KR102391669B1 - Alkylene oxide polymerization catalyst and method for producing polyalkylene oxides using same - Google Patents

Abstract

(상기 일반식 (1) 중, R¹ 및 R²는, 각각 독립적으로, 수소원자 또는 탄소수 1 내지 20의 탄화수소기를 나타낸다. 여기서, R¹과 R²가 서로 결합한 환구조, R¹ 끼리 또는 R² 끼리가 서로 결합한 환구조를 형성해도 된다. X^-는 하이드록시 음이온, 탄소수 1 내지 4의 알콕시 음이온, 카복시 음이온, 탄소수 2 내지 5의 알킬카복시 음이온, 또는 탄산수소 음이온을 나타낸다. Y는 탄소원자 또는 인 원자를 나타내고, a는 Y가 탄소원자일 때 2이며, Y가 인 원자일 때 3이다).An alkylene oxide polymerization catalyst capable of efficiently producing a polyalkylene oxide exhibiting a high molecular weight, a low degree of unsaturation and a narrow molecular weight distribution with a small amount of an expensive phosphazenium salt to be used even under production conditions at a low temperature is provided. An alkylene oxide polymerization catalyst comprising a phosphazenium salt represented by the following general formula (1) and a Lewis acid.

(In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, the ring structure in which R ¹ and R ² are bonded to each other, R ¹ each other, or R may form a ring structure in which ^two are bonded to each other.X ^- represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. Y is a carbon atom or a phosphorus atom, wherein a is 2 when Y is a carbon atom, and 3 when Y is a phosphorus atom).

Description

An alkylene oxide polymerization catalyst and a method for producing a polyalkylene oxide using the same

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

It is industrially known that polyalkylene oxide is manufactured by performing addition polymerization of an alkylene oxide using potassium hydroxide as a catalyst. However, when a high molecular weight polyalkylene oxide is manufactured by this method, since the polyalkylene oxide obtained contains a lot of monool, it includes the subject that unsaturation becomes high.

As a manufacturing method of polyalkylene oxide, the method of manufacturing polyalkylene oxide using a bimetallic cyanide complex as a catalyst (for example, refer patent document 1, 2) is proposed.

Moreover, as a manufacturing method of a polyalkylene oxide with a low degree of unsaturation, the method of manufacturing a polyalkylene oxide using a specific phosphazenium salt as a catalyst is proposed (for example, refer patent documents 3 - 5).

On the other hand, using an alkylene oxide polymerization catalyst obtained by mixing an active hydrogen-containing compound and 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 performing ring-opening polymerization of an alkylene oxide has been proposed (see, for example, Patent Document 6).

In addition, as a method for producing polyalkylene oxide, an alkylene oxide polymerization catalyst obtained by mixing an active hydrogen-containing compound, a phosphazene compound, and triisobutylaluminum in a molar ratio of 1:1:2 is used in a toluene solvent, 20 A method for producing a polyalkylene oxide by performing ring-opening polymerization of an alkylene oxide at °C has been proposed (see, for example, Non-Patent Document 1). The catalytically active species at that time, first, by the reaction of the active hydrogen-containing compound and the phosphazene compound, a deprotonation reaction of the active hydrogen-containing compound proceeds, and thereafter, triisobutylaluminum acts to deprotonate it. A mechanism has been proposed that an active hydrogen-containing compound migrates onto the aluminum phase to become a catalytically active species.

US 5235114 B JPH4-59825 A JP 3497054 B (JPH10-77289 A) JP 3905638 B (JPH11-106500 A) JP 5663856 B (JP2010-150514 A) JP 2011-122134 A

Polymer Chemistry, 2012, 3, 1189

In the method described in patent documents 1 and 2, the molecular weight distribution of the polyalkylene oxide obtained was wide, and the subject that ethylene oxide was difficult to adapt as an alkylene oxide was included.

The method proposed by patent document 3 had the subject that the conversion rate of an alkylene oxide was as low as 9 to 19%. In addition, the polyalkylene oxide obtained was a mixture of a high molecular weight substance having a molecular weight of 17,000,000 to 160,000,000 g/mol and a low molecular weight substance having a molecular weight of 1700 to 2300 g/mol, and did not have any special characteristics even as a polyalkylene oxide.

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 requested. In addition, when the polymerization temperature is lowered, a problem that the catalyst activity is lowered occurs, or, conversely, when the polymerization temperature is made higher, the problem that the degree of unsaturation, which is an index of the amount of impurities in the product, is likely to occur.

The method proposed in Non-Patent Document 1 required the use of a large amount of an expensive phosphazene compound, and thus had a problem as a method for industrially producing an efficient polyalkylene oxide. Moreover, it did not have special characteristics also as polyalkylene oxide obtained.

When the degree of unsaturation of the polyalkylene oxide increases, the crosslinking density when a polyurethane resin is lowered and the storage elastic modulus is lowered, so that physical properties such as hysteresis loss and compression set are reduced.

Moreover, when the molecular weight distribution of a polyalkylene oxide spreads, the subject that the moldability at the time of setting it as a polyurethane resin deteriorates is included.

In addition, when the low molecular weight component in the polyalkylene oxide increases, the crosslinking density when it is made into a polyurethane resin decreases and the storage elastic modulus decreases, so physical properties such as hysteresis loss and compression set are reduced. .

Therefore, an alkylene oxide polymerization catalyst capable of efficiently producing polyalkylene oxide exhibiting high molecular weight, low degree of unsaturation and narrow molecular weight distribution with a small amount of expensive phosphazene compound used even under low-temperature production conditions, and this There is a need for a method for producing polyalkylene oxide used.

As a result of intensive studies 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 degree of unsaturation, and a narrow molecular weight distribution even under low temperature production conditions. It has been found that it is possible to efficiently produce a polyalkylene oxide of, to complete the present invention.

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

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

(In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, the ring structure in which R ¹ and R ² are bonded to each other, R ¹ each other, or R may form a ring structure in which ^two are bonded to each other.X ^- represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. Y is 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] In the above [1], wherein the ratio of the phosphazenium salt represented by the general formula (1) to the Lewis acid is [phosphazenium salt]: [Lewis acid] = 1:0.002 to 500 (molar ratio) A described alkylene oxide polymerization catalyst.

[3] 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 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 organic zinc.

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

[In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, a ring structure in which R ¹ and R ² are bonded to each other, or a ring structure in which R ¹ s or R ² are bonded to each other may be formed. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy 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, as described in [5] above. Alkylene oxide polymerization catalyst.

[7] The alkylene oxide polymerization catalyst according to the above [5] or [6], characterized in that after mixing the phosphazenium salt represented by the general formula (1) and the active hydrogen-containing compound, these are mixed with a Lewis acid manufacturing method.

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

[9] Polyalkylene oxides satisfying all of the following i) to iv):

i) Unsaturation of 0.020 meq/g or less

ii) Mw/Mn of 1.10 or less

iii) Mh/f of 1,000 or more

iv) The 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 material 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], wherein the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the molecular weight calculated from the number of functional groups are in the range of 1000 to 50000 g/mol described polyalkylene oxides.

[11] 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 active hydrogen 1 in the active hydrogen-containing compound The method for producing a polyalkylene oxide according to [9] or [10], wherein the amount of the phosphazene compound used per mole is in the range of 0.001 to 0.1 mole.

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

(In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, the ring structure in which R ¹ and R ² are bonded to each other, R ¹ each other, or R may form a ring structure in which ^two are bonded to each other.X ^- represents a hydroxyl anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. Y is a carbon atom or a phosphorus atom, a is 2 when Y is a carbon atom, and 3 when Y is a phosphorus atom.)

[13] The method for producing a polyalkylene oxide according to [11] or [12], wherein the Lewis acid is at least one compound selected from the group consisting of an aluminum compound, a zinc compound and a boron compound.

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

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

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

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 small amount of low molecular weight components, has improved storage modulus, so hysteresis loss, compression set, etc. can be expected to improve the physical properties of

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the calculation method of the area ratio of the low molecular-weight component of polyalkylene oxide in an Example;
Fig. 2 is a diagram showing a method of calculating the area ratio of low molecular weight components of polyalkylene oxide in Examples;

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

[In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, a ring structure in which R ¹ and R ² are bonded to each other, or a ring structure in which R ¹ s or R ² are bonded to each other may be formed. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy 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.]

Here, as a C1-C20 hydrocarbon group, for example, a methyl group, an ethyl group, a vinyl group, n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, n-butyl group, isobutyl group, t-butyl group Tyl 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 , decyl group, cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and the like.

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 becomes an alkylene group such as an ethylene group, a propylene group, or a butylene group, and the other substituent is bonded to each other. .

And among these, as R< ¹ > and R< ² >, since it becomes an alkylene oxide polymerization catalyst excellent in catalytic activity, it is especially preferable that they are a methyl group, an ethyl group, and an isopropyl group.

X ⁻ in the phosphazenium salt is a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy 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, etc. can be heard

Examples of the alkyl carboxy anion having 2 to 5 carbon atoms include acetoxy anion, ethyl carboxy anion, n-propyl carboxy anion, isopropyl carboxy anion, n-butyl carboxy anion, isobutyl carboxy anion, t-butyl carboxy anion, etc. can be heard

Among these, as X ^- , since it becomes an alkylene oxide polymerization catalyst excellent in catalytic activity, a hydroxyl anion and a hydrogen carbonate anion are especially preferable.

In the present invention, when Y is a carbon atom, the phosphazenium salt is represented by the following general formula (2):

[In the formula (2), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, a ring structure in which R ¹ and R ² are bonded to each other, or a ring structure in which R ¹ s or R ² are bonded to each other may be formed. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or an oxyhydrogen anion.]

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

[In the formula (3), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, a ring structure in which R ¹ and R ² are bonded to each other, or a ring structure in which R ¹ s or R ² are bonded to each other may be formed. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy anion having 2 to 5 carbon atoms, or an oxyhydrogen anion.]

In the present invention, specific examples of the phosphazenium salt include tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide and tetrakis(1,1,3,3-tetraethyl). Guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra (n-propyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraiso Propylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra (n-butyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra Phenylguanidino) 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) guanine Dino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraphenylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetrabenzylguanidino) phosphonium Hydrogen carbonate, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium Hydrogen carbonate, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium Phosphazenium salts, such as hydrogen carbonate, can be illustrated.

Further, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di n-Propylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(din-butylamino) Phosphoranilideneamino]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)phosphoranylidene Amino] phosphonium hydrogen carbonate, tetrakis [tris (di n-propylamino) phosphoranylideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diisopropylamino) phosphoranylidene amino] phosphonium hydro Gen carbonate, tetrakis[tris(din-butylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[ and phosphazenium salts such as tris(1,3-dimethylimidazolidine-2-imino)phosphoranylideneamino]phosphonium hydrogen carbonate.

Among them, tetrakis(1,1,3,3-tetramethylguanidino)phosphazenium hydroxide, tetrakis(1,1,3) Particular preference is given to ,3-tetramethylguanidino)phosphazenium hydrogen carbonate, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide.

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

As an aluminum compound, organic aluminum, inorganic aluminum, aluminoxane etc. are mentioned, for example.

Examples of the organoaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, and diphenylmono. isobutylaluminum, monophenyldiisobutylaluminum, etc. are mentioned.

As inorganic aluminum, aluminum chloride, aluminum hydroxide, aluminum oxide, etc. are mentioned.

Examples of the aluminoxane include compounds represented by the following formula:

(-AlR ₃ -O-) _n

(In the formula, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms. n means an integer of 2 or more).

Here, as a C1-C20 hydrocarbon group, for example, a methyl group, an ethyl group, a vinyl group, n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, n-butyl group, isobutyl group, t-butyl group Tyl 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 , decyl group, cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and the like. Among these, as R< ³ >, a methyl group and an isobutyl group are preferable because it becomes an alkylene oxide polymerization catalyst which is easy to obtain and shows a high conversion rate of an alkylene oxide.

Specific examples of the aluminoxane include methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxane. Moreover, as a commercial item of aluminoxane, For example, (brand name) MMAO-3A (made by Toso Finechem Corporation), (brand name) TMAO-340 series (made by Toso Finechem Corporation), (trade name) TMAO-200 series (Tosoh. Finechem Co., Ltd.), (trade name) PBAO (Toso Finechem Co., Ltd. product), (brand name) Solid-MAO (Toso Finechem Co., Ltd. product), etc. are mentioned.

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, is mentioned.

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

And, among these, since it becomes an alkylene oxide polymerization catalyst excellent in catalytic performance, organoaluminum, aluminoxane, and organozinc are preferable, Especially preferably, organoaluminum is especially preferable.

Moreover, among these, since it becomes an alkylene oxide polymerization catalyst which is easy to obtain and excellent in catalytic activity, triisobutylaluminum, triisopropoxyaluminum, and diethylzinc are especially preferable.

In the alkylene oxide polymerization catalyst of the present invention, the ratio of the phosphazenium salt to the Lewis acid is arbitrary as long as the action as an alkylene oxide polymerization catalyst is expressed, and is not particularly limited. Among these, [phosphazenium salt]:[Lewis acid] = 1:0.002 to 500 (molar ratio) is preferable because it is excellent especially in catalytic activity and becomes a polymerization catalyst with 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 exhibiting a higher molecular weight, a lower degree of unsaturation and a narrow molecular weight distribution, and it becomes a polymerization catalyst with excellent catalytic activity, so that more active hydrogen It is particularly preferred to use an oleaginous compound. Examples of the active hydrogen-containing compound in that case 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, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, sucrose, glucose, 2-naphthol, bisphenol, etc. are mentioned.

As an amine compound, ethylenediamine, N,N'- dimethylethylenediamine, a piperidien, piperazine etc. are mentioned, for example.

As a carboxylic acid compound, benzoic acid, adipic acid, etc. are mentioned, for example.

Examples of the thiol compound include ethanedithiol and butanedithiol.

As polyether polyol which has a hydroxyl group, the polyether polyol etc. of molecular weight 200-3000 are mentioned, for example.

In addition, these active hydrogen containing compounds may be used independently and may mix and use several types.

In addition, when an active hydrogen-containing compound is used, it becomes a polymerization catalyst excellent in catalytic activity, which makes it possible to efficiently produce polyalkylene oxide exhibiting a higher molecular weight, a lower degree of unsaturation, and a narrow molecular weight distribution. With respect to 1 mole of active hydrogen in the compound, 0.001 to 10 moles of the phosphazenium salt are preferable, and particularly preferably 0.001 to 5 moles. Further, the amount of the Lewis acid is preferably 0.001 to 10 moles, particularly preferably 0.001 to 5 moles, with respect to 1 mole 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 any method can be used as long as the polyalkylene oxide of the present invention is possible.

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

In addition, when ring-opening polymerization of an alkylene oxide is performed using an active hydrogen-containing compound as an initiator in the presence of an alkylene oxide polymerization catalyst containing a phosphazenium salt and a Lewis acid, a phosphazenium salt, a Lewis acid and an active hydrogen containing You may use any method, such as the method of mixing a compound simultaneously, the method of mixing two other components with one of these, the method of mixing two of these with the other one component, etc.

Among these, since it becomes possible to prepare a polymerization catalyst excellent in catalytic activity, which makes it possible to efficiently produce a polyalkylene oxide having a higher molecular weight, a lower degree of unsaturation and a narrow molecular weight distribution, the phosphazenium salt and the activity After mixing the hydrogen-containing compound, it is preferable to mix these and a Lewis acid to prepare an alkylene oxide polymerization catalyst. In that case, heating/reducing treatment may be performed, and the temperature of the heat treatment is, for example, 50 to 150°C, preferably 70 to 130°C, and the pressure at the time of the pressure reduction treatment is, for example, For example, 50 kPa or less, Preferably 20 kPa or less is mentioned.

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.

Although it does not specifically limit as an alkylene oxide in that case, For example, a C2-C20 alkylene oxide is mentioned. Specifically, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, butadiene monoxide, pentene oxide, styrene oxide, cyclohexene oxide, etc. are exemplified do.

Among these, ethylene oxide and propylene oxide are preferable because the acquisition of an alkylene oxide is easy and the industrial value of the polyalkylene oxide obtained is high. An alkylene oxide may be used independently or may mix and use 2 or more types. When mixing and using 2 or more types, for example, after making a 1st alkylene oxide react, you may make a 2nd alkylene oxide react, and 2 or more types of alkylene oxides may be made to react 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 polyalkylene oxide of the present invention, polymerization can be carried out in a solvent or in the absence of a solvent. Although it does not specifically limit as a solvent to be used, For example, benzene, toluene, xylene, cyclohexane, 1,2- dichloroethane, chlorobenzene, dichlorobenzene, 1, 4- dioxane, 1,2- Dimethoxyethane etc. are mentioned.

In the method for producing polyalkylene oxide of the present invention, since it becomes an efficient method for producing polyalkylene oxide, it is preferable to show 100 g/mol·min or more as catalytic activity, and 200 g/mol·min or more It is particularly preferred to indicate

The polyalkylene oxide obtained by the production method of the present invention is 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, and is 1000 to 50000 g/mol. It is preferable, and it is especially preferable that it is 3000-30000 g/mol.

Moreover, it is preferable that it is 0.05 meq/g or less, and, as for unsaturation, it is especially preferable that it is 0.03 meq/g or less. In addition, the molecular weight distribution (Mw/Mn) of the polyalkylene oxide calculated from the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polyalkylene oxide is preferably 1.3 or less, and particularly preferably 1.1 or less. .

Next, polyalkylene oxides satisfying all of the following i) to iv) in the present invention will be described:

i) Unsaturation of 0.020 meq/g or less

ii) Mw/Mn of 1.10 or less

iii) Mh/f of 1,000 or more

iv) The area ratio of molecular weight of Mh/3 or less is 2.0% or less.

[However, using polystyrene as a standard material, the number average molecular weight obtained from gel permeation chromatography measurement 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”.]

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 becomes greater than 0.020 meq/g, the storage elastic modulus in the case of a polyurethane resin decreases, and physical properties such as hysteresis loss and compression set decrease, which is not preferable.

Mw/Mn of the polyalkylene oxide of this invention is 1.10 or less, Preferably it is 1.08 or less. When Mw/Mn becomes larger than 1.10, since the storage elastic modulus at the time of setting it as a polyurethane resin falls and moldability deteriorates, it is unpreferable.

Mh/f of the polyalkylene oxide of this invention is 1,000 or more, Preferably it is 1,500 or more. When Mh/f becomes smaller than 1,000, since physical properties, such as flexibility when it is set as a polyurethane resin, deteriorate, it is unpreferable.

The area ratio of molecular weight 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 becomes larger than 2.0%, the storage elastic modulus in the case of a polyurethane resin is lowered, and physical properties such as hysteresis loss and compression set are lowered, which is not preferable.

The polyalkylene oxide of the present invention is preferably 1000 to 50000 g/mol as 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, , it is particularly preferably 3000 to 30000 g/mol.

The polyalkylene oxide of the present invention is, for example, in the presence of an alkylene oxide polymerization catalyst containing a phosphazene compound and a Lewis acid, by using an active hydrogen-containing compound as an initiator to conduct ring-opening polymerization of the alkylene oxide, and By setting the amount of the phosphazene compound to be used in the range of 0.001 to 0.1 mol with respect to 1 mol of active hydrogen in the active hydrogen-containing compound, 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-tetraisopropylguani) dino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra (n-butyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraphenylguani) dino) 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)phos Phonium hydrogen carbonate, tetrakis (1,1,3,3-tetraphenylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetrabenzylguanidino) phosphonium hydrogen carbonate , tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydrogen carbonate, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydrogen carbonate Phosphazenium salts, such as these, can be illustrated.

Further, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diethylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(di n-Propylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(diisopropylamino)phosphoranylideneamino]phosphonium hydroxide, tetrakis[tris(din-butylamino) Phosphoranilideneamino]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)phosphoranylidene Amino] phosphonium hydrogen carbonate, tetrakis [tris (di n-propylamino) phosphoranylideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diisopropylamino) phosphoranylidene amino] phosphonium hydro Gen carbonate, tetrakis[tris(din-butylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[tris(diphenylamino)phosphoranylideneamino]phosphonium hydrogen carbonate, tetrakis[ and phosphazenium salts such as tris(1,3-dimethylimidazolidine-2-imino)phosphoranylideneamino]phosphonium hydrogen carbonate.

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

Here, as a phosphazene compound, the phosphazenium salt represented by the said General formula (1) is preferable.

The polyalkylene oxide of the present invention has a high molecular weight, a low degree of unsaturation, a narrow molecular weight distribution, and a small amount of low molecular weight components. It can be expected to improve the physical properties, such as.

Example

Hereinafter, although an Example demonstrates this invention, this Example does not limit this invention at all.

First, the calculation method of catalyst activity and the analysis method of polyalkylene oxide are demonstrated.

(1) Catalytic activity (unit: g/mol·min)

A (unit: g) the amount of the reacted alkylene oxide, b (unit: mol) for the amount of phosphazenium salt used, and c (unit: minutes) for the time required for polymerization, catalytic activity by the following formula was calculated.

Catalytic activity = a/(b×c).

(2) Molecular weight of polyalkylene oxide (unit: g/mol)

By the method described in JIS K-1557, the hydroxyl value d (unit: mgKOH/g) of the polyalkylene oxide was measured. 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 a gel permeation chromatograph (GPC) (manufactured by Tosoh Corporation, HLC8020), using tetrahydrofuran as a solvent, the measurement was performed at 40° C., and using polystyrene as a standard material, the number average of polyalkylene oxide The molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight of the highest peak (Mh) were calculated.

(3) Area ratio of low molecular weight component of polyalkylene oxide (unit: %)

The area ratio of the low molecular weight component equal to or less than the molecular weight (Mh/3) obtained by dividing Mh calculated in the method (2) by 3 was calculated.

(4) Unsaturation 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 in the method (2), the molecular weight distribution (Mw/Mn) of the polyalkylene oxide was calculated.

Synthesis Example 1 (Synthesis of phosphazenium salt A)

In a nitrogen atmosphere, 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added to a 2-liter four-neck flask equipped with a stirring blade, followed by stirring 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 further 1,1,3,3-tetramethylguanidine 107 g (0.92 mol) was added dropwise over 1 hour. After stirring the obtained white slurry solution at 100 degreeC for 14 hours, it cooled to 80 degreeC, 250 ml of ion-exchange water was added, and it stirred for 30 minutes. When stirring was stopped, all the slurries were dissolved, and a two-phase solution was obtained. Oil-water separation of the obtained two-phase solution was performed, and the aqueous phase was collect|recovered. 100 ml of dichloromethane was added to the obtained aqueous phase, oil-water separation was performed, and the dichloromethane phase was collect|recovered. The obtained dichloromethane solution was washed with 100 ml of ion-exchanged water.

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

Synthesis Example 2 (Synthesis of phosphazenium salt B)

Tetrakis [tris (dimethylamino) phosphoranylidene amino] phosphonium chloride 5.7 g (7.4 mmol, manufactured by Aldrich), 2 in a 100 ml Schlenk tube with a magnetic rotor under nitrogen atmosphere -Propanol (16 ml) was added, and the mixture was dissolved by stirring at 25°C. A solution of 85 wt% potassium hydroxide 0.53 g [8.1 mmol, 1.1 mol equivalent with respect to tris(dimethylamino)phosphoranylideneamino]phosphonium chloride] dissolved in 2-propanol while maintaining stirring was added. After stirring at 25° C. for 5 hours, the precipitated byproduct 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 a hydride 32.7 g of a 2-propanol solution of a hydroxy anion, Y is a phosphorus atom, and a phosphazenium salt corresponding to 3] was obtained at a concentration of 17% by weight 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 the phosphazenium salt A obtained in Synthesis Example 1 was added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and 2-propanol was removed under the pressure reduction of 0.5 kPa. Then, the alkylene oxide polymerization catalyst was obtained by adding and mixing 10 ml (10 mmol) of 1.0 mol/L toluene solutions of triisobutylaluminum.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C., and 108 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 18 to 22 ° C. Residual propylene oxide and toluene were removed under a reduced pressure of 0.5 kPa to obtain 106 g of colorless and odorless polyalkylene oxide. The catalyst 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. A result is shown in Table 1.

Example 2

In an autoclave of 0.2 liters with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) SANNIX GP1000 ; hydroxyl value is 160 mgKOH/g) 18 g (18 mmol, active hydrogen amount 54 mmol) and 0.54 g (0.27 mmol, active hydrogen 1 mol) of a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 0.005 mol) was added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under reduced pressure of 0.5 kPa. Thereafter, 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) 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, it was made to react in the range of 68-72 degreeC of internal temperature, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be maintained at 0.25 MPa or less. Residual ethylene oxide was removed under a reduced pressure of 0.5 kPa 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. A result is shown in Table 1.

Example 3

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 18 g (18 mmol, active hydrogen amount 54 mmol) and a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 (0.14 mmol, 0.0025 mol per 1 mol of active hydrogen) was added. . After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under reduced pressure of 0.5 kPa. Thereafter, 0.27 ml of a 1.0 mol/L toluene solution of triisobutylaluminum (0.27 mmol, 0.005 mol with respect to 1 mol of active hydrogen) was added, 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, it was made to react in the range of 68-72 degreeC of internal temperature, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be maintained at 0.25 MPa or less. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of colorless and odorless polyalkylene oxide. The catalyst 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. A result is shown in Table 1.

Example 4

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 18 g (18 mmol, active hydrogen amount 54 mmol) and a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 (0.27 mmol, 0.005 mol with respect to 1 mol of active hydrogen) was added. . After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under reduced pressure of 0.5 kPa. Thereafter, 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) 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 50 ° C., and 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 48 to 52 ° C. Next, after removing residual propylene oxide under reduced pressure of 0.5 kPa, it was made to react in the range of 48-52 degreeC of internal temperatures, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. Residual ethylene oxide was removed under a 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. A result is shown in Table 1.

Example 5

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 6.0 g (6.0 mmol, active hydrogen amount 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 with respect to 1 mol of active hydrogen)) added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under reduced pressure of 0.5 kPa. Then, 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, , 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 intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, it was made to react in the range of 68-72 degreeC of internal temperature, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be maintained at 0.25 MPa or less. 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. A result is shown in Table 1.

Example 6

Instead of 0.54 ml of 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 1.0 mol/L hexane solution of diethylzinc (0.54 mmol, active An alkylene oxide polymerization catalyst and polyalkylene oxide were prepared in the same manner as in Example 2, except that 0.010 mol) was used with respect to 1 mol of hydrogen. 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 0.016 meq/g, and the molecular weight distribution was 1.06. A result is shown in Table 1.

Comparative Example 1

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 6.0 g (6.0 mmol, active hydrogen amount 18 mmol) and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis(tris(dimethylamino) phosphazene P4 base ) 18 ml of a 1.0 mol/L hexane solution of phosphoranylideneamino)-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 into 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 got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C., and 37 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 18 to 22 ° C. Residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 42 g of colorless and odorless polyalkylene oxide. The catalyst 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. A result is shown in Table 2.

Comparative Example 2

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

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. As a result, when 36 g of propylene oxide was supplied, the reaction was stopped. Residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 36 g of colorless and odorless polyalkylene oxide. The catalyst 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. A result is shown in Table 2.

Comparative Example 1 Comparative Example 2 Phosphazenium salt A amount (mmol) 0 0.27 Phosphazene P4 base amount (mmol) 18 0 Triisobutylaluminum content (mmol) 36 0 Active hydrogen content in active hydrogen-containing compound (mmol) 18 54 Polymerization temperature (℃) 20 70 polymerization time (h) 3 24 Catalytic activity (g/mol.min) 11 46 Molecular weight (g/mol) 6,900 2,000 Unsaturation (meq/g) 0.016 0.013 molecular weight distribution 1.36 1.05

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 the phosphazenium salt A obtained in Synthesis Example 1 was added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and 2-propanol was removed under the pressure reduction of 0.5 kPa. Thereafter, 10 ml of a 1.0 mol/L toluene solution (10 mmol of aluminum atoms) of an aluminoxane having a methyl group and an isobutyl group (manufactured by Toso Finechem, (trade name) MMAO-3A) is added and mixed with an alkylene An oxide polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 35 ° C., and 108 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 33 to 37 ° C. Residual propylene oxide and toluene were removed under a reduced pressure of 0.5 kPa to obtain 106 g of colorless and odorless polyalkylene oxide. The conversion ratio of the 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. A result is shown in Table 3.

Example 8

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 18 g (18 mmol, active hydrogen amount 54 mmol) and a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 (0.27 mmol, 0.005 mol with respect to 1 mol of active hydrogen) was added. . After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under 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 Toso Finechem, (trade name) MMAO-3A) (0.54 mmol of aluminum atoms, 0.010 mol of active hydrogen per 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, it was made to react in the range of 68-72 degreeC of internal temperature, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be maintained at 0.25 MPa or less. Residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 127 g of colorless and odorless polyalkylene oxide. The conversion ratio of the 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. A result is shown in Table 3.

Example 9

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 18 g (18 mmol, active hydrogen amount 54 mmol) and a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 (0.14 mmol, 0.0025 mol per 1 mol of active hydrogen) was added. . After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under 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 Toso Finechem, (trade name) MMAO-3A) (0.27 mmol of aluminum atoms, 0.005 mol of active hydrogen per 1 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, it was made to react in the range of 68-72 degreeC of internal temperature, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be maintained at 0.25 MPa or less. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of colorless and odorless polyalkylene oxide. The conversion ratio of the 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. A result is shown in Table 3.

Example 10

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 18 g (18 mmol, active hydrogen amount 54 mmol) and a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 (0.27 mmol, 0.005 mol with respect to 1 mol of active hydrogen) was added. . After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under 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 Toso Finechem, (trade name) MMAO-3A) (0.54 mmol of aluminum atoms, 0.010 mol of active hydrogen per 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 50 ° C., and 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 48 to 52 ° C. Next, after removing residual propylene oxide under reduced pressure of 0.5 kPa, it was made to react in the range of 48-52 degreeC of internal temperatures, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. Residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 125 g of colorless and odorless polyalkylene oxide. The conversion ratio of the 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. A result is shown in Table 3.

Example 11

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 6.0 g (6.0 mmol, active hydrogen amount 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 with respect to 1 mol of active hydrogen)) added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under 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 Toso Finechem, (trade name) MMAO-3A) (0.36 mmol of aluminum atoms, 0.020 mol of active hydrogen per 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under a reduced pressure of 0.5 kPa, it was made to react in the range of 68-72 degreeC of internal temperature, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be maintained at 0.25 MPa or less. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 112 g of colorless and odorless polyalkylene oxide. The conversion ratio of the 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. A result is shown in Table 3.

Comparative Example 3

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 6.0 g (6.0 mmol, active hydrogen amount 18 mmol) and a 1.0 mol/L toluene solution 36 ml (aluminum atom) of aluminoxane having a methyl group and an isobutyl group (manufactured by Toso Finechem, (trade name) MMAO-3A) 2.0 mol) was added with respect to 36 mmol and 1 mol of active hydrogen, the internal temperature was 80 degreeC, the pressure reduction process of 0.5 kPa was performed, and the alkylene oxide polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 35 ° C., and propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 33 to 37 ° C. As a result, when 12 g of propylene oxide was supplied, the reaction was stopped. 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 ratio of the 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. A result is shown in Table 4.

Comparative Example 4

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

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., and propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. As a result, when 36 g of propylene oxide was supplied, the reaction was stopped. Residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 36 g of colorless and odorless polyalkylene oxide. The conversion ratio of the 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. A result is shown in Table 4.

Comparative Example 3 Comparative Example 4 Phosphazenium salt A amount (mmol) 0 0.27 Atomic weight of aluminum in MMAO-3A (mmol) 36 0 Active hydrogen content in active hydrogen-containing compound (mmol) 18 54 Polymerization temperature (℃) 35 70 Conversion rate of alkylene oxide (%) 25 50 Molecular weight (g/mol) 1,500 2,000 Unsaturation (meq/g) 0.012 0.013 molecular weight distribution 1.42 1.05

Example 12

To a 0.2 liter autoclave equipped with a stirring blade, 11 g (2.5 mmol) of a 17 wt% 2-propanol solution of the phosphazenium salt B obtained in Synthesis Example 2 was added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and 2-propanol was removed under the pressure reduction of 0.5 kPa. Then, the alkylene oxide polymerization catalyst was obtained by adding and mixing 7.5 ml (7.5 mmol) of a 1.0 mol/L toluene solution of triisobutylaluminum.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C., and 108 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Residual propylene oxide and toluene were removed under a reduced pressure of 0.5 kPa to obtain 106 g of colorless and odorless polyalkylene oxide. The catalyst 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. A result is shown in Table 5.

Example 13

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Co., Ltd., (trade name) Sannix GP1000; Hydroxyl group 160 mgKOH/g] 18 g (18 mmol, active hydrogen amount 54 mmol) and 2.0 g (0.45 mmol, active hydrogen 1 mol) of a 17 wt% 2-propanol solution of the phosphazenium salt B obtained in Synthesis Example 2 0.008 mol) was added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under 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, , 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., 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under reduced pressure of 0.5 kPa, it was made to react in the range of the internal temperature of 108-112 degreeC, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. Residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 127 g of colorless and odorless polyalkylene oxide. The catalyst 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. A result is shown in Table 5.

Example 14

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Co., Ltd., (trade name) Sannix GP1000; Hydroxyl group 160 mgKOH/g] 18 g (18 mmol, active hydrogen amount 54 mmol) and 17 wt% 2-propanol solution of phosphazenium salt B obtained in Synthesis Example 2 (0.23 mmol, active hydrogen 1 mol) 0.004 mol) was added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and dehydration process was performed under reduced pressure of 0.5 kPa. Thereafter, 0.68 ml of a 1.0 mol/L toluene solution of triisobutylaluminum (0.68 mmol, 0.013 mol with respect to 1 mol of active hydrogen) was added, 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under reduced pressure of 0.5 kPa, it was made to react in the range of the internal temperature of 108-112 degreeC, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. Residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 126 g of colorless and odorless polyalkylene oxide. The catalyst 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. A result is shown in Table 5.

Example 15

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Co., Ltd., (trade name) Sannix GP1000; Hydroxyl group 160 mgKOH/g] 18 g (18 mmol, active hydrogen amount 54 mmol) and 1.2 g (0.27 mmol, active hydrogen 1 mol) of a 17 wt% 2-propanol solution of the phosphazenium salt B obtained in Synthesis Example 2 0.005 mol) was added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under reduced pressure of 0.5 kPa. Thereafter, 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) 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 ° C., and 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out in the range of an internal temperature of 78 to 82 ° C. Next, after removing residual propylene oxide under reduced pressure of 0.5 kPa, it was made to react in the range of the internal temperature of 108-112 degreeC, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. Residual ethylene oxide was removed under a 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. A result is shown in Table 5.

Example 16

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound (manufactured by Sanyo Kasei Kogyo, (trade name) Sannics GP1000; hydroxyl value of 160 mgKOH/g ) 6.0 g (6.0 mmol, active hydrogen amount 18 mmol) and a 25 wt% 2-propanol solution of the phosphazenium salt B obtained in Synthesis Example 2 (0.18 mmol, 0.010 mol with respect to 1 mol of active hydrogen) added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was made into 80 degreeC, and the dehydration process was performed under reduced pressure of 0.5 kPa. Thereafter, 0.36 ml of a 1.0 mol/L toluene solution of triisobutylaluminum (0.36 mmol, 0.020 mol with respect to 1 mol of active hydrogen) was added, 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 obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 ° C., 92 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 68 to 72 ° C. Next, after removing residual propylene oxide under reduced pressure of 0.5 kPa, it was made to react in the range of the internal temperature of 108-112 degreeC, supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. 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 0.008 meq/g, and the molecular weight distribution was 1.08. A result is shown in Table 5.

Example 17

Instead of 1.35 ml of 1.0 mol/L toluene solution of triisobutylaluminum (1.35 mmol, 0.008 mol with respect to 1 mol of active hydrogen), 0.15 g of triisopropoxy aluminum (0.75 mmol, 0.025 for 1 mol of active hydrogen) mol) was used, and an alkylene oxide polymerization catalyst and polyalkylene oxide were produced in the same manner as in Example 13. 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 0.007 meq/g, and the molecular weight distribution was 1.05. A result is shown in Table 5.

Example 18

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 M solution of triphenylaluminum (1.35 mmol, with respect to 1 mol of active hydrogen) 0.025 mol), an alkylene oxide polymerization catalyst and polyalkylene oxide were produced in the same manner as in Example 13. 127 g of colorless and odorless polyalkylene oxide was obtained. The catalyst 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. A result is shown in Table 6.

Example 19

Instead of 1.35 ml (1.35 mmol, 0.025 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / liter toluene solution of triisobutylaluminum, 0.18 g (1.35 mmol, 0.025 mol for 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 for use. 126 g of colorless and odorless polyalkylene oxide was obtained. The catalyst 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. A result is shown in Table 6.

Example 20

Instead of 1.35 mL of 1.0 mol/L of triisobutylaluminum in toluene solution (1.35 mmol, 0.025 mol relative to 1 mol of active hydrogen), 1.35 mL of 1.0 M hexane solution in pure isobutylaluminoxane (1.35 mmol, An alkylene oxide polymerization catalyst and polyalkylene oxide were produced in the same manner as in Example 13 except that 0.025 mol) was used with respect to 1 mol of active hydrogen. 107 g of colorless and odorless polyalkylene oxide was obtained. The catalyst 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. A result is shown in Table 6.

Example 21

An alkylene oxide polymerization catalyst and polyalkylene oxide were prepared 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 catalyst 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. A result is shown in Table 6.

Example 22

Instead of 1.35 mL of 1.0 mol/L of triisobutylaluminum in toluene solution (1.35 mmol, 0.025 mol relative to 1 mol of active hydrogen), 1.35 mL of 1.0 mol/L of diethylzinc in hexane solution (1.35 mmol, active An alkylene oxide polymerization catalyst and polyalkylene oxide were produced in the same manner as in Example 13 except that 0.025 mol) was used with respect to 1 mol of hydrogen. 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. A result is shown in Table 6.

Comparative Example 5

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Co., Ltd., (trade name) Sannix GP1000; Hydroxyl group 160 mgKOH/g] 6.0 g (6.0 mmol, active hydrogen amount 18 mmol) and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2- which is a phosphazene P4 base 18 ml of a 1.0 mol/L hexane solution of bis(tris(dimethylamino)phosphoranylideneamino)-2λ5,4λ5-catenadi(phosphazene) (18 mmol, 1.0 mol per 1 mol of active hydrogen) was added did After making the inside of the autoclave into 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 got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 20 ° C., and 37 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature of 18 to 22 ° C. Residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 42 g of colorless and odorless polyalkylene oxide. The catalyst 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. A result is shown in Table 7.

Comparative Example 6

An alkylene oxide polymerization catalyst and 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 catalyst 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. A result is shown in Table 7.

Comparative Example 7

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Co., Ltd., (trade name) Sannix GP1000; Hydroxyl group 160 mgKOH/g] 18 g (18 mmol, active hydrogen amount 54 mmol) and 2.0 g (0.45 mmol, active hydrogen 1 mol) of a 17 wt% 2-propanol solution of the phosphazenium salt B obtained in Synthesis Example 2 0.008 mol) was added. After making the inside of an autoclave into nitrogen atmosphere, the internal temperature was 80 degreeC, the dehydration process was performed under the pressure reduction of 0.5 kPa, and the alkylene oxide polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 ° C., and propylene oxide was intermittently supplied so as to maintain a reaction pressure of 0.3 MPa or less, and the reaction was carried out at an internal temperature in the range of 88 to 92 ° C. 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 catalyst 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. A result is shown in Table 3.

Comparative Example 8

In a 0.2 liter autoclave equipped with a stirring blade, a polyether polyol having a molecular weight of 1000 having three hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Co., Ltd., (trade name) Sannix GP1000; Hydroxyl value is 160 mgKOH/g] 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 with respect to 1 mol of active hydrogen) is added And the internal temperature was 80 degreeC, and the pressure reduction process of 0.5 kPa was performed.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was made into 70 degreeC, and propylene oxide was made to react at the reaction pressure of 0.3 MPa or less, and the range of 68-72 degreeC internal temperature. However, after reaching the reaction pressure of 0.3 MPa at the reaction temperature of 70 DEG C, no decrease in pressure 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 polyether polyol as a raw material was recovered. Triisobutylaluminum alone did not show any polymerization activity of propylene oxide. A result is shown in Table 7.

Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Phosphazenium salt B amount (mmol) 0 0 0.45 0 Phosphazene P4 base amount (mmol) 18 0 0 0 KOH amount (mmol) 0 0.45 0 0 Amount of triisobutylaluminum
(m㏖) 36 1.35 0 36 Active hydrogen content in active hydrogen-containing compound (mmol) 18 54 54 18 Polymerization temperature (℃) 20 90 90 90 polymerization time (h) 3 11 9 10 catalytic activity
(g/mol min) 11 61 460 0 Molecular weight (g/mol) 6,900 2,000 7,000 Raw material recovery Unsaturation (meq/g) 0.016 0.030 0.024 molecular weight distribution 1.36 1.05 1.06

Example 23

In a 0.2 liter autoclave with stirring blades under nitrogen atmosphere, 18 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (54 mmol of active hydrogen), 25 of the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a wt % 2-propanol solution was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 reduced pressure was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 127 g of colorless and odorless polyalkylene oxide. The catalytic activity is 600 g/mol.min, the degree of unsaturation of the obtained polyalkylene oxide is 0.006 meq/g, the molecular weight distribution is 1.06, the Mh/f is 3,700 g/mol, the area ratio of the low molecular weight component of Mh/3 or less is 0.1% it was

Example 24

In a 0.2 liter autoclave with stirring blades under nitrogen atmosphere, 18 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (54 mmol of active hydrogen), 25 of the phosphazenium salt A obtained in Synthesis Example 1 0.54 g (0.27 mmol) of 2-propanol solution by weight was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 126 g of colorless and odorless polyalkylene oxide. Catalytic activity is 600 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.005 meq/g, molecular weight distribution is 1.05, Mh/f is 3,600 g/mol, Mh/3 or less, the area ratio of the low molecular weight component is 0.1% it was

Example 25

In a 0.2 liter autoclave with stirring blades under nitrogen atmosphere, 18 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (54 mmol of active hydrogen), 25 of the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a wt % 2-propanol solution was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 reduced pressure was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 70 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under reduced pressure of 0.5 kPa to obtain 125 g of colorless and odorless polyalkylene oxide. Catalyst activity is 400 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.005 meq/g, molecular weight distribution is 1.05, Mh/f is 3,600 g/mol, Mh/3 or less, the area ratio of low molecular weight components is 0.1% it was

Example 26

In a 0.2 liter autoclave with stirring blades under nitrogen atmosphere, 18 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (54 mmol of active hydrogen), 25 of the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a wt % 2-propanol solution was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 reduced pressure was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 120 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 128 g of colorless and odorless polyalkylene oxide. The catalytic activity is 1,500 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.008 meq/g, the molecular weight distribution is 1.06, the Mh/f is 3,700 g/mol, the area ratio of the low molecular weight component of Mh/3 or less is 0.2% it was

Example 27

In a 0.2 liter autoclave equipped with a stirring blade, under a nitrogen atmosphere, 9 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (27 mmol of active hydrogen), 25 of the phosphazenium salt A obtained in Synthesis Example 1 0.45 g (0.23 mmol) of 2-propanol solution by weight was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 117 g of colorless and odorless polyalkylene oxide. The catalytic activity is 500 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.008 meq/g, the molecular weight distribution is 1.06, the Mh/f is 7,000 g/mol, the area ratio of the low molecular weight component of Mh/3 or less is 0.2% it was

Example 28

In a 0.2 liter autoclave equipped with a stirring blade, under a nitrogen atmosphere, 0.90 g (0.45 mmol) of a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 reduced pressure was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 109 g of colorless and odorless polyalkylene oxide. The catalytic activity is 500 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.008 meq/g, the molecular weight distribution is 1.06, the Mh/f is 7,000 g/mol, the area ratio of the low molecular weight component of Mh/3 or less is 0.2% it was

Example 29

In a 0.2 liter autoclave with stirring blades under nitrogen atmosphere, 18 g of polyether polyol (Sanix GP1000 manufactured by Sanyo Kasei Kogyo Co., Ltd.) (active hydrogen amount 54 mmol), 25 weight of the phosphazenium salt A obtained in Synthesis Example 1 % 2-propanol solution, 0.90 g (0.45 mmol) was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 set to 80° C., and reduced pressure was performed at 0.5 kPa, and the alkyl A renoxide polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 127 g of colorless and odorless polyalkylene oxide. Catalytic activity is 600 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.005 meq/g, molecular weight distribution is 1.08, Mh/f is 3,500 g/mol, Mh/3 or less, the area ratio of low molecular weight components is 1.4% it was

Example 30

In a 0.2 liter autoclave with stirring blades under nitrogen atmosphere, 18 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (54 mmol of active hydrogen), 25 of the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a wt % 2-propanol solution was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 reduced pressure treatment was performed at 0.5 kPa, followed by polymerization of alkylene oxide. A catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 127 g of colorless and odorless polyalkylene oxide. Catalytic activity is 600 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.006 meq/g, molecular weight distribution is 1.07, Mh/f is 3,700 g/mol, Mh/3 or less, the area ratio of low molecular weight components is 0.4% it was

Example 31

In a 0.2 liter autoclave with stirring blades under nitrogen atmosphere, 18 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (54 mmol of active hydrogen), 25 of the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a wt % 2-propanol solution was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of aluminoxane having a methyl group and an isobutyl group (manufactured by Toso Finechem, MMAO-3A) 1.0 mol/L hexane solution was added, the internal temperature was set to 80° C., and the temperature was 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 to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 85 g of colorless and odorless polyalkylene oxide. The catalytic activity is 250 g/mol.min, the obtained polyalkylene oxide has an unsaturation degree of 0.005 meq/g, a molecular weight distribution of 1.05, Mh/f is 2,000 g/mol, and the area ratio of low molecular weight components of Mh/3 or less is 0.1% it was

Example 32

In a 0.2 liter autoclave equipped with a stirring blade, under a nitrogen atmosphere, 18 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (active hydrogen amount 54 mmol), 25 of the phosphazenium salt A obtained in Synthesis Example 1 0.90 g (0.45 mmol) of a wt % 2-propanol solution was added. The internal temperature was made into 80 degreeC, and the pressure reduction process was performed at 0.5 kPa. Thereafter, 1.35 ml (1.35 mmol) of a 1.0 mol/L hexane solution of diethylzinc (ZnEt ₂ ) 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. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 85 g of colorless and odorless polyalkylene oxide. The catalytic activity is 250 g/mol.min, the obtained polyalkylene oxide has an unsaturation degree of 0.005 meq/g, a molecular weight distribution of 1.05, Mh/f is 2,000 g/mol, and the area ratio of low molecular weight components of Mh/3 or less is 0.1% it was

Example 33

In a 0.2 liter autoclave with a stirring blade under nitrogen atmosphere, 18 g of polyether polyol (San-Nix GP1000 manufactured by Sanyo Chemical Industries, Ltd.) (54 mmol of active hydrogen), 17 weights of phosphazenium salt B obtained in Synthesis Example 2 % 2-propanol solution 2.0 g (0.45 mmol) was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 reduced pressure was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 127 g of colorless and odorless polyalkylene oxide. The catalytic activity is 600 g/mol.min, the degree of unsaturation of the obtained polyalkylene oxide is 0.006 meq/g, the molecular weight distribution is 1.06, the Mh/f is 3,700 g/mol, the area ratio of the low molecular weight component of Mh/3 or less is 0.1% it was

The above results are combined with Table 8 and Table 9, and are shown.

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 of 0.020 meq/g or less

ii) Mw/Mn of 1.10 or less

iii) Mh/f of 1,000 or more

iv) The 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 material 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).

Comparative Example 9

In a 0.2 liter autoclave under a nitrogen atmosphere, 18 g (18 mmol) of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000), 0.54 of a 25 wt% 2-propanol solution of the phosphazenium salt A obtained in Synthesis Example 1 g (0.27 mmol) was added. The internal temperature was 80 degreeC, the pressure reduction process was performed at 0.5 kPa, and the alkylene oxide polymerization catalyst was obtained.

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 92 g of propylene oxide intermittently so that the reaction pressure might be maintained 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under a reduced pressure of 0.5 kPa. Then, it was made to react, making the internal temperature of an autoclave 110 degreeC, and supplying 18 g of ethylene oxide intermittently so that the reaction pressure might be kept 0.25 MPa or less. After completion of the reaction, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to obtain 127 g of colorless and odorless polyalkylene oxide. Catalytic activity is 500 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.026 meq/g, molecular weight distribution is 1.12, Mh/f is 3,300 g/mol, Mh/3 or less, the area ratio of low molecular weight components is 3.7% it was

Comparative Example 10

In a 0.2 liter autoclave under a nitrogen atmosphere, 1.35 ml (1.35 m) of a 1.0 mol/L toluene solution of 18 g (18 mmol) of polyether polyol (manufactured by Sanyo Kasei Co., Ltd., Sannix GP1000) and triisobutylaluminum (TIBAL) mol) was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed at 0.5 kPa.

The internal temperature of the autoclave was set to 90°C, and 10 g of propylene oxide was intermittently supplied to maintain a reaction pressure of 0.3 MPa or less, while reacting. 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 catalytic activity was 0 g/mol·min, and the obtained polyalkylene oxide was a polyether polyol (Sanyo Chemicals Co., Ltd., Sannix GP1000) as a raw material.

Comparative Example 11

In an autoclave of 0.2 liters under nitrogen atmosphere, 18 g of polyether polyol (manufactured by Sanyo Kasei Kogyo Co., Ltd., Sannix GP1000) (active hydrogen amount 54 mmol), 50 mg (0.45 mmol) of a 50 wt% aqueous solution of potassium hydroxide (KOH) was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 reduced pressure was performed at 0.5 kPa to obtain an alkylene oxide polymerization catalyst. got it

In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was set to 90 degreeC, and it was made to react, supplying 36 g of propylene oxide intermittently so that the reaction pressure might be maintained 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 catalytic activity is 60 g/mol·min, the degree of unsaturation of the obtained polyalkylene oxide is 0.030 meq/g, the molecular weight distribution is 1.12, Mh/f is 500 g/mol, Mh/3 or less, the area ratio of low molecular weight components is 4.3% it was

Comparative Example 12

In an autoclave of 0.2 liters under a nitrogen atmosphere, 6 g of polyether polyol (Sanyo Chemical Co., Ltd., Sannix GP1000) (active hydrogen amount 18 mmol) and 1-tert-butyl-4,4,4 phosphazene P4 base - Tris(dimethylamino)-2,2-bis(tris(dimethylamino)phosphoranylideneamino)-2λ5,4λ5-catenadi(phosphazene) in 1.0 mol/L hexane solution 18ml (18mmol) ) was added. The internal temperature was 80 degreeC, and the pressure reduction process was performed 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 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 degreeC, and it was made to react, supplying 37 g of propylene oxide intermittently so that the reaction pressure might be maintained 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 obtained polyalkylene oxide is 0.016 meq/g, the molecular weight distribution is 1.36, the Mh/f is 3,300 g/mol, the area ratio of the low molecular weight component of Mh/3 or less is 3.7% it was

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

Application example 1

100 parts by weight of polyalkylene oxide obtained in Example 23, 5.8 parts of diphenylmethane diisocyanate (trade name: C-1394), and 0.05 parts of triethylenediamine (trade name: TEDA-L33) were placed in a disposable cup , and stirred. After the stirring was completed, the viscoelasticity was measured using a rotary rheometer (Soliquidmeter MR-500 manufactured by UB) in a nitrogen atmosphere, 25° C., and a frequency of 10 Hz. The storage elastic modulus (G') after 50 minutes from completion of stirring was 45,000 Pa.

Application example 2

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

As mentioned above, although this invention was demonstrated in detail and taking into account specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the essence and range of this invention.

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 to 18.

In addition, in this invention, a suitable combination of a phosphazene compound, a Lewis acid, and the active hydrogen containing compound used as needed is specifically as shown in Tables 19-24.

In addition, the specification, claims and abstract of Japanese Patent Application No. 2014-164289 filed on August 12, 2014, specification of Japanese Patent Application No. 2014-164290 filed on August 12, 2014, claims and Abstract, specification of Japanese Patent Application No. 2015-145645 filed on July 23, 2015, claims and abstract, and specification of Japanese Patent Application No. 2015-145646 filed on July 23, 2015, claims , the entire contents of the drawings and abstract are hereby incorporated by reference and are hereby incorporated as a disclosure of the specification of the present invention.

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

Moreover, the polyalkylene oxide of this invention is useful for a polyurethane raw material, a polyester raw material, surfactant raw material, a lubricant raw material, etc.

The polyalkylene oxide obtained by using the alkylene oxide polymerization catalyst of the present invention is used in rigid foams used for heat insulators, etc., automobile seats, cushions, bedding, etc. by reacting with various isocyanate compounds. It is expected to develop into flexible foams, adhesives, paints, sealing materials, thermosetting elastomers, and thermoplastic elastomers.

Claims (15)

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

(In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a ring structure in which R ¹ and R ² are bonded to each other, R ¹ each other, or R ² You may form a ring structure in which the groups couple|bonded with each other;
X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy 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). The alkylene according to claim 1, wherein the ratio of the phosphazenium salt represented by the general formula (1) to the Lewis acid is [phosphazenium salt]: [Lewis acid] = 1:0.002 to 500 (molar ratio). Oxide polymerization catalyst. The alkylene oxide polymerization catalyst according to claim 1, 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, 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 claim 1, comprising a phosphazenium salt represented by the following general formula (1), a Lewis acid, and an active hydrogen-containing compound:

(In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a ring structure in which R ¹ and R ² are bonded to each other, R ¹ each other, or R ² You may form a ring structure in which the groups couple|bonded with each other;
X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy 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). The alkylene oxide according to claim 5, wherein 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. polymerization catalyst. A method for preparing the alkylene oxide polymerization catalyst of claim 5 or 6,
A method for producing an alkylene oxide polymerization catalyst, characterized in that after mixing the phosphazenium salt represented by the general formula (1) and an active hydrogen-containing compound, these and a Lewis acid are mixed. A method for producing a polyalkylene oxide, characterized in that ring-opening polymerization of an alkylene oxide is carried out in the presence of the alkylene oxide polymerization catalyst according to any one of claims 1 to 5. Polyalkylene oxides satisfying all of the following i) to iv):
i) Unsaturation of 0.008 meq/g or less
ii) Mw/Mn of 1.10 or less
iii) Mh/f of 1,000 or more
iv) The 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 material is Mn, the weight average molecular weight is Mw, the molecular weight of the highest peak is Mh, and the number of functional groups in the polyalkylene oxide is f). The polyalkyl according to claim 9, wherein the hydroxyl value of the polyalkylene oxide calculated by the method described in JIS K-1557 and the molecular weight calculated from the number of functional groups thereof are in the range of 1000 to 50000 g/mol. ren oxide. 11. A method for producing the polyalkylene oxide according to claim 9 or 10, comprising:
In the presence of an alkylene oxide polymerization catalyst comprising a phosphazene compound and a Lewis acid, using an active hydrogen-containing compound as an initiator, performing ring-opening polymerization of an alkylene oxide,
A method for producing a polyalkylene oxide, characterized in that the amount of the phosphazene compound used per 1 mole of active hydrogen in the active hydrogen-containing compound is in the range of 0.001 to 0.1 mole. The method for producing polyalkylene oxide according to claim 11, wherein the phosphazene compound is a phosphazenium salt represented by the following general formula (1):

(In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and a ring structure in which R ¹ and R ² are bonded to each other, R ¹ each other, or R ² You may form a ring structure in which the groups couple|bonded with each other;
X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkylcarboxy 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). The method for producing a polyalkylene oxide according to claim 11, wherein the ratio of the phosphazene compound to the Lewis acid is [phosphazene compound]:[Lewis acid] = 1:0.002 to 500 (molar ratio). 12. The method according to claim 11, wherein the Lewis acid is at least one compound selected from the group consisting of an aluminum compound, a zinc compound, and a boron compound. 12. The method of claim 11, wherein the Lewis acid is at least one compound selected from the group consisting of organoaluminum, aluminoxane and organozinc.

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