JP2001106780A - Method for producing polyoxyalkylene polyol and its derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyoxyalkylene polyol and a derivative thereof by which a remaining catalyst compound is efficiently removed from a crude polyoxyalkylene polyol by a simple method. SOLUTION: The crude polyoxyalkylene polyol is produced by using a compound having P=N bond as the catalyst and carrying out an addition polymerization of an active hydrogen compound with an epoxide compound and then brought into contact with a solid acid having 450-1,200 m2/g specific surface area and 40-1,000 Å mean pore diameter to control the remaining content of the catalyst in the polyoxyalkylene polyol to <=150 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyoxyalkylene polyol, and a method for producing a polymer-dispersed polyol, an isocyanate-terminated prepolymer, and a derivative such as polyurethane to which the production method is applied. Specifically, in the presence of a compound catalyst having a P = N bond, a crude polyoxyalkylene polyol obtained by addition polymerization of an epoxide compound to an active hydrogen compound is brought into contact with a solid acid having a specific shape,
A method for producing a polyoxyalkylene polyol, and
The present invention relates to a method for producing a derivative such as a polymer-dispersed polyol, an isocyanate group-terminated prepolymer, a flexible polyurethane foam, or a polyurethane resin to which the production method is applied.

[0002]

2. Description of the Related Art Generally, polyoxyalkylene polyols are produced on an industrial scale by addition polymerization of an active hydrogen compound with an alkylene oxide in the presence of a potassium hydroxide (KOH) catalyst. KOH
After the catalyst and the active hydrogen compound are dehydrated by heating under reduced pressure to prepare a polymerization initiator (potassium salt of the active hydrogen compound), the reaction temperature is 105 to 150 ° C. while the alkylene oxide is continuously charged into the polymerization initiator. , Maximum reaction pressure 490-
The reaction is performed under a condition of 588 kPa or less until a predetermined molecular weight is obtained to obtain a crude polyoxyalkylene polyol. Next, after the potassium in the crude polyoxyalkylene polyol is neutralized with an acid such as an inorganic acid, the potassium salt precipitated by dehydration and drying is filtered through a purification step such as filtration.

However, when propylene oxide, which is most widely used as an alkylene oxide, is subjected to addition polymerization, it is known that as the molecular weight of the polyoxyalkylene polyol increases, monool having an unsaturated group at the molecular terminal is produced as a by-product. ing.

Usually, the content of the monol corresponds to the total degree of unsaturation of the polyoxyalkylene polyol (hereinafter referred to as C = C). Since the monol has a low molecular weight as compared with the polyoxyalkylene polyol produced by the main reaction, the molecular weight distribution of the polyoxyalkylene polyol is greatly widened and the average number of functional groups is reduced.
Therefore, polyurethane resin using a polyoxyalkylene polyol having a high monol content is a foam,
Irrespective of the type of elastomer, undesired results such as an increase in hysteresis, a decrease in hardness, a decrease in cure property, and an increase in permanent compression set are accompanied.

[0005] Therefore, various studies have been made to suppress the by-product of monool and to improve the productivity of polyoxyalkylene polyol. For example, USP3,8
29,505, USP 4,472,560,
As a catalyst for propylene oxide addition polymerization, double metal cyanide complex (Double Metal Cya)
A method using a catalyst (nide complex; hereinafter referred to as DMC) has been proposed. DMC exhibits excellent performance as a polymerization catalyst for propylene oxide. However, when DMC is used as a catalyst and ethylene oxide is added and polymerized as an alkylene oxide, the DMC is once deactivated by reacting with an oxygen-containing gas, a peroxide, an oxidizing agent such as sulfuric acid, and the like. Since it is necessary to separate the catalyst residue and further subject to addition polymerization of ethylene oxide using an alkali metal hydroxide such as KOH or an alkali metal alkoxide (US Pat.
No. 5,114), the operation becomes complicated.

JP-A-7-278289 discloses a hydroxyl value (hereinafter referred to as O) using cesium hydroxide or the like as a catalyst.
HV), the maximum monool content is 15 mol%, and a head-to-tail (He) by propylene oxide addition polymerization.
A polyoxyalkylene polyol having a minimum bond-selectivity of 96% (ad-to-tail, hereinafter simply referred to as HT) is disclosed. The polyoxyalkylene polyol has a low viscosity even when the monol content is reduced,
The obtained flexible polyurethane foam has good mechanical properties and is a polyoxyalkylene polyol having excellent properties. However, using cesium hydroxide as a catalyst, for example, an OHV of 15 mg KOH / g, a considerable reaction is required to produce a polyoxyalkylene polyol having a high molecular weight and a low monol content of 15 mol% or less and a monol content of 15 mol% or less. Since it takes time, it is not always a satisfactory catalyst in consideration of the productivity of the polyol.

On the other hand, a phosphazene compound has been proposed as a catalyst for producing a metal-free polyoxyalkylene polyol (EP 0 763 555, Macromolecular Rapid Communication (Macromo Rapid Communication)).
l.Rapid Commun.) Vol. 17 pp. 143-148 1996
Year and the Macromolecular Symposium (Macromol.
Symp.) 107, 331-340 (1996)). When these phosphazene compounds are used as a catalyst for producing a polyoxyalkylene polyol, there are advantages that the by-product rate of monool is small and the productivity of polyoxyalkylene polyol is dramatically improved.

[0008] The present applicant has filed International Publication WO98 / 54.
No. 241 (EP09166686A1), a novel phosphazenium compound is used as a catalyst, C = C is low, HT bond selectivity is high, and the molecular weight distribution of a polyol as a main reaction component is sharp. And a method for producing the same. When a phosphazenium compound is used as a catalyst for the production of polyoxyalkylene polyols, the production of polyoxyalkylene polyols is dramatically improved, even when producing polyols using propylene oxide as a monomer, the by-product rate of monools is small. It has the advantage of doing so.

On the other hand, phosphine oxide compounds are known in addition to phosphazene compounds and phosphazenium compounds [Reference: Journal of general chemistry]
ofthe USSR, 55, 1453 (1985)]. The document describes a method for producing a phosphine oxide compound and a reaction example using methyl iodide. However, there is no disclosure of using a phosphine oxide compound as a catalyst for producing a polyol.

[0010] The present applicant has disclosed the above international publication WO98 /
Japanese Patent Application No. 54241 (EP09166686A1) proposed a method for purifying a crude polyoxyalkylene polyol produced by using a phosphazenium compound as a catalyst (page 11 line 21 to page 12 line 17 to e to h). the method of). E in the purification method
The method is based on the synergistic effect of a certain amount of acid, water and adsorbent,
This is an excellent method for purifying a polyol that can control the residual amount of the catalyst to 150 ppm or less. The method f is a method in which a specific amount of an organic solvent inert to the polyol is used in combination in the method e. The e method and the f method both use a specific amount of adsorbent. However, this method is a method in which a neutralization treatment with an acid is performed as a pretreatment, and then the remaining catalyst is removed using an adsorbent, and the process is slightly longer.

Further, the other purification methods without using an adsorbent, the g method and the h method, are both methods using a large amount of water or an organic solvent. Therefore, after the purification treatment, a step of removing water or an organic solvent from the polyoxyalkylene polyol is required. Depending on the molecular structure of the polyoxyalkylene polyol, the operation of contacting with a large amount of water partially dissolves the polyol in water, which may lower the yield of the polyol. All of these methods have long steps and are not necessarily satisfactory methods.

As described above, compounds having a P = N bond, such as phosphazene compounds and phosphazenium compounds, have a low C = C, a high HT bond selectivity, and a molecular weight distribution of a polyol as a main reaction component. Is sharp,
It is extremely useful as a catalyst for producing a polyoxyalkylene polyol having excellent properties such as Therefore, a method for purifying a polyoxyalkylene polyol produced using the compound as a catalyst by a simpler method is desired.

[0013]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to produce a polyoxyalkylene polyol capable of efficiently removing residual catalyst compounds from a crude polyoxyalkylene polyol by a simple method. Method,
And a method for producing the derivative thereof.

[0014]

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 a compound having a P = N bond is used as a catalyst, and an epoxide compound is addition-polymerized to an active hydrogen compound to obtain a crude product. By producing a polyoxyalkylene polyol and further purifying the obtained crude polyoxyalkylene polyol using a solid acid (adsorbent) having a specific shape, a polyoxyalkylene polyol having a small amount of residual catalyst can be obtained. Thus, the present invention has been completed.

That is, in the first invention according to the present invention, P = N
Using a compound having a bond as a catalyst, an epoxide compound is addition-polymerized to an active hydrogen compound to produce a crude polyoxyalkylene polyol, and then the crude polyoxyalkylene polyol has a specific surface area of 450 to 1200 m ^2.
/ G, a solid acid having an average pore diameter of 40 to 100 °, and a catalyst remaining amount in the polyoxyalkylene polyol is controlled to 150 ppm or less.

In a preferred embodiment of the first invention, when the crude polyoxyalkylene polyol is brought into contact with a solid acid,
The method for producing the polyoxyalkylene polyol in the presence of 0.1 to 10% by weight of water, and after contacting the crude polyoxyalkylene polyol with a solid acid, separating the solid acid and the polyoxyalkylene polyol, , A polyoxyalkylene polyol, an inorganic acid,
And at least one acid selected from organic acids and 1 to 25 p
A method for producing the polyoxyalkylene polyol to which pm is added. The temperature at which the crude polyoxyalkylene polyol is brought into contact with the solid acid is preferably in the range of 50 to 150 ° C. Further, the residual amount of the catalyst in the purified polyoxyalkylene polyol is preferably controlled to 90 ppm or less.

The preferred solid acid in the first invention is a composite metal oxide prepared from different oxides including silicon oxide, boron oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, calcium oxide and zinc oxide. Things. Specifically, aluminum silicate, magnesium silicate, zirconium silicate, titanium silicate, calcium silicate, zinc silicate, aluminum borate, magnesium borate, zirconium borate, titanium borate, titanium zirconate, and At least one type of composite metal oxide selected from magnesium zirconate is used. Of these, aluminum silicate, magnesium silicate, and mixtures thereof are preferred.

The compound having a P = N bond includes at least one compound selected from a phosphazenium compound, a phosphine oxide compound, and a phosphazene compound. The phosphazenium compound is represented by the following chemical formula (1):

[0019]

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[A, b, c and d in the chemical formula (1) are:
A, b, c and d, each being a positive integer of 0 to 3
Are not 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. Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion]. A phosphine oxide compound represented by the following chemical formula (2):

[0021]

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[In the chemical formula (2), R represents the same or different hydrocarbon groups having 1 to 10 carbon atoms, x represents the amount of water contained in a molar ratio, and is 0 to 5.] And the compounds represented. A phosphazene compound represented by the following chemical formula (3):

[0023]

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(In the chemical formula (3), l, m and n each represent a positive integer of 0 to 3. D represents the same or different hydrocarbon group having 1 to 20 carbon atoms, alkoxy group, phenoxy group. A thiophenol residue, a monosubstituted amino group, a disubstituted amino group, or a 5- or 6-membered cyclic amino group.
Is a hydrocarbon group having 1 to 20 carbon atoms. Furthermore, two Ds on the same phosphorus atom or on two different phosphorus atoms can be bonded to each other, and D and Q can be bonded to each other to form a ring structure. Compounds to be used.

[0025] The above crude As a method for producing a polyoxyalkylene polyol, with respect to 1 mole of active hydrogen compound in the presence of a catalyst 1 × 10 ^-4 ~5 × 10 ^-1 mol, the reaction temperature 15
A method in which an epoxide compound is addition-polymerized to an active hydrogen compound under the conditions of ~ 130 ° C and a maximum reaction pressure of 882 kPa or less.

The properties of the polyoxyalkylene polyol produced by the method according to the present invention are as follows.
200 mgKOH / g, total unsaturation is 0.07 meq.
/ g or less, the head-to-tail bond selectivity of the oxypropylene group of the polyoxyalkylene polyol by propylene oxide addition polymerization is 95 mol% or more.
In addition to these properties, the content of oxypropylene groups is preferably at least 50% by weight. Further, the hydroxyl value is 9 to 120 mgKOH / g, and the total unsaturation is 0.0
5meq. / g or less, the head-to-tail bond selectivity is 96 mol% or more, and the residual amount of the compound catalyst having a P = N bond is preferably 90 ppm or less.

The second invention is a method for producing a polymer-dispersed polyol in which polymer particles are dispersed in a polyol. The method comprises producing a polyoxyalkylene polyol by the above-mentioned production method,
A polymer-dispersed polyol characterized in that 5-86 parts by weight of an ethylenically unsaturated monomer is polymerized in 100 parts by weight of the polyol at 0 to 200 ° C., and the concentration of the polymer particles is controlled to 5 to 60% by weight. It is a manufacturing method. Ethylenically unsaturated monomers include acrylonitrile,
It is preferably at least one monomer selected from styrene, acrylamide and methyl methacrylate.

The third invention is a method for producing an isocyanate group-terminated prepolymer in which a polyol is reacted with a polyisocyanate, wherein a polyoxyalkylene polyol is produced by the above-mentioned production method,
In the above, the obtained polyoxyalkylene polyol is reacted with an amount of polyisocyanate having an isocyanate index of 1.3 to 10 to obtain an isocyanate group content (NCO%) of 0.3 to 30% by weight. This is a method for producing an isocyanate group-terminated prepolymer having a head-to-tail bond selectivity of the polymer main chain of 95 mol% or more. The content of the free isocyanate compound in the obtained prepolymer is preferably 1% by weight or less.

A fourth invention is a method for producing an isocyanate group-terminated prepolymer in which a polyol is reacted with a polyisocyanate, wherein a polymer-dispersed polyol is produced by the above-mentioned production method and then obtained at 50 to 120 ° C. An isocyanate group-terminated prepolymer having an isocyanate group content (NCO%) of 0.3 to 30% by weight is reacted with a polymer-dispersed polyol with an amount of polyisocyanate having an isocyanate index of 1.3 to 10. It is a manufacturing method.

According to a fifth aspect of the present invention, an isocyanate group-terminated prepolymer is produced by the above production method,
This is a method for producing a polyurethane resin in which the obtained isocyanate group-terminated prepolymer is reacted with a chain extender at 40 ° C. in a range where the isocyanate index is 0.6 to 1.5.

According to a sixth aspect of the present invention, a polyoxyalkylene polyol is produced by the above production method,
This is a method for producing a polyurethane resin in which the obtained polyoxyalkylene polyol is reacted with an isocyanate group-terminated prepolymer at a temperature of 0 ° C. within a range of an isocyanate index of 0.8 to 1.3.

A seventh invention is a method for producing a flexible polyurethane foam in which a polyol and a polyisocyanate are reacted in the presence of water, a catalyst and a foam stabilizer, wherein a polyoxyalkylene polyol is produced by the production method.
Next, there is provided a method for producing a flexible polyurethane foam, comprising using a polyol containing at least 30% by weight of the obtained polyoxyalkylene polyol.

An eighth invention is a method for producing a flexible polyurethane foam in which a polyol and a polyisocyanate are reacted in the presence of water, a catalyst and a foam stabilizer, wherein a polymer-dispersed polyol is produced by the above-mentioned production method, ,
A method for producing a flexible polyurethane foam, comprising using a polyol containing at least 10% by weight of the obtained polymer-dispersed polyol.

A feature of the present invention is that a crude polyoxyalkylene polyol is produced using a compound having a P = N bond as a catalyst, and the resulting crude polyoxyalkylene polyol is contacted with a solid acid having a specific shape, The purpose of the present invention is to remove the residual catalyst and control the residual catalyst in the purified polyoxyalkylene polyol to 150 ppm or less. The purification method using a solid acid according to the present invention does not require a neutralization treatment with an acid and can simplify the process, as compared with a conventional purification method using a solid acid (adsorbent), so that the product loss in the purification process can be reduced. Less is. Further, since the remaining amount of the catalyst is small, there is an advantage that, for example, the stability over time of the isocyanate group-terminated prepolymer which is a derivative of the polyoxyalkylene polyol is improved. Further, the properties of the polyurethane obtained from the prepolymer are excellent. Accordingly, the method for producing the polyoxyalkylene polyol and the derivative thereof according to the present invention includes paints, adhesives, flooring materials, waterproof materials, sealing agents, shoe soles, polyurethane fields such as elastomers, and surfactants, lubricants, It is extremely useful as a method for producing a working fluid and a raw material in the field of sanitary goods and the like.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. <Method for producing polyoxyalkylene polyol>
The method for producing the polyoxyalkylene polyol according to the present invention will be described. The method for producing a polyoxyalkylene polyol according to the present invention comprises producing a crude polyoxyalkylene polyol by addition-polymerizing an epoxide compound to an active hydrogen compound using a compound having a P = N bond as a catalyst, and then producing a crude polyoxyalkylene polyol. It is produced by purifying a polyoxyalkylene polyol by a method of contacting it with a solid acid having a specific shape.

Examples of the compound having a P = N bond used as a catalyst for producing a crude polyoxyalkylene polyol include a phosphazenium compound, a phosphine oxide compound, and a phosphazene compound. As the phosphazenium compound, the compound represented by the above chemical formula (1) or the chemical formula (4)

[0037]

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[A, b, c and d in the chemical formula (4) are:
A, b, c and d, each being a positive integer of 0 to 3
Are not 0 at the same time. R represents the same or different hydrocarbon groups having 1 to 10 carbon atoms,
R 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, and ^Tr- represents an inorganic anion having a valence of r.]. Among these, the compound represented by the chemical formula (1) is preferable.

In the present invention, a in the phosphazenium cation represented by the chemical formula (1) or (4),
b, c and d are each a positive integer of 0 to 3.
However, they are not all 0 at the same time. Preferably it is an integer of 0 to 2. More preferably, regardless of the order of a, b, c and d, (2,1,1,1), (1,1,1,1)
1), (0, 1, 1, 1), (0, 0, 1, 1) or a number in a combination of (0, 0, 0, 1). More preferably, (1,1,1,1), (0,1,1,1)
1), (0, 0, 1, 1) or a number in the combination of (0, 0, 0, 1).

In the present invention, R in the phosphazenium cation of the salt represented by the chemical formula (1) or (4)
Are the same or different hydrocarbon groups having 1 to 10 carbon atoms. Specifically, this R is, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-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-octyl, 2-ethyl-1-hexyl, 1,
1-dimethyl-3,3-dimethylbutyl (tert-octyl), nonyl, decyl, phenyl, 4-toluyl,
It is selected from aliphatic or aromatic hydrocarbon groups such as benzyl, 1-phenylethyl or 2-phenylethyl.
Of these, methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl, ter
An aliphatic hydrocarbon group having 1 to 10 carbon atoms such as t-octyl is preferred. A methyl group or an ethyl group is 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 It is 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. In addition, the main chains thereof are substituted with an alkyl group such as methyl or ethyl. More preferably, it is a tetramethylene or pentamethylene group. Such a ring structure may be adopted for all possible nitrogen atoms in the phosphazenium cation,
It may be a part.

T ^r− in the chemical formula (4) 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, tetrafluoroacid, 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, HSO ₄ ⁻ , HCO
₃ ^- There is also. 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. Chloride anions are more preferred.

When the phosphazenium compound of the formula (4) is used as a catalyst, it is necessary to prepare an alkali metal or alkaline earth metal salt of an active hydrogen compound in advance. The salt may be prepared by a conventionally known method. An alkali metal or alkaline earth metal salt of an active hydrogen compound coexisting with a compound represented by the chemical formula (4) is an alkali metal or alkaline earth metal when active hydrogen of the active hydrogen compound dissociates as hydrogen ions. It is a salt that replaces ions.

Preferred examples of the compound represented by the chemical formula (1) include, for example, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide and tetrakis [tris (dimethylamino) phosphoranylidene Amino] phosphonium methoxide,
Tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium ethoxide, tetrakis [tri (pyrrolidin-1-yl) phosphoranylideneamino] phosphonium tert-butoxide and the like can be mentioned.

Examples of the phosphine oxide compound include a compound represented by the above formula (2). R in the phosphine oxide compound represented by the chemical formula (2) is
The same or different hydrocarbon groups having 1 to 10 carbon atoms. This R is, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-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,
-Heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl, 1,1-dimethyl-
Selected from aliphatic or aromatic hydrocarbon groups such as 3,3-dimethylbutyl (commonly referred to as tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl, or 2-phenylethyl. It is.
Further, R may be in the form of a pyrrolidino group or a piperidino group. Among these R, the same or different carbon atoms having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, tert-pentyl, 1,1-dimethyl-3,3-dimethylbutyl and the like. Are preferred. A methyl group or an ethyl group is more preferred.

The phosphine oxide compound represented by the chemical formula (2) is obtained from the Journal of general chemistry of the US
It can be synthesized by the method described in SR, 55, 1453 (1985) or a method similar thereto. Usually, the phosphine oxide compound represented by the chemical formula (2) has hygroscopicity,
It is likely to be hydrated or hydrated. X representing the amount of water molecules contained in the phosphine oxide compound is represented by a molar ratio to the phosphine oxide compound, and x
Is 0 to 5, preferably 0 to 2. Preferred forms of the phosphine oxide compound include tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide and tris [tris (diethylamino) phosphoranylideneamino] phosphine oxide.

Examples of the phosphazene compound include the compounds disclosed in Japanese Patent Application Laid-Open No. 10-36499 filed by the present applicant. Specifically, the above chemical formula (3)
The compound represented by these is mentioned. Q in chemical formula (3),
That is, examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, and tert. -An alkyl group such as octyl, nonyl or decyl, and allyl, 2-methylallyl, benzyl, phenethyl, o-anisyl, 1-phenylethyl,
An alkyl group having an unsaturated bond or an aromatic group such as diphenylmethyl, triphenylmethyl or cinnamyl; cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 3-propylcyclohexyl, 4-phenylcyclohexyl, cycloheptyl or 1-cyclohexenyl Alicyclic groups such as vinyl, styryl,
An alkenyl group such as propenyl, isopropenyl, 2-methyl-1-propenyl or 1,3-butadienyl; an alkynyl group such as ethynyl or 2-propynyl; phenyl, o-tolyl, m-tolyl, p-tolyl; , 2,3-xylyl, 2,4-xylyl, 3,4-xylyl, mesityl, o-cumenyl, m-cumenyl, p-
Aromatic groups such as cumenyl, 1-naphthyl, 2-naphthyl or p-methoxyphenyl are exemplified.

D in the chemical formula (3), that is, 1 carbon atom
Examples of the hydrocarbon group of ２０20 include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, and tert.
-An alkyl group such as octyl, nonyl or decyl, and an unsaturated bond or an aromatic group such as allyl, 2-methylallyl, benzyl, phenethyl, o-anisyl, 1-phenylethyl, diphenylmethyl, triphenylmethyl or cinnamyl. And an alicyclic group such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 3-propylcyclohexyl, 4-phenylcyclohexyl, cycloheptyl or 1-cyclohexenyl, and vinyl, styryl, propenyl,
An alkenyl group such as isopropenyl, 2-methyl-1-propenyl or 1,3-butadienyl; an alkynyl group such as ethynyl or 2-propynyl; phenyl, o-tolyl, m-tolyl, p-tolyl, , 3-
Xylyl, 2,4-xylyl, 3,4-xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl, 1
And aromatic groups such as -naphthyl, 2-naphthyl and p-methoxyphenyl.

The alkoxy group of D is, for example, an alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, allyloxy, cyclohexyloxy or benzyloxy, and phenoxy of D Examples of the group include C6 to C2 such as phenoxy, 4-methylphenoxy, 3-propylphenoxy or 1-naphthyloxy.
And a thiol residue of D includes, for example, methylthio, ethylthio, propylthio,
Isopropylthio, butylthio, isobutylthio, te
It is a thiol residue containing 1 to 20 carbon atoms such as rt-butylthio, pentylthio, hexylthio, heptylthio, octylthio, tert-octylthio, nonylthio or decylthio.

The thiophenol residue of D includes, for example, phenylthio, o-toluylthio, m-toluylthio, p-toluylthio, 2,3-xylylthio, 2,4
6 to 2 carbon atoms such as -xylylthio, 3,4-xylylthio, 4-ethylphenylthio, or 2-naphthylthio;
And a monosubstituted amino group of D includes, for example, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, hexylamino, Heptylamino, octylamino, tert-octylamino, nonylamino, decylamino, 1-ethylpropylamino, 1-ethylbutylamino, anilino, o-toluylamino, m-toluylamino, p-toluylamino, 2,3-xylinoamino, It is a monosubstituted amino group having 1 to 20 carbon atoms such as 2,4-xylinamino or 3,4-xylinamino.

Examples of the disubstituted amino group of D include dimethylamino, diethylamino, methylethylamino, dipropylamino, methylpropylamino, diisopropylamino, dibutylamino, methylbutylamino, diisobutylamino, di-sec-butylamino, Dipentylamino, dihexylamino, ethylhexylamino,
Diheptylamino, dioctylamino, di-tert-
Octylamino, ethyl-tert-octylamino,
Dinonylamino, didecylamino, diphenylamino,
Methylphenylamino, ethylphenylamino, di-o
1-pyrrolidinyl, 3-methyl-1-pyrrolidinyl, which is an amino group in which the same or different C1-C20 hydrocarbon groups such as -toluylamino, di-2,3-xylylamino or phenyltoluylamino are disubstituted; , 1-pyrrolyl, 3-ethyl-1-pyrrolyl, 1-indolyl, 1-piperidyl, 3-methyl-1-piperidyl, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-imidazolidinyl or 4-morpholinyl And a 5- or 6-membered cyclic amino group.

When two or more Ds on the same phosphorus atom or on two different phosphorus atoms are bonded to each other, all or a part of the possible D forms a ring structure, Examples of the valent group (DD) include ethylene, vinylene, propylene, 1,2-cyclohexanylene, 1,2-phenylene, trimethylene, propenylene, tetramethylene,
It is a saturated or unsaturated aliphatic divalent hydrocarbon group such as 2,2'-biphenylene, 1-butenylene, 2-butenylene or pentamethylene.

Further, an oxygen atom, a sulfur atom, and a hydrogen atom or a methyl group, an ethyl group, a butyl group, a cyclohexyl group, a benzyl group may be attached to one or both of the bonds between both ends of the divalent group and the phosphorus atom. Alternatively, a divalent group in which any one or two of a group consisting of a nitrogen atom to which an aliphatic or aromatic hydrocarbon group such as a phenyl group is bonded is inserted.

Specific examples of these divalent groups include, for example, methyleneoxy, ethylene-2-oxy, trimethylene-3-oxy, methylenedioxy, ethylenedioxy, trimethylene-1,3-dioxy, cyclohexane- 1,2-dioxy, benzene-1,2-dioxy, methylenethio, ethylene-2-thio, trimethylene-3-
Thio, tetramethylene-4-thio, methylenedithio, ethylenedithio, trimethylene-1,3-dithio, iminomethylene, 2-iminoethylene, 3-iminotrimethylene, 4-iminotetramethylene, N-ethyliminomethylene, N -Cyclohexyl-2-iminoethylene, N-
Methyl-3-iminotrimethylene, N-benzyl-4-
Iminotetramethylene, diiminomethylene, 1,2-diiminoethylene, 1,2-diiminovinylene, 1,3-
Diimino trimethylene, N, N'-dimethyldiiminomethylene, N, N'-diphenyl-1,2-diiminoethylene, N, N'-dimethyl-1,2-diiminoethylene, N-methyl-N And groups such as' -ethyl-1,3-diiminotrimethylene, N, N'-diethyl-1,4-diiminotetramethylene or N-methyl-1,3-diiminotrimethylene.

In the case where D and Q are combined with each other and all or a part thereof is possible to form a ring structure, a divalent group (DQ) connecting a nitrogen atom and a phosphorus atom is ,
A saturated or unsaturated aliphatic divalent hydrocarbon group identical to the divalent group on the phosphorus atom shown above, and furthermore, oxygen is added to the bond between the divalent hydrocarbon group and the phosphorus atom. atom,
Sulfur atom and hydrogen atom or methyl group, ethyl group,
A divalent group in which any one of a group consisting of a nitrogen atom to which an aliphatic or aromatic hydrocarbon group such as a butyl group, a cyclohexyl group, a benzyl group or a phenyl group is bonded is inserted.

Specific examples of these divalent groups include, for example, methyleneoxy, ethylene-2-oxy, methylenethio, ethylene-2-thio, iminomethylene, 2-iminoethylene, N-methyliminomethylene, N- Ethyl-
Examples include groups such as 2-iminoethylene, N-methyl-3-iminotrimethylene or N-phenyl-2-iminoethylene.

As specific examples of the phosphazene compound having the structure represented by the chemical formula (3), when D is the same or different alkyl group, for example, 1-
tert-butyl-2,2,2-trimethylphosphazene or 1- (1,1,3,3-tetramethylbutyl)
−2,2,4,4,4-pentaisopropyl-2λ ⁵ ,
4λ ⁵ -catenadi (phosphazene) and the like.

Examples of the case where D is an unsaturated bond or an alkyl group having an aromatic group include, for example, 1-t
tert-butyl-2,2,2-triallylphosphazene, 1-cyclohexyl-2,2,4,4,4-pentaallyl-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) or 1-ethyl-2,4,4 , 4-Tribenzyl-2-tribenzylphosphoranylideneamino-2λ ⁵ , 4λ ⁵ −
Catenadi (phosphazene) and the like.

Examples of the case where D is an alicyclic group include, for example, 1-methyl-2,2,2-tricyclopentylphosphazene or 1-propyl-2,2,4,4,4-
Cyclohexyl-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) and the like. Examples of the case where D is an alkenyl group include, for example, 1-butyl-2,2,2-trivinylphosphazene or 1-tert-butyl-2,2,2.
4,4,4-pentastyryl-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) and the like. Examples of a case where D is an alkynyl group include, for example, 1-tert-butyl-2,2,2-tri (2-phenylethynyl) phosphazene, and an example of the case where D is an aromatic group. Examples thereof include 1-isopropyl-2,4,4,4-tetraphenyl-2-triphenylphosphoranylideneamino-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene).

Examples of the case where D is an alkoxy group include, for example, 1-tert-butyl-2,2,2-trimethoxyphosphazene, 1- (1,1,3,3-tetramethylbutyl) -2 , 2,4,4,4-penta-isopropoxy -2λ ^5, 4λ ⁵ - Katenaji (phosphazene) or 1-phenyl -2,2,4,4,4- penta benzyloxy -2λ ^5, 4λ ⁵ - Katenaji ( Phosphazene). Examples of the case where D is a phenoxy group include, for example, 1-methyl-2,2,2-triphenoxyphosphazene or 1-tert-butyl-2,2,2.
4,4,4-penta (1-naphthyloxy) -2λ ⁵ ,
4λ ⁵ -catenadi (phosphazene) and the like.

Examples of the case where D is a disubstituted amino group include, for example, 1-tert-butyl-2,2,2-tris (dimethylamino) phosphazene, 1- (1,1,
3,3-tetramethylbutyl) -2,2,2-tris (dimethylamino) phosphazene, 1-ethyl-2,
2,4,4,4-pentakis (dimethylamino) -2λ
^{5, 4λ 5} - Katenaji (phosphazene), 1-tert
Butyl-2,4,4,4-tetrakis (dimethylamino) -2-tris (dimethylamino) phosphoranylideneamino-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene),
1-tert-butyl-2,4,4,4-tetrakis (diisopropylamino) -2-tris (diisopropylamino) phosphoranylideneamino-2λ ⁵ , 4λ ⁵ −
Catenadi (phosphazene), 1-tert-butyl-
2,4,4,4-tetrakis (di-n-butylamino)
-2-tris (di-n-butylamino) phosphoranylideneamino-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene), 1-tert-butyl-4,4,4-tris (dimethylamino) -2,2 -Bis [tris (dimethylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene), 1- (1,1,3,3-tetramethylbutyl) -4,4,4-tris ( Dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene), 1- (1,1,3,3-tetramethylbutyl) -4 , 4,4-Tris (methylethylamino)-
2,2-bis [tris (methylethylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene), 1-tert-butyl-4,4,4-tris (diethylamino) -2,2 -Bis [tris (diethylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ −
Catenadi (phosphazene), 1-tert-butyl-
4,4,4-tris (diisopropylamino) -2,2
-Bis [tris (diisopropylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene), 1-tert-butyl-4,4,4-tris (di-n-butylamino) -2, 2-bis [tris (di-n
-Butylamino) phosphoranylideneamino] -2
λ ⁵ , 4λ ⁵ -catenadi (phosphazene), 1-tert
-Butyl-4,4,6,6,6-pentakis (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ , 6λ ⁵ -catenatri (phosphazene) , 1-tert-butyl-
4,4,6,6,6-pentakis (diethylamino)-
2,2-bis [tris (diethylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ , 6λ ⁵ -catenatri (phosphazene), 1-tert-butyl-4,4,4
6,6,6-pentakis (diisopropylamino)-
2,2-bis [tris (diisopropylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ , 6λ ⁵ -catenatri (phosphazene), 1-tert-butyl-4,
4,6,6,6-pentakis (di-n-butylamino)
-2,2-bis [tris (di-n-butylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ , 6λ ⁵ -catenatri (phosphazene), 1-tert-butyl-4,
4,6,6,6-pentakis (dimethylamino) -2-
[2,2,2-tris (dimethylamino) phosphazen-1-yl] -2- [2,2,4,4,4-pentakis (dimethylamino) -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) -1 -Yl] -2λ ⁵ , 4λ ⁵ , 6λ ⁵ -catenatri (phosphazene) or 1-phenyl-2,2-bis (dimethylamino) -4,4-dimethoxy-4-phenylamino-2λ ⁵ , 4λ ⁵ -catenadi (Phosphazene)
And the like.

Further, when D on the same phosphorus atom or on two different phosphorus atoms is bonded to each other to form a ring structure, for example, 2- (tert-butylimino) -2 -Dimethylamino-1,3-dimethyl-
1,3-diaza-2λ ⁵ -phosphinane and the like.

Preferred examples of the phosphazene compound include, for example, 1-tert-butyl-2,2,2-tris (dimethylamino) phosphazene, 1- (1,1,
3,3-tetramethylbutyl) -2,2,2-tris (dimethylamino) phosphazene, 1-ethyl-2,
2,4,4,4-pentakis (dimethylamino) -2λ
^{5, 4λ 5} - Katenaji (phosphazenes), 1-tert
-Butyl-4,4,4-tris (dimethylamino)-
2,2-bis [tris (dimethylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene), 1- (1,1,3,3-tetramethylbutyl)
-4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylideneamino] -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene), 1
-Tert-butyl-2,2,2-tri (1-pyrrolidinyl) phosphazene or 7-ethyl-5,11-dimethyl-1,5,7,11-tetraaza-6λ ⁵ -phosphaspiro [5,5] undeca -1 (6) -ene and the like. Among the compounds having a P = N bond described in detail above, phosphazenium compounds, phosphine oxide compounds, and mixtures thereof are preferable in view of industrial use of catalysts.

The active hydrogen compound used in the present invention includes
Examples include alcohols, phenol compounds, polyamines, alkanolamines, thioalcohols, and the like. For example, water, ethylene glycol, diethylene glycol,
Triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,
5-pentanedyl, neopentyl glycol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4
-Butanediol, 1,4-dimethylolcyclohexane, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4 -Dihydric alcohols such as cyclohexanediol, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, glycerin, diglycerin, trimethylolpropane, trimethylolethane,
Polyhydric alcohols such as trimethylolbutane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sugars such as glucose, sorbitol, dextrose, fructose, sucrose and methylglucoside, or derivatives thereof, ethylenediamine, di ( Fatty acid amines such as 2-aminoethyl) amine and hexamethylenediamine; aromatic amines such as toluylenediamine and diphenylmethanediamine; and phenol compounds such as bisphenol A, bisphenol F, bisphenol S, novolak, resol, and resorcinol. Can be

Further, divalent thioalcohols such as ethylenethioglycol, propylenethioglycol, trimethylenethioglycol and butanedithiol, and alkylenethioglycols such as diethylenethioglycol and triethylenethioglycol can be mentioned. These active hydrogen compounds can be used in combination of two or more.
Further, compounds obtained by addition polymerization of these active hydrogen compounds with an epoxide compound by a conventionally known method can also be used.

Most preferred among these compounds is 2
Compounds obtained by addition polymerization of an alkylene oxide to a dihydric alcohol or dihydric alcohol and having a number average molecular weight of up to 2,000, trivalent alcohols or a compound having an addition alkylene oxide of a trihydric alcohol having a number average molecular weight of up to 2,000 Up to 000 compounds. Those having a number average molecular weight of more than 2,000 after addition of the epoxide compound to dihydric alcohols or trihydric alcohols are not preferred because the amount of by-product monols increases.

Examples of the epoxide compound that is addition-polymerized to the active hydrogen compound include propylene oxide, ethylene oxide, 1,2-butylene oxide, 2,3-
Butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether and the like. These may be used in combination of two or more. Among them, propylene oxide, ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide and styrene oxide are preferred. More preferred are propylene oxide and ethylene oxide. Preferably, at least 50% by weight of the total amount of epoxide compound is propylene oxide. More preferably at least 60% by weight, even more preferably at least 70% by weight. By using an epoxide compound containing such a ratio of propylene oxide, the content of oxypropylene groups in the polyoxyalkylene polyol can be at least 50% by weight. A suitable content of oxypropylene groups is at least 60% by weight, more preferably at least 70% by weight. When the content of the oxypropylene group is 50% by weight or more, the viscosity of the polyoxyalkylene polyol decreases, and the flexibility of the urethane resin obtained from the polyol improves.

The amount of the compound having a P = N bond used as a catalyst is 1 × 10
^{−4 to} 5 × 10 ⁻¹ mol. Preferably 5 × 10 ^-4 to 1
× 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10
^-2 moles. When increasing the molecular weight of the polyoxyalkylene polyol, it is preferable to increase the concentration of the compound having a P = N bond to the active hydrogen compound within the above range. When the amount of the compound having a P = N bond is less than 1 × 10 ⁻⁴ mol per 1 mol of the active hydrogen compound, the polymerization rate of the epoxide compound decreases, and the production time of the polyoxyalkylene polyol increases. Conversely, 5 × 10
^If it exceeds ^-1 mol, the cost of the compound catalyst having a P = N bond in the production cost of the polyoxyalkylene polyol increases.

The temperature at which the epoxide compound is added to the active hydrogen compound is 15 to 130 ° C. Preferably 4
The temperature is in the range of 0 to 120C, more preferably 50 to 110C. When the addition polymerization temperature of the epoxide compound is performed at a low temperature within the above range, P =
It is preferable to increase the concentration of the compound having an N bond within the range described above. When the addition polymerization temperature of the epoxide compound is lower than 15 ° C., the polymerization rate of the epoxide compound decreases, and the production time of the polyoxyalkylene polyol becomes longer. On the other hand, if the addition polymerization temperature exceeds 130 ° C., the total degree of unsaturation (C = C) is 0.0, depending on the hydroxyl value (OHV) of the polyoxyalkylene polyol.
7meq. / G.

The maximum pressure of the addition polymerization reaction of the epoxide compound is 882 kPa or less. Usually, addition polymerization of the epoxide compound is performed in a pressure-resistant reactor. The reaction of the epoxide compound may be started from a reduced pressure state or an atmospheric pressure state. When starting from an atmospheric pressure state, it is desirable to carry out in the presence of an inert gas such as nitrogen or helium. When the maximum reaction pressure of the epoxide compound exceeds 882 kPa, the amount of by-product monol increases. The maximum reaction pressure is preferably 686 kPa or less, more preferably 490 kPa or less. When propylene oxide is used as the epoxide compound,
The maximum reaction pressure is preferably 490 kPa or less.

The method of supplying the epoxide compound to the polymerization system may be a method in which a necessary amount of the epoxide compound is partially supplied in a lump and the remainder is continuously supplied, or all the epoxide compounds are continuously supplied. A method or the like is used.
In the method of supplying a part of the required amount of the epoxide compound at a time, the reaction temperature at the beginning of the polymerization reaction of the epoxide compound is set to a lower temperature within the above temperature range, and the reaction temperature is gradually increased after the epoxide compound is charged. Is preferred.

The polymerization method when propylene oxide and ethylene oxide are used in combination as the epoxide compound is as follows. After polymerization of propylene oxide, an ethylene oxide capping reaction in which ethylene oxide is copolymerized in blocks, and propylene oxide and ethylene oxide are randomly generated. A random reaction for copolymerization, a triblock copolymerization reaction for polymerizing ethylene oxide after polymerization of propylene oxide, and then for polymerizing propylene oxide, may be mentioned. Among these, the preferred polymerization methods are an ethylene oxide capping reaction and a triblock copolymerization reaction.

The maximum pressure of the addition polymerization machine is affected by the charging speed of the epoxide compound, the polymerization temperature, the amount of the catalyst and the like. It is preferable to control the charging speed of the epoxide compound so that the maximum pressure of the addition polymerization machine does not exceed 882 kPa. When the charging of the epoxide compound is completed, the internal pressure of the addition polymerization machine gradually decreases. It is preferable to continue the addition polymerization reaction until no change in the internal pressure is observed. Based on the hydroxyl value (OHV) of the polyoxyalkylene polyol, the addition polymerization is preferably continued until the OHV becomes 2 to 200 mgKOH / g.

In the addition polymerization reaction of the epoxide compound, a solvent can be used if necessary. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, and peptane; ethers such as diethyl ether, tetrahydrofuran, and dioxane; and aprotic polar solvents such as dimethyl sulfoxide and N, N-dimethylformamide. . When a solvent is used, a method of recovering and reusing the solvent after the production is desirable in order not to increase the production cost of the polyoxyalkylene polyol.

In the method for producing a polyoxyalkylene polyol using a phosphine oxide compound as a catalyst according to the present invention, an active hydrogen compound (excluding water) and a polyoxyalkylene polyol having a low water content may be used as a polyoxyalkylene polyol. In the step of preparing a polymerization initiator of the alkylene polyol, heating under reduced pressure dehydration, or,
It is not necessary to perform an operation such as a desalination reaction. Usually, in the most widely used method using a KOH catalyst, KOH and an active hydrogen compound are charged into a reactor before addition polymerization of the epoxide compound to the active hydrogen compound, and
It is necessary to prepare a polymerization initiator (potassium salt of an active hydrogen compound) by performing heating and dehydration under reduced pressure for 3 to 8 hours under conditions of -120 ° C and 1.33 kPa or less. Also, JP
0-77289 or International Publication WO98
In the method using a phosphazenium compound catalyst in which an inorganic compound is a counter anion described in / 54241 (EP09166686A1), a desalination reaction of the active hydrogen compound with a potassium salt must be performed to prepare a polymerization initiator. The preferred water content in the case where it is not necessary to carry out the heating decompression dehydration treatment, the active hydrogen compound, and the total amount of the phosphine oxide compound, the water content is 600 ppm or less, more preferably, 400 ppm or less, most preferably, It is 300 ppm or less.

Next, a method for purifying the crude polyoxyalkylene polyol produced as described above will be described. The main purpose of the purification is to remove compounds having P = N bonds remaining in the crude polyoxyalkylene polyol. The present inventors contact the crude polyoxyalkylene polyol with a specific acid having a specific specific surface area and an average pore diameter, whereby the remaining catalyst is efficiently removed, and the remaining amount of the catalyst is reduced to a specific value or less. I found that I could control it. In particular, the specific surface area is 450 to 1200
m ² / g and an average pore diameter of 40 to 100 °
Are useful.

Considering the ability to remove a compound having a P = N bond (hereinafter referred to as a catalyst), the specific surface area of the solid acid is an important factor. The specific surface area of the solid acid is preferably 500
１1100 m ² / g, more preferably 550 to 1000
m ² / g. When the specific surface area is less than 450 m ² / g, the ability to remove the catalyst in the crude polyoxyalkylene polyol is reduced. On the other hand, in consideration of the efficiency in recovering the purified polyoxyalkylene polyol from the mixed liquid of the crude polyoxyalkylene polyol and the solid acid, the upper limit of the specific surface area is 1200 m ² / g.

The preferred average pore diameter is 50 to 100 °, more preferably 55 to 95 °. Solid acids having an average pore diameter of less than 40 °, such as zeolites, have a low catalyst removal ability. On the other hand, considering the molecular diameter of the catalyst and the specific surface area of the solid acid, the upper limit of the average pore diameter of the solid acid is 100 °. Furthermore, in order to improve the ability to remove the catalyst, it is preferable to use a solid acid having a specific surface area and an average pore diameter in the above-mentioned range, and having pores having a diameter in the range of 10 to 60 °.

Examples of the solid acid having the above shape include acid clay, clay minerals such as montmorillonite, composite metal oxides such as aluminum silicate and magnesium silicate, metal sulfates and phosphates, silica gel-phosphoric acid and the like. Solidified acid and a cation exchange resin. For the purpose of the present invention, a composite metal oxide having the above specific surface area and average pore diameter is suitable. Examples of such a composite metal oxide include a composite metal oxide prepared from different oxides such as silicon oxide, boron oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, calcium oxide, and zinc oxide. Can be Specifically, aluminum silicate, magnesium silicate, zirconium silicate, titanium silicate, calcium silicate, zinc silicate, aluminum borate, magnesium borate, zirconium borate, titanium borate, aluminum zirconate, zirconate Magnesium acid and the like. In addition to these composite metal oxides, a single metal oxide such as silica gel can be used as long as the above-mentioned shape is satisfied.

Particularly preferably used solid acids are aluminum silicate, magnesium silicate and mixtures thereof. These are preferably synthetic products over natural products. Commercially available solid acids having these properties include KW-600BUP-S, KW-, manufactured by Kyowa Chemical Industry Co., Ltd.
700PEL, KW-700SEL, and the like. Of these, KW-700PEL and KW-700SE
L is preferred. Most preferably, it is KW-700SEL.

As an example of the synthetic aluminum silicate, those having a silicon dioxide content of 55 to 75% by weight and an aluminum oxide content of 5 to 25% by weight are preferable. Examples of chemical composition include _{Al 2 O 3 · nSiO 2 ·} mH 2 O (n, m are silicon dioxide to aluminum oxide or coordination number of water,). Those coordinated with water are preferred. As examples of the synthetic magnesium silicate, those having a silicon dioxide content of 55 to 70% by weight and a magnesium oxide content of 5 to 20% by weight are preferable. Examples of chemical composition include _{MgO · xSiO 2 · yH 2 O} (x, y , the silicon dioxide to magnesium oxide or coordination number of water,). In particular, those coordinated with water are preferable.

The contact temperature between the crude polyoxyalkylene polyol and the solid acid may be around room temperature. However, the contact temperature is preferably in the range of 50 to 150 ° C. in consideration of shortening the treatment time, improving the ability to remove the catalyst, and the like. More preferably 60 to 140 ° C, still more preferably 7
0-130 ° C. When the molecular weight of the polyoxyalkylene polyol is large, the viscosity increases, so
It is preferable to make contact as described above. If the temperature is higher than 150 ° C., the crude polyoxyalkylene polyol tends to be colored.

As a method for contacting the crude polyoxyalkylene polyol with the solid acid, there are two methods, a batch method and a continuous method. Batch type means, for example, charging a solid acid to a crude polyoxyalkylene polyol charged to a reactor,
It is a method of stirring and mixing. For the purpose of preventing coloring and deterioration of the polyoxyalkylene polyol, it is preferable to carry out stirring and mixing in the presence of an inert gas. The amount of the solid acid used is 0.01 to 2% by weight based on the crude polyoxyalkylene polyol. Preferably 0.05-1.
It is 5% by weight, more preferably 0.1 to 1% by weight. The contact time depends on the scale, but is 1 to 6 under the above temperature conditions.
Time is preferred. The continuous method is a method in which a crude polyoxyalkylene polyol is passed through a column filled with a solid acid. The superficial velocity depends on the scale, but is 0.1 to 3
(1 / hr) is preferable. After contact with the solid acid, the polyoxyalkylene polyol is recovered by a conventional method such as filtration or centrifugation.

In order to further improve the ability of the solid acid to adsorb the catalyst, when the crude polyoxyalkylene polyol is brought into contact with the solid acid, 0.1 to 10% by weight of water is added to the crude polyoxyalkylene polyol. Is preferably coexisted. More preferably, it is 1 to 8% by weight, further preferably 2 to 7% by weight. The method of allowing the solid acid and water to coexist may be achieved by adding them to the polyol. The order in which both are added does not matter. The temperature at which water is added to the crude polyoxyalkylene polyol is 50 to 150 ° C.
Is preferred. When water is added, for example, the crude polyoxyalkylene polyol and the solid acid are stirred and mixed at 90 ° C. for 5 hours, and then, for example, a dehydration operation under reduced pressure is performed at 110 ° C. and 1.33 kPa or less to remove water. .

For the purpose of preventing deterioration of the polyoxyalkylene polyol, it is preferable to add an antioxidant to the polyoxyalkylene polyol. Antioxidants may be used alone or in combination of two or more. Examples of the antioxidant include tert-butylhydroxytoluene (B
HT), pentaerythrityl-tetrakis-3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, ethylhexyl phosphite, 4,4
'-Bis-α, α'-dimethylbenzyldiphenylamine, 2-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-ethylphenol and the like. The addition amount of the antioxidant is 100 to 2000 ppm based on the polyoxyalkylene polyol.
It is about.

Further, when a purified polyoxyalkylene polyol is reacted with a polyisocyanate compound to produce an isocyanate group-terminated prepolymer, the polyoxyalkylene obtained by the above-mentioned method is used for the purpose of improving the stability with time of the prepolymer. An acid can also be added to the polyol. Acids include inorganic acids and organic acids. As the inorganic acid, for example, phosphoric acid, phosphorous acid,
Examples include hypophosphorous acid, pyrophosphoric acid, and aqueous solutions thereof. Examples of the organic acid include formic acid, oxalic acid, succinic acid, acetic acid, maleic acid, benzoic acid, paratoluenesulfonic acid, and aqueous solutions thereof. Phosphoric acid and maleic acid are preferred, and they are preferably used in the form of an aqueous solution. The amount of the acid is 1 to 25 ppm based on the polyoxyalkylene polyol. Preferably 1 to
20 ppm, more preferably 1 to 15 ppm. The acid is added in the above-described amount, and the pH of the polyoxyalkylene polyol is less than 5, and the acid value is 0.08.
It is preferable to use it within a range that does not exceed mgKOH / g.

Further, the peroxide concentration in the polyoxyalkylene polyol obtained by the above operation is 0.28 mm
ol / kg or less is preferred. More preferably 0.2 mm
ol / kg or less, most preferably 0.15 mmol /
kg or less. Peroxide concentration 0.28mmol / k
If it exceeds g, when a tin-based catalyst is used in the reaction with the polyisocyanate compound, the activity of the tin-based catalyst is reduced by the peroxide, so that the moldability and mechanical properties of the polyurethane are reduced.

The purified polyoxyalkylene polyol obtained as described above has the following characteristics (1) to (4).
That is, (1) OH in the range of 2 to 200 mgKOH / g
V. (2) 0.07 meq. / G total unsaturation in the range (hereinafter C = C). (3) Selectivity of head-to-tail bonds of oxypropylene groups of 95 mol% or more (hereinafter referred to as HT bond selectivity). (4) 150pp
m or less of catalyst remaining. (Hereinafter, these are referred to as the four requirements of the polyoxyalkylene polyol according to the present invention).

OHV of polyoxyalkylene polyol
Is preferably 9 to 120 mgKOH / g, and more preferably 11 to 60 mgKOH / g. If the addition polymerization of an epoxide compound, particularly propylene oxide, is carried out until the OHV becomes less than 2 mgKOH / g, the reaction time of the polyoxyalkylene polyol becomes too long. On the other hand, when the OHV is more than 200 mgKOH / g, the molecular weight of the polyoxyalkylene polyol decreases, and the flexibility of the obtained polyurethane decreases.

C = C of polyoxyalkylene polyol
Is mainly an index of the amount of a monool having an unsaturated group at a molecular terminal generated by a side reaction of propylene oxide. C = C is 0.07 meq. / G or less. If it is larger than this, the mechanical properties of polyurethane resins such as flexible polyurethane foams, elastomers and sealing materials are undesirably deteriorated. From such a viewpoint, C
= C is preferably 0.05 meq. / G or less, more preferably 0.03 meq. / G or less. C = C of the polyoxyalkylene polyol is preferably 0 depending on the use of the polyurethane resin. However, reaction conditions such as reaction temperature and pressure must be extremely relaxed, and the reaction time becomes too long, which is not necessarily industrially preferable. From such a viewpoint, the lower limit of C = C is 0.001 meq. / g is preferred.

In such a polyoxyalkylene polyol having a low C ＝ C, if the HT bond selectivity based on oxypropylene groups by propylene oxide addition polymerization is less than 95%, the viscosity of the polyoxyalkylene polyol increases, or Problems such as deterioration of the moldability of a flexible polyurethane foam due to poor compatibility with an auxiliary such as a silicone foam stabilizer are caused. In addition, the workability decreases because the viscosity of the prepolymer obtained by the reaction with the polyisocyanate compound also increases due to the increase in the viscosity when the polyoxyalkylene polyol is increased in molecular weight. From such a viewpoint, the HT bond selectivity is 95 mol% or more, and preferably 96 mol%.

The remaining amount of the catalyst in the polyoxyalkylene polyol is 150 ppm or less. When the residual amount of the catalyst is more than 150 ppm, the viscosity of the isocyanate group-terminated prepolymer obtained by reacting the polyoxyalkylene polyol with the polyisocyanate compound changes over time. The remaining amount of the catalyst is preferably 90 ppm
Or less, more preferably 50 ppm or less. The lower limit of the remaining amount of the catalyst is preferably as small as possible. Usually, according to the above-mentioned purification method, it is possible to reduce the amount to about 1 ppm.

<Method for Producing Polymer-Dispersed Polyol> Next, a method for producing a polymer-dispersed polyol according to the present invention will be described. As a method for producing a polymer-dispersed polyol, a method in which an ethylenically unsaturated monomer is polymerized in a polyoxyalkylene polyol by a continuous operation or a batch operation to disperse polymer particles in the polyol (hereinafter, referred to as Method I) Or a method in which a polymer solution previously polymerized in a solvent or the like is added to the polyoxyalkylene polyol, the solvent is removed, and polymer particles are dispersed in the polyol (hereinafter, referred to as a method II). Considering the productivity of the polymer-dispersed polyol, I
The process, especially its continuous operation, is preferred. First, the method I will be described.

In the present invention, the polyoxyalkylene polyol used for producing the polymer-dispersed polyol is
It is a polyoxyalkylene polyol satisfying the above four requirements of 1-4. O of polyoxyalkylene polyol
HV is preferably in the range of 10 to 150 mgKOH / g. More preferably, it is in the range of 15 to 100 mgKOH / g.

The ethylenically unsaturated monomer for forming the polymer particles is a compound having at least one polymerizable ethylenically unsaturated group. Such ethylenically unsaturated monomers include, for example, acrylonitrile,
Cyano group-containing monomers such as methacrylonitrile; methacrylate monomers such as methyl acrylate, butyl acrylate, stearyl acrylate, hydroxyethyl acrylate, dimethylaminoethyl acrylate, and dimethylaminopropyl methacrylate; acrylic acid, methacrylic acid, itaconic acid, and maleic Acid, carboxyl group-containing monomer such as fumaric acid, maleic anhydride,
Acid anhydride group-containing monomers such as itaconic anhydride, hydrocarbon monomers such as butadiene, isoprene, and 1,4-pentadiene; aromatic hydrocarbon monomers such as styrene, α-methylstyrene, phenylstyrene, and chlorostyrene; Halogen-containing monomers such as vinyl and vinylidene chloride, vinyl ethers such as vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl ethyl ketone, vinyl esters such as vinyl acetate, acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide , Acrylamides such as N, N-dimethylaminopropylacrylamide and methylenebisacrylamide, and methacrylamides such as N, N-dimethylmethacryloylamide. These can be used alone or in a mixture of two or more.

Among them, preferred are ethylenically unsaturated monomers containing at least one compound selected from acrylonitrile, styrene, acrylamide and methyl methacrylate.

The dispersion concentration of the polymer particles depends on the amount of the ethylenically unsaturated monomer used and its conversion. Although it depends on the production conditions of the polymer-dispersed polyol, the conversion of the ethylenically unsaturated monomer is usually 70% by weight or more. It is preferably at least 80% by weight. The amount of the ethylenically unsaturated monomer used is determined in consideration of the conversion. Specifically, the amount is 5 to 86 parts by weight based on 100 parts by weight of the polyoxyalkylene polyol as the dispersion medium. Preferably 8 to 70 parts by weight, more preferably 9 to 70 parts by weight.
52 parts by weight. Thus, a polymer-dispersed polyol having a concentration of the dispersed polymer particles of 5 to 60% by weight of the total amount of the polyoxyalkylene polyol as the dispersion medium and the polymer particles is obtained. Preferably it is 10 to 50% by weight, more preferably 12 to 45% by weight. If the concentration of the polymer particles is less than 5% by weight, the effect of using the polymer-dispersed polyol, such as the hardness of the polyurethane and the air permeability of the polyurethane foam, cannot be sufficiently improved. When the concentration of the polymer particles exceeds 60% by weight, the viscosity of the resulting polymer-dispersed polyol increases significantly,
Further, the dispersion stability is also deteriorated.

The average particle size of the polymer particles dispersed in the polyoxyalkylene polyol is 0.01 to 10 μm.
Is preferred. More preferably, it is 0.05 to 7 μm, most preferably 0.08 to 5 μm. Average particle size 0.0
If it is less than 1 μm, the viscosity of the polymer-dispersed polyol increases. If the average particle size is larger than 10 μm, the dispersion stability of the polymer will be deteriorated.

For the polymerization of the ethylenically unsaturated monomer, a radical polymerization initiator is used. Specifically, 2,2 '
Azo compounds such as -azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutylnitrile), 2,2'-azobis (isobutyronitrile), benzoyl peroxide And peroxides such as t-butyl peroxide and di-t-butyl peroxide, and peroxydisulfide. The amount of the polymerization initiator used is usually 0.1 to 10% by weight based on the ethylenically unsaturated monomer. Preferably 0.5 to 5
% By weight.

It is preferable to use a chain transfer agent together with the radical polymerization initiator. As the chain transfer agent, for example,
Alcohols such as methanol, ethanol, propanol, isopropanol and pentanol, mercaptans, halogenated hydrocarbons, aliphatic amines such as triethylamine, tripropylamine, tributylamine, N, N-diethylethanolamine, N-methylmorpholine , Morpholines such as N-ethylmorpholine, sodium methallylsulfonate, sodium allylsulfonate,
Examples include toluene, xylene, acetonitrile, hexane, heptane, dioxane, ethylene glycol dimethyl ether, N, N-dimethylformaldehyde, and the like. Of these, preferred are triethylamine and a mixture of triethylamine and isopropanol. The amount of the chain transfer agent used is 0.01 to 1 based on the total weight of the polyoxyalkylene polyol and the ethylenically unsaturated monomer.
0% by weight is preferred. More preferably, it is 0.05 to 5% by weight.

Further, for the purpose of stably dispersing the polymer particles, the polymerization can be carried out in the presence of a dispersion stabilizer. Such a dispersion stabilizer is disclosed in JP-B-49-46.
Examples thereof include a polyester polyol containing a carbon-carbon unsaturated bond and a modified polyol having an acryl group, a methacryl group, an allyl group, or the like at the molecular terminal, as described in JP-A-556. In addition, high molecular weight polyoxyalkylene polyols and polyester polyols containing substantially no carbon-carbon unsaturated bond can be used as the dispersion stabilizer.

To the above polyoxyalkylene polyol, a polymerization reaction is carried out by adding an ethylenically unsaturated monomer, a polymerization initiator, and if necessary, a chain transfer agent, a dispersion stabilizer and the like. The polymerization temperature of the ethylenically unsaturated monomer is determined according to the type of the radical initiator used. Normal,
Polymerizes above the decomposition temperature of the initiator. Preferably 4
It is 0-200 ° C, more preferably 90-150 ° C.
Further, the polymerization reaction can be performed under pressure and under atmospheric pressure. The polymerization reaction can be carried out without solvent.
The reaction can also be performed in the presence of at least one solvent selected from water and an organic solvent. As the organic solvent, toluene,
Xylene, acetonitrile, hexane, heptane, dioxane, ethylene glycol dimethyl ether, N, N
-Dimethylformamide, methanol, ethanol, butanol, isopropanol and the like.

After the completion of the polymerization reaction, the obtained polymer-dispersed polyol can be used as a raw material for polyurethane as it is. However, it is preferable that the unreacted ethylenically unsaturated monomer, the decomposition product of the polymerization initiator, the chain transfer agent, the solvent and the like are used after being distilled off under reduced pressure. The conditions for the distillation under reduced pressure are not particularly limited, but are usually 70 to 15
It is carried out using a device such as a forced thin film evaporator under the condition of 0 ° C. and 1.33 kPa or less.

Next, a method of adding a polymer solution polymerized in a solvent or the like to a polyoxyalkylene polyol, removing the solvent, and dispersing the polymer particles (Method II) will be described. The compounds described above are used as the ethylenically unsaturated monomer, the polymerization initiator and the like for forming the polymer particles. The polymerization temperature depends on the polymerization initiator used and the chemical and physical properties of the ethylenically unsaturated monomer, but is usually 40.
~ 200 ° C. Preferably it is in the range of 90 to 150 ° C. As the solvent used for the polymerization, a polymerization initiator used,
Depending on the chemical and physical properties of the ethylenically unsaturated monomer, at least one solvent selected from the above-mentioned organic solvents and water is used. The amount of the polymerization initiator and the amount of the ethylenically unsaturated monomer used is not particularly limited,
Usually, 0.01 to 10% by weight, 3
６０60% by weight. In the polymerization of the monomer, the above-mentioned chain transfer agent may be used.

After forming polymer particles in a solvent,
The obtained polymer solution and the above-mentioned polyoxyalkylene polyol are mixed. The mixing conditions are not particularly limited, but are usually 15 to 150 ° C. Preferably it is in the range of 20 to 120 ° C. Mixing time is 0.5 ~
Perform under stirring for about 5 hours. After that, a solvent removing operation is performed. Although it depends on the solvent and the chemical and physical properties of the polymer used, usually, the solvent is removed by heating and decompressing at 70 to 150 ° C. and 1.33 kPa or less for about 1 to 6 hours. At that time, in order to promptly remove the solvent, a decompression operation can be performed while passing an inert gas through the polyoxyalkylene polyol.

The average particle size of the polymer contained in the polymer-dispersed polyol affects the dispersion stability of the polymer and the viscosity of the polymer-dispersed polyol.
The average particle size of the polymer is preferably from 0.01 to 10 μm. In order to obtain such a particle size, in addition to the characteristics of the polyoxyalkylene polyol which is a dispersion medium, the above-mentioned chain transfer agents, dispersion stabilizers, types of solvents and the like, and the amounts used thereof, ethylenically unsaturated monomers By appropriately adjusting the weight composition ratio and the like.

<Production method of isocyanate group-terminated prepolymer (1)> A method of producing an isocyanate group-terminated prepolymer using a polyoxyalkylene polyol as a raw material will be described. The isocyanate group-terminated prepolymer is produced by reacting a polyol with a polyisocyanate compound. The polyol used in the present invention is a polyoxyalkylene polyol satisfying the four requirements (1) to (4) or the polymer-dispersed polyol derived from the polyoxyalkylene polyol.

First, a method using a polyoxyalkylene polyol as the polyol will be described. The polyol is a polyoxyalkylene polyol that satisfies the above four requirements (1) to (4). Among them, those having a residual amount of the catalyst of 50 ppm or less are preferable. Furthermore, CPR (Con) of polyoxyalkylene polyol
controlled Polymerization Ra
te, an index indicating the amount of the basic substance in the polyol)
It is preferably 3 or less. More preferably, CPR is 1 or less, and most preferably, CPR is 0. When the CPR is more than 3, the storage stability of the isocyanate group-terminated prepolymer decreases.

The remaining amount of the catalyst in the isocyanate group-terminated prepolymer is preferably 120 ppm or less. It is more preferably at most 70 ppm, most preferably at most 20 ppm. The residual amount of the catalyst in the isocyanate group-terminated prepolymer is achieved by controlling the residual amount of the catalyst in the polyoxyalkylene polyol to 150 ppm or less. When the residual amount of the catalyst in the isocyanate group-terminated prepolymer is more than 120 ppm, the change in viscosity of the prepolymer with time increases. The lower limit of the remaining amount of the catalyst is
The smaller the better, the better. Usually, according to the above-mentioned method for purifying a polyoxyalkylene polyol, it is possible to remove up to about 1 ppm, so that the residual amount of the catalyst in the isocyanate group-terminated prepolymer can be reduced to about 1 ppm.

As the polyisocyanate compound used in the present invention, aromatic, aliphatic and alicyclic compounds having two or more isocyanate groups in one molecule can be used. For example, as aromatic isocyanates, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, 80: 2 of these organic polyisocyanates
0 weight ratio (TDI-80 / 20), 65:35 weight ratio (TDI-65 / 35) isomer mixture, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane Diisocyanate, any isomer mixture of diphenylmethane diisocyanate, toluylene diisocyanate, xylylene diisocyanate, α, α, α ′, α ′
-Hydrogenated tetramethyl xylylene diisocyanate, paraphenylene diisocyanate, naphthalene diisocyanate and the like, and these polyisocyanates (hereinafter, referred to as
Hydrogenated) compounds.

Examples of the aliphatic isocyanates include ethylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, and lysine. And diisocyanates. Examples of the alicyclic isocyanate include isophorone diisocyanate, norbornene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate.

Further, modified isocyanates such as the above-mentioned carbodiimide-modified, buret-modified and isocyanurate-modified polyisocyanates can also be used. or,
The polyisocyanate and the modified polyisocyanate were converted to the above-mentioned active hydrogen compounds, having a number average molecular weight of 10
Polyols of 0 to 6000 g / mol, and monools such as methanol, ethanol, n-propanol, iso-propanol, butanol and allyl alcohol alone or isocyanate compounds modified with a mixture thereof can also be used. Further, an epoxide compound is addition-polymerized to a monol, and the number average molecular weight is 100 to 30.
A polyol in the range of 00 g / mol may be used as a polyisocyanate modifier. The above-mentioned polyisocyanates and modified polyisocyanates can be used as a mixture. The preferred mixing ratio is in the range of 5:95 to 95: 5 by weight ratio of the polyisocyanate and the modified polyisocyanate, more preferably, 1: 1.
0: 90-90: 10, most preferably 30: 70-
70:30.

Of the above polyisocyanates, preferably, 2,4-tolylene diisocyanate (hereinafter, referred to as 2,4-tolylene diisocyanate)
4-TDI), 2,6-tolylene diisocyanate (hereinafter, referred to as 2,6-TDI), and an 80:20 weight ratio of these polyisocyanates (TDI-80 / 2).
0), a mixture of isomers in 65:35 weight ratio (TDI-65 / 35), hydrogenated TDI-80 / 20, hydrogenated TDI-65
/ 35,4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI), hydrogenated MDI, paraphenylene diisocyanate, xylene diisocyanate (hereinafter referred to as MDI)
XDI), hydrogenated XDI, hexamethylene diisocyanate (hereinafter referred to as HDI), isophorone diisocyanate (hereinafter referred to as IPDI), norbornene diisocyanate (hereinafter referred to as NBDI), and dicyclohexylmethane diisocyanate (hereinafter referred to as DCHMDI).

Further, propylene oxide, ethylene oxide and the like are added to the burette-modified and isocyanurate-modified polyisocyanates, the glycerin-modified and trimethylolpropane-modified polyisocyanates, and glycerin and trimethylolpropane. A modified polyisocyanate modified with a polymerized polyol is preferred. Particularly preferably, TDIs, MD
I, XDI, HDI, IPDI, NBDI, isocyanurate-modified, burette-modified, polyol-modified polyisocyanates, and mixtures thereof.

In producing an isocyanate group-terminated prepolymer, the NCO index, which is the equivalent ratio of isocyanate groups to active hydrogen groups in the polyol, is 1.3.
-10. It is preferably from 1.4 to 9, more preferably from 1.5 to 8. The isocyanate group content of the isocyanate group-terminated prepolymer (hereinafter referred to as NC
O%) is 0.3 to 30% by weight. Preferably it is 0.5 to 25% by weight, more preferably 0.8 to 15% by weight, most preferably 1 to 10% by weight. In the isocyanate group-terminated prepolymer used in the one-pack type curable composition obtained by reacting with moisture in the air, the NCO% is designed to be low within the above range. Also, glycols such as 1,4-butanediol, dipropylene glycol, and polyoxyalkylene polyol, and polyamine compounds such as 3,3′-dichloro-4,4′-diaminodiphenylmethane and diethyldiaminotoluene are used as curing agents. In the isocyanate group-terminated prepolymer used for the two-part curable composition, the NCO% is designed to be higher than that of the one-part type.

The HT bond selectivity of the main chain of the isocyanate group-terminated prepolymer produced by the present invention is 95 mol% or more. This is achieved by controlling the HT bond selectivity of the oxypropylene group by propylene oxide addition polymerization of the raw material polyoxyalkylene polyol to 95 mol% or more. By setting the HT bond selectivity of the main chain of the isocyanate group-terminated prepolymer to 95 mol% or more, the viscosity can be reduced even when the molecular weight is increased. The HT bond selectivity of the prepolymer is preferably 96% or more.

As the catalyst in the prepolymerization reaction,
Known catalysts for producing polyurethane such as amine compounds and organometallic compounds can be used. When the molecular weight of the polyoxyalkylene polyol is small, that is, OH
When V is high, it may not be necessary to use a catalyst. As the amine compound, for example, triethylamine, tripropylamine, tributylamine, N, N,
N ', N'-tetramethylhexamethylenediamine, N-
Examples include methylmorpholine, N-ethylmorpholine, dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, triethylenediamine, and salts of triethylenediamine. As the organometallic compound, for example, tin acetate, tin octylate, tin oleate,
Examples include tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate. These catalysts can be used alone, or two or more of them can be used as a mixture. Among these catalysts, an organometallic catalyst is particularly preferable. The amount used is 0.0001 to 2.0 parts by weight based on 100 parts by weight of the polyoxyalkylene polyol. Preferably it is 0.001-1.0 weight part.

The temperature for producing the prepolymer is 50
~ 120 ° C is preferred. More preferably 60 to 110
° C, particularly preferably 70 to 100 ° C. When reacting the polyol and the polyisocyanate compound, it is desirable to react 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. Nitrogen is preferred. The reaction is carried out with stirring for 2 to 10 hours in a nitrogen atmosphere.

An organic solvent inert to the polyisocyanate and the polyol may be used before, during or after the reaction when producing the isocyanate group-terminated urethane prepolymer. The amount of the organic solvent is preferably 100% by weight or less based on the total weight of the polyol and the polyisocyanate. It is more preferably at most 60% by weight, most preferably at most 40% by weight. Examples of such organic solvents include aromatic, aliphatic, alicyclic, ketone, ester, and ester ether solvents. For example, toluene, xylenes, hexanes, acetone, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and the like.

Next, a method for producing an isocyanate group-terminated prepolymer having a free isocyanate compound content of 1% by weight or less will be described. The NCO% of the isocyanate group-terminated prepolymer having a free isocyanate compound content of 1% by weight or less is 0.3 to 30% by weight. Preferably 0.5 to 25% by weight, more preferably 1 to 25% by weight.
１５15% by weight. The content of the free isocyanate compound in the isocyanate group-terminated prepolymer is preferably 0.8% by weight or less. It is more preferably at most 0.5% by weight, most preferably at most 0.1% by weight. If the free isocyanate content exceeds 1% by weight, the hysteresis loss of the polyurethane increases.

In order to control the content of the free isocyanate compound in the isocyanate group-terminated prepolymer to 1% by weight or less, the above-mentioned isocyanate group-terminated prepolymer is subjected to reduced pressure treatment under specific temperature and pressure conditions. .
In addition, the isocyanate group-terminated prepolymer which is a raw material of the isocyanate group-terminated prepolymer having a content of the free isocyanate compound of 1% by weight or less is produced by the method described above. In order to suppress the formation of unreacted isocyanate compound dimers during the reduced pressure treatment, the reduced pressure treatment operation is an important step. Temperature during decompression operation is 70 to 180 ° C
It is. Preferably 80 to 170 ° C, more preferably 8
5 to 160 ° C. When the temperature is lower than 70 ° C., the time for removing the unreacted isocyanate compound becomes longer.
When the temperature exceeds 180 ° C., the viscosity of the prepolymer increases during the pressure reduction process. The pressure is 665 Pa or less.
Preferably 266 Pa or less, more preferably 133 Pa
It is as follows. Most preferably, it is 13.3 Pa or less.
If the pressure exceeds 665 Pa, the time for removing the unreacted polyisocyanate compound becomes longer, and the viscosity of the prepolymer increases during the pressure reduction process.

The reduced pressure treatment is preferably a thin film evaporation method. A forced circulation type stirred membrane type evaporator or a falling film type molecular distillation apparatus can be used (references; 5th revised edition, Chemical Engineering Handbook: edited by Chemical Engineering Association, Maruzen Co., Ltd., 198).
8 years). As such an apparatus, for example, a Smith type thin film evaporator (manufactured by Shinko Pantech Co., Ltd., trade name: Wiperen, Exeva) or a control type thin film evaporator [manufactured by Hitachi, Ltd., trade name: Sunbay type] And the like). The polyisocyanate compound recovered from the prepolymer by the reduced pressure treatment can be used again for the prepolymer reaction. When used, it is preferably a polyisocyanate compound having few impurities such as a dimer.

A curing catalyst, a silicone coupling agent, a filler, a plasticizer, a pigment, a reinforcing agent, a flame retardant,
Stabilizers, defoamers and the like can be added according to the purpose. Furthermore, an inorganic acid, an organic acid, or the like may be added to the prepolymer for the purpose of suppressing a change in viscosity of the prepolymer over time. Examples of the inorganic acids include phosphoric acid and pyrophosphoric acid. Examples of the organic acid include adipic acid, 2-ethylhexanoic acid, and oleic acid. These acids can be used alone or in combination of two or more. The amount used is preferably 0.0001 to 3 parts by weight based on 100 parts by weight of the isocyanate group-terminated prepolymer. More preferably 0.003 to
1 part by weight.

<Production method of isocyanate group-terminated prepolymer (2)> Next, a method of using a polymer-dispersed polyol as the polyol will be described. An isocyanate group-terminated prepolymer using a polymer-dispersed polyol as a raw material is basically produced by a method similar to the above-mentioned method using a polyoxyalkylene polyol. As the polyisocyanate compound, the additive, and the like, the same ones as described above are used. That is, a method using a polymer-dispersed polyol instead of the polyoxyalkylene polyol. As the polymer-dispersed polyol, those obtained by the method for producing a polymer-dispersed polyol according to the present invention described above are used. Considering the viscosity of the isocyanate group-terminated prepolymer, the polymer dispersed polyol of the present invention has a polymer concentration of 5 to 30% by weight.
Are preferred. The NCO% of the isocyanate group-terminated prepolymer is 0.3 to 30% by weight, preferably,
1 to 15% by weight.

<Method for Producing Polyurethane Resin (1)> A method for producing a polyurethane resin using an isonate group-terminated prepolymer as a raw material will be described. The polyurethane resin is produced by reacting a prepolymer containing the isocyanate group-terminated prepolymer produced by the above method with a chain extender. The amounts of the isocyanate group-terminated prepolymer and the chain extender used are such that the isocyanate index is in the range of 0.6 to 1.5. Preferably it is 0.8-1.3, more preferably 0.9-1.2. The resulting polyurethane resin is mainly polyurethane elastomer, polyurethane urea elastomer, paint,
It can be used in the adhesive field and the like.

The prepolymer preferably contains at least 60% by weight of the isocyanate group-terminated prepolymer produced by the above production method. More preferably, it contains at least 70% by weight. Most preferably, it is an isocyanate group-terminated prepolymer alone produced by the above method. Preferred forms of the isocyanate group-terminated prepolymer obtained by a production method other than the method of the present invention include, for example, polytetramethylene glycol, polyoxyethylene adipate and polycaprolactone polyol exemplified in JP-B-6-13593. And a isocyanate group-terminated prepolymer having a polyol component. When the content of the isocyanate group-terminated prepolymer obtained from the polyoxyalkylene polyol obtained by the method of the present invention as a raw material is less than 60% by weight, the viscosity of the prepolymer increases and the workability decreases.

The chain extender is a compound having two or more active hydrogen groups capable of reacting with an isocyanate group in one molecule. For example, at least one kind of active hydrogen group-containing compound of a polyol compound and a polyamine compound may be mentioned. As the polyol compound, for example, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol,
1,3-propanediol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
Dihydric alcohols such as neopentyl glycol and 1,6-hexanediol; trihydric alcohols such as glycerin and trimethylolpropane; cyclohexylene such as 1,4-cyclohexanediol and spirohexanediol; spiro rings and methylene It is a compound containing a chain and containing various bonds such as an ether bond and an ester bond as those connecting the chains.

Further, derivatives containing various substituents can be used as the derivatives thereof. Further, as aromatic alcohols, compounds such as hydroquinone, resorcin and bishydroxyethylene terephthalate, and at least one alkylene oxide selected from 1 to 4 mol of ethylene oxide and propylene oxide per hydroxyl group of these compounds are added. Polyols can also be used.

Examples of the polyamine compound include tolylenediamine, 3,5-diethyl-2,4-diaminotoluene,
3,5-diethyl-2,6-diaminotoluene, diphenylmethanediamine, and a mixture of isomers thereof, m
-Phenylenediamine, 3,3'-dichloro-4,4 '
-Aromatic diamines of diaminodiphenylmethane. Also, alicyclic diamines such as isophorone diamine and norbornene diamine, and linear aliphatic diamines such as ethylene diamine, carbodihydrazide, alkyl dihydrazide such as adipic dihydrazide, or conventionally known polyamine compounds such as derivatives thereof can be used. .
Further, amino group-containing 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. These polyols and polyamines can be mixed at an arbitrary ratio and used as a chain extender.

Of the above compounds, preferred are ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, glycerin, trimethylolpropane, and 3,5-diethyl-2. , 4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 3,3'-dichloro-4,4'-diaminodiphenylmethane, isophoronediamine, norbornenediamine, and addition polymerization of alkylene oxide to these compounds It is a polyol.

The above-mentioned isocyanate group-terminated prepolymer and a chain extender are previously brought to a predetermined temperature, for example,
The temperature is adjusted to 30 to 150 ° C., and a vacuum degassing treatment is performed. Next, the two components are rapidly stirred and mixed to a predetermined temperature, for example, 4 ° C.
It is poured into a mold heated to 0 to 140 ° C. to produce a molded product (polyurethane resin). At this time, a curing catalyst, an inorganic acid, an organic acid, a silicone-based coupling agent, a filler, a plasticizer, a pigment, a reinforcing agent, a flame retardant, a stabilizer, an antifoaming agent, etc. are used according to the intended use of the polyurethane resin. Can be added. As the polyurethane curing catalyst, the above-mentioned conventionally known catalysts for producing polyurethane such as amine compounds and organometallic compounds can be used.

In order to suppress a change in viscosity of the prepolymer with time, an inorganic acid or an organic acid may be added to the prepolymer. Phosphoric acid is preferred as the inorganic acid.
As the organic acid, for example, adipic acid, 2-ethylhexanoic acid, oleic acid and the like can be used. These acids can be used alone or in combination of two or more. The used amount is 0.001 to 10.0 parts by weight based on 100 parts by weight of the isocyanate group-terminated prepolymer. Preferably it is 0.003-5.0 weight part.

As described above, a polyurethane resin is produced by reacting the prepolymer mainly containing the isocyanate group-terminated prepolymer according to the present invention with the chain extender containing an active hydrogen group. In addition to this method, a one-shot method in which a polyol containing at least 60% by weight of the polyoxyalkylene polyol according to the present invention, a polyisocyanate, and a chain extender are mixed and molded at the same time can be applied.

<Method for Producing Polyurethane Resin (2)> Next, a method for producing a polyurethane resin using the polyoxyalkylene polyol obtained by the above method as a curing agent will be described. The polyurethane resin is
It is produced by reacting the polyoxyalkylene polyol obtained by the production method with an isocyanate group-terminated prepolymer. Usually, the polyurethane resin obtained by such a method is used for waterproofing and sealing materials. The polyoxyalkylene polyol used as the curing agent satisfies the requirements (1) to (4) described in the section of the method for producing the polyoxyalkylene polyol. Among them, OHV is 8-100
mg KOH / g is preferred. More preferably, 10
~ 50 mgKOH / g polyoxyalkylene polyol.

In advance, the polyoxyalkylene polyol may be supplemented with a urethanizing catalyst, a plasticizer, an ultraviolet absorber, an antioxidant, a filler, a reinforcing agent, a flame retardant, an antifoaming agent, a pigment, a silicone coupling agent, or the like. Agents may be mixed. Conventionally known compounds can be used for these various auxiliaries. The total amount of the auxiliaries is 10 to 800 parts by weight based on 100 parts by weight of the polyoxyalkylene polyol. Preferably it is 20 to 700 parts by weight. As long as the polyoxyalkylene polyol is obtained by the above method, polyoxyalkylene polyols having different molecular weights (OHV), the number of functional groups, and the content of oxypropylene groups may be mixed at an arbitrary ratio.

Examples of the silicone coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like. The amount used is preferably 0.01 to 8 parts by weight based on 100 parts by weight of the polyoxyalkylene polyol. More preferably, it is 0.03 to 5 parts by weight. Further, the polyamine compound described above may be added to the polyoxyalkylene polyol.

In order to improve the dispersion stability of the polyoxyalkylene polyol and the above-mentioned auxiliary, stirring and mixing are sufficiently performed. The stirring method is preferably a kneading method in which a single or twin screw is mounted. The isocyanate group-terminated prepolymer used as the main agent is preferably an isocyanate group-terminated prepolymer produced by the above method. An isocyanate group-terminated prepolymer produced by another method may be used in combination. In such a case, those containing at least 60% by weight of the isocyanate group-terminated prepolymer produced by the above method are preferred. More preferably, it is 70% by weight.

An isocyanate group-terminated prepolymer as a main component and a polyoxyalkylene polyol as a curing agent are sufficiently mixed by stirring.
Cure at 0 ° C. The curing time is usually from 1 to 7 days, depending on the amount of the catalyst added to the curing agent. The polyoxyalkylene polyol and the isocyanate group-terminated prepolymer are reacted so that the isocyanate index is in the range of 0.8 to 1.3. Preferably it is in the range of 0.85 to 1.2, more preferably 0.9 to 1.1.

<Method for producing flexible polyurethane foam>
Finally, a method for producing a flexible polyurethane foam will be described. Overall density of the flexible foams produced by the present invention is preferably ^{20kg / m 3 ~60kg / m 3} . More preferably, 25 kg / m ^{3 to} 55 kg / m ³ ,
Most preferably, it is 27 kg / m ^{3 to} 50 kg / m ³ .
Foam elongation, an index of mechanical strength, is 90-200.
%. More preferably 100 to 18
0%. The compression set during wet heat is preferably 18% or less. It is more preferably at most 15%, most preferably at most 13%.

The lower limit of the compression set of the flexible urethane foam obtained by the method of the present invention when heated and wet is about 2%, although it depends on the density of the foam. Further, the hardness loss in the repeated compression test of the foam is preferably 20% or less. It is more preferably at most 15%. Most preferably, it is 12% or less. The lower limit of the hardness loss in the repetitive compression test of the flexible foam obtained by the method of the present invention is about 1%, depending on the density of the foam.

The flexible urethane foam according to the present invention comprises:
It is produced by stirring and mixing any one of the following polyols (a) or (b) with a polyisocyanate compound in the presence of water, a catalyst and a foam stabilizer. In producing the polyol foam, a crosslinking agent and other additives may be added alone or in combination of two or more depending on the desired physical properties. At this time, the crosslinking agent and other additives may be added to either one or both of the following polyol (a) or (b) or the polyisocyanate compound. Alternatively, it may be added to a mixer or a reactor for mixing a polyisocyanate compound, water, a catalyst, a foam stabilizer, and a polyol (a) or (b) below. (A) A polyol containing at least 30% by weight of the polyoxyalkylene polyol obtained by the production method of the present invention. (B) A polyol containing at least 10% by weight of the polymer-dispersed polyol obtained by the production method of the present invention.

First, a manufacturing method using (a) will be described. A polyol containing at least 30% by weight of the polyoxyalkylene polyol obtained by the production method of the present invention is used. The preferred content of the polyol is at least 50% by weight. More preferably at least 6
0% by weight. When the content of the polyoxyalkylene polyol according to the present invention is less than 30% by weight, the durability of the obtained flexible urethane foam, the moldability of the foam and the like are reduced.

Other than the polyol obtained by the production method of the present invention, which may be used in combination, US Pat.
Cesium hydroxide described in US Pat.
Examples include polyoxyalkylene polyols having a low monol content (corresponding to C = C of the present invention), polymer-dispersed polyols produced by conventionally known methods, and polyester polyols. Further, two or more polyoxyalkylene polyols having different OHV, C = C, oxypropylene group content, oxyethylene group content, or average number of functional groups may be used in combination.

The preferred molecular structure of the polyoxyalkylene polyol according to the present invention is such that the active hydrogen group is 3 to
Polyol having the compound No. 4 as a polymerization initiator. Examples of the polymerization initiator include glycerin, trimethylolpropane, pentaerythritol and the like among the active hydrogen compounds described above. OHV is 10 to 70 mgKOH /
g are preferred. More preferably 12 to 60 mgK
OH / g. Most preferably 15-55 mg KOH
/ G. The content of oxyethylene groups by addition polymerization of ethylene oxide is preferably 5 to 30% by weight. More preferably 6 to 25% by weight, most preferably 8% by weight.
-20% by weight. When the content of the oxyethylene group in the polyoxyalkylene polyol is more than 30% by weight, the permanent compression strain of the flexible foam at the time of wet heat tends to deteriorate. Further, it is preferable that the oxyethylene group is introduced into a molecular terminal of the polyoxyalkylene polyol. This is because the introduction of the oxyethylene group to the molecular terminal improves the primary hydroxyl group conversion rate at the molecular terminal of the polyoxyalkylene polyol. Among the polyoxyalkylene polyols according to the present invention, those having a primary hydroxyl group conversion at the molecular terminal of 50 mol% or more are preferred. It is more preferably at least 60 mol%, most preferably at least 70 mol%.

Next, a method using (b) will be described. A polyol containing at least 10% by weight of the polymer-dispersed polyol obtained by the production method of the present invention is used. Preferably it is at least 15% by weight, more preferably at least 20% by weight. When the polymer particle concentration of the polymer-dispersed polyol is about 30 to 60% by weight, the upper limit of use of the polymer-dispersed polyol is 60%.
% By weight is preferred. A more preferred upper limit is 50% by weight.

Examples of the polyols which can be used in combination, other than the production method of the present invention, include the above-mentioned polyoxyalkylene polyols of the present invention, USP5 and USP5.
No. 916,994, a cesium hydroxide-catalyzed polyoxyalkylene polyol having a low monol content, a polymer-dispersed polyol using the polyol as a dispersion medium, a polymer-dispersed polyol produced by a conventionally known method, and a polyester Polyols and the like. or,
OHV, C = C, the content of oxypropylene groups, the content of oxyethylene groups, or two or more kinds of polymer-dispersed polyols using a polyoxyalkylene polyol having a different average number of functional groups as a dispersion medium may be used in combination. Further, two or more kinds of polymer-dispersed polyols having different OHV, polymer particle concentration and ethylenically unsaturated monomer unit forming the polymer particles may be used in combination.

In producing a flexible urethane foam,
In addition to the polyol, water serving as a foaming agent, a catalyst, and a foam stabilizer are used. Water functions as a foaming agent because it reacts with the polyisocyanate compound to generate carbon dioxide gas. The amount of water used depends on the amount of the polyoxyalkylenepoly-
100 containing polyol and polymer-dispersed polyol
The amount is preferably 1 to 8 parts by weight with respect to parts by weight. More preferably, it is 2 to 7 parts by weight, most preferably 2.5 to 6 parts by weight. In combination with water, hydrofluorocarbons, hydrochlorofluorocarbons (such as HCFC-134a), hydrocarbons (such as cyclopentane), etc., developed for the purpose of protecting the global environment may be used as foaming aids. The amount of the foaming aid used in combination with water depends on the density of the intended flexible foam, but is preferably 1 to 30 parts by weight based on 100 parts by weight of the polyol. More preferably, 2
２５25 parts by weight.

As the catalyst, conventionally known catalysts can be used. The amount used is usually based on 100 parts by weight of the polyol.
0.005 to 10 parts by weight. Preferably 0.01 to
5 parts by weight. Illustrating a specific catalyst, for example,
Aliphatic amines such as triethylenediamine, bis (N, N-dimethylaminoethyl ether), and morpholines;
Organic tin compounds such as tin octoate and dibutyltin dilaurate are exemplified. These catalysts may be used alone or in combination of two or more.

As the foam stabilizer, conventionally known organosilicon surfactants can be used. The amount used is 0.1 to 4 parts by weight based on 100 parts by weight of the polyol. Preferably it is 0.2 to 3 parts by weight. As the foam stabilizer, for example, Dow Corning Silicone Toray, trade name: SRX
-274C, SF-2969, SF-2961, SF-
2962 or Nippon Unicar, product name: L-5
309, L-3601, L-5307, L-3600 and the like can be used.

As other auxiliaries, there are a crosslinking agent, a flame retardant, a pigment and the like, and each of them can be added as needed. When a crosslinking agent is used, the crosslinking agent may be OHV
200-1800 mg KOH / g polyol is used. For example, active hydrogen compounds such as aliphatic polyhydric alcohols such as glycerin, alkanolamines such as diethanolamine and triethanolamine, and OHV200
For example, a polyoxyalkylene polyol of about 1800 mgKOH / g is used. In addition, conventionally known crosslinking agents are used. The amount of the crosslinking agent used is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the polyol.

The polyoxyalkylene polyol or the polymer-dispersed polyol, water, catalyst, foam stabilizer, and
By mixing a crosslinking agent, a flame retardant, etc. according to the purpose,
A resin premix can be prepared, and a foam can be produced from the obtained resin premix. In the resin premix, pigments, ultraviolet absorbers,
An antioxidant and the like can also be added.

As the polyisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate
Tolylene diisocyanate (2,6-TDI) and mixtures thereof. Typically, tolylene diisocyanate (TDI) is 2,4-TDI and 2,6-TDI
In the form of a mixture of isomers. The weight ratio of isomers in tolylene diisocyanate is 2,4-TDI / 2,6-
The weight ratio of TDI is preferably 80:20 (TDI-8).
0/20). Furthermore, TDI and JP-A-11-140
No. 154, a mixed polyisocyanate with polymethylene polyphenyl polyisocyanate represented by the general formula (3) is preferred. Examples of such a polyisocyanate compound include Cosmonate M-200 and M-3000 manufactured by Mitsui Chemicals, Inc.

In the mixed polyisocyanate compound,
The mixing ratio of TDI and polymethylene polyphenyl polyisocyanate is preferably from 50:50 to 98: 2 by weight. It is more preferably from 65:35 to 95: 5, most preferably from 70:30 to 90:10. A urethane-modified product, a burette-modified polyisocyanate, an isocyanurate-modified product, and an allophanate-modified product obtained by reacting the polyisocyanate with a polyol having an OHV of 100 to 2000 mgKOH / g, an active hydrogen compound, or the like can also be used. NCO in the production of flexible urethane foam
Index is 0.6-1.5, preferably 0.7-
1.4, most preferably 0.7 to 1.3.

In the method for molding a flexible polyurethane foam according to the present invention, a resin premix and a polyisocyanate are usually mixed using a high-pressure foaming machine, a low-pressure foaming machine, or the like.
The molding method is preferred. When using a low pressure foaming machine, mixing of more than two components is possible. for that reason,
Polyols, waters, catalysts, flame retardants, polyisocyanates and the like can be divided and mixed. These mixed liquids are discharged from a mixing head of a foaming machine, foamed and cured as they are to produce a flexible polyurethane foam,
It can also be processed to the desired shape. Alternatively, the mixture may be injected into a mold, foamed, filled, and cured to obtain a molded product having a predetermined shape. Usually, the curing time is between 30 seconds and 30 minutes. A flexible polyurethane foam is produced at a mold temperature of about room temperature to about 80 ° C and a curing temperature of about room temperature to 180 ° C.

When used in the form of a resin premix, it is usually mixed with a polyisocyanate in a high-pressure or low-pressure foaming machine. When a hydrolyzable compound such as an organotin catalyst is used as a catalyst, a method of separating a water component and an organotin catalyst component and mixing them with a mixing head of a foaming machine is preferable to avoid contact with water. .

[0156]

The present invention will be described in more detail with reference to the following examples. In addition, each characteristic value shown in the Example was measured by the following method.

(1) The hydroxyl value (OHV, unit: mgKOH / g), total unsaturation (C = C, unit: meq./g), and viscosity (hereinafter, referred to as “polyoxyalkylene polyol”)
(Unit: mPa · s / 25 ° C.) Measured according to the method described in JIS K-1557.

(2) HT bond selectivity of polyoxyalkylene polyol (unit: mol%) 400 MHz ¹³ C nuclear magnetic resonance (NM) manufactured by JEOL Ltd.
R) Using an apparatus, using deuterated chloroform as a solvent,
The ¹³ C-NMR spectrum of the polyoxyalkylene polyol is taken, and the signal of the methyl group of the oxypropylene unit of the HT bond [16.9 to 17.4 ppm, hereinafter referred to as A] and the head-to-head (Head-t)
o-Head) The signal of the methyl group of the oxypropylene unit of the bond [17.7 to 18.5 ppm, hereinafter B
Is measured and the formula {[A / (A + B)] × 100} is obtained.
Is calculated from The attribution of each signal is Macromolecule
s, Vol. 19, pp. 1373-1343 (1986
Year), FCSchilling and AETonelli.

(3) Residual amount of compound catalyst having P = N bond in polyoxyalkylene polyol (hereinafter referred to as residual catalyst amount; unit: ppm) By quantifying the residual nitrogen amount in the polyol, P =
The remaining amount of the compound having an N bond is calculated backward. The polyol is weighed in a volumetric flask, diluted with toluene (special grade reagent), and then the nitrogen concentration is quantified using a trace total nitrogen analyzer (manufactured by Mitsubishi Chemical Corporation, model: TN-100). .

(4) Catalyst concentration in crude polyoxyalkylene polyol (hereinafter referred to as crude polyol) (unit: ppm) After weighing about 15 g of the crude polyol in a beaker having a capacity of 100 ml, 60 ml of isopropyl alcohol / water (volume ratio) : 10/6) and dissolved in 1 / 100mo
It is quantified using 1 / L hydrochloric acid with a potentiometric titrator (Model: TS-980, manufactured by Hiranuma Sangyo Co., Ltd.).

(5) Sodium concentration in polyoxyalkylene polyol (unit: ppm) The concentration of sodium (hereinafter, referred to as Na) eluted from a solid acid used for removing a catalyst from a crude polyol is measured. Quantification is performed using an atomic absorption spectrometer (manufactured by PerkinElmer, model: 5100PC). The limit of quantification is 0.1 ppm.

(6) Moisture (unit: ppm) in compound catalyst having P = N bond and active hydrogen compound Moisture analyzer (Model: AQV-7, manufactured by Hiranuma Sangyo Co., Ltd.)
Measure using

(7) The oxypropylene group content of the polyoxyalkylene polyol (hereinafter referred to as PO content).
Unit: weight%) and the content of oxyethylene groups at the molecular terminals of the polyoxyalkylene polyol (hereinafter referred to as terminal E)
It is called O amount. Unit:% by weight) A polyoxyalkylene polyol was dissolved in deuterated acetone, and the ^13C -NMR measurement showed that the PO content,
And the amount of terminal EO is measured.

(8) Solid acids and their characteristic values The solid acids used in the examples and comparative examples and their characteristic values were
It is shown in [Table 1]. The composition, specific surface area and average pore diameter of the solid acid were measured by the methods described in the following items (9) to (10). The composition of the solid acid is magnesium oxide (Mg
O), aluminum oxide (Al ₂ O ₃ ), and silicon dioxide (SiO ₂ ). Solid acids A, B, C
And F are products of Kyowa Chemical Industry Co., Ltd. Solid acids D and E are products of Tomita Pharmaceutical Co., Ltd.

[0165]

[Table 1]

(9) Composition of solid acid 5 parts by weight of nitric acid was added to 1 part by weight of solid acid,
Heat at ° C for 24 hours. A homogeneous solution obtained by cooling to room temperature is used as a sample. A sample solution is measured by a high frequency inductively coupled plasma measuring device [manufactured by Shimadzu Corporation, type: ICPS-8
000C] to determine the amounts of silicon, aluminum and magnesium.

(10) Specific surface area of solid acid (unit: m ² /
g), and average pore diameter (unit: Å) measuring device (manufactured by Kantachrome Co., Ltd., type: Autosolve 3)
Is used. Before measurement, the solid acid was heated to 150 ° C and 1.33 kPa.
The heating and depressurizing treatment is performed for 1 hour below. Nitrogen is used as the adsorption / desorption gas.

Production Example 1 Phosphazenium compound (hereinafter referred to as PZN) Phosphorus pentachloride (manufactured by Junsei Chemical Co., Ltd.) 60.20 in a 3000 ml three-necked flask equipped with a thermometer and a dropping funnel.
g was weighed and 525 ml of orthodichlorobenzene (hereinafter referred to as ODCB, manufactured by Mitsui Chemicals, Inc.) was added to form a suspension. This suspension was heated to 30 ° C. and added to 900 ml of ODCB in Reinhard Schwesinger, et al. Angew. Che
m. Int. Ed. Engl. , 1993, 32, 1361-13.
63) Tris (dimethylamino) phosphazene {(Me ₂ N) ₃ P = NH} 439.2 synthesized by the method described in 63).
A solution in which 7 g was dissolved was added dropwise over 1 hour. After stirring at the same temperature for 30 minutes, the temperature was raised to 160 ° C. over about 30 minutes, and further stirred for 20 hours. The generated insolubles were filtered. Ion-exchanged water was added to the filtrate, and a water washing treatment was performed three times.

[0169] 619.2 g of ion-exchanged water was added to 1091.2 g of the water-insoluble layer (hereinafter referred to as an organic layer) after the water washing treatment.
6g and 289.5 ml of 1 mol / L hydrochloric acid were added, the aqueous layer was separated, and tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride {[(M
e ₂ N) ₃ P = N] ₄ P ⁺ Cl ⁻ ｝ was obtained. Further, ion-exchanged water was added to prepare a 2.5% by weight aqueous solution. Then 1
Ion-exchange resin Levatit MP-500 in which the exchange group has been converted to a hydroxyl group with an aqueous sodium hydroxide solution of mol / L.
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)
(ity) 0.5 (1 / hr), the solution was passed through the column from the bottom in ascending flow, and ion exchange was performed with tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide.

Further, a column packed with the ion exchange resin
Pass ion-exchanged water through the
The azenium compound was recovered. Then tetrakis
[Tris (dimethylamino) phosphoranylideneamino]
Aqueous solution of phosphonium hydroxide at 80 ° C., 7.98
Under kPa conditions for 2 hours, 80 ° C, 133 Pa
7 hours of dehydration under reduced pressure
Lakis [tris (dimethylamino) phosphoranylidene
Amino] phosphonium hydroxide {[(Me _TwoN)_ThreeP =
N]_FourP⁺OH^-｝ (PZN) was obtained.

The yield of the compound after drying, determined by weight measurement, was 98% by weight. ¹ H with tetramethylsilane in deuterated dimethylformamide solution as internal standard
The chemical shift of -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.
09, H: 9.72, N: 29.61, P: 20.4
6). In the chemical formula (1), the phosphazenium compound is (1,1,1,1) in the order of a, b, c, and d.
In 1), R is a methyl group, Q ^- is a hydroxy anion ^- is OH.

Production Example 2 Phosphine oxide compound (hereinafter referred to as PZO) Phosphorus oxytrichloride and tris (dimethylamino) phosphazene produced in Production Example 1 were used as raw materials, and toluene was used as a solvent. Of General Chemistry of the USS (U
SSR), Vol. 55, p. 1453 (issued in 1985), and tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide {[(Me ₂ N) ₃ P = N] ₃ P = O・ 0.29 (H
₂ O)} (Me represents a methyl group. Hereinafter, it was synthesized similar). Next, the compound is placed in a desiccator using phosphorus pentoxide as a desiccant, dried at 23 ° C. and 655 Pa for one week, and tris [tris (dimethylamino) phosphoranylideneamino] phosphine oxide containing no water is used. {[(Me ₂ N) ₃ P = N] ₃ P = O} was obtained.
In the obtained compound, R is a methyl (Me) group and x is 0 in the phosphine oxide compound represented by the chemical formula (2). The chemical formula was identified by ³¹ P-NMR, ¹
H-NMR and elemental analysis were performed.

Production Example 3 Phosphazene compound (hereinafter referred to as PZB) manufactured by Fluka, trade name: phosphazene base P <t /
4> -t-Oct adjusted to 1.00 mol / L
-A hexane solution was used. The compound is a phosphazene compound in which, in the chemical formula (3), Q is a tert-octyl group, D is a dimethylamino group, and (1, m, n) are (1, 1, 1) in this order.

<Production of Polyoxyalkylene Polyol> Example 1 Polyoxyalkylene Polyol A Under a nitrogen atmosphere, 5 × 10 ⁻³ mol of PZN was added to 1 mol of dipropylene glycol having a water content of 345 ppm.
(In the form of a 30% by weight toluene solution, the same applies hereinafter), and after purging with nitrogen, the temperature was raised to 105 ° C., and at the same temperature, 1.33 kPa or less while introducing nitrogen into the liquid phase. The heating and decompression treatment was performed for 3 hours under the conditions described above. Then
From a pressure of 8.65 kPa, under the conditions of a polymerization temperature of 80 ° C. and a maximum reaction pressure of 330 kPa, the OHV is 28 mg KOH.
/ G until the propylene oxide addition polymerization reaction. At the time when the pressure change of the autoclave is no longer recognized, at 80 ° C. and 1.33 kPa or less,
A reduced pressure treatment for 0.5 hour was performed to obtain a crude polyoxyalkylene polyol.

Then, 3% by weight of ion-exchanged water and 0.8% by weight of solid acid A were added to the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere.
The adsorption reaction was performed at the same temperature for 2 hours. Thereafter, an antioxidant [Ciba Specialty Chemicals Co., Ltd., trade name: IRGANOX1010,
The same applies to the following, 750 ppm, and 110 ° C., 880
Under the condition of Pa, a heat decompression dehydration treatment was performed for 3 hours. After pressurizing to atmospheric pressure using nitrogen, filter paper having a retention particle size of 1 μm (5C type, manufactured by Advantech Toyo Co., Ltd.)
In the same manner), filtration under reduced pressure was performed to purify the polyoxyalkylene polyol. OHV of the purified polyoxyalkylene polyol A is 28.3 mgKOH / g, and C =
C is 0.013 meq. / G, HT bond selectivity is 9
6.5 mol%, η was 900 mPa · s / 25 ° C., and the residual amount of the catalyst was 2.5 ppm. The PO content is
100% by weight, and the residual amount of sodium (hereinafter referred to as residual amount of Na) is less than 0.1 ppm (less than the detection limit concentration).
Met.

Example 2 Polyoxyalkylene polyol B A heating and dehydration treatment under reduced pressure at 110 ° C. and 655 Pa for 1.5 hours was performed in advance while passing nitrogen gas through, and the water content was reduced to 95%.
6 × 10 6 per 1 mol of glycerin adjusted to ppm
After adding ^-3 mol of PZO and purging with nitrogen, the temperature was raised to 85 ° C. Then, under the conditions of a polymerization temperature of 85 ° C. and a maximum reaction pressure of 455 kPa under atmospheric pressure, the OHV was 28 mg KO.
The addition polymerization reaction of propylene oxide was performed until H / g was reached. When the pressure change in the autoclave is no longer observed, at 85 ° C. and 1.33 kPa or less,
A reduced pressure treatment for 0.5 hour was performed to obtain a crude polyoxyalkylene polyol.

Subsequently, the temperature was raised to 120 ° C.
After performing decompression treatment under the condition of 1.33 kPa or less for 1 hour, the pressure was increased to 230 kPa with nitrogen. OHV is 2
Sequential charging of ethylene oxide was performed until 4 mg KOH / g. After charging the ethylene oxide, the reaction was continued until no change in the pressure of the autoclave was observed. Thereafter, a reduced pressure treatment was performed at the same temperature under a condition of 1.33 kPa or less for 0.5 hour. Then, 2% by weight of ion-exchanged water and 0.8% by weight of solid acid A are added to the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere, and the mixture is adsorbed at 80 ° C. for 1 hour. The reaction was performed. Thereafter, 750 ppm of an antioxidant was added to the crude polyol, and the mixture was subjected to a heat and reduced pressure dehydration treatment at 110 ° C. and 880 Pa for 3 hours. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol.
The OHV of the purified polyoxyalkylene polyol B is 2
4.2 mgKOH / g, C = C is 0.018 meq. /
g, HT bond selectivity is 97.1 mol%, η is 142
0 mPa · s / 25 ° C., and the remaining amount of the catalyst is 23 ppm
Met. The residual amount of Na is less than 0.1 ppm (less than the detection limit concentration), the PO content is 85.1% by weight,
The terminal EO amount was 14.8% by weight.

Example 3 Polyoxyalkylene polyol C In a nitrogen atmosphere, 4 × 10 ⁻³ mol of PZN was added to 1 mol of dipropylene glycol used in Example 1 and nitrogen substitution was performed. , And a heating and depressurizing operation was performed in the same manner as described in Example 1. Then
From a pressure of 8.65 kPa, under the conditions of a polymerization temperature of 85 ° C. and a maximum reaction pressure of 420 kPa, OHV is 37 mg KOH.
/ G, an addition polymerization reaction of a mixed epoxide of propylene oxide and butylene oxide was performed. When the autoclave pressure change is no longer observed,
Under a condition of 85 ° C. and 1.33 kPa or less, a reduced pressure treatment was performed for 0.5 hour to obtain a crude polyoxyalkylene polyol. The mixed epoxide has a weight ratio of propylene oxide to butylene oxide of 85:15.

Next, 5% by weight of ion-exchanged water and 1% by weight of solid acid A were added to the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere.
At the same temperature, an adsorption reaction was performed for 1 hour. Next, after adding 800 ppm of an antioxidant to the polyol,
Under a condition of 110 ° C. and 850 Pa, a heat decompression dehydration treatment was performed for 3 hours. After pressurizing to atmospheric pressure using nitrogen, vacuum filtration was performed using filter paper to purify the polyoxyalkylene polyol. OHV of the purified polyoxyalkylene polyol C is 37.3 mgKOH / g, and C ＝ C is 0.009 meq. / G, HT bond selectivity is 97.4
mol% and η were 550 mPa · s / 25 ° C., and the residual amount of the catalyst was 3.1 ppm. The PO content is 84.8
%, And the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 4 Polyoxyalkylene Polyol D Under a nitrogen atmosphere, 1 × 10 ⁻² mol of PZO was added to 1 mol of pentaerythritol having a water content of 442 ppm, and the mixture was purged with nitrogen. Under the conditions, 20 parts by weight of propylene oxide was added to 100 parts by weight of pentaerythritol, and the temperature was raised to 85 ° C.
After stirring at the same temperature for 1 hour while stirring, the OHV was conducted under the conditions of a polymerization temperature of 85 ° C. and a maximum reaction pressure of 460 kPa.
Until 28 mgKOH / g was obtained, an addition polymerization reaction of a mixed epoxide of propylene oxide and butylene oxide was performed. When the pressure change in the autoclave was no longer observed, the pressure was reduced for 0.5 hour at 85 ° C. and 1.33 kPa or less to obtain a crude polyoxyalkylene polyol. The mixed epoxide has a weight ratio of propylene oxide to butylene oxide of 9
0:10. Thereafter, nitrogen pressurization was performed to 180 kPa, the polymerization temperature was 125 ° C., and the maximum reaction pressure was 480 kPa.
Under the conditions described above, addition polymerization of ethylene oxide was carried out until the OHV became 24 mgKOH / g. At the time when the pressure change in the autoclave is no longer observed, 125 ° C.,
Under a condition of 1.33 kPa or less, a reduced pressure treatment was performed for 0.5 hour to obtain a crude polyoxyalkylene polyol.

Next, 3% by weight of ion-exchanged water and 0.8 part by weight of solid acid A were added to the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere. A time adsorption reaction was performed. Thereafter, 600 pp relative to the crude polyoxyalkylene polyol
m of antioxidant was added and dehydration was performed under reduced pressure. Finally, the same operation was performed at 110 ° C. and 880 Pa for 3 hours. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. OHV of the purified polyoxyalkylene polyol D is 24.3 mgKOH / g, and C ＝ C is 0.016 meq. / G, HT bond selectivity is 97.6
mol% and η were 1540 mPa · s / 25 ° C., and the residual amount of the catalyst was 26 ppm. The PO content is 76.3
%, The amount of terminal EO was 15.1% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 5 Polyoxyalkylene polyol E In a nitrogen atmosphere, 1.2 × 10 ⁻² mol of PZN was added to 1 mol of glycerin used in Example 2, and nitrogen substitution was performed. The heating and depressurizing operation was performed in the same manner as described in 1. Then, under the conditions of a polymerization temperature of 80 ° C. and a maximum reaction pressure of 410 kPa under atmospheric pressure, the OHV is 32.5
The addition polymerization reaction of propylene oxide was performed until the concentration reached mg KOH / g. When the pressure change in the autoclave is no longer observed, a pressure reduction treatment is performed for 0.5 hour at 85 ° C. and 1.33 kPa or less, and then the pressure is increased to 182 kPa with nitrogen. Is 410 kPa, and OHV is 28 mg KOH.
/ G until ethylene oxide was added to obtain a crude polyoxyalkylene polyol.

Next, 5% by weight of ion-exchanged water and 0.7% by weight of solid acid B were charged into the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere. The adsorption reaction was performed for one hour. Thereafter, 600 p with respect to the crude polyoxyalkylene polyol
pm of an antioxidant was added, and dehydration was performed under reduced pressure. Further, dehydration under reduced pressure is continued, and finally, 110 ° C., 880 P
The same operation was performed for 3 hours under the condition of a. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. The OHV of the purified polyoxyalkylene polyol E is 28.1 m.
gKOH / g, C = C is 0.014 meq. / G, H-
T bond selectivity is 96.8 mol%, η is 1150 mPa
S / 25 ° C., and the residual amount of the catalyst was 25 ppm. The PO content was 85.4% by weight, the amount of terminal EO was 14.5% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 6 Polyoxyalkylene polyol F In a nitrogen atmosphere, 7.5 × 10 ⁻³ mol of PZN was added to 1 mol of glycerin used in Example 2 and nitrogen substitution was performed. The heating and depressurizing operation was performed in the same manner as described in 1. Then, under the conditions of a polymerization temperature of 80 ° C. and a maximum reaction pressure of 410 kPa under atmospheric pressure, OHV was 40 mg.
The addition polymerization reaction of propylene oxide was performed until KOH / g was reached. When the pressure change in the autoclave is no longer observed, the pressure is reduced for 0.5 hour at 80 ° C. and 1.33 kPa or less, and then the pressure is increased by 18% with nitrogen.
OHV is 33 mgKOH / g under the conditions of a polymerization temperature of 125 ° C. and a maximum reaction pressure of 480 kPa.
Until ethylene oxide addition polymerization reaction,
A crude polyoxyalkylene polyol was obtained.

Then, 5% by weight of ion-exchanged water and 1% by weight of solid acid A were added to the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere, and the mixture was added at 80 ° C. for 3 hours. Was subjected to an adsorption reaction. Thereafter, 600 pp relative to the crude polyoxyalkylene polyol
m of antioxidant was added and dehydration was performed under reduced pressure. Further, dehydration under reduced pressure is continued, and finally, 110 ° C., 880 P
The same operation was performed for 3 hours under the condition of a. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. The OHV of the purified polyoxyalkylene polyol F is 33.5 m
gKOH / g, C = C is 0.012 meq. / G, H-
T bond selectivity is 97.2 mol%, η is 900 mPa ·
s / 25 ° C., and the residual amount of the catalyst was 1.3 ppm. The PO content was 84.6% by weight, the amount of terminal EO was 15.3% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 7 Polyoxyalkylene polyol G In a nitrogen atmosphere, 5.5 × 10 ⁻³ mol of PZN was added to 1 mol of glycerin used in Example 2 and nitrogen substitution was performed. The heating and depressurizing operation was performed in the same manner as described in 1. Then, at 6.65 kPa, the polymerization temperature is 95 ° C. and the maximum reaction pressure is 410 kPa,
An addition polymerization reaction of a mixed epoxide of propylene oxide and butylene oxide was performed until the HV reached 53 mgKOH / g. The weight ratio of propylene oxide to butylene oxide in the mixed epoxide was 90:10.
It is. When the pressure change in the autoclave is no longer observed, the autoclave is controlled to a pressure of 0.3 ° C or less at 95 ° C.
After performing a reduced pressure treatment for 5 hours, the pressure was reduced to 182 kPa with nitrogen.
To a polymerization temperature of 125 ° C and a maximum reaction pressure of 480.
Under the conditions of kPa, an addition polymerization reaction of ethylene oxide was carried out until OHV became 45 mgKOH / g to obtain a crude polyoxyalkylene polyol.

Then, 5% by weight of ion-exchanged water and 0.75% by weight of solid acid A were added to the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere.
The mixture was charged and an adsorption reaction was performed at 80 ° C. for 2 hours. afterwards,
600 to the crude polyoxyalkylene polyol
ppm antioxidant was added and dehydration was performed under reduced pressure.
Furthermore, dehydration under reduced pressure is continued, and finally, 110 ° C., 880
The same operation was performed for 3 hours under the condition of Pa. After pressurizing to atmospheric pressure using nitrogen, vacuum filtration is performed using filter paper,
The polyoxyalkylene polyol was purified. The OHV of the purified polyoxyalkylene polyol G is 44.9.
mgKOH / g, C = C is 0.010 meq. / G, H
-T bond selectivity is 97.7 mol%, η is 620 mPa
S / 25 ° C., and the residual amount of the catalyst was 2.5 ppm. The PO content was 76.8% by weight, the terminal EO amount was 14.2% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 8 Polyoxyalkylene polyol H In a nitrogen atmosphere, 8 × 10 ⁻³ mol of PZO was added to 1 mol of the dipropylene glycol used in Example 1 and nitrogen substitution was carried out. The temperature rose. Then 2.6
At 6 kPa, the polymerization temperature is 75 ° C. and the maximum reaction pressure is 3
Under the condition of 50 kPa, OHV is 18.5 mgKOH / g.
Until the addition of propylene oxide. At the time when the pressure change of the autoclave is no longer observed, 0.5 ° C. under the condition of 90 ° C. and 1.33 kPa or less.
A reduced pressure treatment was performed for a time to obtain a crude polyoxyalkylene polyol.

Then, 5% by weight of ion-exchanged water and 0.9% by weight of solid acid A were charged into the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere. The adsorption reaction was performed for 2 hours. Thereafter, 600 p with respect to the crude polyoxyalkylene polyol
pm of an antioxidant was added, and dehydration was performed under reduced pressure. Further, dehydration under reduced pressure is continued, and finally, 110 ° C., 880 P
The same operation was performed for 3 hours under the condition of a. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. The OHV of the purified polyoxyalkylene polyol H is 18.6 m
gKOH / g, C = C is 0.025 meq. / G, H-
T bond selectivity is 98.1 mol%, η is 1500 mPa
S / 25 ° C., and the residual amount of the catalyst was 4.2 ppm. The PO content was 100% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 9 Polyoxyalkylene polyol I Under a nitrogen atmosphere, 3 × 10 ⁻³ mol of PZN and 3 × 10 ⁻³ mol of PZN per 1 mol of glycerin used in Example 2
After adding O and purging with nitrogen, a heating and depressurizing operation was performed in the same manner as described in Example 1. Then 2.66
At kPa, the polymerization temperature is 75 ° C. and the maximum reaction pressure is 35
Under the condition of 0 kPa, the addition polymerization reaction of propylene oxide was performed until OHV became 33.2 mgKOH / g. When the pressure change in the autoclave was no longer observed, the pressure was reduced for 0.5 hour at 90 ° C. and 1.33 kPa or less to obtain a crude polyoxyalkylene polyol.

Then, 5% by weight of ion-exchanged water and 0.8% by weight of solid acid A were charged into the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere. The adsorption reaction was performed for 2 hours. Thereafter, 600 p with respect to the crude polyoxyalkylene polyol
pm of an antioxidant was added, and dehydration was performed under reduced pressure. Further, dehydration under reduced pressure is continued, and finally, 110 ° C., 880 P
The same operation was performed for 3 hours under the condition of a. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. OHV of the purified polyoxyalkylene polyol I is 33.5 m
gKOH / g, C = C is 0.014 meq. / G, H-
T bond selectivity is 97.9 mol%, η is 920 mPa ·
s / 25 ° C., and the residual amount of the catalyst was 6.6 ppm. The PO content was 99.6% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 10 Polyoxyalkylene polyol J Under a nitrogen atmosphere, 1.2 × 10 ⁻² mol of PZO was added to 1 mol of glycerin used in Example 2 and nitrogen substitution was performed. The temperature rose. Then, 6.65 kPa
At a polymerization temperature of 80 ° C and a maximum reaction pressure of 450 kP
Under the conditions of a, until OHV becomes 11 mgKOH / g,
An addition polymerization reaction of propylene oxide was performed. When the pressure change in the autoclave is no longer observed, 80
Under reduced pressure of 1.33 kPa or lower at 1 ° C. for 1 hour, a crude polyoxyalkylene polyol was obtained.

Then, 5% by weight of ion-exchanged water and 0.7% by weight of solid acid A were charged into the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere. The adsorption reaction was performed for 3 hours. Thereafter, 600 p with respect to the crude polyoxyalkylene polyol
pm of an antioxidant was added, and dehydration was performed under reduced pressure. Further, dehydration under reduced pressure is continued, and finally, 110 ° C., 880 P
The same operation was performed for 3 hours under the condition of a. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. The OHV of the purified polyoxyalkylene polyol J is 11.3 m
gKOH / g, C = C is 0.037 meq. / G, H-
T bond selectivity is 97.5 mol%, η is 3950 mPa
S / 25 ° C., and the residual amount of the catalyst was 5.1 ppm. The PO content was 100% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 11 Polyoxyalkylene polyol K In a nitrogen atmosphere, 6 × 10 ⁻³ mol of PZN was added to 1 mol of glycerin used in Example 2 and nitrogen substitution was performed. The heating and decompression operation was performed in the same manner. Then, at 86.5 kPa, a polymerization temperature of 78
° C, the maximum reaction pressure is 475 kPa, and the OHV is 5
The addition polymerization reaction of propylene oxide was performed until the concentration reached 6 mgKOH / g. When the change in the pressure of the autoclave was not observed, the pressure was reduced for 1 hour at 80 ° C. and 1.33 kPa or less to obtain a crude polyoxyalkylene polyol.

Then, 5% by weight of ion-exchanged water and 0.8% by weight of solid acid A were charged into the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere. The adsorption reaction was performed for one hour. Thereafter, 600 p with respect to the crude polyoxyalkylene polyol
pm of an antioxidant was added, and dehydration was performed under reduced pressure. Further, dehydration under reduced pressure is continued, and finally, 110 ° C., 880 P
The same operation was performed for 3 hours under the condition of a. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. The OHV of the purified polyoxyalkylene polyol K is 56.3 m.
gKOH / g, C = C is 0.009 meq. / G, H-
T bond selectivity is 97.6 mol%, η is 480 mPa ·
s / 25 ° C., and the residual amount of the catalyst was 2.1 ppm. The PO content was 100% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 12 Polyoxyalkylene polyol L Under a nitrogen atmosphere, 5 × 10 ⁻³ mol of PZO was added to 1 mol of glycerin used in Example 2, and after nitrogen substitution, the temperature was raised to 88 ° C. Warmed. Next, at 86.5 kPa, under the conditions of a polymerization temperature of 88 ° C. and a maximum reaction pressure of 475 kPa, an addition polymerization reaction of propylene oxide is performed until the OHV becomes 98 mgKOH / g. At the same temperature, O
The addition polymerization reaction of ethylene oxide was performed until the HV became 76 mgKOH / g. Further, at the same temperature, after no change in the pressure of the autoclave was observed,
Was 56 mgKOH / g until the propylene oxide addition polymerization reaction was carried out. When the change in the pressure of the autoclave was not observed, the pressure was reduced for 1 hour at 90 ° C. and 1.33 kPa or less to obtain a crude polyoxyalkylene polyol.

Then, 5% by weight of ion-exchanged water and 0.7% by weight of solid acid A were charged into the crude polyoxyalkylene polyol adjusted to 80 ° C. under a nitrogen atmosphere. The adsorption reaction was performed for one hour. Thereafter, 600 p with respect to the crude polyoxyalkylene polyol
pm of an antioxidant was added, and dehydration was performed under reduced pressure. Further, dehydration under reduced pressure is continued, and finally, 110 ° C., 880 P
The same operation was performed for 3 hours under the condition of a. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. OHV of the purified polyoxyalkylene polyol L is 56.1 m.
gKOH / g, C = C is 0.010 meq. / G, H-
T bond selectivity is 97.8 mol%, η is 540 mPa ·
s / 25 ° C., and the residual amount of the catalyst was 34 ppm.
The PO content is 75.8% by weight, and the amount of terminal EO is
It was 7.8% by weight. The residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 13 Polyoxyalkylene polyol M Under a nitrogen atmosphere, 7.2 × 10 ⁻³ mol of PZO was added to 1 mol of dipropylene glycol used in Example 1 and nitrogen substitution was performed. The temperature was raised to 80 ° C. Then
At 86.5 kPa, the OHV is 18.7 mg KO under the conditions of a polymerization temperature of 80 ° C. and a maximum reaction pressure of 475 kPa.
The addition polymerization reaction of propylene oxide was performed until H / g was reached. When no change in the pressure of the autoclave was observed, the pressure was reduced for 1 hour at 80 ° C. and 1.33 kPa or less to obtain a crude polyoxyalkylene polyol (hereinafter, referred to as crude polyol m). At this time, the catalyst concentration in the crude polyol was 682 p.
pm.

Then, 3% by weight of ion-exchanged water and 0.8% by weight of solid acid A were charged into the crude polyol m adjusted to 85 ° C. under a nitrogen atmosphere.
A time adsorption reaction was performed. Furthermore, dehydration under reduced pressure was continued, and finally the same operation was performed at 105 ° C. and 1.33 kPa for 3 hours. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. OHV of the purified polyoxyalkylene polyol M is 18.6 mgKOH / g,
C = C is 0.025 meq. / G, HT bond selectivity was 98.1 mol%, η was 1500 mPa · s / 25 ° C., and the amount of remaining catalyst was 3.8 ppm. The PO content was 100% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 14 Polyoxyalkylene Polyol N The crude polyol m prepared in Example 13 was used. Purification was carried out in the same manner as in Example 13, except that the amount of the solid acid A added was 0.5% by weight based on the crude polyol m, and a polyoxyalkylene polyol was recovered. The OHV of the purified polyoxyalkylene polyol N is 18.7 mgKOH /
g, C = C is 0.025 meq. / G, HT bond selectivity is 98.1 mol%, η is 1500 mPa · s / 25
° C, and the residual amount of the catalyst was 42.4 ppm. PO
The content is 100% by weight, and the residual amount of Na is 0.1 pp.
m (less than the detection limit concentration).

Example 15 Polyoxyalkylene polyol O In a nitrogen atmosphere, 9.2 × 10 ⁻³ mol of PZO was added to 1 mol of glycerin used in Example 2 and nitrogen substitution was performed. The temperature rose. Next, 86.5 kPa
At a polymerization temperature of 80 ° C and a maximum reaction pressure of 475 kP
Under the condition a, the propylene oxide addition polymerization reaction was carried out until the OHV became 18.5 mgKOH / g. When no change in the pressure of the autoclave was observed, the pressure was reduced for 1 hour at 80 ° C. and 1.33 kPa or less to obtain a crude polyoxyalkylene polyol (hereinafter, referred to as crude polyol o1). At this time, the catalyst concentration in the crude polyol was 872 ppm.

Then, purification was carried out in the same manner as in Example 13 except that solid acid A was used and the amount added was 1.0% by weight based on crude polyol o1, and polyoxyalkylene polyol was recovered. The OHV of the purified polyoxyalkylene polyol O is 18.7 mgKOH / g, and C =
C is 0.026 meq. / G, HT bond selectivity is 9
7.6 mol%, η was 1880 mPa · s / 25 ° C., and the residual amount of the catalyst was 3.5 ppm. The PO content is
It was 100% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 16 Polyoxyalkylene Polyol P In a nitrogen atmosphere, 5.6 × 10 ^-3 mol of PZN was added to 1 mol of glycerin used in Example 2 and nitrogen substitution was carried out. The heating and depressurizing operation was performed in the same manner as described in 1. Next, at 86.5 kPa, the polymerization temperature was 80 ° C., and the maximum reaction pressure was 405 kPa.
The addition polymerization reaction of propylene oxide was performed until the HV became 33 mgKOH / g. When no change in the pressure of the autoclave was observed, the temperature was set to 80 ° C. and 1.33.
Pressure reduction treatment was performed for 1 hour under the condition of kPa or less to obtain a crude polyoxyalkylene polyol (hereinafter, referred to as crude polyol p1). At this time, the catalyst concentration in the crude polyol was 852 ppm.

Next, 5% by weight of ion-exchanged water and 0.35% by weight of solid acid A were charged into the crude polyol p1 previously heated to 80 ° C. in a nitrogen atmosphere.
The mixture was stirred and mixed at a temperature of 3 ° C for 3 hours. Then, while raising the temperature,
Vacuum dehydration was started. Finally, 105 ° C, 1.33k
After performing a heating and depressurizing treatment under a condition of Pa or less for 3 hours, a polyoxyalkylene polyol was purified by performing a vacuum filtration with a filter paper. The OHV of the purified polyoxyalkylene polyol P is 33.7 mgKOH / g, and CＣC is 0.3.
014meq. / G, HT bond selectivity is 98.1 mo
1% and η were 830 mPa · s / 25 ° C., and the residual amount of the catalyst was 8.0 ppm. PO content is 100% by weight
And the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Example 17 Polyoxyalkylene Polyol Q The crude polyol p1 obtained in Example 16 was used. A polyoxyalkylene polyol was purified in the same manner as in Example 16, except that the addition amount of the solid acid A was 0.5% by weight based on the crude polyol p1. The OHV of the purified polyoxyalkylene polyol Q is 33.7 mgK
OH / g, C = C is 0.014 meq. / G, HT bond selectivity is 98.1 mol%, η is 830 mPa · s /
The temperature was 25 ° C., and the residual amount of the catalyst was 1.2 ppm. P
The O content is 100% by weight, and the residual amount of Na is 0.1 p.
pm (less than the detection limit concentration).

Example 18 Polyoxyalkylene polyol R In a nitrogen atmosphere, 1.2 × 10 ⁻² mol of PZB was added to 1 mol of glycerin used in Example 2 and nitrogen substitution was performed. The heating and depressurizing operation was performed in the same manner as described in 1. Next, at 86.5 kPa, the polymerization temperature was 80 ° C., and the maximum reaction pressure was 405 kPa.
The addition polymerization reaction of propylene oxide was performed until the HV became 18.4 mgKOH / g. When the change in the pressure of the autoclave is no longer observed, 80 ° C., 1.
Decompression treatment was performed for 1 hour under the condition of 33 kPa or less to obtain a crude polyoxyalkylene polyol (hereinafter, referred to as crude polyol r1). At this time, the catalyst concentration in the crude polyol was 930 ppm.

Then, under a nitrogen atmosphere, a polyoxypropylene was prepared in the same manner as in Example 16 except that 0.7% by weight of solid acid B was added to crude polyol r1 previously heated to 80 ° C. The alkylene polyol was purified.
The OHV of the purified polyoxyalkylene polyol R is 1
8.5 mgKOH / g, C = C is 0.027 meq. /
g, HT bond selectivity is 97.9 mol%, η is 155
0 mPa · s / 25 ° C., and the remaining amount of the catalyst is 27.9 p.
pm. The PO content is 100% by weight, Na
The residual amount was less than 0.1 ppm (less than the detection limit concentration).

Example 19 Polyoxyalkylene Polyol S Under a nitrogen atmosphere, 5.0 × 10 ⁻³ mol of PZN was added to 1 mol of dipropylene glycol used in Example 1 and nitrogen substitution was performed. The heating and depressurizing operation was performed in the same manner as described in Example 1. Next, 86.5 kPa
At a polymerization temperature of 80 ° C. and a maximum reaction pressure of 385 kP
Under the conditions of a, until OHV becomes 37 mgKOH / g,
An addition polymerization reaction of propylene oxide was performed. When no change in autoclave pressure is observed, 8
Under a condition of 0 ° C. and 1.33 kPa or less, a reduced pressure treatment for 1 hour was performed to obtain a crude polyoxyalkylene polyol (hereinafter, referred to as “polyoxyalkylene polyol”).
A crude polyol s1) was obtained. At this time, the catalyst concentration in the crude polyol was 1253 ppm.

Then, under a nitrogen atmosphere, the polyoxysilane was prepared in the same manner as in Example 16 except that 0.7% by weight of the solid acid C was added to the crude polyol s1 previously heated to 80 ° C. The alkylene polyol was purified.
The OHV of the purified polyoxyalkylene polyol S is 3
7.1 mgKOH / g, C = C 0.010 meq. /
g, HT bond selectivity is 97.4 mol%, η is 550
mPa · s / 25 ° C., and the catalyst remaining amount is 85.3 pp.
m. The PO content was 100% by weight, and the residual amount of Na was less than 0.1 ppm (less than the detection limit concentration).

Comparative Example 1 Polyoxyalkylene Polyol T The crude polyol m prepared in Example 13 was used. Purification was carried out in the same manner as in Example 13 except that the amount of the solid acid D added was 0.8% by weight based on the crude polyol m, and a polyoxyalkylene polyol was recovered. The residual amount of the catalyst in the purified polyoxyalkylene polyol T is 296.5 p
pm and OHV were 18.9 mgKOH / g, and Na was 0.2 ppm. The HT bond selectivity is 98.1.
mol%, η is 1500 mPa · s / 25 ° C., C = C is 0.025 meq. / G, and the PO content was 100% by weight.

Comparative Example 2 Polyoxyalkylene Polyol U The crude polyol o1 prepared in Example 15 was used. The amount of the solid acid D added was 1.0 to the crude polyol o1.
The crude polyol o1 was purified and the polyoxyalkylene polyol was recovered in the same manner as in Example 15 except that the amount was changed to wt%. The residual amount of the catalyst in the purified polyoxyalkylene polyol U was 182.0 ppm, and the OHV was 18.8 mg.
KOH / g and Na was 0.3 ppm. H-
T bond selectivity is 97.6 mol%, η is 1880 mP
a · s / 25 ° C., C = C is 0.026 meq. / G, and the PO content was 100% by weight.

Comparative Example 3 Polyoxyalkylene Polyol V The crude polyol o1 prepared in Example 15 was used. A crude polyol o1 was purified and a polyoxyalkylene polyol was recovered in the same manner as in Example 15, except that the addition amount of the solid acid E was 1.0% by weight based on the crude polyol. The residual amount of the catalyst in the purified polyoxyalkylene polyol V is 248.7 ppm, and the OHV is 18.7 mg KO.
H / g and Na was 0.4 ppm. The HT bond selectivity is 97.6 mol%, and η is 1880 mPa ·
s / 25 ° C, C = C is 0.026 meq. / G,
The PO content was 100% by weight.

Comparative Example 4 Polyoxyalkylene Polyol W The crude polyol m prepared in Example 13 was used. A crude polyol m was purified in the same manner as in Example 13 except that the solid acid D was set to 1.3% by weight based on the crude polyol, and a polyoxyalkylene polyol was recovered. The residual amount of the catalyst in the purified polyoxyalkylene polyol W is 1
35.2 ppm, OHV was 18.8 mgKOH / g, and Na was 0.5 ppm. The HT bond selectivity is 98.1 mol%, and η is 1500 mPa · s / 25.
° C, C = C is 0.025 meq. / G, and the PO content was 100% by weight.

Comparative Example 5 Polyoxyalkylene polyol X Under a nitrogen atmosphere, 8 × 10 ⁻³ mol of PZO was added to 1 mol of the dipropylene glycol used in Example 1 and nitrogen substitution was performed. The temperature rose. Then 8
At 6.5 kPa, the OHV is 8.5 mg KOH under the conditions of a polymerization temperature of 135 ° C. and a maximum reaction pressure of 582 kPa.
/ G until the propylene oxide addition polymerization reaction. When no change in the pressure of the autoclave was observed, the pressure was reduced for 1 hour at 120 ° C. and 1.33 kPa or less to obtain a crude polyoxyalkylene polyol.

Next, 3% by weight of ion-exchanged water was added to the crude polyol adjusted to 85 ° C. under a nitrogen atmosphere.
And 1 mol of PZO in the crude polyol.
2 mol of phosphoric acid (in the form of a 75.1% by weight aqueous solution) was added, and a neutralization reaction was performed at 85 ° C. for 2 hours. Thereafter, an antioxidant was added to the crude polyol in an amount of 600 ppm.
The same operation was performed for 3 hours at a temperature of 1.33 kPa or lower. After pressurizing to atmospheric pressure using nitrogen, filtration under reduced pressure was performed using a filter paper to purify the polyoxyalkylene polyol. OHV of the purified polyoxyalkylene polyol X is 8.7 mgKOH / g, and C ＝ C is 0.07.
7meq. / G, HT bond selectivity is 97.5 mol
%, Η was 7450 mPa · s / 25 ° C., and the residual amount of the catalyst was 353.4 ppm. The PO content was 100% by weight.

Comparative Example 6 Polyoxyalkylene Polyol Y The crude polyol r1 produced in Example 18 was used. A crude polyol r1 was purified in the same manner as in Example 18 except that the solid acid E was used, and a polyoxyalkylene polyol was recovered. Purified polyoxyalkylene polyol Y
OHV was 18.7 mgKOH / g, and C = C was not measurable. The HT bond selectivity is 97.9 mol%, η is 1550 mPa · s / 25 ° C., and the remaining amount of the catalyst is 79
It was 3 ppm. The PO content is 100% by weight,
The residual amount of Na was 5.6 ppm.

Comparative Example 7 Polyoxyalkylene Polyol Z The crude polyol p1 produced in Example 16 was used. A crude polyol p1 was purified in the same manner as in Example 16 except that solid acid D was used, and a polyoxyalkylene polyol was recovered. Purified polyoxyalkylene polyol Z
Has an OHV of 34.1 mg KOH / g and C = C is 0.01
5meq. / G, HT bond selectivity is 98.1 mol
% And η were 830 mPa · s / 25 ° C., and the residual amount of the catalyst was 262 ppm. The PO content was 100% by weight, and the residual amount of Na was 0.8 ppm.

Comparative Example 8 Polyoxyalkylene Polyol Z1 The crude polyol s1 produced in Example 19 was used. A crude polyol s1 was purified in the same manner as in Example 19 except that the solid acid F was used, and a polyoxyalkylene polyol was recovered. Purified polyoxyalkylene polyol Z
The OHV of 1 was 37.4 mgKOH / g, and C = C was not measurable. HT bond selectivity is 97.4 mol%, η
Is 550 mPa · s / 25 ° C. and the remaining amount of the catalyst is 91
It was 5 ppm. The PO content is 100% by weight,
The residual amount of Na was 0.7 ppm.

Catalysts, epoxide compounds, and solid acids used for removing the catalysts for the production of the polyoxyalkylene polyols (hereinafter referred to as polyols) obtained in Examples 1 to 19 and Comparative Examples 1 to 8, Kind of acid and its use amount, OHV, C = C, HT bond selectivity, η, remaining amount of compound catalyst having P = N bond (simply referred to as catalyst remaining amount), Na remaining amount (simply Na ), PO content, and terminal EO content are shown in Tables 2 to 5. The abbreviations described in the table indicate the following substances, respectively. DPG: dipropylene glycol, Gly: glycerin, PE: pentaerythritol, PZN: phosphazenium compound, PZO: phosphine oxide compound, P
ZB: phosphazene compound, PO: propylene oxide, EO: ethylene oxide, BO: butylene oxide.

[0220]

[Table 2]

[0221]

[Table 3]

[0222]

[Table 4]

[0223]

[Table 5]

<Consideration 1 of Examples> The following findings are obtained from the results of Examples 1 to 19 and Comparative Examples 1 to 8. By using a solid acid (A, B, C) having a specific shape and composition, it is possible to efficiently reduce the residual amount of the catalyst in the polyol to 150 ppm or less. In Example 13 and Comparative Example 1, the same crude polyol m using a phosphine oxide compound (PZO) catalyst was
Purification was performed under the same adsorption conditions using the same amount of solid acid. Residual amount of catalyst in polyol in Example 13 (3.8 pp
m) is considerably lower than that of Comparative Example 1 (296.5 ppm). This result is based on the fact that in Example 13, the solid acid A having the shape specified by the present invention was used, and in Comparative Example 1, the solid acid C having a specific surface area lower than the range specified by the present invention was used. . The remaining amount of the catalyst in the polyol greatly changes depending on the shape of the solid acid.

Similarly, in Example 15 (solid acid A),
Comparing Comparative Example 2 (Solid Acid D) and Comparative Example 3 (Solid Acid E), it can be seen that the PZO catalyst can be efficiently removed by using the solid acid having the shape specified in the present invention. . For the PZN catalyst polyol, a comparison between Example 16 (Solid Acid A) and Comparative Example 7 (Solid Acid D),
Regarding the PZB-catalyzed polyol, from the comparison between Example 18 (solid acid B) and Comparative Example 6 (solid acid E), the use of the solid acid having the shape specified in the present invention allows the catalyst remaining in the purified polyol. It can be seen that the amount can be controlled to 150 ppm or less.

On the other hand, the polyoxyalkylene polyol X (Comparative Example 5), which was purified by neutralizing the PZO catalyst in the crude polyol with phosphoric acid, had a PZO catalyst residual amount of 1%.
It did not fall below 50 ppm. Further, in comparison between Example 18 and Comparative Example 6, and between Example 19 and Comparative Example 8,
The catalyst concentrations in the polyols Y and Z1 purified in Comparative Examples 6 and 8 were 793 ppm and 915 ppm. Not fully purified. 150 pp remaining catalyst
If it exceeds m, coloring was observed in the appearance of the polyol.
In addition, according to the method defined in JIS K-1557, O
It was found that HV, C = C could not be measured with high accuracy.
Further, by purifying a crude polyol using a solid acid having a shape defined in the present invention, Na
The elution amount (Na) is small, and a high quality polyoxyalkylene polyol can be obtained.

Potassium hydroxide commonly used,
And an alkali metal catalyst such as cesium hydroxide which is a catalyst whose monool content can be reduced, and a catalyst neutralization method using an acid in order to remove the catalyst from a crude polyol using a double metal cyanide complex. Is the most common. However, in order to remove the excessively used acid or to adsorb the alkali metal remaining without being neutralized, a step using a conventionally known adsorbent is required. However, according to the method for producing a polyoxyalkylene polyol of the present invention, the remaining amount of the catalyst can be efficiently reduced in a short time, so that the production efficiency of the polyol on an industrial scale is greatly improved.

<Production of polymer-dispersed polyol> The properties of the polymer-dispersed polyol were determined by the following methods (11) to (14). (11) The hydroxyl value (OHV,
Unit: mgKOH / g) and viscosity (hereinafter, η (PO
P). (Unit: mPa · s / 25 ° C.) Determined by the method described in (1) above.

(12) Polymer concentration of the polymer-dispersed polyol (hereinafter, referred to as polymer concentration; unit: wt%) After methanol was added to the polymer-dispersed polyol and thoroughly dispersed, the mixture was centrifuged at 5,000 rpm for 1 hour. Separation is performed, and the weight of the methanol-insoluble component is measured and determined. However, for a polymer-dispersed polyol using acrylonitrile (AN) alone as a vinyl monomer, the polymer concentration is determined from the nitrogen concentration by elemental analysis.

(13) Average particle size of polymer particles in polymer-dispersed polyol (hereinafter referred to as average particle size; unit: μ)
m) dispersing the polymer-dispersed polyol in isopropanol,
Particle Analyzer (Coulter, Model: LS23
The measurement is performed using 0). Incidentally, the average particle size of the particles,
Shows the volume average particle size.

(14) Dispersion stability of polymer particles in polymer-dispersed polyol (hereinafter referred to as “dispersion stability; no unit”) The polymer-dispersed polyol was subjected to 5000 revolutions per minute,
Centrifuge for 1 hour, then invert the centrifuge tube upside down and let it flow naturally for 24 hours, and visually determine the presence of non-flowable cake at the bottom of the centrifuge tube. When a non-flowable cake is present, the dispersion stability is poor (bad or p
oor), when no non-flowable cake is present, the dispersion stability is evaluated as good.

The raw materials used in the examples and their abbreviations are shown below. (Polyol) B, F, K, L;
(B), Example 6 (F), Example 11 (K), Example 1
The polyoxyalkylene polyol obtained by 2 (L). (Ethylenically unsaturated monomer 1); acrylonitrile (hereinafter referred to as AN). (Ethylenically unsaturated monomer 2); styrene (hereinafter referred to as S
t) (chain transfer agent); triethylamine (hereinafter referred to as TEA), isopropanol (hereinafter referred to as IPA). (Radical initiator); 2,2′-azobis (2-methylbutyronitrile) (hereinafter referred to as V-59). (Polyol A1); dispersion stabilizer. OH obtained by addition polymerization of glycerin with propylene oxide and then ethylene oxide with KOH as a catalyst.
A polyetherester polyol having an OHV of 29 mgKOH / g obtained by reacting succinic anhydride and ethylene oxide with a polyol having a V of 34 mgKOH / g and a terminal EO content of 14% by weight.

Examples 20 to 23 A thermometer, a stirrer, a pressure gauge and a liquid feeder were mounted.
The polyol was charged into an L pressure-resistant autoclave until the polyol was completely filled, and the temperature was raised to 120 ° C. with stirring. Polyol, V-59, AN, St, chain transfer agent (TE
A, IPA) and a mixed solution of polyol A1 were continuously charged into the autoclave, and a polymer-dispersed polyol was continuously obtained from an outlet. The reaction conditions are as follows:
C. and a reaction pressure of 440 kPa, the residence time was 50 minutes. The obtained reaction solution was subjected to a heating and depressurizing treatment for 3 hours under conditions of 120 ° C. and 655 Pa or less to remove an unreacted ethylenically unsaturated monomer, a decomposition product of a polymerization initiator, a chain transfer agent, and the like. . [Table 6] shows the amounts of the raw materials charged and the properties of the polymer-dispersed polyol.

[0234]

[Table 6]

<Consideration 2 of Example> P =
A polymer-dispersed polyol using a polyoxyalkylene polyol produced by using a compound having an N bond (PZO, PZN) as a catalyst has a low viscosity, a small average particle size of polymer particles, and further has a low dispersion stability of polymer particles. Are better.

<Production of isocyanate group-terminated prepolymer> Compounds having P = N bond (PZN, PZO, PZN)
B) An isocyanate group-terminated prepolymer was produced using polyols having different catalyst remaining amounts. In addition, the stability with time of the prepolymer was evaluated by the following method (15).

(15) Stability with time of isocyanate group-terminated prepolymer (unit:%) The viscosity (n) of the prepolymer immediately after preparation and the viscosity (m) of the prepolymer after storage at 60 ° C. for 14 days are shown below. Then, the viscosity change rate is calculated from the formula [(mn) × 100 / n]. Viscosity of prepolymer (η (PRE)) (unit:
mPa · s / 25 ° C.) is measured by the method described in JIS K-1557. It is judged that the smaller the viscosity change rate, the better the stability of the prepolymer with time.

Polyol M (Example 13), Polyol N (Example 14), Polyol O (Example 15), Polyol P (Example 16), Polyol Q (Example 1)
7), polyol S (Example 19), polyol T (Comparative Example 1), polyol U (Comparative Example 2), polyol V
Using (Comparative Example 3), polyol W (Comparative Example 4), polyol Z (Comparative Example 7), and polyol Z1 (Comparative Example 8), an isocyanate group-terminated prepolymer obtained by reacting these with polyisocyanate was used. It was prepared and its stability over time was measured and evaluated by the method described in (15) above.
In addition, when synthesizing the prepolymer in Table 7, the polyol, the polyisocyanate, and the auxiliary agents xylene (manufactured by Wako Pure Chemical Industries, Ltd.) and dioctyl phthalate (manufactured by Kyowa Yuka Co., Ltd.) DOP) (unit: parts by weight). Examples of the polyisocyanate include Cosmonate PH (manufactured by Mitsui Chemicals, Inc., 4,4′-diphenylmethane diisocyanate) and Cosmonate T-65
(2,4-TDI and 2,6-TDI manufactured by Mitsui Chemicals, Inc.)
Of mixed TDI having a weight ratio of 65:35).

Example 24 In a nitrogen atmosphere, 488.3 parts by weight of the polyol M obtained in Example 13 and 42% by weight of the polyol O obtained in Example 15 were placed in a separable flask equipped with a thermometer.
9.4 parts by weight were charged and mixed with stirring. The catalyst concentration in the mixed polyol was 3.6 ppm. Thereafter, 82.3 parts by weight of Cosmonate PH was added to the mixed polyol, the temperature was raised to 80 ° C, and the mixture was reacted at the same temperature for 3 hours.
After the reaction at the same temperature for 6 hours, the temperature was lowered to 60 ° C.
0 parts by weight of xylene was added, and the mixture was stirred at the same temperature for 1 hour. Next, the temperature was lowered to 50 ° C., and the prepolymer was sealed in a metal container under a nitrogen atmosphere, and the above-described stability test with time was performed. The stability with time of the prepolymer was 10%.

Example 25 The polyol N obtained in Example 14 was mixed with 4
Charge 88.3 parts by weight separable flask,
Based on the polyol, 8.9 ppm of phosphoric acid (6.5 ppm)
% By weight of a phosphoric acid aqueous solution). After stirring and mixing,
In order to remove water, heating and decompression treatment were performed at 105 ° C. and 1.33 kPa or less for 2 hours. Further, Example 15
429.4 parts by weight of the polyol O obtained in the above was added,
Stir and mix for 0.5 hour. The catalyst concentration in the mixed polyol was 24.2 ppm. Thereafter, the temperature was lowered to 55 ° C., 82.3 parts by weight of Cosmonate PH was charged, and the same reaction procedure as in Example 24 was performed to obtain a prepolymer. Under a nitrogen atmosphere, the prepolymer was sealed in a metal container, and the above-mentioned temporal stability test was performed. The stability over time of the prepolymer was 16%.

Example 26 Under a nitrogen atmosphere, 528 parts by weight of the polyol Q obtained in Example 17 and 330 parts by weight of the polyol S obtained in Example 19 were placed in a separable flask equipped with a thermometer. Charge and stirring and mixing were performed. The catalyst concentration in the polyol was 28.3 ppm. Then 80
After raising the temperature to 0 ° C and adding 48 parts by weight of DOP to the mixed polyol, 95 parts by weight of Cosmonate T-65 were charged, and a prepolymerization reaction was performed at the same temperature for 6 hours. The temperature was lowered to 50 ° C., the prepolymer was sealed in a metal container under a nitrogen atmosphere, and the above-mentioned stability test with time was performed. The stability over time of the prepolymer was 11%.

Example 27 Under a nitrogen atmosphere, 711 parts by weight of the polyol S obtained in Example 19 was charged into a separable flask equipped with a thermometer, and then 6.8 ppm of phosphoric acid (6 (In the form of a 0.5% by weight aqueous phosphoric acid solution). After stirring and mixing, water was removed at 105 ° C and 1.3 ° C.
The heating and depressurizing treatment was performed for 2 hours under the condition of 3 kPa or less.
The catalyst concentration in the polyol was 85.3 ppm. Thereafter, the temperature was lowered to 80 ° C., and the cosmonate PH was reduced to 23.
One part by weight was charged, and a prepolymerization reaction was performed at the same temperature for 5 hours. The temperature was lowered to 50 ° C., the prepolymer was sealed in a metal container under a nitrogen atmosphere, and the above-mentioned stability test with time was performed. The stability over time of the prepolymer was 24%.

Comparative Example 9 In a nitrogen atmosphere, 488.3 parts by weight of the polyol W obtained in Comparative Example 4 was placed in a separable flask equipped with a thermometer.
In addition, 429.4 parts by weight of the polyol V obtained in Comparative Example 3 was charged and stirred and mixed. The catalyst concentration in the mixed polyol was 188.3 ppm. Thereafter, 82.3 parts by weight of Cosmonate PH was charged to the mixed polyol, the temperature was raised to 80 ° C., and after reacting at the same temperature for 3 hours,
After the temperature was raised to 90 ° C. and the reaction was performed at the same temperature for 6 hours, the temperature was lowered to 60 ° C., 90 parts by weight of xylene was added, and the mixture was stirred at the same temperature for 1 hour. Next, the temperature was lowered to 50 ° C., and the prepolymer was sealed in a metal container under a nitrogen atmosphere, and the above-described stability test with time was performed. After the aging stability test, the prepolymer was gelled in the metal container.

Comparative Example 10 In a nitrogen atmosphere, 488.3 parts by weight of the polyol T obtained in Comparative Example 1 was placed in a separable flask equipped with a thermometer.
Then, 429.4 parts by weight of the polyol U obtained in Comparative Example 2 was charged, and the mixture was stirred and mixed. The catalyst concentration in the polyol was 242.9 ppm. afterwards,
82.3 parts by weight of cosmonate PH was charged into the mixed polyol, and the same reaction procedure as in Comparative Example 9 was performed to obtain a prepolymer. Next, the temperature is lowered to 50 ° C., and under a nitrogen atmosphere,
The prepolymer was sealed in a metal container and subjected to the above-mentioned stability test with time. After the aging stability test, the prepolymer was gelled in the metal container.

Comparative Example 11 Under a nitrogen atmosphere, 330 parts by weight of the polyol S obtained in Example 19 and 528 parts by weight of the polyol Z obtained in Comparative Example 7 were charged into a separable flask equipped with a thermometer. And stirring and mixing. The catalyst concentration in the polyol was 162 ppm. Thereafter, the temperature was raised to 80 ° C, 48 parts by weight of DOP was added to the polyol, 95 parts by weight of Cosmonate T-65 were charged, and a prepolymerization reaction was performed at the same temperature for 6 hours. Cool down to 50 ° C,
Under a nitrogen atmosphere, the prepolymer was sealed in a metal container, and the above-mentioned temporal stability test was performed. The stability with time of the prepolymer was 122%.

Comparative Example 12 In a nitrogen atmosphere, 528 parts by weight of the polyol P obtained in Example 16 and 330 parts by weight of the polyol Z1 obtained in Comparative Example 8 were charged into a separable flask equipped with a thermometer. And stirring and mixing. The catalyst concentration in the polyol was 303 ppm. Thereafter, the temperature was raised to 80 ° C., and 48 parts by weight of DOP was added to the polyol.
95 parts by weight of Cosmonate T-65 was charged, and
The prepolymerization reaction was performed for a time. The temperature was lowered to 50 ° C., the prepolymer was sealed in a metal container under a nitrogen atmosphere, and the above-mentioned stability test with time was performed. After the aging stability test, the prepolymer was gelled in the metal container.
Table 7 shows the results of Examples 24 to 27 and Comparative Examples 9 to 12.

[0247]

[Table 7]

<Consideration of Example 3> From the results obtained in Examples 24 to 27, the use of a polyoxyalkylene polyol in which the residual amount of the catalyst was controlled to 150 ppm or less provided an isocyanate group-terminated preform having excellent stability over time. It can be seen that a polymer is obtained. Further, when the remaining amount of the catalyst is 18
At 8.3 ppm or more, the prepolymer gelled.

<Production of isocyanate group-terminated prepolymer using polymer-dispersed polyol> Next, the polymer-dispersed polyol produced by the method of the present invention is reacted with polyisocyanate to produce an isocyanate-terminated prepolymer. Shows stability. The aging stability test of the prepolymer was evaluated by the method described in (15) above.

Example 28 In a nitrogen atmosphere, 112.8 parts by weight of cosmonate T-80 (manufactured by Mitsui Chemicals, Inc.) was added as a polyisocyanate to 707.2 parts by weight of the polymer-dispersed polyol AA obtained in Example 20. A mixed TDI having a weight ratio of 2,4-TDI and 2,6-TDI of 80:20, the same applies hereinafter), and 9
By stirring at 0 ° C. for 4 hours, an isocyanate group-terminated prepolymer was obtained. The NCO index is 5.0
It is. The NCO% of the obtained prepolymer is 5.30.
%, And η (PRE) is 15300 mPa · s
/ 25 ° C. Under a nitrogen atmosphere, the prepolymer 55
0 parts by weight was sealed in a metal container, and the stability test with time of the prepolymer was performed by the method described in (15) above. The aging stability was 29%, and an isocyanate group-terminated prepolymer having excellent aging stability was obtained.

<Production of isocyanate group-terminated prepolymer and polyurethane resin> The isocyanate group-terminated prepolymer is hereinafter abbreviated as a prepolymer.

(16) HT bond selectivity of prepolymer (unit: mol%) Determined by the method of (2). (17) NCO% (unit: wt%) and viscosity (hereinafter referred to as η (PRE) of the prepolymer; unit: mPa · s
/ 25 ° C) NCO% is JIS K-7301, η (PRE) is
It is determined by the method described in JIS K-1557.

(18) Residual amount of compound catalyst having P = N bond in prepolymer (hereinafter referred to as residual amount of prepolymer catalyst. Unit: ppm) Capillary electrophoresis apparatus (Waters, fully automatic CIA system) Is used to measure the residual amount of the catalyst in the prepolymer. Add hydrochloric acid aqueous solution to the pretreated sample,
Shaker (Tokyo Rika Kiki Co., Ltd., EYELA SH
AKER) to extract the catalyst into an aqueous hydrochloric acid solution. Thereafter, liquid separation is performed by standing, the aqueous layer is separated, and the remaining amount of the catalyst is quantified using a capillary electrophoresis analyzer. The prepolymer pretreatment method is to react isocyanate groups in the prepolymer with methanol (special reagent grade),
C., and the pressure is reduced to 1.33 kPa or less to remove the remaining methanol. (19) Removable time of polyurethane elastomer (unit: h) The time during which the elastomer does not crack or deform and can be released from the mold is referred to as the removable time. After bending the cured sheet by hand, the time during which no cracks occur is defined as the demoldable time, and the time is measured.

(20) Mechanical properties of polyurethane elastomer Measured according to the method described in JIS K-7312. Hereinafter, the measurement items are shown. Hardness (hereinafter referred to as Hs), 10
0% stress (hereinafter, referred to as M100; unit: MPa);
300% stress (hereinafter referred to as M300; unit: MP)
a), tensile strength (hereinafter, referred to as TS, unit: MPa),
The elongation (hereinafter, referred to as EL; unit:%), the compression set (hereinafter, referred to as Cs; unit:%), and the rebound resilience (hereinafter, referred to as R; unit:%) are measured. The measurement of compression set is performed under the conditions of compression at 70 ° C. for 24 hours.

Example 29 Prepolymer AA1 and polyurethane elastomer Under nitrogen atmosphere, 210.3 parts by weight of Cosmonate T-8
After charging 1789.7 parts by weight of polyol C to 0, 8
The mixture was stirred at 0 ° C. for 6 hours to perform a prepolymerization reaction. The NCO index at this time is 2. NCO% is 2.
41% by weight, η (PRE) 7,150 mPa · s / 25
The prepolymer AA1 having an HT bond selectivity of 97.3 mol% and a residual catalyst amount of 31 ppm was obtained. Then 10
100 parts by weight of prepolymer AA1 degassed under reduced pressure at 0 ° C.
4,4′-diamino-3, previously melted at 130 ° C.
6.9 parts by weight of 3′-dichlorodiphenylmethane (hereinafter, referred to as MBOCA) was added and mixed quickly and uniformly. The mixture was poured into a metal mold preheated to 110 ° C. and cured at 110 ° C. for 24 hours to obtain a urethane elastomer. At this time, the mold releasing time of the polyurethane elastomer was 3.5 hours.
Further, the above-mentioned sheet of polyurethane elastomer,
After allowing to stand for 7 days in an atmosphere at 23 ° C. and a relative humidity of 60%, the mechanical properties of the polyurethane elastomer were measured. The results are shown in [Table 8].

Example 30 Prepolymer AA2 and polyurethane elastomer Under nitrogen atmosphere, 113.1 parts by weight of Cosmonate T-8
After charging 1886.9 parts by weight of polyol H to
The mixture was stirred at a temperature of 6 ° C. for 6 hours to perform a prepolymerization reaction. NC
O% is 1.14% by weight, η (PRE) 13,400 mP
a · s / 25 ° C., HT bond selectivity 98.2 mol%,
A prepolymer AA2 having a catalyst remaining amount of 7.2 ppm was obtained. The NCO index at this time is 2. A polyurethane elastomer was obtained in the same manner as in Example 29 except that MBOCA 3.3 parts by weight was added to 100 parts by weight of the prepolymer AA2. At this time, the demoldable time of the polyurethane elastomer was 5 hours. Further, the mechanical properties of the polyurethane elastomer were measured in the same manner as in Example 29. The results are shown in [Table 8].

Example 31 Prepolymer AA3 and Polyurethane Elastomer In a nitrogen atmosphere, 891.3 parts by weight of cosmonate PH were charged with 712.6 parts by weight of polyol C and 396.1 parts by weight of polyol I. Stir at 80 ° C for 5 hours,
A prepolymerization reaction was performed. NCO% is 13.3% by weight, η (PRE) 2,520 mPa · s / 25 ° C, H-
T bond selectivity 97.4 mol%, remaining amount of catalyst is 14 pp
m of prepolymer AA3 were obtained. The NCO index at this time is 10. Next, 1,4-butanediol (hereinafter, referred to as 1,1) which was degassed under reduced pressure by the method described above was added to 100 parts by weight of prepolymer AA3 previously degassed under reduced pressure at 25 ° C.
4-BG, hereinafter the same) 12.8 parts by weight, and
0.005 parts by weight of dibutyltin dilaurate (manufactured by Sankyoki Gosei Co., Ltd., trade name: Stann BL, the same applies hereinafter) was added, and a polyurethane elastomer was obtained in the same manner as described in Example 29. At this time, the demoldable time of the polyurethane elastomer was 5 hours. Further, the mechanical properties of the polyurethane elastomer were measured in the same manner as in Example 29. The results are shown in [Table 8].

[0258]

[Table 8]

<Consideration of Example 4> From an isocyanate group-terminated prepolymer using a polyoxyalkylene polyol produced using a compound having a P = N bond (PZN, PZO) and purified by the method according to the present invention. The obtained polyurethane elastomer has a short mold release time of the polyurethane elastomer, and has a rapid expression of mechanical properties of the resin. Further, by using the above isocyanate group-terminated prepolymer, Hs, M10, M300, TS,
A polyurethane elastomer having excellent mechanical properties such as R and Cs can be obtained.

<Production of Prepolymer and Polyurethane Resin with Low Free Isocyanate Compound Concentration> (21) Concentration of free isocyanate compound in prepolymer (hereinafter referred to as free isocyanate compound concentration. Unit:% by weight) Gas chromatography [ ) The free isocyanate compound in the prepolymer is quantified by the model: GC-14A, manufactured by Shimadzu Corporation. In addition, the NCO%, η (PRE), HT bond selectivity, and remaining amount of the catalyst of the prepolymer are measured by the methods described above.

Example 32 Prepolymer AA4 and polyurethane elastomer Under nitrogen atmosphere, 642.0 parts by weight of Cosmonate T-8
1243.6 parts by weight of polyol C and 11
4.4 parts by weight of 1,3-butanediol (hereinafter, referred to as 1,3
-BG), stirred at 80 ° C for 5 hours,
An isocyanate group-terminated prepolymer having an O% of 13.5% by weight was obtained. The NCO index at this time is 8. Using a molecular distillation apparatus (manufactured by Shibata Kagaku KK, model: MS-800 type), the isocyanate group-terminated prepolymer was subjected to a wiper rotation speed of 400 r. p. The pressure was reduced under the conditions of m and 150 ° C. for 5 hours to remove the free polyisocyanate compound. The free isocyanate compound concentration was 0.3% by weight, NCO% was 2.50% by weight, η (P
RE) Prepolymer AA4 having 5,400 mPa · s / 25 ° C., HT bond selectivity of 97.6 mol%, and a residual amount of catalyst of 21 ppm was obtained. 100 parts by weight of prepolymer AA
Example 2 except that 7.2 parts by weight of MBOCA was added to Example 4.
In the same manner as in 9, a polyurethane elastomer was obtained. At this time, the mold releasing time of the polyurethane elastomer was 4.5 hours. Further, the mechanical properties of the polyurethane elastomer were measured in the same manner as in Example 29.

As a result, Hs (Shore A) 70, M
100 is 2.9 MPa, M300 is 5.2 MPa, TS
Is 14.7 MPa, EL is 870%, R is 98%, Cs
Was 30%. still,
An isocyanate-terminated prepolymer AA1 in Example 29 above having an equivalent level of NCO% as in this example
As a result of measuring the free isocyanate compound concentration of 1.
It was 9% by weight. By performing the operation of removing the free isocyanate compound, the viscosity of the isocyanate group-terminated prepolymer is reduced even when the NCO% is the same level (the concentration of the free isocyanate compound in the prepolymer AA1 in Example 29 is 1%). The free isocyanate compound concentration in the prepolymer AA4 of Example 32 is 0.3% by weight with respect to 0.9% by weight), and the workability is excellent.

<Production of Polyurethane Resin Using Polyoxyalkylene Polyol as Curing Agent> (22) Mechanical Properties of Polyurethane Resin According to the method described in JIS A-6021, tensile strength (T
S, unit: MPa), elongation (EL, unit:%), tear strength (hereinafter, referred to as TR, unit: kN / m) are measured.

(23) Surface Contamination of Polyurethane Resin The tackiness of the resin surface by touch is measured as the surface contamination of the polyurethane resin. Under the conditions described below, the surface of the polyurethane resin after curing for 7 days is evaluated as good when there is no tack, and as bad when there is tack.

Example 33 5.6 parts by weight of the polyol H obtained in Example 8, 7.1 parts by weight of the polyol I obtained in Example 9, 3,3 ′
-Dichloro-4,4'-diaminodiphenylmethane (M
BOCA) 10.7 parts by weight, dioctyl phthalate (D
OP) 26.4 parts by weight, 61.2 parts by weight of calcium carbonate, 1.8 parts by weight of lead octylate (trade name: Minico P-24, manufactured by Active Materials Chemical Co., Ltd.) as a curing catalyst, and weather resistance 1.2 parts by weight of a stabilizer (trade name: Nocrack 300, manufactured by Ouchi Shinko Chemical Co., Ltd.) is mixed, and a kneading apparatus (a dissolver manufactured by Inoue Seisakusho Co., Ltd., model: DHC-)
1000r. p. m with stirring speed of 50 m
C. for 1 hour to obtain a curing agent. Next, 517 parts by weight of the polyol H obtained in Example 8 and 960 parts by weight of the polyol I obtained in Example 9 were added to 143 parts by weight of Cosmonate T-80 under a nitrogen atmosphere. The prepolymerization reaction was performed while stirring at 90 ° C. for 4 hours. Thereafter, the prepolymer was cooled to room temperature, and 100 parts by weight of the aforementioned curing agent and
The weight part was uniformly mixed for 3 minutes so that air bubbles did not mix, poured into a Teflon-coated 1 mm thick mold, and cured at 23 ° C. and a relative humidity of 55% to obtain a polyurethane resin. In order to evaluate the progress of curing of the polyurethane resin, the mechanical properties and surface contamination of the polyurethane resin were measured after 1 day and 7 days under the above curing conditions. As a result, TS one day after curing was 4.3 MPa, E
L is 990%, TR is 20 kN / m, TS after curing 7 days is 5.7 MPa, EL is 810%, TR is 23
kN / m. The surface contamination of the polyurethane resin 7 days after curing was good without tack.

The polyoxyalkylene polyol produced by using the compound having a P = N bond according to the present invention as a catalyst is
The polyurethane resin of the present invention used for the curing agent and the isocyanate group-terminated prepolymer as a main component is TS, T
In addition to rapid development of physical properties such as R, it has excellent mechanical properties. The physical property development is based on a magnification obtained by dividing the TS and TR values 7 days after curing by the TS and TR 1 day after curing. It is determined that the smaller the magnification, the faster the property development. Furthermore, since there is no tack on the resin surface, a polyurethane resin with less surface contamination can be obtained.

<Production of Flexible Polyurethane Foam> Hereinafter, a flexible polyurethane foam is referred to as a flexible foam. (24) Density of flexible foam (unit: kg / m ³ ) The apparent density determined by the method described in JIS K-6400 is shown. The total density is measured using a rectangular sample having a skin skin, and the core density is measured using a rectangular sample having no skin skin.

(25) Hardness of flexible foam (unit: N /
314 cm ² ) Determined by the method described in Method A of JIS K-6400.
A flexible foam having a thickness of 94 mm to 100 mm is used.

(26) Elongation percentage of flexible foam (unit:
%) It is determined by the method described in JIS K-6400. (27) Compression set of flexible foam (unit:%) Determined by the method described in JIS K-6400. At the time of measurement, the core portion of the molded flexible foam was 50 × 50 ×
Cut out to 25 mm and use. Using a plane-parallel plate, the specimen is compressed to a thickness of 50% of the original foam and then left at 70 ° C. for 22 hours. Thirty minutes after removing the test piece from the parallel flat plate, its thickness is measured, and the permanent compression set is measured.

(28) Permanent set under wet heat compression of flexible foam (unit:%) Determined by the method described in JIS K-6400. At the time of measurement, the core portion of the molded flexible foam was 50 × 50 ×
Cut out to 25 mm and use. Using a plane-parallel plate, the test piece is compressed to a thickness of 50% of the original foam, and then left for 22 hours at 50 ° C. and 95% relative humidity. Thirty minutes after removing the test piece from the parallel flat plate, its thickness is measured, and the wet heat compression set is measured.

(29) Hardness loss (unit:%) and height loss (unit; unit) of a flexible foam in a repeated compression test
%) It is determined by the method described in JIS K-6400. At the time of measurement, the core portion of the molded flexible foam was 100 × 10
Cut out to 0x50 mm and use. The test piece is sandwiched between parallel flat plates and subjected to a continuous compression strain of 50% with respect to the original foam thickness at room temperature at a rate of 60 times per minute for 80,000 times. Thirty minutes after removing the test piece, the hardness of the foam is measured by the method described above, and the hardness loss is measured.
Further, the height of the foam before and after the test is measured, and the height loss is measured.

In the production of the flexible foam, the following compounds were used in addition to the polyoxyalkylene polyol and the polymer-dispersed polyol. (Polyisocyanate-1): Cosmonate TM-2
0; 2,4-TDI and 2,6-TD manufactured by Mitsui Chemicals, Inc.
A mixture of 80 parts by weight of mixed TDI having a weight ratio of 80:20 and 20 parts by weight of polymethylene polyphenyl polyisocyanate. The polymethylene polyphenyl polyisocyanate is a polyisocyanate comprising 43% by weight of a binuclear component based on a benzene ring, 24% by weight of a trinuclear component, and 9% by weight of a tetranuclear component. (Polyisocyanate-
2): Cosmonate T-80; manufactured by Mitsui Chemicals, Inc.
A mixed TDI having a weight ratio of 2,4-TDI and 2,6-TDI of 80:20. (Catalyst-1): Minico L-102
0; an amine catalyst (33% diethylene glycol solution of triethylenediamine) manufactured by Active Materials Chemical Co., Ltd. (Catalyst-
2): Minico TMDA; an amine catalyst manufactured by Active Materials Chemical Company. (Crosslinking agent-1): KL-210; a crosslinking agent with a hydroxyl value of 830 mgKOH / g, manufactured by Mitsui Chemicals, Inc.
(Foam stabilizer-1): L-3601; a silicone foam stabilizer manufactured by Nippon Unicar.

Example 34 A resin premix was prepared by mixing the following seven components. Polyoxyalkylene polyol: 50 parts by weight,
Polymer-dispersed polyol: 50 parts by weight, crosslinking agent-1:
3.0 parts by weight, water: 3.4 parts by weight, catalyst-1: 0.4 parts by weight, catalyst-2: 0.1 parts by weight, foam stabilizer-1: 1.0 parts by weight. Polyoxyalkylene polyol B was used as the polyoxyalkylene polyol, and polymer dispersed polyol AA was used as the polymer dispersed polyol. To 107.9 parts by weight of the resin premix, 43.3 parts by weight of polyisocyanate-1 was added and mixed. Immediately, the mixture was poured into a mold having an internal size of 400 × 400 × 100 mm adjusted to 65 ° C. Closed and foamed. Then 100
After heating and curing in a hot air oven at 7 ° C. for 7 minutes, the flexible polyurethane foam was removed from the mold. After curing in an oven at 23 ° C. and a relative humidity of 50% for one day, the physical properties of the flexible foam were measured. The physical properties of the obtained flexible foam are shown in [Table 9]. The NCO index in this embodiment is 1.00.

Examples 35 to 39 Example 34 was repeated except that the polyoxyalkylene polyol and the polymer-dispersed polyol shown in Table 9 were changed and the apparent density of the flexible foam was controlled according to Table 9.
A flexible foam was produced in the same manner as described above. The physical properties of the obtained flexible foam are shown in [Table 9].

[0275]

[Table 9]

Examples 40 to 43 The combinations of the polyoxyalkylene polyols and the polymer-dispersed polyols shown in Table 10 and polyisocyanate-1 were changed to polyisocyanate-2, and the apparent density was controlled according to Table 10. Except for the above, a flexible foam was produced in the same manner as in Example 34. The NCO index was 1.00. The physical properties of the obtained flexible polyurethane foam are shown in [Table 10].

[0277]

[Table 10]

<Consideration 5 of Example> [Table 9] and [Table 10]
Thus, a flexible polyurethane foam using a polyoxyalkylene polyol produced using a compound having a P = N bond (PZN, PZO) as a catalyst has excellent hardness, elongation, compression set, wet heat compression set, and durability ( Hardness loss and height loss in a repeated compression test).

[0279]

The purification method using a solid acid according to the present invention is different from the conventional purification method using a solid acid (adsorbent).
Since a neutralization treatment with an acid or the like is unnecessary and the process can be simplified, product loss in the purification process is small. Further, since the remaining amount of the catalyst is small, there is an advantage that, for example, the stability over time of the isocyanate group-terminated prepolymer which is a derivative of the polyoxyalkylene polyol is improved. Further, the properties of the polyurethane obtained from the prepolymer are excellent.
According to the present invention, a high-purity polyoxyalkylene polyol can be easily produced by a simple method that does not require complicated steps. Further, by applying the method for producing a polyoxyalkylene polyol according to the present invention, a polymer-dispersed polyol, an isocyanate group-terminated prepolymer, a flexible polyurethane foam, and a polyurethane resin, which are derivatives thereof, can be easily produced.

A crude polyoxyalkylene polyol is produced by using a compound having a P = N bond, in particular, a compound represented by any of the above chemical formulas (1) to (3) as a catalyst, and the obtained crude polyoxyalkylene polyol is obtained. Is purified with a solid acid having a specific shape, whereby the residual amount of the catalyst can be efficiently controlled to 150 ppm or less. Therefore, a high-quality polyoxyalkylene polyol having a small content of impurities can be produced. By controlling the residual amount of the catalyst in the polyol to 150 ppm or less, the stability over time of the isocyanate group-terminated prepolymer obtained by reacting the polyol with the polyisocyanate compound is improved.
Further, the polyoxyalkylene polyol obtained by the present invention has a high HT bond selectivity, and thus has a low viscosity and a low monool content.

It is known that double metal cyanide complex catalysts can produce polyoxyalkylene polyols having a low C ＝ C. However, the catalyst cannot be used when ethylene oxide is addition-polymerized. Therefore, in addition polymerization of ethylene oxide, it is necessary to switch to another catalyst, and a complicated reaction operation is required. On the other hand, the compound catalyst having a P = N bond according to the present invention does not require the complicated reaction operation as described above. In addition, when a phosphine oxide compound (PZO) is used as a catalyst among the compounds having a P = N bond, the active hydrogen compound and the water content in the catalyst are 600 ppm in the step of preparing the polymerization initiator for the polyoxyalkylene polyol.
If it is below, dehydration operation, desalting operation, etc. are unnecessary. Therefore, the productivity of the polyoxyalkylene polyol is improved.

The polymer-dispersed polyol produced by the method of the present invention uses a polyoxyalkylene polyol having a low catalyst residual amount and a low monol content and a high HT bond selectivity as a dispersion medium. Therefore, it has low viscosity. Therefore, even when the polymer particle concentration is increased, a polymer-dispersed polyol having a lower viscosity and excellent particle dispersion stability can be produced as compared with a conventional product. The isocyanate group-terminated prepolymer produced by the method of the present invention has a low residual catalyst content and a low monol content,
Since a polyoxyalkylene polyol having a high -T bond selectivity is used, it exhibits excellent performance in mechanical properties, its expression, and appearance in a wide range of polyurethane applications. Moreover, the isocyanate group-terminated prepolymer is also excellent in stability over time. Further, the flexible polyurethane foam produced by the method of the present invention is excellent in moldability and exhibits excellent performance in durability such as compression set, wet heat compression set, and repeated compression test.

Accordingly, the method for producing the polyoxyalkylene polyol and the derivative thereof according to the present invention is described in the field of polyurethane such as paints, adhesives, flooring materials, waterproofing materials, sealing agents, shoe soles, elastomers, etc .; It is extremely useful as a method for producing a lubricant, a hydraulic fluid, and a raw material in the field of sanitary products and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 10-324599 (32) Priority date November 16, 1998 (November 16, 1998) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 11-220628 (32) Priority date August 4, 1999 (1999.8.4) (33) Priority claim country Japan (JP) (72) Inventor Yama ▲ Fumio Saki ▼ 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi, Japan Mitsui Chemicals, Inc. (72) Inventor Mikio Matsuto 2-1-1 Tango-dori, Minami-ku, Nagoya, Aichi, Japan Mitsui Chemicals, Inc. (72) Nishikawa, inventor Mitsu Chemical Co., Ltd. 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi (72) Inventor Shinsuke Matsumoto 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Izugawa Work 2-1, Tango-dori, Minami-ku, Nagoya-shi, Aichi No. Mitsui Chemicals Co., Ltd. (72) Inventor Masahiro Isobe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Within Mitsui Chemicals Co., Ltd. (72) Inventor Kazuhiko Okabo 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals Co., Ltd. (72 ) Inventor Kaoru Ueno 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture F-term (reference) 4J005 AA02 AA06 AA09 AA10 BB02 4J034 CA01 CA04 CA05 CA14 CA15 CA17 CB03 CB04 CB07 CC03 CC08 CC09 CC12 CC26 CC45 CC52 CC55 CC61 CC62 CC67 CD13 DA01 DB03 DG02 DG03 DQ02 DQ15 DQ16 HA01 HA02 HA06 HA07 HB11 HC03 HC12 HC13 HC17 HC18 HC22 HC33 HC34 HC35 HC46 HC61 HC64 HC67 HC71 HC73 JA42 KA01 KB04 KB05 KC17 KC18 KD02 KD03 KD11 KD12 Q01 Q02 Q06 QC04 QD03 RA07 RA08 RA10

Claims (23)

[Claims] 1. A crude polyoxyalkylene polyol is produced by addition-polymerizing an epoxide compound to an active hydrogen compound using a compound having a P = N bond as a catalyst, and then a crude polyoxyalkylene polyol having a specific surface area of 450 to 1200 m ² / g, average pore diameter 40-1
A method for producing a polyoxyalkylene polyol, which comprises contacting a solid acid having a solid content of 100 ° C. with the catalyst and controlling the residual amount of the catalyst in the polyoxyalkylene polyol to 150 ppm or less. 2. The solid acid is a composite metal oxide prepared from different oxides including silicon oxide, boron oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, calcium oxide, and zinc oxide. The method for producing a polyoxyalkylene polyol according to claim 1, wherein 3. The composite metal oxide is at least one selected from aluminum silicate and magnesium silicate.
3. The method for producing a polyoxyalkylene polyol according to claim 2, wherein the composite metal oxide is a kind of composite metal oxide. 4. The polyoxyalkylene polyol according to claim 1, wherein the compound having a P ＝ N bond is at least one compound selected from a phosphazenium compound, a phosphine oxide compound, and a phosphazene compound. Production method. 5. The phosphazenium compound represented by the chemical formula (1): ## STR1 ## [A, b, c and d in the chemical formula (1) are each 0 to
Is a positive integer of 3, but not all of a, b, c and d are simultaneously 0. R is the same or different and has 1 to 10 carbon atoms.
Hydrocarbon groups, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. Q ⁻ represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion.] The method for producing a polyoxyalkylene polyol according to claim 4, wherein 6. A phosphine oxide compound represented by the following chemical formula (2): [In the chemical formula (2), R represents the same or different hydrocarbon group having 1 to 10 carbon atoms, x represents the amount of water contained in a molar ratio, and is 0 to 5.] The method for producing a polyoxyalkylene polyol according to claim 4, which is a compound. 7. The phosphazene compound represented by the formula (3)
[Chemical Formula 3] [Chemical Formula 3] (In the chemical formula (3), l, m and n each represent a positive integer of 0 to 3. D represents the same or different carbon number of 1 to 2.
A hydrocarbon group, an alkoxy group, a phenoxy group, a thiophenol residue, a monosubstituted amino group, a disubstituted amino group, or a 5- or 6-membered cyclic amino group. Q is a hydrocarbon group having 1 to 20 carbon atoms. Further, two D's on the same phosphorus atom or on two different phosphorus atoms can be bonded to each other, and D and Q can be bonded to each other to form a ring structure. The method for producing a polyoxyalkylene polyol according to claim 4, which is a compound to be prepared. 8. The method for producing a polyoxyalkylene polyol according to claim 1, wherein the crude polyoxyalkylene polyol is brought into contact with a solid acid at 50 to 150 ° C. 9. The method according to claim 1, wherein when the crude polyoxyalkylene polyol is brought into contact with the solid acid, 0.1 to 10% by weight of water is present in the crude polyoxyalkylene polyol. A method for producing a polyoxyalkylene polyol. 10. After contacting a crude polyoxyalkylene polyol with a solid acid, the solid acid and the polyoxyalkylene polyol are separated, and then the polyoxyalkylene polyol is mixed with at least one selected from an inorganic acid and an organic acid. The method for producing a polyoxyalkylene polyol according to claim 1, wherein 1 to 25 ppm of one kind of acid is added. 11. A catalyst 1 per mole of an active hydrogen compound
× 10^-Four~ 5 × 10 ^-1Reaction temperature 15-1 in the presence of moles
Under conditions of 30 ° C. and a maximum reaction pressure of 882 kPa or less,
Addition polymerization of epoxide compound to reactive hydrogen compound
Characterized by producing polyoxyalkylene polyol
The polyoxyalkylene polyol according to claim 1,
Manufacturing method. 12. The polyoxyalkylene polyol has a hydroxyl value of 2 to 200 mg KOH / g and a total degree of unsaturation of 0.
07meq. / g or less, the head-to-tail bond selectivity of the oxypropylene group of the polyoxyalkylene polyol by propylene oxide addition polymerization is 95 mol%.
2. The method for producing a polyoxyalkylene polyol according to claim 1, wherein: 13. The method for producing a polyoxyalkylene polyol according to claim 1, wherein the oxypropylene group content of the polyoxyalkylene polyol is at least 50% by weight. 14. A hydroxyl value of 9 to 120 mgKOH /
g, the total degree of unsaturation is 0.05 meq. / g or less, head-
The toe-tail bond selectivity is 96 mol% or more, and the remaining amount of the compound catalyst having a P = N bond is 90 pp.
The method for producing a polyoxyalkylene polyol according to claim 1, wherein m is equal to or less than m. 15. A method for producing a polymer-dispersed polyol in which polymer particles are dispersed in a polyol, wherein a polyoxyalkylene polyol is produced by the method according to any one of claims 1 to 14, and then radical polymerization is initiated. At 40 to 200 ° C. in the presence of an
A method for producing a polymer-dispersed polyol, comprising polymerizing 5 to 86 parts by weight of an ethylenically unsaturated monomer in 0 part by weight and controlling the concentration of polymer particles to 5 to 60% by weight. 16. The process according to claim 15, wherein the ethylenically unsaturated monomer is at least one monomer selected from acrylonitrile, styrene, acrylamide and methyl methacrylate. 17. A method for producing an isocyanate group-terminated prepolymer in which a polyol is reacted with a polyisocyanate, wherein a polyoxyalkylene polyol is produced by the method according to any one of claims 1 to 14,
At 50 to 120 ° C., the obtained polyoxyalkylene polyol is reacted with an amount of polyisocyanate having an isocyanate index of 1.3 to 10 to give an isocyanate group content (NCO%) of 0.3 to
A method for producing an isocyanate group-terminated prepolymer having a head-to-tail bond selectivity of 95% by weight or more in the main chain of the prepolymer at 30% by weight. 18. The method for producing an isocyanate group-terminated prepolymer according to claim 17, wherein the content of the free isocyanate compound is 1% by weight or less. 19. A method for producing an isocyanate group-terminated prepolymer in which a polyol is reacted with a polyisocyanate, wherein a polymer-dispersed polyol is produced by the method according to any one of claims 15 to 16;
At 120 ° C., the obtained polymer-dispersed polyol is reacted with an amount of polyisocyanate having an isocyanate index of 1.3 to 10 at an isocyanate group content (NCO%) of 0.3 to 30% by weight. A method for producing an isocyanate group-terminated prepolymer. 20. An isocyanate group-terminated prepolymer is produced by the method according to any one of claims 17 to 19,
Next, a method for producing a polyurethane resin in which the obtained isocyanate group-terminated prepolymer is reacted with a chain extender at 60 to 140 ° C. in a range where the isocyanate index is 0.6 to 1.5. 21. A polyoxyalkylene polyol is produced by the method according to any one of claims 1 to 14, and then, at 10 to 50 ° C., the obtained polyoxyalkylene polyol and the isocyanate group-terminated prepolymer are mixed. And a method for producing a polyurethane resin in which the isocyanate index is reacted within a range of 0.8 to 1.3. 22. A method for producing a flexible polyurethane foam, comprising reacting a polyol with a polyisocyanate in the presence of water, a catalyst and a foam stabilizer, wherein the method comprises the steps of: A method for producing a flexible polyurethane foam, comprising producing an oxyalkylene polyol, and then using a polyol containing at least 30% by weight of the obtained polyoxyalkylene polyol. 23. A process for producing a flexible polyurethane foam, comprising reacting a polyol with a polyisocyanate in the presence of water, a catalyst, and a foam stabilizer.
A method for producing a flexible polyurethane foam, comprising producing a polymer-dispersed polyol by the method according to any one of the above, and then using a polyol containing at least 10% by weight of the obtained polymer-dispersed polyol.