WO2021215327A1

WO2021215327A1 - Halogen-containing polyether polyol

Info

Publication number: WO2021215327A1
Application number: PCT/JP2021/015427
Authority: WO
Inventors: 鈴木茉由加; 大浜俊生; 大谷泰歩
Original assignee: 東ソー株式会社
Priority date: 2020-04-21
Filing date: 2021-04-14
Publication date: 2021-10-28

Abstract

The present disclosure addresses the problem of providing a chlorine-containing polyether polyol which is highly reactive with an isocyanate and serves as a starting material for a polyurethane that exhibits excellent mechanical properties.　A halogen-containing polyether polyol which is represented by formula (1) and has a molecular weight of from 500 to 10,000 and a degree of unsaturation of 0.02 meq/g or less, wherein the ratio of having structural unit (II) at an end is from 2 mol% to 99.5 mol%. (In formula (1), Q represents a polymer component that contains structural unit (I) and structural unit (II); m represents an integer from 2 to 3; and R¹ represents an active hydrogen-containing compound residue.) (In formula (I), X represents a halogen atom.) (In structural unit (II), A represents a hydrogen atom or a hydrocarbon group having from 1 to 10 carbon atoms.)

Description

Halogen-containing polyether polyol

The present disclosure relates to a halogen-containing polyether polyol having good reactivity with isocyanate, which is a raw material of polyurethane having excellent mechanical properties.

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 and flame retardancy (see, for example, Patent Document 1). The halogen-containing polyether polyol can be synthesized by ring-opening polymerization of the 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 residual strain rate 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 also been developed for the polymerization of halogen-containing alkylene oxides (see, for example, Non-Patent Document 1).

Japanese Patent Application Laid-Open No. 2-202573

However, since such a chlorinated polyether polyol has low reactivity between the terminal hydroxyl group and isocyanate, there is a problem in curability when producing polyurethane. Therefore, one aspect of the present invention is directed to providing a halogen-containing polyether polyol having excellent reactivity with isocyanate and having good curability, which is a raw material for producing polyurethane having excellent mechanical properties.

Each aspect of the present invention is [1] to [7] shown below.
[1]
It is represented by the following formula (1), the molecular weight is 500 or more and 10,000 or less, the degree of unsaturation is 0.02 meq / g or less, and the ratio of having the structural unit [II] at the terminal is 2 mol% or more and 99.5 mol%. The following halogen-containing polyether polyols.

(In the above formula (1), Q represents a polymer component containing the following structural unit [I] and the following structural unit [II], m is an integer of 2 to 3, and R ¹ is an active hydrogen-containing compound residue. show.)

(In formula [I], X represents a halogen atom.)

(In the structural unit [II], A represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
[2]
The halogen-containing polyether polyol according to [1] represented by the above formula (1), wherein Q represents a polymer component containing the following structural unit [III] and the following structural unit [IV].

(In the above structural unit [III], l represents an integer of 2 or more and 100 or less)

(In the structural unit [IV], n represents an integer of 2 or more and 100 or less.)
[3]
The halogen-containing polyether polyol according to [1] or [2], wherein X is a chlorine atom in the structural unit [I] and A is a hydrogen atom, a methyl group or an ethyl group in the structural unit [II]. ..
[4]
The halogen-containing polyether polyol according to any one of [1] to [3], wherein the proportion having the structural unit [II] at the terminal is 50 mol% or more and 99.5 mol% or less.
[5]
A method for producing a halogen-containing polyether polyol in which ring-opening polymerization of an alkylene oxide is carried out in the presence of a composition containing an onium salt, a Lewis acid and an active hydrogen-containing compound, wherein the active hydrogen in the active hydrogen-containing compound is 1 mol. [1] to [1] to [1], wherein the amount of the onium salt used is in the range of 0.001 to 0.1 mol, and the amount of the Lewis acid used is in the range of 0.002 to 0.2 mol. 4] The method for producing a halogen-containing polyether polyol according to any one of.
[6]
A polyurethane characterized by containing the halogen-containing polyether polyol residue according to any one of [1] to [4] in the molecular structure.
[7]
A polyurethane foam having a foaming ratio of 1.2 times or more and 100 times or less, which comprises the halogen-containing polyether polyol residue according to any one of [1] to [4] in the molecular structure.

The halogen-containing polyether polyol, which is one aspect of the present invention, is a raw material for producing polyurethane having excellent reactivity with isocyanate and excellent mechanical properties with good curability.

<Halogen-containing polyether polyol>
The halogen-containing polyether polyol according to one aspect of the present invention is represented by the above formula (1), has a molecular weight of 500 or more and 10,000 or less, an degree of unsaturation of 0.02 meq / g or less, and a structural unit at the terminal. It is a halogen-containing polyether polyol having a proportion of [II] of 2 mol% or more and 99.5 mol% or less.

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

In the above formula (1), the proportion of the structural unit [II] at the terminal is 2 mol% or more and 99.5 mol% or less, and the reactivity with isocyanate is improved. Therefore, 50 mol% or more and 99.5 mol% or less is preferable. , 70 mol% or more and 0.5 mol% or less is more preferable.

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 structural unit [II], the hydrogen atom represented by A or the hydrocarbon having 1 to 10 carbon atoms is not particularly limited, and is, for example, a hydrogen atom, a methyl group, an ethyl group, a vinyl group, or n-propyl. Group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, t-butyl group, cyclobutyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, phenyl group, Examples thereof include 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 from the viewpoint of easy availability of a precursor and easy progress of polymerization.

In the above formula (1), Q is a polymer component containing the above structural unit [I] and the above structural unit [II], and the arrangement of the structural units may be random or block, but the isocyanate of the halogen-containing polyether polyol is isocyanate. Since the reactivity with the compound tends to be good, the structural unit [III] which is a polymer component of the structural unit [I] and the structural unit [IV] which is a polymer component of the structural unit [II] are included. It is preferably a block.

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.

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, a polyester polyol, and the like. Examples thereof include a polycarbonate polyol.

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 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 polypropylene glycol, polyethylene glycol, polybutylene glycol having a molecular weight of 200 to 2000, and a copolymer thereof. As the active hydrogen-containing compound containing an active hydrogen-containing compound residue, since the halogen-containing polyether polyol according to one aspect of the present invention can be efficiently produced, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol can be efficiently produced. , Tripropylene glycol, 1,9-nonanediol, 2,5-hexanediol, 2-methylpentane-2,4-diol, ethylenediamine, polypropylene glycol with a molecular weight of 200 to 2000, polyester polyol with a molecular weight of 350 to 2500, molecular weight Is preferably 350 to 1000, and more preferably tripropylene glycol, 2,5-hexanediol, 1,9-nonanediol, polypropylene glycol having a molecular weight of 200 to 1000, and polyester polyol having a molecular weight of 350 to 2500.

The molecular weight of the halogen-containing polyether polyol according to one aspect of the present invention is 500 or more and 10,000 or less, and the molecular weight is 500 or more because it is excellent in handleability when used as a raw material for polyurethane and the production efficiency of polyurethane. It is preferably 7,000 or less, and more preferably 500 or more and 5,000 or less.

The degree of unsaturation of the halogen-containing polyether polyol according to one aspect of the present invention is 0.02 meq / g or less, and physical properties such as hysteresis loss and compression residual strain rate of the obtained polyurethane are improved. Therefore, 0.015 meq / g. It is preferably g or less.

The Mw / Mn of the halogen-containing polyether polyol according to one aspect of the present invention is preferably 2.00 or less, more preferably 1.50 or less, because the moldability when made into a polyurethane resin is improved. , Polystyrene is used as a standard substance, and the number average molecular weight determined by gel permeation chromatography measurement is Mn, and the weight average molecular weight is Mw).

The primaryization rate of the terminal hydroxyl group in the halogen-containing polyether polyol according to one aspect 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 are uniform. It is preferable that it is less than 10%.

The halogen-containing polyether polyol according to one aspect of the present invention is not particularly limited and can be produced by a conventionally known production method.
For example, it can be obtained by ring-opening polymerization of two or more types of alkylene oxides using 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.

Examples of the first alkylene oxide at that time include halogen-containing alkylene oxides, and specific examples thereof include epichlorohydrin, epibromohydrin, and epifluorohydrin. Among these, epichlorohydrin is preferable because it is easily available and the obtained polyalkylene oxide has a high industrial value.

Examples of the second alkylene oxide include alkylene oxides having 2 to 12 carbon atoms, and specifically, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and isobutylene oxide. , Butadiene monooxide, pentene oxide, styrene oxide, cyclohexene oxide and the like. Among these, ethylene oxide, propylene oxide, and 1,2-butylene oxide are preferable because alkylene oxide is easily available and the obtained polyalkylene oxide has high industrial value.

The first and second alkylene oxides may be used alone or in combination of two or more.

The onium salt is not particularly limited, and examples thereof include phosphazenium salt, ammonium salt, and phosphonium salt.

The structure of the phosphazenium salt is not particularly limited, but is represented by, for example, the following formula (2).

In the above formula (2), 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 to} each other. ring structure but bonded to each other, Z ^- represents an hydroxy anion, alkoxy anion having 1 to 4 carbon atoms, carboxy anion, alkyl carboxy anion having 2 to 5 carbon atoms, chlorine anion, bromine anion, iodine anion or bicarbonate anions ..

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, an n-propyl group, an isopropyl group, a cyclopropyl group, and an allyl group. 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 (2) 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.

The phosphazenium salt represented by the above formula (2) is not particularly limited, but specifically, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide and 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 hydroxyd Do, 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 (1,3-dimethylimidazolidine-2-imino) 1,3,3-Tetramethylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetraethylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-propyl) guanidino) phosphonium Hydrogen carbonate, tetrakis (1,1,3,3-tetraisopropylguanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3,3-tetra (n-butyl) guanidino) phosphonium hydrogen carbonate, tetrakis (1,1,3) , 3-Tetraphenylguanidino) phosphonium 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, Tetrax [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 one aspect of the present invention, the structure of the ammonium salt or the phosphonium salt is represented by, for example, the following formula (3).

In the formula (3), D represents a nitrogen atom or a phosphorus ^{^{^{atom, R 4, R 5, R}}} 6 and ^{R 7} are each independently an alkyl group which may having 1 to 20 carbon atoms may include a hetero atom, an aryl It represents a group, an alkoxy group, a dialkylamino group, a halogen atom or a hydrogen atom, and E represents a counterion composed of an inorganic or organic group. Two to four of R ⁴ to R ⁷ may be bonded to form a cyclic structure, or a hetero atom may be contained in the cyclic structure.

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, ethyl group, vinyl group, normal propyl group and 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 Examples include a group, a benzyl group, a trill group, an octyl group, a cyclooctyl group, a xsilyl group, and the like, and examples of the alkoxy group include a methoxy group, an ethoxy group, a vinyloxy group, a normal propoxy group, an isopropoxy group, a cyclopropoxy group, and an allyloxy group. , Normal butoxy group, Isobutoxy group, t-butoxy group, Cyclobutoxy group, Normalpentyloxy group, Neopentyloxy group, Cyclopentyloxy group, Normalhexyloxy group, Cyclohexyloxy group, Phenoxy group, Propyloxy group, Cycloheptyloxy group Examples include a group, an octyloxy group, a benzyloxy group, a triloxy group, a cyclooctyloxy group, and a xsilyloxy group, and examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a pyrrolidino group, a piperidino group, a dinormal propylamino group, and a diisopropyl. Examples thereof include an amino 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 can independently contain an alkyl group or an aryl group having 1 to 10 carbon atoms which may contain a hetero atom. It is 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.

E in the above formula (3) is an inorganic or organic group.

Among these, although not particularly limited, specifically, a halogen atom, a hydroxyl group, an alkoxyl group, an amino group, a carboxyl group, a sulfonic acid group, a boron hydride group, and a hexafluorophosphate group are exemplified and used for catalytic activity. Since it is an excellent catalyst for producing a halogen-containing polyether polyol, it is preferably any 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 (3) is not particularly limited, but specifically, tetramethylammonium bromide, tetraethylammonium bromide, tetranormal propylammonium bromide, tetranormal butylammonium bromide, tetranormalal. 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, tetra. Normal 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, Tetranormalpropylphosphonium bromide, Tetranormal butylphosphonium bromide, Tetranormal pentylphosphonium bromide, Tetranormalhexylphosphonium bromide, Tetranormal heptylphosphonium bromide, Tetranormal octylphosphonium bromide, Tetramethylphosphonium Chloride, tetraethylphosphonium chloride, tetranormalpropylphosphonium chloride, tetranormal butylphosphonium chloride, tetranormalpentylphosphonium chloride, tetranormalhexylphosphonium chloride, tetranormalheptylphosphonium chloride, tetranormaloctylphosphonium chloride, bromotris (dimethylamino) phosphonium hexafluoro Phosphate 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 one aspect of 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 method for producing a halogen-containing polyether polyol according to one aspect of the present invention, since the halogen-containing polyether polyol can be efficiently produced, an onium salt is added to 1 mol of active hydrogen in the active hydrogen-containing compound. Is preferably 0.001 to 0.1 mol, particularly preferably 0.001 to 0.05 mol.

Since the halogen-containing polyether polyol according to one aspect of the present invention can be efficiently produced, the amount of Lewis acid is 0.002 to 0.2 mol with respect to 1 mol of active hydrogen in the active hydrogen-containing compound. It is preferably 0.002 to 0.1 mol, and particularly preferably 0.002 to 0.1 mol.

In the method for producing a halogen-containing polyether polyol according to one aspect 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 according to one aspect 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 according to one aspect of the present invention, the polymerization reaction can be carried out in a solvent-free manner or in a solvent. When a solvent is used, examples of the solvent include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, 1,2-dimethoxyethane and the like. ..
<Polyurethane>
The structure of the polyurethane according to one aspect of the present invention is not particularly limited as long as the halogen-containing polyether polyol residue according to one aspect of the present invention is contained in the molecular structure, and may be a crosslinked product or a linear structure. However, it may be branched.

Further, the method for producing polyurethane according to one aspect of the present invention is not particularly limited, and examples thereof include reacting a halogen-containing polyether polyol according to one aspect of the present invention with 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-undecanetriisocyanis, 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 isocyanate compound or its derivative may be used alone or in combination of two or more.

When a polyurethane is obtained by reacting a halogen-containing polyether polyol and a polyisocyanate compound according to one aspect of the present invention, for example, the composition may be heated up to 200 ° C., or dioctyltin dilaurate or dibutyltin dilaurate. , Triethylamine, triethylenediamine, stanas octoate, dibutyltin di-2-ethylhexanoate, sodium o-phenylphenate, potassium oleate, tetra (2-ethylhexyl) titanate, stannic chloride, second chloride When a catalyst such as iron or antimony trichloride 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.

The polyurethane according to one aspect of the present invention can be used for urethane foam applications such as hard foam or soft foam. It can also be used for coatings / coatings, adhesives / adhesives, sealants, thermoplastic or thermosetting elastomers, leather, spandex, various inks and the like. ..
<Polyurethane foam>
Polyurethane-based foams are roughly classified into soft-based and hard-based foams. However, when a polyurethane foam is to be obtained by using the halogen-containing polyether polyol according to one aspect of the present invention, both soft and hard foams have been conventionally used. A known production method can be applied.

For example, a room temperature liquid mixture in which the halogen-containing polyether polyol according to one aspect of the present invention is mixed with other known polyols, catalysts, foam stabilizers, cross-linking agents, foaming agents, communicating agents and the like, if necessary. Examples thereof include a method in which the liquid is stirred and mixed, then mixed with the polyisocyanate compound by stirring, injected into an appropriate mold, and foamed and cured.

Further, the halogen-containing polyether polyol according to one aspect of the present invention is mixed with other known polyols, catalysts, foam stabilizers, foaming agents and polyisocyanate compounds by a known stirring and mixing machine to obtain an effervescent mixture. Examples thereof include a method of preparing the mixture, injecting it into a mold having an open top surface, freely foaming it, and curing and molding it as a slab.

The foaming ratio of the polyurethane foam according to one aspect of the present invention is not particularly limited, but is preferably 1.2 times or more and 100 times or less, and 10 times or more and 80 times or less in order to improve handleability. It is particularly preferable to have.

The polyurethane foam according to one aspect of the present invention is not particularly limited in its intended use, and is for automobiles and vehicles because of the characteristics of the polyurethane foam composed of the reaction product of the composition according to one aspect of the present invention. It can be used for applications to which soft polyurethane foam is applied, such as ceiling materials, seats, pillows, furniture / interior, bedding, shoe soles, sponges, various cushions, tennis balls, and landing mats. Further, the polyurethane foam according to one aspect of the present invention can be used in applications to which a hard polyurethane foam such as a heat insulating / cold insulating material, a vibration isolating / sound absorbing material, a cushioning material, and a buoyancy material is applied. For example, for ships such as fishing boats, large ships, refrigerated cargo ships, LNG ships, LPG ships, liquefied gas ships, container insulation materials, FRP boat core materials, and large ships, life-saving boats, buoys, and floats. For vehicles such as refrigerated vehicles / cold storage vehicles / railway containers, tank lorry insulation materials, vehicle / truck ceiling insulation materials, chemical industry equipment tank / piping insulation materials, heavy oil tank / piping insulation materials, LPG / LNG low temperature liquefied gas cold insulation / pipe insulation, insulation cover, tank lid for plants, refrigerator / refrigerator insulation, air conditioner insulation, showcase / stocker / vending machine / water heater / hot water tank, etc. Insulation materials for various types of insulation equipment, as well as insulation materials for houses and office buildings (walls, underfloor, ceiling, under roof, etc.), insulation building materials (laminated boards, composite panels, siding materials, etc.), bathtubs (stainless steel / FRP)・ Insulation of road floors for insulation of horo), insulation of frozen warehouses, refrigerated warehouses, agricultural warehouses, livestock barns, void filling (insulation sashes), insulation of constant temperature greenhouses and centralized heating and cooling For civil engineering as materials and anti-vibration materials, as well as chair core materials, door panels, decorative crafts, entertainment equipment (cooler boxes / water cylinders), teaching materials (three-dimensional maps, etc.), mold materials / jigs, surfing cores Materials, RIM method products (ski core materials, racket core materials, housings), packing materials, etc. can be mentioned.

Hereinafter, the present invention will be described with reference to Examples, but the present Examples do not limit the present invention at all. 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) Percentage of halogen-containing polyether polyol having the terminal structure [II] (unit: mol%)
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.

1) In the above formula (1), when X is a chlorine atom and A is a hydrogen atom, the terminal structure [II] rate (mol%) = [(s / 2) / (r + s / 2)] × 100.

Here, r is the integrated value of the signal derived from the methine group to which the secondary hydroxyl group derived from the structural unit [I] derived at about 5.3-5.4 ppm is bonded, and s is the methylene group to which the primary hydroxyl group is bonded near 4.3 ppm. Represents the integral value of the signal derived from the group.

2) In the above formula (1), when X is a chlorine atom and A is a methyl group, the terminal structure [II] ratio (mol%) = [(t / 3) / (u + s / 2)] × 100.

Here, t is the integrated value of the signal derived from the methyl group bonded to the carbon to which the secondary hydroxyl group is bonded in the vicinity of 1.3-1.4 ppm, and r is the structural unit [I] in the vicinity of 5.2-5.4 ppm and the structural unit [I]. The integrated value of the signal derived from the methine group to which the secondary hydroxyl group derived from [II] is bonded, and s represents the integrated value of the signal derived from the methylene group to which the primary hydroxyl group is bonded near 4.3 ppm.

3) In the above formula (1), when X is a chlorine atom and A is an ethyl group, the terminal structure [II] ratio (mol%) = [v / (r + v + s / 2)] × 100.

Here, r is the integrated value of the signal derived from the methine group to which the secondary hydroxyl group derived from the structural unit [I] derived from the structural unit [I] is bonded at about 5.3-5.4 ppm, and v is the structural unit around 5.1-5.2 ppm [ II] represents the integrated value of the signal derived from the methine group to which the secondary hydroxyl group is bonded, and s represents the integrated value of the signal derived from the methylene group to which the primary hydroxyl group is bonded at around 4.3 ppm.

Example 1.
Polypropylene glycol (PPG) with a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Sanyo Chemical Industries, Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g ] 214.3 g and tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4.32 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 40.2 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TiBAL) was added, the internal temperature was set to 100 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours to compose the composition. The thing [A-1] was obtained. The temperature of the obtained composition [A-1] was raised to 95 ° C., and 840 mL of epichlorohydrin (ECH) was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual epichlorohydrin was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Next, 140 g of ethylene oxide (EO) was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to remove pale yellow halogen. A contained polyether polyol [A-1] was obtained. The obtained halogen-containing polyether polyol [A-1] had a molecular weight of 2500 g / mol, an unsaturated degree of 0.002 meq / g, Mw / Mn of 1.36, and a terminal [II] ratio of 90 mol%.

Example 2.
Polypropylene glycol (PPG) with a molecular weight of 600 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Sanyo Chemical Industries, Ltd. (trade name) Sanniks PP600; hydroxyl value 187 mgKOH / g ] 242.7 g and tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3.26 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 30.3 mL of a 1.0 mol / L toluene solution of triisopropoxyaluminum (PADM manufactured by Kawaken Fine Chemicals Co., Ltd.) was added, the internal temperature was set to 100 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours to prepare the composition. [A-2] was obtained. The temperature of the obtained composition [A-2] was raised to 95 ° C., and 720 mL of epichlorohydrin (ECH) was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual epichlorohydrin was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Next, 150 mL of propylene oxide (PO) was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, residual PO was removed under a reduced pressure of 0.5 kPa to obtain a pale yellow color. A halogen-containing polyether polyol [A-2] was obtained. The obtained halogen-containing polyether polyol [A-2] had a molecular weight of 3020 g / mol, an unsaturated degree of 0.008 meq / g, Mw / Mn of 1.40, and a terminal [II] ratio of 89 mol%.

Example 3.
Polypropylene glycol (PPG) with a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Sanyo Chemical Industries, Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g ] 226.6 g and tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4.56 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 42.5 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TiBAL) was added, the internal temperature was set to 100 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours to compose the composition. The thing [A-3] was obtained. The obtained composition [A-3] was heated to 95 ° C., and 720 mL of ECH was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual epichlorohydrin was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Next, 100 mL of PO was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, residual PO was removed under a reduced pressure of 0.5 kPa to remove a pale yellow halogen-containing polyether polyol. [A-3] was obtained. The obtained halogen-containing polyether polyol [A-3] had a molecular weight of 2040 g / mol, an unsaturated degree of 0.004 meq / g, Mw / Mn of 1.45, and a terminal [II] ratio of 54 mol%.

Example 4.
Polypropylene glycol (PPG) with a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Sanyo Chemical Industries, Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g ] 226.6 g and tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4.56 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 42.5 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TiBAL) was added, the internal temperature was set to 100 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours to compose the composition. The thing [A-4] was obtained. The obtained composition [A-4] was heated to 95 ° C., and 720 mL of ECH was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual epichlorohydrin was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Next, while intermittently supplying 65 mL of PO so as to maintain the reaction pressure of 0.25 MPa or less, after the reaction was completed, residual PO was removed under a reduced pressure of 0.5 kPa to remove a pale yellow halogen-containing polyether polyol. [A-4] was obtained. The obtained halogen-containing polyether polyol [A-4] had a molecular weight of 2020 g / mol, an unsaturated degree of 0.003 meq / g, Mw / Mn of 1.45, and a terminal [II] ratio of 35 mol%.

Example 5.
Polypropylene glycol (PPG) with a molecular weight of 1000 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Sanyo Chemical Industries, Ltd. (trade name) Sanniks PP1000; hydroxyl value 112 mgKOH / g ] 291.5 g and tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2.38 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 21.86 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (TiBAL manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, the internal temperature was set to 100 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours to compose the composition. The thing [A-5] was obtained. The obtained composition [A-5] was heated to 95 ° C., and 840 mL of ECH was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual epichlorohydrin was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Next, 105 mL of PO was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, residual PO was removed under a reduced pressure of 0.5 kPa to remove a pale yellow halogen-containing polyether polyol. [A-5] was obtained. The obtained halogen-containing polyether polyol [A-5] had a molecular weight of 4700 g / mol, an unsaturated degree of 0.004 meq / g, Mw / Mn of 1.45, and a terminal [II] ratio of 83 mol%.

Example 6.
Polypropylene glycol (PPG) with a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Sanyo Chemical Industries, Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g ] 180.2 g and tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3.63 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 33.8 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (TiBAL manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, the internal temperature was set to 100 ° C., and a vacuum treatment of 0.5 kPa was performed for 2 hours to compose the composition. The thing [A-6] was obtained. The obtained composition [A-6] was heated to 95 ° C., and 840 mL of ECH was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual ECH was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Then, 220 mL of butylene oxide (BO) was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, residual BO was removed under a reduced pressure of 0.5 kPa to obtain a pale yellow color. A halogen-containing polyether polyol [A-6] was obtained. The obtained halogen-containing polyether polyol [A-6] had a molecular weight of 3010 g / mol, an unsaturated degree of 0.008 meq / g, Mw / Mn of 1.48, and a terminal [II] ratio of 82 mol%.

Example 7.
Polypropylene glycol (PPG) with a molecular weight of 1000 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Sanyo Chemical Industries, Ltd. (trade name) Sanniks PP1000; hydroxyl value 112 mgKOH / g ] 136.0 g and tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 1.00 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 9.3 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (TiBAL manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, the internal temperature was set to 100 ° C., and a reduced pressure treatment of 0.5 kPa was performed for 2 hours to compose the composition. The thing [A-7] was obtained. The obtained composition [A-7] was heated to 95 ° C., and 840 mL of ECH was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual ECH was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Then, while intermittently supplying 134 mL of butylene oxide (BO) so as to maintain the reaction pressure of 0.25 MPa or less, after the reaction was completed, the residual BO was removed under a reduced pressure of 0.5 kPa to obtain a pale yellow color. A halogen-containing polyether polyol [A-7] was obtained. The obtained halogen-containing polyether polyol [A-7] had a molecular weight of 9300 g / mol, an unsaturated degree of 0.016 meq / g, Mw / Mn of 1.62, and a terminal [II] ratio of 85 mol%.

Example 8.
Polyester polyol (PES) for hard foam with a molecular weight of 600 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Kawasaki Kasei Co., Ltd., (trade name) Maximol RLK-087; hydroxyl group Value 203 mgKOH / g] 335.6 g and tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 9.78 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 9.30 g of triisopropoxyaluminum (PADM manufactured by Kawaken Fine Chemical Co., Ltd.) was added, the internal temperature was set to 100 ° C., and a reduced pressure treatment of 0.5 kPa was carried out for 2 hours to obtain the composition [A-8]. The obtained composition [A-8] was heated to 95 ° C., and 360 mL of ECH was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual epichlorohydrin was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Next, while intermittently supplying 330 mL of PO so as to maintain the reaction pressure of 0.25 MPa or less, after the reaction was completed, residual PO was removed under a reduced pressure of 0.5 kPa to remove a pale yellow halogen-containing polyether polyol. [A-8] was obtained. The obtained halogen-containing polyether polyol [A-8] had a molecular weight of 1730 g / mol, an unsaturated degree of 0.014 meq / g, Mw / Mn of 1.64, and a terminal [II] ratio of 88 mol%.

The results of Examples 1 to 8 above are also shown in Table 1.

Comparative example 1.
Polypropylene glycol (PPG) with a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound in a 2-liter four-flask equipped with a stirring blade [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / G] 181.54 g and Tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 3.66 g were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours. Then, 34.0 mL of a 1.0 mol / L toluene solution of triisobutylaluminum (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., TiBAL) was added, the internal temperature was set to 100 ° C., and a vacuum treatment of 0.5 kPa was performed for 2 hours to compose the composition. The thing [B-1] was obtained. The temperature of the obtained composition [B-1] was raised to 95 ° C., and 1000 mL of epichlorohydrin (ECH) was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was performed at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual epichlorohydrin was removed under a reduced pressure of 95 ° C. and 0.5 kPa to remove pale yellow halogen-containing poly. An ether polyol [B-1] was obtained. The obtained halogen-containing polyether polyol [B-1] had a molecular weight of 3010 g / mol, an unsaturated degree of 0.005 meq / g, Mw / Mn of 1.46, and a terminal [II] ratio of 1 mol%.

Comparative example 2.
Polypropylene glycol (PPG) having a molecular weight of 400 having two hydroxyl groups as an active hydrogen-containing compound in a 2 liter autoclave equipped with a stirring blade [manufactured by Sanyo Kasei Kogyo Co., Ltd. (trade name) Sanniks PP400; hydroxyl value 280 mgKOH / g ] 269.0 g and 3.59 g of boron trifluoride diethyl ether complex [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] were added. After the inside of the flask was made to have a nitrogen atmosphere, the internal temperature was set to 100 ° C., and dehydration treatment was carried out under a reduced pressure of 0.5 kPa for 2 hours to obtain a composition [B-2]. The temperature of the obtained composition [B-2] was raised to 95 ° C., and 840 mL of epichlorohydrin (ECH) was intermittently supplied over 4 hours. After supplying epichlorohydrin, aging was carried out at an internal temperature of 85 to 90 ° C. for 2 hours, and then residual epichlorohydrin was removed under a reduced pressure of 95 ° C. and 0.5 kPa. Next, 140 g of ethylene oxide (EO) was intermittently supplied so as to maintain the reaction pressure of 0.25 MPa or less, and after the reaction was completed, residual ethylene oxide was removed under a reduced pressure of 0.5 kPa to remove pale yellow halogen. A contained polyether polyol [B-2] was obtained. The obtained halogen-containing polyether polyol [B-2] had a molecular weight of 2200 g / mol, an unsaturated degree of 0.08 meq / g, Mw / Mn of 2.46, and a terminal [II] ratio of 53 mol%.

The results of Comparative Example 1.2 above are also shown in Table 2.

<Adjustment of polyol premix>
(1) Raw material << Commercially available PPG >>
In all of the examples and comparative examples, Sanniks GP-3000 manufactured by Sanyo Kasei Co., Ltd. was used.
<foaming agent>
In all of the examples and comparative examples, ion-exchanged water was used as the foaming agent.
<Foaming agent>
In each of the Examples and Comparative Examples, SZ-1327 manufactured by Toray Dow Corning Co., Ltd. was used as the silicone-based defoaming agent.
<Catalyst>
In both Examples and Comparative Examples, a solution (TEDA-L33 manufactured by Tosoh Corporation) in which triethylenediamine was dissolved in dipropylene glycol at a concentration of 33% by weight as a catalyst and tin octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., Nikkaoku) were used. Chix tin) was used.
<Isocyanate compound>
In each of the Examples and Comparative Examples, tolylene diisocyanate (Coronate T-80 manufactured by Tosoh Corporation) having a mixing ratio of 2,4 / 2,6 isomers of 80/20 was used.

The halogen-containing polyether polyol and water are mixed at the blending ratios shown in Table 3, and a catalyst and a foam stabilizer are further mixed with the mixture, and the mixture is mixed with a small high-speed stirrer (PRIMIX manufactured by PRIMIX Corporation). The mixture was stirred and mixed at 2000 rpm for 20 minutes to obtain a stirred mixture (hereinafter referred to as premix) excluding the isocyanate compound.

<Making polyurethane foam>
Isocyanate group reactive groups (NCO reactivity) capable of reacting the premixes 1 to 9 prepared as described above with the NCO group including the total amount of isocyanate groups (NCO group) and the hydroxyl group (OH group) contained in water. A predetermined amount of isocyanate compound is added so that the ratio of (groups), that is, NCO / NCO reactive group = 1.0, and the mixture is stirred at 4000 rpm for 8 seconds using a small high-speed stirrer (PRIMIX manufactured by Primix). After mixing, it was immediately poured into a 250 mm × 250 mm × 250 mm acrylic water tank to obtain a polyurethane foam.
(Evaluation method of polyurethane foam)
(1) Foaming Magnification The premix density measured by the method described in JIS Z-8804 was divided by the density of the polyurethane foam measured by the method described in JIS Z-8807 to obtain the value.
(2) Curability The produced polyurethane foam was allowed to stand in a constant temperature room at 23 ° C. and 50 Rh% for 4 hours, and then the tactile sensation when the cross section cut with a foam cutter was pressed with a finger and FT-IR (). The conversion rate was calculated from the peak reduction amount derived from the NCO group near 2250 cm ^{-1 and the curability was evaluated.}
A: No stickiness and NCO conversion rate is 85% or more B: No stickiness and NCO conversion rate is 75% or more and less than 85%, or there is some stickiness and NCO conversion rate is 75% or more only when pressed strongly C: Sticky or NCO conversion rate is less than 75% (3) Tensile strength After allowing the produced polyurethane foam to stand in a constant temperature room at 23 ° C and 50 Rh% for 24 hours, the tensile strength is determined by a method based on JIS K-6400. It was measured.
A: 70 kPa or more B: 50 kPa or more, less than 60 kPa C: less than 50 kPa (4) Compression hardness A method based on JIS K-6400 after allowing the produced polyurethane foam to stand in a constant temperature room at 23 ° C and 50 Rh% for 24 hours. 25% compression hardness was measured in.
A: 70N / 314cm ² or more B: 60N / 314cm ² or more, 70N / 314cm ^{less than 2} C: 60N / 314cm ^{less than 2} (5) Compression residual strain rate The produced polyurethane foam was placed in a constant temperature room at 23 ° C and 50Rh% for 24 hours. After allowing to stand still, the compression residual strain rate was measured by the A method based on JIS K-6400.
A: Less than 10%
B: 10% or more, less than 20% C: 20% or more (6) Flame-retardant After allowing the produced polyurethane foam to stand in a constant temperature room at 23 ° C. and 50 Rh% for 24 hours, a 200 mm × 10 mm × 10 mm test piece. Hold the flame horizontally for 15 seconds from the left end and measure the combustion distance from the A mark line (38 mm from the left end). The number of tests was 10, and the average value was taken as the burning distance of the test piece.
A: Less than 51 mm B: 51 mm or more and less than 127 mm C: 127 mm or more

Example 9.
A polyurethane foam was prepared using Premix 1 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 36 times and was excellent in curability, tensile strength, compressive hardness, and compressive residual strain rate.

Example 10.
A polyurethane foam was prepared using Premix 2 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 35 times and was excellent in curability, tensile strength, compressive hardness, and compressive residual strain rate.

Example 11.
A polyurethane foam was prepared using Premix 3 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 32 times and was excellent in curability, tensile strength, compressive hardness, and compressive residual strain rate.

Example 12.
A polyurethane foam was prepared using Premix 4 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 33 times, and had good curability, tensile strength, compressive hardness, and compressive residual strain rate.

Example 13.
A polyurethane foam was prepared using Premix 5 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 34 times and was excellent in curability, tensile strength, compressive hardness, and compressive residual strain rate.

Example 14.
A polyurethane foam was prepared using Premix 6 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 35 times and was excellent in curability, tensile strength, compressive hardness, and compressive residual strain rate.

Example 15.
A polyurethane foam was prepared using Premix 7 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 30 times, was excellent in curability, and had good tensile strength, compressive hardness, and compressive residual strain rate.

Example 16.
A polyurethane foam was prepared using Premix 8 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 31 times, was excellent in curability, and had good tensile strength, compressive hardness, and compressive residual strain rate.

The results of Examples 9 to 16 are also shown in Table 4.

Comparative example 3.
A polyurethane foam was prepared using Premix 8 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 28 times and was inferior in curability, tensile strength, compressive hardness, and compressive residual strain rate.

Comparative example 4.
A polyurethane foam was prepared using Premix 9 according to the above-mentioned method for producing a polyurethane foam, and evaluated. The polyurethane foam had a foaming ratio of 33 times and had good curability, but was inferior in tensile strength, compressive hardness, and compressive residual strain rate.

The results of Comparative Examples 3 and 4 above are also shown in Table 5.

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

The specification, claims, drawings and abstracts of Japanese Patent Application No. 2020-075198 filed on April 21, 2020 and Japanese Patent Application No. 2021-032276 filed on March 2, 2021. The entire contents of the document are cited herein and incorporated as disclosure of the specification of the present invention.

Claims

It is represented by the following formula (1), the molecular weight is 500 or more and 10,000 or less, the degree of unsaturation is 0.02 meq / g or less, and the ratio of having the following structural unit [II] at the end is 2 mol% or more and 99.5 mol. % Or less halogen-containing polyether polyol.

(In the above formula (1), Q represents a polymer component containing the following structural unit [I] and the following structural unit [II], m is an integer of 2 to 3, and R 1 is an active hydrogen-containing compound residue. show.)

(In formula [I], X represents a halogen atom.)

(In the structural unit [II], A represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
The halogen-containing polyether polyol according to claim 1, wherein Q represents a polymer component containing the following structural unit [III] and the following structural unit [IV].

(In the above structural unit [III], l represents an integer of 2 or more and 100 or less)

(In the structural unit [IV], n represents an integer of 2 or more and 100 or less.)
The halogen-containing polyether polyol according to claim 1 or 2, wherein X is a chlorine atom in the structural unit [I] and A is a hydrogen, methyl group or ethyl group in the structural unit [II].
The halogen-containing polyether polyol according to any one of claims 1 to 3, wherein the proportion having the structural unit [II] at the terminal is 50 mol% or more and 99.5 mol% or less.
In a method for producing a halogen-containing polyether polyol in which a ring-opening polymerization of an alkylene oxide is carried out in the presence of a composition containing an onium salt, a Lewis acid and an active hydrogen-containing compound, the above-mentioned method with respect to 1 mol of active hydrogen in the active hydrogen-containing compound. Any of claims 1 to 4, wherein the amount of the onium salt used is in the range of 0.001 to 0.1 mol, and the amount of the Lewis acid used is in the range of 0.002 to 0.2 mol. A method for producing a halogen-containing polyether polyol according to the above.
A polyurethane characterized by containing the halogen-containing polyether polyol residue according to any one of claims 1 to 4 in the molecular structure.
A polyurethane foam having a foaming ratio of 1.2 times or more and 100 times or less, which comprises the halogen-containing polyether polyol residue according to any one of claims 1 to 4 in the molecular structure.