WO2016024577A1

WO2016024577A1 - Alkylene oxide polymerization catalyst and method for producing polyalkylene oxides using same

Info

Publication number: WO2016024577A1
Application number: PCT/JP2015/072706
Authority: WO
Inventors: 井上善彰; 山本敏秀; 森勝朗
Original assignee: 東ソー株式会社
Priority date: 2014-08-12
Filing date: 2015-08-10
Publication date: 2016-02-18
Also published as: CN106661220B; CN106661220A; CN109337060A; KR20170039674A; TW201630971A; KR102391669B1; CN109337060B

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 process for producing a polyalkylene oxide using the same, and in particular, polyalkylene oxide exhibiting a high molecular weight, a low degree of unsaturation and a narrow molecular weight distribution under the production conditions at a low temperature. However, the present invention relates to a novel alkylene oxide polymerization catalyst that can be efficiently produced, and a method for producing a polyalkylene oxide using the same.

It is industrially known that polyalkylene oxide is produced by addition polymerization of alkylene oxide using potassium hydroxide as a catalyst. However, when a high molecular weight polyalkylene oxide is produced by this method, the resulting polyalkylene oxide has a problem that the degree of unsaturation increases because it contains a large amount of monool.

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

Also, as a method for producing a polyalkylene oxide having a low degree of unsaturation, a method for producing a polyalkylene oxide using a specific phosphazenium salt as a catalyst has been proposed (see, for example, Patent Documents 3 to 5).

On the other hand, an alkylene oxide obtained by mixing an active hydrogen-containing compound and an aluminoxane so that the ratio of active hydrogen in the active hydrogen-containing compound to aluminum atoms in the aluminoxane is 0.2 to 1: 1 (molar ratio). A method for producing a polyalkylene oxide by carrying out ring-opening polymerization of an alkylene oxide using a polymerization catalyst has been proposed (for example, see Patent Document 6).

Furthermore, as a method for producing a polyalkylene oxide, an alkylene oxide polymerization catalyst obtained by mixing an active hydrogen-containing compound, a phosphazene compound, and triisobutylaluminum at a molar ratio of 1: 1: 2 is used, and at 20 ° C. in a toluene solvent. A method for producing a polyalkylene oxide by ring-opening polymerization of an alkylene oxide has been proposed (for example, see Non-Patent Document 1). In this case, the catalytically active species is such that the deprotonation reaction of the active hydrogen-containing compound proceeds by the reaction between the active hydrogen-containing compound and the phosphazene compound, and then the deprotonated active hydrogen is reacted with triisobutylaluminum. A mechanism has been proposed in which the contained compound moves onto aluminum to become a catalytically active species.

US Pat. No. 5,235,114 Japanese Laid-Open Patent Publication No. 4-59825 Japanese Patent No. 3,497,054 (Japanese Unexamined Patent Publication No. 10-77289) Japanese Patent No. 3905638 (Japanese Unexamined Patent Publication No. 11-106500) Japanese Patent No. 5663856 (Japanese Unexamined Patent Publication No. 2010-150514) Japanese Unexamined Patent Publication No. 2011-122134

The methods described in

Patent Documents

1 and 2 have problems such that the molecular weight distribution of the obtained polyalkylene oxide is wide and ethylene oxide is difficult to adapt as alkylene oxide.

The method proposed in Patent Document 3 has a problem that the conversion rate of alkylene oxide is as low as 9 to 19%. Further, the polyalkylene oxide obtained was a mixture of a high molecular weight product having a molecular weight of 17000000 to 160000000 g / mol and a low molecular weight product having a molecular weight of 1700 to 2300 g / mol, and the polyalkylene oxide had no particular characteristics.

In the methods described in Patent Documents 4 to 6, the degree of unsaturation of the obtained polyalkylene oxide is still high, and further reduction has been demanded. In addition, if the polymerization temperature is lowered, the problem that the catalyst activity is reduced occurs. Conversely, if the polymerization temperature is increased, the problem that the degree of unsaturation, which is an index of the amount of impurities in the product, is increased. It was easy to do.

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

If the degree of unsaturation of the polyalkylene oxide is increased, the crosslink density when the polyurethane resin is used is lowered, and the storage elastic modulus is lowered, so that physical properties such as hysteresis loss and compression set are lowered. Further, when the molecular weight distribution of the polyalkylene oxide is widened, there is a problem that the moldability at the time of forming a polyurethane resin is deteriorated. In addition, if the low molecular weight component in the polyalkylene oxide is increased, the crosslink density in the case of a polyurethane resin is lowered and the storage elastic modulus is lowered, so that the physical properties such as hysteresis loss and compression set are lowered. ing.

Therefore, an alkylene oxide that can efficiently produce a polyalkylene oxide that uses a small amount of an expensive phosphazene compound and exhibits a high molecular weight, a low degree of unsaturation, and a narrow molecular weight distribution even under low-temperature production conditions. There is a need for a polymerization catalyst and a method for producing a polyalkylene oxide using the same.

As a result of intensive investigations to solve the above problems, the present inventors have found that an alkylene oxide polymerization catalyst containing a specific phosphazenium salt and a Lewis acid has a high molecular weight, a low viscosity, even under low-temperature production conditions. The inventors have found that it is possible to efficiently produce a polyalkylene oxide having a saturation degree and a narrow molecular weight distribution, and have completed the present invention.

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

[1] An alkylene oxide polymerization catalyst containing a phosphazenium salt represented by the general formula (1) and a Lewis acid.

(In the general formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, R ¹ and R ² are bonded to each other. , R ¹ or R ² may be bonded to each other to form a ring structure, X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or Y represents a hydrogen carbonate anion, Y represents a carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and 3 when Y is a phosphorus atom.

[2] The ratio of the phosphazenium salt represented by the general formula (1) and the Lewis acid is [phosphazenium salt]: [Lewis acid] = 1: 0.002 to 500 (molar ratio) The alkylene oxide polymerization catalyst according to the above [1].

[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 the above [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 the above [1] to [4], comprising a phosphazenium salt represented by the general formula (1), a Lewis acid, and an active hydrogen-containing compound.

[In the general formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, ring structure R ¹ and R ² are bonded to each other to form a ring structure R ¹ s or R ² together are bonded to each other. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. Y represents a carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and 3 when Y is a phosphorus atom. ].

[6] The active hydrogen-containing compound is at least one 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. [5] The alkylene oxide polymerization catalyst according to [5].

[7] The alkylene oxide according to the above [5] or [6], wherein the phosphazenium salt represented by the general formula (1) and the active hydrogen-containing compound are mixed and then mixed with a Lewis acid. A method for producing a polymerization catalyst.

[8] A method for producing a polyalkylene oxide, comprising carrying out ring-opening polymerization of alkylene oxide in the presence of the alkylene oxide polymerization catalyst according to any one of [1] to [5].

[9] A polyalkylene oxide satisfying all of the following i) to iv).
i) 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) Mh / 3 or less molecular weight area ratio is 2.0% or less ( However, the number average molecular weight obtained from gel permeation chromatography measurement using polystyrene as a standard substance is Mn, 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] In the above [9], the molecular weight calculated from the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups thereof is in the range of 1000 to 50000 g / mol. The polyalkylene oxide described.

[11] ring-opening polymerization of alkylene oxide using an active hydrogen-containing compound as an initiator in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and a Lewis acid, and relative to 1 mol of active hydrogen in the active hydrogen-containing compound, The method for producing a polyalkylene oxide according to the above [9] or [10], wherein the amount of the phosphazene compound used is in the range of 0.001 to 0.1 mol.

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

[13] The production of the polyalkylene oxide according to the above [11] or [12], 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. Method.

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

[15] The above [11] to [14], wherein the ratio of the phosphazene compound to the Lewis acid is [phosphazene compound]: [Lewis acid] = 1: 0.002 to 500 (molar ratio). The manufacturing method of the polyalkylene oxide in any one of.

According to the present invention, it is possible to obtain an alkylene oxide polymerization catalyst that produces a small amount of impurities due to side reactions and has high catalytic activity at low temperatures. Moreover, a polyalkylene oxide having a high molecular weight, a low degree of unsaturation, and a narrow molecular weight distribution can be produced by polymerizing an alkylene oxide using the alkyleneoxy polymerization catalyst of the present invention.

In addition, the urethane resin obtained by using the polyalkylene oxide of the present invention, which has a high molecular weight, a low degree of unsaturation, a narrow molecular weight distribution, and a low low molecular weight component, improves the storage elastic modulus. Improvements in physical properties such as permanent distortion can be expected.

It is a figure which shows the calculation method of the area ratio of the low molecular-weight component of the polyalkylene oxide in an Example. It is a figure (enlarged view) which shows the calculation method of the area ratio of the low molecular-weight component of the polyalkylene oxide in an Example.

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

Here, as the hydrocarbon group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, t -Butyl group, cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, Examples include decyl group, cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and nonadecyl group.

Examples of the case where R ¹ and R ² are bonded to each other to form a ring structure include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, and an isoindolyl group.

Examples of the ring structure in which R ¹ or R ² are bonded to each other include a ring structure in which one substituent is an alkylene group such as an ethylene group, a propylene group, or a butylene group and is bonded to the other substituent. Can be mentioned.

Among these, R ¹ and R ² are particularly preferably a methyl group, an ethyl group, or an isopropyl group because it becomes an alkylene oxide polymerization catalyst having excellent catalytic activity.

X ⁻ in the phosphazenium salt is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion.

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

Examples of the alkylcarboxy anion having 2 to 5 carbon atoms include an acetoxy anion, an ethyl carboxy anion, an n-propyl carboxy anion, an isopropyl carboxy anion, an n-butyl carboxy anion, an isobutyl carboxy anion, and a t-butyl carboxy anion. Can do.

Among these, X ⁻ is particularly preferably a hydroxy anion or a hydrogen carbonate anion since it becomes an alkylene oxide polymerization catalyst having excellent catalytic activity. In the present invention, when Y is a carbon atom, the phosphazenium salt is represented by the following general formula ( 2).

[In the general formula (2), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, ring structure R ¹ and R ² are bonded to each other to form a ring structure R ¹ s or R ² together are bonded to each other. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or an oxyhydrogen anion. ]
In the present invention, when Y is a phosphorus atom, the phosphazenium salt is represented by the following general formula (3).

[In the general formula (3), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, ring structure R ¹ and R ² are bonded to each other to form a ring structure R ¹ s or R ² together are bonded to each other. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or an oxyhydrogen anion. ]
In the present invention, the phosphazenium salt specifically includes tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraethylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra (n-propyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraisopropylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra (N-Butyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraphenylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetrabenzylguanidino) phosphonium hydroxide, tetrakis (1 , 3-Dimethylimidazo Gin-2-imino) phosphonium hydroxide, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydroxide, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydrogen carbonate, tetrakis (1, 1,3,3-tetraethylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-propyl) guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraisopropylguanidino) phosphonium Hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-butyl) guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraphenylguanidino) phosphoniu Hydrogen carbonate, tetrakis (1,1,3,3-tetrabenzylguanidino) phosphonium hydrogen carbonate, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydrogen carbonate, tetrakis (1,3-dimethylimidazolidine-2 -Phosphazenium salts such as imino) phosphonium hydrogen carbonate can be exemplified.

Also, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide, tetrakis [tris (diethylamino) phosphoranylideneamino] phosphonium hydroxide, tetrakis [tris (di-n-propylamino) phosphoranylideneamino] phosphonium hydroxy Tetrakis [tris (diisopropylamino) phosphoranylideneamino] phosphonium hydroxide, tetrakis [tris (di-n-butylamino) phosphoranylideneamino] phosphonium hydroxide, tetrakis [tris (diphenylamino) phosphoranylideneamino] phosphonium Hydroxide, tetrakis [tris (1,3-dimethylimidazolidine-2-imino) phosphoranylideneamino] phosphonium hydroxide, tetrakis Tris (dimethylamino) phosphoranylideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diethylamino) phosphoranylideneamino] phosphonium hydrogen carbonate, tetrakis [tris (di-n-propylamino) phosphoranylideneamino] phosphonium hydrogen carbonate, tetrakis [ Tris (diisopropylamino) phosphoranylideneamino] phosphonium hydrogen carbonate, tetrakis [tris (di-n-butylamino) phosphoranylideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diphenylamino) phosphoranylideneamino] phosphonium hydrogen carbonate, tetrakis [Tris (1,3-dimethylimidazolidine-2-imino) phospho Niriden'amino] phosphazenium salt such as phosphonium hydrogensulfate carbonate can be exemplified.

Among these, tetrakis (1,1,3,3-tetramethylguanidino) phosphazenium hydroxide, tetrakis (1,1,3,3-) are used as catalysts for producing polyalkylene oxides having excellent catalytic performance. Tetramethylguanidino) phosphazenium hydrogen carbonate and tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide are particularly preferred.

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 organic aluminum, inorganic aluminum, and aluminoxane.

As organic aluminum, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum, etc. Can be mentioned.

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

Examples of the aluminoxane include, for example, the following formula (—AlR ³ —O—) _n
(In the formula, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms. N represents an integer of 2 or more.)
The compound shown by can be mentioned.

Here, as the hydrocarbon group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, t -Butyl group, cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, Examples include decyl group, cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and nonadecyl group. Among these, as R ³ , a methyl group and an isobutyl group are preferable because they are easily available and serve as an alkylene oxide polymerization catalyst exhibiting a high conversion rate of alkylene oxide.

Specific examples of the aluminoxane include methylaluminoxane, isobutylaluminoxane, methyl-isobutylaluminoxane, and the like. Examples of commercially available products of aluminoxane include (trade name) MMAO-3A (manufactured by Tosoh Finechem), (trade name) TMAO-340 series (manufactured by Tosoh Finechem), and (trade name) TMAO-200 series ( (Trade name) PBAO (manufactured by Tosoh Finechem), (brand name) Solid-MAO (manufactured by Tosoh Finechem), and the like.

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

Examples of boron compounds include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris (pentafluorophenyl) borane, and trifluoroborane.

Of these, organoaluminum, aluminoxane, and organozinc are preferred, and organoaluminum is particularly preferred, since it becomes an alkylene oxide polymerization catalyst having excellent catalytic performance.

Of these, triisobutylaluminum, triisopropoxyaluminum, and diethylzinc are particularly preferable because they are readily available and become an alkylene oxide polymerization catalyst having excellent catalytic activity.

The ratio of the phosphazenium salt and the Lewis acid in the alkylene oxide polymerization catalyst of the present invention is arbitrary as long as the action as an alkylene oxide polymerization catalyst is expressed, and is not particularly limited. Among them, [phosphazenium salt]: [Lewis acid] = 1: 0.002 to 500 (molar ratio) is preferable because it is a polymerization catalyst having particularly excellent catalytic activity and a high conversion rate of alkylene oxide.

As the alkylene oxide polymerization catalyst of the present invention, it becomes possible to efficiently produce a polyalkylene oxide having a higher molecular weight, a lower degree of unsaturation and a narrow molecular weight distribution, and it becomes a polymerization catalyst excellent in catalytic activity. It is particularly preferable to use an active hydrogen-containing compound. Examples of the active hydrogen-containing compound at that 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-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, triglyceride, and the like. Mention may be made of methylolpropane, 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 and adipic acid.

Examples of the thiol compound include ethanedithiol and butanedithiol.

Examples of the polyether polyol having a hydroxyl group include a polyether polyol having a molecular weight of 200 to 3000.

These active hydrogen-containing compounds may be used alone or in combination of several kinds.

In addition, when an active hydrogen-containing compound is used, it becomes a polymerization catalyst excellent in catalytic activity, which can efficiently produce a polyalkylene oxide having a higher molecular weight, a lower degree of unsaturation, and a narrow molecular weight distribution. Therefore, the amount of the phosphazenium salt is preferably 0.001 to 10 mol, particularly preferably 0.001 to 5 mol, per 1 mol of active hydrogen in the active hydrogen-containing compound. The Lewis acid is preferably 0.001 to 10 mol, particularly preferably 0.001 to 5 mol, per 1 mol of active hydrogen in the active hydrogen-containing compound.

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

For example, a method of mixing a phosphazenium salt and a Lewis acid can be mentioned. In that case, for example, benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, 1,2-dimethoxyethane may be used as the solvent.

In the presence of an alkylene oxide polymerization catalyst containing a phosphazenium salt and a Lewis acid, an active hydrogen-containing compound is used as an initiator, and when ring-opening polymerization of alkylene oxide is performed, the phosphazenium salt, Lewis acid, and active hydrogen-containing compound are mixed simultaneously. Any method may be used, such as a method of mixing other two components with one of these components, or a method of mixing one other component with two of these components.

Among them, since it becomes possible to efficiently produce a polyalkylene oxide having a higher molecular weight, a lower degree of unsaturation and a narrow molecular weight distribution, it is possible to prepare a polymerization catalyst excellent in catalytic activity. After mixing the phosphazenium salt and the active hydrogen-containing compound, it is preferable to prepare an alkylene oxide polymerization catalyst by mixing them with a Lewis acid. In that case, heating / decompression treatment or the like may be performed. The temperature of the heat treatment may be, for example, 50 to 150 ° C., preferably 70 to 130 ° C. Is, for example, 50 kPa or less, preferably 20 kPa or less.

The alkylene oxide polymerization catalyst of the present invention is useful for the production of 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 that time is not particularly limited, and examples thereof include alkylene oxides having 2 to 20 carbon atoms. Specific examples include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, butadiene monooxide, pentene oxide, styrene oxide, cyclohexene oxide and the like.

Among these, ethylene oxide and propylene oxide are preferred because alkylene oxide is easily available and the resulting polyalkylene oxide has high industrial value. An alkylene oxide may be used alone or in combination of two or more. When two or more types are used in combination, for example, the first alkylene oxide may be reacted and then the second alkylene oxide may be reacted, or two or more alkylene oxides may be reacted simultaneously.

In the method for producing a polyalkylene oxide of the present invention, the polymerization pressure is in the range of 0.05 to 1.0 MPa, preferably in the range of 0.1 to 0.6 MPa. In the production of the polyalkylene oxide of the present invention, the polymerization temperature is in the range of 0 to 130 ° C, preferably in the range of 10 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 without a solvent. 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, 1,2-dimethoxyethane, and the like. be able to.

In the method for producing a polyalkylene oxide of the present invention, since it becomes an efficient method for producing a polyalkylene oxide, the catalyst activity is preferably 100 g / mol · min or more, preferably 200 g / mol · min or more. It is particularly preferable that

The polyalkylene oxide obtained by the production method of the present invention has a molecular weight calculated from the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups of 1000 to 50000 g / mol. It is particularly preferably 3000 to 30000 g / mol.

Further, the degree of unsaturation is preferably 0.05 meq / g or less, 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 1.1 or less. Are particularly preferred.

Next, the polyalkylene oxide satisfying all the following i) to iv) in the present invention will be described.
i) 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) Area ratio of molecular weight of Mh / 3 or less is 2.0% or less.
[However, the number average molecular weight obtained from gel permeation chromatography measurement using polystyrene as a standard substance is “Mn”, the weight average molecular weight is “Mw”, the molecular weight of the highest peak is “Mh”, and the number of polyalkylene oxide functional groups is Let it be “f”. ]
The degree of unsaturation of the polyalkylene oxide of the present invention is 0.020 meq / g or less, preferably 0.010 meq / g or less. When the degree of unsaturation is greater than 0.020 meq / g, the storage elastic modulus of the polyurethane resin is lowered, and physical properties such as hysteresis loss and compression set are lowered.

Mw / Mn of the polyalkylene oxide of the present invention is 1.10 or less, preferably 1.08 or less. When Mw / Mn is greater than 1.10, the storage elastic modulus at the time of forming a polyurethane resin is lowered, and the moldability is deteriorated.

Mh / f of the polyalkylene oxide of the present invention is 1,000 or more, preferably 1,500 or more. When Mh / f is smaller than 1,000, physical properties such as flexibility when a polyurethane resin is used deteriorate, 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 of the polyurethane resin is lowered, and physical properties such as hysteresis loss and compression set are lowered.

The polyalkylene oxide of the present invention preferably has a molecular weight calculated from the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups of 1000 to 50000 g / mol. It is particularly preferred that it is ˜30000 g / mol.

The polyalkylene oxide of the present invention performs, for example, ring-opening polymerization of an alkylene oxide using an active hydrogen-containing compound as an initiator in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and a Lewis acid, and the active hydrogen-containing compound contains By using the phosphazene compound in an amount of 0.001 to 0.1 mol per mol of active hydrogen, it can be easily produced.

Here, as the phosphazene compound, specifically, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraethylguanidino) phosphonium hydroxide, tetrakis ( 1,1,3,3-tetra (n-propyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraisopropylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra ( n-butyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraphenylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetrabenzylguanidino) phosphonium hydroxide, tetrakis (1, 3-Dimethylimidazolidine 2-Imino) phosphonium hydroxide, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydroxide, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1, 3,3-tetraethylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-propyl) guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraisopropylguanidino) phosphonium hydrogen carbonate Tetrakis (1,1,3,3-tetra (n-butyl) guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraphenylguanidino) phosphonium high Logene carbonate, tetrakis (1,1,3,3-tetrabenzylguanidino) phosphonium hydrogen carbonate, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydrogen carbonate, tetrakis (1,3-dimethylimidazolidine-2 -Phosphazenium salts such as imino) phosphonium hydrogen carbonate can be exemplified.

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

Here, the phosphazene compound is preferably a phosphazenium salt represented by the above general 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 low low molecular weight component, the urethane resin obtained by using it has an improved storage elastic modulus, hysteresis loss, Improvements in physical properties such as compression set can be expected.

Hereinafter, although an example explains the present invention, the present example does not restrict the present invention at all.

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 reacted alkylene oxide was a (unit: g), the amount of phosphazenium salt used was b (unit: mol), and the time required for polymerization was c (unit: min). .

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 by the following formula.

Molecular weight = (56100 / d) × e.

In addition, using gel permeation chromatograph (GPC) (HLC8020, manufactured by Tosoh Corporation), measurement is performed at 40 ° C. using tetrahydrofuran as a solvent, polystyrene is used as a standard substance, and the number average molecular weight (Mn) of polyalkylene oxide. The weight average molecular weight (Mw) and the highest peak molecular weight (Mh) were calculated.

(3) Area ratio of low molecular weight components of polyalkylene oxide (unit:%)
The area ratio of the low molecular weight component which is equal to or less than the molecular weight (Mh / 3) obtained by dividing Mh calculated by the above method (2) by 3 was calculated.

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

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

Synthesis Example 1 (Synthesis of phosphazenium salt A)
A 2 liter four-necked flask equipped with a stirring blade was placed in a nitrogen atmosphere, 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added, and the mixture was stirred at 20 ° C. While maintaining stirring, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise over 3 hours, and then the temperature was raised to 100 ° C., and 1,1,3,3-tetramethyl was further added. 107 g (0.92 mol) of guanidine was added dropwise over 1 hour. The obtained white slurry solution was stirred at 100 ° C. for 14 hours, cooled to 80 ° C., added with 250 ml of ion-exchanged water, and stirred for 30 minutes. When the stirring was stopped, all the slurry was dissolved and a two-phase solution was obtained. 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, oil / water separation was performed, and the dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion exchange water.

The obtained dichloromethane solution was transferred to a 2 liter four-necked flask equipped with a stirring blade, and after adding 900 g of 2-propanol, the temperature was raised to 80-100 ° C. under normal pressure to remove dichloromethane. did. The obtained 2-propanol solution was allowed to cool to 60 ° C. with stirring, and then 31 g of 85 wt% potassium hydroxide (0.47 mol, 1.1 mol equivalent to the iminophosphazenium salt) was added. And reacted at 60 ° C. for 2 hours. The temperature is cooled to 25 ° C., and the precipitated by-product salt is removed by filtration, whereby the target iminophosphazenium salt A [R ¹ in the above general formula (1) is a methyl group and R ² is a methyl group. Then, 860 g of a 2-propanol solution of a phosphazenium salt in which X ⁻ is a hydroxy anion, Y is a carbon atom and a is 2] was obtained in a concentration of 25% by weight and a yield of 92%.

Synthesis Example 2 (Synthesis of phosphazenium salt B)
A 100 ml Schlenk tube with a magnetic rotor was placed under a nitrogen atmosphere, 5.7 g of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride (7.4 mmol, manufactured by Aldrich) and 16 ml of 2-propanol were added. Stir at 0 ° C. to dissolve. A solution in which 0.53 g [8.1 mmol, 1.1 mol equivalent to tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride] was dissolved in 2-propanol while maintaining stirring. Was added. After stirring at 25 ° C. for 5 hours, the precipitated by-product salt is removed by filtration, whereby the target phosphazenium salt B [in the general formula (1), R ¹ is a methyl group, R ² is a methyl group, and X ⁻ is 32.7 g of a 2-propanol solution of a hydroxy anion, Y being a phosphorus atom, and a phosphazenium salt corresponding to a being 3] was obtained in a concentration of 17 wt% and a yield of 98%.

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C., and 108 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the reaction was carried out at an internal temperature of 18 to 22 ° C. I let you. Residual propylene oxide and toluene were removed under reduced pressure of 0.5 kPa to obtain 106 g of colorless and odorless polyalkylene oxide. The catalytic activity was 350 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 20000 g / mol, the degree of unsaturation was 0.018 meq / g, and the molecular weight distribution was 1.08. The results are shown in Table 1.

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out at an internal temperature of 68 to 72 ° C. while 18 g of ethylene oxide is intermittently supplied so as to keep the reaction pressure at 0.25 MPa or less. It was. 0.5k
Residual ethylene oxide was removed under reduced pressure of Pa to obtain 127 g of colorless and odorless polyalkylene oxide. The catalyst activity was 840 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 6900 g / mol, the degree of unsaturation was 0.017 meq / g, and the molecular weight distribution was 1.07. The results are shown in Table 1.

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out at an internal temperature of 68 to 72 ° C. while 18 g of ethylene oxide is intermittently supplied so as to keep the reaction pressure at 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of colorless and odorless polyalkylene oxide. The catalytic activity was 1100 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 6800 g / mol, the degree of unsaturation was 0.016 meq / g, and the molecular weight distribution was 1.06. The results are shown in Table 1.

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 50 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain the reaction pressure of 0.3 MPa or less, while the reaction was performed within the internal temperature range of 48 to 52 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out in an internal temperature range of 48 to 52 ° C. while 18 g of ethylene oxide is intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 125 g of colorless and odorless polyalkylene oxide. The catalyst activity was 550 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 6800 g / mol, the degree of unsaturation was 0.014 meq / g, and the molecular weight distribution was 1.05. The results are shown in Table 1.

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out at an internal temperature of 68 to 72 ° C. while 18 g of ethylene oxide is intermittently supplied so as to keep the reaction pressure at 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 112 g of colorless and odorless polyalkylene oxide. The catalyst activity was 980 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 18000 g / mol, the degree of unsaturation was 0.022 meq / g, and the molecular weight distribution was 1.08. The results are shown in Table 1.

Example 6
Instead of 0.54 ml of a 1.0 mol / l toluene solution of triisobutylaluminum (0.54 mmol, 0.010 mol with respect to 1 mol of active hydrogen), 0.54 ml of a 1.0 mol / l hexane solution of diethylzinc (0 An alkylene oxide polymerization catalyst and a polyalkylene oxide were produced in the same manner as in Example 2 except that .54 mmol and 0.010 mol per 1 mol of active hydrogen were used. 127 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity was 750 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 6900 g / mol, the degree of unsaturation was 0.016 meq / g, and the molecular weight distribution was 1.06. The results are shown in Table 1.

Comparative Example 1
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Chemical Industries, (trade name) Sannics GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade 6.0 g (6.0 mmol, active hydrogen content 18 mmol) and phosphazene P4 base 1-tert-butyl-4,4,4-tris (dimethylamino) -2,2-bis (tris (dimethylamino) phospho Ranilideneamino) -2λ5,4λ5-catenadi (phosphazene) in a 1.0 mol / l hexane solution 18 ml (18 mmol, 1.0 mol with respect to 1 mol of active hydrogen) was added. After making the inside of the autoclave a nitrogen atmosphere, 18 ml of a 2.0 mol / l toluene solution of triisobutylaluminum (36 mmol, 2.0 mol with respect to 1 mol of active hydrogen) was added and mixed to obtain an alkylene oxide polymerization catalyst. .

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

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave is set to 70 ° C., and propylene oxide is allowed to react in an internal temperature range of 68 to 72 ° C. while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. It was. As a result, the reaction was stopped when 36 g of propylene oxide was supplied. Residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 36 g of colorless and odorless polyalkylene oxide. The catalytic activity was 46 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 2000 g / mol, the degree of unsaturation was 0.013 meq / g, and the molecular weight distribution was 1.05. The results are shown in Table 2.

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 35 ° C., and 108 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the reaction was performed within the internal temperature range of 33 to 37 ° C. I let you. Residual propylene oxide and toluene were removed under reduced pressure of 0.5 kPa to obtain 106 g of colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 98%, the molecular weight of the obtained polyalkylene oxide was 19000 g / mol, the degree of unsaturation was 0.016 meq / g, and the molecular weight distribution was 1.07. The results are shown in Table 3.

Example 8
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Chemical Industries, (trade name) Sannics GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade 18 g (18 mmol, active hydrogen amount 54 mmol), and 0.54 g (0.27 mmol, 1 mol of active hydrogen) of a 25 wt% 2-propanol solution of phosphazenium salt A obtained in Synthesis Example 1
. 005 mol) was added. After making the inside of the autoclave a nitrogen atmosphere, the internal temperature was set to 80 ° C., and dehydration was performed under a reduced pressure of 0.5 kPa. Thereafter, 0.54 ml of a 1.0 mol / l toluene solution of aluminoxane having a methyl group and an isobutyl group (manufactured by Tosoh Finechem, (trade name) MMAO-3A) (0.54 mmol of aluminum atoms, 1 mol of active hydrogen) 0.010 mol) was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed to obtain an alkylene oxide polymerization catalyst.

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out at an internal temperature of 68 to 72 ° C. while 18 g of ethylene oxide is intermittently supplied so as to keep the reaction pressure at 0.25 MPa or less. It was. 0.5k
Residual ethylene oxide was removed under reduced pressure of Pa to obtain 127 g of colorless and odorless polyalkylene oxide. The conversion rate of alkylene oxide was 99%, the molecular weight of the obtained polyalkylene oxide was 7000 g / mol, the degree of unsaturation was 0.016 meq / g, and the molecular weight distribution was 1.06. The results are shown in Table 3.

Example 9
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Chemical Industries, (trade name) Sannics GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade 18 g (18 mmol, active hydrogen amount 54 mmol) and 0.27 g of a 25 wt% 2-propanol solution of phosphazenium salt A obtained in Synthesis Example 1 (0.14 mmol, 0.0025 mol with respect to 1 mol of active hydrogen) were added. . After making the inside of the autoclave a nitrogen atmosphere, the internal temperature was set to 80 ° C., and dehydration was performed under a reduced pressure of 0.5 kPa. Thereafter, 0.27 ml of a 1.0 mol / l toluene solution of aluminoxane having a methyl group and an isobutyl group (manufactured by Tosoh Finechem, (trade name) MMAO-3A) (0.27 mmol of aluminum atoms, 1 mol of active hydrogen) 0.005 mol) was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed to obtain an alkylene oxide polymerization catalyst.

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out at an internal temperature of 68 to 72 ° C. while 18 g of ethylene oxide is intermittently supplied so as to keep the reaction pressure at 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 98%, the molecular weight of the obtained polyalkylene oxide was 6900 g / mol, the degree of unsaturation was 0.014 meq / g, and the molecular weight distribution was 1.05. The results are shown in Table 3.

Example 10
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Chemical Industries, (trade name) Sannics GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade 18 g (18 mmol, active hydrogen amount 54 mmol) and 0.54 g of a 25 wt% 2-propanol solution of phosphazenium salt A obtained in Synthesis Example 1 (0.27 mmol, 0.005 mol with respect to 1 mol of active hydrogen) were added. . After making the inside of the autoclave a nitrogen atmosphere, the internal temperature was set to 80 ° C., and dehydration was performed under a reduced pressure of 0.5 kPa. Thereafter, 0.54 ml of a 1.0 mol / l toluene solution of aluminoxane having a methyl group and an isobutyl group (manufactured by Tosoh Finechem, (trade name) MMAO-3A) (0.54 mmol of aluminum atoms, 1 mol of active hydrogen) 0.010 mol) was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed to obtain an alkylene oxide polymerization catalyst.

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 50 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain the reaction pressure of 0.3 MPa or less, while the reaction was performed within the internal temperature range of 48 to 52 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out in an internal temperature range of 48 to 52 ° C. while 18 g of ethylene oxide is intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 125 g of colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 97%, the molecular weight of the obtained polyalkylene oxide was 6700 g / mol, the degree of unsaturation was 0.012 meq / g, and the molecular weight distribution was 1.04. The results are shown in Table 3.

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out at an internal temperature of 68 to 72 ° C. while 18 g of ethylene oxide is intermittently supplied so as to keep the reaction pressure at 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 112 g of colorless and odorless polyalkylene oxide. The conversion of alkylene oxide was 96%, the molecular weight of the obtained polyalkylene oxide was 18000 g / mol, the degree of unsaturation was 0.021 meq / g, and the molecular weight distribution was 1.08. The results are shown in Table 3.

Comparative Example 3
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Chemical Industries, (trade name) Sannics GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade 6.0 ml (6.0 mmol, active hydrogen amount 18 mmol), and 36 ml of 1.0 mol / l toluene solution of aluminoxane having a methyl group and an isobutyl group (manufactured by Tosoh Finechem, (trade name) MMAO-3A) (aluminum 36 mmol of atoms and 2.0 mol per 1 mol of active hydrogen) were added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed to obtain an alkylene oxide polymerization catalyst.

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

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

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

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C., and 108 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the reaction was performed within the internal temperature range of 68 to 72 ° C. I let you. Residual propylene oxide and toluene were removed under reduced pressure of 0.5 kPa to obtain 106 g of colorless and odorless polyalkylene oxide. The catalytic activity was 400 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 20000 g / mol, the degree of unsaturation was 0.008 meq / g, and the molecular weight distribution was 1.08. The results are shown in Table 5.

Example 13
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (Sanyo Chemical Industries, Ltd., (trade name) Sannix GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade ] 18 g (18 mmol, active hydrogen amount 54 mmol) and 2.0 g of a 17 wt% 2-propanol solution of phosphazenium salt B obtained in Synthesis Example 2 (0.45 mmol, 0.008 mol with respect to 1 mol of active hydrogen) were added. It was. After making the inside of the autoclave a nitrogen atmosphere, the internal temperature was set to 80 ° C., and dehydration was performed under a reduced pressure of 0.5 kPa. Thereafter, 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, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed. Thus, an alkylene oxide polymerization catalyst was obtained.

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out in an internal temperature range of 108 to 112 ° C. while 18 g of ethylene oxide is intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 127 g of colorless and odorless polyalkylene oxide. The catalytic activity was 1040 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 6900 g / mol, the degree of unsaturation was 0.007 meq / g, and the molecular weight distribution was 1.07. The results are shown in Table 5.

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out in an internal temperature range of 108 to 112 ° C. while 18 g of ethylene oxide is intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of colorless and odorless polyalkylene oxide. The catalytic activity was 1300 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 6800 g / mol, the degree of unsaturation was 0.005 meq / g, and the molecular weight distribution was 1.06. The results are shown in Table 5.

Example 15
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (Sanyo Chemical Industries, Ltd., (trade name) Sannix GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade ] 18 g (18 mmol, active hydrogen amount 54 mmol) and 1.2 g of a 17 wt% 2-propanol solution of phosphazenium salt B obtained in Synthesis Example 2 (0.27 mmol, 0.005 mol with respect to 1 mol of active hydrogen) were added. It was. After making the inside of the autoclave a nitrogen atmosphere, the internal temperature was set to 80 ° C., and dehydration was performed under a reduced pressure of 0.5 kPa. Thereafter, 0.54 ml (0.54 mmol, 0.010 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisobutylaluminum was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed. Thus, an alkylene oxide polymerization catalyst was obtained.

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

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

In the presence of the resulting alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, while the internal temperature was in the range of 68 to 72 ° C. I let you. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, the reaction is carried out in an internal temperature range of 108 to 112 ° C. while 18 g of ethylene oxide is intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. It was. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 112 g of colorless and odorless polyalkylene oxide. The catalytic activity was 980 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 18000 g / mol, the degree of unsaturation was 0.008 meq / g, and the molecular weight distribution was 1.08. The results are shown in Table 5.

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

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

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

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

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

Example 22
Instead of 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), 1.35 ml of a 1.0 mol / l hexane solution of diethylzinc (1 An alkylene oxide polymerization catalyst and a polyalkylene oxide were produced in the same manner as in Example 13, except that .35 mmol and 0.025 mol per 1 mol of active hydrogen were used. 127 g of colorless and odorless polyalkylene oxide was obtained. The catalyst activity was 750 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 6900 g / mol, the degree of unsaturation was 0.010 meq / g, and the molecular weight distribution was 1.07. The results are shown in Table 6.

Comparative Example 5
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (Sanyo Chemical Industries, Ltd., (trade name) Sannix GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade ] 6.0 g (6.0 mmol, active hydrogen content 18 mmol), and phosphazene P4 base 1-tert-butyl-4,4,4-tris (dimethylamino) -2,2-bis (tris (dimethylamino) 18 ml of a 1.0 mol / l hexane solution of phosphoranilideneamino) -2λ5,4λ5-catenadi (phosphazene) (18 mmol, 1.0 mol with respect to 1 mol of active hydrogen) was added. After making the inside of the autoclave a nitrogen atmosphere, 18 ml of a 2.0 mol / l toluene solution of triisobutylaluminum (36 mmol, 2.0 mol with respect to 1 mol of active hydrogen) was added and mixed to obtain an alkylene oxide polymerization catalyst. .

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

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

Comparative Example 7
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (Sanyo Chemical Industries, Ltd., (trade name) Sannix GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade ] 18 g (18 mmol, active hydrogen amount 54 mmol) and 2.0 g of a 17 wt% 2-propanol solution of phosphazenium salt B obtained in Synthesis Example 2 (0.45 mmol, 0.008 mol with respect to 1 mol of active hydrogen) were added. It was. After making the inside of the autoclave a nitrogen atmosphere, the internal temperature was set to 80 ° C. and dehydration treatment was performed under a 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 is set to 90 ° C., and propylene oxide is allowed to react in the range of 88 to 92 ° C. while being intermittently supplied so as to maintain the reaction pressure of 0.3 MPa or less. It was. As a result, 110 g of propylene oxide was supplied. Residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 125 g of colorless and odorless polyalkylene oxide. The catalytic activity was 460 g / mol · min, the molecular weight of the obtained polyalkylene oxide was 7000 g / mol, the degree of unsaturation was 0.024 meq / g, and the molecular weight distribution was 1.06. The results are shown in Table 3.

Comparative Example 8
A polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (Sanyo Chemical Industries, Ltd., (trade name) Sannix GP1000; hydroxyl value 160 mgKOH / g) in a 0.2 liter autoclave equipped with a stirring blade ] 18 g (18 mmol, active hydrogen amount 54 mmol), 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) were added, and the internal temperature was adjusted to 80 ° C. , Reduced pressure treatment of 0.5 kPa.

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 reacted at a reaction pressure of 0.3 MPa or less and an internal temperature of 68 to 72 ° C. However, after reaching a reaction pressure of 0.3 MPa at a reaction temperature of 70 ° C., no pressure decrease was observed. After continuing the reaction at 70 ° C. for 5 hours, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. 10 g of the raw material polyether polyol was recovered. Triisobutylaluminum alone did not show any propylene oxide polymerization activity. The results are shown in Table 7.

Example 23
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, 18 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (the amount of active hydrogen 54 mmol), and the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and a reduced pressure 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 set at 90 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 127 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 600 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.006 meq / g, the molecular weight distribution is 1.06, Mh / f is 3,700 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 0.1%.

Example 24
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, 18 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (the amount of active hydrogen 54 mmol), and the phosphazenium salt A obtained in Synthesis Example 1 0.54 g (0.27 mmol) of a 25 wt% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 0.54 ml (0.54 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and a reduced pressure 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 set at 90 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 126 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 600 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.005 meq / g, the molecular weight distribution is 1.05, Mh / f is 3,600 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 0.1%.

Example 25
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, 18 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (the amount of active hydrogen 54 mmol), and the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and a reduced pressure 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 set to 70 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 125 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 400 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.005 meq / g, the molecular weight distribution is 1.05, Mh / f is 3,600 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 0.1%.

Example 26
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, 18 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (the amount of active hydrogen 54 mmol), and the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and a reduced pressure 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 120 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 128 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 1,500 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.008 meq / g, the molecular weight distribution is 1.06, Mh / f is 3,700 g / mol, Mh / 3 or less. The area ratio of the low molecular weight component was 0.2%.

Example 27
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, and 9 g of polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (the amount of active hydrogen was 27 mmol) and the phosphazenium salt A obtained in Synthesis Example 1 0.45 g (0.23 mmol) of a 25 wt% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 0.68 ml (0.68 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and reduced pressure 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 set at 90 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 117 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 500 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.008 meq / g, the molecular weight distribution is 1.06, Mh / f is 7,000 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 0.2%.

Example 28
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, and 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution of phosphazenium salt A obtained in Synthesis Example 1 was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and a reduced pressure 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 set at 90 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 109 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 500 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.008 meq / g, the molecular weight distribution is 1.06, Mh / f is 7,000 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 0.2%.

Example 29
A 0.2 liter autoclave equipped with a stirring blade was placed in a nitrogen atmosphere, 18 g of polyether polyol (Sanix GP1000 manufactured by Sanyo Chemical Industries, Ltd.) (active hydrogen amount 54 mmol), 25 of phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a weight% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l hexane solution of aluminum isopropoxide (Al (OiPr) 3) was added, the internal temperature was adjusted to 80 ° C., and a reduced pressure treatment was performed at 0.5 kPa. A polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set at 90 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 127 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 600 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.005 meq / g, the molecular weight distribution is 1.08, Mh / f is 3,500 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 1.4%.

Example 30
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, 18 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (the amount of active hydrogen 54 mmol), and the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l dibutyl ether solution of triphenylaluminum (AlPh3) was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. It was.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set at 90 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 127 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 600 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.006 meq / g, the molecular weight distribution is 1.07, Mh / f is 3,700 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 0.4%.

Example 31
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, 18 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (the amount of active hydrogen 54 mmol), and the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l hexane solution having a methyl group and an isobutyl group (MMAO-3A, manufactured by Tosoh Finechem Co., Ltd.) was added, the internal temperature was adjusted to 80 ° C., and 0.5 kPa. A reduced pressure treatment was performed 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 at 90 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 85 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 250 g / mol · min, the degree of unsaturation of the obtained polyalkylene oxide is 0.005 meq / g, the molecular weight distribution is 1.05, Mh / f is 2,000 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 0.1%.

Example 32
A 0.2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, 18 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (the amount of active hydrogen 54 mmol), and the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l hexane solution of diethyl zinc (ZnEt ₂ ) was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. .

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

The above results are also shown in Tables 8 and 9.

As is clear from Tables 8 and 9, the polyalkylene oxides obtained in Examples 23 to 33 satisfy all of the following i) to iv).
i) 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) Mh / 3 or less molecular weight area ratio is 2.0% or less ( However, the number average molecular weight obtained from gel permeation chromatography measurement using polystyrene as a standard substance is Mn, the weight average molecular weight is Mw, the highest peak molecular weight is Mh, and the number of functional groups of polyalkylene oxide is f).

Comparative Example 9
A 0.2 liter autoclave was placed under a nitrogen atmosphere, 18 g (18 mmol) of a polyether polyol (Sanyox GP1000, manufactured by Sanyo Chemical Industries, Ltd.), a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 0 .54 g (0.27 mmol) was added. The internal temperature was set to 80 ° C., and reduced pressure 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 set at 90 ° C., and 92 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Subsequently, the internal temperature of the autoclave was set to 110 ° C., and 18 g of ethylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.25 MPa or less. After the reaction was completed, the residual ethylene oxide was removed under a reduced pressure of 0.5 kPa. And 127 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 500 g / mol · min, the degree of unsaturation of the obtained polyalkylene oxide is 0.026 meq / g, the molecular weight distribution is 1.12, Mh / f is 3,300 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 3.7%.

Comparative Example 10
A 0.2 liter autoclave was put under a nitrogen atmosphere, 18 g (18 mmol) of polyether polyol (manufactured by Sanyo Chemical Industries, Sannix GP1000), 1.35 ml (1 mol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) (1 .35 mmol) was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa.

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

Comparative Example 11
A 0.2 liter autoclave was placed in a nitrogen atmosphere, 18 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Kasei Kogyo Co., Ltd.), 50 mg (0.45 mmol) of a 50 wt% aqueous solution of potassium hydroxide (KOH). ) Was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and a reduced pressure 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 set to 90 ° C., and 36 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. 27 g of colorless and odorless polyalkylene oxide was obtained. The catalyst activity is 60 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.030 meq / g, the molecular weight distribution is 1.12, Mh / f is 500 g / mol, and the low molecular weight component is less than Mh / 3. The area ratio was 4.3%.

Comparative Example 12
A 0.2 liter autoclave was placed in a nitrogen atmosphere, 6 g of a polyether polyol (Sanix GP1000, manufactured by Sanyo Chemical Industries, Ltd.) (active hydrogen content 18 mmol), and 1-tert-butyl-4,4, which is a phosphazene P4 base. 18 ml (18 mmol) of a 1.0 mol / l hexane solution of 4-tris (dimethylamino) -2,2-bis (tris (dimethylamino) phosphoranylideneamino) -2λ5,4λ5-catenadi (phosphazene) was added. The internal temperature was set to 80 ° C., and the pressure was reduced at 0.5 kPa. Thereafter, 18 ml (36 mmol) of a 2.0 mol / l toluene solution of triisobutylaluminum (TIBAL) was added, the internal temperature was set to 80 ° C., and a reduced pressure 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 set to 20 ° C., and 37 g of propylene oxide was reacted while being intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. 42 g of colorless and odorless polyalkylene oxide was obtained. The catalytic activity is 10 g / mol · min, the degree of unsaturation of the resulting polyalkylene oxide is 0.016 meq / g, the molecular weight distribution is 1.36, Mh / f is 3,300 g / mol, and the low molecular weight is Mh / 3 or less. The area ratio of the components was 3.7%.

Table 10 shows the results of Comparative Examples 9 to 12.

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 part of triethylenediamine (trade name: TEDA-L33) were placed in a Despo cup and stirred. After completion of the stirring, viscoelasticity was measured using a rotary rheometer (Solid Meter MR-500 manufactured by UBM) under conditions of 25 ° C. and a frequency of 10 Hz in a nitrogen atmosphere. The storage elastic modulus (G ′) after 50 minutes from the completion of 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 part of triethylenediamine (trade name: TEDA-L33) were placed in a Despo cup and stirred. After completion of the stirring, viscoelasticity was measured using a rotary rheometer (Solid Meter MR-500 manufactured by UBM) under conditions of 25 ° C. and a frequency of 10 Hz in a nitrogen atmosphere. The storage elastic modulus (G ′) after 50 minutes from the completion of stirring was 15,000 Pa.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. is there.

In the present invention, a suitable combination of a phosphazenium salt (Y, R ¹ , R ² , X) represented by the general formula (1), a Lewis acid, and an active hydrogen-containing compound used as necessary is, for example, As shown in Tables 11-18.

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

The specification, claims and abstract of Japanese Patent Application No. 2014-164289 filed on August 12, 2014, Japanese Patent Application No. 2014-164290 filed on August 12, 2014 , Claims and abstract, Japanese Patent Application No. 2015-145645 filed on July 23, 2015, claims and abstract, and July 23, 2015 The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2015-145646 filed are incorporated herein by reference for the disclosure of the specification of the present invention.

By using the alkylene oxide polymerization catalyst of the present invention, polyalkylene oxide can be produced efficiently. The resulting polyalkylene oxide is useful for polyurethane raw materials, polyester raw materials, surfactant raw materials, lubricant raw materials and the like.

The polyalkylene oxide of the present invention is useful for polyurethane raw materials, polyester raw materials, surfactant raw materials, lubricant raw materials, and the like.

The polyalkylene oxide obtained by using the alkylene oxide polymerization catalyst of the present invention is used for rigid foams used for heat insulating materials, automobile seats / cushions, bedding, etc., particularly by reacting with various isocyanate compounds. Expansion to flexible foams, adhesives, paints, sealants, thermosetting elastomers and thermoplastic elastomers is expected.

Claims

An alkylene oxide polymerization catalyst comprising a phosphazenium salt represented by the general formula (1) and a Lewis acid.

(In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, R 1 and R 2 are bonded to each other. , R 1 or R 2 may be bonded to each other to form a ring structure, X − represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or Y represents a hydrogen carbonate anion, Y represents a carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and 3 when Y is a phosphorus atom.
The ratio of the phosphazenium salt represented by the general formula (1) and the Lewis acid is [phosphazenium salt]: [Lewis acid] = 1: 0.002 to 500 (molar ratio). The alkylene oxide polymerization catalyst described in 1.
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, comprising a phosphazenium salt represented by the general formula (1), a Lewis acid, and an active hydrogen-containing compound.

(In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, R 1 and R 2 are bonded to each other. , R 1 or R 2 may be bonded to each other to form a ring structure, X − represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or Y represents a hydrogen carbonate anion, Y represents a carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and 3 when Y is a phosphorus atom.
6. The active hydrogen-containing compound is at least one 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. An alkylene oxide polymerization catalyst.
The method for producing an alkylene oxide polymerization catalyst according to claim 5 or 6, wherein the phosphazenium salt represented by the general formula (1) and the active hydrogen-containing compound are mixed and then mixed with a Lewis acid.
6. A process for producing a polyalkylene oxide, which comprises carrying out ring-opening polymerization of an alkylene oxide in the presence of an alkylene oxide polymerization catalyst according to claim 1.
A polyalkylene oxide satisfying all of the following i) to iv).
i) 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) Mh / 3 or less molecular weight area ratio is 2.0% or less ( However, the number average molecular weight obtained from gel permeation chromatography measurement using polystyrene as a standard substance is Mn, 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 according to claim 9, wherein the molecular weight calculated from the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the number of functional groups thereof is in the range of 1000 to 50000 g / mol. Oxide.
Performing ring-opening polymerization of alkylene oxide using an active hydrogen-containing compound as an initiator in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and a Lewis acid, and the phosphazene compound for 1 mol of active hydrogen in the active hydrogen-containing compound The method for producing a polyalkylene oxide according to claim 9 or 10, wherein the amount used is in the range of 0.001 to 0.1 mol.
The method for producing a polyalkylene oxide according to claim 11, wherein the phosphazene compound is a phosphazenium salt represented by the general formula (1).

(In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, R 1 and R 2 are bonded to each other. , R 1 or R 2 may be bonded to each other to form a ring structure, X − represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or Y represents a hydrogen carbonate anion, Y represents a carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and 3 when Y is a phosphorus atom.
The 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 (molar ratio). Manufacturing method.
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.