JP6878861B2 - A composition containing a phosphazenium compound, a Lewis acid, and an active hydrogen-containing compound. - Google Patents

Description

The present invention relates to compositions containing specific phosphazenium compounds, Lewis acids, and active hydrogen-containing compounds. The composition of the present invention is, for example, a novel composition that is useful as a ring-opening polymerization catalyst for halogen-containing alkylene oxides and enables the production of halogen-containing polyalkylene glycols having a high molecular weight and a narrow molecular weight distribution.

As a catalyst for producing a polyalkylene oxide having a small amount of monool produced by a side reaction, a catalyst composed of a phosphazenium compound and an active hydrogen-containing compound has been reported (see, for example, Patent Documents 1 and 2).

Further, as a polymerization catalyst of the halogen-containing alkylene oxide, a catalyst composition composed of an ammonium halide salt, a phosphonium halide salt and an alkylaluminum has been reported (see, for example, Patent Document 3 and Non-Patent Document 1).

Further, as a method for producing polyalkylene oxide, a composition obtained by mixing an active hydrogen-containing compound, a phosphazenium compound, and triisobutylaluminum at a molar ratio of 1: 1: 2 is used as an alkylene oxide polymerization catalyst in a toluene solvent. A method for producing a polyalkylene oxide by performing ring-opening polymerization of an alkylene oxide at 20 ° C. has been proposed (see, for example, Non-Patent Document 2).

Here, it is said that the catalyst composition composed of the phosphazenium compound and the active hydrogen-containing compound described in Patent Documents 1 and 2 cannot be used as a polymerization catalyst for the halogen-containing alkylene oxide because the phosphazenium compound is a basic substance. There are challenges.

The composition composed of an ammonium halide salt or a phosphonium halide salt and alkylaluminum described in Non-Patent Document 1 can polymerize a halogenated alkylene oxide, but one end of the obtained halogen-containing polyalkylene oxide is always present. Since it becomes a halogen atom, in order to obtain a halogen-containing polyalkylene glycol, a step of converting the terminal halogen atom into a hydroxyl group is required, which cannot be said to be an efficient method.

In the composition composed of the phosphazenium compound, triisobutylaluminum and the active hydrogen-containing compound described in Non-Patent Document 2, polymerization of propylene oxide has been reported, but polymerization of halogen-containing alkylene oxide has not been reported at all. In order to further improve the activity, it is necessary to use a large amount of the phosphazenium compound with respect to the active hydrogen-containing compound, which is extremely uneconomical.

Japanese Patent No. 3905638 (Japanese Unexamined Patent Publication No. 11-106500) Japanese Patent No. 5663856 (Japanese Unexamined Patent Publication No. 2010-150514) International Publication No. 2012/133769

Macromolecules, 2008, 41, 7058. Polymer Chemistry, 2012, 3, 1189.

The present invention has been made in view of the above background techniques, and an object of the present invention is to enable efficient production of halogen-containing polyalkylene glycols having a small amount of expensive phosphazenium compounds and exhibiting a high molecular weight and a narrow molecular weight distribution. It is an object of the present invention to provide a composition capable of polymerizing a halogen-containing alkylene oxide, and a method for producing a halogen-containing polyalkylene glycol using the same.

As a result of diligent studies to solve the above problems, the present inventors have found that a composition containing a specific phosphazenium compound, a Lewis acid, and an active hydrogen-containing compound has a high molecular weight and narrow molecular weight distribution of a halogen-containing polyalkylene. We have found that glycol can be efficiently produced, and have completed the present invention.

That is, the present invention relates to the composition as shown below and a method for producing a halogen-containing polyalkylene glycol using the same composition.

[1] A composition containing a phosphazenium compound represented by the following general formula (1), a Lewis acid, and an active hydrogen-containing compound.

(In the above general formula (1), R ¹ and R ² are independently each of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ^{a ring structure in which R 1} and R ² are bonded to each other, R ^{1 to} each other, or R ² represents a ring structure in which they are bonded to each other, and X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, a chlorine anion, a bromine anion, or an iodine anion. Y represents a carbon atom or a phosphorus atom, and a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.)
[2] The composition according to the above [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.

[3] The ratio of the phosphazenium compound represented by the general formula (1) to Lewis acid is [phosphasenium compound]: [Lewis acid] = 1: 1.01 to 100 (molar ratio), and the active hydrogen-containing compound. The phosphazenium compound is in the range of 0.001 to 10 mol with respect to 1 mol of active hydrogen in the compound, and the Lewis acid is in the range of 0.001 to 10 mol with respect to 1 mol of active hydrogen in the active hydrogen-containing compound. The composition according to the above [1] or [2].

[4] The active hydrogen-containing compound is at least one selected from the group consisting of a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group. The composition according to any one of [3].

[5] The composition according to any one of the above [1] to [4], which comprises mixing a phosphazenium compound represented by the following general formula (1) and an active hydrogen-containing compound, and then mixing a Lewis acid. How to make things.

(In the above general formula (1), R ¹ and R ² are independently each of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ^{a ring structure in which R 1} and R ² are bonded to each other, R ^{1 to} each other, or R ² represents a ring structure in which they are bonded to each other, and X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, a chlorine anion, a bromine anion, or an iodine anion. Y represents a carbon atom or a phosphorus atom, and a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.)
[6] A halogen-containing alkylene oxide polymerization catalyst comprising the composition according to any one of the above [1] to [4].

[7] A method for producing a halogen-containing polyalkylene glycol, which comprises performing ring-opening polymerization of a halogen-containing alkylene oxide in the presence of the composition according to any one of the above [1] to [4].

According to the present invention, it is possible to obtain a composition having a polymerization activity of a halogen-containing alkylene oxide having a high catalytic activity. Further, by polymerizing a halogen-containing alkylene oxide using the composition of the present invention, a halogen-containing polyalkylene glycol showing a high molecular weight and a narrow molecular weight distribution can be produced.

The present invention will be described in detail below.

The composition of the present invention contains a phosphazenium compound represented by the following general formula (1), a Lewis acid, and an active hydrogen-containing compound.

(In the above general formula (1), R ¹ and R ² are independently each of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ^{a ring structure in which R 1} and R ² are bonded to each other, R ^{1 to} each other, or R ² represents a ring structure in which they are bonded to each other, and X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, a chlorine anion, a bromine anion, or an iodine anion. Y represents a carbon atom or a phosphorus atom, and a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.)
Here, examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an allyl group, an n-butyl group, an isobutyl group, and t. -Butyl group, cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, Examples thereof include a decyl group, a cyclodecyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and a nonadecil group.

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

The ring structure R ¹ s or R ² together are linked together, for example, one substituent is an ethylene group, a propylene group, is an alkylene group such as butylene group, a ring structure connected with each other with other substituent Can be mentioned.

Among these, R ¹ and R ² are particularly preferably methyl group, ethyl group, or isopropyl group because they are halogen-containing alkylene oxide polymerization catalysts having excellent catalytic activity.

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

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

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

Among these ^{, hydroxy anion and hydrogen carbonate anion are particularly preferable because X −} is a halogen-containing alkylene oxide polymerization catalyst having excellent catalytic activity. In the present invention, when Y is a carbon atom, the phosphazenium compound is generally described below. It is represented by the formula (2).

(In the above general 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. , may form a ring structure R ₁ s or R ₂ together are linked together .X ^- hydroxy anion, alkoxy anion of 1 to 4 carbon atoms, carboxy anion, alkyl carboxy anion having 2 to 5 carbon atoms, chlorine Represents an anion, bromine anion, iodine anion or hydrocarbon anion.)
Further, in the present invention, when Y is a phosphorus atom, the phosphazenium compound is represented by the following general formula (3).

(In the above general 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. , may form a ring structure R ₁ s or R ₂ together are linked together .X ^- hydroxy anion, alkoxy anion of 1 to 4 carbon atoms, carboxy anion, alkyl carboxy anion having 2 to 5 carbon atoms, chlorine Represents an anion, bromine anion, iodine anion or hydrocarbon anion.)
In the present invention, specific examples of the phosphazenium compound include tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraethylguanidino) phosphonium hydroxide, and tetrakis. (1,1,3,3-tetra (n-propyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraisopropylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra) (N-butyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraphenylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetrabenzylguanidino) phosphonium hydroxide, tetrakis (1) , 3-Dimethylimidazolidine-2-imino) phosphonium hydroxydo, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydroxydo, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydrogen carbonate , Tetrax (1,1,3,3-tetraethylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-propyl) guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3- Tetraisopropylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-butyl) guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraphenylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraphenylguanidino) 1,1,3,3-tetrabenzylguanidino) phosphonium hydroxygen carbonate, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydroxygen carbonate, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydroxygen Phosphazenium compounds such as carbonate can be exemplified.

In addition, tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (diethylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (din-propylamino) phosphoranilideneamino] phosphonium hydroxyd Do, tetrakis [tris (diisopropylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (di-n-butylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (diphenylamino) phosphoranilideneamino] phosphonium Hydroxide, Tetrakis [Tris (1,3-dimethylimidazolidine-2-imino) Phosphoranilideneamino] Phosphonium Hydroxide, Tetrakis [Tris (Dimethylamino) Phoslanylideneamino] Phosnium Hydrogen Carbonate, Tetrakis [Tris (diethylamino) Phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (di-propylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diisopropylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (din) -Butylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diphenylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (1,3-dimethylimidazolidine-2-imino) phosphoranilideneamino] Phosphazenium compounds such as phosphonium hydrogen carbonate can be exemplified.

Among these, since it is a halogen-containing polyalkylene glycol production catalyst having excellent catalytic performance, tetrakis (1,1,3,3-tetramethylguanidino) phosphazenium hydroxide and tetrakis (1,1,3) 3-Tetramethylguanidino) phosphazenium hydrogen carbonate, tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium hydroxide are particularly preferred.

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

Examples of the aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum and the like. Organic aluminum; aluminoxane such as methylaluminoxane, isobutylaluminoxan, methyl-isobutylaluminoxan; inorganic aluminum such as aluminum chloride, aluminum hydroxide, aluminum oxide can be mentioned.

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

Examples of the boron compound include boron trifluoride, boron tribromide, boron triiodide, triethylboron, trimethoxyboron, triethoxyboron, triisopropoxyboron, tri-n-propoxyboron, triphenylboron and tris. (Pentafluorophenyl) boron and the like can be mentioned.

Among these Lewis acids, organoaluminum, aluminoxane, organozinc, and boron compounds are preferable, and organoaluminum is particularly preferable, because the composition has excellent catalytic performance.

In the present invention, examples of the active hydrogen-containing compound 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, and triol. Examples thereof include methylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, shoeclaw, glucose, 2-naphthol, bisphenol and the like.

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

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

Examples of the thiol compound include ethanedithiol and butanedithiol.

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

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

In the composition of the present invention, the ratio of the phosphazenium compound to the Lewis acid is preferably phosphazenium compound: Lewis acid = 1: 1.01 to 100 (molar ratio), and more preferably phosphasenium compound: Lewis acid = 1: 1. .1 to 10 (molar ratio), particularly preferably phosphazenium compound: Lewis acid = 1: 1.2 to 5 (molar ratio).

In the composition of the present invention, the ratio of active hydrogen to the phosphazenium compound in the active hydrogen-containing compound is preferably active hydrogen: phosphazenium compound = 1: 0.001 to 10 (molar ratio) in the active hydrogen-containing compound, and more. Preferably, the active hydrogen in the active hydrogen-containing compound: phosphazenium compound = 1: 0.001 to 1 (molar ratio), and particularly preferably, the active hydrogen in the active hydrogen-containing compound: phosphasenium compound = 1: 0.001 to 0. .1 (molar ratio).

In the composition of the present invention, the ratio of active hydrogen to Lewis acid in the active hydrogen-containing compound is preferably active hydrogen: Lewis acid = 1: 0.001 to 10 (molar ratio) in the active hydrogen-containing compound. Preferably, active hydrogen in the active hydrogen-containing compound: Lewis acid = 1: 0.001 to 1 (molar ratio), and particularly preferably, active hydrogen in the active hydrogen-containing compound: Lewis acid = 1: 0.001 to 0. .1 (molar ratio).

As a method for producing the composition of the present invention, any method can be used as long as the composition of the present invention can be prepared, and the present invention is not particularly limited. For example, a method of mixing a phosphazenium compound, a Lewis acid, and an active hydrogen-containing compound can be mentioned. In that case, for example, benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, 1,2-dimethoxyethane and the like may be used as the solvent.

Further, any method such as a method of mixing two components of a phosphazenium compound, a Lewis acid, and an active hydrogen-containing compound and then mixing and preparing the remaining one component, a method of mixing and preparing the remaining two components mixed in advance with one component, and the like. The preparation method may be used. Among them, since the composition is excellent in catalytic performance, it is preferable to prepare the composition by mixing the phosphazenium compound and the active hydrogen-containing compound and then mixing with Lewis acid.

When preparing the composition of the present invention, heat / depressurization treatment or the like may be performed. The temperature of the heat treatment may be, for example, 50 to 150 ° C., preferably 70 to 130 ° C. Further, as the pressure during the depressurization treatment, for example, 50 kPa or less, preferably 20 kPa or less can be mentioned.

Since the composition of the present invention is excellent in catalytic performance, it is useful for producing halogen-containing polyalkylene glycols.

The method for producing a halogen-containing polyalkylene glycol of the present invention is characterized in that ring-opening polymerization of a halogen-containing alkylene oxide is carried out in the presence of the above-mentioned composition of the present invention.

In the method for producing a halogen-containing polyalkylene glycol of the present invention, examples of the halogen-containing alkylene oxide include halogen-containing alkylene oxides having 2 to 20 carbon atoms, and specifically, epichlorohydrin and epibromohydrin. Phosphorus, epichlorohydrin, 3,3-dichloropropylene oxide, 3-chloro1,2-epoxybutane, 3,4-dichloro-1,2-epoxybutane, 1,4-dichloro-2,3-epoxybutane And 3,3,3-trichloropropylene oxide and the like. Among these, epichlorohydrin and 3,4-dichloro-1,2-epoxybutane are preferable because they are easily available and the obtained halogen-containing polyalkylene glycol has a high industrial value. The halogen-containing alkylene oxide may be used alone or in combination of two or more. When two or more kinds are mixed and used, for example, the first halogen-containing alkylene oxide may be reacted and then the second and third halogen-containing alkylene oxides may be reacted, or two or more kinds of halogen-containing alkylene oxides may be reacted. The oxides may be reacted at the same time.

Further, in the present invention, it is also possible to copolymerize an alkylene oxide. Examples of copolymerizable alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide.

In the method for producing a halogen-containing polyalkylene glycol of the present invention, the polymerization pressure is preferably in the range of normal pressure to 1.0 MPa, preferably in the range of normal pressure to 0.5 MPa. In the method for producing a halogen-containing polyalkylene glycol of the present invention, the polymerization temperature is in the range of 0 to 180 ° C, more preferably in the range of 50 to 130 ° C.

In the method for producing a halogen-containing polyalkylene glycol of the present invention, the polymerization reaction is carried out without a solvent, but it can also be carried out in a solvent. Examples of the solvent used include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, 1,2-dimethoxyethane and the like.

In the method for producing a halogen-containing polyalkylene glycol of the present invention, since it is an efficient method for producing a halogen-containing polyalkylene glycol, it is preferable that the catalytic activity is 100 g / mol · min or more, and particularly 150 g. It is preferable that the value is / mol · min or more.

The halogen-containing polyalkylene glycol obtained by the method for producing a halogen-containing polyalkylene glycol of the present invention has a molecular weight of 1000 to 100,000 g / calculated from the hydroxyl value calculated by the method described in JIS K-1557 and the number of functional groups thereof. Those having mol, particularly those having 3000 to 30000 g / mol are preferable. Further, the degree of unsaturation calculated by the method described in JIS K-1557 is preferably 0.03 meq / g or less, particularly preferably 0.02 meq / g or less. Further, the molecular weight distribution calculated by gel permeation chromatography (GPC) is preferably 1.5 or less, particularly 1.3 or less.

Hereinafter, the present invention will be described with reference to Examples, but the present Examples do not limit the present invention in any way. First, a method for calculating the catalytic activity in the present invention and a method for analyzing the halogen-containing polyalkylene glycol produced by the present invention will be described.

~ Conversion rate of halogen-containing alkylene oxide ~
Using a nuclear magnetic resonance spectrum measuring device (manufactured by JEOL Ltd., (trade name) JNM-ECZ400S / LI), ¹ H-NMR was measured using deuterated chloroform as a deuterated solvent, and the monomer was derived from 2.6 to 2.8 ppm. It was calculated from the integral ratio of the peak of 3.3 to 4.1 ppm and the peak derived from the polymer.

~ Catalytic activity (unit: g / mol · min) ~
The amount of the reacted halogen-containing alkylene oxide is a (unit: g), the amount of the phosphazenium compound used is b (unit: mol), the time required for polymerization is c (unit: min), and the catalytic activity is determined by the following formula. Calculated.
Catalytic activity = a / (b × c)
~ Molecular weight of halogen-containing polyalkylene glycol (unit: g / mol) ~
The hydroxyl value d (unit: mgKOH / g) of the halogen-containing polyalkylene glycol was measured by the method described in JIS K-1557. The number of functional groups of the obtained halogen-containing polyalkylene oxide was defined as e, and the molecular weight of the halogen-containing polyalkylene glycol was calculated by the following formula.
Molecular weight = (56100 / d) x e
~ Degree of unsaturation of halogen-containing polyalkylene glycol (unit: meq / g) ~
The degree of unsaturation of the halogen-containing polyalkylene glycol was calculated by the method described in JIS K-1557.

~ Molecular weight distribution of halogen-containing polyalkylene glycol (unit: none) ~
Using a gel permeation chromatograph (GPC) (manufactured by Toso Co., Ltd., (trade name) HLC8020), measurement was performed at 40 ° C. using tetrahydrofuran as a solvent, polystyrene was used as a standard substance, and halogen-containing polyalkylene glycol was used. The molecular weight distribution of

~ Phosphazenium compound ~
Phosphazenium compound A: Tetrakis (tetramethylguanidineno) Phosphonium hydroxide: ((Me ₂ N) ₂ C = N) ₄ P ⁺ OH ⁻ was synthesized according to Synthesis Example 1 below.

Phosphazenium halogen compound B: Tetrakis [Tris (dimethylaminophosphoranylidene) amino] Phosphonium hydroxide: [(Me ₂ N) ₃ P = N] ₄ P ⁺ OH ⁻ was synthesized according to Synthesis Example 2 below. used.

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

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

Synthesis Example 2 (Synthesis of phosphazenium salt B)
A 100 ml Schlenk tube with a magnetic rotor was placed in a nitrogen atmosphere, and 5.7 g (7.4 mmol, manufactured by Aldrich) of tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium chloride and 16 ml of 2-propanol were added to 25 It was stirred and dissolved at ° C. A solution in which 0.53 g [8.1 mmol, 1.1 mol equivalents of tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium chloride] of 85 wt% potassium hydroxide was dissolved in 2-propanol while maintaining stirring. Was added. After stirring at 25 ° C. for 5 hours, the precipitated by-product salt is removed by filtration to form the target phosphazenium salt B [R ¹ is a methyl group, R ² is a methyl group, and X ^{− in the above general formula (1).} A 2-propanol solution of hydroxy anion, Y as a phosphorus atom, and a as a phosphazenium salt corresponding to 3] was obtained in a concentration of 17% by weight and a yield of 98%.

Example 1.
A 0.5 liter four-necked flask equipped with a stirring blade, a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g] 90.9 g (227 mmol, amount of active hydrogen 454 mmol) and 11.5 g (5.7 mmol, 0.012 mol with respect to 1 mol of active hydrogen) of the phosphazenium compound A obtained in Synthesis Example 1 were added. After setting the inside of the flask to a nitrogen atmosphere, the temperature was set to 80 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 17 ml (17 mmol, 0.037 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 for 2 hours to compose the composition. I got the thing A.

(Polymerization of epichlorohydrin)
20.2 g (phosphazenium compound: 1.2 mmol) of the composition A obtained in Example 1 was taken in a 0.5 liter four-necked flask equipped with a stirring blade and a dropping funnel, and the inside of the flask was replaced with nitrogen. The internal temperature was raised to 90 ° C., and 75 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 4.5 hours under normal pressure. Aging was performed for 2 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 85 to 90 ° C. Then, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 95 g of colorless and odorless polyepichlorohydrin glycol. The conversion rate was 99.9%, the catalytic activity was 169 g / mol · min, the molecular weight of the obtained polyepichlorohydrin glycol was 1900 g / mol, the degree of unsaturation was 0.007 meq / g, and the molecular weight distribution was 1. It was 1.

Example 2.
A 0.5 liter four-necked flask equipped with a stirring blade, a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g] 90.9 g (227 mmol, amount of active hydrogen 454 mmol) and 11.5 g (5.7 mmol, 0.012 mol with respect to 1 mol of active hydrogen) of the phosphazenium compound A obtained in Synthesis Example 1 were added. After setting the inside of the flask to a nitrogen atmosphere, the temperature was set to 80 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 17 ml (17 mmol, 0.037 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisopropoxyaluminum was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours. Composition B was obtained.

(Polymerization of epichlorohydrin)
20.1 g (phosphazenium compound: 1.2 mmol) of the composition B obtained in Example 2 was taken in a 0.5 liter four-necked flask equipped with a stirring blade and a dropping funnel, and the inside of the flask was replaced with nitrogen. The internal temperature was raised to 90 ° C., and 75 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 4 hours under normal pressure. Aging was performed for 2 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 85 to 90 ° C. Then, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 95 g of colorless and odorless polyepichlorohydrin glycol. The conversion rate was 99.8%, the catalytic activity was 190 g / mol · min, the molecular weight of the obtained polyepichlorohydrin glycol was 1910 g / mol, the degree of unsaturation was 0.008 meq / g, and the molecular weight distribution was 1. It was 2.

Example 3.
A 0.5 liter four-necked flask equipped with a stirring blade, a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g] 90.9 g (227 mmol, amount of active hydrogen 454 mmol) and 25.1 g (5.7 mmol, 0.012 mol with respect to 1 mol of active hydrogen) of the phosphazenium compound B obtained in Synthesis Example 2 were added. After setting the inside of the flask to a nitrogen atmosphere, the temperature was set to 80 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 17 ml (17 mmol, 0.037 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisopropoxyaluminum was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours. Composition C was obtained.

(Polymerization of epichlorohydrin)
20.4 g (phosphazenium compound: 1.2 mmol) of the composition obtained in Example 3 was taken in a 0.5 liter four-necked flask equipped with a stirring blade and a dropping funnel, and the inside of the flask was replaced with nitrogen. The internal temperature was raised to 90 ° C., and 75 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 4 hours under normal pressure. Aging was performed for 2 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 85 to 90 ° C. Then, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 95 g of colorless and odorless polyepichlorohydrin glycol. The conversion rate was 99.9%, the catalytic activity was 191 g / mol · min, the molecular weight of the obtained polyepichlorohydrin glycol was 1910 g / mol, the degree of unsaturation was 0.009 meq / g, and the molecular weight distribution was 1. It was 15.

Example 4.
A 0.5 liter four-necked flask equipped with a stirring blade, a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g] 90.9 g (227 mmol, amount of active hydrogen 454 mmol) and 11.5 g (5.7 mmol, 0.012 mol with respect to 1 mol of active hydrogen) of the phosphazenium compound A obtained in Synthesis Example 1 were added. After setting the inside of the flask to a nitrogen atmosphere, the temperature was set to 80 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 17 ml (17 mmol, 0.037 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of diethylzinc was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was carried out for 2 hours to prepare the composition. I got D.

(Polymerization of epichlorohydrin)
19.9 g (phosphazenium compound: 1.2 mmol) of the composition B obtained in Example 4 was taken in a 0.5 liter four-necked flask equipped with a stirring blade and a dropping funnel, and the inside of the flask was replaced with nitrogen. The internal temperature was raised to 90 ° C., and 75 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 6 hours under normal pressure. Aging was performed for 3 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 85 to 90 ° C. Then, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 85 g of colorless and odorless polyepichlorohydrin glycol. The conversion rate was 86.7%, the catalytic activity was 102 g / mol · min, the molecular weight of the obtained polyepichlorohydrin glycol was 1650 g / mol, the degree of unsaturation was 0.007 meq / g, and the molecular weight distribution was 1. It was 3.

Example 5.
A 0.5 liter four-necked flask equipped with a stirring blade, a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g] 90.9 g (227 mmol, amount of active hydrogen 454 mmol) and 11.5 g (5.7 mmol, 0.012 mol with respect to 1 mol of active hydrogen) of the phosphazenium compound A obtained in Synthesis Example 1 were added. After setting the inside of the flask to a nitrogen atmosphere, the temperature was set to 80 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 17 ml (17 mmol, 0.037 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisopropoxyaluminum was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours. Composition B was obtained.
(Copolymerization of epichlorohydrin and ethylene oxide)
80.4 g (phosphazenium compound: 4.8 mmol) of the composition B obtained in Example 5 was taken into a 2 liter autoclave, and the inside of the autoclave was replaced with nitrogen. The internal temperature was raised to 90 ° C., and 300 g of epichlorohydrin as a halogen-containing alkylene oxide was continuously supplied under normal pressure by a liquid feed pump over 4.5 hours. Aging was performed for 2 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 85 to 90 ° C. Then, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa. After removing epichlorohydrin, the reaction temperature was raised to 130 ° C. After setting the nitrogen pressure to a gauge pressure of 0.12 mpa, 50 g of ethylene oxide was supplied over 0.5 hours so that the gauge pressure did not exceed 0.4 MPa. Aging was carried out for 0.5 hours after the supply of ethylene oxide, and ethylene oxide was removed under reduced pressure at 130 ° C. to obtain 430 g of a colorless and odorless polyepichlorohydrin / polyethylene oxide copolymer. The conversion was 99.9%, the obtained polyepichlorohydrin-polyethylene glycol had a molecular weight of 2170 g / mol, an degree of unsaturation of 0.006 meq / g, and a molecular weight distribution of 1.1.

Comparative example 1.
A 0.5 liter four-necked flask equipped with a stirring blade, a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g] 90.9 g (227 mmol, amount of active hydrogen 454 mmol) and 11.5 g (5.7 mmol, 0.012 mol with respect to 1 mol of active hydrogen) of the phosphazenium compound A obtained in Synthesis Example 1 were added. After setting the inside of the flask to a nitrogen atmosphere, the internal temperature was set to 80 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours to obtain composition E.

(Polymerization of epichlorohydrin)
19.5 g (phosphazenium compound: 1.2 mmol) of the composition E obtained in Comparative Example 1 was taken in a 0.5 liter four-necked flask equipped with a stirring blade and a dropping funnel, and the inside of the flask was replaced with nitrogen. The internal temperature was raised to 90 ° C., and 25 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 2 hours under normal pressure. Aging was performed for 2 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 85 to 90 ° C. Then, the residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa, but the conversion rate was only 7%.

Comparative example 2.
A 0.5 liter four-necked flask equipped with a stirring blade, a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g] 90.9 g (227 mmol, amount of active hydrogen 454 mmol) and 17 ml of a 1.0 mol / l toluene solution of triisobutylaluminum (17 mmol, 0.037 mol with respect to 1 mol of active hydrogen) were added. After setting the inside of the flask to a nitrogen atmosphere, the internal temperature was set to 80 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours to obtain a composition F.

(Polymerization of epichlorohydrin)
19.6 g of the composition F obtained in Comparative Example 1 was taken in a 0.5 liter four-necked flask equipped with a stirring blade and a dropping funnel, and the inside of the flask was replaced with nitrogen. The internal temperature was raised to 90 ° C., and 25 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 2 hours under normal pressure. Aging was performed for 2 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 85 to 90 ° C. Then, the residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa, but the conversion rate was only 17%.

Comparative example 3.
A 0.5 liter four-necked flask equipped with a stirring blade, a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g] 90.9 g (227 mmol, amount of active hydrogen 454 mmol) and 1.9 g (5.7 mmol, 0.012 mol with respect to 1 mol of active hydrogen) of tetra (n-octyl) ammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.). added. After setting the inside of the flask to a nitrogen atmosphere, the temperature was set to 80 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 17 ml (17 mmol, 0.037 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisopropoxyaluminum was added, the internal temperature was set to 80 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours. Composition G was obtained.

(Polymerization of epichlorohydrin)
19.6 g of the composition G obtained in Comparative Example 3 was taken in a 0.5 liter four-necked flask equipped with a stirring blade and a dropping funnel, and the inside of the flask was replaced with nitrogen. The internal temperature was raised to 90 ° C., and 25 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 2 hours under normal pressure. Aging was performed for 2 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 85 to 90 ° C. Then, the residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa, but the conversion rate was only 5%.

By using the composition of the present invention, a halogen-containing polyalkylene glycol can be efficiently produced. The obtained halogen-containing polyalkylene glycol is useful as a polyurethane raw material, a polyester raw material, a surfactant raw material, a lubricant raw material, and the like. In particular, by reacting with various isocyanate compounds, it is expected to develop into adhesives, paints, sealants, thermosetting elastomers, and thermoplastic elastomers.

Claims (6)

A halogen-containing alkylene oxide polymerization catalyst containing a phosphazenium compound represented by the following general formula (1), a Lewis acid, and an active hydrogen-containing compound.

(In the above general formula (1), R ¹ And R ² Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ And R ² Ring structure in which are bonded to each other, R ¹ Mutual or R ² It may have a ring structure in which they are bonded to each other. X ⁻ Represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, a chlorine anion, a bromine anion, or an iodine anion. Y represents a carbon atom or a phosphorus atom, and a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom. ) The halogen-containing 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 ratio of the phosphazenium compound represented by the general formula (1) to Lewis acid is [phosphasenium compound]: [Lewis acid] = 1: 1.01 to 100 (molar ratio), and the activity in the active hydrogen-containing compound. The phosphazenium compound is in the range of 0.001 to 10 mol with respect to 1 mol of hydrogen, and the Lewis acid is in the range of 0.001 to 10 mol with respect to 1 mol of active hydrogen in the active hydrogen-containing compound. The halogen-containing alkylene oxide polymerization catalyst according to claim 1 or 2, wherein the halogen-containing alkylene oxide polymerization catalyst is characterized . The active hydrogen-containing compound is at least one selected from the group consisting of a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group, according to any one of claims 1 to 3. The halogen-containing alkylene oxide polymerization catalyst according to any one . The halogen-containing alkylene oxide polymerization according to any one of claims 1 to 4, wherein the phosphazenium compound represented by the following general formula (1) and the active hydrogen-containing compound are mixed, and then Lewis acid is mixed. Method for producing a catalyst.

(In the above 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 to each other or R ² together may be a ring structure connected with each other X ^-. is hydroxy anion, alkoxy anion of 1 to 4 carbon atoms, carboxy anion, alkyl carboxy anion having 2 to 5 carbon atoms, chlorine anion, bromine anion , Or a hydrocarbon anion. Y represents a carbon atom or a phosphorus atom, and a is 2 when Y is a carbon atom and 3 when Y is a phosphorus atom.) A method for producing a halogen-containing polyalkylene glycol, which comprises performing ring-opening polymerization of the halogen-containing alkylene oxide in the presence of the halogen-containing alkylene oxide polymerization catalyst according to any one of claims 1 to 4.