactured by Bayer).
5 ° C., SV (Space Velocity) 0.5
At (1 / hr), the solution was passed from the bottom of the column in ascending flow to perform ion exchange. Thereafter, the aqueous solution of the recovered phosphazenium ion-exchanged to OH groups is heated at 80 ° C. and at a reduced pressure of 60 mmH.
gabs. (7980 Pa) for 2 hours and then 8
0 ° C., 1 mmHgabs. (133 Pa), a phosphazenium hydroxide was obtained by performing dehydration under reduced pressure for 7 hours. The yield determined by weight measurement of the compound after drying was 95%. 0.0 per mole of glycerin
6 mol of the phosphazenium hydroxide and 1 mol of toluene (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) were added, nitrogen was introduced through a capillary tube, and 105 ° C., 10 mmHgabs. (1330
Pa) Thereafter, dehydration under reduced pressure and toluene removal for 4 hours were performed. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen.
0 ° C and the maximum pressure during the reaction is 4.0 kgf / cm
² OHV 28.0 mg KOH under the condition of (392 kPa)
/ G until propylene oxide was added. Subsequently, the gauge pressure is 1.2 kgf / cm with nitrogen.
² (219 kPa), and addition polymerization of ethylene oxide was carried out under the conditions of a reaction temperature of 100 ° C. and a maximum pressure during the reaction of 4 kgf / cm ² (392 kPa) until the OHV became 24.0 mgKOH / g. When the internal pressure of the autoclave is no longer changed, the temperature is 105 ° C and 5 mmHgab.
s. (665 Pa) for 30 minutes under reduced pressure to obtain a crude polyoxyalkylene polyol. 4 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyoxyalkylene polyol containing the phosphazenium compound, and then 2.1 mol of hydrochloric acid (1 mol per 1 mol of the phosphazenium compound in the crude polyoxyalkylene polyol) (1% by weight hydrochloric acid aqueous solution), and a neutralization reaction was performed at 85 ° C. for 3 hours. After the neutralization reaction is completed, 1000 ppm of t-butylhydroxytoluene (BHT) is added to 100 parts by weight of the crude polyoxyalkylene polyol, and 105 wt.
° C, 10 mmHgabs. (1330 Pa) or less for 4 hours. Then, after reducing the pressure to the atmospheric pressure with nitrogen, 5C manufactured by Advantech Toyo Co., Ltd.
Vacuum filtration was performed using filter paper (retained particle size: 1 μm) to purify the polyoxyalkylene polyol. The hydroxyl value (OHV) of the polyoxyalkylene polyol after the phosphazenium compound removal operation was 24.2 mgKOH / g, and the total degree of unsaturation (C = C) was 0.021 meq. / G and a viscosity (η) of 1170 mPa · s / 25 ° C., and have almost the same physical properties as the polyoxyalkylene polyol obtained by using the phosphazenium compound before recovery in Example 1 as a catalyst.

[0061]

According to the method of the present invention, it is possible to efficiently recover a phosphazenium compound from a crude polyoxyalkylene polyol using a phosphazenium compound as a catalyst. An excellent quality polyoxyalkylene polyol can be produced without impairing the properties of the alkylene polyol.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor: Sanji Takagi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Within Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor: Yasunori Hara 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Address: Mitsui Toatsu Chemical Co., Ltd. (72) Inventor: Saku Izugawa 2-1-1, Tango-dori, Minami-ku, Nagoya-shi, Aichi Prefecture: Mitsui Toatsu Chemical Co., Ltd.

Claims (10)

[Claims] (Step 1) (Step 1a) Chemical formula (1) (A, b, c and d in the chemical formula (1) are each 0
And a, b, c and d are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations;
^r- represents an inorganic anion having a valence of r. A) a process of producing a crude polyoxyalkylene polyol by addition-polymerizing an alkylene oxide in the presence of a salt of a phosphazenium cation and an inorganic anion represented by the formula) and an alkali metal or alkaline earth metal salt of an active hydrogen compound Or (Step 1b) Chemical Formula (2) (In the chemical formula (2), a, b, c and d are integers from 0 to 3, but all of a, b, c and d are not simultaneously 0. R is the same or different carbon number of 1 to 3. It is 10 hydrocarbon groups, and two Rs on the same nitrogen atom may combine with each other to form a ring structure, and Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion. A) a process of producing a crude polyoxyalkylene polyol by addition-polymerizing an alkylene oxide in the presence of a phosphazenium compound and an active hydrogen compound represented by (2), (Step 2) adding water to the crude polyoxyalkylene polyol obtained in Step 1; A neutralization step of adding at least one neutralizing agent selected from inorganic acids or organic acids, (Step 3) the liquid obtained in Step 2 is dehydrated and dried, A step of recovering a phosphazenium salt for separating a zenium salt and a polyoxyalkylene polyol, and (step 4) converting the alkylene oxide in the presence of the phosphazenium salt recovered in step 3 and an alkali metal or alkaline earth metal salt of an active hydrogen compound. A process for producing a polyoxyalkylene polyol, which comprises carrying out addition polymerization. 2. A phosphazenium in which water or water and an organic solvent are added to the crude polyoxyalkylene polyol obtained in the step 1a according to the step 1a, liquid separation is performed, an aqueous phase is separated, and water is removed. Salt recovery step, and (Step 6)
A process for producing a polyoxyalkylene polyol, wherein the alkylene oxide is addition-polymerized in the presence of the phosphazenium salt and the alkali metal or alkaline earth metal salt of the active hydrogen compound recovered in Step 5. A method for producing a polyoxyalkylene polyol. 3. A phosphazenium in which water or water and an organic solvent are added to the crude polyoxyalkylene polyol obtained in the step 1b according to the step 1b, liquid separation is performed, an aqueous phase is separated, and water is removed. Salt recovery step, and (Step 8)
A process for producing a polyoxyalkylene polyol, which comprises subjecting an alkylene oxide to addition polymerization in the presence of the phosphazenium compound and the active hydrogen compound recovered in Step 7. 4. The compound derived from the chemical formula (1) or (2) according to claim 1 by bringing the phosphazenium salt obtained in the step 3 according to claim 1 into contact with an OH type anion exchange resin as an aqueous solution. A method for producing a polyoxyalkylene polyol, comprising: after obtaining phosphazenium hydroxide, addition-polymerizing an alkylene oxide in the presence of the phosphazenium hydroxide and an active hydrogen compound. 5. The compound derived from the chemical formula (1) or (2) according to claim 1, wherein the phosphazenium salt obtained in the step 5 according to claim 2 is brought into contact with an OH type anion exchange resin as an aqueous solution. A method for producing a polyoxyalkylene polyol, comprising: after obtaining phosphazenium hydroxide, addition-polymerizing an alkylene oxide in the presence of the phosphazenium hydroxide and an active hydrogen compound. 6. A phosphazenium compound obtained by reacting the phosphazenium salt obtained in step 3 with an alkali metal or alkaline earth metal hydroxide, alkoxide, aryloxide or carboxide and an activity. A method for producing a polyoxyalkylene polyol, comprising subjecting an alkylene oxide to addition polymerization in the presence of a hydrogen compound. 7. A phosphazenium compound obtained by reacting the phosphazenium salt obtained in step 5 with an alkali metal or alkaline earth metal hydroxide, alkoxide, aryloxide or carboxide and an activity. A method for producing a polyoxyalkylene polyol, comprising subjecting an alkylene oxide to addition polymerization in the presence of a hydrogen compound. 8. A method for recovering a phosphazenium salt from a polyoxyalkylene polyol, comprising: (step 2) a neutralization step and (step 3) a recovery step according to claim 1. 9. A method for recovering a phosphazenium salt from a polyoxyalkylene polyol, comprising the step of recovering (step 5) according to claim 2. 10. A method for recovering a phosphazenium salt from a polyoxyalkylene polyol, comprising a recovery step according to claim 3 (step 7).