TW201630971A - Alkylene oxide polymerization catalyst and method for producing polyalkylene oxides using same - Google Patents

Abstract

Provided is an alkylene oxide polymerization catalyst enabling efficient production of, even with production conditions at low temperature, polyalkylene oxides that have high molecular weight, low unsaturation, and narrow molecular weight distribution by using a small amount of expensive phosphazenium salts. The alkylene oxide polymerization catalyst includes a phosphazenium salt represented by general formula (1) and a Lewis acid. (In general formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1-20 carbon atoms. R1 and R2 optionally bind with each other to form a ring structure, and R1s or R2s optionally bind among themselves to form a ring structure. X- represents a hydroxy anion, an alkoxy anion having 1-4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2-5 carbon atoms, or a hydrogen carbonate anion. Y represents a carbon atom or a phosphorus atom. When Y is a carbon atom, a is 2; and when Y is a phosphorus atom, a is 3.).

Description

Alkylene oxide polymerization catalyst and method for producing polyalkylene oxide using the same

The present invention relates to an alkylene oxide polymerization catalyst and a method for producing a polyalkylene oxide using the same, and more particularly to a production process which exhibits high molecular weight and low quality even at a low temperature production condition. A novel alkylene oxide polymerization catalyst of a saturated and narrow molecular weight distribution polyalkylene oxide and a method for producing a polyalkylene oxide using the same.

Industrially known polyalkylene oxides are produced by addition polymerization of alkylene oxide by using potassium hydroxide as a catalyst. However, in the case of producing a high molecular weight polyalkylene oxide by this method, since the obtained polyalkylene oxide contains a large amount of monoalcohol, there is a problem that the degree of unsaturation becomes high.

A method for producing a polyalkylene oxide using a double metal cyanide complex as a catalyst has been proposed as a method for producing a polyalkylene oxide (see, for example, Patent Document 1 and Patent Document 2).

In addition, as a method for producing a polyalkylene oxide having a low degree of unsaturation, a method of producing a polyalkylene oxide using a specific phosphazene salt as a catalyst has been proposed (for example, refer to Patent Document 3 to Patent Document 5). .

On the other hand, there has been proposed a method of reacting an active hydrogen-containing compound with a ratio of active hydrogen in an active hydrogen-containing compound to aluminum atom in an aluminoxane of 0.2 to 1:1 (mole ratio). The aluminoxane is mixed to obtain an alkylene oxide polymerization catalyst, and the alkylene oxide polymerization catalyst is used to carry out ring-opening polymerization of an alkylene oxide to produce a polyalkylene oxide (see, for example, Patent Document 6).

Further, as a method for producing a polyalkylene oxide, a method is proposed in which an active hydrogen-containing compound, a phosphazene compound, and triisobutylaluminum are mixed at a molar ratio of 1:1:2 to obtain an epoxy resin. The alkane polymerization catalyst is subjected to ring-opening polymerization of an alkylene oxide at 20 ° C in a toluene solvent using the alkylene oxide polymerization catalyst to produce a polyalkylene oxide (see, for example, Non-Patent Document 1). The catalytically active species at this time proposes the following mechanism: First, the deprotonation reaction of the active hydrogen-containing compound is carried out by reacting an active hydrogen-containing compound with a phosphazene compound, and then, the triisobutylaluminum functions, The deprotonated active hydrogen-containing compound moves onto the aluminum, thereby becoming a catalytically active species. [Prior Art Document] [Patent Literature]

[Patent Document 1] U.S. Patent No. 5,235,114, the disclosure of which is hereby incorporated by reference. [Patent Document 2] Japanese Patent Laid-Open No. Hei 4-59825 (Patent Document 3) Japanese Patent No. 3,497, 504 (Japanese Patent Laid-Open No. Hei 10-77289) [Patent Document 5] Japanese Patent No. 5663856 (Japanese Patent Laid-Open Publication No. 2010-150514) [Patent Document 6] Japanese Patent Laid-Open Publication No. JP-A No. Hei. JP-A-2011-122134 [Non-Patent Document] [Non-Patent Document 1] "Polymer Chemistry" 2012, 3, 1189.

[Problems to be solved by the invention]

In the methods described in Patent Document 1 and Patent Document 2, the obtained polyalkylene oxide has a wide molecular weight distribution and is difficult to be used as an alkylene oxide or ethylene oxide.

The method proposed in Patent Document 3 has a problem that the conversion ratio of alkylene oxide is as low as 9% to 19%. Further, the obtained polyalkylene oxide is a mixture of a high molecular weight body having a molecular weight of 17,000,000 g/mol to 160,000,000 g/mol and a low molecular weight body having a molecular weight of 1700 g/mol to 2300 g/mol as a polyalkylene oxide. Does not have special features.

The degree of unsaturation of the polyalkylene oxide obtained in the methods described in Patent Documents 4 to 6 is still high, and further reduction is required. Further, when the polymerization temperature is lowered, the catalyst activity is lowered. On the other hand, when the polymerization temperature is raised, the problem of an increase in the degree of unsaturation, which is an indicator of the amount of impurities in the product, is likely to occur.

The method proposed in Non-Patent Document 1 requires the use of a large amount of a high-priced phosphazene compound, and has a problem as an efficient method for industrially producing a polyalkylene oxide. Further, the obtained polyalkylene oxide does not have any special characteristics.

When the degree of unsaturation of the polyalkylene oxide is increased, the crosslinking density at the time of forming the polyurethane resin is lowered, and the storage elastic modulus is lowered. Therefore, there is a problem that physical properties such as hysteresis loss and compression set are lowered. In addition, when the molecular weight distribution of the polyalkylene oxide is broadened, there is a problem that the formability when the polyurethane resin is formed is deteriorated. In addition, when the amount of the low molecular weight component in the polyalkylene oxide is increased, the crosslinking density is lowered when the polyurethane resin is formed, and the storage elastic modulus is lowered. Therefore, physical properties such as hysteresis loss and compression set are deteriorated. Question.

Therefore, the use amount of the expensive phosphazene compound is required to be small, and even in the production conditions at a low temperature, the alkylene oxide polymerization of the polyalkylene oxide exhibiting high molecular weight, low unsaturation, and narrow molecular weight distribution can be efficiently produced. A catalyst and a method for producing a polyalkylene oxide using the same. [Means for solving the problem]

The present inventors have conducted intensive studies to solve the above problems, and as a result, it has been found that an alkylene oxide polymerization catalyst containing a specific phosphazene salt and a Lewis acid can be efficiently produced at high temperatures even under low-temperature production conditions. A polyalkylene oxide having a molecular weight, a low degree of unsaturation, and a narrow molecular weight distribution, thereby completing the present invention.

That is, the present invention relates to an alkylene oxide polymerization catalyst as described below and a method for producing a polyalkylene oxide using the same.

[1] An alkylene oxide polymerization catalyst comprising a phosphazene salt represented by the formula (1) and a Lewis acid,

[Chemical 1] (In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; and here, a ring structure in which R ¹ and R ² are bonded to each other, and R ¹ may be formed. a ring structure in which each other or R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogencarbonate anion; It represents a carbon atom or a phosphorus atom. When Y is a carbon atom, a is 2, and when Y is a phosphorus atom, a is 3).

[2] The alkylene oxide polymerization catalyst according to [1], wherein the ratio of the phosphazene salt represented by the formula (1) to the Lewis acid is [phosphazene salt]: [Lewis acid] = 1 : 0.002 ~ 500 (Morbi).

[3] The alkylene oxide polymerization catalyst according to [1] or [2], wherein the Lewis acid is at least one compound selected from the group consisting of an aluminum compound, a zinc compound, and a boron compound.

[4] The alkylene oxide polymerization catalyst according to [1] or [2], wherein the Lewis acid is at least one compound selected from the group consisting of organoaluminum, aluminoxane, and organozinc.

[5] The alkylene oxide polymerization catalyst according to any one of [1] to [4], which comprises a phosphazene salt represented by the formula (1), a Lewis acid, and an active hydrogen-containing compound ,

[Chemical 2] [In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; and here, a ring structure in which R ¹ and R ² are bonded to each other, and R ¹ may be formed. a ring structure in which each other or R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogencarbonate anion; It represents a carbon atom or a phosphorus atom. When Y is a carbon atom, a is 2, and when Y is a phosphorus atom, a is 3].

[6] The alkylene oxide polymerization catalyst according to [5], wherein the active hydrogen-containing compound is selected from the group consisting of water, a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether having a hydroxyl group. At least one of the groups consisting of polyols.

[7] A method for producing an alkylene oxide polymerization catalyst, which comprises the alkylene oxide polymerization catalyst according to [5] or [6], wherein the phosphorus represented by the formula (1) is used. After the nitrile salt is mixed with the active hydrogen-containing compound, they are mixed with a Lewis acid.

[8] A method for producing a polyalkylene oxide, wherein the alkylene oxide is opened in the presence of the alkylene oxide polymerization catalyst according to any one of [1] to [5] polymerization.

[9] A polyalkylene oxide which satisfies all of the following i) to iv): i) an unsaturation of 0.020 meq/g or less; ii) a Mw/Mn of 1.10 or less; iii) a Mh/f of 1,000 or more ; iv) an area ratio of molecular weight of Mh/3 or less of 2.0% or less; (wherein, the number average molecular weight determined by gel permeation chromatography using polystyrene as a standard substance is Mn, and The weight average molecular weight is Mw, the molecular weight of the highest peak is Mh, and the number of functional groups of the polyalkylene oxide is f).

[10] The polyalkylene oxide according to [9], wherein the molecular weight calculated from the hydroxyl group of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups thereof is 1000 g/mol. ～50000 g/mol range.

[11] A method for producing a polyalkylene oxide, which comprises the polyalkylene oxide according to [9] or [10], which is characterized in that it is an alkylene oxide polymerization contact comprising a phosphazene compound and a Lewis acid. Ring-opening polymerization of alkylene oxide with an active hydrogen-containing compound as a starting agent in the presence of a medium; and use amount of the phosphazene compound relative to 1 mol of active hydrogen in the active hydrogen-containing compound It is in the range of 0.001 mol to 0.1 mol.

[12] The method for producing a polyalkylene oxide according to [11], wherein the phosphazene compound is a phosphazene salt represented by the formula (1):

[Chemical 3] (In the general formula (1), R ¹ is and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; herein, may form a ring structure R ¹ and R ² are bonded, R & lt ¹ a ring structure in which each other or R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogencarbonate anion; It represents a carbon atom or a phosphorus atom. When Y is a carbon atom, a is 2, and when Y is a phosphorus atom, a is 3).

[13] The method for producing a polyalkylene oxide according to [11], wherein the Lewis acid is at least one compound selected from the group consisting of an aluminum compound, a zinc compound, and a boron compound.

[14] The method for producing a polyalkylene oxide according to [11] or [12] wherein the Lewis acid is at least one compound selected from the group consisting of organoaluminum, aluminoxane and organozinc.

[15] The method for producing a polyalkylene oxide according to any one of [11] to [14] wherein the ratio of the phosphazene compound to the Lewis acid is [phosphazene compound]: [Lewis acid] = 1 : 0.002 ~ 500 (Morbi). [Effects of the Invention]

According to the present invention, an alkylene oxide polymerization catalyst having a small amount of impurities due to a side reaction and having high catalytic activity at a low temperature can be obtained. Further, by using the alkylene oxide polymerization catalyst of the present invention to polymerize an alkylene oxide, a polyalkylene oxide having a high molecular weight, a low degree of unsaturation, and a narrow molecular weight distribution can be produced.

Further, since a urethane resin obtained by using the polyalkylene oxide of the present invention having a high molecular weight, a low degree of unsaturation, a narrow molecular weight distribution, and a small amount of a low molecular weight component is used, since the storage elastic modulus is improved, hysteresis loss and compression can be expected. Physical properties such as permanent deformation are improved.

The alkylene oxide polymerization catalyst of the present invention comprises a phosphazene salt represented by the formula (1) and a Lewis acid.

[Chemical 4] [In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; and here, a ring structure in which R ¹ and R ² are bonded to each other, and R ¹ may be formed. a ring structure in which each other or R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogencarbonate anion; It represents a carbon atom or a phosphorus atom. When Y is a carbon atom, a is 2, and when Y is a phosphorus atom, a is 3].

Here, examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, and third group. Base, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, heptyl, cycloheptyl, octyl, cyclooctyl, decyl, cyclodecyl, fluorenyl , cyclodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, etc. .

When R ¹ and R ² are bonded to each other to form a ring structure, for example, a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, a fluorenyl group or an isodecyl group may, for example, be mentioned.

Examples of the ring structure in which R ¹ or R ² are bonded to each other include a ring in which one substituent is an alkyl group such as an exoethyl group, a propyl group or a butyl group, and the other substituent is bonded to each other. structure.

Further, in the ring structure, in terms of forming an alkylene oxide polymerization catalyst having excellent catalytic activity, R ¹ and R ^{2 are} particularly preferably a methyl group, an ethyl group or an isopropyl group.

X ^- in the phosphazene salt is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogencarbonate anion.

Examples of the alkoxy anion having 1 to 4 carbon atoms include a methoxy anion, an ethoxy anion, a n-propoxy anion, an isopropoxy anion, a n-butoxy anion, an isobutoxy anion, and a third. Butoxy anion and the like.

Examples of the alkylcarboxyl anion having 2 to 5 carbon atoms include an ethoxylated anion, an ethylcarboxy anion, a n-propylcarboxy anion, an isopropylcarboxy anion, a n-butylcarboxy anion, an isobutyl carboxyl anion, and the like. Tributyl carboxyl anion and the like.

The plurality of anion, to form an alkylene oxide in terms of excellent catalytic activity of polymerization catalyst, X ^- is particularly preferably a hydroxy anion, bicarbonate anion.

In the present invention, when Y is a carbon atom, the phosphazene salt is represented by the following formula (2).

[Chemical 5] [In the above formula (2), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; and here, a ring structure in which R ¹ and R ² are bonded to each other, and R ¹ may be formed. a ring structure in which each other or R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or an acid hydrogenate anion]

Further, in the present invention, when Y is a phosphorus atom, the phosphazene salt is represented by the following formula (3).

[Chemical 6] [In the above formula (3), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; and here, a ring structure in which R ¹ and R ² are bonded to each other, and R ¹ may be formed. a ring structure in which each other or R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or an acid hydrogenate anion]

In the present invention, specifically, the phosphazene salt can be exemplified by tetrakis(1,1,3,3-tetramethylindenyl)phosphonium hydroxide and tetrakis(1,1,3,3-tetraethylindenyl). Barium hydroxide, tetrakis(1,1,3,3-tetra(n-propyl)decyl)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropyldecyl)phosphonium hydroxide, tetrakis 1,1,3,3-tetra(n-butyl)fluorenyl)phosphonium hydroxide, tetrakis(1,1,3,3-tetraphenylindenyl)phosphonium hydroxide, tetrakis (1,1,3,3 -tetrabenzylguanidino)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidin-2-imido)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidin-2-ylidene)鏻Barium hydroxide, tetrakis(1,1,3,3-tetramethylindenyl)hydrocarbonate, tetrakis(1,1,3,3-tetraethylindenyl)hydrocarbonate, tetrakis (1,1) , 3,3-tetra(n-propyl)decyl)phosphonium hydrogencarbonate, tetrakis(1,1,3,3-tetraisopropyldecyl)phosphonium hydrogencarbonate, tetrakis (1,1,3,3-tetra (n-butyl)fluorenyl)phosphonium hydrogencarbonate, tetrakis(1,1,3,3-tetraphenylindenyl)hydrocarbonate, tetrakis(1,1,3,3-tetrabenzylindenyl) hydrogencarbonate A phosphazene salt such as hydrazine, tetrakis(1,3-dimethylimidazolidin-2-imido)phosphonium hydrogencarbonate or tetrakis(1,3-dimethylimidazolidin-2-imido)phosphonium hydrogencarbonate.

Further, tetrakis[tris(dimethylamino)phosphoranylidene amino]phosphonium hydroxide, tetrakis[tris(diethylamino)phosphoric acid, tetrakis(trimethyl)phosphoranylidene aminophosphonium hydroxide Phosphonimidoamino]phosphonium hydroxide, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diisopropylamino)phosphoranylideneamino] Barium hydroxide, tetrakis[tris(di-n-butylamino)phosphoranylidene]phosphonium hydroxide, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydroxide, tetra [three (1,3-Dimethylimidazolidine-2-imino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetra [Tris(diethylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetrakis[tris(diisopropyl) Amino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetrakis[tris(diphenylamino)phosphorane) An amine group] a phosphazene salt such as cesium hydrogencarbonate or tetrakis[tris(1,3-dimethylimidazolidin-2-ylidene)phosphoranylideneamino]phosphonium hydrogencarbonate.

Among these compounds, in terms of forming a catalyst for producing a polyalkylene oxide excellent in catalytic performance, it is particularly preferable to use tetrakis(1,1,3,3-tetramethylindenyl)phosphazene hydroxide, Tetrakis(1,1,3,3-tetramethylindenyl)phosphazene hydrogencarbonate, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide.

In the present invention, examples of the Lewis acid include an aluminum compound, a zinc compound, and a boron compound.

Examples of the aluminum compound include organoaluminum, inorganic aluminum, aluminoxane, and the like.

Examples of the organoaluminum include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, triethoxy aluminum, triisopropoxy aluminum, triisobutoxy aluminum, and three. Phenyl aluminum, diphenyl monoisobutyl aluminum, monophenyl diisobutyl aluminum, and the like.

Examples of the inorganic aluminum include aluminum chloride, aluminum hydroxide, and aluminum oxide.

The aluminoxane may, for example, be a compound represented by the following formula (-AlR ³ -O-) _n (wherein R ³ represents a hydrocarbon group having 1 to 20 carbon atoms; and n represents an integer of 2 or more).

Here, examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, and third group. Base, cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, heptyl, cycloheptyl, octyl, cyclooctyl, decyl, cyclodecyl, fluorenyl , cyclodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, etc. . Among these hydrocarbon groups, an alkylene oxide polymerization catalyst which is easily obtained as R ³ and which exhibits a high conversion ratio of alkylene oxide is preferably a methyl group or an isobutyl group.

Specific examples of the aluminoxane include methyl aluminoxane, isobutyl aluminoxane, and methyl-isobutyl aluminoxane. In addition, the commercial product of the aluminoxane is MMAO-3A (made by Tosoh Finechem Co., Ltd.), and the product name TAO-340 series (made by Tosoh Fine Chemical Co., Ltd.). ), (trade name) TMAO-200 series (manufactured by Tosoh Fine Chemical Co., Ltd.), (trade name) PBAO (manufactured by Tosoh Fine Chemical Co., Ltd.), (product name) Solid-MAO (manufactured by Tosoh Fine Chemical Co., Ltd.) )Wait.

Examples of the zinc compound include organic zinc such as dimethyl zinc, diethyl zinc, and diphenyl zinc; and inorganic zinc such as zinc chloride or zinc oxide.

The boron compound may, for example, be triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris(pentafluorophenyl)borane or trifluoroethylene. Borane and the like.

Further, among these compounds, in view of forming an alkylene oxide polymerization catalyst excellent in catalytic performance, organoaluminum, aluminoxane, and organozinc are preferable, and organoaluminum is particularly preferable.

Further, among these compounds, it is easy to obtain, and in view of forming an alkylene oxide polymerization catalyst having excellent catalyst activity, triisobutylaluminum, triisopropoxyaluminum, and diethylzinc are particularly preferable.

The ratio of the phosphazene salt to the Lewis acid in the alkylene oxide polymerization catalyst of the present invention is not particularly limited as long as it exhibits an action as an alkylene oxide polymerization catalyst. Among these, in terms of a polymerization catalyst which is particularly excellent in catalytic activity and high in conversion of alkylene oxide, [phosphazene salt]: [Lewis acid] = 1: 0.002 to 500 (mole) ratio).

As the alkylene oxide polymerization catalyst of the present invention, it is possible to efficiently produce a polyalkylene oxide which exhibits a high molecular weight, a low degree of unsaturation, and a narrow molecular weight distribution, and forms a polymerization catalyst excellent in catalytic activity. It is particularly preferable to further use an active hydrogen-containing compound. Examples of the active hydrogen-containing compound at this time include water, a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group.

Examples of the hydroxy compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, and 1,6-hexanediol. Glycerol, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, 2-naphthol, bisphenol, and the like.

Examples of the amine compound include ethylenediamine, N,N'-dimethylethylenediamine, piperidine, piperazine and the like.

Examples of the carboxylic acid compound include benzoic acid, adipic acid, and the like.

Examples of the thiol compound include ethane dithiol and butane dithiol.

Examples of the polyether polyol having a hydroxyl group include a polyether polyol having a molecular weight of 200 to 3,000.

Further, the active hydrogen-containing compounds may be used singly or in combination of several kinds.

Further, when an active hydrogen-containing compound is used, it is possible to efficiently produce a polyalkylene oxide which exhibits a high molecular weight, a low degree of unsaturation, and a narrow molecular weight distribution, and forms a polymerization catalyst excellent in catalytic activity. The phosphazene salt is preferably from 0.001 mol to 10 mol, particularly preferably from 0.001 mol to 5 mol, relative to 1 mol of active hydrogen in the active hydrogen-containing compound. Further, the Lewis acid is preferably from 0.001 mol to 10 mol, particularly preferably from 0.001 mol to 5 mol, relative to 1 mol of active hydrogen in the active hydrogen-containing compound.

In the present invention, as long as the polyalkylene oxide of the present invention can be formed, any method can be used for the method for preparing the alkylene oxide polymerization catalyst, and is not particularly limited.

For example, a method of mixing a phosphazene salt with a Lewis acid can be mentioned. At this time, for example, benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, 1,2-dimethoxy group can also be used. Ethane or the like is used as a solvent.

Further, in the case where ring-opening polymerization of an alkylene oxide is carried out using an active hydrogen-containing compound as a starting agent in the presence of an alkylene oxide polymerization catalyst containing a phosphazene salt and a Lewis acid, any of the following methods may be used. a method of simultaneously mixing a phosphazene salt, a Lewis acid, and an active hydrogen-containing compound; a method of mixing the other two components in one of the compounds; and mixing the other component in the two components of the compounds Method etc.

Among these methods, it is preferable to efficiently produce a polyalkylene oxide which exhibits a high molecular weight, a low degree of unsaturation, and a narrow molecular weight distribution, and is capable of producing a polymerization catalyst excellent in catalytic activity. After mixing the phosphazene salt with the active hydrogen-containing compound, they are mixed with a Lewis acid to prepare an alkylene oxide polymerization catalyst. In this case, the temperature of the heat treatment may be, for example, 50 ° C to 150 ° C, preferably 70 ° C to 130 ° C, and the pressure at the time of the pressure reduction treatment may be, for example, 50 kPa or less. It is preferably 20 kPa or less.

The alkylene oxide polymerization catalyst of the present invention can be used for producing a polyalkylene oxide because of its excellent catalytic activity, and ring-opening polymerization of alkylene oxide can be carried out in the presence of the alkylene oxide polymerization catalyst of the present invention.

The alkylene oxide at this time is not particularly limited, and examples thereof include alkylene oxide having 2 to 20 carbon atoms. Specifically, it can be exemplified: ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, butadiene monooxide, pentene oxidation , styrene oxide, cyclohexene oxide, and the like.

Among these alkylene oxides, an alkylene oxide is easily obtained, and in view of high industrial value of the obtained polyalkylene oxide, ethylene oxide or propylene oxide is preferable. The alkylene oxide may be used singly or in combination of two or more. When two or more types are used in combination, for example, after the first alkylene oxide is reacted, the second alkylene oxide may be reacted, or two or more alkylene oxides may be simultaneously reacted.

In the method for producing a polyalkylene oxide of the present invention, the polymerization pressure is preferably in the range of 0.05 MPa to 1.0 MPa, preferably in the range of 0.1 MPa to 0.6 MPa. In the production of the polyalkylene oxide of the present invention, the polymerization temperature is preferably in the range of 0 °C to 130 °C, preferably in the range of 10 °C to 110 °C.

In the method for producing a polyalkylene oxide of the present invention, the polymerization can be carried out in a solvent or in a solvent-free medium. The solvent to be used is not particularly limited, and examples thereof include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, and 1, 2-Dimethoxyethane and the like.

In the method for producing a polyalkylene oxide of the present invention, in order to obtain an efficient method for producing a polyalkylene oxide, the catalyst activity is preferably 100 g/mol·min or more, and particularly preferably 200. Those with g/mol·min or more.

The polyalkylene oxide obtained by the production method of the present invention is preferably 1000 g/mol based on the molecular weight of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups. ～50000 g/mol, particularly preferably from 3000 g/mol to 30,000 g/mol.

Further, the degree of unsaturation is preferably 0.05 meq/g or less, and particularly preferably 0.03 meq/g or less. Furthermore, the molecular weight distribution (Mw/Mn) of the polyalkylene oxide calculated from the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polyalkylene oxide is preferably 1.3 or less, and particularly preferably 1.1 or less.

Next, all of the polyalkylene oxides satisfying the following i) to iv) in the present invention will be described. i) the degree of unsaturation is 0.020 meq/g or less; ii) Mw/Mn is 1.10 or less; iii) Mh/f is 1,000 or more; iv) The area ratio of molecular weight of Mh/3 or less is 2.0% or less. [The number average molecular weight determined by gel permeation chromatography using polystyrene as a standard material is "Mn", the weight average molecular weight is "Mw", and the molecular weight of the highest peak is set. "Mh", the number of functional groups of the polyalkylene oxide is "f"]

The polyalkylene oxide of the present invention has an unsaturation degree of 0.020 meq/g or less, preferably 0.010 meq/g or less. When the degree of unsaturation is larger than 0.020 meq/g, the storage elastic modulus at the time of forming the polyurethane resin is lowered, and physical properties such as hysteresis loss and compression set are deteriorated, which is not preferable.

The polyalkylene oxide of the present invention has Mw/Mn of 1.10 or less, preferably 1.08 or less. When the Mw/Mn is larger than 1.10, the storage elastic modulus at the time of forming the polyurethane resin is lowered, and the formability is deteriorated, which is not preferable.

The polyalkylene oxide of the present invention has Mh/f of 1,000 or more, preferably 1,500 or more. When Mh/f is smaller than 1,000, the physical properties such as flexibility at the time of forming the polyurethane resin are deteriorated, which is not preferable.

The area ratio of the molecular weight of Mh/3 or less of the polyalkylene oxide of the present invention is 2.0% or less, preferably 1.0% or less. When the area ratio of the molecular weight of Mh/3 or less is larger than 2.0%, the storage elastic modulus at the time of forming the polyurethane resin is lowered, and physical properties such as hysteresis loss and compression set are deteriorated, which is not preferable.

The polyalkylene oxide of the present invention is preferably from 1000 g/mol to 50,000 g/, based on the molecular weight of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups. Those with mol, particularly preferably from 3000 g/mol to 30,000 g/mol.

The polyalkylene oxide of the present invention can be subjected to ring-opening polymerization of an alkylene oxide by using an active hydrogen-containing compound as a starting agent in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and a Lewis acid, for example. The amount of the phosphazene compound used in the active hydrogen-containing compound in the active hydrogen-containing compound is preferably in the range of 0.001 mol to 0.1 mol, and is easily produced.

Here, specifically, the phosphazene compound can be exemplified by tetrakis(1,1,3,3-tetramethylindenyl)phosphonium hydroxide and tetrakis(1,1,3,3-tetraethylindenyl)hydrogen. Cerium oxide, tetrakis(1,1,3,3-tetra(n-propyl)fluorenyl)phosphonium hydroxide, tetrakis(1,1,3,3-tetraisopropyldecyl)phosphonium hydroxide, tetrakis (1) , 1,3,3-tetra(n-butyl)fluorenyl)phosphonium hydroxide, tetrakis(1,1,3,3-tetraphenylindenyl)phosphonium hydroxide, tetrakis (1,1,3,3- Tetrabenzylindenyl)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidin-2-imido)phosphonium hydroxide, tetrakis(1,3-dimethylimidazolidin-2-ylidene) Barium hydroxide, tetrakis(1,1,3,3-tetramethylindenyl)hydrocarbonate, tetrakis(1,1,3,3-tetraethylindenyl)hydrogen hydrazine, tetrakis (1,1, 3,3-tetrakis(n-propyl)decyl)phosphonium hydrogencarbonate, tetrakis(1,1,3,3-tetraisopropyldecyl)phosphonium hydrogencarbonate, tetrakis (1,1,3,3-tetra n-Butyl) mercapto) bismuth bicarbonate, tetrakis(1,1,3,3-tetraphenylindenyl)hydrocarbonate, tetrakis(1,1,3,3-tetrabenzylindenyl)hydrocarbonate And a phosphazene salt such as tetrakis(1,3-dimethylimidazolidin-2-imido)phosphonium hydrogencarbonate or tetrakis(1,3-dimethylimidazolidin-2-imido)phosphonium hydrogencarbonate.

Further, it can be exemplified by tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydroxide, tetra [three (di-n-propylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di-n-butylamine) (n-phosphoranylidene) ruthenium hydroxide, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(1,3-dimethylimidazolidin-2- Imino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetrakis[tris(diethylamino)phosphorane) Amino] bismuth hydrogencarbonate, tetrakis[tris(di-n-propylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydrogencarbonate , tetrakis[tris(di-n-butylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydrogencarbonate, tetra[3 (1, a phosphazene salt such as 3-dimethylimidazolidin-2-ylidene)phosphoranylideneamino]phosphonium hydrogencarbonate.

Further, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5 can be exemplified. , 4λ5-linked di(phosphazene).

Here, the phosphazene compound is preferably a phosphazene salt represented by the above formula (1).

Since the polyalkylene oxide of the present invention has a high molecular weight, a low degree of unsaturation, a narrow molecular weight distribution, and a small amount of a low molecular weight component, the storage modulus of the urethane resin obtained by using it is improved, and hysteresis loss and compression can be expected. Physical properties such as permanent deformation are improved. [Examples]

Hereinafter, the present invention will be described by way of examples, but the present examples are not limited by the present invention.

First, a method for calculating catalyst activity and a method for analyzing polyalkylene oxide will be described.

(1) Catalytic activity (unit: g/mol·min) The amount of the alkylene oxide to be reacted is a (unit: g), and the amount of the phosphazene salt to be used is b (unit: mol) The time required for the polymerization was set to c (unit: min), and the catalyst activity was calculated according to the following formula. Catalyst activity = a / (b × c).

(2) Molecular weight of polyalkylene oxide (unit: g/mol) The hydroxyl value d (unit: mgKOH/g) of the polyalkylene oxide was measured by the method described in JIS K-1557. The number of functional groups of the obtained polyalkylene oxide was set to e, and the molecular weight of the polyalkylene oxide was calculated from the following formula. Molecular weight = (56100 / d) × e.

In addition, using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC 8020), tetrahydrofuran was used as a solvent, and measurement was carried out at 40 ° C, and polystyrene was used as a standard material to calculate a polycyclic ring. The number average molecular weight (Mn), the weight average molecular weight (Mw), and the highest peak molecular weight (Mh) of the oxyalkylene.

(3) Area ratio of the low molecular weight component of the polyalkylene oxide (unit: %) The low molecular weight component of the molecular weight (Mh/3) or less obtained by dividing Mh calculated by the above-mentioned method (2) by 3 is calculated. Area ratio.

(4) Unsaturation of polyalkylene oxide (unit: meq/g) The degree of unsaturation of polyalkylene oxide was calculated by the method described in JIS K-1557.

(5) Molecular weight distribution of polyalkylene oxide (unit: none) The molecular weight distribution (Mw) of the polyalkylene oxide was calculated from the number average molecular weight (Mn) and the weight average molecular weight (Mw) calculated in the above method (2). /Mn).

Synthesis Example 1 (Synthesis of Phosphazinate A) In a 2-liter four-necked flask equipped with a stirring blade, 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added under a nitrogen atmosphere. Stirring was carried out at 20 °C. While maintaining the stirring, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours, and the temperature was raised to 100 ° C, and 107 g (0.92 mol) was added dropwise for 1 hour. 1,1,3,3-tetramethylguanidine. The obtained white slurry solution was stirred at 100 ° C for 14 hours, and then cooled to 80 ° C, and 250 ml of ion-exchanged water was added thereto, followed by stirring for 30 minutes. When the stirring is stopped, the slurry is completely dissolved to obtain a two-phase solution. The obtained two-phase solution was subjected to oil-water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the obtained aqueous phase to carry out oil-water separation, and the dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water.

The obtained dichloromethane solution was pipetted into a 2-liter four-necked flask equipped with a stirring blade, and after adding 900 g of 2-propanol, the temperature was raised to 80 ° C to 100 ° C under normal pressure to remove dichloroethylene. Methane. While stirring the obtained 2-propanol solution, the internal temperature was allowed to stand to 60 ° C, and then 31 g (0.47 mol, 1.1 mol equivalent relative to the iminophosphazene salt) of 85% by weight of hydrogen was added. Potassium oxide was reacted at 60 ° C for 2 hours. The temperature was cooled to 25 ° C, and the precipitated by-product salt was removed by filtration, whereby the target imidophosphazene salt A was obtained at a concentration of 25% by weight and a yield of 92% [the above formula (1) 860 g of a 2-propanol solution in which R ¹ is a methyl group, R ² is a methyl group, X ^- is a hydroxy anion, Y is a carbon atom, and a corresponds to 2 phosphazene salt.

Synthesis Example 2 (Synthesis of Phosphazide B) A 100 ml Schlenk tube with a magnetic rotor was placed under a nitrogen atmosphere, and 5.7 g of tetrakis[tris(dimethylamino)phosphorane was added. Aminoamine] ruthenium chloride (7.4 mmol, manufactured by Aldrich Co., Ltd.) and 16 ml of 2-propanol were stirred at 25 ° C to dissolve. While maintaining the stirring, 0.53 g [8.1 mmol, relative to tetrakis[tris(dimethylamino)phosphoranylidene]phosphonium chloride was added to 1.1 mol equivalents of 85% by weight of potassium hydroxide. A solution obtained by dissolving in 2-propanol. After stirring at 25 ° C for 5 hours, the precipitated by-product salt was removed by filtration, whereby the target phosphazene salt B was obtained at a concentration of 17% by weight and a yield of 98% [in the above formula (1) 32.7 g of a 2-propanol solution in which R ¹ is a methyl group, R ² is a methyl group, X ^- is a hydroxy anion, Y is a phosphorus atom, and a is equivalent to 3 phosphazene salt.

Example 1 In a 0.2-liter autoclave equipped with a stirring blade, 10 g (5 mmol) of a 25% by weight 2-propanol solution of phosphazene salt A obtained by Synthesis Example 1 was added. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and 2-propanol was removed under reduced pressure of 0.5 kPa. Then, 10 ml (10 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum was added and mixed, whereby an alkylene oxide polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C, and 108 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 18 ° C. The reaction was carried out in the range of ~22 °C. The residual propylene oxide and toluene were removed under reduced pressure of 0.5 kPa to obtain 106 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 350 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 20,000 g/mol, an unsaturation of 0.018 meq/g, and a molecular weight distribution of 1.08. The results are shown in Table 1.

Example 2 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (Sanyo Chemical Industries, Ltd., Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25 wt% 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1 0.54 g (0.27) M, 0.005 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, 0.54 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (0.54 mmol, 0.010 mol based on 1 mol of active hydrogen) was added, and the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 68 ° C to 72 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 840 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.017 meq/g, and a molecular weight distribution of 1.07. The results are shown in Table 1.

Example 3 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as active hydrogen-containing compound, and 25 wt% 2-propanol solution of phosphazene salt A obtained in Synthesis Example 1, 0.27 g (0.14) M, 0.0025 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, 0.27 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (0.27 mmol, 0.005 mol with respect to 1 mol of active hydrogen) was added, and the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 68 ° C to 72 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 1100 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6800 g/mol, an unsaturation of 0.016 meq/g, and a molecular weight distribution of 1.06. The results are shown in Table 1.

Example 4 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25 wt% 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1 0.54 g (0.27) M, 0.005 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, 0.54 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (0.54 mmol, 0.010 mol based on 1 mol of active hydrogen) was added, and the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 50 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 48 ° C. The reaction was carried out in the range of -52 °C. Then, after removing the residual propylene oxide under a reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 48 ° C to 52 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 125 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 550 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6800 g/mol, an unsaturation of 0.014 meq/g, and a molecular weight distribution of 1.05. The results are shown in Table 1.

Example 5 In a 0.2-liter autoclave equipped with a stirring blade, 6.0 g (6.0 mmol, active hydrogen amount: 18 mmol) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25 wt% 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1, 0.36 g (0.18) M, which is 0.010 mol relative to 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, 0.36 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (0.36 mmol, 0.020 mol with respect to 1 mol of active hydrogen) was added, and the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 68 ° C to 72 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 112 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 980 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 18,000 g/mol, an unsaturation degree of 0.022 meq/g, and a molecular weight distribution of 1.08. The results are shown in Table 1.

Example 6 In place of 0.54 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (0.54 mmol, 0.010 mol relative to 1 mol of active hydrogen), 1.0 mol/l of hexane using diethylzinc was used. An alkylene oxide polymerization catalyst or a polyalkylene oxide was produced in the same manner as in Example 2 except that 0.54 ml of a solution (0.54 mmol, 0.010 mol based on 1 mol of active hydrogen) was used. 127 g of a colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 750 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.016 meq/g, and a molecular weight distribution of 1.06. The results are shown in Table 1.

[Table 1]

Comparative Example 1 In a 0.2-liter autoclave equipped with a stirring blade, 6.0 g (6.0 mmol, active hydrogen amount: 18 mmol) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value of 160 mgKOH/g) as active hydrogen-containing compound, and 1-tert-butyl-4,4,4-tris (dimethyl) as phosphazene P4 base Alkyl)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5,4λ5- bis(phosphazene) 1.0 mol/l hexane solution 18 ml (18 M, 1.0 mol relative to 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, 18 ml of a 2.0 mol/l toluene solution of triisobutylaluminum (36 mmol, 2.0 mol based on 1 mol of active hydrogen) was added and mixed to obtain an epoxy resin. Alkane polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C, and 37 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 18 ° C. The reaction was carried out in the range of ~22 °C. The residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 42 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 11 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.016 meq/g, and a molecular weight distribution of 1.36. The results are shown in Table 2.

Comparative Example 2 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25 wt% 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1 0.54 g (0.27) M, 0.005 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was carried out under reduced pressure of 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C, and propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C to 72 ° C. The reaction is carried out within the range. As a result, the reaction was stopped at the time when 36 g of propylene oxide was supplied. The residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 36 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 46 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 2000 g/mol, an unsaturation of 0.013 meq/g, and a molecular weight distribution of 1.05. The results are shown in Table 2.

[Table 2]

Example 7 In a 0.2-liter autoclave equipped with a stirring blade, 10 g (5 mmol) of a 25% by weight 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1 was added. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and 2-propanol was removed under reduced pressure of 0.5 kPa. Then, 10 ml of a 1.0 mol/l toluene solution (10 mmol of aluminum atom) of aluminoxane (manufactured by Tosoh Fine Chemical Co., Ltd., trade name MMAO-3A) having methyl and isobutyl groups was added. Mixing, thereby obtaining an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 35 ° C, and 108 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 33 ° C. The reaction was carried out in the range of ~37 °C. The residual propylene oxide and toluene were removed under reduced pressure of 0.5 kPa to obtain 106 g of a colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 98%, and the obtained polyalkylene oxide had a molecular weight of 19,000 g/mol, an unsaturation of 0.016 meq/g, and a molecular weight distribution of 1.07. The results are shown in Table 3.

Example 8 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25 wt% 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1 0.54 g (0.27) M, 0.005 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, an aluminoxane having a methyl group and an isobutyl group (manufactured by Tosoh Fine Chemical Co., Ltd., trade name MMAO-3A) was added to a 1.0 mol/l toluene solution of 0.54 ml (aluminum atom was 0.54 mmol, relative to The active hydrogen was 1 mol to 0.010 mol), the internal temperature was set to 80 ° C, and a reduced pressure treatment of 0.5 kPa was carried out to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 68 ° C to 72 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of a colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 99%, and the obtained polyalkylene oxide had a molecular weight of 7,000 g/mol, an unsaturation of 0.016 meq/g, and a molecular weight distribution of 1.06. The results are shown in Table 3.

Example 9 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, active hydrogen amount: 54 mmol) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as active hydrogen-containing compound, and 25 wt% 2-propanol solution of phosphazene salt A obtained in Synthesis Example 1, 0.27 g (0.14) M, 0.0025 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, an aluminoxane having a methyl group and an isobutyl group (manufactured by Tosoh Fine Chemical Co., Ltd., trade name MMAO-3A) was added to a 1.0 mol/l toluene solution of 0.27 ml (aluminum atom was 0.27 mmol, as opposed to The active hydrogen was 0.00 mol (0.005 mol), the internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 68 ° C to 72 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of a colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 98%, and the obtained polyalkylene oxide had a molecular weight of 6,900 g/mol, an unsaturation of 0.014 meq/g, and a molecular weight distribution of 1.05. The results are shown in Table 3.

Example 10 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25 wt% 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1 0.54 g (0.27) M, 0.005 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, an aluminoxane having a methyl group and an isobutyl group (manufactured by Tosoh Fine Chemical Co., Ltd., trade name MMAO-3A) was added to a 1.0 mol/l toluene solution of 0.54 ml (aluminum atom was 0.54 mmol, relative to The active hydrogen was 1 mol to 0.010 mol), the internal temperature was set to 80 ° C, and a reduced pressure treatment of 0.5 kPa was carried out to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 50 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 48 ° C. The reaction was carried out in the range of -52 °C. Then, after removing the residual propylene oxide under a reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 48 ° C to 52 ° C. Carry out the reaction. The residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 125 g of a colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 97%, and the obtained polyalkylene oxide had a molecular weight of 6,700 g/mol, an unsaturation of 0.012 meq/g, and a molecular weight distribution of 1.04. The results are shown in Table 3.

Example 11 In a 0.2-liter autoclave equipped with a stirring blade, 6.0 g (6.0 mmol, active hydrogen amount: 18 mmol) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25 wt% 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1, 0.36 g (0.18) M, which is 0.010 mol relative to 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, an aluminoxane having a methyl group and an isobutyl group (manufactured by Tosoh Fine Chemical Co., Ltd., trade name MMAO-3A) was added to a 1.0 mol/l toluene solution of 0.36 ml (aluminum atom was 0.36 mmol, relative to The active hydrogen was 1 mol to 0.020 mol), the internal temperature was set to 80 ° C, and a reduced pressure treatment of 0.5 kPa was carried out to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 68 ° C to 72 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 112 g of a colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 96%, and the obtained polyalkylene oxide had a molecular weight of 18,000 g/mol, an unsaturation degree of 0.021 meq/g, and a molecular weight distribution of 1.08. The results are shown in Table 3.

[table 3]

Comparative Example 3 In a 0.2-liter autoclave equipped with a stirring blade, 6.0 g (6.0 mmol, active hydrogen amount: 18 mmol) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as active hydrogen-containing compound, and aluminoxane with methyl and isobutyl groups (manufactured by Tosoh Fine Chemical Co., Ltd., trade name MMAO-3A) 1.3 mol/l toluene solution 36 ml (36 mmol of aluminum atom, 2.0 mol relative to 1 mol of active hydrogen), the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 35 ° C, and propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 33 ° C to 37 ° C. The reaction is carried out within the range. As a result, the reaction was stopped at the time when 12 g of propylene oxide was supplied. The residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 9.0 g of a colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 25%, the obtained polyalkylene oxide had a molecular weight of 1500 g/mol, an unsaturation of 0.012 meq/g, and a molecular weight distribution of 1.42. The results are shown in Table 4.

Comparative Example 4 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25 wt% 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1 0.54 g (0.27) M, 0.005 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was carried out under reduced pressure of 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C, and propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C to 72 ° C. The reaction is carried out within the range. As a result, the reaction was stopped at the time when 36 g of propylene oxide was supplied. The residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 36 g of a colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 50%, and the obtained polyalkylene oxide had a molecular weight of 2000 g/mol, an unsaturation of 0.013 meq/g, and a molecular weight distribution of 1.05. The results are shown in Table 4.

[Table 4]

Example 12 In a 0.2-liter autoclave equipped with a stirring blade, 11 g (2.5 mmol) of a 17 wt% 2-propanol solution of phosphazene salt B obtained by Synthesis Example 2 was added. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and 2-propanol was removed under reduced pressure of 0.5 kPa. Then, 7.5 ml (7.5 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum was added and mixed, whereby an alkylene oxide polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C, and 108 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. The residual propylene oxide and toluene were removed under reduced pressure of 0.5 kPa to obtain 106 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 400 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 20,000 g/mol, an unsaturation of 0.008 g/g, and a molecular weight distribution of 1.08. The results are shown in Table 5.

Example 13 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added [manufactured by Sanyo Chemical Industries Co., Ltd., (trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g] as an active hydrogen-containing compound, and a 17% by weight 2-propanol solution of the phosphazene salt B obtained in Synthesis Example 2 (2.0 g ( 0.45 mmol, 0.008 mol relative to 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, 1.35 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (1.35 mmol, 0.025 mol with respect to 1 mol of active hydrogen) was added, and the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under a reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 108 ° C to 112 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 1040 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6,900 g/mol, an unsaturation of 0.007 meq/g, and a molecular weight distribution of 1.07. The results are shown in Table 5.

Example 14 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added [manufactured by Sanyo Chemical Industries Co., Ltd., (trade name) Sannix GP1000; hydroxyl value of 160 mgKOH/g] as an active hydrogen-containing compound, and a 17 wt% 2-propanol solution of 1.0 g of the phosphazene salt B obtained in Synthesis Example 2 ( 0.23 mmol, 0.004 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, 0.68 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (0.68 mmol, 0.013 mol with respect to 1 mol of active hydrogen) was added, and the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under a reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 108 ° C to 112 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 1300 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6800 g/mol, an unsaturation of 0.005 meq/g, and a molecular weight distribution of 1.06. The results are shown in Table 5.

Example 15 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added [manufactured by Sanyo Chemical Industry Co., Ltd., (trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g] 1.2 g of a 17 wt% 2-propanol solution of the active hydrogen-containing compound and the phosphazene salt B obtained in Synthesis Example 2. 0.27 mmol, 0.005 mol based on 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, 0.54 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (0.54 mmol, 0.010 mol based on 1 mol of active hydrogen) was added, and the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 78 ° C. The reaction was carried out in the range of -82 °C. Then, after the residual propylene oxide was removed under a reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 108 ° C to 112 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 125 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 650 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6800 g/mol, an unsaturation of 0.007 meq/g, and a molecular weight distribution of 1.05. The results are shown in Table 5.

Example 16 In a 0.2-liter autoclave equipped with a stirring blade, 6.0 g (6.0 mmol, active hydrogen amount: 18 mmol) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added (manufactured by Sanyo Chemical Industries, ( Trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g) as an active hydrogen-containing compound, and a 25% by weight 2-propanol solution of the phosphazene salt B obtained in Synthesis Example 2, 0.54 g (0.18) M, which is 0.010 mol relative to 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was performed under a reduced pressure of 0.5 kPa. Then, 0.36 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (0.36 mmol, 0.020 mol with respect to 1 mol of active hydrogen) was added, and the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed. An alkylene oxide polymerization catalyst is obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and 92 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 68 ° C. The reaction was carried out in the range of -72 °C. Then, after the residual propylene oxide was removed under a reduced pressure of 0.5 kPa, 18 g of ethylene oxide was intermittently supplied while maintaining the reaction pressure at 0.25 MPa or less, and the internal temperature was in the range of 108 ° C to 112 ° C. Carry out the reaction. The residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 112 g of a colorless and odorless polyalkylene oxide. The catalytic activity was 980 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 18,000 g/mol, an unsaturation of 0.008 g/g, and a molecular weight distribution of 1.08. The results are shown in Table 5.

Example 17 In addition to 1.35 ml (1.35 mmol, 0.008 mol, relative to active hydrogen 1 mol) of 1.0 mol/l toluene in place of triisobutylaluminum, 0.15 g (0.75 mmol, relative to active hydrogen 1 mol) was used. An alkylene oxide polymerization catalyst or a polyalkylene oxide was produced in the same manner as in Example 13 except that 0.025 mol of aluminum triisopropoxide was used. 127 g of a colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 750 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.007 meq/g, and a molecular weight distribution of 1.05. The results are shown in Table 5.

[table 5]

Example 18 In addition to 1.35 ml (1.35 mmol, 0.025 mol relative to 1 mol of active hydrogen) of a 1.0 mol/l toluene solution instead of triisobutylaluminum, 1.35 ml (1.35 mmol, relative to active hydrogen 1 mol) was used. An alkylene oxide polymerization catalyst or a polyalkylene oxide was produced in the same manner as in Example 13 except that a 0.05 mol) triphenylaluminum 1.0 M solution was used. 127 g of a colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 680 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.006 meq/g, and a molecular weight distribution of 1.06. The results are shown in Table 6.

Example 19 In place of 1.35 ml of a 1.0 mol/l toluene solution of triisobutylaluminum (1.35 mmol, 0.025 mol relative to 1 mol of active hydrogen), 0.18 g of aluminum chloride (1.35 mmol, relative to activity) was used. An alkylene oxide polymerization catalyst or a polyalkylene oxide was produced in the same manner as in Example 13 except that 1 mol of hydrogen was used as 0.025 mol. 126 g of a colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 650 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.006 meq/g, and a molecular weight distribution of 1.07. The results are shown in Table 6.

Example 20 A pure isobutylaluminoxane 1.0 M hexane solution was used instead of 1.35 ml (1.35 mmol, 0.025 mol relative to 1 mol of active hydrogen) of a 1.0 mol/l toluene solution instead of triisobutylaluminum. An alkylene oxide polymerization catalyst or a polyalkylene oxide was produced in the same manner as in Example 13 except that 1.35 ml (1.35 mmol, 0.025 mol based on 1 mol of active hydrogen). 107 g of a colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 350 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.006 meq/g, and a molecular weight distribution of 1.06. The results are shown in Table 6.

Example 21 An alkylene oxide polymerization catalyst or a polyalkylene oxide was produced by the same method as in Example 13 except that the internal temperature of the autoclave was changed from 70 °C to 120 °C. 127 g of a colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 850 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.006 meq/g, and a molecular weight distribution of 1.06. The results are shown in Table 6.

Example 22 In place of 1.35 ml (1.35 mmol, 0.025 mol relative to 1 mol of active hydrogen) of 1.0 mol/l toluene in place of triisobutylaluminum, 1.0 mol/l of hexane using diethylzinc. An alkylene oxide polymerization catalyst or a polyalkylene oxide was produced in the same manner as in Example 13 except that 1.35 ml of a solution (1.35 mmol, 0.025 mol based on 1 mol of active hydrogen) was used. 127 g of a colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 750 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.010 meq/g, and a molecular weight distribution of 1.07. The results are shown in Table 6.

[Table 6]

Comparative Example 5 In a 0.2-liter autoclave equipped with a stirring blade, 6.0 g (6.0 mmol, active hydrogen amount: 18 mmol) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added [manufactured by Sanyo Chemical Industry Co., Ltd., (trade name) Sannix GP1000; hydroxyl value of 160 mgKOH/g] as active hydrogen-containing compound, and 1-tert-butyl-4,4,4-tris (as phosphazene P4 base) Methylamino)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5,4λ5- bis(phosphazene) 1.0 mol/l hexane solution 18 ml ( 18 mmol, 1.0 mol relative to 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, 18 ml of a 2.0 mol/l toluene solution of triisobutylaluminum (36 mmol, 2.0 mol based on 1 mol of active hydrogen) was added and mixed to obtain an epoxy resin. Alkane polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C, and 37 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 18 ° C. The reaction was carried out in the range of ~22 °C. The residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 42 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 11 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 6900 g/mol, an unsaturation of 0.016 meq/g, and a molecular weight distribution of 1.36. The results are shown in Table 7.

Comparative Example 6 An alkylene oxide polymerization catalyst or a polyalkylene oxide was produced in the same manner as in Example 13 except that 0.45 mmol of the phosphazene salt was changed to 0.45 mmol of KOH. 36 g of colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 61 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 2000 g/mol, an unsaturation of 0.030 meq/g, and a molecular weight distribution of 1.05. The results are shown in Table 7.

Comparative Example 7 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1000 having three hydroxyl groups was added [manufactured by Sanyo Chemical Industry Co., Ltd., (trade name) Sannix GP1000; hydroxyl value: 160 mgKOH/g] as an active hydrogen-containing compound, and a 17% by weight 2-propanol solution of the phosphazene salt B obtained in Synthesis Example 2 (2.0 g ( 0.45 mmol, 0.008 mol relative to 1 mol of active hydrogen. After setting the inside of the autoclave to a nitrogen atmosphere, the internal temperature was set to 80 ° C, and dehydration treatment was carried out under reduced pressure of 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 ° C, and propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, while the internal temperature was 88 ° C to 92 ° C. The reaction is carried out within the range. As a result, 110 g of propylene oxide was supplied. The residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 125 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 460 g/mol·min, and the obtained polyalkylene oxide had a molecular weight of 7000 g/mol, an unsaturation of 0.024 meq/g, and a molecular weight distribution of 1.06. The results are shown in Table 3.

Comparative Example 8 In a 0.2-liter autoclave equipped with a stirring blade, 18 g (18 mmol, 54 mmol of active hydrogen) of a polyether polyol having a molecular weight of 1,000 having three hydroxyl groups was added [manufactured by Sanyo Chemical Industries Co., Ltd., (trade name) Sannix GP1000; hydroxyl value 160 mg KOH/g] 1.0.5 ml (1.35 mmol, relative to active hydrogen) of an active hydrogen-containing compound, 1.0 mol/l toluene solution of triisobutylaluminum 1 mol to 0.025 mol), the internal temperature was set to 80 ° C, and a reduced pressure of 0.5 kPa was performed.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C, and propylene oxide was allowed to react at a reaction pressure of 0.3 MPa or less and an internal temperature of 68 ° C to 72 ° C. However, after the reaction pressure of 0.3 MPa was reached at a reaction temperature of 70 ° C, no decrease in pressure was observed at all. After the reaction was continued at 70 ° C for 5 hours, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. 10 g of the polyether polyol of the raw material was recovered. The triisobutylaluminum alone did not show the polymerization activity of propylene oxide at all. The results are shown in Table 7.

[Table 7]

Example 23 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) was added. A solution of 25% by weight of 2-phosphanol of phosphazene salt A obtained in Synthesis Example 1 was 0.90 g (0.45 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 600 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.006 meq/g, a molecular weight distribution of 1.06, a Mh/f of 3,700 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.1%.

Example 24 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) was added. A solution of 25 wt% 2-propanol of the phosphazene salt A obtained in Synthesis Example 1 was 0.54 g (0.27 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 0.54 ml (0.54 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 600 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.005 meq/g, a molecular weight distribution of 1.05, a Mh/f of 3,600 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.1%.

Example 25 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) was added. A solution of 25% by weight of 2-phosphanol of phosphazene salt A obtained in Synthesis Example 1 was 0.90 g (0.45 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 70 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After the end of the reaction, the residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 125 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 400 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.005 meq/g, a molecular weight distribution of 1.05, a Mh/f of 3,600 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.1%.

Example 26 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) was added. A solution of 25% by weight of 2-phosphanol of phosphazene salt A obtained in Synthesis Example 1 was 0.90 g (0.45 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 120 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 128 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 1,500 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.008 g/g, a molecular weight distribution of 1.06, a Mh/f of 3,700 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.2%.

Example 27 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 9 g (active hydrogen amount: 27 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) was added. 0.45 g (0.23 mmol) of a 25% by weight 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1. The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 0.68 ml (0.68 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 117 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 500 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.008 g/g, a molecular weight distribution of 1.06, a Mh/f of 7,000 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.2%.

Example 28 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 0.90 g (0.45 mmol) of a 25% by weight 2-propanol solution of the phosphazene salt A obtained in Synthesis Example 1 was added. The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After the completion of the reaction, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 109 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 500 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.008 g/g, a molecular weight distribution of 1.06, a Mh/f of 7,000 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.2%.

Example 29 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of polyether polyol (Sannix GP1000 manufactured by Sanyo Chemical Industries Co., Ltd.) was added. A solution of 25% by weight of 2-phosphanol of phosphazene salt A obtained in Synthesis Example 1 was 0.90 g (0.45 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol/l hexane solution of aluminum isopropoxide (Al(OiPr) 3) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa to obtain an alkylene oxide. Polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 600 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.005 meq/g, a molecular weight distribution of 1.08, a Mh/f of 3,500 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 1.4%.

Example 30 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) was added. A solution of 25% by weight of 2-phosphanol of phosphazene salt A obtained in Synthesis Example 1 was 0.90 g (0.45 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol/l dibutyl ether solution of triphenylaluminum (AlPh3) was added, and the internal temperature was set to 80 ° C, and the pressure was reduced at 0.5 kPa to obtain an alkylene oxide polymerization contact. Media.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 600 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.006 meq/g, a molecular weight distribution of 1.07, a Mh/f of 3,700 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.4%.

Example 31 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) was added. A solution of 25% by weight of 2-phosphanol of phosphazene salt A obtained in Synthesis Example 1 was 0.90 g (0.45 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, aluminoxane (manufactured by Tosoh Fine Chemical Co., Ltd., MMAO-3A) 1.0 mol/l hexane solution 1.35 ml (1.35 mmol) was added, and the internal temperature was set to 80 ° C. The pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 85 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 250 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.005 meq/g, a molecular weight distribution of 1.05, a Mh/f of 2,000 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.1%.

Example 32 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) was added. A solution of 25% by weight of 2-phosphanol of phosphazene salt A obtained in Synthesis Example 1 was 0.90 g (0.45 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of 1.0 mol/l hexane solution of diethylzinc (ZnEt ₂ ) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. .

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 85 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 250 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.005 meq/g, a molecular weight distribution of 1.05, a Mh/f of 2,000 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.1%.

Example 33 A 0.2 liter autoclave equipped with a stirring blade was placed under a nitrogen atmosphere, and 18 g (active amount of hydrogen: 54 mmol) of polyether polyol (Sannix GP1000 manufactured by Sanyo Chemical Industries, Ltd.) was added. Further, 2.0 g (0.45 mmol) of a 17 wt% 2-propanol solution of the phosphazene salt B obtained in Synthesis Example 2. The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of a colorless and odorless polyalkylene oxide. The catalyst activity was 600 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.006 meq/g, a molecular weight distribution of 1.06, a Mh/f of 3,700 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 0.1%.

The above results are shown in Tables 8 and 9.

[Table 8]

[Table 9]

As clearly shown in Tables 8 and 9, the polyalkylene oxides obtained in Examples 23 to 33 satisfied all of the following i) to iv). i) the degree of unsaturation is 0.020 meq/g or less; ii) Mw/Mn is 1.10 or less; iii) Mh/f is 1,000 or more; iv) The area ratio of molecular weight of Mh/3 or less is 2.0% or less.

(The number average molecular weight determined by gel permeation chromatography using polystyrene as a standard substance is Mn, the weight average molecular weight is Mw, and the molecular weight of the highest peak is Mh, and Set the number of functional groups of the polyalkylene oxide to f)

Comparative Example 9 A 0.2 liter autoclave was placed under a nitrogen atmosphere, and 18 g (18 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) and phosphorus obtained in Synthesis Example 1 were added. 0.54 g (0.27 mmol) of a 25% by weight 2-propanol solution of nitrile salt A. The internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and the reaction was carried out while intermittently supplying 92 g of propylene oxide so that the reaction pressure was maintained at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. Then, the internal temperature of the autoclave was changed to 110 ° C, and the reaction was carried out while intermittently supplying 18 g of ethylene oxide so that the reaction pressure was maintained at 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of a colorless and odorless polyalkylene oxide. The catalytic activity was 500 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.026 meq/g, a molecular weight distribution of 1.12, a Mh/f of 3,300 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 3.7%.

Comparative Example 10 A 0.2 liter autoclave was placed under a nitrogen atmosphere, and 18 g (18 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) and triisobutylaluminum (TIBAL) were added. A 1.0 mol/l toluene solution of 1.35 ml (1.35 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa.

The internal temperature of the autoclave was changed to 90° C., and 10 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less, and the reaction was carried out. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. 18 g of colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 0 g/mol·min, and the obtained polyalkylene oxide was a polyether polyol (Sannix GP1000 manufactured by Sanyo Chemical Industries, Ltd.) as a raw material.

Comparative Example 11 A 0.2 liter autoclave was placed under a nitrogen atmosphere, and 18 g (active hydrogen amount: 54 mmol) of a polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000), potassium hydroxide was added. (KOH) 50% by weight aqueous solution 50 mg (0.45 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 1.35 ml (1.35 mmol) of a 1.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 90 ° C, and 36 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. 27 g of colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 60 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.030 meq/g, a molecular weight distribution of 1.12, a Mh/f of 500 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 4.3%.

Comparative Example 12 A 0.2 liter autoclave was placed under a nitrogen atmosphere, and 6 g (18 mmol of active hydrogen) polyether polyol (manufactured by Sanyo Chemical Industries, Inc., Sannix GP1000) and phosphorus were added. 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5, a nitrile P4 base, 4 λ5- bis (phosphazene) 1.0 mol/l hexane solution 18 ml (18 mmol). The internal temperature was set to 80 ° C, and the pressure reduction treatment was performed at 0.5 kPa. Then, 18 ml (36 mmol) of a 2.0 mol/l toluene solution of triisobutylaluminum (TIBAL) was added, and the internal temperature was set to 80 ° C, and the pressure reduction treatment was carried out at 0.5 kPa to obtain an alkylene oxide polymerization catalyst.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was changed to 20 ° C, and 37 g of propylene oxide was intermittently supplied while maintaining the reaction pressure at 0.3 MPa or less. After the reaction was completed, the residual propylene oxide was removed under reduced pressure of 0.5 kPa. 42 g of colorless and odorless polyalkylene oxide were obtained. The catalyst activity was 10 g/mol·min, and the obtained polyalkylene oxide had an unsaturation of 0.016 meq/g, a molecular weight distribution of 1.36, a Mh/f of 3,300 g/mol, and a low molecular weight component of Mh/3 or less. The area ratio is 3.7%.

The results of Comparative Examples 9 to 12 are shown in Table 10.

[Table 10]

Application Example 1 100 parts by weight of the polyalkylene oxide obtained in Example 23, 5.8 parts of diphenylmethane diisocyanate (trade name: C-1394), and 0.05 parts of triethylenediamine (trade name: TEDA-) were used. Add L33) to a disposable cup and stir. After the completion of the stirring, the viscoelasticity was measured under the conditions of a nitrogen atmosphere at 25 ° C and a frequency of 10 Hz using a rotary rheometer (Tholiquidmeter MR-500 manufactured by UBM Corporation). The storage elastic modulus (G') after 50 minutes after the completion of the stirring was 45,000 Pa.

Application Example 2 100 parts by weight of the polyalkylene oxide obtained in Comparative Example 9, 5.8 parts of diphenylmethane diisocyanate (trade name: C-1394), and 0.05 parts of triethylenediamine (trade name: TEDA-) Add L33) to a disposable cup and stir. After the completion of the stirring, the viscoelasticity was measured under the conditions of a nitrogen atmosphere at 25 ° C and a frequency of 10 Hz using a rotary rheometer (Tholiquidmeter MR-500 manufactured by UBM Corporation). The storage elastic modulus (G') after 50 minutes after the completion of the stirring was 15,000 Pa.

As described above, the present invention has been described in detail with reference to the specific embodiments thereof, and it is understood by those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the invention.

In the present invention, preferred combinations of the phosphazene salt, the Lewis acid, and the active hydrogen-containing compound represented by the formula (1) are shown in Tables 11 to 18.

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

Further, in the present invention, preferred combinations of the phosphazene compound, the Lewis acid, and the active hydrogen-containing compound to be used are specifically shown in Tables 19 to 24.

[Table 19]

[Table 20]

[Table 21]

[Table 22]

[Table 23]

[Table 24]

In addition, the specification, patent application scope and abstract of Japanese Patent Application No. 2014-164289, filed on August 12, 2014, the specification of Japanese Patent Application No. 2014-164290 filed on August 12, 2014 Japanese Patent Application No. 2015-145645 filed on July 23, 2015, the scope and abstract of the patent application, and the Japanese Patent Application No. 2015 filed on July 23, 2015. The entire contents of the specification, the claims, the drawings, and the abstract of the specification of the disclosure of the disclosure of the disclosure of [Industrial availability]

By using the alkylene oxide polymerization catalyst of the present invention, a polyalkylene oxide can be efficiently produced. The obtained polyalkylene oxide can be used for a polyurethane raw material, a polyester raw material, a surfactant raw material, a lubricant raw material, and the like.

Further, the polyalkylene oxide of the present invention can be used for a polyurethane raw material, a polyester raw material, a surfactant raw material, a lubricant raw material, and the like.

The polyalkylene oxide obtained by using the alkylene oxide polymerization catalyst of the present invention is expected to react with various isocyanate compounds, and is expected to be used for a rigid foam or a car seat used for a heat insulating material or the like. Soft foams, adhesives, paints, sealing materials, thermosetting elastomers, and thermoplastic elastomers used in cushions, bedding, and the like are developed.

no

Fig. 1 is a view showing a method of calculating an area ratio of a low molecular weight component of a polyalkylene oxide in Examples. 2 is a view (enlarged view) showing a method of calculating an area ratio of a low molecular weight component of a polyalkylene oxide in the examples.

Claims (15)

An alkylene oxide polymerization catalyst comprising a phosphazene salt represented by the formula (1) and a Lewis acid, In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; here, a ring structure in which R ¹ and R ² are bonded to each other, and R ¹ each other may be formed. Or a ring structure in which R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogencarbonate anion; A carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and a is 3 when Y is a phosphorus atom. The alkylene oxide polymerization catalyst according to claim 1, wherein the ratio of the phosphazene salt represented by the formula (1) to the Lewis acid is [phosphazene salt]: [Lewis acid] = 1: 0.002 ~500 (Morbi). The alkylene oxide polymerization catalyst according to claim 1 or 2, wherein the Lewis acid is at least one compound selected from the group consisting of an aluminum compound, a zinc compound, and a boron compound. The alkylene oxide polymerization catalyst according to claim 1 or 2, wherein the Lewis acid is at least one compound selected from the group consisting of organoaluminum, aluminoxane and organozinc. The alkylene oxide polymerization catalyst according to any one of claims 1 to 4, which comprises a phosphazene salt represented by the formula (1), a Lewis acid, and an active hydrogen-containing compound, In the general formula (1), R ¹ is and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; herein, may form a ring structure R ¹ and R ² are bonded, R & lt another ¹ Or a ring structure in which R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogencarbonate anion; A carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and a is 3 when Y is a phosphorus atom. The alkylene oxide polymerization catalyst according to claim 5, wherein the active hydrogen-containing compound is selected from the group consisting of water, a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group. At least one of the group consisting of. A method for producing an alkylene oxide polymerization catalyst, which comprises the alkylene oxide polymerization catalyst according to claim 5 or 6, which is characterized in that the phosphazene salt represented by the general formula (1) After mixing with the active hydrogen-containing compound, they are mixed with a Lewis acid. A method for producing a polyalkylene oxide, which is characterized in that ring-opening polymerization of alkylene oxide is carried out in the presence of an alkylene oxide polymerization catalyst according to any one of claims 1 to 5. A polyalkylene oxide which satisfies all of the following i) to iv): i) an unsaturation of 0.020 meq/g or less ii) a Mw/Mn of 1.10 or less; iii) a Mh/f of 1,000 or more; iv) Mh The area ratio of the molecular weight of /3 or less is 2.0% or less. Among them, the number average molecular weight determined by gel permeation chromatography using polystyrene as a standard substance is Mn, and the weight average molecular weight is set to Mw, the molecular weight of the highest peak is Mh, and the number of functional groups of the polyalkylene oxide is set to f. The polyalkylene oxide according to claim 9, wherein the molecular weight calculated from the hydroxyl group of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups thereof is from 1000 g/mol to 50,000. The range of g/mol. A method for producing a polyalkylene oxide, which comprises the polyalkylene oxide according to claim 9 or 10, characterized in that the alkylene oxide polymerization catalyst comprising a phosphazene compound and a Lewis acid is present The ring-opening polymerization of an alkylene oxide is carried out using an active hydrogen-containing compound as a starter; and the phosphazene compound is used in an amount of 0.001 with respect to 1 mol of active hydrogen in the active hydrogen-containing compound. Moer ~ 0.1 mole range. The method for producing a polyalkylene oxide according to claim 11, wherein the phosphazene compound is a phosphazene salt represented by the formula (1): In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; here, a ring structure in which R ¹ and R ² are bonded to each other, and R ¹ each other may be formed. Or a ring structure in which R ^{2 is} bonded to each other; X ^- represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxyl anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogencarbonate anion; A carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and a is 3 when Y is a phosphorus atom. The method for producing a polyalkylene oxide according to claim 11 or 12, wherein the ratio of the phosphazene compound to the Lewis acid is [phosphazene compound]: [Lewis acid] = 1: 0.002 to 500 (Mo Ear ratio). The method for producing an alkylene oxide according to any one of claims 11 to 13, wherein the Lewis acid is at least one compound selected from the group consisting of an aluminum compound, a zinc compound, and a boron compound. The method for producing an alkylene oxide according to any one of claims 11 to 13, wherein the Lewis acid is at least one compound selected from the group consisting of organoaluminum, aluminoxane and organozinc. .