JPH1160719A - Production of polyoxyalkylenepolyamine and production of polyurethaneurea resin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound that is useful as a raw material for polyurethane-urea resin with high amination ratio of terminal hydroxyl groups in a lower viscosity without undergoing complicated processes by aminating the terminal hydroxyl groups of polyoxyalkylene polyol prepared by polyaddition polymerization via a specific process. SOLUTION: In the presence of a phosphazene compound of the formula (Q is a 1-20 hydrocarbon), typically 1-(1,1,3,3-tetramethylbutyl)-2,2,2-tris(dimethylamino)phosphazene, the terminal hydroxyl groups of polyoxyalkylene polyol prepared by polyaddition polymerization of an alkylene oxide as propylene oxide to an active hydrogen atom-bearing compound as glycerol at 15-130 deg.C under the maximum pressure of 9 kgf/cm<2> is aminated with ammonia in the presence of a hydrogenation-dehydrogenation catalyst as Ni on kieselgur at 60-280 deg.C under the maximum pressure of 150 kgf/cm<2> to give the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyoxyalkylene polyamine and a method for producing a polyurethane urea resin. Specifically, a method for producing a polyoxyalkylene polyamine using a polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound in the presence of a phosphazene compound, and reacting a polyol containing the polyoxyalkylene polyamine with a polyisocyanate compound The present invention relates to a method for producing a polyurethane urea resin. Polyoxyalkylene polyamine having an amino group at the molecular terminal provides polyurea by a polyaddition reaction with a polyisocyanate compound,
Polyurea-based elastomer, flexible polyurethane foam, hard polyurethane foam, paint, flooring, waterproofing material,
Used as a raw material for adhesives and vehicle parts. Further, it is a compound useful as various plastic raw materials such as epoxy resin, polyamide, and polyimide.

[0002]

2. Description of the Related Art Polyoxyalkylene polyamines have high reactivity with polyisocyanate compounds, and are mainly used for spraying or reaction injection molding (Reaction Injection Molding).
junction Mold, hereinafter abbreviated as RIM. )
It is used as a raw material for polyurethane urea resin molded by the method. The spray method or RIM method is a process having an extremely fast cycle time in which a molded product is usually obtained in 2 to 4 seconds, so that considerable reaction heat is generated in a short time. Therefore, the thermal characteristics of the resin during the molding process are important factors.

[0003] In JP-A-6-16763, a "double metal cyanide catalyst" (referred to as a double metal cyanide complex in the present application. Double Metal Cyanide).
complex. Hereinafter, it is abbreviated as DMC. ) As a catalyst, and polyamines obtained by amine capping the polyol.
Furthermore, the elastomers prepared using them have a low "ethylenically unsaturated group content" (corresponding to the total degree of unsaturation in the present application; hereinafter, abbreviated as C = C) in the polyol, and therefore low heat. It has been described to have excellent thermal properties, characterized by sagging and high heat distortion temperature (column 13,
Line 19 to column 14, lines 20).

[0004] By using DMC as a polymerization catalyst for alkylene oxides, especially propylene oxide,
The total unsaturation (C = C) in the polyol is low, and a high molecular weight polyol is obtained. However, there is a disadvantage that the viscosity of the obtained polyoxyalkylene polyol is high.
US Pat. No. 5,300,535 teaches the use of acrylate-based and vinyl ether-based compounds as viscosity reducing agents because of the high viscosity of high molecular weight polyoxyalkylene polyols catalyzed by DMC (column 2,5 to column 4,14).

As a result of investigations by the present inventors, polyoxyalkylene polyamines using polyols obtained using DMC as a catalyst have a high viscosity, and in the field of molding resins by impingement mixing such as spraying and RIM methods, the use of liquid The mixing property deteriorated, and the resin physical properties expected by the present inventors could not be obtained. JP-A-6-16763 discloses that the polyol which is a polyamine precursor is preferably propylene oxide or a mixture with ethylene oxide using random or stepwise alkylation (columns 8, 19 to 21).
However, in the case of addition polymerization of ethylene oxide as an alkylene oxide, the DMC catalyst loses the catalyst by a reaction with an oxidizing agent such as a gas containing oxygen, a peroxide, or sulfuric acid. It is necessary to separate the catalyst residue from the polyol, and to carry out addition polymerization of ethylene oxide using an alkali metal hydroxide such as potassium hydroxide (KOH) or an alkali metal alkoxide thereof (US Pat. No. 5,144,093). , USP5,23
5,114).

[0006] In order to deactivate the catalyst, a method using an alkali metal alkoxide or an alkaline earth metal alkoxide in addition to an oxidizing agent (Japanese Patent Application Laid-Open No. 5-508833), a treatment method using a strong base and an ion exchange resin (USP
No. 4,355,188) have been proposed, but each of these methods has a problem that the manufacturing process is complicated and the cost is low. In addition, as a result of investigations by the present inventors, polyoxyalkylene polyamine using a polyol catalyzed by DMC has a high viscosity, so that the miscibility with the polyisocyanate compound is reduced, and pinholes are formed on the surface of the polyurethane urea resin. It was found to happen.

[0007] Macromol. Rapid Comm
un. 17, 143-148 (1996), describes polymerization of ethylene oxide catalyzed by a polyiminophosphazene base (t-Bu-P4).
By using the polyiminophosphazene base as a polymerization catalyst for ethylene oxide, polyethylene oxide having a narrow molecular weight distribution can be obtained.However, the polymerization of propylene oxide, which is the main monomer of polyoxyalkylene polyol, and There is no description on the method for producing the alkylene polyamine.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polymer having a low viscosity even when a high molecular weight is obtained, and a total unsaturation ( Method for producing polyoxyalkylene polyamine using polyoxyalkylene polyol having low C = C), and polyurethane urea using this polyoxyalkylene polyamine with excellent heat resistance, excellent mechanical properties, and excellent appearance with few pinholes An object of the present invention is to provide a method for producing a resin.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that polyoxyalkylene obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound using a phosphazene compound as a catalyst. Polyol, preferably the concentration of the phosphazene compound,
Reaction temperature, using a polyoxyalkylene polyol obtained by specifying the reaction pressure, to aminate the terminal hydroxyl group thereof to produce a polyoxyalkylene polyamine, and further comprising a polyol containing the polyoxyalkylene polyamine and a polyisocyanate compound To produce a polyurethane urea resin to achieve the above object.

That is, a first object of the present invention is a method for producing a polyoxyalkylene polyamine by aminating a terminal hydroxyl group of a polyoxyalkylene polyol,
Partial structural formula (1) [Chemical formula 3]

[0011]

Embedded image (Wherein, Q represents a hydrocarbon group having 1 to 20 carbon atoms.) A polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound in the presence of a phosphazene compound represented by the formula: Is a method for producing a polyoxyalkylene polyamine.

A second object of the present invention is to provide a hydroxyl value (hereinafter abbreviated as OHV) of a polyoxyalkylene polyol catalyzed by the phosphazene compound of the first object of the present invention.
Is 2 to 200 mgKOH / g, and the total degree of unsaturation in the polyoxyalkylene polyol (hereinafter abbreviated as C = C) is 0.0001 to 0.07 meq. / G, and Head-to-Ta of polyoxyalkylene polyol by propylene oxide addition polymerization.
il) The method for producing a polyoxyalkylene polyamine, which comprises using a polyoxyalkylene polyol having a bond selectivity of 95 mol% or more.

A third object of the present invention is to provide a phosphazene compound represented by the formula (2):

[0014]

Embedded image (In the formula, l, m and n each represent a positive integer of 0 to 3. D is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, a phenoxy group, a thiophenol residue, Substituted amino group, disubstituted amino group or 5 or 6
It is a membered cyclic amino group. Q is 1-20 carbon atoms
Is a hydrocarbon group. Further, two Ds on the same phosphorus atom or on two different phosphorus atoms may be bonded to each other, and D and Q may be bonded to each other to form a ring structure. ), Wherein the polyoxyalkylene polyamine is produced.

[0015] A fourth object of the present invention is that l, m and n in the chemical formula (2) are (2, 1,
1), (1, 1, 1), (1, 1, 0), (1, 0,
The method for producing a polyoxyalkylene polyamine as described above, wherein a polyoxyalkylene polyol using a phosphazene compound that is a number in a combination selected from (0) and (0, 0, 0) as a catalyst is used.

A fifth object of the present invention is to provide a partial structural formula (1)
And Q in the chemical formula (2) is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, tert-butyl, pentyl, neopentyl,
Hexyl, heptyl, octyl, tert-octyl,
The method for producing a polyoxyalkylene polyamine using a polyoxyalkylene polyol using a phosphazene compound which is a hydrocarbon group selected from the group consisting of nonyl and decyl as a catalyst.

A sixth object of the present invention is to provide a phosphazene compound of the formula (2) wherein 1-tert-butyl-2,2,2
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 -catenadi (phosphazene), 1-t
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
^The method for producing the polyoxyalkylene polyamine, which is ⁵ -phosphaspiro [5,5] undec-1 (6) -ene.

A seventh object of the present invention is to provide an active hydrogen compound 1 in the presence of a phosphazene compound represented by the chemical formula (2).
The phosphazene compound represented by the chemical formula (2) is prepared in the range of 5 × 10 ^-5 to 1 mol with respect to mol, the reaction temperature is 15 to 130 ° C., and the maximum reaction pressure is 9 kgf / cm ² (8
The method for producing a polyoxyalkylene polyamine is characterized by using a polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide under a condition of 82 kPa).

An eighth object of the present invention is to provide a method for aminating a terminal hydroxyl group, wherein a polyoxyalkylene polyol, ammonia and a primary amine are used in the presence of a hydrogenation-dehydrogenation catalyst.
It is characterized by reacting with at least one nitrogen-containing active hydrogen compound selected from secondary amines and diamines under the conditions of a reaction temperature of 60 to 280 ° C. and a maximum reaction pressure of 150 kgf / cm ² (14.7 MPa). The method for producing a polyoxyalkylene polyamine described above.

A ninth object of the present invention is to provide a method for aminating a terminal hydroxyl group, comprising the steps of:
A method for producing the polyoxyalkylene polyamine, which comprises performing a hydrogenation reaction under pressure after reacting a functional group capable of reacting with a hydroxyl group in a molecule, and a compound having a cyano group or a nitro group. .

A tenth object of the present invention is a method for producing a polyurethane urea resin, which comprises reacting a polyol containing the polyoxyalkylene polyamine with a polyisocyanate compound as the first to ninth objects of the present invention. It is.

The polyoxyalkylene polyamine obtained by the method of the present invention is a double metal cyanide complex (DM
The viscosity is lower than the method using polyoxyalkylene polyamine using C). In the case of a DMC-based copolymer, when the ethylene oxide copolymerization reaction is performed, DMC must be once deactivated by a reaction with an alkali metal compound (potassium methylate), and then the catalyst must be used to polymerize ethylene oxide. It is complicated. On the other hand, the method of the present invention does not require a complicated operation in the copolymerization reaction with ethylene oxide, and can obtain a polyoxyalkylene polyamine having a low viscosity and a high amination ratio of a hydroxyl group.

Further, the polyurethane urea resin obtained by the method of the present invention is a double metal cyanide complex (DM
Compared with the method using a polyamine obtained from a polyol using C) as a catalyst, the number of pinholes is small and the surface state of a molded article is good. It is also excellent in mechanical properties such as elongation, hardness and tensile strength, and heat resistance.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The partial structural formula (1) in the present invention
And the phosphazene compound represented by the chemical formula (2)
It is well known that it has strong basicity. Q and chemical formula (2) in partial structural formula (1) and chemical formula (2)
D in the formula (I) may contain any substituent as long as it does not inhibit the reaction of the present invention.

First, the phosphazene compound used in the present invention will be described. Examples of the hydrocarbon group of Q having 1 to 20 carbon atoms in the partial structural formula (1) and the chemical formula (2) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and ter
alkyl groups such as t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, tert-octyl, nonyl or decyl, allyl, 2-methylallyl, benzyl, phenethyl, o-anisyl, 1-phenylethyl, diphenylmethyl, triphenyl An alkyl group having an unsaturated bond or an aromatic group such as methyl or cinnamyl, an alicyclic group such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 3-propylcyclohexyl, 4-phenylcyclohexyl, cycloheptyl or 1-cyclohexenyl, Alkenyl groups such as vinyl, styryl, propenyl, isopropenyl, 2-methyl-1-propenyl or 1,3-butadienyl, alkynyl groups such as ethynyl or 2-propynyl, phenyl, o-
Tolyl, m-tolyl, p-tolyl, 2,3-xylyl,
2,4-xylyl, 3,4-xylyl, mesityl, o-
And aromatic groups such as cumenyl, m-cumenyl, p-cumenyl, 1-naphthyl, 2-naphthyl and p-methoxyphenyl.

In formula (2), D has 1 to 20 carbon atoms.
Examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and sec.
Alkyl groups such as -butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, tert-octyl, nonyl or decyl, allyl, 2-
Methylallyl, benzyl, phenethyl, o-anisyl,
An alkyl group having an unsaturated bond or an aromatic group such as 1-phenylethyl, diphenylmethyl, triphenylmethyl or cinnamyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 3-propylcyclohexyl, 4-phenylcyclohexyl, cycloheptyl or 1 Alicyclic groups such as cyclohexenyl, vinyl, styryl, propenyl, isopropenyl, 2-methyl-1
Alkenyl groups such as -propenyl or 1,3-butadienyl, alkynyl groups 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.

Examples of the alkoxy group D include alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, allyloxy, cyclohexyloxy and benzyloxy. As the phenoxy group of D,
For example, carbon number 6 such as phenoxy, 4-methylphenoxy, 3-propylphenoxy or 1-naphthyloxy.
And phenoxy groups containing -20. Examples of the thiol residue of D include a carbon number of 1 to 2 such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, heptylthio, octylthio, tert-octylthio, nonylthio or decylthio.
Thiol residues including 0.

Examples of the thiophenol residue of D include phenylthio, o-toluylthio, m-toluylthio, p-toluylthio, 2,3-xylylthio, 2,4
6 to 20 carbon atoms such as -xylylthio, 3,4-xylylthio, 4-ethylphenylthio or 2-naphthylthio
And a thiophenol residue containing Examples of the monosubstituted amino group D include, for example, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, hexylamino, heptylamino, octylamino, tert-octylamino , Nonylamino,
Such as decylamino, 1-ethylpropylamino, 1-ethylbutylamino, anilino, o-toluylamino, m-toluylamino, p-toluylamino, 2,3-xylinamino, 2,4-xylinamino or 3,4-xylinamino A monosubstituted amino group having 1 to 20 carbon atoms is exemplified.

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
An amino group di-substituted by the same or different C1-C20 hydrocarbon group such as -toluylamino, di-2,3-xylylamino or phenyltoluylamino;
Pyrrolidinyl, 3-methyl-1-pyrrolidinyl, 1-pyrrolyl, 3-ethyl-1-pyrrolyl, 1-indolyl,
Examples thereof include 5- to 6-membered cyclic amino groups such as 1-piperidyl, 3-methyl-1-piperidyl, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-imidazolidinyl and 4-morpholinyl.

When all or some of two D's on the same phosphorus atom or on two different phosphorus atoms are bonded to each other to form a ring structure, a divalent group (D −
D) includes ethylene, vinylene, propylene, 1,
Saturated or unsaturated aliphatic divalent carbonization such as 2-cyclohexanylene, 1,2-phenylene, trimethylene, propenylene, tetramethylene, 2,2'-biphenylene, 1-butenylene, 2-butenylene or pentamethylene; And a hydrogen group.

Further, one or both of the bonds between both ends of the divalent group and the phosphorus atom may be 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. And a divalent group in which any one or two selected from the group consisting of a nitrogen atom to which an aliphatic or aromatic hydrocarbon group such as a phenyl group is bonded are 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.

When all or a part of D and Q are bonded to each other to form a ring structure, the divalent group (DQ) connecting the nitrogen atom and the phosphorus atom is as described above. And the same saturated or unsaturated aliphatic divalent hydrocarbon group as the divalent group on the phosphorus atom. Further, the bond between the divalent hydrocarbon group and the phosphorus atom, an oxygen atom, a sulfur atom and a hydrogen atom or an aliphatic or a methyl group, an ethyl group, a butyl group, a cyclohexyl group, a benzyl group or a phenyl group. A divalent group in which any one of a group consisting of a nitrogen atom to which an aromatic hydrocarbon 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-2. -Iminoethylene, N-methyl-3-iminotrimethylene or N-phenyl-2-iminoethylene.

Specific examples of the phosphazene compound having the structure represented by the chemical formula (2) are given below. When D is the same or different alkyl group, for example, 1-t
tert-butyl-2,2,2-trimethylphosphazene or 1- (1,1,3,3-tetramethylbutyl)-
2,2,4,4,4-pentaisopropyl-2λ ⁵ , 4
λ ⁵ -catenadi (phosphazene) and the like. Examples of the case where D is an alkyl group having an unsaturated bond or an aromatic group include, for example, 1-tert-butyl-
2,2,2-triallylphosphazene, 1-cyclohexyl-2,2,4,4,4-pentaallyl-2λ ⁵ , 4
λ 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 - Katenaji (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,
4,4,4-pentastyryl-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) and the like.

Examples of the case where D is an alkynyl group include, for example, 1-tert-butyl-2,2,2-tri (2
-Phenylethynyl) phosphazene and the like. D
Is an aromatic group, for example, 1-isopropyl-2,4,4,4-tetraphenyl-2-triphenylphosphoranylideneamino-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) and the like. No.

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-pentaisopropoxy-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) or 1-phenyl-2,2,4,4,4-pentabenzyloxy-2λ ⁵ , 4λ ⁵ -catenadi ( Phosphazene)
And the like. 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,
4,4,4-penta (1-naphthyloxy) -2λ ⁵ ,
4λ ⁵ -catenadi (phosphazene) and the like.

Examples of the case where D is a thiol residue include, for example, 1-tert-butyl-2,2,2-trimethylthiophosphazene or 1-methyl-2,4,
4,4-tetraisopropylthio-2-triisopropylthiophosphoranylideneamino-2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) and the like. Examples of the case where D is a thiophenol residue include, for example, 1-allyl-4,4,4-triphenylthio-2,2-bis (triphenylthiophosphoranylideneamino) -2λ ⁵ , 4
λ ⁵ -catenadi (phosphazene) and the like.

When D is a monosubstituted amino group,
Is, for example, 1-tert-butyl-2,2,2-tri
(Methylamino) phosphazene, 1- (1,1,3,3
-Tetramethylbutyl) -2,2,4,4,4-pentane
(Isopropylamino) -2λ^Five, 4λ^Five-Katenaji
(Phosphazene), 1-tert-butyl-2,4,
4,4-tetra (methylamino) -2-tri (methyla
Mino) phosphoranylideneamino-2λ^Five, 4λ^Five−f
Tenazi (phosphazene), 1-tert-butyl-2,
4,4,4-tetra (isopropylamino) -2-tri
(Isopropylamino) phosphoranylideneamino-2
λ^Five, 4λ^Five-Catenazi (phosphazene), 1-ter
t-butyl-2,4,4,4-tetra (tert-butyl
Ruamino) -2-tri (tert-butylamino) phos
Foranylideneamino-2λ^Five, 4λ ^Five-Katenaji (e)
Sphazen), 1-tert-butyl-2,4,4,4
-Tetra (allylamino) -2-tri (allylamino)
Phosphoranylideneamino-2λ^Five, 4λ^Five-Katenaji
(Phosphazene), 1-tert-butyl-4,4,4
-Tri (methylamino) -2,2-bis [tri (methyl
Amino) phosphoranylideneamino] -2λ^Five, 4λ^Five
-Catenadi (phosphazene), 1-tert-butyl-
4,4,4-tri (isopropylamino) -2,2-bi
[Tri (isopropylamino) phosphoranylidenea
Mino] -2λ^Five, 4λ^Five-Catenazi (phosphazene),
1-tert-butyl-4,4,4-tri (tert-
Butylamino) -2,2-bis [tri (tert-butyl)
Ruamino) phosphoranylideneamino] -2λ^Five, 4λ
^Five-Catenadi (phosphazene), 1-tert-butyl
-4,4,6,6,6-penta (methylamino) -2,
2-bis [tri (methylamino) phosphoranylidenea
Mino] -2λ^Five, 4λ^Five, 6λ^Five-Catenatri (phosph
Azene), 1-tert-butyl-4,4,6,6,6
-Penta (isopropylamino) -2,2-bis [tri
(Isopropylamino) phosphoranylideneamino]-
2λ^Five, 4λ^Five, 6λ^Five-Catenatri (phosphase
), 1-tert-butyl-4,4,6,6,6-pe
N- (tert-butylamino) -2,2-bis [tri
(Tert-butylamino) phosphoranylidenea
No) -2λ^Five, 4λ^Five, 6λ^Five-Catenatri (phospha
Zen) or 1-tert-butyl-4,4,6,6
6-penta (methylamino) -2- [2,2,2-tri
(Methylamino) phosphazen-1-yl] -2-
[2,2,4,4,4-penta (methylamino) -2λ
^Five, 4λ^Five-Catenadi (phosphazene) -1-yl]-
2λ^Five, 4λ^Five, 6λ^Five-Catenatri (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 (phosphazenes), 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 , 4
? ⁵ -Catenadi (phosphazene), 1-tert-butyl-2,4,4,4-tetrakis (di-n-butylamino) -2-tris (di-n-butylamino) phosphoranylideneamino-2? ^{5, 4λ 5} - Katenaji (phosphazene), 1-tert-butyl-4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylideneamino Rani isopropylidene amino] 2 [lambda] ^5, 4.lamda ^Five
-Catenazi (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} - Katenaji (phosphazenes), 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
4-tris (di-n-butylamino) -2,2-bis [tris (di-n-butylamino) phosphoranylideneamino] -2λ 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} - Katenatori (phosphazenes), 1
-Tert-butyl-4,4,6,6,6-pentakis (diethylamino) -2,2-bis [tris (diethylamino) phosphoranylideneamino] -2λ ⁵ , 4
λ ⁵ , 6λ ⁵ -catenatri (phosphazene), 1-te
rt-butyl-4,4,6,6,6-pentakis (diisopropylamino) -2,2-bis [tris (diisopropylamino) phosphoranylideneamino] -2λ ⁵ ,
4λ ⁵ , 6λ ⁵ -catenatri (phosphazene), 1-t
tert-butyl-4,4,6,6,6-pentakis (di-n-butylamino) -2,2-bis [tris (di-n
-Butylamino) phosphoranylideneamino] -2
λ 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, 4.lamda ⁵ - Katenaji (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.

D is a 5- or 6-membered cyclic amino group
Examples of the case include, for example, 1-tert-butyl-
2,2,2-tri (1-pyrrolidinyl) phosphazene,
1-tert-butyl-2,2,4,4,4-pentane
(1-pyrrolidinyl) -2λ^Five , 4λ^Five -Katenaji (e)
Sphazen), 1-tert-butyl-2,2,4,
4,4-penta (4-morpholinyl) -2λ^Five, 4λ^Five
-Catenadi (phosphazene), 1-tert-butyl-
2,2,4,4,4-penta (1-piperidinyl) -2
λ^Five, 4λ^Five-Catenazi (phosphazene), 1-ter
t-butyl-2,2,4,4,4-penta (4-methyl
-1-piperidinyl) -2λ^Five, 4λ^Five-Katenaji (e)
Sphazen), 1-tert-butyl-2,2,4,
4,4-penta (1-imidazolyl) -2λ^Five, 4λ^Five
-Catenadi (phosphazene), 1-tert-butyl-
2,4,4,4-tetra (1-pyrrolidinyl) -2-to
Tri (1-pyrrolidinyl) phosphoranylideneamino-2
λ^Five, 4λ^Five-Catenazi (phosphazene), 1-ter
t-butyl-2,4,4,4-tetra (1-piperidini
Ru) -2-tri (1-piperidinyl) phosphoranilide
Amino-2λ^Five, 4λ^Five-Catenazi (phosphase
), 1-tert-butyl-2,4,4,4-tetra
(4-morpholinyl) -2-tri (4-morpholinyl)
Phosphoranylideneamino-2λ^Five, 4λ^Five-Katenaji
(Phosphazene), 1-tert-butyl-2,4,
4,4-tetra (4-methyl-1-piperazinyl) -2
-Tri (4-methyl-1-piperazinyl) phosphorani
Lidenamino-2λ^Five, 4λ^Five-Catenazi (phosphase
), 1-tert-butyl-2,4,4,4-tetra
(1-imidazolyl) -2-tri (1-imidazolyl)
Phosphoranylideneamino-2λ^Five, 4λ^Five-Katenaji
(Phosphazene), 1-tert-butyl-4,4,4
-Tri (1-pyrrolidinyl) -2,2-bis [tri (1
-Pyrrolidinyl) phosphoranylideneamino] -2
λ^Five, 4λ^Five-Catenazi (phosphazene), 1-ter
t-butyl-4,4,4-tri (4-morpholinyl)-
2,2-bis [tri (4-morpholinyl) phosphorani
Ridenamino] -2λ^Five, 4λ^Five-Catenazi (phospha
Zen), 1-tert-butyl-4,4,4-tri (1
-Piperidinyl) -2,2-bis [tri (1-piperidinyl)
Nyl) phosphoranylideneamino] -2λ^Five, 4λ^Five−
Catenadi (phosphazene), 1-tert-butyl-
4,4,4-tri (4-methyl-1-piperazinyl)-
2,2-bis [tri (4-methyl-1-piperazinyl)
Phosphoranylideneamino] -2λ^Five, 4λ^Five-Catena
Di (phosphazene), 1-tert-butyl-4,4,
4-tri (1-imidazolyl) -2,2-bis [tri
(1-imidazolyl) phosphoranylideneamino] -2
λ^Five, 4λ^Five-Catenazi (phosphazene), 1-ter
t-butyl-4,4,6,6,6-penta (1-pyrroli
Dinyl) -2,2-bis [tri (1-pyrrolidinyl) ho
Sphoranylideneamino] -2λ^Five, 4λ^Five, 6λ^Five−
Catenatri (phosphazene), 1-tert-butyl-
4,4,6,6,6-penta (1-piperidinyl)-
2,2-bis [tri (1-piperidinyl) phosphorani
Ridenamino] -2λ ^Five, 4λ^Five, 6λ^Five-Catenatri
(Phosphazene), 1-tert-butyl-4,4,
6,6,6-penta (4-morpholinyl) -2,2-bi
[Tri (4-morpholinyl) phosphoranylideneamido
No) -2λ^Five, 4λ^Five, 6λ^Five-Catenatri (phospha
Zen), 1-tert-butyl-4,4,6,6,6-
Penta (4-methyl-1-piperazinyl) -2,2-bi
[Tri (4-methyl-1-piperazinyl) phosphora
Nilideneamino] -2λ^Five, 4λ^Five, 6λ^Five-Catenate
Li (phosphazene) or 1-tert-butyl-4,
4,6,6,6-penta (1-pyrrolidinyl) -2-
[2,2,4,4,4-penta (1-pyrrolidinyl)-
2λ^Five, 4λ^Five-Catenadi (phosphazene) -1-a
2-] [2-, 2,2-tri (1-pyrrolidinyl) ho
Sphazen-1-yl] -2λ^Five, 4λ^Five, 6λ^Five−f
Tenatri (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.

Examples of the case where D and Q are bonded to each other to form a ring structure include, for example, 5, 7, 11
-Trimethyl-1,5,7,11-tetraaza-6λ ⁵
-Phosphaspiro [5,5] undeca-1 (6) -ene, 7-ethyl-5,11-dimethyl-1,5,7,1
1-tetraaza -6Ramuda ⁵ - phosphaspiro [5.5] undec-1 (6) - ene, 6,8,13, - trimethyl -1,6,8,13- tetraaza -7Ramuda ⁵ - phosphaspiro [6,6] Trideca-1 (7) -ene, 7-methyl-1,7-diaza-5,11-dioxa-6λ5-phosphaspiro [5,5] undeca-1 (6) -ene, 7-
Methyl-1,7-diaza-5-oxa-11-thia-6
λ ⁵ -phosphaspiro [5,5] undeca-1 (6)-
Ene, 1-tert-butylimino-1-dimethylamino-1,3-diphosphor-2-aza-3,3-dimethyl-2-cyclohexene, 6λ ⁵ -phosphaspiro-
[5,5] Undeca-1 (6) -ene or 1-dimethylamino-1- (2-dimethylamino-2,2-trimethylenediaminophosphazen-1-yl) -1λ ⁵ -phospho2,6-diaza -1-cyclohexene and the like.

The synthesis method of these phosphazene compounds is as follows.
H., Earl, Earlcock, "Phosphorus-Nitrogen Compound", Academic Press Publishing, 1972 (HR Allcock, Phosp).
horus-NitrogenCompounds, A
Cademic Press 1972) or Reinhard Schwezinger "Nahiriten Hemy Technique Laboratorium", Vol. 38, No. 10, 1214-122
Page 6, 1990 [Reinhard Schwesin
ger, Nachr. Chem. Tec. Lab. , 3
8 (1990), Nr. 10, 1214-1226] and Reinhard Schwezinger et al., "Hemisch
Berichte, Vol. 127, pages 2435-2454, 1994 (Reinhard Schwesinger, Che.
m. Ber. , 1994, 127, 2435-245.
4) and the like.

For example, 1-tert-butyl-2,2,
2-triallyl phosphazene is the above-mentioned H, R,
As shown on page 114 of Earlcock's book, it can be easily synthesized by reacting triallylphosphine with tert-butylazide in ether.
-Phenyl-2,2-bis (dimethylamino) -4,4
-Dimethoxy-4-phenylamino-2λ ⁵ , 4λ ^5-
Catenazi (phosphazene) is obtained by reacting bis (dimethylamino) chlorophosphine with phenylazide and then with triethylammonium azide, as shown on page 115 of the same book.
Azido-2,2-bis (dimethylamino) phosphazene can be synthesized by further reacting with dimethoxyphenylaminophosphine.

In the phosphazene compound represented by the chemical formula (3) in the present invention, l, m and n are each 0 to 3
Indicates a positive integer of. It is preferably a positive integer of 0 to 2. More preferably, l, m and n are (2, 1, 1), (1, 1, 1), (1, 1,
0), (1, 0, 0) or (0, 0, 0).

In the phosphazene compound represented by the chemical formula (3), D is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenoxy group having 6 to 20 carbon atoms, A mono-substituted amino group containing numbers 1 to 20, a homo- or hetero-type homo- or hetero-group selected from the group consisting of a di-substituted amino group having 1 to 20 carbon atoms and a 5- or 6-membered cyclic amino group; And D is, for example, dimethylamino, diethylamino, methylethylamino, dipropylamino, methylpropylamino, diisopropylamino, dibutylamino, methylbutylamino, diisobutylamino, di-sec-butylamino. An amino group in which the same or different alkyl groups having 1 to 6 carbon atoms are disubstituted; Cycloalkenyl, 1-pyrrolyl, 1-piperidyl, such as 1-piperazinyl or 4-morpholinyl 5
More preferably, they are the same or different substituents selected from a 6-membered cyclic amino group. Further, it is more preferable that D is a disubstituted amino group selected from dimethylamino, methylethylamino and diethylamino.

Q in the partial structural formula (1) and the chemical formula (2) is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, ter
Alkyl groups having 1 to 10 carbon atoms such as t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, tert-octyl, nonyl and decyl are preferred.

In the case where two Ds on the same phosphorus atom or two different phosphorus atoms in the chemical formula (3) are bonded to each other to form a ring structure, Is preferably 1,2-diiminoethylene, 1,3-diiminotrimethylene or 1,2-diiminoethylene.
Bivalent N, N'- in which two nitrogen atoms of 4-diiminotetramethylene are substituted with one methyl group or one ethyl group
A methyl or ethyl-α, ω-diiminoalkylene group.

Further, when D and Q in the chemical formula (3) are bonded to each other to form a ring structure, the divalent group (DQ) connecting the nitrogen atom and the phosphorus atom is preferable. Is iminomethylene, 2-iminoethylene or 3-
It is a divalent N-methyl or ethyl-ω-iminoalkylene group in which the nitrogen atom of iminotrimethylene is substituted by a methyl group or an ethyl group. As these phosphazene compounds, preferably, 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, 7-ethyl-5,11-dimethyl-1,5,7,11-tetraaza-6λ ⁵ -phosphaspiro [5.5] undeca- 1 (6) -ene.

In the method of the present invention, these phosphazene compounds may be used alone or in combination of two or more.

The method for producing the polyoxyalkylene polyamine of the present invention will be described. First, a method for producing a polyoxyalkylene polyol will be described. Examples of the active hydrogen compound coexisting with the phosphazene compound represented by the partial structural formula (1) and the chemical formula (2) include alcohols, phenol compounds, polyamines, and alkanolamines. For example, water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol,
Dihydric alcohols such as 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-cyclohexanediol, monoethanolamine, diethanolamine,
Alkanolamines such as triethanolamine, polyhydric alcohols such as glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol; sugars such as glucose, sorbitol, dextrose, fructose, sucrose, methyl glucoside, etc. Or derivatives thereof, fatty acid amines such as ethylenediamine, di (2-aminoethyl) amine, and hexamethylenediamine; aromatic amines such as toluylenediamine and diphenylmethanediamine;
Examples thereof include phenol compounds such as bisphenol A, bisphenol F, bisphenol S, novolak, resole, resorcin, and hydroquinone. These active hydrogen compounds can be used in combination of two or more.
Further, a compound obtained by addition polymerization of an alkylene oxide to these active hydrogen compounds by a conventionally known method in an amount of about 2 to 8 equivalents per equivalent of the active hydrogen group can also be used.

A solvent may be used to make the contact between the phosphazene compound represented by the partial structural formula (1) and the chemical formula (2) and the active hydrogen compound effective. Any solvent may be used as long as it does not inhibit the alkylene oxide addition polymerization reaction.
-Aliphatic or aromatic hydrocarbons such as pentane, n-hexane, cyclohexane, benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform, bromoform, carbon tetrachloride, dichloroethane, orthodichlorobenzene, acetic acid Ethyl, esters such as methyl propionate or methyl benzoate, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether or triethylene glycol dimethyl ether,
Examples thereof include nitriles such as acetonitrile and propionitrile, and polar aprotic solvents such as N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.

These solvents are selected according to the chemical stability of the raw materials used for the reaction. Preferably, aliphatic or aromatic hydrocarbons such as n-hexane, n-heptane, benzene, toluene or xylene, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane or ethylene glycol dimethyl ether, Nitriles such as acetonitrile. The solvents may be used alone or in combination of two or more. It is preferable that the raw materials are dissolved, but they may be in a suspended state.

The temperature is not uniform depending on the type, amount and concentration of the active hydrogen compound and the phosphazene compound to be used, but is usually 150 ° C. or lower, preferably from 0 to 150 ° C.
℃, more preferably in the range of 10 to 110 ℃. The reaction pressure can be reduced, normal pressure and pressurization,
It is preferably 0.1 to 10 kgf / cm ² (absolute pressure, hereinafter 9.8 to 980 kPa), and more preferably 1 to 3 kgf / cm ² (98 to 294 kPa). The reaction time is usually in the range of 1 minute to 24 hours,
Preferably it is 1 minute to 10 hours, more preferably 5 minutes to 6 hours.

The alkylene oxide to be addition-polymerized to an active hydrogen compound in the presence of a phosphazene compound includes:
Examples include propylene oxide, ethylene oxide, 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. Of these, propylene oxide, butylene oxide and ethylene oxide are preferred. Particularly preferred is a polyoxyalkylene polyol using propylene oxide in an amount of 40 mol% or more. Most preferably, it is a polyoxyalkylene polyol using 50 mol% or more of propylene oxide.

As a polymerization method, when propylene oxide and ethylene oxide are used as an example, after polymerization of propylene oxide, an ethylene oxide cap reaction in which ethylene oxide is copolymerized in blocks, and a random copolymerization in which propylene oxide and ethylene oxide are randomly copolymerized. The reaction may further include a triblock copolymerization reaction in which ethylene oxide is polymerized after propylene oxide polymerization, and then propylene oxide is polymerized. Among these, preferable polymerization methods are an ethylene oxide cap reaction and a triblock copolymerization reaction.

The polyoxyalkylene polyol obtained by addition-polymerizing an active hydrogen compound with an alkylene oxide in the presence of a phosphazene compound preferably satisfies the following conditions. a. The hydroxyl value (OHV) is in the range of 2 to 200 mgKOH / g. b. The total degree of unsaturation (C = C) in the polyoxyalkylene polyol is 0.0001 to 0.07 meq. / G. c. Head-to-tail (Head) of polyoxyalkylene polyol by propylene oxide addition polymerization
-To-Tail) bond selectivity is 95 mol% or more.

OHV of polyoxyalkylene polyol
Is from 2 to 200 mgKOH / g. Preferably 9-1
20 mgKOH / g. More preferably, 11 to 60
mg KOH / g. If the addition polymerization of alkylene oxides, especially propylene oxide, is carried out until the OHV becomes less than 2 mgKOH / g, the reaction time of the polyoxyalkylene polyol becomes longer. OHV is 200
The total degree of unsaturation (C = C) of the polyoxyalkylene polyol we are interested in when it exceeds mgKOH / g
Is not significantly different from the polyoxyalkylene polyol obtained with the conventional KOH catalyst system.

The total degree of unsaturation in the polyoxyalkylene polyol serves mainly as an index of the amount of monool having an unsaturated group at a molecular terminal generated by a side reaction of propylene oxide. C = C is 0.0001 to 0.07 meq. /
g. Preferably 0.0001 to 0.05 meq.
/ G. More preferably 0.001 to 0.05 m
eq. / G range. It is preferable that there is no monool (C = C) at all. However, in order to eliminate the monool (C = C) at all in the above-mentioned range of OHV, conditions such as reaction temperature and pressure must be relaxed. The time gets longer. C = C is 0.07 meq. / G is not preferred because the mechanical properties and curing properties of the polyurethane urea resin deteriorate.

The head-to-tail (Head-to-Ta) of such a polyoxyalkylene polyol having a low total unsaturation by propylene oxide addition polymerization.
il) If the bond selectivity is less than 95%, problems such as an increase in the viscosity of the polyoxyalkylene polyol due to a decrease in the head-to-tail bond selectivity, or deterioration in the moldability of the polyurethane urea resin may occur. Occurs.

The following conditions are preferably exemplified as conditions for producing a polyoxyalkylene polyol having a controlled structure as described above. That is, the phosphazene compound represented by the chemical formula (2) is 5 × 10 ⁻⁵ to 1 mol, preferably 1 × 10 ^{−4 to} 5 × 10 with respect to 1 mol of the active hydrogen compound.
^-1 mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol. When increasing the molecular weight of the polyoxyalkylene polyol, it is preferable to increase the concentration of the phosphazene compound relative to the active hydrogen compound within the above range. When the amount of the phosphazene compound represented by the chemical formula (2) is lower than 5 × 10 ⁻⁵ mol per mol of the active hydrogen compound,
The polymerization rate of the alkylene oxide decreases, and the production time of the polyoxyalkylene polyol increases. When the amount of the phosphazene compound represented by the chemical formula (2) is more than 1 mol per 1 mol of the active hydrogen compound, the cost of the phosphazene compound in the production cost of the polyoxyalkylene polyol increases.

The reaction temperature of the alkylene oxide is in the range of 15 to 130 ° C., preferably 40 to 120 ° C., more preferably 50 to 110 ° C. When the reaction temperature of the alkylene oxide is lower than the above range, the concentration of the phosphazene compound with respect to the active hydrogen compound is preferably increased within the range described above. A method of supplying alkylene oxide to an active hydrogen compound using a phosphazene compound charged in a pressure-resistant reactor as a catalyst is a method of supplying a part of a required amount of alkylene oxide at a time,
Alternatively, a method of continuously or intermittently supplying an alkylene oxide is used. In a method in which a part of the required amount of alkylene oxide is supplied collectively, a method in which the reaction temperature at the beginning of the alkylene oxide polymerization reaction is set to a lower temperature within the above range and the reaction temperature is gradually increased after charging the alkylene oxide is preferable. . Reaction temperature 15
When the temperature is lower than ℃, the polymerization rate of the alkylene oxide decreases, and the production time of the polyoxyalkylene polyol increases. When propylene oxide is used as the alkylene oxide when the reaction temperature exceeds 130 ° C.,
When the total degree of unsaturation (C = C) is 0.07 meq. / G.

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

In the alkylene oxide addition polymerization reaction, a solvent can be used if necessary. Examples of the solvent to be used 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. And so on. When a solvent is used, a method of collecting and reusing the solvent after the production is desirable in order not to increase the production cost of the polyoxyalkylene polyol.

In some cases, the polyoxyalkylene polyol obtained by the method of the present invention can be used as a raw material for the polyoxyalkylene polyamine by simply removing the solvent when the solvent is used in the polymerization reaction. Usually, inorganic salts such as hydrochloric acid, phosphoric acid, phosphorous acid, and sulfuric acid, formic acid, acetic acid,
A method of treating with at least one neutralizing agent selected from organic acids such as oxalic acid, succinic acid, phthalic acid, and maleic acid, and carbon dioxide, as well as Tomix AD-600, Tomix AD-700 (manufactured by Tomita Pharmaceutical), and Kyo. Word 40
0, KYOWARD 500, KYOWARD 600, KYOWARD 700 (manufactured by Kyowa Chemical Industry), MAGNESOL
A phosphazene compound is removed by a method of treating with an adsorbent commercially available under various trade names such as (manufactured by DALLAS) or a method of using the above-mentioned neutralization treatment and the adsorbent in combination. Further, the polyoxyalkylene polyol can be used after purification of the polyoxyalkylene polyol using water, a solvent inert to the polyoxyalkylene polyol, or a mixture thereof.

For the purpose of stabilizing the quality of the polyoxyalkylene polyol, an antioxidant such as t-butylhydroxytoluene (BHT) may be added after the above-mentioned purification treatment. The addition amount of the antioxidant is usually 100 to 5000 pp with respect to the polyoxyalkylene polyol.
m.

Next, a method for producing a polyoxyalkylene polyamine will be described. The polyoxyalkylene polyol used preferably satisfies the following requirements a to c. a. The hydroxyl value (OHV) is in the range of 2 to 200 mgKOH / g. b. Total degree of unsaturation (C = C) is 0.0001 to 0.07 m
eq. / G. c. Head-to-tail (Head) of polyoxyalkylene polyol by propylene oxide addition polymerization
-To-Tail) bond selectivity is 95 mol% or more. Such a polyoxyalkylene polyol is obtained by the method described above.

A part or all of the terminal hydroxyl groups of the above polyoxyalkylene polyol are aminated to produce a polyoxyalkylene polyamine. As a method for amination, (e) a polyoxyalkylene polyol and ammonia, a primary amine,
A method of reacting at least one or more nitrogen-containing active hydrogen compounds selected from secondary amines and diamines, (f) adding a polyoxyalkylene polyol and a functional group capable of reacting with a hydroxyl group in the molecule, and a cyano group or a nitro group; A hydrogenation reaction (hereinafter, abbreviated as hydrogenation reaction) after the compound is reacted with a compound having the compound.

First, the method (e) will be described. As the hydrogenation-dehydrogenation catalyst, a conventionally known catalyst can be used. For example, a supported catalyst in which Ni, Co, or the like is supported on a carrier such as diatomaceous earth, silica, or alumina, a Ni, Co-based Raney-type catalyst , Ni / Zn catalyst, Co / Zn catalyst,
Ni / Co / Zn catalysts and Cu / Cr catalysts are typical examples. Among them, a supported catalyst is one of particularly suitable catalysts.

The primary amine is usually an amine compound having 1 to 20 carbon atoms, preferably an amine compound having 1 to 10 carbon atoms. Specifically, methylamine, ethylamine, n-propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, t-butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, tetradecyl Alkylamines such as amine, tetradecylamine, hexadecylamine, octadecylamine and oleylamine; alkylamines having substituents such as β-aminopropylmethyl ether and β-aminopropylethyl ether; benzylamine;
Examples thereof include aralkylamines such as methylbenzylamine and alicyclic amines such as cyclopentylamine and cyclohexylamine. Further, a mixture of two or more selected from the above primary amines can also be used.

The secondary amine is usually an amine compound having 2 to 40 carbon atoms, specifically, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, methylethylamine, methylethylamine. Examples thereof include alkylamines such as propylamine, methylisopropylamine, ethylpropylamine, ethylisopropylamine and N-methyldodecylamine, and aralkylamines such as dibenzylamine and N-methylbenzylamine. Further, a mixture of two or more selected from the above secondary amines can also be used.

Examples of the diamine include ethylenediamine, diaminopropane, diaminobutane, diaminotoluene, m-phenylenediamine, diaminodiphenylmethane, diaminophenylsulfone, diethyldiaminotoluene, and diaminoindane derivatives. Further, a mixture of two or more selected from the above diamines can also be used.

The amount of these nitrogen-containing active hydrogen compounds used is
The amount is determined according to the use of the polyoxyalkylene polyamine, and is usually 0.2 to 50 equivalents, preferably 1 to 10 equivalents, per equivalent of the hydroxyl group. The above-mentioned catalyst is based on 100 parts by weight of the polyoxyalkylene polyol.
Usually, 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, most preferably 0.5 to 5 parts by weight are used.

In the method (e), in order to obtain a polyoxyalkylene polyamine having a high secondary amination rate, the reaction is carried out by coexisting a monohydric alcohol with ammonia, which is a nitrogen-containing active hydrogen compound, and a primary amine. You can do it too. As the monohydric alcohol, one having 1 to 10 carbon atoms is used.
Grade or secondary alcohols are included. Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, se
c-butanol, amyl alcohol, hexanol, heptanol, octanol, nonyl alcohol, alkyl alcohols such as decyl alcohol, β-hydropropylmethyl alcohol, alkyl alcohols having a substituent such as β-hydropropylethyl alcohol, benzyl alcohol, p-methylbenzyl alcohol, o-
Examples thereof include aralkyl alcohols such as methylbenzyl alcohol, and cycloalkyl alcohols such as cyclopentyl alcohol and cyclohexyl alcohol.

An amination reaction is carried out using the above-mentioned polyoxyalkylene polyol, catalyst, nitrogen-containing active hydrogen compound and, depending on the purpose, a monohydric alcohol. The reaction conditions are not particularly limited, but generally, the reaction temperature is 60 to 280 ° C, preferably 130 to 250 ° C, and the reaction pressure is 5 to 150 kgf / cm ² (490 to 14700).
kPa), preferably 30-100 kgf / cm ² (2
940-9800 kPa), the reaction time is 1-20 hours,
It is preferably carried out for 5 to 10 hours. Hydrogen may be allowed to coexist in the reaction system. When the reaction temperature is lower than 60 ° C., the reaction time becomes longer. If the reaction temperature is higher than 280 ° C., the polyoxyalkylene polyol is undesirably thermally degraded.

After the completion of the reaction, if an unreacted nitrogen-containing active hydrogen compound and a monohydric alcohol are allowed to coexist, the alcohol can be recovered by reduced pressure treatment, the catalyst can be separated by filtration, washed with water, dried, and the like, as appropriate. Polyoxyalkylene polyamine can be obtained.

Next, the method (f) will be described. The compound having a functional group capable of reacting with a hydroxyl group and a cyano group or a nitro group is a cyano compound or a nitro compound having an ethylenically unsaturated group, an ester group, a carboxyl group, a halogen substituent, or the like. Specifically, α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile, nitrobenzoic acid esters such as methyl p-nitrobenzoate and ethyl p-nitrobenzoate, o-nitrobenzoic acid, p-nitrobenzoic acid Such as nitrobenzoic acid, halogen-substituted benzonitrile such as o-chlorobenzonitrile and p-chlorobenzonitrile, cyanobenzyl halide such as o-cyanobenzyl chloride and p-cyanobenzyl chloride, p-nitrochlorobenzene, p-nitrobromo Examples include nitrohalobenzenes such as benzene, nitrobenzyl halides such as p-nitrobenzyl chloride and p-nitrobenzyl bromide.

When an α, β-unsaturated nitrile is used, the polyoxyalkylene polyol is usually cyanoalkylated in the presence of an alkali metal hydroxide and water, and a cyano group is introduced into the terminal of the polyoxyalkylene polyol. I do. When the concentration of the residual phosphazene compound in the polyoxyalkylene polyol is high, it is not necessary to use an alkali metal hydroxide, but generally, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc. The reaction time is reduced by using the alkali metal hydroxide. In order to suppress the polymerization reaction of the α, β-unsaturated nitrile and react with the terminal hydroxyl group of the polyoxyalkylene polyol, it is important to carry out the reaction in the presence of water.
In order to promote the intended cyanoalkylation reaction, the amounts of the polyoxyalkylene polyol, α, β-unsaturated nitrile, the alkali metal hydroxide used, and the amount of water are appropriately selected according to the purpose. Usually, 2 to 15 parts by weight of water is used for 100 parts by weight of the polyoxyalkylene polyol. In the case where an alkali metal hydroxide is used, 0.1 parts by weight per 100 parts by weight of the polyoxyalkylene polyol is used.
Use from 0.01 to 7.0 parts by weight. The α, β-unsaturated nitrile is used in an amount of 0.2 to 5 equivalents to 1 equivalent of the hydroxyl group of the polyoxyalkylene polyol. The α, β-unsaturated nitrile may be appropriately added according to the progress of the reaction, or may be charged at once. The reaction conditions are not particularly limited, but the reaction is usually performed at a reaction temperature of 10 to 130 ° C and a reaction time of 5 to 20 hours. After completion of the reaction, a cyanoalkylated polyoxyalkylene polyol is obtained by, for example, neutralizing the alkali metal hydroxide catalyst with an acid and dehydrating the catalyst.

When nitrobenzoic acid ester or nitrobenzoic acid is used, the polyoxyalkylene polyol is usually subjected to a transesterification reaction or a direct esterification reaction in the presence of a basic catalyst or an acid catalyst. A nitro group is introduced at the terminal of the alkylene polyol. When the concentration of the residual phosphazene compound in the polyoxyalkylene polyol is high, a basic catalyst or an acid catalyst may not be used, but generally, a basic catalyst or an acid catalyst exemplified below is used.

As the basic catalyst, sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide, rubidium hydroxide and cesium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate and carbonate Alkali metal bicarbonates such as cesium hydrogen; alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, barium hydroxide and strontium hydroxide; tertiary amine compounds such as trimethylamine, triethylamine and dimethyl palmitylamine Is mentioned.

Examples of the acid catalyst include protic acids such as sulfuric acid, hydrochloric acid and p-toluenesulfonic acid, and Lewis acids such as boron trifluoride etherate. The nitrobenzoic acid ester and nitrobenzoic acid are usually used in an amount of 0.2 to 20 equivalents based on 1 equivalent of the hydroxyl group of the polyoxyalkylene polyol. When a basic catalyst or an acid catalyst is used, the amount used is 0.0 to 1 equivalent of nitrobenzoate.
02 to 0.5 equivalent, 0.0 equivalent to 1 equivalent of nitrobenzoic acid
001-0.5 equivalents are used.

The reaction conditions are not particularly limited, but usually the reaction temperature is 50 to 250 ° C. and the reaction time is 1 to
The test is performed for 20 hours. The reaction pressure may be under reduced pressure or under pressure. Further, a solvent may be present in the reaction system. As the solvent, those which do not inhibit the above reaction and which form an azeotrope with water are particularly preferred. Specifically, benzene, toluene, xylene and the like can be mentioned. After completion of the reaction, the desired product nitrobenzoated polyoxyalkylene polyol is obtained by appropriately combining methods such as neutralization of the catalyst, recovery of unreacted nitrobenzoic acid ester or nitrobenzoic acid, washing with water, and drying.

When a halogen-substituted benzonitrile, cyanobenzyl halide, nitrohalobenzene or nitrohalobenzyl (hereinafter abbreviated as aromatic cyano / nitro compound) is used, a basic catalyst as a hydrogen halide scavenger is used. By subjecting the polyoxyalkylene polyol to a dehydrohalogenation reaction in the presence, a cyano group or a nitro group is introduced into the molecular terminal of the polyoxyalkylene polyol. When the concentration of the residual phosphazene compound in the polyoxyalkylene polyol is high, a basic catalyst may not be used, but generally, a basic catalyst exemplified below is used. Examples of the basic catalyst include alkali metals such as sodium metal, potassium metal, metal rubidium and cesium, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, sodium carbonate and potassium carbonate. Alkali metal carbonates such as sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, calcium hydroxide, magnesium hydroxide, barium hydroxide, hydroxide Examples include alkaline earth metal hydroxides such as strontium, and tertiary amine compounds such as trimethylamine, triethylamine, and dimethyl palmitylamine. The amount of the aromatic cyano / nitro compound to be used is determined according to the use, but usually, 0.2 to 20 equivalents is used per 1 equivalent of a hydroxyl group. When a basic catalyst is used, usually 1 to 10 equivalents are used per equivalent of the aromatic cyano / nitro compound.

The reaction conditions are not particularly limited, but usually the reaction temperature is 50 to 250 ° C., and the reaction time is 1 to
The test is performed for 20 hours. The reaction pressure may be under reduced pressure or under pressure. Further, a solvent may be present in the reaction system. As the solvent, a polar solvent that does not inhibit the above reaction and is particularly preferable. Specific examples include dimethylformamide, dimethylsulfoxide, dimethylimidazolidinone, and sulfolane. After completion of the reaction, at least one cyano group or nitro group is added to the molecular end of the target substance by appropriately combining methods such as neutralization of a basic catalyst, recovery of an unreacted aromatic cyano / nitro compound, washing with water, and drying. A compound having

According to the method described above, a compound having at least one cyano group or nitro group at the molecular terminal is subjected to a hydrogenation reaction in the presence of a catalyst to obtain a polyoxyalkylene polyamine. As the catalyst, a conventionally known compound can be used. For example, a supported catalyst in which Ni, Co, or the like is supported on a carrier such as diatomaceous earth, silica, or alumina;
i, a Co-based Raney-type catalyst, and a supported catalyst in which a noble metal such as Pd, Pt, or Ru is supported on a carrier such as carbon, alumina, or silica. Among them, a supported catalyst is one of particularly suitable catalysts. The catalyst is a compound 10 having at least one cyano group or nitro group at the molecular terminal as described above.
Usually, 0.1 to 20 parts by weight is used with respect to 0 parts by weight.

The reaction conditions are not particularly limited, but are generally 30 to 200 ° C., preferably 50 to 200 ° C.
１５０150 ° C., reaction pressure 1１〜90 kgf / cm ² (98
８８8820 kPa), preferably 10 to 50 kgf / c
m ² (980-4900 kPa), reaction time is 1-20
Time, preferably 5 to 10 hours. A solvent may be present in the reaction system. Examples of the solvent include those that do not inhibit the above reaction, for example, lower alcohols such as methanol and ethanol, and aromatic hydrocarbons such as toluene and xylene. Further, ammonia may be present in the reaction system. After completion of the reaction, the target polyoxyalkylene polyamine can be obtained by appropriately combining the methods such as filtration with a catalyst, washing with water, and drying.

The method for producing a polyoxyalkylene polyamine by aminating a part or all of the terminal hydroxyl groups of the polyoxyalkylene polyol is described in the above (e) and (f).
Other methods are also possible. For example, a method by a transesterification reaction between a polyoxyalkylene polyol and an aminobenzoic acid ester, a method of reacting a polyoxyalkylene polyol with p-nitrobenzoic acid chloride in the presence of a hydrogen halide scavenger, and then reducing the nitro group ,
Examples include a method of reacting a polyoxyalkylene polyol with isatoic anhydride in the presence of a strong base, a method of prepolymerizing with a polyisocyanate compound, and then hydrolyzing the remaining isocyanate groups to amino groups.

Next, a method for producing a polyurethane urea resin will be described. The polyurethane urea resin is produced by rapidly mixing a polyol containing a polyoxyalkylene polyamine obtained by the method of the present invention and a chain extender with a polyisocyanate compound. The polyol used as a raw material of the polyurethane urea resin contains the polyoxyalkylene polyamine described above in an amount of 20 to 100 parts by weight based on 100 parts by weight of the polyol. Preferably 30 to
100 parts by weight, more preferably 40 to 100 parts by weight. When the amount of the polyoxyalkylene polyamine used is less than 20 parts by weight based on 100 parts by weight of the polyol, the effect of modifying the aminated polyoxyalkylene polyamine in the polyurethane urea resin is not exhibited.

Examples of the polyol other than the polyoxyalkylene polyamine used in the present invention include a polyoxyalkylene polyol used as a starting material for the polyoxyalkylene polyamine obtained by the method of the present invention, and a polyoxyalkylene prepared by a conventionally known method. Examples include polyols, polyoxyalkylene polyamines produced by a conventionally known method, polymer-dispersed polyols, polytetramethylene glycol, polyester polyols, polybutadiene-based polyols, and polycarbonate-based polyols. Preferably, it is a polyoxyalkylene polyol used as a starting material for the polyoxyalkylene polyamine obtained by the method of the present invention.

Examples of the polyisocyanate compound for producing the polyurethane urea resin include known polyisocyanate compounds used for producing aromatic, aliphatic, and alicyclic polyurethanes having two or more isocyanate groups in one molecule. Things can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 80/20 weight ratio of these organic polyisocyanates (TDI-80 /
20), isomer mixture in 65/35 weight ratio (TDI-65 / 35), crude tolylene diisocyanate containing polyfunctional tar (polyfunctional tar is a by-product of isocyanate production, Group in the molecule
It is a mixture of tar-like substances containing more than one. same as below. ), 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate,
2,2′-diphenylmethane diisocyanate, any isomer mixture of diphenylmethane diisocyanate, 3
Crude diphenylmethane diisocyanate (polymeric MDI) containing core or higher polyfunctional tar, toluylene diisocyanate, xylylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, norbornene diisocyanate and carbodiimide-modified buret-modified products of these organic polyisocyanates, or modified polyols, monools alone or in combination with these. A prepolymer and the like.

The above-mentioned polyisocyanate compounds can be used by mixing at an arbitrary ratio. Particularly preferred are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 8 of these organic polyisocyanates.
0/20 weight ratio (TDI-80 / 20), 65/35 weight ratio (TDI-65 / 35) isomer mixture, 4,4 ′
-Diphenylmethane diisocyanate and its modified products.

The chain extender is a compound having two or more active hydrogen groups in one molecule capable of reacting with an isocyanate group. At least one of a polyol compound having a molecular weight of 1,000 or less and a polyamine compound is used. Examples of the polyol compound include dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol; cyclohexanediol; A spiro ring such as spirohexanediol and a methylene chain may be used, and those linking them may include various bonds such as an ether bond and an ester bond, and derivatives containing various substituents may be used.

The polyamine compounds include diphenylmethanediamine, m-phenylenediamine, 3,3 ′
-Dichloro-4,4'-diaminodiphenylmethane,
4,4'-diamino-2,2 ', 3,3'-tetrachlorodiphenylmethane, 4,4'-diamino-3,3'-
Aliphatic diamines such as diethyl-5,5'-dimethyldiphenylmethane and diethyltoluenediamine, aliphatic dicyclodiamines such as isophoronediamine and norbornenediamine, alkyldihydrazides such as linear aliphatic diamines, carbodihydrazide and adipic dihydrazide. And their derivatives or conventionally known polyamine compounds described in JP-A-2-41310 can be used.

The chain extender is generally used in an amount of 1 part by weight based on 100 parts by weight of the polyol containing the polyoxyalkylene polyamine.
Use ５０50 parts by weight. The isocyanate index (hereinafter, abbreviated as NCO index), which is the ratio of the isocyanate group concentration to the active hydrogen group concentration in the polyol containing the polyoxyalkylene polyamine and the chain extender, is 0.7 to 20.

The liquid containing the polyol and the chain extender described above is rapidly mixed with the polyisocyanate compound, and the mixture is poured into a mold heated to a predetermined temperature, for example, 40 to 130 ° C., to produce a molded product. At this time, a curing catalyst, a filler, a plasticizer, a dye / pigment, a reinforcing agent, a flame retardant, a stabilizer, an internal mold release agent, a foaming agent, a foam stabilizer, a pigment and the like can be used according to the purpose. .

As the curing catalyst, a conventionally known catalyst for producing a polyurethane such as an amine compound or an organometallic compound can be used. For example, amine catalysts include triethylamine, tripropylamine, tributylamine,
N, N, N ′, N′-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine,
Dibutylamine-2- such as dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, triethylenediamine and salts of triethylenediamine;
Examples of amine salts such as ethylhexoate and organometallic catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and tin 2-ethylhexylate. , Lead octoate, lead naphthenate, nickel naphthenate and cobalt naphthenate. These catalysts can be arbitrarily mixed and used. The amount used is the polyol 10 containing the polyoxyalkylene polyamine of the present invention.
It is 0.001 to 5.0 parts by weight, preferably 0.01 to 1.0 part by weight, based on 0 parts by weight.

Examples of fillers include fumed silica, silica, silicic anhydride, carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, talc, titanium oxide, bentonite, ferric oxide, hydrogenated castor oil,
Zinc stearate and the like, and the amount of the polyoxyalkylene polyamine-containing polyol 1 of the present invention.
The amount is 0.01 to 40 parts by weight, preferably 0.1 to 10 parts by weight based on 00 parts by weight.

As the plasticizer, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, butyl benzyl phthalate, butyl phthalyl butyl glycolate,
Dioctyl sebacate, tricresyl phosphate, tributyl phosphate, chlorinated paraffin, petroleum ether, and the like, and the amount of addition is 0.1 to 40 parts by weight based on 100 parts by weight of the polyol containing the polyoxyalkylene polyamine of the present invention. , Preferably 5 to 15 parts by weight.

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

Examples of the flame retardant include tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, tris (2,2-chloroethyl) phosphate, hexabromocyclododecane, manufactured by Daihachi Chemical Co., Ltd. CR-505 and CR-507, Phosaga manufactured by Monsanto Chemical Co., Ltd.
rd 2XC-20 and C-22-R, Fyrol-6 manufactured by Stoffer Chemical Co., Ltd., and the like, and the amount thereof is 0.1 to 30 parts by weight based on 100 parts by weight of the polyol containing the polyoxyalkylene polyamine of the present invention. , Preferably 0.2 to 20 parts by weight.

Examples of the stabilizer include an antioxidant, an ultraviolet absorber and a heat stabilizer. The antioxidant is not particularly limited. For example, butylhydroxyanisole, t-
Butylhydroxytoluene, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5,
5) Undecane, distearyl thiodipropionate and the like. Examples of the ultraviolet absorber include pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like. Examples of the heat stabilizer include tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, trilauryl phosphite and the like. The amount of each of these additives is 2 to the polyol containing the polyoxyalkylene polyamine of the present invention.
00-5000 ppm is preferable.

As the internal release agent, zinc stearate,
Polyolefin-based wax or Tokushusho 60-50
Compounds exemplified in Japanese Patent No. 0418 are preferred.
The amount of the internal release agent used is 0.1 to 100 parts by weight of the polyol containing the polyoxyalkylene polyamine of the present invention.
-10 parts by weight is preferred.

Examples of the foaming agent include water, low-boiling hydrocarbon compounds, and hydrochlorofluorocarbon (hereinafter referred to as HCF).
Abbreviated as C. ) Or hydrofluorocarbons (hereinafter abbreviated as HFC) or fluorinated ethers (hereinafter abbreviated as FC). Examples of the low-boiling hydrocarbon compound include cyclopentane, n-pentane, and isopentane. As HCFCs, HCFC-141b is HF
For Class C, HFC-134a, HFC-356 or H
FC-245fa, etc., as the FC compound include C ₅ F _12. When water alone is used as the foaming agent, it is used in an amount of 0.1 to 9 parts by weight based on 100 parts by weight of the polyol containing the polyoxyalkylene polyamine of the present invention. When at least one foaming agent selected from water, a low-boiling hydrocarbon compound, HCFCs, HFCs or FCs is used, 1 to 100 parts by weight of the polyol containing the polyoxyalkylene polyamine of the present invention is used. Use 40 parts by weight. Most preferred among these are blowing agents containing water.

As the foam stabilizer, a conventionally known organosilicon-based surfactant can be used.
520, L-532, L-540, L-544, L-5
50, L-3600, L-3601, L-5305, L
-5307, L-5309, etc., SRX-253, SRX-274C, SF-296 manufactured by Dow Corning Toray Co., Ltd.
1, SF-2962, Shin-Etsu Silicone F-11
4, F-121, F-122, F-220, F-23
0, F-258, F-260B, F-317, F-34
1, F-601 and F-606, and TFA-420 and TFA-4202 manufactured by Toshiba Silicone Co., Ltd. These foam stabilizers can be arbitrarily mixed and used, and the used amount is 0.05 to 10 parts by weight based on 100 parts by weight of the polyol containing the polyoxyalkylene polyamine of the present invention.

[0106]

EXAMPLES Examples of the present invention will be shown below to clarify aspects of the present invention, but the present invention is not limited to these examples. The hydroxyl value (OHV) of the polyoxyalkylene polyols of Examples and Comparative Examples is JIS K155.
It was determined by the measurement method described in 7. Hydroxyl value (abbreviated as OHV; unit: mgKOH / g); the hydroxyl terminal of polyoxyalkylene polyol is esterified with a pyridine solution of phthalic anhydride, and excess phthalic anhydride is titrated with a sodium hydroxide solution (JIS K 1).
557).

The amine value of the polyoxyalkylene polyamine is determined by the “practical method for determining organic compounds by functional group” (Fred
erick T. Weiss, translated by Akira Ejima, published by Hirokawa Shoten). That is, the total amine value (e), the primary amine value (c), the secondary and tertiary amine values (f) are fractionated and quantified by the azomethine titration method, and the tertiary amine value (f) is further determined by the acetylation-perchloric acid method. g)
This is a method for calculating a secondary amine value (d) (Formula 1). e ^* = c ^* + d + g ^* = c ^* + f ^* (Equation 1) (In Equation 1, * represents actual measurement data.)

The active hydrogen value (a) of the polyoxyalkylene polyamine was measured according to the method described in JIS K0070. The active hydrogen value (a) of the polyoxyalkylene polyamine represents the sum of the hydroxyl value (b), the primary amine value (c), and the secondary amine value (d) obtained from (Formula 1). By such an analysis method, hydroxyl group, primary amino group, secondary amino group, and tertiary amino group at the molecular terminal of the polyoxyalkylene polyamine are all determined. Active hydrogen value (a: unit: mgKOH / g); hydroxyl terminal, primary amino terminal and secondary amino terminal of polyoxyalkylene polyamine were acetylated with a pyridine solution of acetic anhydride to hydrolyze excess acetic anhydride. Thereafter, acetic acid is titrated with a potassium hydroxide solution (JIS K 0070).
Method). Amine value (unit: mgKOH / g): A polyoxyalkylene polyamine is treated with salicylaldehyde in a methanol solvent to make only the primary amine a weak base, azomethine, and subjected to potentiometric titration with a solution of hydrochloric acid in isopropanol.
The secondary and tertiary amine values (f) up to the first inflection point are the total amine values (e) up to the next inflection point, and the difference is the primary amine value (c) (azomethine titration method). ). The tertiary amine and the secondary amine are acetylated by treating with acetic anhydride, and the remaining tertiary amine is titrated with a perchloric acetic acid solution (acetylation-perchloric acid method).

Viscosity (abbreviated as η: unit mPa · s / 2)
5 ° C); measured value at 25 ° C using a rotational viscometer (JIS
K 1557).

[0110] Head-to-tail
Tail, HT. : Unit mol%) bond selection
Rate: 400MHz manufactured by JEOL¹³C nuclear magnetic resonance (NMR)
Using deuterated chloroform as a solvent
Oxyalkylene polyamine ¹³C-NMR spectrum
And head-to-tail (Head-to-Ta)
il) The methyl group of the oxypropylene unit of the bond
Gunnar (16.9-17.4 ppm) and head-toe
Oxypro with Head-to-Head Bond
Signal of methyl group of pyrene unit (17.7 to 1
8.5 ppm).

The assignment of each signal is based on Macromo
recules VOL. 19, 1373-1343
(1986); C. Schilling, A .; E. FIG.
The values described in Tonelli's report were referred to.

In the synthesis of polyoxyalkylene polyol, a phosphazene base P (trade name, manufactured by Fulka) was used.
<T / 4>-n- adjusted to 1.00 M of t-Oct
A hexane solution was used. The present compound is a phosphazene compound in which Q is a tert-octyl group, D is a dimethylamino group, and (l, m, n) are (1, 1, 1) in the order of the partial structural formula (1) and the chemical formula (2). It is. Hereinafter, the compound is abbreviated as P4-t-Oct.

The synthesis result of the polyoxyalkylene polyamine will be described below in detail. An apparatus for synthesizing a polyoxyalkylene polyol which is a precursor of a polyoxyalkylene polyamine (hereinafter, abbreviated as autoclave A) is
1. Internal volume equipped with a stirrer, thermometer, pressure gauge, nitrogen inlet and alkylene oxide inlet which is a monomer.
A 5 L pressure-resistant autoclave (Nitto Koatsu) was used. A polyoxyalkylene polyamine synthesizing apparatus (hereinafter abbreviated as autoclave B) is a pressure-resistant autoclave (1.0 L in internal volume) equipped with a stirrer, a thermometer, a pressure gauge, a nitrogen inlet, a hydrogen and liquid ammonia inlet. Nitto Koatsu) was used.

Example 1 Polyoxyalkylene polyamine A 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
of a glycerin per mole of 0.0
12 mol of P4-t-Oct (in the form of a 1.00 M n-hexane solution, the same applies hereinafter) was added, and nitrogen was introduced through a capillary tube at 105 ° C. and 10 mmHgabs. (1
The pressure-reduced toluene operation was performed under the condition of 330 Pa) for 3 hours. Thereafter, the contents of the flask were charged into an autoclave A, and the atmosphere in the flask was replaced with nitrogen. (1
The addition polymerization of propylene oxide was carried out under a condition of a reduced pressure of 330 Pa) at a reaction temperature of 80 ° C. and a maximum pressure during the reaction of 4 kgf / cm ² (392 kPa) until the OHV became 33.4 mgKOH / g. When the internal pressure of the autoclave A stops changing, 105 ° C and 10 mmHga
bs. (1330 Pa) under reduced pressure for 40 minutes to obtain a crude polyoxyalkylene polyol. 5 parts by weight of a Ni diatomaceous earth catalyst (Ni content: 50%) is charged to 100 parts by weight of a crude polyoxyalkylene polyol containing a phosphazene compound in an autoclave B, and nitrogen is added under a condition of 10 kgf / cm ² (980 kPa). The substitution was performed 5 times. After charging liquid ammonia so as to be 10 equivalents to 1 equivalent of the hydroxyl group of the crude polyoxyalkylene polyol, hydrogen is supplied at a pressure of 50 kgf / c.
m ² (4900 kPa). The temperature was raised to 210 ° C. with stirring, and the reaction was carried out for 8 hours. At this time, the maximum pressure was 63 kgf / cm ² (6174
kPa). After completion of the reaction, 105 ° C, 10 mmH
gabs. (1330 Pa) Drying under reduced pressure was performed for 50 minutes under the following conditions, and excess ammonia in the polyoxyalkylene polyamine was distilled off. Thereafter, adsorbent AD-600 was added to 100 parts by weight of polyoxyalkylene polyamine.
NS [manufactured by Yoshitomi Pharmaceutical Co., Ltd.]
The treatment was performed at a temperature of 2 ° C. for 2 hours. Next, the catalyst and the adsorbent were removed by vacuum filtration using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. The resulting polyoxyalkylene polyamine has an active hydrogen value of 33.5.
mg KOH / g, total amine value 30.8 mg KOH / g,
A primary amine value of 29.5 mgKOH / g, a secondary amine value of 1.3 mgKOH / g, and a tertiary amine value were not detected. The viscosity (η) was 710 mPa · s / 25 ° C., and the head-to-tail (HT) was 96.3 mol%.

Example 2 Polyoxyalkylene polyamine B 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
1 to a 4-neck flask, 0.008 mol of P4-t-Oct was added to 1 mol of dipropylene glycol, and nitrogen was introduced through a capillary tube at 105 ° C and 10 mmH.
gabs. (1330 Pa), the toluene removal operation under reduced pressure was performed for 3 hours. Thereafter, the contents of the flask were charged into an autoclave A, and the atmosphere in the flask was replaced with nitrogen.
gabs. (1330 Pa) to a reaction temperature of 8
0 ° C., the maximum pressure during the reaction is 4 kgf / cm ² (392 k
Under the condition of Pa), addition polymerization of propylene oxide was carried out until the OHV became 32 mgKOH / g. Thereafter, a gauge pressure of 1.2 kgf / cm ² (219 kP
a), the reaction temperature was 80 ° C, and the maximum pressure during the reaction was 4
OHV 28 m under the condition of kgf / cm ² (392 kPa)
Addition polymerization of ethylene oxide was carried out until gKOH / g. Furthermore, when the internal pressure of the autoclave A no longer changed, the temperature was changed to 105 ° C and 5 mmHgabs. (665
After performing a pressure reduction treatment for 20 minutes under the condition of Pa), the reaction temperature was changed from the atmospheric pressure to 80 ° C., and the maximum pressure during the reaction was 4 kgf /
OHV is 18.4 mg under the condition of cm ² (392 kPa).
Addition polymerization of propylene oxide was performed until the KOH / g was reached, whereby a crude polyoxyalkylene polyol was obtained.
5 parts by weight of Ni per 100 parts by weight of the crude polyoxyalkylene polyol containing the phosphazene compound
A diatomaceous earth catalyst (Ni content: 50%) was charged into the autoclave B, and the atmosphere was replaced with nitrogen five times under the conditions of 10 kgf / cm 2 (980 kPa). Liquid ammonia is added to 1 equivalent of hydroxyl group of crude polyoxyalkylene polyol.
After charging to 0 equivalents, the pressure of hydrogen was reduced to 50 kgf.
/ Cm ² (4900 kPa). The temperature was raised to 230 ° C. with stirring, and the reaction was carried out for 8 hours. At this time, the maximum pressure is 60 kgf / cm ² (588
0 kPa). After completion of the reaction, 105 ° C, 10 mm
Hgabs. (1330 Pa) Drying under reduced pressure was performed for 20 minutes under the following conditions, and excess ammonia in the polyoxyalkylene polyamine was distilled off. Thereafter, polyoxyalkylene polyamine was purified by vacuum filtration using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. The resulting polyoxyalkylene polyamine has an active hydrogen value of 18.7 mgKOH / g and a total amine value of 15.7.
mgKOH / g, primary amine value 15.0 mgKOH /
g, secondary amine value 0.70 mgKOH / g, tertiary amine value was not detected. Viscosity (η) 1120 mPa · s
/ 25 ° C., head-to-tail (HT) 96.1 mol%.

Example 3 Polyoxyalkylene polyamine C 500 m equipped with a stirrer, a nitrogen inlet tube and a thermometer
of a glycerin per mole of 0.0
10 mol of P4-t-Oct was added, and while introducing nitrogen through a capillary tube, 105 ° C., 10 mmHgabs.
(1330 Pa), the toluene removal operation under reduced pressure was performed for 3 hours. Then, the contents of the flask were transferred to autoclave A.
, And after purging with nitrogen, 10 mmHgabs.
(1330 Pa) from the reduced pressure to a reaction temperature of 75 ° C. and a maximum pressure during the reaction of 5.0 kgf / cm ² (490 kP
Under the condition (a), multistage addition polymerization of propylene oxide was carried out until the OHV became 28.0 mgKOH / g. When the internal pressure of the autoclave stops changing, 105 ° C,
10 mmHgabs. (1330 Pa) under reduced pressure for 50 minutes to obtain a crude polyoxyalkylene polyol. 5 parts by weight of a Ni diatomaceous earth catalyst (Ni content: 50%) was charged to 100 parts by weight of a crude polyoxyalkylene polyol containing a phosphazene compound in an autoclave B, and 10 kgf / cm ² (980 k
Under the condition of Pa), nitrogen substitution was performed five times. Liquid ammonia was charged so as to be 10 equivalents to 1 equivalent of hydroxyl groups of the crude polyoxyalkylene polyol, and then hydrogen was charged until the pressure became 50 kgf / cm ² (4900 kPa). The temperature was raised to 220 ° C. with stirring, and the reaction was carried out for 8 hours. At this time, the maximum pressure is 65 kgf / cm
² (6370 kPa). After the reaction, 105
° C, 10 mmHgabs. (1330 Pa) Drying under reduced pressure was performed for 20 minutes under the following conditions, and excess ammonia in the polyoxyalkylene polyamine was distilled off. Next, 0.1 parts by weight of the polyoxyalkylene polyamine is added.
Add 3 parts by weight of adsorbent AD-600NS,
Purification treatment was performed for 3 hours. The adsorbent and the catalyst were removed by filtration under reduced pressure using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Corporation. The resulting polyoxyalkylene polyamine has an active hydrogen value of 28.2 mg KOH.
/ G, total amine value 24.5 mgKOH / g, primary amine value 23.9 mgKOH / g, secondary amine value 0.60 mg
KOH / g, tertiary amine value was not detected. The viscosity (η) was 1150 mPa · s / 25 ° C., and the head-to-tail (HT) was 96.2 mol%.

Hereinafter, a comparative example will be described in detail. The catalyst for synthesizing polyoxyalkylene polyol used as a comparative example is a double metal cyanide complex [Zn ₃ [Co (CN) described in US Pat. No. 5,144,093 (column 4, line 52 to column 5, line 4). ) _{6] 2} · 2.48DME ·
4.65H ₂ O · 0.94ZnCl ₂ ; hereinafter abbreviated as DMC. DME is an abbreviation for dimethoxyethane. ]
It was used. As an alkali metal catalyst for performing ethylene oxide addition polymerization to a polyoxypropylene polyol obtained using DMC as a catalyst, a product of Wako Pure Chemical Industries, Ltd.
A methanol solution of weight% of potassium methylate (hereinafter abbreviated as KOMe) was used.

Comparative Example 1 Polyoxyalkylene polyamine D Polypropylene polyol MN1000 obtained by adding propylene oxide to glycerin [Mitsui Toatsu Chemical Co., Ltd.]
OHV 168 mg KOH / g] 0.5 parts by weight of double metal cyanide complex [hereinafter referred to as DMC
Abbreviated. Zn ₃ [Co (CN) _{6] 2} · 2.48DM
E · 4.65H ₂ O · 0.94ZnCl ₂ ],
105 ° C., 10 mmHgabs. (1330 Pa) Dehydration under reduced pressure was performed for 3 hours under the following conditions. Next, the compound was charged into autoclave A, and addition polymerization of propylene oxide was carried out under the conditions of a reaction temperature of 80 ° C. and a maximum pressure during the reaction of 4 kgf / cm ² (392 kPa) until the OHV became 33.6 mgKOH / g, and DMC was contained. To obtain a crude polyoxypropylene polyol. A methanol solution of 2.22 parts by weight of 30% by weight of potassium methylate (KOMe) was added to 100 parts by weight of the polyoxypropylene polyol, and the methanol removal reaction was performed at 90 ° C.
20 mmHgabs. (2660 Pa) for 2 hours. Thereafter, 3 parts by weight of water and 5 parts by weight of AD-600NS (manufactured by Tomita Pharmaceutical Co., Ltd.) were added, and the mixture was stirred at 90 ° C. under a nitrogen atmosphere for 2 hours. Thereafter, 5C filter paper (manufactured by Advantech Toyo Co., Ltd.) 1 μ) to perform vacuum filtration. After filtration, 120 ° C., 10 mmHgabs. (133
0Pa) Dehydration under reduced pressure was performed for 2 hours under the following conditions to remove DMC. 5 parts by weight of a Ni diatomaceous earth catalyst (Ni content: 50%) was charged into an autoclave B based on 100 parts by weight of the obtained polyoxyalkylene polyol, and nitrogen substitution was performed five times under the conditions of 10 kgf / cm ² (980 kPa). Was. After charging the liquid ammonia so that it becomes 10 equivalents with respect to 1 equivalent of the hydroxyl group of the polyoxyalkylene polyol, hydrogen is added under a pressure of 50 kgf / cm ² (4
Until 900 kPa). 22 with stirring
The temperature was raised to 0 ° C., and the reaction was carried out for 8 hours. At this time, the maximum pressure was 69 kgf / cm ² (6762 kPa). After completion of the reaction, 105 ° C., 10 mmHgabs.
(1330 Pa) Drying under reduced pressure was performed for 20 minutes under the following conditions, and excess ammonia in the polyoxyalkylene polyamine was distilled off. Thereafter, the catalyst was removed by vacuum filtration using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. The active hydrogen value of the obtained polyoxyalkylene polyamine was 33.6 mgKOH / g, the total amine value was 29.9 mgKOH / g, and the primary amine value was 29.3.
mg KOH / g, secondary amine value 0.6 mg KOH / g,
No tertiary amine value was detected. Viscosity (η) 2500
mPa · s / 25 ° C, head-to-tail (HT)
It was 87.5 mol%.

Comparative Example 2 Polyoxyalkylene Polyol E 0.03 parts by weight of DMC was added to 100 parts by weight of a polypropylene polyol Diol 400 (manufactured by Mitsui Toatsu Chemicals, Inc.) obtained by addition-polymerizing propylene oxide to propylene glycol. 105 ° C., 10 mmHgabs.
(1330 Pa) or less for 3 hours under reduced pressure. Next, the compound was charged into an autoclave A, and the reaction temperature was set at 8.
0 ° C., maximum pressure during reaction 4 kgf / cm ² (392 kP
Under the conditions of a), addition polymerization of propylene oxide was carried out until the OHV became 32.0 mgKOH / g, to obtain a crude polyoxypropylene polyol containing DMC.
2.9 parts by weight of 30% by weight of potassium methylate (K
OMe) in methanol was added, and the methanol removal reaction was carried out at 90 ° C., 20 mmHgabs. (2660Pa) 2
Time went. Then, 3 parts by weight of water and AD-600NS
[Tomita Pharmaceutical Co., Ltd.] (5 parts by weight) was added, the mixture was stirred at 90 ° C. under a nitrogen atmosphere for 2 hours, and filtered under reduced pressure using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd.
After filtration, 120 ° C., 10 mmHgabs. (1330P
a) Dehydration under reduced pressure was performed for 2 hours under the following conditions to remove DMC. Polyoxypropylene polyol 1 after removal of DMC to perform addition polymerization of ethylene oxide
To 100 parts by weight, 2.5 parts by weight of a 30% by weight KOMe methanol solution was added, and the methanol removal reaction was carried out at 100 ° C.
10 mmHgabs. (1330 Pa) 3 under the following conditions
Time went. After charging the compound in autoclave A and purging with nitrogen, the reaction temperature was 80 ° C., and the maximum pressure during the reaction was 4 kg.
OHV is 28.0 under the condition of f / cm ² (392 kPa).
Ethylene oxide was charged until the reaction reached mg KOH / g and reacted. After the reaction, a reduced pressure treatment was performed to obtain a crude polyoxyalkylene polyol. Further, in order to carry out addition polymerization of propylene oxide using DMC, potassium was removed from the polyoxyalkylene polyol.

1.2 mol of phosphoric acid (75.1 mol) per mol of potassium in the crude polyoxyalkylene polyol.
(Weight% phosphoric acid aqueous solution) and 100 parts by weight of crude polyoxyalkylene polyol were charged with 4 parts by weight of ion-exchanged water, and a neutralization reaction was performed at 90 ° C. for 2 hours. Adsorbent KW-700SN [Kyowa Chemical Industry Co., Ltd.
Manufactured at 105 ° C., 10 mmHgabs. (1330
Dehydration under reduced pressure was performed for 3 hours at Pa). After reducing the pressure from nitrogen to the atmospheric pressure with nitrogen, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to recover the polyoxyalkylene polyol. To 100 parts by weight of the polyoxyalkylene polyol, 0.01 parts by weight of the DMC previously used was added, and 105 ° C., 10 m
mHgabs. (1330 Pa) After performing dehydration under reduced pressure for 3 hours, the reaction temperature was 80 ° C., and the maximum pressure during the reaction was 4 kgf.
OHV 18.7 mg / cm ² (392 kPa)
Addition polymerization of propylene oxide was carried out until KOH / g. D from the polyoxyalkylene polyol
The MC removal operation was performed by the method using KOMe described in detail above. Obtained polyoxyalkylene polyol 10
5 parts by weight of Ni diatomaceous earth catalyst (Ni part
(Content 50%) into autoclave B, 10 kg
Nitrogen substitution was performed five times under the condition of f / cm ² (980 kPa). After charging liquid ammonia so that it becomes 10 equivalents with respect to 1 equivalent of the hydroxyl group of the polyoxyalkylene polyol, hydrogen is applied under a pressure of 50 kgf / cm ² (4900 kP
a). The temperature was raised to 220 ° C. with stirring, and the reaction was carried out for 8 hours. The maximum pressure at this time was 62 kgf / cm ² (6664 kPa).
After completion of the reaction, 105 ° C., 10 mmHgabs. (133
0Pa) Under the following conditions, drying was performed under reduced pressure for 20 minutes to remove excess ammonia in the polyoxyalkylene polyamine. Next, the catalyst was removed by vacuum filtration using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. The resulting polyoxyalkylene polyamine has an active hydrogen value of 18.6 mgKOH / g and a total amine value of 1
6.0 mg KOH / g, primary amine value 15.5 mg KO
H / g, secondary amine value 0.5 mgKOH / g, tertiary amine value was not detected. Viscosity (η) 3200 mPa
s / 25 ° C., head-to-tail (HT) 86.0
Mole%.

Comparative Example 3 Polyoxyalkylene polyamine F Polypropylene polyol MN1000 obtained by adding propylene oxide to glycerin [Mitsui Toatsu Chemical Co., Ltd.]
OHV 168 mg KOH / g], 100 parts by weight of 0.7 parts by weight of DMC, 105 ° C, 10 mm
Hgabs. (1330 Pa) or less for 3 hours under reduced pressure. Next, the compound was charged into an autoclave A, the reaction temperature was 80 ° C., and the maximum pressure during the reaction was 4 kgf / cm.
² OHV 28.0 mg KOH under the condition of (392 kPa)
/ G to obtain a crude polyoxypropylene polyol containing DMC. Next, DMC was removed from the crude polyoxyalkylene polyol. To 100 parts by weight of the polyoxypropylene polyol containing DMC, 3.9 parts by weight of a methanol solution of 30% by weight of potassium methylate (KOMe) was added, and the methanol removal reaction was carried out at 90 ° C. and 20 mmHgabs. (2660 Pa)
For 2 hours. Then, 5 parts by weight of water and AD-600
5 parts by weight of NS (manufactured by Tomita Pharmaceutical Co., Ltd.) was added, the mixture was stirred at 90 ° C. under a nitrogen atmosphere for 2 hours, and filtered under reduced pressure using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. After filtration, 120 ° C., 10 mmHgabs. (133
(0 Pa) under reduced pressure for 2 hours to recover the polyoxyalkylene polyol. 5 parts by weight of Ni diatomaceous earth catalyst (Ni content: 50%) was charged into autoclave B with respect to 100 parts by weight of the obtained polyoxyalkylene polyol, and 10 kgf / cm ² (980 kP
Nitrogen substitution was performed 5 times under the condition of a). After charging the liquid ammonia so that it becomes 10 equivalents with respect to 1 equivalent of the hydroxyl group of the polyoxyalkylene polyol, the pressure of hydrogen is reduced to 50 k.
It was charged until gf / cm ² (4900 kPa).
The temperature was raised to 220 ° C. with stirring, and the reaction was carried out for 8 hours. The maximum pressure at this time is 65 kgf / cm
² (6370 kPa). After the reaction, 105
° C, 10 mmHgabs. (1330 Pa) Under reduced pressure drying for 20 minutes, excess ammonia in the polyoxyalkylene polyamine was distilled off. Next, the catalyst was removed by vacuum filtration using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. The resulting polyoxyalkylene polyamine has an active hydrogen value of 28.1.
mg KOH / g, total amine value 24.4 mg KOH / g,
A primary amine value of 23.7 mgKOH / g, a secondary amine value of 0.7 mgKOH / g, and a tertiary amine value were not detected. Viscosity (η) 2350mPa · s / 25 ° C, head
The toe-tail (HT) content was 86.3 mol%.

The active hydrogen value, amine value, viscosity (η), and head-to-tail of the polyoxyalkylene polyamine (hereinafter abbreviated as “polyamine”) obtained in Examples and Comparative Examples were obtained. ) Bond selectivity (HT) is shown in [Table 1]. In the initiators in Table 1, Gly is an abbreviation for glycerin and DPG is an abbreviation for dipropylene glycol. MN-1000 and Diol-4
00 is an abbreviation for polyoxyalkylene polyol manufactured by Mitsui Toatsu Chemicals, Inc. DMC is an abbreviation for double metal cyanide complex. PO is an abbreviation for propylene oxide, and EO is an abbreviation for ethylene oxide. The analytical values of polyoxyalkylene polyamine in Table 1 were determined by the method described in detail above.

[0123]

[Table 1]

The polyoxyalkylenepolyamine using a polyoxyalkylene polyol in which the phosphazene compound of the present invention is used as a polymerization catalyst for alkylene oxide is obtained from the polyoxyalkylenepolyamine using a double metal cyanide complex (DMC). Low viscosity compared to. In the case of a DMC-based copolymer, when the ethylene oxide copolymerization reaction is performed, DMC must be once deactivated by a reaction with an alkali metal compound (potassium methylate), and then the catalyst must be used to polymerize ethylene oxide. It is complicated. On the other hand, in the phosphazene compound of the present invention, a polyoxyalkylene polyamine having a low viscosity and a high amination ratio of a hydroxyl group can be obtained without requiring a complicated operation in the copolymerization reaction with ethylene oxide.

Next, the polyoxyalkylene polyamine obtained by the method of the present invention (hereinafter abbreviated as polyamine).
Examples and comparative examples will be described for the purpose of clarifying the effects of the present invention, but the present invention is not limited to these examples. Examples 4 and 5, Comparative Examples 4 and 5 RIM molding was performed in a mold using an injection molding machine for polyurethane using the polyamine obtained in the above Examples and Comparative Examples. As the injection molding machine for polyurethane, Toho Kikai Co., Ltd. NR-230 and Cincinnati Milactone LRM-150M were used. Polyamine and chain extender DETDA manufactured by Ethyl Corporation
(3,5-diethyl-2,4-diaminotoluene and 3,5
The weight ratio of 5-diethyl-2,6-diaminotoluene is 8
(0:20 mixture) was preliminarily mixed, and then sufficiently degassed under reduced pressure (hereinafter, this component is abbreviated as an amine mixture).
Mitsui Toatsu Chemical Co., Ltd. as a polyisocyanate compound
Free isocyanate group content (hereinafter abbreviated as NCO%) obtained by reacting Cosmonate PH (4,4'-diphenylmethane diisocyanate) manufactured by Nissan Co., Ltd. with tripropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 22.5% (Hereinafter abbreviated as prepolymer). The prepolymer was also sufficiently degassed under reduced pressure before molding. The temperature of the above-mentioned amine mixture was adjusted to 35 ° C. and that of the prepolymer to 45 ° C.
The molding was performed under the conditions of seconds and an injection time of 2 seconds. The mold was 500 mm × 400 mm × 3.
A 0 mm aluminum product was used. After injection into the mold, the mold was released in 30 seconds, and the surface condition of the molded product and the presence or absence of pinholes were examined. A test piece was cut out from the molded product,
After heating in an oven for 2 hours, the mechanical properties of the resin were measured. The measurement was performed according to JIS K7312. For the purpose of examining the heat resistance of the resin, a test piece cut out of the molded product was heated in an oven at 220 ° C. for 12 hours, and after returning to room temperature, the tensile strength was examined. The value obtained by dividing the tensile strength of the test piece after heating by the tensile strength before heating is defined as the strength retention rate (unit%). Table 2 shows the mixing ratio of the raw materials, the filling property immediately after molding, the surface state, and the measurement results of physical properties. In Table 2, polyamine is an abbreviation of polyoxyalkylene polyamine, DETDA is an abbreviation of diethyldiaminotoluene described above, and prepolymer is an abbreviation of isocyanate group-terminated prepolymer.

[0126]

[Table 2]

According to Examples 4 and 5 and Comparative Examples 4 and 5, a polyurethane urea resin using a polyoxyalkylene polyamine obtained by the method of the present invention uses a polyol catalyzed by a double metal cyanide complex (DMC). As compared with the polyamine which was used, there were few pinholes and the surface condition of the molded article was good. It is also excellent in mechanical properties such as elongation, hardness and tensile strength, and heat resistance.

[0128]

The polyoxyalkylenepolyamine using a polyoxyalkylene polyol in which the phosphazene compound of the present invention is used as a polymerization catalyst for an alkylene oxide is a polyoxyalkylenepolyamine using a double metal cyanide complex (DMC). Viscosity is lower than that of. In the case of a DMC-based copolymer, when the ethylene oxide copolymerization reaction is performed, DMC must be once deactivated by a reaction with an alkali metal compound (potassium methylate), and then the catalyst must be used to polymerize ethylene oxide. It is complicated. On the other hand, in the phosphazene compound of the present invention, a polyoxyalkylene polyamine having a low viscosity and a high amination ratio of a hydroxyl group can be obtained without requiring a complicated operation in the copolymerization reaction with ethylene oxide. Furthermore, the polyurethane urea resin using the polyoxyalkylene polyamine obtained by the method of the present invention has fewer pinholes than the polyamine using a polyol catalyzed by a double metal cyanide complex (DMC), and has fewer pinholes. The condition is good. It is also excellent in mechanical properties such as elongation, hardness and tensile strength, and heat resistance.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor: Sanji Takagi, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Within Mitsui Toatsu Chemicals Co., Ltd. No. 1 Inside Mitsui Toatsu Chemical Co., Ltd.

Claims (7)

[Claims] 1. A method for producing a polyoxyalkylene polyamine by aminating a terminal hydroxyl group of a polyoxyalkylene polyol, comprising a partial structural formula (1): ## STR1 ## (Wherein, Q represents a hydrocarbon group having 1 to 20 carbon atoms.) A polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide to an active hydrogen compound in the presence of a phosphazene compound represented by the formula: A method for producing a polyoxyalkylene polyamine. 2. The phosphazene compound represented by the chemical formula (2): ## STR2 ## (In the formula, l, m and n each represent a positive integer of 0 to 3. D is the same or different and is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, a phenoxy group, a thiophenol residue, Substituted amino group, disubstituted amino group or 5 or 6
It is a membered cyclic amino group. Q is 1-20 carbon atoms
Is a hydrocarbon group. Further, two Ds on the same phosphorus atom or on two different phosphorus atoms may be bonded to each other, and D and Q may be bonded to each other to form a ring structure. The method for producing a polyoxyalkylene polyamine according to claim 1, wherein the compound is represented by the following formula: 3. The phosphazene compound represented by the chemical formula (2) is added in an amount of 5 × 10 ^-5 to 1 per mole of the active hydrogen compound.
It is characterized by using a polyoxyalkylene polyol prepared by addition polymerization of an alkylene oxide under the condition that the reaction temperature is 15 to 130 ° C. and the maximum reaction pressure is 9 kgf / cm ² (882 kPa). The method for producing a polyoxyalkylene polyamine according to claim 1. 4. A method for aminating a terminal hydroxyl group, comprising the steps of: a polyoxyalkylene polyol and at least one nitrogen-containing compound selected from ammonia, primary amine, secondary amine and diamine in the presence of a hydrogenation-dehydrogenation catalyst Reaction temperature 60-280 ° C with active hydrogen compound, maximum reaction pressure 150kg
^{2. The} method for producing a polyoxyalkylene polyamine according to claim 1, wherein the reaction is carried out under a condition of f / cm ² (14.7 MPa). 5. A method for aminating a terminal hydroxyl group, the method comprising reacting a polyoxyalkylene polyol with a compound having a functional group capable of reacting with a hydroxyl group in a molecule and a compound having a cyano group or a nitro group, and then reacting under pressure. The method for producing a polyoxyalkylene polyamine according to claim 1, wherein a hydrogenation reaction is performed. 6. A method for producing a polyurethane urea resin, comprising reacting a polyol containing a polyoxyalkylene polyamine obtained by the production method according to claim 1 with a polyisocyanate compound. 7. The polyoxyalkylene polyamine content in the polyol is 2 to 100 parts by weight of the polyol.
The method for producing a polyurethane urea resin according to claim 6, wherein the amount is 0 to 100 parts by weight.