JP6953850B2 - Halogen-containing polyether polyol and polyurethane composed of it - Google Patents

Description

The present invention relates to a novel low-unsaturation halogen-containing polyether polyol used as a polyurethane raw material.

The polyether polyol can be obtained by ring-opening polymerization of alkylene oxide, and is used as a soft segment of polyurethane in a wide range of applications such as paints, adhesives, sealants, and foams for automobile seats.

Further, a halogen-containing polyether polyol is known as a raw material for a polyurethane-based adhesive having excellent shear strength, moisture resistance, and water resistance (see, for example, Patent Document 1). Such a halogen-containing polyether polyol can be synthesized by ring-opening polymerization of a halogen-containing alkylene oxide using an acid catalyst such as a boron trifluoride compound. However, such halogen-containing polyether polyols contain a large amount of by-products such as unsaturated components produced by side reactions during production. Therefore, the obtained polyurethane has many defective portions and the crosslink density is lowered, so that there is a problem that physical properties such as hysteresis loss and compression set are lowered.

A compound metal cyanide complex is known as a polymerization catalyst for an alkylene oxide that can obtain a polyol having a low degree of unsaturation, and has been developed into the polymerization of halogen-containing alkylene oxides (see, for example, Non-Patent Document 1). However, there is no description that mentions the degree of unsaturation of the halogen-containing polyether polyol synthesized by such a method.

Japanese Unexamined Patent Publication No. 2-202573

RSC Advances, 2014, 4, 21765-21771

The present invention has been made in view of the background art described above, and an object of the present invention is to provide a halogen-containing polyether polyol having a low content of unsaturated components and a polyurethane using the same.

As a result of diligent studies to solve the above problems, the present inventors have found the halogen-containing polyether polyol of the present invention and have completed the present invention.

That is, the present invention includes the following embodiments.

[1] A halogen-containing polyether polyol having a molecular weight of 200 to 100,000 and an unsaturated degree of 0.02 meq / g or less, which is represented by the following formula (1).

(In the above formula (1), Q represents a polymer component containing the following structural unit [I], m is an integer of 2 to 8, and R ¹ represents an active hydrogen-containing compound residue.)

(In the structural unit [I], X represents a halogen atom.)

[2] The halogen-containing polyether polyol according to the above [1], wherein Q represents a polymer component containing the above structural unit [I] and the following structural unit [II] in the above formula (1). ..

(In the structural unit [II], A represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
[3] A halogen-containing polyether polyol having a molecular weight of 200 to 100,000 and an unsaturated degree of 0.02 meq / g or less, which is represented by the following formula (2).

(In the above formula (2), X is a halogen atom, n is an integer of 1 to 500, m is an integer of 2 to 8, and R ¹ is an active hydrogen-containing compound residue.)
[4] The halogen-containing polyether polyol according to any one of the above [1] to [3], wherein the degree of unsaturation is 0.01 meq / g or less.

[5] The halogen-containing polyether polyol according to any one of the above [1] to [4], characterized in that Mw / Mn is 1.50 or less (however, gel permeation chromatography using polystyrene as a standard substance). The number average molecular weight obtained from the measurement is Mn, and the weight average molecular weight is Mw).

[6] Ring-opening polymerization of a halogen-containing alkylene oxide in the presence of a composition containing an onium salt, a Lewis acid and an active hydrogen-containing compound, and the onium salt with respect to 1 mol of active hydrogen in the active hydrogen-containing compound. The method for producing a halogen-containing polyether polyol according to any one of the above [1] to [5], wherein the amount used is in the range of 0.001 to 0.1 mol.

[7] The production method according to the above [6], wherein the onium salt is a phosphazenium salt represented by the following formula (3), or an ammonium salt or a phosphonium salt represented by the following formula (4).

(In the above formula (3), R ² and R ³ are independently each of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ^{a ring structure in which R 2} and R ³ are bonded to each other, R ^{2 to} each other or R ³ Ring structure in which they are bonded to each other, Z ⁻ 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, a chlorine anion, a bromine anion, an iodine anion or a hydrogen carbonate anion. Represents. 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.)

(In the above formula (4), D represents a nitrogen atom or a phosphorus atom, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently alkyl groups, aryl groups and alkoxy groups having 1 to 20 carbon atoms. dialkylamino group, a halogen atom or a hydrogen atom, E is may form a 2 to 4 but ring structure by bonding with one of the .R ⁴ to R ⁷ representing a counter ion of an inorganic or organic group and Heteroatoms may be contained in the cyclic structure.)
[8] The production method according to the above [6] or [7], wherein the Lewis acid is at least one compound selected from the group consisting of an aluminum compound and a zinc compound.

[9] A polyurethane-forming composition containing the halogen-containing polyether polyol according to any one of the above [1] to [5] and a polyisocyanate compound.

[10] A polyurethane containing the halogen-containing polyether polyol according to any one of the above [1] to [5] as a monomer unit.

[11] A method for producing a polyurethane, which comprises reacting the halogen-containing polyether polyol according to any one of the above [1] to [5] with a polyisocyanate compound.

According to the present invention, a halogen-containing polyether polyol having a low degree of unsaturation can be obtained. Further, the halogen-containing polyether polyol of the present invention improves the crosslink density and the storage elastic modulus when reacted with the polyisocyanate compound, so that a polyurethane having good physical properties such as hysteresis loss and compression set can be obtained. Obtainable.

Hereinafter, the present invention will be described in detail.

The halogen-containing polyether polyol of the present invention is represented by the above formula (1).

In the above formula (1), Q represents a polymer component containing the above structural unit [I]. In the structural unit [I], X represents a halogen atom.

The halogen atom represented by X in the structural unit [I] is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom, a chlorine atom, and a bromine atom are preferable from the viewpoint of ease of handling, and a fluorine atom or a chlorine atom is more preferable.

In the above formula (1), Q may be a polymer component containing the above structural unit [I] and the above structural unit [II]. In the structural unit [II], A represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

In the structural unit [II], the hydrogen atom represented by A or the hydrocarbon having 1 to 10 carbon atoms is not particularly limited, but for example, a hydrogen atom, a methyl group, an ethyl group, a vinyl group, and the like. n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, t-butyl group, cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, Examples thereof include a phenyl group, a heptyl group, a cycloheptyl group, an octyl group, a cyclooctyl group, a nonyl group, a cyclononyl group and a decyl group. Of these, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom or a methyl group is more preferable, from the viewpoint of availability of a precursor.

In the above formula (1), when Q is a polymer component containing the above structural unit [I] and the above structural unit [II], the arrangement of each structural unit may be block or random.

In the present invention, among the halogen-containing polyether polyols represented by the above formula (1), those having the structure represented by the above formula (2) are more preferable.

In the above formula (1), the ^{active hydrogen-containing compound residue represented by R 1} is not particularly limited, and examples thereof include a hydroxy residue, an amine residue, a carboxylic acid residue, and a thiol residue. Be done.

The active hydrogen-containing compound containing such an active hydrogen-containing compound residue is not particularly limited, but for example, a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, a polyether polyol having a hydroxyl group, or the like. Can be mentioned.

Examples of the hydroxy compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. , 1,6-hexanediol, 1,9-nonanediol, 2,5-hexanediol, 1,3-cyclohexanediol, 2-methylpentane-2,4-diol, 2,5-dimethyl-2,5- Examples thereof include hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, shoeclaw, glucose, 2-naphthol, bisphenol and the like.

Examples of the amine compound include ethylenediamine, 1,3-propylenediamine, 1,4-, 1,2-butylenediamine and the like.

Examples of the carboxylic acid compound include phthalic 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 2000.

Since the halogen-containing polyether polyol of the present invention can be efficiently produced, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,9-nonanediol, and 2,5-hexanediol can be produced efficiently. , 2-Methylpentane-2,4-diol, ethylenediamine, polyether polyol having a molecular weight of 200 to 2000 is preferable, and polypropylene glycol, 2,5-hexanediol, 1,9-nonanediol, and a poly having a molecular weight of 200 to 1000 are preferable. Ether polyols are particularly preferred.

The halogen-containing polyether polyol of the present invention has a molecular weight of 200 to 100,000, and has an excellent molecular weight of 200 to 20,000 because it is excellent in handleability and polyurethane production efficiency when used as a raw material for polyurethane. Is preferable, and 500 to 10,000 is particularly preferable.

The degree of unsaturation of the halogen-containing polyether polyol of the present invention is 0.02 meq / g or less, and is preferably 0.010 meq / g or less because the physical properties such as hysteresis loss and compression set of the obtained polyurethane are improved.

The Mw / Mn of the halogen-containing polyether polyol of the present invention is preferably 2.00 or less, particularly preferably 1.50 or less (however, polystyrene is used as a standard substance) because the moldability of the polyurethane resin is improved. The number average molecular weight determined from the gel permeation chromatography measurement is Mn, and the weight average molecular weight is Mw).

The primary rate of the terminal hydroxyl group in the halogen-containing polyether polyol of the present invention is not particularly limited, but the variation in reactivity is small, the reaction is uniform, and the molecular weight distribution and composition of the obtained polyurethane tend to be uniform. It is preferably less than 10%.

The halogen-containing polyether polyol of the present invention is subjected to ring-opening polymerization of a halogen-containing alkylene oxide using, for example, an active hydrogen-containing compound as an initiator in the presence of a composition containing an onium salt, a Lewis acid and an active hydrogen-containing compound. Obtained by

In the present invention, the onium salt is not particularly limited, and examples thereof include a phosphazenium salt, an ammonium salt, and a phosphonium salt.

In the present invention, the structure of the phosphazenium salt is not particularly limited, but is represented by, for example, the above formula (3).

In the above formula (3), ^{the hydrocarbon group having 1 to 20 carbon atoms represented by R 2} and R ³ is not particularly limited, but for example, a methyl group, an ethyl group, a vinyl group and an n-propyl group. Group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, t-butyl group, cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, Heptyl group, cycloheptyl group, octyl group, cyclooctyl group, nonyl group, cyclononyl group, decyl group, cyclodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group , Nonadecil group and the like.

Examples of the case where R ² and R ³ are bonded to each other to form a ring structure include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indrill group, an isoindrill group and the like.

The ring structure R ² s or R ³ together are bonded to each other, it is not particularly limited, for example, one substituent is an ethylene group, a propylene group, is an alkylene group such as butylene group, together with the other substituent The bonded ring structure can be mentioned.

Among these, R ² and R ³ are preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoint that they are alkylene oxide polymerization catalysts having particularly excellent catalytic activity and the raw materials are easily available.

^{Further, Z −} in the above formula (3) 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.

The alkoxy anion having 1 to 4 carbon atoms is not particularly limited, and examples thereof include methoxy anion, ethoxy anion, n-propoxy anion, isopropoxy anion, n-butoxy anion, isobutoxy anion, and t-butoxy anion. Can be done.

The alkylcarboxy anion having 2 to 5 carbon atoms is not particularly limited, and for example, acetoxy anion, ethyl carboxy anion, n-propyl carboxy anion, isopropyl carboxy anion, n-butyl carboxy anion, iso butyl carboxy anion, and t-butyl carboxy anion. Anions and the like can be mentioned.

Among these, ^{as Z −} , a hydroxy anion and a hydrogen carbonate anion are particularly preferable because they are halogen-containing alkylene oxide polymerization catalysts having excellent catalytic activity.

In the present invention, the phosphazenium salt represented by the above formula (3) is not particularly limited, but specifically, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide, tetrakis ( 1,1,3,3-tetraethylguanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetra (n-propyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraisopropylguanidino) ) Phosphonium hydroxide, tetrakis (1,1,3,3-tetra (n-butyl) guanidino) phosphonium hydroxide, tetrakis (1,1,3,3-tetraphenylguanidino) phosphonium hydroxide, tetrakis (1,1) , 3,3-Tetrabenzylguanidino) phosphonium hydroxide, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydroxide, tetrakis (1,3-dimethylimidazolidine-2-imino) phosphonium hydroxide, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraethylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-propyl)) Guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraisopropylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-butyl) guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3) 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 and the like can be exemplified.

In addition, tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (diethylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (din-propylamino) phosphoranilideneamino] phosphonium hydroxydo Do, 1-tert-butyl-4,4,4-tris (dimethylamino) -2,2-bis (tris (dimethylamino) phosphoranilideneamino) -2λ5,4λ5-catenadi (phosphazene), tetrakis [tris (tris (dimethylamino) Diisopropylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (din-butylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris (diphenylamino) phosphoranilideneamino] phosphonium hydroxide, tetrakis [tris] (1,3-Dimethylimidazolidine-2-imino) Phospholanylideneamino] Phosphonium hydroxide, Tetrakiss [Tris (dimethylamino) phosphoranylideneamino] Phosphonium Hydrogen carbonate, Tetrakiss [Tris (diethylamino) Phoslanylideneamino] Phosphonium Hydrogen carbonate, tetrakis [tris (di-propylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diisopropylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (di-n-butylamino) phosphorani Examples include lideneamino] phosphonium hydrogen carbonate, tetrakis [tris (diphenylamino) phosphoranilideneamino] phosphonium hydrogen carbonate, tetrakis [tris (1,3-dimethylimidazolidine-2-imino) phosphoranilideneamino] phosphonium hydrogen carbonate, etc. can do.

Among these, tetrakis (1,1,3,3-tetramethylguanidino) phospasenium hydroxide and tetrakis (1,1,3) are used as catalysts for producing halogen-containing polyether polyols having excellent catalytic performance. 3-Tetramethylguanidino) phosphazenium hydrogen carbonate, tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium hydroxide are particularly preferred.

In the present invention, the structure of the ammonium salt or the phosphonium salt is represented by the above formula (4).

In the above formula (4), the alkyl group or aryl group having 1 to 20 carbon atoms represented by ^{R 4} , R ⁵ , R ⁶ and R ^{7 is not particularly limited, but for example, methyl group or ethyl.} Group, vinyl group, normal propyl group, isopropyl group, cyclopropyl group, allyl group, normal butyl group, isobutyl group, t-butyl group, cyclobutyl group, normalpentyl group, neopentyl group, cyclopentyl group, normalhexyl group, cyclohexyl group , Phenyl group, heptyl group, cycloheptyl group, benzyl group, tolyl group, octyl group, cyclooctyl group, xsilyl group and the like, and examples of the alkoxy group include methoxy group, ethoxy group, vinyloxy group and normal propoxy group. Isopropoxy group, cyclopropoxy group, allyloxy group, normal butoxy group, isobutoxy group, t-butoxy group, cyclobutoxy group, normalpentyloxy group, neopentyloxy group, cyclopentyloxy group, normalhexyloxy group, cyclohexyloxy group, Phenoxy group, heptyloxy group, cycloheptyloxy group, octyloxy group, benzyloxy group, tolyloxy group, cyclooctyloxy group and xsilyloxy group are exemplified, and the dialkylamino group includes dimethylamino group, diethylamino group, pyrrolidino group and the like. Examples thereof include a piperidino group, a dinormal propylamino group, a diisopropylamino group and a dicyclopropylamino group.

Since it is a halogen-containing polyether polyol production catalyst having excellent catalytic activity, R ⁴ , R ⁵ , R ⁶ and R ⁷ may independently contain an alkyl group having 1 to 10 carbon atoms or may contain a hetero atom. It is preferably an aryl group, and particularly preferably a methyl group, an ethyl group, a normal butyl group or a normal octyl group or a phenyl group.

Examples of the structure of the ammonium salt in which two or three of R ^{4 to} R ⁷ are bonded to form a cyclic structure include a pyridinium salt and an imidazolium salt, which serve as a catalyst for producing a halogen-containing polyether polyol having excellent catalytic activity. Therefore, it is preferably an imidazolium salt.

In the above formula (4), the inorganic or organic group represented by E is not particularly limited, but specifically, a halogen atom, a hydroxyl group, an alkoxyl group, an amino group, a carboxyl group, a sulfonic acid group, and a hydrogenation. A boron group and a hexafluorophosphate group are exemplified, and since it is a halogen-containing polyether polyol production catalyst having excellent catalytic activity, it is preferably any one of a bromine atom, a chlorine atom, an iodine atom and a hexafluorophosphate group. ..

The ammonium salt or phosphonium salt represented by the above formula (4) is not particularly limited, but specifically, tetramethylammonium bromide, tetraethylammonium bromide, tetranormalpropylammonium bromide, tetranormal butylammonium bromide. , Tetranormal pentylammonium bromide, tetranormal hexyl ammonium bromide, tetranormal heptyl ammonium bromide, tetranormal octyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium chloride, tetranormal propyl ammonium chloride, tetranormal butyl ammonium chloride, tetranormal pentyl ammonium. Chloride, tetranormal hexyl ammonium chloride, tetranormal heptyl ammonium chloride, tetranormal octyl ammonium chloride, 1-butyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-3- Methylimidazolium chloride, tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetranormal propylphosphonium bromide, tetranormal butyl phosphonium bromide, tetranormal pentylphosphonium bromide, tetranormal hexylphosphonium bromide, tetranormal heptyl phosphonium bromide, tetranormal octylphosphonium bromide, Tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetranormalpropylphosphonium chloride, tetranormal butylphosphonium chloride, tetranormalpentylphosphonium chloride, tetranormalhexylphosphonium chloride, tetranormalheptylphosphonium chloride, tetranormaloctylphosphonium chloride, bromotris (dimethylamino) Phosphonium hexafluorophosphate and the like are exemplified.

Among these, tetranormal octyl ammonium chloride, tetranormal octyl ammonium bromide, and tetranormal butyl phosphonium bromide are preferably used because they serve as catalysts for producing halogen-containing polyether polyols having excellent catalytic activity.

In the present invention, examples of Lewis acid include aluminum compounds, zinc compounds, and boron compounds.

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 triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris (pentafluorophenyl) borane, trifluoroborane and the like.

Among these, organoaluminum, aluminoxane, and organozinc are preferable, and organoaluminum is particularly preferable, because it is a catalyst for producing a halogen-containing polyether polyol having excellent catalytic performance.

In the present invention, the active hydrogen-containing compound used for producing the halogen-containing polyether polyol is not particularly limited, but for example, a hydroxy compound, an amine compound, a carboxylic acid compound, a thiol compound, and a polyether polyol having a hydroxyl group. And so on.

Examples of the hydroxy compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. 1,6-hexanediol, 1,9-nonanediol, 2,5-hexanediol, 1,3-cyclohexanediol, 2-methylpentane-2,4-diol, 2,5-dimethyl-2,5-hexane Examples thereof include diol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, shoeclaw, glucose, 2-naphthol and bisphenol.

Examples of the amine compound include ethylenediamine, 1,3-propylenediamine, 1,4-, 1,2-butylenediamine and the like.

Examples of the carboxylic acid compound include phthalic 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 2000.

Since the halogen-containing polyether polyol of the present invention can be efficiently produced, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,9-nonanediol, and 2,5-hexanediol can be produced efficiently. , 2-Methylpentane-2,4-diol, ethylenediamine, polyether polyol having a molecular weight of 200 to 2000 is preferable, and polypropylene glycol, 2,5-hexanediol, 1,9-nonanediol, and a poly having a molecular weight of 200 to 1000 are preferable. Ether polyols are particularly preferred.

Since the halogen-containing polyether polyol of the present invention can be efficiently produced, the onium salt is preferably 0.001 to 0.1 mol, based on 1 mol of active hydrogen in the active hydrogen-containing compound. It is particularly preferably 001 to 0.05 mol.

In the present invention, as a method for preparing a composition containing an onium salt, a Lewis acid and an active hydrogen-containing compound, any method can be used as long as the composition can be prepared, and the present invention is not particularly limited. For example, a method of mixing an onium salt, 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 an onium salt, 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 has excellent catalytic performance, it is preferable to prepare the composition by mixing the onium salt and the active hydrogen-containing compound and then mixing with Lewis acid.

When preparing the above-mentioned composition, 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.

In the method for producing a halogen-containing polyether polyol 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 polyether polyol 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 polyether polyol 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.

The polyurethane-forming composition of the present invention is characterized by containing the halogen-containing polyether polyol of the present invention and a polyisocyanate compound.

Here, the polyisocyanate compound is not particularly limited, and examples thereof include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds, and polyisocyanate derivatives thereof.

Among these, examples of the aromatic isocyanate compound include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI) and phenylenedi isocyanate (m- or p). -Phenylene diisocyanate or a mixture thereof), 4,4'-diphenyldiisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisocyanate, or a mixture thereof) (MDI), 4,4'-toluidine isocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate, or a mixture thereof) (TMXDI), ω, ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4- Or 1,8-naphthalenediisocyanate, or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, polymethylenepolyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3 Examples thereof include'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropanediisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate and the like.

Examples of the aliphatic isocyanate compound include trimethylene diisocyanate, 1,2-propylene diisocyanate, and butylene diisocyanate (tetramethylene diisosianate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene). Diisocyanis), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanis methyl capate, lysine diisocyanis, lysine ester triisocyanis, Examples thereof include 1,6,11-undecantriisocyanis, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate.

Examples of the monocyclic alicyclic isocyanate compound include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), and the like. 3-Isocyanate Methyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate, IPDI), methylenebis (cyclohexylisocyanate (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate, or them) (Hydrocyanate MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, bis (isosinate methyl) cyclohexane (1,3- or 1,4-bis) (Isocyanate methyl) cyclohexane or a mixture thereof) (hydrogenated XDI), dimerate diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated) TMXDI) and the like.

Examples of the crosslinked cyclic alicyclic isocyanate compound include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, siisocyanatomethylbicycloheptane, and di (diisocyanatomethyl) tricyclodecane.

Examples of derivatives of these polyisocyanates include multimers of the above-mentioned isocyanate compounds (dimeric, trimeric, pentameric, hepta, uretidinedione, ureitoneimine, isocyanurate-modified, polycarbodiimide, etc.). , Urethane modified product (for example, urethane modified product obtained by modifying or reacting a part of isocyanate groups in the above isocyanate compound or multimer with monool or polyol), Biuret modified product (for example, reaction between the above isocyanate compound and water). (For example, a biuret modified product produced by the above), an allophanate modified product (for example, an allophanate modified product produced by the reaction of the above isocyanate compound with a monool or polyol component), a urea modified product (for example, a reaction between the above isocyanate compound and a diamine). (Urea modified product, etc. produced by

The above-mentioned isocyanate compound or its derivative may be used alone or in combination of two or more.

The polyurethane of the present invention is characterized by containing the above-mentioned halogen-containing polyether polyol of the present invention as a monomer unit.

Further, the method for producing polyurethane of the present invention is characterized in that the halogen-containing polyether polyol of the present invention is reacted with the above-mentioned polyisocyanate compound.

The structure of the polyurethane of the present invention is not particularly limited as long as it contains the halogen-containing polyether polyol of the present invention as a monomer unit, and may be a crosslinked product, a linear or branched structure, and the terminal structure may be NCO or OH. It may be.

When the halogen-containing polyether polyol of the present invention is reacted with the polyisocyanate compound to obtain polyurethane, for example, the composition may be heated up to 150 ° C., or dioctyltin dilaurate, dibutyltin dilaurate, triethylamine, triethylenediamine. , Stanas Octate, Dibutyltin Di-2-ethylhexanoate, Sodium o-phenylphenate, Potassium oleate, Tetra (2-ethylhexyl) titanate, Stannous chloride, Fertan chloride, Antimonite trichloride When a catalyst such as the above is added, the reaction between the halogen-containing polyether polyol and the isocyanate compound is accelerated, and polyurethane can be obtained in a short time.

Hereinafter, applications of the polyurethane of the present invention will be described.

The polyurethane of the present invention can be used for various purposes, and the use is not particularly limited, but it can be used for urethane foam applications such as hard foam or soft foam. In addition, the English acronyms for these four uses are taken, such as coatings / coatings, adhesives / adhesives, sealants, and thermoplastic or thermosetting elastomers. It can be used for an application called CASE in the present technology.

Among these, due to the characteristics of the polyurethane of the present invention, the coating material can be used for many purposes such as intermediate coating of buildings / public structures, woodworking, ships, and automobiles.

Further, from the characteristics of the polyurethane of the present invention, the adhesive may be, for example, a laminated laminated bag for flexible packaging materials, that is, a food laminated bag for snacks, boil, retort, a non-food laminated bag such as a detergent. In the field of construction, it can be used for wrapping, floor warming, and flooring, and in the field of electronics, it can be used for back sheets of solar cells, liquid crystal televisions, and other adhesives around batteries.

Further, due to the characteristics of the polyurethane of the present invention, in the use of the sealing material, for the sealing of the building exterior, for example, ALC panel and sash, the jointing of the RC wall, the sealing for the frame under the tile and the window outer frame, and the building interior. For sealing around water and gypsum boards, for sealing for building materials such as waterproof bases and roofs, for sealing special vehicles such as cold storage cars and automobile window frames, and for electrical and electronic equipment and communications. It can be used as a gasket or the like in a device, particularly a hard disk device.

Further, due to the characteristics of the polyurethane of the present invention, in the use of elastomers, as thermoplastic elastomers, hoses such as high pressure hoses, fire hoses, pesticide hoses, coating hoses, pneumatic tubes, hydraulic tubes, fuel tubes, dialysis Tubes for tubes, tubes for arteries / veins / hearts, scratch prevention films / sheets for automobiles, scratch prevention films for instrument panel skin materials sofas, air mats, nursing bed sheets, diaphragms, keyboard sheets, rubber screens, conveyor belts, Gaskets, synthetic leather, elastic sheets, flexible films, tarpaulins, clothing, life jackets, wet suits, hot melts, diaper supplies, packing cushioning films, medical surgical films and other films / sheets, various gears, various grips , Solid tires, casters, rollers, vibration and soundproof parts, pickers, bushes, bearings, anti-slip, building materials, packing, caps, watch belts, connectors, rubber screens, printed drums, grease covers, hammers, dust covers, hose parts , Industrial parts such as ball joints, instrument panel skins, gear knob skins, console box skins, leather seats, bumpers / side moldings, tail lamp seals, snow chains, bushes, dust covers, gears, bearings, caps, ball joints, pedal stoppers, Automotive parts such as door lock strikers, spring covers and anti-vibration parts, conveyor belts, timing belts, round belts, V-belts, flat belts and other belts, power / communication cables, automotive ABS sensor cables, robot cables, industry Can be used for electric wires such as cables and computer wiring, as well as sports shoes, mountain climbing shoes, ski shoes, ski boards, snowboards, motocross boots, safety shoes, high heels, snorkels, fins, golf ball covers, stairs non-slip. , Road pole cones, roller skate wheels, various tags, sailboard supplies, ski parts, various ropes, binders, medical dressing materials, catheters, medical ropes, adhesive plasters, etc. Elastomers include papermaking, iron plate rolling rolls, printing, small rolls for office equipment, platen rolls, rolls such as skate rollers, solid tires, casters, battery fork lifts, work carriers (pared lifts, etc.), industrial truck wheels. Wheels, rubber, etc. Abelt idlers, guide rolls and prairie springs for cables and belts, belt shock absorbers, belts such as oil seals, OA equipment such as electronic equipment parts and cleaning grades for copiers, round bars, pipes, square columns, plates, sheets. It can be used for secondary processing materials such as, and can be used for a wide range of applications such as various gears, connection ring liners, pump linings, impeller cyclone cones, cyclone liners, and polishing pads.

Furthermore, in addition to these applications called CASE, it can be used for leather, spandex, various inks, etc. due to the characteristics of the polyurethane of the present invention.

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, an analysis method and a production method of the halogen-containing polyether polyol will be described.

(Analytical method of halogen-containing polyether polyol)
(1) Molecular weight of halogen-containing polyether polyol (unit: g / mol)
The hydroxyl value d (unit: mgKOH / g) of the halogen-containing polyether polyol was measured by the method described in JIS K-1557. The number of functional groups of the obtained halogen-containing polyether polyol was defined as e, and the molecular weight of the halogen-containing polyether polyol was calculated by the following formula.

Molecular weight = (56100 / d) x e.

(2) Molecular weight distribution of halogen-containing polyether polyol (unit: none)
Using a gel permeation chromatograph (GPC) (HLC8020 manufactured by Tosoh Corporation), measurement was performed at 40 ° C. using tetrahydrofuran as a solvent, polystyrene was used as a standard substance, and the number average molecular weight (Mn) of the halogen-containing polyether polyol (Mn). , Weight average molecular weight (Mw).

From the Mn and Mw calculated by the above method, the molecular weight distribution (Mw / Mn) of the halogen-containing polyether polyol was calculated.

(3) Degree of unsaturation of halogen-containing polyether polyol (unit: meq / g)
The degree of unsaturation of the halogen-containing polyether polyol was calculated by the method described in JIS K-1557.

(4) Primaryization rate of halogen-containing polyether polyol (unit:%)
Proton nuclear magnetic resonance spectroscopy (JNM-ECZ400S, manufactured by JEOL Ltd.) was used to obtain trifluoroacetic anhydride by reacting a halogen-containing polyether polyol with trifluoroacetic anhydride in d-chloroform. ^{1 1} H-NMR) spectral analysis was performed, and the primaryization rate of the terminal hydroxyl group was calculated by the following formula.

First grade rate (%) = [r / (r + 2s)] × 100.

Here, r is the integrated value of the signal derived from the methylene group to which the primary hydroxyl group is bonded at around 5.3-5.4 ppm, and s is the integrated value of the signal derived from the methine group to which the secondary hydroxyl group is bonded at around 4.3 ppm. Represents.

Synthesis Example 1 (Synthesis of phosphazenium salt 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, the temperature was raised to 100 ° C., and 107 g (0) of 1,1,3,3-tetramethylguanidine was further added. .92 mol) was added dropwise. 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 was transferred to a 2-liter four-necked flask equipped with a stirring blade, 900 g of 2-propanol was added, and then the temperature was raised to 80 to 100 ° C. under normal pressure to remove dichloromethane. .. The obtained 2-propanol solution was allowed to cool to 60 ° C. with stirring, and then 31 g (0.47 mol) of 85 wt% potassium hydroxide was added and reacted at 60 ° C. for 2 hours. By cooling the temperature to 25 ° C. and removing the precipitated by-product salt by filtration, the target phosphazenium salt A [R ² in the above formula (2) is a methyl group, R ³ is a methyl group, and Z ⁻ is hydroxy. An 860 g of a 2-propanol solution of an anion, a phosphazenium salt in which Y corresponds to a carbon atom and a corresponds to 2] was obtained in a concentration of 25% by weight and a yield of 92%.

Synthesis Example 2 (Synthesis of phosphazenium salt B)
A 100 ml Schlenk tube with a magnetic rotor was placed 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 of 0.53 g [8.1 mmol, 1.1 mol equivalents of tetrakis [tris (dimethylamino) phosphoranilideneamino] phosphonium chloride] 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 obtain the desired phosphazenium salt B [R ² is a methyl group, R ³ is a methyl group, and Z ⁻ is hydroxy in the above formula (2). A 2-propanol solution of an anion, a phosphorus atom in Y, and a phosphazenium salt in which a corresponds to 3] was obtained in a concentration of 17% by weight and a yield of 98%.

Example 1.
A 0.2 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] 12.5 g (31 mmol, amount of active hydrogen 63 mmol) and 1.1 g of the phosphazenium salt A obtained in Synthesis Example 1 (0.78 mmol, 0.012 mol with respect to 1 mol of active hydrogen) were added. After the inside of the flask was made to have 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. Then, 2.3 ml (2.3 mmol, 0.037 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisobutylaluminum (TiBAL) was added to bring the internal temperature to 80 ° C. and reduce the pressure by 0.5 kPa. The treatment was carried out for 2 hours to obtain composition A. The temperature of the obtained composition A was raised to 90 ° C., and 50 g of epichlorohydrin (ECH) as a halogen-containing alkylene oxide was intermittently supplied under normal pressure over 4 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 to obtain 64.0 g of a pale yellow odorless polyol [A-1]. The conversion rate was 99.9%, the molecular weight of the obtained polyol [A-1] was 2020 g / mol, the degree of unsaturation was 0.003 meq / g, Mw / Mn was 1.23, and the primary conversion rate was 4. %Met.

Example 2.
The composition A obtained in Example 1 was heated to 70 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied under normal pressure over 3 hours. Aging was performed for 4 hours after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 65 to 70 ° C. Next, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 63.4 g of a pale yellow odorless polyol [A-2]. The conversion rate was 99.0%, the molecular weight of the obtained polyol [A-2] was 2040 g / mol, the degree of unsaturation was 0.002 meq / g, Mw / Mn was 1.20, and the primary conversion rate was 5. %Met.

Example 3.
The composition A obtained in Example 1 was heated to 120 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied under normal pressure over 4 hours. Aging was performed for 1 hour after the supply of epichlorohydrin. During the supply of epichlorohydrin and aging, the internal temperature was in the range of 115 to 120 ° C. Then, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 63.9 g of a pale yellow odorless polyol A-3. The conversion rate was 99.8%, the molecular weight of the obtained polyol A-3 was 2040 g / mol, the degree of unsaturation was 0.008 meq / g, Mw / Mn was 1.29, and the primary conversion rate was 4%. there were.

Example 4.
A 0.2 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] 3.0 g (7.6 mmol, amount of active hydrogen 15 mmol) and 0.26 g of the phosphazenium salt A obtained in Synthesis Example 1 (0.19 mmol, 0.013 mol with respect to 1 mol of active hydrogen) were added. After the inside of the flask was made to have 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. Then, 0.6 ml (0.6 mmol, 0.040 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. After a period of time, composition B was obtained. The temperature of the obtained composition B was raised to 90 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 4 hours under normal pressure. Aging was performed for 4 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 53.1 g of a pale yellow odorless polyol [A-4]. The conversion rate was 99.5%, the molecular weight of the obtained polyol [A-4] was 7010 g / mol, the degree of unsaturation was 0.008 meq / g, Mw / Mn was 1.26, and the primary conversion rate was 4. %Met.

Example 5.
A 0.2 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 GP400; hydroxyl value 365 mgKOH / g] 12.5 g (31 mmol, amount of active hydrogen 94 mmol) and 1.1 g of the phosphazenium salt A obtained in Synthesis Example 1 (0.78 mmol, 0.008 mol with respect to 1 mol of active hydrogen) were added. After the inside of the flask was made to have 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. Then, 2.3 ml (2.3 mmol, 0.024 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 by 2. After a period of time, the composition C was obtained. The temperature of the obtained composition C was raised to 90 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 4 hours under normal pressure. Aging was performed for 2.5 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 63.9 g of a pale yellow odorless polyol [A-5]. The conversion rate was 99.7%, the molecular weight of the obtained polyol [A-5] was 2010 g / mol, the degree of unsaturation was 0.007 meq / g, Mw / Mn was 1.22, and the primary conversion rate was 3. %Met.

Example 6.
5.3 g (27.7 mmol, amount of active hydrogen 55.3 mmol) of tripropylene glycol [manufactured by TCI] having two hydroxyl groups as an active hydrogen-containing compound in a 0.2 liter four-necked flask equipped with a stirring blade. , And 1.0 g (0.69 mmol, 0.012 mol with respect to 1 mol of active hydrogen) of the phosphasenium salt A obtained in Synthesis Example 1 was added. After the inside of the flask was made to have 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. Then, 2.1 ml (2.3 mmol, 0.038 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 by 2. After a period of time, the composition D was obtained. The temperature of the obtained composition D was raised to 90 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied under normal pressure over 4 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 to obtain 56.6 g of a pale yellow odorless polyol [A-6]. The conversion rate was 99.8%, the molecular weight of the obtained polyol [A-6] was 2020 g / mol, the degree of unsaturation was 0.004 meq / g, Mw / Mn was 1.23, and the primary conversion rate was 4. %Met.

Example 7.
A 0.2 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] 12.5 g (31 mmol, amount of active hydrogen 63 mmol) and 1.1 g of the phosphazenium salt A obtained in Synthesis Example 1 (0.78 mmol, 0.012 mol with respect to 1 mol of active hydrogen) were added. After the inside of the flask was made to have 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. Then, 2.3 ml (2.3 mmol, 0.037 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisopropoxyaluminum (Al (OiPr) _{3) was added to bring the internal temperature to 80 ° C.} The vacuum treatment at 0.5 kPa was carried out for 2 hours to obtain the composition E. The temperature of the obtained composition E was raised to 90 ° C., and 50 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 64.0 g of a pale yellow odorless polyol [A-7]. The conversion rate was 99.9%, the molecular weight of the obtained polyol [A-7] was 2090 g / mol, the degree of unsaturation was 0.004 meq / g, Mw / Mn was 1.25, and the primary conversion rate was 4. %Met.

Example 8.
A 0.2 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] 12.5 g (31 mmol, amount of active hydrogen 63 mmol) and 1.1 g of the phosphazenium salt A obtained in Synthesis Example 1 (0.78 mmol, 0.012 mol with respect to 1 mol of active hydrogen) were added. After the inside of the flask was made to have 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. Then, 2.3 ml (2.3 mmol, 0.037 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of diethylzinc (ZnEt _{2) was added, the internal temperature was set to 80 ° C., and the pressure was reduced by 0.5 kPa.} The treatment was carried out for 2 hours to obtain composition F. The temperature of the obtained composition F was raised to 90 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 4 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 62.9 g of a pale yellow odorless polyol [A-8]. The conversion rate was 98.5%, the molecular weight of the obtained polyol [A-8] was 1990 g / mol, the degree of unsaturation was 0.008 meq / g, Mw / Mn was 1.30, and the primary conversion rate was 4. %Met.

Example 9.
The composition A obtained in Example 1 was heated to 90 ° C., and 50 g of epifluorohydrin (EFH) as a halogen-containing alkylene oxide was intermittently supplied under normal pressure over 4 hours. Aging was performed for 2 hours after the supply of epichlorohydrin. Epifluorohydrin was supplied and aging was carried out in an internal temperature range of 85 to 90 ° C. Then, residual epifluorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 63.6 g of a pale yellow odorless polyol A-9. The conversion rate was 99.5%, the molecular weight of the obtained polyol A-9 was 2050 g / mol, the degree of unsaturation was 0.008 meq / g, Mw / Mn was 1.27, and the primary conversion rate was 4%. there were.

Example 10.
A 0.2 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] 12.5 g (31 mmol, amount of active hydrogen 63 mmol) and 1.6 g of the phosphazenium salt B obtained in Synthesis Example 2 (0.78 mmol, 0.012 mol with respect to 1 mol of active hydrogen) were added. After the inside of the flask was made to have 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. Then, 2.3 ml (2.3 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 by 2. After a period of time, the composition G was obtained. The temperature of the obtained composition G was raised to 90 ° C., and 50 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. Next, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 64.0 g of a pale yellow odorless polyol [A-10]. The conversion rate was 99.9%, the molecular weight of the obtained polyol [A-10] was 2020 g / mol, the degree of unsaturation was 0.007 meq / g, Mw / Mn was 1.26, and the primary conversion rate was 5. %Met.

Example 11.
A 0.2 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] 12.5 g (31 mmol, amount of active hydrogen 63 mmol) and 1.2 g of tetranormal octyl ammonium bromide (0.78 mmol, 0.012 mol with respect to 1 mol of active hydrogen) were added. After the inside of the flask was made to have 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. Then, 2.3 ml (2.3 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 by 2. After a period of time, the composition H was obtained. The temperature of the obtained composition H was raised to 90 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied under normal pressure over 5.5 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. Next, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 63.9 g of a pale yellow odorless polyol [A-11]. The conversion rate was 99.9%, the molecular weight of the obtained polyol [A-11] was 1900 g / mol, the degree of unsaturation was 0.004 meq / g, Mw / Mn was 1.22, and the primary conversion rate was 3. %Met.

Example 12.
A 0.2 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] 12.5 g (31 mmol, amount of active hydrogen 63 mmol) and 9.4 g (6.3 mmol, 0.10 mol with respect to 1 mol of active hydrogen) of the phosphazenium salt A obtained in Synthesis Example 1 were added. After the inside of the flask was made to have 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. Then, 12.5 ml (12.5 mmol, 0.20 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. After a period of time, composition I was obtained. The temperature of the obtained composition I was raised to 90 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently supplied over 1 hour under normal pressure. Aging was performed for 0.5 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 73.3 g of a pale yellow odorless polyol [A-12]. The conversion rate was 99.9%, the molecular weight of the obtained polyol [A-12] was 2040 g / mol, the degree of unsaturation was 0.012 meq / g, Mw / Mn was 1.37, and the primary conversion rate was 2. %Met.

Example 13.
In a 0.2 liter autoclave equipped with a stirring blade, 23.6 g (59 mmol, active hydrogen amount 118 mmol) of 2,5-hexanediol [manufactured by Tokyo Kasei Co., Ltd.] and 0.74 g of phosphazenium salt A obtained in Synthesis Example 1 (1.48 mmol, 0.013 mol with respect to 1 mol of active hydrogen) was added. After the inside of the flask was made to have 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. Then, 4.4 ml (4.4 mmol, 0.038 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisobutylaluminum (TiBAL) was added to bring the internal temperature to 80 ° C. and reduce the pressure by 0.5 kPa. The treatment was carried out for 2 hours to obtain composition J. The temperature of the obtained composition J was raised to 90 ° C., and 71 g of epichlorohydrin (ECH) and 24 g of propylene oxide (PO) were intermittently supplied at ~ 0.06 MPa over 11 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 95 to 100 ° C. Then, the residual monomer was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 118.0 g of a pale yellow odorless polyol [A-13]. The conversion rate was 99.5%, the molecular weight of the obtained polyol [A-13] was 1970 g / mol, the degree of unsaturation was 0.005 meq / g, Mw / Mn was 1.77, and the primary conversion rate was 3. %Met.

Example 14.
A 0.2 liter autoclave equipped with a stirring blade and a polyether polyol having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound [manufactured by Sanyo Chemical Industries, Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g ] 14.7 g (37 mmol, amount of active hydrogen 73 mmol) and 1.3 g of the phosphasenium salt A obtained in Synthesis Example 1 (092 mmol, 0.013 mol with respect to 1 mol of active hydrogen) were added. After the inside of the flask was made to have 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. Then, 2.8 ml (2.8 mmol, 0.038 mol with respect to 1 mol of active hydrogen) of a 1.0 mol / l toluene solution of triisobutylaluminum (TiBAL) was added, the internal temperature was set to 80 ° C., and the pressure was reduced by 0.5 kPa. The treatment was carried out for 2 hours to obtain composition K. The temperature of the obtained composition K was raised to 90 ° C., and 44 g of epichlorohydrin (ECH) and 18 g of propylene oxide (PO) were intermittently supplied at ~ 0.06 MPa over 6 hours. Aging was performed for 2 hours after the supply of epichlorohydrin. During epichlorohydrin supply and aging, the internal temperature was in the range of 90 to 95 ° C. Then, the residual monomer was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 77.5 g of a pale yellow odorless polyol [A-14]. The conversion rate was 99.1%, the molecular weight of the obtained polyol [A-14] was 2030 g / mol, the degree of unsaturation was 0.006 meq / g, Mw / Mn was 1.34, and the primary conversion rate was 5. %Met.

The results of the above examples are also shown in Tables 1 and 2.

Comparative example 1.
A 0.2 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] 12.5 g (31 mmol, amount of active hydrogen 63 mmol) was added to create a nitrogen atmosphere in the flask, and then dehydration treatment was performed for 2 hours under a reduced pressure of 0.5 kPa at an internal temperature of 80 ° C. Then, 0.38 g (2.66 mmol, 0.042 mol with respect to 1 mol of active hydrogen) of boron trifluoride diethyl ether complex [manufactured by Wako Pure Chemical Industries, Ltd.] was added. Composition J was obtained. To the obtained composition J, 25 g of ultra-dehydrated toluene [manufactured by Wako Pure Chemical Industries, Ltd.] was added, the internal temperature was raised to 60 ° C., and 50 g of epichlorohydrin as a halogen-containing alkylene oxide was intermittently added under normal pressure for 2 hours. It was supplied over. 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 55 to 60 ° C. After completion of the reaction, after neutralization with a 10% aqueous sodium carbonate solution, residual epichlorohydrin and toluene are removed under a reduced pressure of 90 ° C. and 0.5 kPa, and the mixture is filtered to obtain a yellow odorless polyol [B-. 1] was obtained in an amount of 47.5 g. The conversion rate was 95.0%, the molecular weight of the obtained polyol [B-1] was 1800 g / mol, the degree of unsaturation was 0.051 meq / g, Mw / Mn was 3.1, and the primary conversion rate was 56. %Met.

Comparative example 2.
To a 200 mL autoclave in a nitrogen atmosphere, 600 mg of a compound metal cyanide complex synthesized according to the conditions described in Non-Patent Document 1 (RSC Advances, 2014, 4, 21765-21771) and 100 mL of epichlorohydrin were added. The temperature was set to 60 ° C. and aging was performed for 7 hours. Aging was carried out in the range of internal temperature of 55 to 60 ° C. Then, residual epichlorohydrin was removed at 90 ° C. under a reduced pressure of 0.5 kPa to obtain 44.8 g of a pale yellow odorless polyol [B-2]. The conversion rate was 38.0%, the molecular weight of the obtained polyol [B-2] was 1900 g / mol, the degree of unsaturation was 0.025 meq / g, Mw / Mn was 1.56, and the primary conversion rate was 38. %Met.

The results of the above comparative example are also shown in Table 3.

Hereinafter, a method, preparation, and evaluation of the physical properties of polyurethane containing the halogen-containing polyol of the present invention as a monomer unit will be described.

Example 15.
10 g of the polyol [A-1] synthesized in Example 1, hexamethylene diisocyanate (manufactured by Tosoh Co., Ltd., Coronate C-HXVL) 3, 1 g, and 5 mg of dibutyl tin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) are put into a 50 mL screw tube. A polyurethane mixture A was prepared by weighing, defoaming using a defoaming mixer (ARE-310 manufactured by THINKY), stirring, and mixing. The obtained polyurethane mixture A is sandwiched between two parallel flat plates of a rotary rheometer (a liquid meter manufactured by UBM) with a parallel flat plate (parallel plate), and the temperature inside the apparatus is adjusted to 80 ° C. under a nitrogen atmosphere. By keeping, the halogen-containing polyether polyol in the mixture reacts with the isocyanate compound over time, and polyurethane is obtained between the parallel plates of the rotary rheometer. While holding the composition between the parallel plates, the parallel plates were occasionally vibrated at a strain of 1% and a frequency of 10 Hz, and the storage elastic modulus of the polyurethane measured was 510 kPa.

Example 16.
Weigh 10 g of the polyol [A-4] synthesized in Example 4, 3, 1 g of hexamethylene diisocyanate (Coronate C-HXVL manufactured by Tosoh Corporation), and 5 mg of dibutyl tin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) in a 50 mL screw tube. Then, a polyurethane mixture B was prepared by defoaming, stirring and mixing using a defoaming mixer (ARE-310, manufactured by THINKY). The obtained polyurethane mixture B is sandwiched between two parallel flat plates of a rotary rheometer (a liquid meter manufactured by UBM) with a parallel flat plate (parallel plate), and the inside of the apparatus is heated to 80 ° C. under a nitrogen atmosphere. By keeping, the halogen-containing polyether polyol in the mixture reacts with the isocyanate compound over time, and polyurethane is obtained between the parallel plates of the rotary rheometer. While holding the composition between the parallel plates, the parallel plates were occasionally vibrated at a strain of 1% and a frequency of 10 Hz, and the storage elastic modulus of the polyurethane measured was 490 kPa.

Example 17.
10 g of the polyol [A-12] synthesized in Example 12, hexamethylene diisocyanate (manufactured by Tosoh Co., Ltd., Coronate C-HXVL) 3, 1 g, and 5 mg of dibutyl tin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) are put into a 50 mL screw tube. A polyurethane mixture C was prepared by weighing, defoaming using a defoaming mixer (ARE-310 manufactured by THINKY), stirring, and mixing. The obtained polyurethane mixture C is sandwiched between two parallel flat plates of a rotary rheometer (a liquid meter manufactured by UBM) with a parallel flat plate (parallel plate), and the inside of the apparatus is heated to 80 ° C. under a nitrogen atmosphere. By keeping, the halogen-containing polyether polyol in the mixture reacts with the isocyanate compound over time, and polyurethane is obtained between the parallel plates of the rotary rheometer. While holding the composition between the parallel plates, the parallel plates were occasionally vibrated at a strain of 1% and a frequency of 10 Hz, and the storage elastic modulus of the polyurethane measured was 460 kPa.

Example 18.
10 g of the polyol [A-13] synthesized in Example 13, 3, 1 g of hexamethylene diisocyanate (Tosoh Co., Ltd., Coronate C-HXVL), and 5 mg of dibutyl tin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) are put into a 50 mL screw tube. A polyurethane mixture D was prepared by weighing, defoaming using a defoaming mixer (ARE-310 manufactured by THINKY), stirring, and mixing. The obtained polyurethane mixture D is sandwiched between two parallel flat plates of a rotary rheometer (a liquid meter manufactured by UBM) with a parallel flat plate (parallel plate), and the inside of the apparatus is heated to 80 ° C. under a nitrogen atmosphere. By keeping, the halogen-containing polyether polyol in the mixture reacts with the isocyanate compound over time, and polyurethane is obtained between the parallel plates of the rotary rheometer. While holding the composition between the parallel plates, the parallel plates were occasionally vibrated at a strain of 1% and a frequency of 10 Hz, and the storage elastic modulus of the polyurethane measured was 530 kPa.

The results of the above examples are also shown in Table 4.

Comparative example 3.
10 g of the polyol [B-1] synthesized in Comparative Example 1, 3, 1 g of hexamethylene diisocyanate (Tosoh Co., Ltd., Coronate C-HXVL), and 5 mg of dibutyl tin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) were put into a 50 mL screw tube. A polyurethane mixture D was prepared by weighing, defoaming using a defoaming mixer (ARE-310 manufactured by THINKY), stirring, and mixing. The obtained polyurethane mixture D is sandwiched between two parallel flat plates of a rotary rheometer (Soly Liquid Meter manufactured by UBM) with a parallel flat plate (parallel plate), and the inside of the apparatus is heated to 80 ° C. under a nitrogen atmosphere. The halogen-containing polyether polyol in the mixture reacts with the isocyanate compound over time, and polyurethane is obtained between the parallel plates of the rotary rheometer. While holding the composition between the parallel plates, the parallel plates were occasionally vibrated at a strain of 1% and a frequency of 10 Hz, and the storage elastic modulus of the polyurethane measured was 380 kPa.

Comparative example 4.
10 g of the polyol [B-2] synthesized in Comparative Example 2, 3, 1 g of hexamethylene diisocyanate (Tosoh Co., Ltd., Coronate C-HXVL), and 5 mg of dibutyl tin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) were put into a 50 mL screw tube. A polyurethane mixture E was prepared by weighing, defoaming, stirring and mixing using a defoaming mixer (ARE-310, manufactured by THINKY). The obtained polyurethane mixture E is sandwiched between two parallel flat plates of a rotary rheometer (a liquid meter manufactured by UBM) with a parallel flat plate (parallel plate), and the inside of the apparatus is heated to 80 ° C. under a nitrogen atmosphere. By keeping, the halogen-containing polyether polyol in the mixture reacts with the isocyanate compound over time, and polyurethane is obtained between the parallel plates of the rotary rheometer. While holding the composition between the parallel plates, the parallel plates were occasionally vibrated at a strain of 1% and a frequency of 10 Hz, and the storage elastic modulus of the polyurethane measured was 420 kPa.

The results of the above comparative example are also shown in Table 5.

The halogen-containing polyether polyol in the present invention is a coating agent (paint) adhesive, a sealant, a thermosetting elastomer, and a thermoplastic elastomer. It can be used as a raw material polyol for polyurethane that can be suitably used for various purposes, mainly for the so-called applications or urethane foam applications such as hard foam and soft foam.

Claims (11)

Is represented by the following formula (1), molecular weight of 200 to 100,000, and the degree of unsaturation Ri der less 0.02 meq / g, a halogen-containing poly 1 quaternizing rate of terminal hydroxyl groups is less than 10% Ether polyol.

(In the above formula (1), Q represents a polymer component containing the following structural unit [I], m is an integer of 2 to 8, and R ¹ represents an active hydrogen-containing compound residue.)

(In the structural unit [I], X represents a halogen atom.) The halogen-containing polyether polyol according to claim 1, wherein in the above formula (1), Q represents a polymer component containing the above structural unit [I] and the following structural unit [II].

(In the structural unit [II], A represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) A halogen-containing polyether polyol having a molecular weight of 200 to 100,000 and an unsaturated degree of 0.02 meq / g or less, which is represented by the following formula (2).

(In the above formula (2), X is a halogen atom, n is an integer of 1 to 500, m is an integer of 2 to 8, and R ¹ is an active hydrogen-containing compound residue.) The halogen-containing polyether polyol according to any one of claims 1 to 3, wherein the degree of unsaturation is 0.01 meq / g or less. The halogen-containing polyether polyol according to any one of claims 1 to 4, characterized in that Mw / Mn is 1.50 or less (however, the number average obtained from gel permeation chromatography measurement using polystyrene as a standard substance). The molecular weight is Mn, and the weight average molecular weight is Mw). Ring-open polymerization of halogen-containing alkylene oxide in the presence of a composition containing an onium salt, Lewis acid and an active hydrogen-containing compound, and the amount of the onium salt used with respect to 1 mol of active hydrogen in the active hydrogen-containing compound. The method for producing a halogen-containing polyether polyol according to any one of claims 1 to 5, wherein the amount is in the range of 0.001 to 0.1 mol. The production method according to claim 6, wherein the onium salt is a phosphazenium salt represented by the following formula (3), or an ammonium salt or a phosphonium salt represented by the following formula (4).

(In the above formula (3), R ² and R ³ are independently each of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ^{a ring structure in which R 2} and R ³ are bonded to each other, R ^{2 to} each other or R ³ Ring structure in which they are bonded to each other, Z ⁻ 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, a chlorine anion, a bromine anion, an iodine anion or a hydrogen carbonate anion. Represents. 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.)

(In the above formula (4), D represents a nitrogen atom or a phosphorus atom, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently alkyl groups, aryl groups and alkoxy groups having 1 to 20 carbon atoms. dialkylamino group, a halogen atom or a hydrogen atom, E is may form a 2 to 4 but ring structure by bonding with one of the .R ⁴ to R ⁷ representing a counter ion of an inorganic or organic group and Heteroatoms may be contained in the cyclic structure.) The production method according to claim 6 or 7, wherein the Lewis acid is at least one compound selected from the group consisting of an aluminum compound and a zinc compound. A polyurethane-forming composition containing the halogen-containing polyether polyol according to any one of claims 1 to 5 and a polyisocyanate compound. A polyurethane containing the halogen-containing polyether polyol according to any one of claims 1 to 5 as a monomer unit. A method for producing a polyurethane, which comprises reacting the halogen-containing polyether polyol according to any one of claims 1 to 5 with a polyisocyanate compound.