JP2000239374A - Production of polyalkylene oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply and efficiently obtain a polyalkylene oxide using a metal- free initiator which leaves no odor by addition polymerization of an alkylene oxide compound in the presence of phosphonium salt or the like. SOLUTION: This method is to produce a polyalkylene oxide by addition polymerization of an alkylene oxide compound (preferably ethylene oxide, propylene oxide or the like) in the presence of at least one type of quaternary phosphonium or ammonium salt shown by the formula R1 to R4 are each an aliphatic hydrocarbon, aromatic hydrocarbon or the like; A is N or phosphorus; [(R1)(R2)(R3)(R4)A+] is cation having a maximum electrostatic potential of 300 kJ/mol or less, determined by computational chemical procedure with OH- as the counteranion; Bn- is an anion derived from an activated hydrogen compound; and (n) is an integer}, preferably under the conditions of temperature: 50 to 120 deg.C, pressure: 1 to 10 kg/cm2 and reaction time: 0.5 to 24 hours. The activated hydrogen compound from which Bn- is derived is preferably water, a 1-20C alcohol or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyalkylene oxide. For more details, a counter anion OH ^- as, of values of computational chemically determined maximum electrostatic potential was the quaternary phosphonium cations and quaternary ammonium cations derived from cation and an active hydrogen compound comprising less 300 kJ / mol anion The present invention relates to a method for producing a polyalkylene oxide by polymerizing an alkylene oxide compound in the presence of a quaternary phosphonium salt or a quaternary ammonium salt. Polyalkylene oxide is an important polymer used as a raw material such as a polyurethane foam or an elastomer obtained by reacting with an organic polyisocyanate compound or a surfactant.

[0002]

2. Description of the Related Art A method of extracting a proton from an active hydrogen compound to an anion to obtain a salt with a counter cation has been well known for a long time, and various methods are used depending on the acidity of the active hydrogen compound. Have been. For example, carboxylic acids, nitroalkanes, alcohols or phenols can form salts relatively easily by reaction with alkali metal hydroxides and, in some cases, alkali metal carbonates, ketones, Alkyl nitriles, cyclopentadienes, amines, amides or imides are generally made into salts using alkali metals such as alkali metals, alkali metal hydrides, alkali metal amides or alkali metal alkyls or compounds thereof. It is a target. However, the salts obtained by these methods are:
It is a salt of an anion derived from an active hydrogen compound and an alkali metal cation. In order to make the reactivity of the anion of the active hydrogen compound effective, it is necessary to dissolve the active hydrogen compound in a solvent. However, solvents capable of sufficiently dissolving such a salt having an alkali metal cation are extremely limited. Further, the reactivity of the anion may be greatly affected by the size of the cation as a counterpart, but when the cation is limited to an alkali metal cation, the size is also limited.

[0003] Alkali metal or alkaline earth metal hydroxides are also extremely important compounds in the field of organic reactions because of their basicity. When these hydroxides are used in an organic reaction, it is important to dissolve them in a solvent in order to make their effects more effective. However, although these hydroxides are water-soluble, they are poorly soluble in common organic solvents, and have an aspect unsuitable for organic reactions that dislike water.

[0004] Industrially conducting an organic reaction using a salt of an anion derived from an active hydrogen compound and an alkali metal cation or an alkali metal or alkaline earth metal hydroxide has the following problems. .

In producing a polyalkylene oxide by polymerization of an alkylene oxide compound, a combination of an active hydrogen compound such as a polyhydric alcohol and a basic alkali metal compound such as potassium hydroxide is used as an initiator system. Is the most common, and has been practically used industrially. However, a more efficient initiator system is desired from the viewpoints of polymerization activity and physical properties of the produced polymer. For other combinations of initiator systems,
In USP3,829,505, active hydrogen compounds and for example, using a _{Zn 3 [Fe (CN) 6} ] compound represented by ₂ · H ₂ O · dioxane, indicates that obtaining the polymer from propylene oxide And JP-A-2-276821
Discloses that a polyol prepared from a zinc hexacyanocobaltate complex is reacted with sodium methylate and then polymerized by ethylene oxide to obtain a polymer. Japanese Patent Application Laid-Open No. 62-232433 discloses that fumed silica hexane is used. This shows that ethylene oxide is polymerized using a product obtained by adding a hexane solution of diethyl zinc to a dispersion obtained by adding 1,4-butanediol and a nonionic surfactant to a slurry to obtain a polymer. ing. Each of these contains a special metal component, and if these metal components remain in the produced polyalkylene oxide, they may adversely affect the reaction during polyurethane production or the physical properties of the polyurethane. In the production of, a special method and a complicated process for sufficiently removing these metal components are required.
On the other hand, as an initiator system containing no metal, JP-A-50-1
No. 59595, a polymer thereof is obtained from ethylene oxide by a combination of an alkane polyol which is an active hydrogen compound and an ether adduct of boron trifluoride. However, it is also known that a unique impurity in the polymer adversely affects the physical properties of the polyurethane in the initiator system, and a complicated process is required to sufficiently remove the impurities. In JP-A-57-12026, a polymer of an alkylene oxide is obtained by using an alcohol and an aminophenol. In JP-A-56-38323, propylene oxide is polymerized by using sorbitol and tetramethylammonium hydroxide. I have. However, all of them have problems such as insufficient polymerization activity and residual amine odor.

Further, Japanese Patent Application Laid-Open No. 7-233111,
2-62814, JP-A-56-38322 and JP-A-5-58
6-38323 also discloses a quaternary ammonium salt compound as a polymerization catalyst for alkylene oxide.
However, although the patent describes the effectiveness as a catalyst, the counter anion species is limited, and furthermore, the standard of its catalytic performance was not clear.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to prepare a polyalkylene oxide by polymerizing an alkylene oxide compound without containing any special metal component or without any metal component. An object of the present invention is to provide a simple and efficient method for producing a polyalkylene oxide using an initiator system that does not leave odor.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, the general formula (1)
It has been found that the polymerization reaction of an alkylene oxide occurs efficiently by using at least one of the compounds represented by the following formulas, and the present invention has been completed. That is, the present invention
This is a method for producing a polyalkylene oxide shown in the following (1) to (3).

(1) General formula

Embedded image

(Wherein, R _{1 to} R ₄ are each independently an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group containing a hetero atom;
Is a nitrogen element or a phosphorus element, and [(R ₁ ) (R ₂ )
(R ₃ ) (R ₄ ) A ⁺ ] is a cation having a maximum anion potential of 300 kJ / mol or less, which is obtained by computational chemistry with the counter anion being OH ⁻ , and B ⁿ⁻ is derived from an active hydrogen compound. At least one selected from the group of anions to be added, and n is an integer. A process for producing a polyalkylene oxide, comprising subjecting an alkylene oxide compound to addition polymerization in the presence of at least one of a quaternary phosphonium salt or a quaternary ammonium salt represented by the formula (1).

(2) An active hydrogen compound from which B ^n- is derived is
Water, alcohols having 1 to 20 carbon atoms, polyhydric alcohols having 2 to 8 carbon atoms and having 2 to 8 hydroxyl groups, saccharides or derivatives thereof, having 2 to 8 terminal ends, and terminal ends thereof Polyalkylene oxides having a molecular weight of 100 or more and 50,000 or less having 1 to 8 hydroxyl groups, primary or secondary monoamines having 20 or less carbon atoms, and two to three primary amines having 2 to 20 carbon atoms Or a polyvalent amine having a secondary amino group, a saturated cyclic secondary amine having 4 to 20 carbon atoms, and a C4 or more 2
The process for producing a polyalkylene oxide according to (1), which is an active hydrogen compound selected from the group consisting of cyclic polyamines containing 2 or 3 secondary amino groups of 0 or less.

(3) The method for producing a polyalkylene oxide according to (1), wherein the alkylene oxide compound is a compound selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide.

[0013]

Quaternary phosphonium cation or quaternary ammonium cation constituting the quaternary phosphonium salt or a quaternary ammonium salt represented by the general formula (1) used in the present invention DETAILED DESCRIPTION OF THE INVENTION, the counter anion OH ^- calculated as It is a cation whose maximum electrostatic potential value obtained chemically is 300 kJ / mol or less. The calculation chemically determined maximum electrostatic potential were referred to in the present invention, the counter anion as OH ^- assuming, OH ^- and cations refer to electrostatic potential indicating the largest value in advance distances can approach stereoscopically. In the present invention, the electrostatic potential obtained by computational chemistry is calculated as the energy for a positive charge when a positive charge is arranged at a certain distance from a molecule of interest, and the MNDO Hamiltonian of the semi-empirical molecular orbital method Is a value obtained by using. Specifically, first, as the molecular structure of the cation, a structure optimized using the MNDO Hamiltonian of the semi-empirical molecular orbital method is used. When the electrostatic potential is determined, the electrostatic potential is determined at a rate of at least one point in every 0.05 angstrom square with respect to the space around the target cation molecule where the anion can be approached. Specifically, MOPAC9
After optimizing the structure using EF, GNORM = 0.5, LET, DDMIN = 0.0 using 3
ESP, POTWRT, SCALE = 1.8, SCINCR = 0.05, NSURF = 10 are used to calculate the electrostatic potential in a specific space.

Here, the counter anion referred to in the present invention is O
The maximum electrostatic potential of a cation calculated chemically as an H ^- ion is defined as the anion of OH as an anion with respect to the electrostatic potential at an arbitrary point determined by the molecular orbital calculation.
^- assuming, to calculate the distance between all of the atoms that constitute an arbitrary point and molecular distances of the atoms that constitute an arbitrary point and cationic molecules in all combinations constitute a Van der Waals radius and molecular oxygen This is the electrostatic potential value at which the value of the electrostatic potential becomes maximum when the value is larger than the sum of van der Waals radii of the atoms. R ₁ to quaternary phosphonium cation or quaternary ammonium cation
R ₄ is specifically isopropyl, tert-butyl, 2
-Butenyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, isopentyl, tert-pentyl, 3
-Methyl-2-butyl, neopentyl, 4-methyl-2
-Pentyl, cyclopentyl, cyclohexyl, 3-heptyl, 2-octyl, 2-ethyl-1-hexyl,
1,1-dimethyl-3,3-dimethylbutyl (commonly known as t
tert-octyl), o-methylphenyl, o-tert-butylphenyl, diisopropylamino, di-tert-butylamino, phenyl, benzyl, cumyl, naphthyl, pyridyl, dipyridyl and the like. ,

As described above, the quaternary phosphonium cation and the quaternary ammonium cation in the present invention are composed of these hydrocarbon groups, and the quaternary phosphonium cation and the quaternary ammonium cation are calculated by using OH ^- ion as a counter anion. It is essential that the maximum electrostatic potential calculated in (1) is not more than 300 kJ / mol. The above-mentioned maximum electrostatic potential of 300 kJ / mol or less is generally achieved by increasing the ionic radius of the cation. Therefore, a relatively bulky hydrocarbon group 4
It becomes a quaternary phosphonium cation or a quaternary ammonium cation, and the maximum electrostatic potential is not always 300 kJ / mol or less in all combinations of the above-described hydrocarbon groups. Further, these hydrocarbon groups are merely examples, and the present invention is not limited to only these hydrocarbon groups.

Accordingly, the maximum electrostatic potential of the cations of the quaternary phosphonium salt and the quaternary ammonium salt represented by the chemical formula (1) in the present invention calculated by using the OH ^- ion as a counter anion is 300 kJ /. mol
Specific examples of the following cations include tetra-ter
t-butylphosphonium cation, tetracyclohexylphosphonium cation, tetra (o-methylphenyl) phosphonium cation, tetra (o-tert-butylphenyl) phosphonium cation, tetra (o-methoxyphenyl) phosphonium cation, tri (isopropylmethylamino) ( 1,1,3,3-teretramethylbutylmethylamino) phosphonium cation, tetra-tert-butylammonium cation, tetracyclohexylammonium cation, tetra (o-methylphenyl) ammonium cation, tetra (o-tert-butylphenyl) ammonium cation, but and the like, these are merely exemplified, and a counter anion OH ^- as calculated chemically maximum electrostatic potential of the obtained cation 300 kJ / mol
Any quaternary phosphonium cation and any quaternary ammonium cation may be used as long as the combination of R _{1 to} R ₄ is as follows.

In the present invention, the active hydrogen compound for deriving an anion represented by B ^n- in the general formula (1) is a compound which forms an anion by extracting active hydrogen, and morphologically generates active anion. Any compound may be used as long as it is removed and takes the form of an anion.Specifically, water is exemplified as the most common compound, formic acid, acetic acid,
C1-C20 carboxylic acids such as propionic acid, butyric acid, isobutyric acid, lauric acid, stearic acid, oleic acid, phenylacetic acid, dihydrocinnamic acid or cyclohexanecarboxylic acid, benzoic acid, paramethylbenzoic acid or 2-carboxynaphthalene 2 to 20 carbon atoms such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, butanetetracarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or pyromellitic acid Carboxylic acids having 2 to 6 carboxyl groups, such as N, N-diethylcarbamic acid, N-carboxypyrrolidone, N-carboxyaniline or N, N'-dicarboxy-2,4-toluenediamine. Carbamic acids, methanol, ethanol, normal-propa Knol, isopropanol,
Normal-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, normal-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methyl Alcohols having 1 to 20 carbon atoms such as vinyl carbinol, benzyl alcohol, 1-phenylethyl alcohol, triphenyl carbinol or cinnamyl alcohol;

Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
1,3-propanediol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol,
C2-C2 such as 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or dipentaerythritol
0 polyhydric alcohols having 2 to 8 hydroxyl groups, sugars such as glucose, sorbitol, dextrose, fructose or sucrose or derivatives thereof;
C6 to C2 such as phenol, 2-naphthol, 2,6-dihydroxynaphthalene or bisphenol A
Aromatic compounds having 0 to 3 hydroxyl groups,
Polyethylene oxide, polypropylene oxide or copolymers thereof having a molecular weight of 10 having 2 to 8 terminals and having 1 to 8 hydroxyl groups at the terminals.
0 to 50,000 polyalkylene oxides, methylamine, ethylamine, normal-propylamine, isopropylamine, normal-butylamine, isobutylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine,
1 carbon atom such as β-phenylethylamine, aniline, o-toluidine, m-toluidine or p-toluidine
To 20 aliphatic or aromatic primary amines, dimethylamine, methylethylamine, diethylamine, di-normal-propylamine, ethyl-normal-butylamine, methyl-sec-butylamine, dipentylamine, dicyclohexylamine, N-methyl Aliphatic or aromatic secondary amines having 2 to 20 carbon atoms such as aniline or diphenylamine, such as ethylenediamine, di (2-aminoethyl) amine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, tri (2 -Aminoethyl) amine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine or di (2-methylaminoethyl) amine
Polyamines having from 20 to 2 to 3 primary or secondary amino groups,

C4 such as pyrrolidine, piperidine, morpholine or 1,2,3,4-tetrahydroquinoline
To 20 saturated cyclic secondary amines, 3-pyrroline,
Pyrrole, indole, carbazole, imidazole,
Unsaturated cyclic secondary amines having 4 to 20 carbon atoms such as pyrazole or purine, and 2 to 3 secondary groups having 4 to 20 carbon atoms such as piperazine, pyrazine or 1,4,7-triazacyclononane. C2-C20 such as cyclic polyamines containing an amino group, acetamide, propionamide, N-methylpropionamide, N-methylbenzoic acid amide or N-ethylstearic acid amide;
Unsubstituted or N-monosubstituted acid amides, 5- to 7-membered cyclic amides such as 2-pyrrolidone or ε-caprolactam, and C4 to C10 such as succinimide, maleimide or phthalimide. Examples of imides of dicarboxylic acids are examples of compounds that are easily available. However, the method of the present invention may be any compound capable of forming an anion by extracting hydrogen as described above, and it is a matter of course that the present invention is not limited to only these active hydrogen compounds.

In the present invention, 4 represented by the general formula (1)
Commercially available reagents can be used for the primary phosphonium salt and the quaternary ammonium salt, but a salt of a phosphonium cation and an inorganic anion or a salt of an ammonium salt and an inorganic anion with an alkali metal salt of an active hydrogen compound can be used. It is also obtained by doing. As the alkali metal salt of the active hydrogen compound, an ordinary method of reacting the above active hydrogen compound with a metal of an alkali metal or a basic alkali metal compound is used. Examples of the alkali metal metal include lithium metal, sodium metal, potassium metal, and cesium metal.Examples of the basic alkali metal compound include amides of an alkali metal such as sodium amide or potassium amide, and normal-propyl. Lithium, normal-butyl lithium, vinyl lithium, cyclopentadienyl lithium, α-naphthyl lithium, ethynyl sodium, normal-butyl sodium, phenyl lithium, cyclopentadienyl sodium, fluorenyl sodium, tetraphenylethylene disodium, sodium Organic alkali metal compounds such as naphthalenide, ethyl potassium, cyclopentadienyl potassium, phenyl potassium or benzyl potassium, and sodium hydride or potassium hydride And alkali metal hydride compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate. Salt and the like.

The metal of these alkali metals or the basic alkali metal compound is selected according to the acidity of the active hydrogen compound. In some cases, the alkali metal salt of the active hydrogen compound thus obtained acts as a basic alkali metal compound, and another active hydrogen compound can be converted to the alkali metal salt. However, the present invention is not limited only to these methods, it is essential that the phosphonium salt and ammonium salt in the form of the cations and anions derived from active hydrogen,
Therefore, any quaternary phosphonium salt or quaternary ammonium salt which can take the above salt form in the reaction system can be used in the present invention.

Specific examples of the quaternary phosphonium salt and the quaternary ammonium salt used in the present invention are shown below. Note the parentheses counter anion OH ^- it is the maximum electrostatic potential calculation chemically obtained cation as the unit is kJ / m
ol. Examples of the phosphonium salt include tetra-tert-butylphosphonium hydroxide (257.7), tetracyclohexylphosphonium hydroxide (264.1), and tetra (2,2-dimethylpropyl) phosphonium hydroxide
(258.9), tetra (1-methyl-2,2-dimethylpropyl) phosphonium hydroxide (239.6), tetra (2,2,2-triisopropylethyl) phosphonium hydroxide (29.6
16.4), tetra (o-methylphenyl) phosphonium hydroxide (244.4), tetra (o-tert-butylphenyl)
Phosphonium hydroxide (223.4), tetra (o-methoxyphenyl) phosphonium hydroxide (231.4),
Tris (2,4,6-trimethylphenyl) methylphosphonium hydroxide (232.6), tris (o-dimethylaminophenyl) (2,2-dimethylpropyl) phosphonium hydroxide (236.1), tetra (o-amino-p- Dimethylaminophenyl) phosphonium hydroxide (214.8), tri (isopropylmethylamino) (1,1,3,3-teretramethylbutylmethylamino) phosphonium hydroxide
(259.4),

As ammonium salts, tetra-tert-butylammonium hydroxide (260.0), tetracyclohexylammonium hydroxide (269.7), tetra (2,2-dimethylpropyl) ammonium hydroxide (266.3), tetra (1-methyl) -2,2-dimethylpropyl)
Ammonium hydroxide (244.1), tetra (2,2,2-
Triisopropylethyl) ammonium hydroxide
(213.1), tris (2,4,6-trimethylphenyl) methylammonium hydroxide (235.9), tetra (o-methylphenyl) ammonium hydroxide (241.5), tetra (o-methoxyphenyl) ammonium hydroxide (241.5) , Tetra (o-tert-butylphenyl) ammonium hydroxide (225.2), tris (o-dimethylaminophenyl) (2,2-dimethylpropyl) ammonium hydroxide (239.6), tetra (o-amino-p-dimethylamino) Phenyl) ammonium hydroxide (224.1), but the invention is not limited only to these quaternary phosphonium salts or quaternary ammonium salts.

The alkylene oxide compound used as a raw material in the production method of the present invention includes, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide,
Epoxy compounds such as 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether and phenyl glycidyl ether. These may be used in combination of two or more.
When used in combination, a method of simultaneously using a plurality of alkylene oxide compounds, a method of sequentially using a plurality of alkylene oxide compounds, or a method of repeatedly repeating the steps can be employed.

Of these alkylene oxide compounds, ethylene oxide, propylene oxide, 1,2-
Butylene oxide or styrene oxide is preferred,
Ethylene oxide and propylene oxide are more preferred.

The reaction temperature of the polymerization reaction is not uniform depending on the kind and amount of the alkylene oxide compound and other components used, but is usually 150 ° C. or lower, preferably 10 ° C. or lower.
To 130 ° C, more preferably 50 to 120 ° C. The pressure during the reaction is not uniform depending on the type or amount of the alkylene oxide compound or other component used or the polymerization temperature, but is usually 30 kg / cm ² (absolute pressure, hereinafter the same) as the pressure during the polymerization reaction. And preferably in the range of 0.1 to 15 kg / cm ² , more preferably 1 to 10 kg / cm ² . The reaction time is not uniform depending on the kind or amount of the substance to be used or the polymerization temperature or pressure, but is usually 70 hours or less, preferably 0.1 to 30 hours, more preferably 0.5 to 24 hours. It is.

In the polymerization reaction, a solvent can be used if necessary. Examples of the solvent to be used include, for example, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, diethyl ether, tetrahydrofuran, 1,3-dioxane and anisole. Aprotic polar solvents such as ethers or dimethyl sulfoxide, N, N-dimethylformamide, hexamethylphosphoramide and N, N'-dimethylimidazolidinone; In addition, any solvent can be used as long as it does not inhibit the polymerization reaction of the method of the present invention. The polymerization reaction in the method of the present invention can be carried out in the presence of an inert gas such as nitrogen or argon if necessary.

The polyalkylene oxide obtained by the method of the present invention can be used as a raw material for polyurethane foams or elastomers or as a surfactant by simply removing the solvent when a solvent is used in the polymerization reaction. However, it can also be used after being treated with a mineral acid such as hydrochloric acid, phosphoric acid or sulfuric acid, an organic carboxylic acid such as formic acid, acetic acid or propionic acid, carbon dioxide or an acid-type ion exchange resin. Further, conventional purification such as washing with water, an organic solvent or a mixture thereof can also be performed.

[0029]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. Example 1 To 1.38 g (0.015 mol) of glycerin, 15.0 ml (0.015 mol) of a 1.0 N aqueous potassium hydroxide solution was added at room temperature to obtain a uniform solution. The crystals were concentrated to dryness under reduced pressure to obtain colorless crystals, and further dried by heating at 100 ° C. under reduced pressure to synthesize a monopotassium glycerin salt. This salt is added to tetra (tert-butyl)
5.19 g of phosphonium tetrafluoroborate (0.015 m
ol) in 50 ml of THF was added and stirred at room temperature for 24 hours. After the precipitated KBF ₄ was filtered under a nitrogen atmosphere, the filtrate was concentrated under reduced pressure to remove THF, and mono {tetra (tert-butyl) phosphphosphonium} salt of glycerin, ie, [(t-Bu) ₄ P ⁺ ] (Gl
^{y) -} (Gly - represents a monovalent anion of glycerin.
The same applies hereinafter). Tetra obtained from the calculation (tert
The value of the electrostatic potential of the (-butyl) phosphonium cation was 257.7 kJ / mol.

In an autoclave equipped with a temperature measuring tube, a pressure gauge, a stirrer, and an alkylene oxide introducing tube, mono (tetra) tertiary glycerin synthesized by the above method was added.
5.26 g of t-butyl) phosphonium salt in 50 ml of TH
F, and then add glycerin 2
0.0g was added. The temperature was raised while stirring, and THF was distilled off under reduced pressure. Thereafter, the inside of the reactor was replaced with nitrogen, the temperature was raised to 110 ° C, and propylene oxide was supplied intermittently at 110 ° C for 650 minutes while intermittently supplying propylene oxide so as to keep the reaction pressure around 3.0 kg / cm ² (absolute pressure, the same applies hereinafter). Reacted. Thereafter, the content was cooled to room temperature, and the remaining unreacted propylene oxide was distilled off under reduced pressure. 284 g of polyoxypropylene triol was obtained as a viscous liquid.

Example 2 0.015 mol of triglycol was added to 1.38 g (0.015 mol) of glycerin.
(Isopropylmethylamino) (1,1,3,3-tetramethyl
Butylmethylamino) phosphonium hydroxide
Add a solution dissolved in 50 ml THF and add at room temperature
A homogeneous solution was added. Colorless crystals after concentration to dryness under reduced pressure
And dried by heating under reduced pressure at 100 ° C.
Tri (isopropylmethylamino) (1,1,3,3-tetra
Lamethylbutylmethylamino) phosphonium salt, ie
[[(Iso-C_ThreeH₇) (CH_Three) N]_Three[(CH_Three)_TwoCCH _Two(CH_Three)_TwoC) (CH_Three) N]
P⁺(Gly)^-] Was synthesized. Tri (iso)
Propylmethylamino) (1,1,3,3-tetramethylbutyl
Electrostatic potential of methylamino) phosphonium cation
Value was 259.4 kJ / mol.

An autoclave equipped with a temperature measuring tube, a pressure gauge, a stirrer, and an alkylene oxide introducing tube was placed in a tri (isopropylmethylamino) glycerol, a phosphonium salt of an active hydrogen compound synthesized by the above method.
A solution in which 7.21 g (0.015 mol) of (1,1,3,3-tetramethylbutylmethylamino) phosphonium salt was dissolved in 50 ml of THF was charged, and 20.0 g of glycerin was further added. The temperature was raised while stirring, and THF was distilled off under reduced pressure.
Thereafter, the inside of the reactor was purged with nitrogen, the temperature was raised to 110 ° C, and 700 ° C at 110 ° C while intermittently supplying propylene oxide so as to keep the reaction pressure around 3.0 kg / cm ² (absolute pressure).
Minutes. Thereafter, the content was cooled to room temperature, and the remaining unreacted propylene oxide was distilled off under reduced pressure. Polyoxypropylene triol as a viscous liquid
308 g were obtained.

Comparative Example 1 0.015 mol of tetramethylphosphonium hydroxide was added to 1.38 g (0.015 mol) of glycerin in 50 ml of TH.
A solution dissolved in F was added, and the mixture was added at room temperature to obtain a uniform solution. It was concentrated to dryness under reduced pressure to obtain colorless crystals, and further dried by heating at 100 ° C. under reduced pressure to synthesize a tetramethylphosphonium salt of glycerin, ie, [(CH ₃ ) ₄ P ⁺ (Gly) ⁻ ]. The value of the electrostatic potential of the tetramethylphosphonium cation obtained from the calculation was 347.7 kJ / mol.

In an autoclave equipped with a temperature measuring tube, a pressure gauge, a stirrer, and an alkylene oxide introducing tube, 2.73 g of glycerin tetramethylphosphonium salt, which is a phosphonium salt of an active hydrogen compound synthesized by the above method, was placed.
(0.015 mol) in 50 ml of THF was charged, and 20.0 g of glycerin was further added. The temperature was raised while stirring, and THF was distilled off under reduced pressure. Thereafter, the inside of the reactor was replaced with nitrogen, the temperature was raised to 110 ° C, and the reaction was carried out at 110 ° C for 1950 minutes while intermittently supplying propylene oxide so as to keep the pressure at around 3.0 kg / cm ² during the reaction. Thereafter, the content was cooled to room temperature, the propylene oxide was distilled off by depressurizing the autoclave, and the content of the reactor was 23.5 g, which was almost equal to the weight of glycerin itself charged in the reactor. Triol was not obtained.

Comparative Example 2 0.015 mol of tetramethylammonium hydroxide was added to 50 ml of TH for 1.38 g (0.015 mol) of glycerin.
A solution dissolved in F was added, and the mixture was added at room temperature to obtain a uniform solution. It was concentrated to dryness under reduced pressure to obtain colorless crystals, and further dried by heating at 100 ° C. under reduced pressure to synthesize a tetramethylammonium salt of glycerin, ie, [(CH ₃ ) ₄ N ⁺ (Gly) ⁻ ]. The value of the electrostatic potential of the tetramethylammonium cation obtained from the calculation was 346.4 kJ / mol.

In an autoclave equipped with a temperature measuring tube, a pressure gauge, a stirrer, and an alkylene oxide introducing tube, 2.48 g of tetramethylammonium salt of glycerin, which is a phosphonium salt of an active hydrogen compound synthesized by the above method, was placed.
(0.015 mol) in 50 ml of THF was charged, and 20.0 g of glycerin was further added. The temperature was raised while stirring, and THF was distilled off under reduced pressure. Thereafter, the inside of the reactor was replaced with nitrogen, the temperature was raised to 110 ° C, and the pressure during the reaction was 3.
The reaction was carried out at 110 ° C. for 2100 minutes while intermittently supplying propylene oxide so as to keep the pressure at around 0 kg / cm ² . Thereafter, the content was cooled to room temperature, the autoclave was depressurized, and propylene oxide was distilled off.The content of the reactor was 23.2 g, which was almost equal to the weight of glycerin itself charged in the reactor. Triol was not obtained.

[0037]

According to the present invention, the phosphonium salt or ammonium salt of the active hydrogen compound represented by the chemical formula (1) can prepare cations of various sizes, has high solubility in an organic solvent, and has a high activity. The reactivity of the anion of the hydrogen compound is enhanced, and it is extremely useful as a reaction reagent for an organic reaction, and the polyalkylene oxide can be easily and efficiently produced.

Claims (3)

[Claims] 1. A compound of the general formula (Wherein, R _{1 to} R ₄ are each independently an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group containing a hetero atom, and A is a nitrogen element or A phosphorus element, [(R ₁ ) (R ₂ ) (R ₃ ) (R ₄ )
A ⁺ ] is a cation having a maximum anion potential of 300 kJ / mol or less obtained by computational chemistry with the counter anion being OH ⁻ , and B ⁿ⁻ is at least one selected from the group of anions derived from active hydrogen compounds. One kind and n is an integer. A process for producing a polyalkylene oxide, comprising subjecting an alkylene oxide compound to addition polymerization in the presence of at least one of a quaternary phosphonium salt or a quaternary ammonium salt represented by the formula (1). 2. An active hydrogen compound from which B ^n- is derived is water,
Alcohols having 1 to 20 carbon atoms, 2 to 2 carbon atoms
Polyhydric alcohols, saccharides or derivatives thereof having a hydroxyl group of 0 or less and 2 or more and 8 or less, having a terminal of 2 or more and 8 or less and having a hydroxyl group of 1 or more and 8 or less at the terminal. Polyalkylene oxides, primary or secondary monoamines having 20 or less carbon atoms,
Polyvalent amines having from 2 to 20 carbon atoms and having from 2 to 3 primary or secondary amino groups, from 4 to 2 carbon atoms;
An active hydrogen compound selected from the group consisting of zero saturated cyclic secondary amines and cyclic polyamines containing 2 to 3 secondary amino groups having 4 to 20 carbon atoms. A method for producing the polyalkylene oxide according to claim 1. 3. The method according to claim 1, wherein the alkylene oxide compound is a compound selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide.