JPH115833A - Polyether-ester polyol and production of polyurethane resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polyether-esterpolyol low in mono-ol content without passing a complicated process by obtaining a specific crude polyoxyalkylene-polyol from active hydrogen containing compound in the presence of a specific phosphazenium compound under a specific reaction condition, then reacting polycarboxylic anhydride and alkylene oxide to this crudepolyol under a specific condition. SOLUTION: The subject polyol is obtained by carrying out the addition polymerization of the alkylene oxide in the presence of the salt, etc., of phosphazenium cation, for example, expressed by formula(a, b, c, d are each an integer of 0-3, while a+b+c+d+≠0; R is an 1-10C hydrocarbon, etc.,; r is an integer of 1-3; T is an organic anion having r valence) and an inorganic anion, using 5×10<-5> to 1×10<-5> mole amount of the compound of the formula to 1 mole of the active hydrogen containing compound, at 15-130 deg.C, under the maximum reaction pressure of 9 kgf/cm<2> , to afford the crude polyoxyalkylene polyol having hydroxyl value of 10 to 500 mgKOH/g, reacting this polyol with polycarboxylic anhydride and an alkyleneoxide at the same temperature and maximum reaction pressure described above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyetherester polyol and a method for producing a polyurethane resin using the same. Specifically, the present invention provides a method for producing a polyetherester polyol in which an alkylene oxide is addition-polymerized in the presence of a phosphazenium compound to an active hydrogen compound, and then the polycarboxylic anhydride is reacted with the alkylene oxide, and a polyurethane resin using the same. And a method for producing the same. Polyetherester polyols are used as raw materials for rigid polyurethane foams, flexible polyurethane foams, polyurethane elastomers and the like, or as raw materials for synthetic resins other than polyurethane.

[0002]

2. Description of the Related Art In the field of flexible polyurethane foams, polyetherester polyols have been used in combination with polyoxyalkylene polyols and the like in order to improve the hardness, tensile strength or adhesiveness to fibrous materials of foams. On the other hand, in the field of polyurethane elastomers, it is known that the use of polyetherester polyols improves heat resistance and mechanical properties as compared with polyurethane elastomers using only polyoxyalkylene polyols. JP-A-3-72525
In the publication, double metal cyanide complex (Double Me)
tal Cyanide complex; hereinafter, DM
Abbreviated as C. ), A method for producing a polyetherester polyol in which a polyether polyol having a hydroxyl value of 400 or less, a polycarboxylic acid anhydride, and a monoepoxide are reacted. JP-A-3-72
No. 525 discloses that when producing a modified polyetherester polyol having an ester modified at the terminal, it is very difficult to synthesize with the same catalyst by the conventional technique,
For the terminal ester modification, a weak base catalyst is used.However, even if a weak base catalyst is used, a large amount of by-products including a short-chain polyester component is inevitable. It is described that the rebound resilience, the compression set, and the like are significantly reduced (described in [Problem to be Solved by the Invention] in the publication).

[0003] The DMC catalyst used in JP-A-3-72525 is known as a catalyst for producing polyester and polyether as described in the publication. DMC
When used as a catalyst for the production of polyether polyol, DMC has excellent side effects such as low polymerization and high polymerization activity as a polymerization catalyst for propylene oxide.
Deactivate DMC by reacting with oxygen containing gas, peroxide, sulfuric acid and other oxidizing agents, separate catalyst residue from polyol, and further use alkali metal hydroxide or alkali metal alkoxide such as KOH. Need to be subjected to addition polymerization of ethylene oxide (USP 5,144,09).
3, USP 5,235,114). In order to deactivate the DMC catalyst, a method using an alkali metal alkoxide or an alkaline earth metal alkoxide in addition to the oxidizing agent (JP-A-5-508833), a treatment method using a strong base and an ion exchange resin (US Pat. No. 4,355,355) 188) has been proposed, but both methods have complicated manufacturing steps.
When producing a polyether polyol without performing a complicated operation, usable alkylene oxides are limited. Further, if a trace amount of catalyst residue remains in the polyol, there is a problem that an undesirable side reaction (allophanate reaction) is induced in the reaction with the polyisocyanate. As far as the present inventors have examined, Japanese Patent Application Laid-Open No. 3-72
No. 525, that is, after the production of polyetherester polyol,
It was found that the viscosity change with time of the prepolymer reacted with an isocyanate compound such as 4,4'-diphenylmethane diisocyanate was increased without the MC removal operation. Further, when DMC and phthalic anhydride, ethylene oxide and propylene oxide are added to the raw material polyol as in the polyols H and I of the examples described in JP-A-3-72525 and reacted at 120 ° C. for 6 hours, phthalic anhydride is obtained. It was found that a low-molecular-weight compound obtained by reacting ethylene oxide by-produced partly as a by-product, and the viscosity of the polyetherester polyol increased.

When a polyether is produced using DMC as described in JP-A-4-59825, a monoepoxide reaction occurs when the initiator (polymerization initiator) has a low molecular weight. However, there is a problem that the reaction speed is extremely low. In order to solve these problems, Japanese Patent Application Laid-Open No. Hei 4-59825 proposes to use, as a polymerization initiator, polyoxypropylene glycol obtained by addition-polymerizing propylene oxide in advance. In addition, the manufacturing process becomes complicated. JP-A-3-7252
In JP-A-5 (1999), polyether polyols used as raw materials for polyether ester polyols are obtained, for example, by reacting a monohydroxide such as an alkylene oxide with a polyvalent initiator such as a polyhydric alcohol, a polyhydric phenol, an amine or a polyamine. It is described that an alkali catalyst or DMC or another catalyst can be used as a catalyst for reacting a monoepoxide. However, as a result of investigation by the present inventors, a polyvalent initiator ( In our notation, polymerization of propylene oxide (hereinafter abbreviated as an alkylene oxide reaction step) is performed by DMC using an active hydrogen compound which is a polymerization initiator, and then phthalic anhydride and propylene oxide are reacted. Polymerization (hereinafter abbreviated as esterification reaction step) was carried out. It has been found sharp down oxide reaction process time is insufficient for the production of a long, industrial scale.

Further, when the polyoxyalkylene polyol is made to have a high molecular weight, the viscosity of the polyoxyalkylene polyol tends to increase, but when DMC is used, the viscosity of the polyoxyalkylene polyol increases remarkably. . This is due to the manner in which the oxirane ring is cleaved during the propylene oxide addition polymerization as the alkylene oxide.
ail) It is considered that the cause is that the bond selectivity is low. U
SP5,300,535 has high viscosity of high molecular weight polyoxyalkylene polyol using DMC as catalyst,
It is taught to use acrylate and vinyl ether compounds as viscosity reducing agents (columns 2, 5).
Row to column 4, line 12). It was found that when a raw material polyether polyol having a high molecular weight, that is, a low hydroxyl value, was used, the viscosity of the resulting polyether ester polyol was increased, and the moldability of the flexible polyurethane foam was reduced.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the content of monool, which is a by-product of propylene oxide, and to reduce the viscosity of polyalkylene oxide without going through complicated steps in the polymerization of alkylene oxide. Provided is a method for producing a polyetherester polyol obtained by reacting a polycarboxylic anhydride with an alkylene oxide using an oxyalkylene polyol as a starting material, and a method for producing a polyurethane resin using a polyol containing the polyetherester polyol. Is to provide.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that when a specific phosphazenium compound is used as a catalyst for an active hydrogen compound and alkylene oxide is subjected to addition polymerization, the phosphazenium compound is converted to an active hydrogen compound. The concentration, the reaction temperature, the reaction pressure is specified to produce a specific crude polyoxyalkylene polyol, and then the above-mentioned object can be achieved by reacting a specific amount of polycarboxylic anhydride and alkylene oxide under specific conditions. I found it. That is, a first object of the present invention is to provide a (first reaction step) chemical formula (1)

[0008]

Embedded image (A, b, c and d in the chemical formula (1) are each 0
And a, b, c and d are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations;
^r- represents an inorganic anion having a valence of r. ) In the presence of a salt of a phosphazenium cation and an inorganic anion and an alkali metal or alkaline earth metal salt of an active hydrogen compound, or a compound of the formula (2)

[0009]

Embedded image (In the chemical formula (2), a, b, c and d are integers of 0 to 3, but all of a, b, c and d are not simultaneously 0. R is the same or different carbon number of 1 to 3.) 10 hydrocarbon groups, two Rs on the same nitrogen atom may combine with each other to form a ring structure, and Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion. In the presence of a phosphazenium compound represented by the formula (1) and an active hydrogen compound, the chemical formula (1) or the chemical formula (2) is added to 1 mol of the active hydrogen compound.
The phosphazenium compound represented by the formula is 5 × 10 ⁻⁵ to 1 ×
It is prepared in the range of 10 ^-1 mol and the reaction temperature is 15-130.
° C, maximum reaction pressure is 9 kgf / cm ² (882 kPa)
A polyoxyalkylene polyol production step for producing a crude polyoxyalkylene polyol having a hydroxyl value of 10 to 500 mgKOH / g obtained by addition-polymerizing an alkylene oxide under the following conditions, and (second reaction step) obtained in the first reaction step Crude polyoxyalkylene polyol 1
1 to 80 parts by weight of the polycarboxylic acid anhydride to 00 parts by weight and 0.3 to
20 mol of alkylene oxide is reacted at a reaction temperature of 15-13.
0 ° C., maximum reaction pressure is 9 kgf / cm ² (882 kP
a process for producing a polyetherester polyol which is reacted under the condition of a). A second object of the present invention is a method for producing a polyurethane resin, which comprises reacting the polyetherester polyol obtained for the first object with a polyol containing 2 to 100% by weight and a polyisocyanate compound.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the first reaction step will be described. Chemical formula (1) or chemical formula (2) in the present invention
The phosphazenium cation in the phosphazenium compound represented by is represented by the ultimate structural formula in which the positive charge is localized on the central phosphorus atom, Has its positive charge delocalized as a whole.

In the present invention, a in the phosphazenium cation represented by the chemical formula (1) or (2),
b, c and d are each an integer of 0 to 3. Preferably it is an integer of 0 to 2. However, in all cases, all are not simultaneously 0. More preferably, regardless of the order of a, b, c and d, (2,1,1,1), (1,
(1,1,1), (0,1,1,1), (0,0,1,
1) or a number in the combination of (0,0,0,1). More preferably, (1,1,1,1), (0,
1,1,1), (0,0,1,1) or (0,0,
(0, 1).

In the present invention, R in the phosphazenium cation represented by the chemical formulas (1) and (2) is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms. R is, for example, methyl, ethyl, n
-Propyl, isopropyl, allyl, n-butyl, se
c-butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1
-Butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-
Methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-
It is selected from aliphatic or aromatic hydrocarbon groups such as octyl, 2-ethyl-1-hexyl, tert-octyl, nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl. Among these, an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl, 1-octyl or tert-octyl is preferable, and a methyl group or ethyl Groups are more preferred.

When two Rs on the same nitrogen atom in the phosphazenium cation combine to form a ring structure, the divalent hydrocarbon group on the nitrogen atom is 4 to 6 A divalent hydrocarbon group having a main chain composed of carbon atoms (the ring is a 5- to 7-membered ring containing a nitrogen atom), preferably, for example, tetramethylene, pentamethylene or hexamethylene; These are those whose main chains are substituted by an alkyl group such as methyl or ethyl. More preferably, it is a tetramethylene or pentamethylene group. Such a ring structure may be employed for all possible nitrogen atoms in the phosphazenium cation, or a part thereof may be employed.

In the present invention, T ^r- in the chemical formula (1) represents an inorganic anion having a valence of r. And r is an integer of 1 to 3. Such inorganic anions include, for example, boric acid, tetrafluoroboric acid, hydrocyanic acid, thiocyanic acid, hydrofluoric acid, hydrohalic acid such as hydrochloric acid or hydriodic acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid Inorganic anions such as acids, hexafluorophosphoric acid, carbonic acid, hexafluoroantimonic acid, hexafluorothallic acid and perchloric acid are included. In addition, H as an inorganic anion
SO ₄ ^-, HCO ₃ ^- in some cases.

In some cases, these inorganic anions can be exchanged with each other by an ion exchange reaction. Among these inorganic anions, anions of inorganic acids such as boric acid, tetrafluoroboric acid, hydrohalic acid, phosphoric acid, hexafluorophosphoric acid and perchloric acid are preferred, and chlorine anions are more preferred. Regarding the synthesis of the salt of the phosphazenium cation represented by the chemical formula (1) and the inorganic anion of the present invention, the following method is mentioned as a general example. (A) One equivalent and three equivalents of a disubstituted amine (HN
R ₂ ) and 1 equivalent of ammonia, and then treated with a base to give a compound of the formula (3)

[0016]

Embedded image 2,2,2-tris (disubstituted amino) -2λ represented by
Synthesize ⁵ -phosphazene. (B) This phosphazene compound (chemical formula (3)) and bis (disubstituted amino) phosphorochloridate {(R
₂ N) of ₂ P (O) a Cl} are reacted to obtain bis (disubstituted amino) tris (disubstituted amino) phosphoranylideneamino Rani isopropylidene-amino phosphine oxide was chlorinated with phosphorus oxychloride, then reacting this with ammonia After treatment with a base, the compound of formula (4)

[0017]

Embedded image To obtain 2,2,4,4-pentakis (disubstituted amino) -2λ ⁵ , 4λ ⁵ -phosphazene. (C) The phosphazene compound (chemical formula (4)) is used in place of the phosphazene compound (chemical formula 3) used in (b) and reacted by the same operation as in (b) to obtain a compound of formula (5)

[0018]

Embedded image (In the formula, q represents an integer of 0 and 1 to 3. When q is 0, it is a disubstituted amine, when 1 is a compound of formula (3), when 2 is 2, a compound of formula (4) and In the case of 3, the oligophosphazene in which q is 3 among the compounds represented by (c) represents the oligophosphazene obtained in (c). (D) reacting the compounds of formula (5) of different q and / or R sequentially or simultaneously with the same compounds of formula (5) of the same q and R with phosphorus pentachloride in 4 equivalents to obtain the compound of formula (1) r = 1, in) T ^r- = Cl ^- salt with the desired phosphazenium cation and chlorine anion is obtained. When it is desired to obtain a salt of an inorganic anion other than a chloride anion, ion exchange is performed by a usual method, for example, a method of treating with a salt of an alkali metal cation and a desired inorganic anion or a method of using an ion exchange resin. be able to. Thus, a salt of a general phosphazenium cation represented by the chemical formula (1) and an inorganic anion is obtained.

An alkali metal or alkaline earth metal salt of an active hydrogen compound coexisting with the chemical formula (1) is obtained by dissociating active hydrogen of the active hydrogen compound as a hydrogen ion and replacing it with an alkali metal or alkaline earth metal ion. It is a salt in the form. As the active hydrogen compound which gives such a salt, dihydric or higher alcohols, phenol compounds, polyamines, alkanolamines and the like are preferable. For example, water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol And dihydric alcohols such as 1,4-cyclohexanediol, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Polyhydric alcohols, glucose, sorbitol,
Saccharides such as dextrose, fructose, sucrose, methylglucoside or derivatives thereof, fatty acid amines such as ethylenediamine, di (2-aminoethyl) amine, hexamethylenediamine, aromatic amines such as toluylenediamine, diphenylmethanediamine, bisphenol A And phenol compounds such as bisphenol F, bisphenol S, novolak, resole, and resorcinol. These active hydrogen compounds can be used in combination of two or more. Further, a compound obtained by addition polymerization of an alkylene oxide to these active hydrogen compounds by a conventionally known method in an amount of about 2 to 8 mol per equivalent of an active hydrogen group can also be used.

In order to obtain an alkali metal or alkaline earth metal salt from these active hydrogen compounds, the active hydrogen compound and a metal selected from alkali metals or alkaline earth metals or a basic alkali metal or A usual method of reacting with a compound of an alkaline earth metal is used. Examples of the metal selected from alkali metals or alkaline earth metals include lithium metal, sodium metal, potassium metal, cesium metal, rubidium metal, magnesium metal, calcium metal, strontium metal, and metal barium, and the like. As the alkali metal or alkaline earth metal compound,
Amides of alkali metals or alkaline earth metals such as sodium amide, potassium amide, magnesium amide or barium amide; n-propyl lithium, n-butyl lithium, vinyl lithium, cyclopentadienyl lithium, ethynyl sodium, n- Butyl sodium, phenyl sodium, cyclopentadienyl sodium, ethyl potassium, cyclopentadienyl potassium, phenyl potassium, benzyl potassium, diethyl magnesium, ethyl isopropyl magnesium,
Organic alkalis such as di-n-butylmagnesium, di-tert-butylmagnesium, vinylmagnesium bromide, phenylmagnesium bromide, dicyclopentadienylmagnesium, dimethylcalcium, potassium acetylide, ethylstrontium bromide, and phenylbarium iodide A metal or alkaline earth metal compound, sodium hydride, potassium hydride, a hydride compound of an alkali metal or alkaline earth metal such as calcium hydride, sodium hydroxide, potassium hydroxide,
Lithium hydroxide, rubidium hydroxide, cesium hydroxide,
Magnesium hydroxide, calcium hydroxide, alkali metal or alkaline earth metal hydroxides such as strontium hydroxide or barium hydroxide, lithium carbonate,
Alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate and barium carbonate, and hydrogencarbonate such as potassium hydrogencarbonate, sodium hydrogencarbonate and cesium hydrogencarbonate Salt and the like.

A metal selected from these alkali metals or alkaline earth metals or a compound of a basic alkali metal or alkaline earth metal is selected according to the acidity of the active hydrogen compound. The alkali metal or alkaline earth metal salt of the active hydrogen compound thus obtained acts as a basic alkali metal or alkaline earth metal compound, and the other active hydrogen compound is converted to the alkali metal or alkaline earth metal. In some cases, it can be converted into a salt of a class of metals.

In the active hydrogen compound having a plurality of active hydrogens, all of the active hydrogens are eliminated to form a metal selected from alkali metals or alkaline earth metals or a basic alkali metal or alkaline earth metal. In some cases, the compound leads to an anion, but in some cases, only a part of the compound is eliminated to become an anion. Of these alkali metal or alkaline earth metal salts of active hydrogen compounds, alkali metal salts of active hydrogen compounds are preferred, and the cation of the alkali metal salt of the active hydrogen compound is lithium, sodium, potassium, rubidium or cesium. The cation chosen is more preferred.

The alkylene oxide is subjected to addition polymerization in the presence of a salt of a phosphazenium cation represented by the chemical formula (1) and an inorganic anion and an alkali metal or alkaline earth metal salt of an active hydrogen compound. At this time, a salt of a cation of an alkali metal or an alkaline earth metal and an inorganic anion is by-produced. If the by-product salt inhibits the polymerization reaction, the salt is removed by a method such as filtration prior to the polymerization reaction. You can keep it. Further, a phosphazenium salt of an active hydrogen compound derived from a salt represented by the chemical formula (1) and an alkali metal or alkaline earth metal salt of the active hydrogen compound is previously isolated, and the alkylene oxide is polymerized in the presence of the phosphazenium salt. You can also.

As a method for previously obtaining the phosphazenium salt of the active hydrogen compound, a salt represented by the chemical formula (1) is reacted with an alkali metal or alkaline earth metal salt of the active hydrogen compound. The use ratio of the salt is not particularly limited as long as the desired salt is formed, and there is no particular problem even if any salt is excessive. Usually, the amount of the alkali metal or alkaline earth metal salt of the active hydrogen compound to be used is 0.2 to 5 equivalents, preferably 0 to 1 equivalent of the salt of the phosphazenium cation and the inorganic anion. 0.5 to 3 equivalents, more preferably 0.7 to
It is in the range of 1.5 equivalents.

It is also possible to use a solvent to make the contact between them effective. Any solvent may be used as long as it does not inhibit the reaction. Examples thereof include water, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, n-pentane, n-hexane and cyclohexane. Aliphatic or aromatic hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as dichloromethane, chloroform, bromoform, carbon tetrachloride, dichloroethane, orthodichlorobenzene, ethyl acetate, methyl propionate or benzoic acid Esters such as methyl, diethyl ether, tetrahydrofuran,
Ethers such as 1,4-dioxane, ethylene glycol dimethyl ether or triethylene glycol dimethyl ether, nitriles such as acetonitrile or propionitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide or 1,3 Polar aprotic solvents such as -dimethyl-2-imidazolidinone. These solvents are selected depending on the chemical stability of the raw material salt used in the reaction. Preferably, aromatic hydrocarbons such as benzene, toluene or xylene, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane or ethylene glycol dimethyl ether, nitriles such as acetonitrile, N, N -Dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide or 1,3-dimethyl-
Polar aprotic solvents such as 2-imidazolidinone; The solvents may be used alone or in combination of two or more. It is preferable that the raw material salt is dissolved, but it may be in a suspended state. The temperature of this reaction is not uniform depending on the kind, amount and concentration of the salt used, but is usually 150 ° C. or lower, preferably −78 to 80 ° C., more preferably 0 ° C.
~ 50 ° C. The reaction pressure can be reduced, normal pressure or increased pressure, preferably 0.1 to 10 k
gf / cm ² (absolute pressure, the same applies hereinafter to 9.8 to 980 kP
a), more preferably 1 to 3 kgf / cm ² (9
8 to 294 kPa). The reaction time is usually 1
Minutes to 24 hours, preferably 1 minute to 10 hours, more preferably 5 minutes to 6 hours.

When isolating the target phosphazenium salt of the active hydrogen compound from the reaction solution, a conventional method combining conventional means is used. The method is not uniform depending on the type of the target salt, the type and excess ratio of the salt of the two raw materials used, the type and amount of the solvent used, and the like. Usually, the by-product salt of an alkali metal or alkaline earth metal cation and an inorganic anion is precipitated as a solid, so it is used as it is or after a slight concentration, and then subjected to solid-liquid separation by filtration or centrifugation. Then, this is removed, and the liquid is concentrated to dryness to obtain a target salt. If the by-produced salt is still dissolved after concentration, a poor solvent is added as it is or after concentration to precipitate either the by-produced salt or the target salt, or after concentration to dryness, one is extracted. It can be separated by such a method. When the salt of the raw material used in excess is mixed in a large amount with the target salt, the salt can be extracted as it is or after redissolution with another suitable solvent, and separated. Further, if necessary, it can be purified by recrystallization or column chromatography. The desired salt is usually obtained as a high viscosity liquid or solid.

The alkylene oxide is subjected to addition polymerization in the presence of a salt of a phosphazenium cation represented by the chemical formula (1) and an inorganic anion and an alkali metal or alkaline earth metal salt of an active hydrogen compound. At this time,
An active hydrogen compound of the same or different type as the active hydrogen compound constituting the alkali metal or alkaline earth metal salt of the active hydrogen compound or the phosphazenium salt of the active hydrogen compound derived therefrom may be present in the reaction system. When the salt is present, the amount thereof is not particularly limited, but is 1 × 10 ^{−15 to} 5 × 1 with respect to 1 mol of the alkylene oxide.
0 ^-1 mol, preferably in the range of 1 × 10 ^-7 to 1 × 10 ^-1 mol.

In another case of the method for producing the polyoxyalkylene polyol of the present invention, that is, the chemical formula (2)
The case where a polyoxyalkylene polyol is produced by addition-polymerizing an alkylene oxide in the presence of a phosphazenium compound represented by and an active hydrogen compound will be described. Q ⁻ in the phosphazenium compound represented by the chemical formula (2) is a hydroxy anion, an alkoxy anion,
An anion selected from the group consisting of an aryloxy anion and a carboxy anion.

[0029] These Q ^- of, preferably, hydroxy anions, such as methanol, ethanol,
An alkoxy anion derived from an aliphatic alcohol such as n-propanol and isopropanol, for example, an aryloxy anion derived from an aromatic hydroxy compound such as phenol and cresol, and a carboxy derived from formic acid, acetic acid, propionic acid, etc. Is an anion.

Of these, hydroxy anions such as alkoxy anions derived from low boiling alkyl alcohols such as methanol, ethanol and n-propanol, and carboxy anions derived from carboxylic acids such as formic acid and acetic acid are more preferred. More preferred are a hydroxy anion, a methoxy anion, an ethoxy anion and an acetate anion. These phosphazenium compounds may be used alone or as a mixture of two or more.

As a general method for synthesizing the phosphazenium compound represented by the chemical formula (2), first, in the same manner as the method for synthesizing the salt represented by the chemical formula (1), r = 1 , A phosphazenium chloride wherein T ^r− = Cl ⁻ is synthesized. Then, the phosphazenium chloride is treated with a hydroxide, alkoxide, aryloxide or carboxide of, for example, an alkali metal or an alkaline earth metal, or a method using an ion exchange resin to convert the chloride anion into the desired anion Q. ^-
Can be replaced by Thus, a general phosphazenium compound represented by the chemical formula (2) is obtained.

The active hydrogen compound coexisting with the chemical formula (2) is the same as that described in detail above as the active hydrogen compound which gives the alkali metal or alkaline earth metal salt of the active hydrogen compound.

In the method of the present invention in which an alkylene oxide is addition-polymerized in the presence of a phosphazenium compound represented by the chemical formula (2) and an active hydrogen compound, the excess of the active hydrogen compound usually used in excess remains as it is. In addition, water, alcohol, aromatic hydroxy compound or carboxylic acid is by-produced depending on the type of phosphazenium compound. If necessary, these by-products are removed prior to the addition polymerization reaction of the alkylene oxide. Depending on the physical properties of these by-products, conventional methods such as a method of distilling off by heating or reduced pressure, a method of passing an inert gas, and a method of using an adsorbent are used.

The alkylene oxide to be addition-polymerized to the active hydrogen compound in the presence of the phosphazenium compound includes propylene oxide, ethylene oxide,
2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide,
Epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether and the like can be mentioned. These may be used in combination of two or more. Of these, propylene oxide, 1,2-butylene oxide and ethylene oxide are preferred. Particularly preferred are propylene oxide and ethylene oxide.

In the production of the crude polyoxyalkylene polyol in the present invention, the following conditions need to be selected. That is, the phosphazenium compound represented by the chemical formula (1) or (2) per mol of the active hydrogen compound is 5 × 10 ^-5 to 1 × 10 ^-1 mol, preferably 1 × 10 ^{-4 to} 5 × 10 ^-1. Mole, more preferably 1 × 10
^-3 to 8 × 10 ^-2 mol. When increasing the molecular weight of the polyoxyalkylene polyol, it is preferable to increase the concentration of the phosphazenium compound relative to the active hydrogen compound within the above range. When the amount of the phosphazenium compound represented by the chemical formula (1) or the chemical formula (2) is lower than 5 × 10 ⁻⁵ mol per mol of the active hydrogen compound, the polymerization rate of the alkylene oxide decreases, and Manufacturing time is longer. When the amount of the phosphazenium compound represented by the chemical formula (1) or (2) is more than 1 × 10 ⁻¹ mol per 1 mol of the active hydrogen compound, the cost of the phosphazenium compound in the production cost of the polyetherester polyol increases.

The reaction temperature of the alkylene oxide is in the range of 15 to 130 ° C., preferably 40 to 120 ° C., and more preferably 50 to 110 ° C. When the reaction temperature of the alkylene oxide is lower than the above range, the concentration of the phosphazenium compound with respect to the active hydrogen compound is preferably increased within the range described above. A method for supplying an alkylene oxide to an active hydrogen compound catalyzed by a phosphazenium compound charged in a pressure-resistant reactor,
A method in which a required amount of alkylene oxide is partially supplied, or a method in which alkylene oxide is supplied continuously or intermittently is used. In a method in which a part of the required amount of alkylene oxide is supplied collectively, a method in which the reaction temperature at the beginning of the alkylene oxide polymerization reaction is set to a lower temperature within the above range and the reaction temperature is gradually increased after charging the alkylene oxide is preferable. . When the reaction temperature is lower than 15 ° C., the polymerization rate of the alkylene oxide decreases, and the production time of the polyoxyalkylene polyol increases. When the reaction temperature exceeds 130 ° C., when propylene oxide is used as the alkylene oxide, the content of by-product monols increases.

The maximum pressure during the reaction of the alkylene oxide is preferably 9 kgf / cm ² (882 kPa, absolute pressure, the same applies hereinafter). Usually, the reaction of alkylene oxide is carried out by a pressure-resistant reactor. The reaction of the alkylene oxide may be started from a reduced pressure state or from an atmospheric pressure state. When starting the reaction from atmospheric pressure,
It is desirable to carry out the reaction in the presence of an inert gas such as nitrogen or helium. Maximum reaction pressure of alkylene oxide is 9k
If it exceeds gf / cm ² (882 kPa), the amount of by-product monol increases. Preferably 7 kg as maximum reaction pressure
f / cm ² (686 kPa), more preferably 5 kgf
/ Cm ² (490 kPa). When propylene oxide is used as the alkylene oxide, the maximum reaction pressure is preferably 5 kgf / cm ² (490 kPa).

In the alkylene oxide addition polymerization reaction, a solvent can be used if necessary. As the solvent when used, for example, pentane, hexane, aliphatic hydrocarbons such as peptane, tetrahydrofuran, ethers such as dioxane or dimethyl sulfoxide,
Aprotic polar solvents such as N, N-dimethylformamide; When a solvent is used, a method of collecting and reusing the solvent after the production is desirable in order not to increase the production cost of the polyoxyalkylene polyol.

The hydroxyl value (hereinafter abbreviated as OHV) of the crude polyoxyalkylene polyol produced by the above-mentioned method is from 8 to 550 mgKOH / g. Preferably, it is 15 to 400 mgKOH / g, more preferably 20 to 250 mgKOH / g. OHV is 8mgK
When it is smaller than OH / g, the viscosity of the polyetherester polyol obtained by reacting the carboxylic anhydride with the alkylene oxide increases. OHV is 550mgKOH /
When it is larger than g, when the polyetherester polyol is used for flexible urethane foam, the adhesiveness to the fibrous base material, which is a characteristic of the polyetherester polyol, tends to decrease.

The above-mentioned polyoxyalkylene polyol has a head-to-tail bond selectivity of 95 mol% or more. When the head-to-tail bond selectivity is less than 95 mol%, the viscosity of the polyoxyalkylene polyol tends to increase. Further, the total unsaturation, which is an index of the monol content in the polyoxyalkylene polyol, is 0.07 meq. / G is preferred.

Next, the second reaction step will be described.
The polyetherester polyol is produced by reacting the above-mentioned crude polyoxyalkylene polyol with a polycarboxylic anhydride and an alkylene oxide. As the polycarboxylic acid anhydride, aliphatic, alicyclic and aromatic polycarboxylic acid anhydrides are used, and aromatic polycarboxylic acid anhydrides are particularly preferable. Such polycarboxylic anhydrides include, for example, succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride and the like. Acids are most preferred.
These acids can be used alone or in combination of two or more. The polycarboxylic anhydride is used in an amount of 1 to 80 parts by weight based on 100 parts by weight of the crude polyoxyalkylene polyol. If the amount of the polycarboxylic acid anhydride is less than 1 part by weight, the effect of ester modification with the polyurethane resin cannot be obtained. If the amount of the polycarboxylic acid anhydride is more than 80 parts by weight, the viscosity of the mixture of the crude polyoxyalkylene polyol and the polycarboxylic acid anhydride becomes high, and the production of the polyetherester polyol becomes difficult.

The amount of the alkylene oxide to be reacted with the polycarboxylic anhydride is 0.3 to 20 mol per 1 mol of the polycarboxylic anhydride. Preferably 0.
It is in the range of 8 to 15 moles, more preferably in the range of 1.0 to 12 moles. When the amount of the alkylene oxide is less than 0.3 mol, the acid value of the polyetherester polyol increases, and the reactivity with the polyisocyanate compound tends to decrease. When the amount of the alkylene oxide is more than 20 mol, the characteristics of the polyetherester polyol when used for a flexible polyurethane foam are deteriorated. When producing the polyetherester polyol used for the flexible polyurethane foam, the alkylene oxide is used in an amount of 1.1 to 6 per mole of the polycarboxylic anhydride.
A molar range is preferred. As the alkylene oxide, those used in producing the above-mentioned crude polyoxyalkylene polyol are preferable.

The reaction temperature for reacting the polyoxyalkylene polyol with the polycarboxylic anhydride and the alkylene oxide is 15 to 130 ° C. Preferably,
The range is 50 to 128 ° C, more preferably 70 to 125 ° C. When the reaction temperature is lower than 15 ° C., the polymerization rate of the alkylene oxide decreases, and the production time of the polyoxyalkylene polyol increases. Reaction temperature 130
When the temperature exceeds ℃, when propylene oxide is used as the alkylene oxide, the content of by-product monol increases. The maximum reaction pressure is 9 kgf / cm ² (882 kPa,
Absolute pressure, the same applies hereinafter). Usually, the reaction between the polycarboxylic anhydride and the alkylene oxide is carried out by a pressure-resistant reactor. The reaction between the polycarboxylic anhydride and the alkylene oxide may be started from a reduced pressure state or from an atmospheric pressure state. When starting the reaction from an atmospheric pressure state, it is desirable to carry out the reaction in the presence of an inert gas such as nitrogen or helium. Maximum reaction pressure is 9kgf / cm
^If it exceeds ² (882 kPa), the amount of by-product monol increases when propylene oxide is used. The maximum reaction pressure is preferably 7 kgf / cm ² (686 kP
a), more preferably 5 kgf / cm ² (490 kP
a). When propylene oxide is used as the alkylene oxide, the maximum reaction pressure is 5 kgf.
/ Cm ² (490 kPa) is preferred.

The reaction of the polycarboxylic acid anhydride and the alkylene oxide with respect to the crude polyoxyalkylene polyol includes: (a) the addition polymerization of the alkylene oxide after the esterification reaction between the crude polyoxyalkylene polyol and the polycarboxylic anhydride. Method (hereinafter abbreviated as “sequential reaction”). (B) A method in which a polycarboxylic acid anhydride and an alkylene oxide are simultaneously charged and reacted in a crude polyoxyalkylene polyol (hereinafter, abbreviated as a simultaneous reaction). There are two methods. In the present invention, either a sequential reaction or a simultaneous reaction may be used. However, when a sequential reaction is carried out, if the esterification reaction time between the crude polyoxyalkylene polyol and the polycarboxylic anhydride becomes too long (for example, at 120 ° C. for 8 hours or more), the polyoxyalkylene by the polycarboxylic anhydride becomes too long. As the transesterification reaction between polyol molecules progresses, the molecular weight of the polyetherester polyol tends to increase, and the viscosity tends to increase.

In the above-mentioned second reaction step, an amine compound can be used as a catalyst for the purpose of shortening the reaction time. Such amine compounds include dibutylamine, dimethyloctylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dimethyloleylamine, dimethylethanolamine, tetramethylenediamine, pyridine, triethylamine, tripropylamine , Tributylamine, methyldiethylamine, N-methylmorpholine, N-ethylmorpholine and the like. Preferred are dimethyllaurylamine, dimethylpalmitylamine and triethylamine. These amine compounds may be used alone or in combination of two or more.
The amount of the amine compound used is 0.005 to 5 parts by weight based on the total charged amount of the crude polyoxyalkylene polyol, polycarboxylic anhydride and alkylene oxide.
1.5 parts by weight, preferably 0.01 to
1.0 parts by weight, more preferably in the range of 0.02 to 0.7 parts by weight.

The polyetherester polyol is produced through the first and second reaction steps described above. If the amount of the phosphazenium compound used in the first reaction step is low within the above range, the phosphazenium compound can be used as it is without performing the phosphazenium compound removal operation. The removal of the phosphazenium compound in the polyetherester polyol is carried out using at least one neutralizing agent selected from water, an inorganic acid or an organic acid (hereinafter, abbreviated as a neutralization method), carbon dioxide. And a phosphazenium compound to react with an adsorbent (hereinafter abbreviated as a carbon dioxide method), a method of removing with an adsorbent only (hereinafter abbreviated as an adsorbent treatment method), or an ion exchange resin. (Hereinafter, abbreviated as an ion exchange treatment method). Further, a method of washing with water or a mixed solvent of water and an organic solvent inert to the polyetherester polyol to remove the phosphazenium compound (hereinafter abbreviated as a water washing treatment method) can be applied. Among these methods, a neutralization treatment method and an adsorbent treatment method are preferable. The operation of removing the amine compound used in the second reaction step is performed by the above-described method. In particular, when triethylamine is used as the amine compound,
The compound has a low boiling point (boiling point 89.7 ° C./760 mmH
g (101 kPa)).
° C, 5 mmHgabs. (665 Pa) or less for 5 hours), most of which can be removed.

The neutralization method will be described. The phosphazenium compound in the polyetherester polyol is neutralized by adding at least one neutralizing agent selected from water, an inorganic acid or an organic acid at 40 to 120 ° C. As the water, industrial water, city water, ion-exchanged water, distilled water or the like is used according to the purpose. The addition amount is 0.1 to 20 parts by weight based on 100 parts by weight of the polyetherester polyol. Preferably 0.2 to
20 parts by weight, more preferably 0.5 to 15 parts by weight. If the amount of water is more than 20 parts by weight with respect to 100 parts by weight of the polyetherester polyol, it is not preferable because hydrolysis of the ester group is easily caused by water. In order to suppress the hydrolysis reaction, it is preferable to add a neutralizing agent almost simultaneously with the addition of water.

At this time, an organic solvent inert to the polyetherester polyol can be used together with water. The organic solvent inert to the polyetherester polyol includes, among hydrocarbon solvents, toluene, hexanes, pentanes, heptanes, butanes, lower alcohols, cyclohexane, cyclopentane, xylenes and the like. In order to evaporate these organic solvents from the polyoxyalkylene polyol, a method of performing heating and decompression operations may be used. The temperature is 100 ~ 140 ℃ and the degree of decompression is 10mmHg
abs. (1330 Pa) or less.

An inorganic or organic acid is used as an acid for neutralizing the phosphazenium compound. Examples of the inorganic acid include phosphoric acid, phosphorous acid, hydrochloric acid, sulfuric acid, sulfurous acid, and aqueous solutions thereof. As organic acids, for example, formic acid, oxalic acid, succinic acid, acetic acid, maleic acid,
Examples include phthalic acid, salicylic acid, malic acid and aqueous solutions thereof. Particularly preferably, sulfuric acid, phosphoric acid, hydrochloric acid,
Maleic acid and oxalic acid are preferably used in the form of an aqueous solution. These neutralizing agents can be used alone or in combination of two or more kinds. The amount of the neutralizing agent is 0.5 to 2.0 to 1 mol of the phosphazenium compound contained in the crude polyoxyalkylene polyol. 5 moles. Preferably, it is 0.7 to 2.4 mol, more preferably 0.9 to 2.3 mol. The neutralization time is 0.5 to 3 hours, depending on the reaction scale.

After the above-described neutralization treatment, the polyetherester polyol can be purified using an adsorbent according to the purpose. The amount of the adsorbent that adsorbs the acid and alkali components is 0.005 to 1.5 parts by weight based on 100 parts by weight of the polyetherester polyol. Preferably, it is 0.02 to 1.2 parts by weight, more preferably 0.03 to 1.1 parts by weight. As an adsorbent,
For example, synthetic magnesium silicate, synthetic aluminum silicate, activated clay, and acid clay are used. Since the treatment with sodium hydroxide is performed in the step of producing the adsorbent, an adsorbent with a small sodium elution content is preferable. Specific adsorbents include Tomix AD-600, Tomix AD-700 (manufactured by Tomita Pharmaceutical Co., Ltd.), Kyoward 400, Kyoward 500, Kyoward 600,
It is commercially available under various trade names such as Kyoword 700 (manufactured by Kyowa Chemical Industry Co., Ltd.). The temperature at the time of the adsorption treatment is not particularly limited, but is usually in the temperature range of 30 to 130 ° C. The adsorbent treatment method for removing the phosphazenium compound using the adsorbent alone is also performed by the above-described operation. Further, it is preferable to add an antioxidant such as t-butylhydroxytoluene (BHT) which is an antioxidant after the neutralization treatment. The antioxidant is used in an amount of 200 to 5000 pp based on 100 parts by weight of the crude polyoxyalkylene polyol.
m. Preferably it is 300-4000 ppm, More preferably, it is 350-2000 ppm.

The polyetherester polyol treated by the above-mentioned method is recovered by a filtration operation, a centrifugation operation or the like. Because polyetherester polyol has a higher viscosity than polyoxyalkylene polyol,
The polyetherester polyol during the recovery operation is 45-45
It is preferable to heat to 130 ° C.

The polyetherester polyol obtained in the present invention is reacted with a polyisocyanate compound in the presence of a foaming agent such as water, a foam stabilizer such as an organosilicon surfactant, a crosslinking agent, and other auxiliary agents. Polyurethane foam and elastomers, sealing materials, paints, adhesives, waterproof materials,
It is also applicable to polyurethane resin such as flooring and elastic fiber.

First, a method for producing a polyurethane foam will be described. In the polyols used as a raw material of the polyurethane resin of the present invention, the above-mentioned polyetherester polyol is 2 to 100% by weight, preferably 10 to 85% by weight, more preferably 20 to 60% by weight based on 100 parts by weight of the polyol. % Used. Polyol 1
If the amount of the polyetherester polyol used is less than 2% by weight based on 00 parts by weight, the effect of modifying the ester-modified polyetherester polyol is not exhibited. Examples of the polyol other than the polyetherester polyol used in the present invention include conventionally known polyoxyalkylene polyols, polymer-dispersed polyols, polytetramethylene glycol, polyester polyols, polybutadiene-based polyols, and polycarbonate-based polyols. When used for polyurethane foam, as polyols other than polyetherester polyol,
Polyoxyalkylene polyols and polymer-dispersed polyols are preferred, and the OHV of these polyols is 10 to 10.
It is in the range of 450 mg KOH / g. Among the polyurethane foams, the rigid polyurethane foam has the OH
It is preferable to use those having a high V range and those having a low V range for a flexible polyurethane foam.

The foaming agent used for producing the polyurethane foam is slightly different between the flexible polyurethane foam and the rigid polyurethane foam. In the case of producing a flexible polyurethane foam, water alone may be used as a foaming agent, but in the case of producing a rigid polyurethane foam, water, a low-boiling hydrocarbon-based compound, a hydrochlorofluorocarbon, (Hereinafter HC
Abbreviated as FC. ) Or hydrofluorocarbons (hereinafter abbreviated as HFC). Examples of the low-boiling hydrocarbon compound include cyclopentane, n-pentane, and isopentane. As HCFCs, HCFC-141b is H
FCs include HFC-134a, HFC-356 and HFC-245fa. When water alone is used as the blowing agent, it is used in an amount of 1 to 9 parts by weight based on 100 parts by weight of the polyol containing the polyetherester polyol of the present invention. When using at least one blowing agent selected from a low-boiling hydrocarbon compound, HCFCs or HFCs, it is used in an amount of 1 to 40 parts by weight based on 100 parts by weight of the polyol containing the polyetherester polyol of the present invention. . At this time, these blowing agents and water may be used in combination.

As the polyisocyanate compound used in the present invention, known compounds used in the production of aromatic, aliphatic, alicyclic and other polyurethanes having two or more isocyanate groups in one molecule can be used. . For example, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 80 of these polyisocyanate compounds
/ 20 weight ratio (hereinafter abbreviated as TDI-80 / 20), 65/35 weight ratio (hereinafter TDI-65 / 35).
Abbreviated. ), A crude tolylene diisocyanate containing a polyfunctional tar (a polyfunctional tar is a by-produced tar-like substance containing two or more isocyanate groups in the molecule). The same applies hereinafter.), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, any isomer mixture of diphenylmethane diisocyanate, and trinuclear or higher polyfunctional Diphenylmethane diisocyanate (hereinafter abbreviated as polymeric MDI) containing a neutral tar, toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, paraphenylene Isocyanate, carbodiimide modified product of norbornene diisocyanate and these polyisocyanate compounds, biuret modified products, or they polyol, a mono hydroxy compound alone, or a prepolymer can be mentioned in combination with denatured. The above-mentioned polyisocyanate compounds can be used by mixing at an arbitrary ratio.

As the catalyst, a conventionally known catalyst for producing a polyurethane such as an amine compound or an organometallic compound can be used. Examples of the amine compound include, for example, triethylamine, tripropylamine, tributylamine, N,
Organics such as N, N ′, N′-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, triethylenediamine, and salts of triethylenediamine Examples of the metal compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate. No. These catalysts can be used alone, but usually two or more kinds are used in combination. The amount of the catalyst used is 0.0001 to 10.0 parts by weight based on 100 parts by weight of the polyol.

When producing a polyurethane foam,
A foam stabilizer is required. As the foam stabilizer, a conventionally known organic silicon-based surfactant can be used. For example, L-520, L-532, L-540, L-54 manufactured by Nippon Unicar Co., Ltd.
4, L-550, L-3600, L-3601, L-5
305, L-5307, L-5309, etc., SRX-253, SRX-274C, S manufactured by Dow Corning Toray Co., Ltd.
F-2961, SF-2962, F-114, F-121, F-122, F-220 manufactured by Shin-Etsu Silicone Co., Ltd.
F-230, F-258, F-260B, F-317,
Examples include F-341, F-601, and F-606, and TFA-420 and TFA-4202 manufactured by Toshiba Silicone Co., Ltd. These foam stabilizers can be arbitrarily mixed and used. The amount of the foam stabilizer is 0.1 to 100 parts by weight of the polyol.
05 to 10 parts by weight.

In producing a flexible polyurethane foam, a crosslinking agent is usually used. Examples of the crosslinking agent include dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, and 1,4-butanediol;
Alkanolamines such as triethanolamine, diethanolamine and monoethanolamine; aliphatic amine compounds such as ethylenediamine, diethylenetriamine and triethylenetetramine; aromatics such as aniline, 2,4-tolylenediamine and 2,6-tolylenediamine OHV200 obtained by adding an aromatic alcohol such as amine, hydroquinone, resorcinol, novolak, and resol, and an alkylene oxide such as propylene oxide and ethylene oxide to these active hydrogen compounds.
800 mg KOH / g polyol.

A flame retardant is used depending on the intended use of the polyurethane foam. Tris (2-chloropropyl) phosphate, tris (dichloropropyl) as flame retardant
Phosphate, tris (dibromopropyl) phosphate, tris (2,2-chloroethyl) phosphate, hexabromocyclododecane, CR-50 manufactured by Daihachi Chemical Co.
5 and CR-507, Phos from Monsanto Chemical
agard 2XC-20 and C-22-R; , Preferably 0.2 to 20 parts by weight.

A plasticizer, a colorant, an antioxidant, an anti-scorch agent and the like can be added to the polyols according to the purpose. Further, an adhesiveness improver can be used for the purpose of improving the adhesiveness of the flexible polyurethane foam using the polyetherester polyol of the present invention to a substrate. Examples of such an adhesion improver include an organic phosphorus compound and a thermoplastic polyolefin. Compounds such as phosphates, phosphites, and pyrophosphates are exemplified, and examples thereof include tris (2,2-chloroethyl) phosphate, triphenyl phosphate, and trioctyl phosphate. These compounds also have the effect as the flame retardant exemplified above. Also,
A conventionally known polyol obtained by adding an alkylene oxide to a phosphoric acid or a phosphoric acid ester compound (Reference: plastic flammability Nobuyuki Kita Industrial Research Committee:
Abbreviated as phosphorus-containing polyol. ) Can also be used as an adhesion promoter. However, when a phosphorus-containing polyol is used, it is easily deteriorated by a hydrolysis reaction. Therefore, after mixing with a polyol containing the polyetherester polyol of the present invention, avoid contact with water and use it within at least 4 months. It is desirable. On the other hand, examples of the thermoplastic polyolefin include fine particles of polypropylene and polyethylene having a particle size of 0.1 to 10 μm. The amount of these adhesion improvers is 0.01 to 100 parts by weight of the polyol containing the polyetherester polyol of the present invention.
Use up to 20 parts by weight.

For the polyurethane foam, a liquid (hereinafter, abbreviated as “resin premix”) in which a predetermined amount of the above-mentioned auxiliary agents such as the polyol, the foaming agent, the catalyst, the foam stabilizer, and the crosslinking agent is mixed is prepared. For example, it is adjusted to a range of 20 to 30 ° C. A predetermined amount of the polyisocyanate compound is measured and adjusted to a predetermined temperature, for example, a range of 20 to 30 ° C. Usually, the amount of the polyisocyanate compound to be used is calculated from the ratio of the concentration of the isocyanate group in the polyisocyanate compound to the concentration of the active hydrogen group in the active hydrogen compound (hereinafter, abbreviated as NCO index). Thereafter, the resin premix and the polyisocyanate compound are rapidly mixed, and the resin premix and the polyisocyanate compound are injected directly into a mold whose temperature is adjusted to a predetermined temperature, for example, 20 to 70 ° C. A polyurethane foam is produced by a method of spraying and molding a mixture with an isocyanate compound.

A method for producing a polyurethane resin other than the polyurethane foam, such as an elastomer and a sealing, will be described. The following two methods can be used to produce these polyurethane resins. (C) A method of simultaneously mixing and molding a polyol containing the polyetherester polyol of the present invention, a polyisocyanate compound and a chain extender (hereinafter abbreviated as a one-shot method). (D) a method of reacting a polyol containing the polyetherester polyol of the present invention with a polyisocyanate compound to synthesize a prepolymer having an isocyanate group at a molecular terminal, and reacting the prepolymer with a chain extender to form a prepolymer (hereinafter referred to as a molding method); , Abbreviated as prepolymer method). In addition, a thermoplastic polyurethane resin is synthesized and heated and melted.
Injection molding, extrusion molding, a method of obtaining a desired molded product by calendering, or the like, a thermoplastic polyurethane resin is synthesized in a solvent, or a thermoplastic polyurethane resin is dissolved in a solvent, and a polyurethane solution is prepared. fiber,
A method of producing a polyurethane film by applying it to an iron plate or the like can be mentioned, but the basic molding method can be roughly classified into the above (c) and (d).

First, the one-shot method (c) will be described. The polyol other than the polyetherester polyol of the present invention used in the one-shot method is the same as the polyol described above. When producing urethane foam, polyoxyalkylene polyols or polymer-dispersed polyols are preferably used, but for the production of polyurethane resins other than foams, all the polyols described above can be used. However, for example, since the polyester polyol and the polytetramethylene glycol become incompatible depending on the mixing ratio, the appearance of the mixture may become cloudy. The mixing of the polyols is carried out after understanding the chemical and physical properties of each.

As the polyisocyanate compound, the polyisocyanate compound described in the above-mentioned method for producing a urethane foam is used. The chain extender is a compound having two or more active hydrogen groups capable of reacting with an isocyanate group in one molecule, and at least one of a polyol compound and a polyamine compound is used. Examples of the polyol compound include dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol; glycerin; It contains trihydric alcohols such as methylolpropane, cyclohexylene such as cyclohexanediol and spirohexanediol, a spiro ring and a methylene chain, and includes various bonds such as an ether bond and an ester bond as those linking them. Derivatives containing various substituents can be used. Further, as the polyamine compound, tolylenediamine, 3,5-diethyl-2,4-diaminotoluene,
3,5-diethyl-2,6-diaminotoluene, diphenylmethanediamine, m-phenylenediamine, 3,
Aromatic diamines such as 3′-dichloro-4,4′-diaminodiphenylmethane and diethyltoluenediamine;
Conventionally known polyamine compounds such as aliphatic, alicyclic diamines such as isophorone diamine and norbornene diamine, linear aliphatic diamines, alkyl dihydrazides such as carbodihydrazide and adipic dihydrazide, and derivatives thereof can be used. Further, polyols obtained by adding an alkylene oxide to these active hydrogen compounds by a conventionally known method can also be used as a chain extender.

The above-mentioned polyol, polyisocyanate compound and chain extender are rapidly mixed, subjected to defoaming under reduced pressure, and poured into a mold heated to a predetermined temperature, for example, 40 to 130 ° C. to prepare a molded product. At this time, a curing catalyst, a filler, a plasticizer, a dye / pigment, a reinforcing agent, a flame retardant, a stabilizer and the like can be used according to the purpose. The catalyst described above can be used as the polyurethane curing catalyst. The amount used is 0.01 to 4.0 parts by weight, preferably 0.03 to 2.0 parts by weight, per 100 parts by weight of the polyol containing the polyetherester polyol of the present invention.

As the filler, fumed silica, silica, silicic acid, carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, talc, titanium oxide, bentonite, ferric oxide, hydrogenated castor oil,
Zinc stearate and the like, and the amount of the polyol 1 containing the polyetherester polyol of the present invention
2 to 60% by weight, preferably 10 to 100% by weight
50% by weight.

As the plasticizer, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, butyl benzyl phthalate, butyl phthalyl butyl glycolate,
Dioctyl sebacate, tricresyl phosphate, tributyl phosphate, chlorinated paraffin, petroleum ether and the like, the amount of addition of which is 1 to 40 parts by weight, preferably 100 parts by weight of the polyol containing the polyetherester polyol of the present invention, preferably Is 5 to 15 parts by weight.

Examples of the reinforcing agent include black filler carbon black, white filler white carbon and silica, silicates such as kaolin, bentonite, anhydrous fine silica, barite, gypsum, bone powder, and dolomite. Is 1 to 50 with respect to 100 parts by weight of the polyol containing the polyetherester polyol of the present invention.
% By weight, preferably 2 to 30% by weight.

As the flame retardant, the compounds exemplified above can be used. The amount used is 0.0 to 100 parts by weight of the polyol containing the polyetherester polyol of the present invention.
It is 5 to 30 parts by weight, preferably 0.2 to 20 parts by weight.

Examples of the stabilizer include an antioxidant, an ultraviolet absorber, a heat stabilizer and the like. The antioxidant is not particularly limited. For example, butylhydroxyanisole, t
-Butylhydroxytoluene, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-
Hydroxybenzyl) benzene, 3,9-bis [2- [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl]
-2,4,8,10-tetraoxaspiro (5,5) undecane, distearylthiodipropionate and the like. Examples of the ultraviolet absorber include pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like. As a heat stabilizer, Tris (2, 4
-Di-t-butylphenyl) phosphite, triphenyl phosphite, trilauryl phosphite and the like. The amount of these additives is preferably 100 to 8000 ppm with respect to 100 parts by weight of the polyol containing the polyetherester polyol of the present invention. In the present invention, a pigment, the above-mentioned organic solvent, a water removing agent and the like can be used according to the purpose.

Next, the prepolymer method (d) will be described. As the polyisocyanate compound used in the present invention, the compounds exemplified above are used. Prepolymer (hereinafter,
It is called an isocyanate group-terminated prepolymer. )), The NCO index is from 1.3 to 20.0,
Preferably 1.4 to 12.0, more preferably 1.5
９9.0.

The isocyanate group-terminated prepolymer has a free isocyanate group content (hereinafter abbreviated as NCO%) of 0.1 to 40.0% by weight, preferably 0.3% by weight.
~ 25.0% by weight, more preferably 0.4 ~ 18.0.
% By weight. The isocyanate group-terminated prepolymer used in the one-pack type curable composition obtained by using water in the air as a curing agent has a low NCO% and glycols such as 1,4-butanediol and polyoxyalkylene polyol; The isocyanate group-terminated prepolymer used in a two-part curable composition using a polyamine compound such as'-dichloro-4,4'-diaminodiphenylmethane as a curing agent has a higher NCO% than that of a one-part type. You.

The temperature at the time of producing the isocyanate group-terminated prepolymer is preferably from 50 to 120 ° C. Particularly preferably, it is 70 to 105 ° C. At the time of the reaction, it is desirable to carry out the reaction in the presence of an inert gas in order to avoid contact with moisture in the air. Examples of the inert gas include nitrogen and helium, and nitrogen is preferable. The reaction is carried out with stirring under a nitrogen atmosphere for 2 to 20 hours. A catalyst may not be used, but when it is used, the above-mentioned amine compound or organometallic compound can be used. These catalysts can be arbitrarily mixed and used. Among these catalysts,
Organometallic catalysts are preferred, and the amount used is 0.0001 to 2.0 parts by weight, preferably 0.01 to 1.0 part by weight, based on 100 parts by weight of the polyol containing the polyetherester polyol of the present invention. is there.

In preparing the isocyanate group-terminated prepolymer, an organic solvent which is inert to the polyisocyanate compound or the polyol before or after the reaction can be used. The amount of the organic solvent is at most 40% by weight, preferably at most 20% by weight, based on the total weight of the polyol and the polyisocyanate compound. As such a solvent, aromatic, aliphatic, alicyclic, ketone, ester and ester ether solvents can be used. For example,
Toluene, xylenes, hexanes, cyclohexane,
Methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and the like.

The isocyanate group-terminated prepolymer includes:
Fillers, plasticizers, flame retardants, stabilizers and the like can be blended. These auxiliaries use those described above. It is preferable that the curing catalyst is blended with the chain extender exemplified above. When molding a polyurethane resin by the prepolymer method,
To the isocyanate group-terminated prepolymer blended with an auxiliary according to the purpose, a chain extender blended with a curing catalyst according to the purpose is rapidly mixed, and the mixture is degassed under reduced pressure, and is heated to a predetermined temperature, for example, 30 to 130 ° C. Injection into a heated mold and molding,
Alternatively, it is carried out by a method of reacting an isocyanate group-terminated prepolymer applied to a substrate with moisture in the air to obtain a cured product.

[0076]

EXAMPLES Examples and comparative examples of the present invention are shown below.
Embodiments of the present invention will be clarified, but the present invention is not limited to these embodiments.

Hydroxyl value (abbreviated as OHV: unit mgKOH / g) and viscosity (abbreviated as η: unit mPa · s / 25 ° C.) of the polyoxyalkylene polyol and the polyetherester polyol of Examples and Comparative Examples. And pH were determined by the method described in JIS K 1557.

In the synthesis of the polyetherester polyol, the following phosphazenium compounds were used as alkylene oxide catalysts. A phosphazenium compound (hereinafter abbreviated as P5NMe2OH);
Tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride {[(Me ₂
N) ₃ P = N] ₄ P ⁺ Cl ⁻ ｝ is converted to MILLI-QLabo
A 2.5% by weight aqueous solution was prepared using water (hereinafter, abbreviated as ultrapure water) adjusted to have a specific resistance of 16 MΩ-cm using a (compact ultrapure water device manufactured by Japan Millipore Limited). Next, an ion-exchange resin Levatit MP-500 in which the exchange group was converted to a hydroxyl group with a 1N aqueous sodium hydroxide solution.
A 2.5-inch tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride was placed in a polycarbonate cylindrical column packed with (manufactured by Bayer AG).
Weight% aqueous solution at 23 ° C., SV (Space Veloc)
At 0.7 (1 / hr), the solution was passed through the column from the bottom of the column in ascending flow, and ion exchange was performed with tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide. Further, ultrapure water was passed through the column filled with the ion exchange resin, and the phosphazenium compound remaining in the column was recovered. Then tetrakis
[Tris (dimethylamino) phosphoranylideneamino]
An aqueous solution of phosphonium hydroxide is heated at 80 ° C. under a reduced pressure of 6 ° C.
0 mmHgabs. (7980 Pa) for 2 hours, at 80 ° C., 1 mmHgabs. (133 Pa) for 7 hours under reduced pressure to obtain powdered tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me ₂ N) ₃ P
^{_{= N] 4 P + OH -}} } was obtained. The yield determined by weight measurement of the compound after drying was 97%. Using tetramethylsilane with deuterated dimethylformamide solution as internal standard ¹
The chemical shift of H-NMR (400 MHz NMR, manufactured by JEOL) was 2.6 ppm (d, J = 9.9 Hz, 72H). Elemental analysis values were C 38.28, H 9.82,
N 29.43, P 19.94 (theoretical C 38.0
9, H 9.72, N 29.61, P 20.46)
Met. In the chemical formula (2), the phosphazenium compound is represented by (1,1,1,1) in the order of a, b, c, and d,
There is a methyl group, Q ^- is a hydroxy anion ^- is OH.

For the purpose of shortening the reaction time of the crude polyoxyalkylene polyol with the polycarboxylic anhydride and alkylene oxide, triethylamine (special grade of Wako Pure Chemical Reagent) was used. Comparative examples include USP 5,144,
093 (column 4, line 52 to column 5, line 4), a double metal cyanide complex (Zn ₃ [Co (CN)
_{6] 2 · 2.48DME · 4.65H 2} O · 0.94ZnC
l ₂ ; hereinafter abbreviated as DMC. DME is an abbreviation for dimethoxyethane. ) Was used as a catalyst to synthesize a polyetherester polyol.

The synthesis result of the polyetherester polyol will be described below in detail. A crude polyoxyalkylene polyol and a polyetherester polyol are synthesized using a pressure-resistant autoclave having an internal volume of 1.0 L and 2.5 L equipped with a stirrer, a thermometer, a pressure gauge, a nitrogen inlet, and an alkylene oxide inlet as a monomer. (Manufactured by Nitto Koatsu) was used. Hereinafter, the synthesis device is abbreviated as an autoclave.

Example 1 Polyetherester polyol A 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
of a glycerin per mole of 0.0
12 mol of P5NMe2OH and 0.03 mol of toluene (special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.) were added, and nitrogen was introduced through a capillary tube. (1330
Pa) Thereafter, dehydration under reduced pressure and toluene removal for 4 hours were performed. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen.
0 ° C and the maximum pressure during the reaction is 4.0 kgf / cm
² OHV 84.1 mg KOH under the condition of (392 kPa)
/ G until propylene oxide was added. 1 when there is no change in the internal pressure of the autoclave
05 ° C, 5 mmHgabs. (665 Pa),
Vacuum treatment was performed for 20 minutes to obtain a crude polyoxyalkylene polyol. With respect to 100 parts by weight of the crude polyoxyalkylene polyol, 36.5 parts by weight of phthalic anhydride (manufactured by Mitsui Toatsu Chemicals, Inc .; hereinafter, similar products were used) and 0.3 part by weight of triethylamine were used. In addition,
After the temperature was raised to 115 ° C., 1.2 mol of propylene oxide was added to the internal temperature of 115 mol per mol of phthalic anhydride used.
° C, the maximum pressure during the reaction is 4.0 kgf / cm ² (392k
Pa). After reacting at the same temperature for 6 hours, 105 ° C., 5 mmHgabs. (665 Pa), a reduced pressure treatment was performed for 50 minutes to obtain a polyetherester polyol. 2.01 mol of phosphoric acid (in the form of a 75.2% by weight phosphoric acid aqueous solution) is added to 1 mol of the phosphazenium compound in the polyetherester polyol, and a neutralization reaction is performed at 80 ° C. for 0.5 hour. Was. After completion of the neutralization reaction, t-butylhydroxytoluene (BHT)
Was added to 100 parts by weight of polyetherester polyol, dehydration was performed under reduced pressure, and the pressure in the autoclave was 400 mmHgabs. (53kP
In the state of a), 5000 ppm of KW-300 (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added. Furthermore, while dehydrating under reduced pressure, finally 105 ° C., 10 mmHgabs. (1
The same operation was performed for 3 hours under the following conditions. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to recover polyetherester polyol. The hydroxyl value (OHV) of the polyetherester polyol after the purification operation is 5
9.2 mgKOH / g, viscosity (η) 15,500 mPa
-PH was 6.4 at s / 25 ° C.

Example 2 Polyetherester polyol B 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
of a glycerin per mole of 0.0
18 mol of P5NMe2OH and 0.06 mol of toluene (special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.) were added, nitrogen was introduced through a capillary tube, and 105 ° C., 10 mmHgabs. (1330
Pa) Thereafter, dehydration under reduced pressure and toluene removal for 4 hours were performed. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen.
0 ° C and the maximum pressure during the reaction is 4.0 kgf / cm
² OHV 112.2 mg KO under the condition of (392 kPa)
The addition polymerization of propylene oxide was performed until H / g was reached. When the internal pressure of the autoclave is no longer changed, 105 ° C., 5 mmHgabs. (665 Pa) under reduced pressure for 20 minutes to obtain a crude polyoxyalkylene polyol. 51.3 parts by weight of phthalic anhydride and 0.2 parts by weight of triethylamine were added to 100 parts by weight of the crude polyoxyalkylene polyol to give 1 part by weight.
After the temperature was raised to 15 ° C., 2.45 mol of propylene oxide was added to the internal temperature of 115 mol per mol of phthalic anhydride used.
° C, the maximum pressure during the reaction is 5.5 kgf / cm ² (539 k
Pa). After reacting at the same temperature for 7 hours, 105 ° C., 5 mmHgabs. (665 Pa) under reduced pressure for 1 hour to obtain a polyetherester polyol. 1.95 mol of phosphoric acid (in the form of a 75.2% by weight phosphoric acid aqueous solution) was added to 1 mol of the phosphazenium compound in the polyetherester polyol, and a neutralization reaction was performed at 80 ° C. for 2 hours. After completion of the neutralization reaction, 10 parts by weight of t-butylhydroxytoluene (BHT) was added to 100 parts by weight of the polyetherester polyol.
00 ppm, dehydrated under reduced pressure, and the pressure in the autoclave was 400 mmHgabs. AD-600 (manufactured by Tomita Pharmaceutical Co., Ltd.) at a pressure of (53 kPa)
5000 ppm was added. Furthermore, while dehydrating under reduced pressure, finally 105 ° C., 10 mmHgabs. (1330P
a) The same operation was performed for 4 hours under the following conditions. Then, a 5C filter paper (retained particle size 1) manufactured by Advantech Toyo Co., Ltd.
μ), filtration under reduced pressure was performed to recover the polyetherester polyol. The hydroxyl value (OHV) of the polyetherester polyol after the purification treatment operation is 58.2 m.
gKOH / g, viscosity (η) 14,800 mPa · s / 2
At 5 ° C. the pH was 5.9.

Example 3 500 m equipped with a polyetherester polyol C stirrer, a nitrogen inlet tube and a thermometer
of a glycerin per mole of 0.0
27 mol of P5NMe2OH and 0.1 mol of toluene (special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.) were added, and nitrogen was introduced through a capillary tube. (1330
Pa) Thereafter, dehydration under reduced pressure and toluene removal for 4 hours were performed. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen.
0 ° C and the maximum pressure during the reaction is 4.0 kgf / cm
² OHV 91.5 mgKOH under the condition of (392 kPa)
/ G until propylene oxide was added. Subsequently, the gauge pressure is 1.2 kgf / cm with nitrogen.
² (219 kPa), and addition polymerization of ethylene oxide was carried out under the conditions of a reaction temperature of 105 ° C. and a maximum pressure during the reaction of 5 kgf / cm ² (490 kPa) until the OHV reached 84.1 mgKOH / g. When the internal pressure of the autoclave is no longer changed, the temperature is 105 ° C and 5 mmHgab.
s. (665 Pa) under reduced pressure for 40 minutes to obtain a crude polyoxyalkylene polyol. 36.5 parts by weight of phthalic anhydride was added to 100 parts by weight of the crude polyoxyalkylene polyol, the temperature was raised to 115 ° C., and 1.39 to 1 mol of phthalic anhydride used.
Mole of propylene oxide was charged under the conditions of an internal temperature of 115 ° C. and a maximum pressure of 4.5 kgf / cm ² (441 kPa) during the reaction. After reacting at the same temperature for 6 hours, 105 ° C,
5 mmHgabs. (665 Pa) under reduced pressure for 1 hour to obtain a polyetherester polyol. 2.2 moles of phosphoric acid (75.2 moles) per mole of the phosphazenium compound in the polyetherester polyol.
2% by weight phosphoric acid aqueous solution) at 80 ° C.
A neutralization reaction was performed for 0 minutes. After the neutralization reaction was completed, 1000 ppm of t-butylhydroxytoluene (BHT) was added to 100 parts by weight of the polyetherester polyol, dehydration was performed under reduced pressure, and the pressure in the autoclave was 400 mmHgabs. AD-600 (manufactured by Tomita Pharmaceutical Co., Ltd.) as an adsorbent at a pressure of 53 kPa (3,000 kPa)
pm and KW-300 (manufactured by Kyowa Chemical Industry Co., Ltd.)
00 ppm was added. Furthermore, while dehydrating under reduced pressure, finally 105 ° C., 10 mmHgabs. (1330 Pa) The same operation was performed for 4 hours under the following conditions. Thereafter, filtration under reduced pressure was carried out using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd., and polyetherester polyol was recovered. The hydroxyl value (OHV) of the polyetherester polyol after the purification treatment operation was 55.2 mgKOH /
g, viscosity (η) 12,500 mPa · s / pH at 25 ° C
Was 6.5.

Example 4 Polyetherester polyol D 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
l to a 4-neck flask, 0.016 mol of P5NMe2OH and 0.02 mol of toluene with respect to 1 mol of dipropylene glycol were added, and while introducing nitrogen through a capillary tube, 88 ° C and 10 mmHgabs. (1330 Pa),
Under the conditions of 3 hours, dehydration under reduced pressure and toluene removal were performed. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen. (1330P
From the reduced pressure state of a), the reaction temperature is 75 to 78 ° C. and the maximum pressure during the reaction is 4 kgf / cm ² (392 kPa).
Addition polymerization of propylene oxide was performed until HV became 140.3 mgKOH / g. Subsequently, the pressure was increased to 1.2 kgf / cm ² (219 kPa) with nitrogen, the reaction temperature was 105 ° C., and the maximum pressure during the reaction was 5 kgf.
/ Cm ² (490 kPa) under the condition of OHV 112.0 m
Addition polymerization of ethylene oxide was carried out until gKOH / g. When the internal pressure of the autoclave is no longer changed, 105 ° C., 5 mmHgabs. (665 Pa) under reduced pressure for 40 minutes to obtain a crude polyoxyalkylene polyol. 47.4 parts by weight of phthalic anhydride and 0.2 parts by weight of triethylamine were added to 100 parts by weight of the crude polyoxyalkylene polyol, and
After the temperature was raised to 5 ° C., 3.2 moles of propylene oxide were added to 1 mole of phthalic anhydride used at an internal temperature of 115 ° C. and the maximum pressure during the reaction was 4.5 kgf / cm ² (441 kPa).
Was charged under the following conditions. After reacting at the same temperature for 6 hours, 10
5 ° C, 5 mmHgabs. (665 Pa), 1
The pressure reduction treatment was performed for a time to obtain a polyetherester polyol. 2.0 mol of oxalic acid (in the form of an 8% by weight oxalic acid aqueous solution) is added to 1 mol of the phosphazenium compound in the polyetherester polyol, and 80 ° C.
For 1 hour to carry out a neutralization reaction. After completion of the neutralization reaction, t-
Butylhydroxytoluene (BHT) is 1000 ppm based on 100 parts by weight of the polyetherester polyol.
The mixture was dehydrated under reduced pressure, and the pressure in the autoclave was changed to 450 mmHgabs. AD-600 (manufactured by Tomita Pharmaceutical Co., Ltd.) as an adsorbent at a pressure of 60 kPa (1000 kPa).
ppm and KW-300 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added at 500 ppm. Furthermore, while dehydrating under reduced pressure, finally 105 ° C., 10 mmHgabs. (1330 Pa) or less for 4 hours. Thereafter, filtration under reduced pressure was carried out using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd., and polyetherester polyol was recovered. The hydroxyl value (OHV) of the polyetherester polyol after the purification treatment operation is 55.2 mgKOH / g,
The viscosity (η) is 9,800 mPa · s / 25 ° C. and the pH is 6.
It was 3.

Example 5 Polyetherester polyol E 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
1 mol of dipropylene glycol was added to 0.020 mol of P5NMe2OH and 0.1 mol of toluene, and nitrogen was introduced through a capillary tube at 85 ° C. and 10 mmHgabs. (1330 Pa), 4
Dehydration under reduced pressure and toluene removal were performed under the conditions of time. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen. Then, the OHV was reduced to 80.1 mgKOH / g from the atmospheric pressure at a reaction temperature of 80 ° C. under a maximum pressure of 4 kgf / cm ² (392 kPa) during the reaction. The addition polymerization of propylene oxide was performed until the temperature reached the limit. When the internal pressure of the autoclave is no longer changed, the temperature is 105 ° C and 5 mmHgab.
s. (665 Pa) under reduced pressure for 40 minutes to obtain a crude polyoxyalkylene polyol. 24.3 parts by weight of phthalic anhydride was added to 100 parts by weight of the crude polyoxyalkylene polyol, the temperature was raised to 115 ° C., and 2.12 parts per mole of phthalic anhydride used.
Mole of propylene oxide was charged under the conditions of an internal temperature of 115 ° C. and a maximum pressure of 4.5 kgf / cm ² (441 kPa) during the reaction. After reacting at the same temperature for 6 hours, 105 ° C,
5 mmHgabs. (665 Pa), a vacuum treatment was performed for 1 hour to obtain a polyetherester polyol. 2.0 mol of oxalic acid (in the form of an 8 wt% oxalic acid aqueous solution) was added to 1 mol of the phosphazenium compound in the polyetherester polyol, and a neutralization reaction was performed at 80 ° C. for 1 hour. After the neutralization reaction, 1000 ppm of t-butylhydroxytoluene (BHT) was added to 100 parts by weight of the polyetherester polyol, dehydration was performed under reduced pressure, and the pressure in the autoclave was 450 mmHg.
abs. AD-6 which is an adsorbent at (60 kPa)
00 (manufactured by Tomita Pharmaceutical Co., Ltd.) at 1500 ppm and KW
-300 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added at 500 ppm. Further, while dehydrating under reduced pressure, finally 105 ° C, 10
mmHgabs. (1330 Pa) The same operation was performed for 4 hours under the following conditions. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to recover polyetherester polyol.
The hydroxyl value (OHV) of the polyetherester polyol after the purification treatment operation was 56.1 mgKOH / g, the viscosity (η) was 5,600 mPa · s / 25 ° C, and the pH was 6.0.

The following is a comparative example. In the comparative example, the double metal cyanide complex (DMC) described above was used as a catalyst for the reaction between the polycarboxylic anhydride and the alkylene oxide. An addition polymerization of an alkylene oxide was attempted on an active hydrogen compound (glycerin and dipropylene glycol in this comparative example) as a polymerization initiator using DMC as a catalyst, which is described in JP-A-4-59825. Since addition polymerization to an active hydrogen compound to which propylene oxide has not been added was difficult as described above, a polyoxyalkylene polyol was synthesized using potassium hydroxide as a catalyst, and then a polyetherester polyol was synthesized using a DMC catalyst. went.

Comparative Example 1 Polyetherester Polyol F 500 m equipped with a stirrer, nitrogen inlet tube and thermometer
0.2 mol / mol glycerin
2 moles of potassium hydroxide (Wako Pure Chemicals reagent: 50% by weight
In the form of an aqueous potassium hydroxide solution. ) Was added, and nitrogen was introduced through a capillary tube.
abs. (1330 Pa) A dehydration operation under reduced pressure was performed for 3 hours under the following conditions. Thereafter, the contents of the flask were charged into an autoclave, and after the atmosphere in the flask was replaced with nitrogen, the reaction temperature was increased from atmospheric pressure to 110 ° C., and the maximum pressure during the reaction was 4.0 k.
OHV 84.1 under the condition of gf / cm ² (392 kPa)
Addition polymerization of propylene oxide was performed until the concentration reached mg KOH / g. When the internal pressure of the autoclave is no longer changed, 105 ° C., 5 mmHgabs. (665P
a), reduced pressure treatment was performed for 20 minutes to obtain a crude polyoxyalkylene polyol. 1.02 mol of phosphoric acid (in the form of a 75.2% by weight phosphoric acid aqueous solution) per 1 mol of potassium in the crude polyoxyalkylene polyol and 4 parts by weight per 100 parts by weight of the crude polyoxyalkylene polyol , And a neutralization reaction was performed at 80 ° C. for 2 hours. Subsequently, dehydration was performed under reduced pressure, and the pressure in the autoclave was 400 mmHgabs. (53
In the state of kPa), 5000 ppm of KW-300 (Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added. Furthermore, while dehydrating under reduced pressure, finally 105 ° C., 10 mmHgabs.
(1330 Pa) The same operation was performed for 4 hours under the following conditions. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol. The polyoxyalkylene polyol after purification treatment has a hydroxyl value (OHV) of 8
It was 4.2 mgKOH / g. Next, 36.5 parts by weight of phthalic anhydride and 0.1 part by weight of DMC were added to 100 parts by weight of the polyoxyalkylene polyol,
After the temperature was raised to 120 ° C., 1.2 mol of propylene oxide was added to the internal temperature of 120 mol per 1 mol of phthalic anhydride used.
° C, the maximum pressure during the reaction is 4.0 kgf / cm ² (392k
Pa). After reacting at the same temperature for 6 hours, 105 ° C., 5 mmHgabs. (665 Pa), a reduced pressure treatment was performed for 50 minutes to obtain a polyetherester polyol. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to recover polyetherester polyol.
The hydroxyl value (OHV) of the polyetherester polyol after the recovery operation was 61.5 mgKOH / g, and the viscosity (η) 2
7,500 mPa · s / 25 ° C., pH is 6.9,
The appearance was cloudy.

Comparative Example 2 Polyetherester Polyol G 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
0.2 mol / mol glycerin
1 mol of potassium hydroxide (in the form of a 50% by weight aqueous solution of potassium hydroxide) was added, nitrogen was introduced through a capillary tube, and 105 ° C, 10 mmHgabs. (1330 Pa)
Under the following conditions, a vacuum dehydration operation was performed for 4 hours. Thereafter, the contents of the flask were charged into an autoclave, and after purging with nitrogen, the reaction temperature was increased from atmospheric pressure to 110 ° C., and the maximum pressure during the reaction was 4.0 kgf / cm ² (392).
Under the conditions of kPa), addition polymerization of propylene oxide was performed until the OHV became 91.5 mgKOH / g. Subsequently, a gauge pressure of 1.2 kgf / cm ² (219
kPa), and OHV under conditions of a reaction temperature of 110 ° C. and a maximum pressure of 5 kgf / cm ² (490 kPa) during the reaction.
Addition polymerization of ethylene oxide was carried out until it reached 84.0 mgKOH / g. When the internal pressure of the autoclave is no longer changed, 105 ° C., 5 mmHgabs. (665
Under the condition of Pa), a reduced pressure treatment was performed for 40 minutes to obtain a crude polyoxyalkylene polyol. For 1 mol of potassium in the crude polyoxyalkylene polyol, 1.
02 mol phosphoric acid (in the form of a 75.2% by weight aqueous phosphoric acid solution) and crude polyoxyalkylene polyol 100
3 parts by weight of ion-exchanged water is added to 80 parts by weight,
A neutralization reaction was performed at 2 ° C. for 2 hours. Subsequently, dehydration was performed under reduced pressure, and the pressure in the autoclave was 400 mmHgab.
s. (53 kPa) KW-300 as an adsorbent
5000 ppm (Kyowa Chemical Industry Co., Ltd.) was added. Finally 105 ° C, 10mmH while dehydrating under reduced pressure
gabs. (1330 Pa) The same operation was performed for 4 hours under the following conditions. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol. The hydroxyl value (OH) of the polyoxyalkylene polyol after the purification treatment
V) was 84.1 mgKOH / g. Next, 1 part by weight of DMC and 51.3 parts by weight of phthalic anhydride were added to 100 parts by weight of the polyoxyalkylene polyol, and 1 part by weight was added.
After the temperature was raised to 20 ° C., 2.45 mol of propylene oxide was added to the internal temperature of 120 mol per mol of phthalic anhydride.
° C and the maximum pressure during the reaction was 4.5 kgf / cm ² (441
kPa). After reacting at the same temperature for 6 hours, 105 ° C., 5 mmHgabs. (665 Pa), a reduced pressure treatment was performed for 50 minutes to obtain a polyetherester polyol. After that, vacuum filtration was performed using 5C filter paper (retained particle size: 1μ) manufactured by Advantech Toyo Co., Ltd.
The polyetherester polyol was recovered. The hydroxyl value (OHV) of the polyetherester polyol after the recovery operation was 59.2 mgKOH / g, and the viscosity (η) 2
3,500 mPa · s / 25 ° C., pH is 6.0,
The appearance was cloudy.

Comparative Example 3 Polyetherester polyol H 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
0.14 mol of potassium hydroxide (in the form of a 50% by weight aqueous solution of potassium hydroxide) per mol of dipropylene glycol was added to a four-necked flask having a capacity of 88 ° C. and 10 mmHgabs while introducing nitrogen through a capillary tube. . (1
Dehydration under reduced pressure was performed under the condition of 330 Pa) for 5 hours. Thereafter, the contents of the flask were charged into an autoclave, and the atmosphere in the flask was replaced with nitrogen. (1330P
From the reduced pressure state of a), at a reaction temperature of 110 ° C. and a maximum pressure of 4 kgf / cm ² (392 kPa) during the reaction, OH
Addition polymerization of propylene oxide was performed until V became 140.3 mgKOH / g. Subsequently, the pressure was increased to 1.2 kgf / cm ² (219 kPa) with nitrogen, the reaction temperature was 105 ° C., and the maximum pressure during the reaction was 5 kgf / c.
OHV 112.0 mgK under the condition of m ² (490 kPa)
Addition polymerization of ethylene oxide was carried out until OH / g. When the internal pressure of the autoclave is no longer changed, 105 ° C., 5 mmHgabs. (665 Pa) under reduced pressure for 40 minutes to obtain a crude polyoxyalkylene polyol. 1.02 mol of phosphoric acid (in the form of a 75.2% by weight phosphoric acid aqueous solution) per 1 mol of potassium in the crude polyoxyalkylene polyol and 3 parts by weight per 100 parts by weight of the crude polyoxyalkylene polyol , And a neutralization reaction was performed at 80 ° C. for 2 hours. Subsequently, dehydration was performed under reduced pressure, and the pressure in the autoclave was 400 mmHgabs. (53k
In the state of Pa), 5000 ppm of KW-300 (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added. Furthermore, while dehydrating under reduced pressure, finally 105 ° C., 10 mmHgabs.
(1330 Pa) The same operation was performed for 4 hours under the following conditions. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol. The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification treatment is 1
13.4 mg KOH / g. Next, 1 part by weight of D per 100 parts by weight of polyoxyalkylene polyol
Add MC and 47.4 parts by weight of phthalic anhydride,
After the temperature had risen to 3. mol per 3 mol of phthalic anhydride used.
20 mol of propylene oxide was charged under the conditions of an internal temperature of 120 ° C. and a maximum pressure of 4.5 kgf / cm ² (441 kPa) during the reaction. After reacting at the same temperature for 6 hours, 105
° C, 5 mmHgabs. (665 Pa) under reduced pressure for 1 hour to obtain a polyetherester polyol. Thereafter, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to recover polyetherester polyol. The hydroxyl value (OHV) of the polyetherester polyol after the recovery operation was 59.0 mgKOH / g, and the viscosity (η) was 14,200 mP.
a · s / 25 ° C, pH was 6.1, and the appearance was cloudy.

The hydroxyl value (hereinafter abbreviated as OHV), viscosity (hereinafter abbreviated as η), and pH of the polyetherester polyol (hereinafter abbreviated as polyol) obtained in Examples and Comparative Examples. Are summarized in Tables 1 and 2 (Examples) and Table 3 (Comparative Examples). In the initiators in the table, Gly is an abbreviation for glycerin, and DPG is an abbreviation for dipropylene glycol. Further, a crude polyoxyalkylene polyol is used as a crude polyol, and phthalic anhydride used as a polycarboxylic acid is used as a P.
AA, AO for alkylene oxide, PO for propylene oxide, and EO for ethylene oxide. The phosphazenium compound used in the examples as a catalyst is abbreviated as PZ, triethylamine as TEA, potassium hydroxide used in the comparative example as KOH, and the double metal cyanide complex as DMC. Further, the molar ratio of propylene oxide to 1 mole of phthalic anhydride was defined as PO / PAA (unit;
Dimensionless).

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

The Examples and Comparative Examples show that the polyetherester polyol using the phosphazenium compound of the present invention as a catalyst does not require a catalyst removal step when a crude polyoxyalkylene polyol is produced, as compared with a system using DMC. Moreover, it has low viscosity and excellent workability.

Production of Polyurethane Foam Examples 6, 7 and Comparative Example 4 In order to clarify the effects of the polyetherester polyol obtained according to the present invention, a flexible polyurethane foam using a polyetherester polyol was produced below. Was. The present invention is not limited to these examples. Raw materials, abbreviations, and analytical methods used in Examples and Comparative Examples are described below. (Polyetherester polyol) A, C; Example 6
(A) The polyetherester polyol obtained by Example 7 (C) and Comparative Example 4 (F). (Polyol I): Mitsui Toatsu Chemical's polyoxyalkylene polyol MN-3050ONE. Hydroxyl value 56mg
KOH / g (flame retardant) TCPP; Daihachi Chemical's tris (2-chloropropyl) phosphate) (Catalyst-1) DABCO T-9; Air Products Organotin-based catalyst (Stannas octoate) (Catalyst-2) Minico L-1020; 3 manufactured by Active Materials Chemical
Grade amine catalyst (70% diethylene glycol solution of triethylenediamine) (foam stabilizer) L-6202; a silicone foam stabilizer manufactured by Nippon Unicar. (Isocyanate) Cosmonate T-80; polyisocyanate manufactured by Mitsui Toatsu Chemicals, Inc. Various physical properties of flexible polyurethane foam; JIS K-63
01 and the method described in JIS K-6401. Further, the adhesiveness of the foam was examined by the following method. First, a sheet having a width of 100 mm, a width of 25 mm and a thickness of 10 mm was cut out from a block of a flexible polyurethane foam. The above-mentioned sheet-like foam was placed on a nylon cloth having a width of 30 mm and a length of 120 mm, and the foam was thermally fused to the nylon cloth with a nichrome wire type electric heater.
After leaving the fused material under a constant load for 24 hours, a test piece having a width of 25 mm was cut out, and the adhesiveness (unit: g / 25 mm) was examined with a strograph R-1 (manufactured by Toyo Seiki Co., Ltd.).

30. Polyetherester polyol
0 parts by weight, 68.5 parts by weight of polyoxyalkylene polyol (polyol I), 4.0 parts by weight of water, TCPP
1.5 parts by weight, 0.15 parts by weight of DABCO T-9, 0.1 parts by weight of Minico L-1020 and 1.5 parts by weight of L-6202, and stirred and mixed to form a resin premix. , 23 ° C. Equivalent ratio of active hydrogen to isocyanate groups in the resin premix (NCO / H, hereinafter,
Abbreviated as NCO index. ) Was 1.05, and the cosmonate T-80 was weighed and adjusted to 20 ° C. Next, the mixture was vigorously stirred and mixed with the previously prepared resin premix for 6 seconds to foam and harden. Table 4 shows properties of the obtained flexible polyurethane foam.

[0097]

[Table 4]

The flexible polyurethane foam using the polyetherester polyol catalyzed by the phosphazenium compound of the present invention has a higher tensile strength, elongation and permanent compression than the flexible polyurethane foam formed by the DMC-catalyzed polyetherester polyol. It has excellent mechanical properties such as distortion and rebound resilience and adhesiveness.

In order to clarify the effects of the polyetherester polyol of the present invention, a polyurethane elastomer was prepared and its mechanical properties were measured. The present invention is not limited to these examples.

The polyurethane elastomer was prepared by a prepolymer method. 4,4'-Diphenylmethane diisocyanate (Cosmonate PH; manufactured by Mitsui Toatsu Chemicals, Inc.) was weighed with respect to 100 parts by weight of the polyetherester polyol so that the NCO index became 3.01. The reaction was performed under a nitrogen atmosphere under the condition of time. The resulting isocyanate group-terminated prepolymer was adjusted to 65 ° C. while defoaming under reduced pressure, and 1,4-butane weighed so that the NCO index was 1.05 with respect to the free isocyanate group concentration in the prepolymer. Diol (manufactured by Wako Pure Chemical) and dibutyltin dilaurate in a 1% by weight solution of dioctyl phthalate are added in an amount of 0.2 part by weight based on 100 parts by weight of the prepolymer. Was. Pour evenly into a Teflon-coated mold having a length of 20 cm, a width of 20 cm and a thickness of 2 mm, which has been previously heated to 100 ° C.
Cured at 00 ° C. for 24 hours. 23 after removal from mold
After standing for 1 week in an oven at a constant temperature and humidity of 40 ° C. and a relative humidity of 40%, physical properties were measured. Physical property measurement is JIS K63
01. Also, in order to examine the storage stability of the isocyanate group-terminated prepolymer, the prepolymer immediately after synthesis was sealed in a metal container under a nitrogen atmosphere,
For 14 days and the change in viscosity was measured.
In Example 8, polyetherester polyol D was used, and in Comparative Example 5, polyetherester polyol H was used. Further, a diol-based polyoxyalkylene polyol not subjected to ester modification in Comparative Example 6 (DIOL2000, Mitsui Toatsu Chemicals, Ltd .; abbreviated as polyol J).
3 shows the physical properties of a polyurethane elastomer using the same. Table 5 shows the measurement results of the physical properties of these polyurethane elastomers. The storage stability in the table was evaluated as x when the change in viscosity of the prepolymer after 14 days at 60 ° C was large, and evaluated as ○ when the change in viscosity was small.

[0101]

[Table 5]

From the Examples and Comparative Examples, the polyurethane elastomer using the polyetherester polyol of the present invention was compared with an elastomer made of a polyetherester polyol using DMC as a catalyst and an elastomer made of a non-ester-modified polyoxyalkylene polyol. It has excellent mechanical properties such as hardness, tensile strength, elongation, rebound resilience and permanent compression set. Further, the polyetherester polyol of the present invention can produce an isocyanate group-terminated prepolymer having excellent storage stability.

[0103]

The polyetherester polyol using the phosphazenium compound of the present invention as a catalyst undergoes a complicated process such as switching of an alkylene oxide polymerization catalyst as compared with a method using a double metal cyanide complex (DMC). It can be manufactured without any problems, and has low viscosity and excellent workability. The flexible polyurethane foam using the polyetherester polyol of the present invention has high adhesiveness to a cloth material and excellent mechanical properties such as hardness and elongation. Furthermore, the polyurethane elastomer using the polyetherester polyol of the present invention has a higher hardness, tensile strength, elongation, rebound resilience and permanent as compared with a DMC-catalyzed polyetherester polyol and a non-ester-modified polyoxyalkylene polyol. Excellent mechanical properties such as compression strain. Moreover, an isocyanate group-terminated prepolymer having excellent storage stability can be produced by the polyetherester polyol of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Sanji Takagi, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Within Mitsui Toatsu Chemicals Co., Ltd. Address: Mitsui Toatsu Chemicals Co., Ltd. 2-1-1, Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. (First reaction step) Chemical formula (1) (A, b, c and d in the chemical formula (1) are each 0
And a, b, c and d are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations;
^r- represents an inorganic anion having a valence of r. ) In the presence of a salt of a phosphazenium cation and an inorganic anion and an alkali metal or alkaline earth metal salt of an active hydrogen compound, or a compound of the formula (2) (In the chemical formula (2), a, b, c and d are integers of 0 to 3, but all of a, b, c and d are not simultaneously 0. R is the same or different carbon number of 1 to 3.) 10 hydrocarbon groups, two Rs on the same nitrogen atom may combine with each other to form a ring structure, and Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion. In the presence of the phosphazenium compound represented by the formula (1) and an active hydrogen compound, the chemical formula (1) or the chemical formula (2) is added to 1 mol of the active hydrogen compound.
The phosphazenium compound represented by the formula is 5 × 10 ⁻⁵ to 1 ×
It is prepared in the range of 10 ^-1 mol and the reaction temperature is 15-130.
° C, maximum reaction pressure is 9 kgf / cm ² (882 kPa)
A polyoxyalkylene polyol production step for producing a crude polyoxyalkylene polyol having a hydroxyl value of 10 to 500 mgKOH / g obtained by addition-polymerizing an alkylene oxide under the following conditions, and (second reaction step) obtained in the first reaction step Crude polyoxyalkylene polyol 1
1 to 80 parts by weight of the polycarboxylic acid anhydride to 00 parts by weight and 0.3 to
20 mol of alkylene oxide is reacted at a reaction temperature of 15-13.
0 ° C., maximum reaction pressure is 9 kgf / cm ² (882 kP
A process for producing a polyetherester polyol, which comprises a step of producing a polyetheresterpolyol to be reacted under the condition of a). 2. A process for producing a polyurethane resin, comprising reacting a polyether ester polyol obtained by the process according to claim 1 with a polyol containing 2 to 100% by weight and a polyisocyanate compound.