JPH11302352A - Prepolymer terminated with isocyanate group and polyurethane elastomer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an isocyanate group-terminated prepolymer having excellent storage stability, and a polyurethane elastomer using the prepolymer and having excellent dynamic physical properties, thermal stability, or the like. SOLUTION: This isocyanate group-terminated prepolymer is obtained by reacting a polyisocyanate compound with a polyol component containing a polyoxyalkylenepolyol produced by the addition polymerization of an epoxide compound to an active hydrogen compound in the presence of a phosphazenium compound catalyst. Therein, the residual content of the phosphazenium compound catalyst is <=120 ppm. The polyurethane elastomer contains the prepolymer as a raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an isocyanate group-terminated prepolymer, a polyoxyalkylene polyol for producing the prepolymer, and a polyurethane elastomer using the prepolymer. In detail, using a phosphazenium compound as a catalyst, containing a phosphazenium compound catalyst having a specific concentration or less produced from a polyol component containing a polyoxyalkylene polyol obtained by addition polymerization of an epoxide compound to an active hydrogen compound, and having improved storage stability. Excellent isocyanate group-terminated prepolymer,
The present invention relates to a polyoxyalkylene polyol for producing the prepolymer, and a polyurethane elastomer using the prepolymer.

[0002]

2. Description of the Related Art Generally, polyoxyalkylene polyol is industrially produced by addition polymerization of an active hydrogen compound with an alkylene oxide in the presence of a potassium hydroxide (hereinafter abbreviated as KOH) catalyst which is an alkali metal hydroxide. Being manufactured. While continuously charging the alkylene oxide into a reactor charged with an active hydrogen compound as a KOH catalyst and a polymerization initiator, a reaction is performed at a reaction temperature of 105 to 150 ° C. and a maximum reaction pressure of 490 to 588 kPa to a predetermined molecular weight. The reaction is allowed to reach to obtain a crude polyoxyalkylene polyol. Subsequently, water is added to the crude polyoxyalkylene polyol, KOH is neutralized with an acid such as an inorganic acid, then dehydrated, dried, and subjected to a post-treatment purification step such as filtering off a precipitated potassium salt. .

However, in the conventional production method using a KOH catalyst, when propylene oxide, which is most widely used as an alkylene oxide, is used, a chain transfer reaction of propylene oxide occurs with an increase in the molecular weight of the polyoxyalkylene polyol, Polyoxyalkylene monool having an unsaturated group at a molecular terminal is by-produced. Since the monol has a lower molecular weight than the polyoxyalkylene polyol generated by the main reaction of propylene oxide, the molecular weight distribution of the obtained polyoxyalkylene polyol is widened and the average number of functional groups is reduced. Polyurethane resin using polyoxyalkylene polyol with high monol content is foam,
Regardless of the elastomer, undesired results such as an increase in hysteresis, a decrease in hardness, a decrease in cure property, an increase in permanent compression set, and the like are brought.

[0004] Further, isocyanate group-terminated prepolymers and polyoxyalkylene polyols, which are raw materials for polyurethane resins, are often stored for a long period of time, so that the storage stability of these compounds is regarded as important.

[0005]

Heretofore, various studies have been made on polymerization catalysts capable of improving the productivity of polyoxyalkylene polyols. For example, EP-A-0791
No. 600 discloses a method using a phosphazenium compound as a polymerization catalyst for alkylene oxide. As a result of investigations by the present inventors, when the phosphazenium compound disclosed in the publication is used as a polymerization catalyst for propylene oxide, potassium hydroxide and alkali metal hydroxides such as cesium hydroxide are used under the same reaction conditions. In comparison, it has been found that not only the polymerization activity of propylene oxide is high, but also the amount of by-products of monool decreases.

In view of the above problems, an object of the present invention is to provide an isocyanate group-terminated prepolymer having excellent storage stability, and a polyurethane elastomer using the prepolymer and having excellent mechanical properties, heat stability and the like. . Also,
Another object of the present invention is to provide a polyoxyalkylene polyol having a low monool content and a small residual amount of a catalyst, which can be suitably used as a raw material for an isocyanate group-terminated prepolymer having the above-mentioned properties.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the monool content and the residual amount of the catalyst obtained using a phosphazenium compound as a polymerization catalyst are small. The present inventors have found that, by reacting a polyoxyalkylene polyol with a polyisocyanate compound, an isocyanate group-terminated prepolymer having a small amount of a residual phosphazenium compound catalyst and excellent storage stability can be obtained. In addition, they have found that the isocyanate group-terminated prepolymer gives a polyurethane elastomer excellent in mechanical properties, thermal stability, and the like, and have reached the present invention.

That is, according to the present invention, there is provided an isocyanate group-terminated prepolymer obtained by reacting a polyol component with a polyisocyanate compound, wherein at least one of the polyol components is an active hydrogen compound in the presence of a phosphazenium compound catalyst. And a polyoxyalkylene polyol produced by addition polymerization of an epoxide compound with a polyisocyanate group-terminated prepolymer, wherein the residual amount of the phosphazenium compound catalyst in the prepolymer is 120 ppm or less.

As the polyoxyalkylene polyol used in the production of the above isocyanate group-terminated prepolymer, the residual amount of the phosphazenium compound used as the catalyst for producing the polyol is not more than 150 ppm, and further shows the monool content in the polyol. The total degree of unsaturation is 0.07 meq. / G or less, and the CP of the polyol
Those having R of 5 or less are preferred. It is preferable to use a polyol component containing at least 30% by weight of the polyoxyalkylene polyol. More preferably, it contains at least 50% by weight.

Further, the isocyanate group-terminated prepolymer according to the present invention has an isocyanate index of 0.1.
By reacting an active hydrogen compound having a functional group number greater than 1 in the range of 5 to 2.0, a polyurethane elastomer having excellent mechanical properties and heat stability can be obtained. The isocyanate group-terminated prepolymer of the present invention having an isocyanate group content of 0.3 to 3% by weight is used as a curing component, and is reacted with moisture in the air to obtain mechanical properties.
A moisture-curable polyurethane elastomer having excellent weather resistance and the like can be obtained.

Accordingly, the isocyanate group-terminated prepolymer of the present invention can be used in a wide range of fields such as paints, adhesives, flooring materials, waterproof materials, sealing agents, shoe soles, elastic reinforcing agents and rollers, timing belts and the like. In the present invention, the remaining amount of the phosphazenium compound catalyst means the remaining amount of the phosphazenium compound and / or the neutralized salt of the compound.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyoxyalkylene polyol according to the present invention is produced by adding an epoxide compound to an active hydrogen compound using a phosphazenium compound described later as a catalyst, and purifying the resulting crude polyoxyalkylene polyol. Examples of the phosphazenium compound include EP-A-0791 filed earlier by the present applicant.
It is preferable to use the compounds described in JP-A-600.

Specifically, the chemical formula (1)

[0014]

Embedded image [In the formula (1), a, b, c and d are each 0 to 3
Where a, b, c and d are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. r is an integer of 1 to 3 and represents the number of phosphazenium cations;
^r- represents an inorganic anion having a valence of r] or a chemical formula (2)

[0015]

Embedded image [In the formula (2), a, b, c and d are each 0 to 3
Where a, b, c and d are not all 0 at the same time. R is the same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. Q ^- represents a hydroxy anion, an alkoxy anion, an aryloxy anion or a carboxy anion].

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

R in the phosphazenium cation of the salt represented by the above formula (1) or (2) is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms. Specifically, this R is, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-
Butyl, tert-butyl, 2-butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, isopentyl, tert-pentyl, 3-methyl-2-butyl, neopentyl, n-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl,
1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl, 1,1-dimethyl-
3,3-dimethylbutyl (tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-
It is selected from an aliphatic or aromatic hydrocarbon group such as phenylethyl or 2-phenylethyl. Of these, methyl, ethyl, n-propyl, isopropyl, t
Aliphatic hydrocarbon groups having 1 to 10 carbon atoms, such as tert-butyl, tert-pentyl and tert-octyl, are preferred. A methyl group or an ethyl group is more preferred.

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

T in the above chemical formula (1)^r-Is inorganic with valence r
Represents an anion. And r is an integer of 1 to 3. This
As inorganic anions such as, for example, boric acid, tet
Lafluoro acid, hydrocyanic acid, thiocyanic acid, fluorinated
Halogenated water such as hydrochloric acid, hydrochloric acid or oxalic acid
Acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, hexafluoro
Phosphoric acid, carbonic acid, hexafluoroantimonic acid, hexafu
Inorganic anions such as luorothalic acid and perchloric acid
No. Also, HSO as an inorganic anion _Four ^-, HC
O_Three ^-There is also. These inorganic anions are involved in the ion exchange reaction.
More can be exchanged for each other. These inorganic anions
Boric acid, tetrafluoroboric acid, halogenated water
Acid, phosphoric acid, hexafluorophosphoric acid, perchloric acid, etc.
Anions of inorganic acids are preferred, and chlorine anions are more preferred.
Good.

When a phosphazenium compound represented by the chemical formula (1) is used as a catalyst, an alkali metal or alkaline earth metal salt of an active hydrogen compound is prepared in advance. The preparation method may be a known method. An alkali metal or alkaline earth metal salt of an active hydrogen compound coexisted with the phosphazenium compound represented by the chemical formula (1) is an alkali metal or alkaline earth metal ion in which active hydrogen of the active hydrogen compound dissociates as a hydrogen ion. It is a salt that has been replaced.

Examples of the active hydrogen compound that provides such a salt include alcohols, phenol compounds, polyamines,
And alkanolamines. For example, water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol Dihydric alcohols such as 1,4-cyclohexanediol, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol,
Polyhydric alcohols such as tripentaerythritol and polyglycerol, sugars such as glucose, sorbitol, dextrose, fructose, sucrose, methyl glucoside, hydroxyethyl glucoxide or derivatives thereof, ethylenediamine, di (2-aminoethyl) amine, hexamethylene Examples thereof include fatty acid amines such as diamines, aromatic amines such as toluylenediamine, diphenylmethanediamine, phenol compounds such as bisphenol A, bisphenol F, bisphenol S, novolak, resole, resorcinol, hydroquinone, and Mannich compounds.

These active hydrogen compounds can be used in combination of two or more. Furthermore, these active hydrogen compounds are prepared by a conventionally known method with respect to one equivalent of active hydrogen groups.
A compound obtained by addition polymerization of 6 mol or less of the epoxide compound can also be used. In order to obtain an alkali metal or alkaline earth metal salt from these active hydrogen compounds, the active hydrogen compound and a metal selected from alkali metals or alkaline earth metals or a basic alkali metal or alkaline earth metal are used. The usual method of reacting with a metal compound is used.

The polyoxyalkylene polyol according to the present invention is prepared in the presence of a salt of a phosphazenium cation represented by the chemical formula (1) and an inorganic anion, and an alkali metal or alkaline earth metal salt of an active hydrogen compound. And an epoxide compound is subjected to addition polymerization. At this time, a salt of a cation of an alkali metal or an alkaline earth metal and an inorganic anion is by-produced. If the by-product salt inhibits the polymerization reaction, the salt is removed by a method such as filtration prior to the polymerization reaction. You can keep it.

Further, a phosphazenium salt of an active hydrogen compound derived from a salt represented by the chemical formula (1) and an alkali metal or alkaline earth metal salt of the active hydrogen compound is isolated in advance, and the epoxide compound is isolated in the presence of the phosphazenium salt. Can also be polymerized.

Another method for producing the polyoxyalkylene polyol of the present invention, that is, an epoxide compound is subjected to addition polymerization in the presence of a phosphazenium compound represented by the chemical formula (2) and an active hydrogen compound to convert the polyoxyalkylene polyol. The case of manufacturing will be described.

The phosphazenium compound represented by the chemical formula (2) Q ^- are hydroxy anion, alkoxy anion, anion selected from the group consisting of aryloxy anions and carboxylate anions. These Q ^- of, preferably a hydroxy anion, for example, methanol, ethanol, n- propanol, alkoxyalkyl anion derived from an aliphatic alcohol such as isopropanol, for example, phenol, an aromatic hydroxy cresol An aryloxy anion derived from a compound, for example, a carboxy anion derived from formic acid, acetic acid, propionic acid, or the like.

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

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

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

Epoxide compounds to be addition-polymerized to an active hydrogen compound in the presence of a phosphazenium compound include propylene oxide, ethylene oxide,
2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide,
Epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, trifluoropropylene oxide and the like. These may be used in combination of two or more. Of these, propylene oxide, 1,2-butylene oxide and ethylene oxide are preferred.

As a polymerization method, propylene oxide homopolymerization or, in the case of propylene oxide and ethylene oxide, for example, after polymerization of propylene oxide, an ethylene oxide capping reaction in which ethylene oxide is copolymerized in a block, and propylene oxide and ethylene oxide are reacted. A random reaction in which copolymerization is performed at random, a triblock copolymerization reaction in which ethylene oxide is polymerized after propylene oxide polymerization, and then propylene oxide is polymerized, and a method in which these polymerization methods are combined are exemplified.

A polyoxyalkylene polyol obtained by addition polymerization of an epoxide compound to an active hydrogen compound in the presence of a phosphazenium compound has a total degree of unsaturation (hereinafter abbreviated as C = C) of 0.07 meq. / G or less. Other physical properties preferably satisfy the following conditions. a) The hydroxyl value (hereinafter abbreviated as OHV) is 2 to 200 m
gKOH / g. b) Head-to-tail of polyoxyalkylene polyol by propylene oxide addition polymerization (Head)
-To-Tail) bond selectivity is 95 mol% or more.

The total degree of unsaturation (C = C) in the polyoxyalkylene polyol serves as an index of the amount of monool having an unsaturated group at a molecular terminal generated mainly by a side reaction of propylene oxide. C = C is 0.07 meq. / G
It is as follows. Preferably 0.05 meq. / G or less. More preferably, 0.03 meq. / G or less. C = C is 0.07 meq. / G is not preferred because the mechanical properties, thermal stability, curing properties and the like of the polyurethane elastomer are reduced.

OHV of polyoxyalkylene polyol
Is preferably 2 to 200 mgKOH / g. More preferably, it is 9 to 120 mgKOH / g. More preferably, it is 11 to 60 mgKOH / g. OHV is 2mgKO
If the addition polymerization of an epoxide compound, especially propylene oxide, is carried out until it becomes smaller than H / g, the reaction time of the polyoxyalkylene polyol becomes longer. Also, OHV
Is greater than 200 mg KOH / g, the total degree of unsaturation (C = C) of the polyoxyalkylene polyol of which we are paying attention is not significantly different from the polyoxyalkylene polyol obtained with the conventional KOH catalyst system.

In such a polyoxyalkylene polyol having a low total degree of unsaturation (C = C), propylene oxide addition polymerization is used to prepare a head-to-tail (Head-to-tail).
When the to-Tail bond selectivity is less than 95%, the viscosity when the polyoxyalkylene polyol is made to have a high molecular weight is remarkably increased due to a decrease in the head-to-tail (Head-to-Tail) bond selectivity. Therefore, the viscosity of the prepolymer obtained by the reaction with the polyisocyanate compound also increases, and the workability decreases.

As described above, the structure of polyoxy is controlled.
The production of the alkylene polyol is performed under the following conditions.
Is preferred. That is, one mole of the active hydrogen compound is
Represented by the chemical formula (1) or (2)
5 x 10 azenium compounds ^-Five~ 5 mol, preferably 1
× 10^-Four~ 5 × 10^-1Mole, more preferably 1 × 10 ^-3
~ 1 × 10^-2Range of moles. Polyoxyalkylene
When increasing the molecular weight of the polyol, the active hydrogen compound
Phosphazenium compound concentration within the above range.
Is preferred. For 1 mol of active hydrogen compound,
Phosphase represented by chemical formula (1) or chemical formula (2)
5 × 10^-FiveIf lower than the mole,
The polymerization rate of the oxide compound decreases,
The production time of the len polyol increases. Active hydrogen compound
Represented by chemical formula (1) or chemical formula (2) per mole
More than 5 moles of the phosphazenium compound
E in the production cost of polyoxyalkylene polyol
The cost of the sphazenium compound increases.

The temperature of the addition polymerization reaction of the epoxide compound 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 epoxide compound is lower than the above range, the concentration of the phosphazenium compound with respect to the active hydrogen compound is preferably increased within the range described above. A method for supplying an epoxide compound to an active hydrogen compound catalyzed by a phosphazenium compound charged in a pressure-resistant reactor,
A method in which a necessary amount of the epoxide compound is partially supplied, or a method in which the epoxide compound is supplied continuously or intermittently is used. In the method of supplying a part of the required amount of the epoxide compound at a time, the reaction temperature at the beginning of the polymerization reaction of the epoxide compound is set to a lower temperature within the above range, and the reaction temperature is gradually increased after the epoxide compound is charged. preferable.

When the reaction temperature is lower than 15 ° C., the polymerization rate of the epoxide compound decreases, and the production time of the polyoxyalkylene polyol increases. Reaction temperature 13
When the temperature exceeds 0 ° C., when propylene oxide is used as the epoxide compound, the total degree of unsaturation (C = C) becomes 0.0 with increasing the molecular weight of the polyoxyalkylene polyol.
7meq. / G.

The maximum pressure during the reaction of the epoxide compound is preferably 882 kPa. Usually, the reaction of the epoxide compound is performed by a pressure-resistant reactor. The reaction of the epoxide compound may be started from a reduced pressure state or an atmospheric pressure state. When starting the reaction from an atmospheric pressure state, it is desirable to carry out the reaction in the presence of an inert gas such as nitrogen or helium. Maximum reaction pressure of epoxide compound is 8
If it exceeds 82 kPa, the amount of by-product monol increases. The maximum reaction pressure is preferably 686 kPa, more preferably 490 kPa. As an epoxide compound,
When using propylene oxide, the maximum reaction pressure is preferably 490 kPa.

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

A method for purifying a crude polyoxyalkylene polyol after addition polymerization of an epoxide compound to an active hydrogen compound using a phosphazenium compound as a catalyst will be described. c) 1 to 40 parts by weight of water is added to 100 parts by weight of the crude polyoxyalkylene polyol, and then 1 mol of the phosphazenium compound in the crude polyoxyalkylene polyol under the condition that the oxygen concentration in the gas phase is 2% or less. For
50 to 1 mol of at least one neutralizing agent selected from inorganic acids, inorganic acid acid salts and organic acids, in an amount of 0.5 to 8 mol.
Neutralize the phosphazenium compound at 30 ° C. afterwards,
100 to crude polyoxyalkylene polyol
４4000 ppm of an antioxidant is added, a reduced pressure treatment is performed, water is distilled off, and a polyoxyalkylene polyol is recovered. d) To 100 parts by weight of the crude polyoxyalkylene polyol, 1 to 40 parts by weight of a mixture of an inert organic solvent and water is added to the polyoxyalkylene polyol, and the oxygen concentration in the gas phase is 2% or less. With respect to 1 mol of the phosphazenium compound in the crude polyoxyalkylene polyol, 50 to 130 mol of at least one neutralizing agent selected from inorganic acids, inorganic acid acid salts or organic acids is used. Neutralize the phosphazenium compound at ° C.
Thereafter, 100 to 4000 ppm of an antioxidant is added to the crude polyoxyalkylene polyol, and the mixture is subjected to a reduced pressure treatment, water and an organic solvent are distilled off, and the polyoxyalkylene polyol is recovered. e) To 100 parts by weight of the crude polyoxyalkylene polyol, 1 to 200 parts by weight of water alone or a mixture of water and a solvent selected from a hydrocarbon solvent inert to the polyoxyalkylene polyol is added, and the mixture is separated and washed with water. Water and organic solvent are distilled off by a reduced pressure treatment. f) 10 to 200 parts by weight of water is added to 100 parts by weight of the crude polyoxyalkylene polyol, and the mixture is brought into contact with the ion exchange resin at 15 to 100 ° C. or lower, and then dehydrated by a vacuum treatment.

The oxygen concentration in the gas phase during the purification of the crude polyoxyalkylene polyol is 2% or less. Preferably, it is at most 1.5%, most preferably at most 1%.
If the oxygen concentration in the gas phase exceeds 2%, peroxide or aldehyde compounds are likely to be produced as by-products when water or a mixture of water and an organic solvent is removed by heating under reduced pressure. The compound may cause odor and may deteriorate the stability of the polyoxyalkylene polyol over time. The control of the oxygen concentration in the gas phase
A replacement operation with an inert gas such as nitrogen, helium, or argon is preferable. By reducing the oxygen concentration in the gas phase, the oxygen concentration in the crude polyoxyalkylene polyol (liquid phase) is also reduced, so that by-products of peroxides or aldehyde compounds can be suppressed.

Usually, the purification operation of the crude polyoxyalkylene polyol is carried out in a reactor equipped with a stirrer.
The operation of pressurizing and replacing the inside of the reactor with an inert gas several times, or the operation of reducing the inside of the reactor under a reduced pressure, for example, a state of 6650 Pa or less, leaving it for a while, and performing the pressurizing and replacing with an inert gas is repeated several times Thereby, the oxygen concentration in the gas phase is reduced to 2% or less. At this time, the oxygen concentration in the gas phase is measured by a trace oxygen analyzer. In particular, the oxygen concentration in the liquid phase is significantly reduced by reducing the pressure inside the reactor and then performing a pressure substitution operation with an inert gas. The oxygen concentration in the liquid phase after performing such an operation is 1.3 ppm.
The following is preferred.

The method c) is a method using water alone, and the method d) is a method using water and a polyoxyalkylene polyol in combination with an inert organic solvent. OHV is low (OHV2-30m
(The range of gKOH / g) The polyoxyalkylene polyol has a high molecular weight and a low concentration of hydrophilic hydroxyl groups. In the polymerization reaction of the epoxide compound, when the use amount of the phosphazenium compound relative to the active hydrogen compound is large, the amount of water or the organic solvent used for neutralizing the phosphazenium compound is to reduce the phosphazenium compound concentration from the polyoxyalkylene polyol. Is an important factor.

For neutralization, 1 to 40 parts by weight of water (method c) or a mixture of water and an organic solvent inert to the polyoxyalkylene polyol (method d) is used. Preferably 1-3
0 parts by weight, more preferably 1.2 to 20 parts by weight.
Water is an essential component, and when using an organic solvent and water inert to the polyoxyalkylene polyol, at least 20% by weight of water in the mixed solvent is required. When the polyoxyalkylene polyol contains 10 mol% or more of oxyethylene groups as hydrophilic groups, the amount of water used may be small. When there is no oxyethylene group, the amount of water used increases. When the amount is less than 1 part by weight, the concentration of the phosphazenium compound in the product increases. If it exceeds 40 parts by weight, the energy consumed for dehydration and desolvation increases.

Organic solvents inert to polyoxyalkylene polyols include toluene, hexanes, pentanes, heptane, butanes, lower alcohols, cyclohexane, cyclopentane and xylene among hydrocarbon solvents. No. The removal of these organic solvents from the polyoxyalkylene polyol is carried out by heating and depressurizing. The temperature is 100-140 ° C and the degree of decompression is 133
A method of reducing the pressure to 0 Pa or less is preferable.

As the acid for neutralizing the phosphazenium compound, at least one neutralizing agent selected from inorganic acids, inorganic acid salts and organic acids is used. Examples of the inorganic acid include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, hydrochloric acid, sulfuric acid, sulfurous acid, and aqueous solutions thereof. Examples of the inorganic acid acid salt include dilithium phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate,
Lithium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, lithium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acid pyrophosphate (for example, pyrroline Sodium hydrogen oxyoxide) and the like.

Examples of the organic acid include formic acid, oxalic acid, succinic acid, acetic acid, maleic acid, benzoic acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, and aqueous solutions thereof. In particular, phosphoric acid, sulfuric acid, hydrochloric acid, maleic acid, and oxalic acid are preferred, and they are preferably used in the form of an aqueous solution.

These acids are used in an amount of 0.5 to 8 mol per 1 mol of the phosphazenium compound contained in the crude polyoxyalkylene polyol. Preferably, 0.7
６6 mol, more preferably 0.9-5 mol. Neutralization is performed in the range of 50 to 130 ° C. Particularly preferably 7
0-95 ° C. The neutralization time is 0.5 to 3 hours, depending on the reaction scale. Phosphazenium compound 1
When the amount of the acid is close to 8 mol with respect to the mol, it is preferable to use an acid adsorbent together. When the amount is less than 0.5 mol, the concentration of the phosphazenium compound in the polyoxyalkylene polyol of the product tends to increase.

After completion of the neutralization reaction, 100 to 4000 ppm of an antioxidant is used based on the crude polyoxyalkylene polyol. Preferably, 150 to 3000 pp
m, most preferably from 200 to 1800 ppm.
If the content of the antioxidant is less than 100 ppm, a peroxide or an aldehyde compound is easily produced as a by-product. 4000 ppm
As the number increases, the cost of the antioxidant in the cost of the polyol increases.

Examples of the antioxidant include phenol compounds, amine compounds, phosphite compounds and cinnamate esters. For example, 2,6-di-te
rt-butyl-4-methylphenol (hereinafter abbreviated as BHT), 2-tert-butyl-4-methoxyphenol (hereinafter abbreviated as BHA), 6-tert-butyl-2.4-methylphenol, , 6-di-tert-
Butylphenol, 2-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-ethylphenol, n-octadecyl-3- (4'-hydroxy-3,5-di-tert-butylphenyl ) Propionate, dioctadecyl-4-hydroxy-3,5-
Di-tert-butylbenzylphosphonate, diethyl-4-hydroxy-3,5-di-tert-butylbenzylphosphonate, 2-ethylhexyl phosphite,
6- (4-oxy-3,5-di-tert-butyl-anilino) -2,4-bis- (n-octylthio) -1,
3,5-triazine, 4,4′-thiobis (6-ter
t-butyl-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-methylenebis (6-tert-butylphenol), 4,4′-bis ( 2,6-di-ter
t-butylphenol), 4,4'-thiobis (6-t
tert-butyl-o-cresol), 2,2′-methylenebis (4-methyl-6-tert-butyl-phenol), 2,2′-thiobis (6-tert-butyl-4)
-Methylphenol), 1,6-bis (3,5-di-t)
tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane,
2,4,6-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) mesitylene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, 1,3,5-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [β- (3,5-di-ter
[tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, di-tert-para-sec-butylphenol, pentaerythrityl-tetrakis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl) -propionate and the like.

Examples of the amine compound include n-butyl-p-aminophenol, 4,4'-dimethyldiphenylamine, 4,4'-dioctyldiphenylamine,
4,4′-bis-α, α′-dimethylbenzyldiphenylamine, 2- (2′-hydroxy-3 ′, 5′-di-
tert-butylphenyl) -5-chlorobenzotriazole and the like.

Further, stabilizers described in JP-A-8-104802 can also be used. These antioxidants may be used alone or in combination of two or more. Among these antioxidants, preferably, BHT, BHA, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
Octadecyl-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) -propionate, ethylhexyl phosphite, DOA, 4,4′-bis-α,
α'-dimethylbenzyldiphenylamine, 2-ter
t-butyl-4-ethylphenol, 2,6-di-te
rt-butyl-4-ethylphenol.

An adsorbent may be charged together with the antioxidant. The charging time of the adsorbent may be either after the neutralization reaction or in the dehydration process under reduced pressure. An adsorbent for adsorbing an acid and an alkali component is added in an amount of 0.005 to 2.5 parts by weight based on 100 parts by weight of the crude polyoxyalkylene polyol. Preferably, it is 0.02 to 1.5 parts by weight, more preferably 0.03 to 1.1 parts by weight.

As the adsorbent, for example, synthetic magnesium silicate, synthetic aluminum silicate, activated clay, zeolite, acid clay, synthetic aluminum magnesium silicate and the like are used. Since the treatment with sodium hydroxide is performed in the step of producing the adsorbent, an adsorbent with a small sodium elution content is preferable. Specific adsorbents include Tomix series, for example, Tomix AD-1
00, Tomix AD-200, Tomix AD-30
0, Tomix AD-400, Tomix AD-50
0, Tomix AD-600, Tomix AD-70
0, Tomix AD-800, Tomix AD-900
[Manufactured by Tomita Pharmaceutical Co., Ltd.], Kyoword series, for example, Kyoword 200, Kyoword 300, Kyoword 400, Kyoword 500, Kyoword 60
0, Kyoward 700, Kyoward 1000, Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.), MAGN
It is commercially available under various trade names such as ESOL (manufactured by DALLAS).

These adsorbents may be used alone or in combination of two or more. After charging the adsorbent, water or water and the organic solvent are distilled off under reduced pressure. Although it depends on the reaction scale, 3 to 30 ° C and 1330 Pa
Perform for ~ 12 hours. In particular, in order to remove low molecular weight aldehyde compounds, after adding an antioxidant, 70-160
It is preferable to introduce an inert gas such as nitrogen, helium, or argon at a temperature of 39.9 kPa, preferably 26.6 kPa, and more preferably 13.3 kPa or lower. The decompression operation includes a method using a vacuum pump, a thin film evaporation method, and the like. At that time, a forced circulation type stirred film type evaporator or a falling film type molecular distillation apparatus can be used.

After the operations c) to f), the polyoxyalkylene polyol is recovered by a filtration operation.
At that time, a filter aid such as diatomaceous earth and celite may be used.

By the above operation, the remaining amount of the catalyst in the polyoxyalkylene polyol is controlled to 150 ppm or less. The concentration of the catalyst in the polyol is preferably 90 ppm or less, more preferably 50 ppm or less. The remaining amount of the catalyst in the polyoxyalkylene polyol is 150
When the content exceeds ppm, when the polyoxyalkylene polyol catalyzed by the phosphazenium compound according to the present invention is used alone as the polyol component, the polyoxyalkylene polyol obtained by reacting with the polyisocyanate compound depends on the isocyanate group content in the prepolymer. The storage stability of the resulting isocyanate group-terminated prepolymer is reduced.

The polyoxyalkylene polyol obtained by the above operation has a CPR (a value indicating the amount of a basic substance in the polyol) of 5 or less. Preferably, CP
R is 3 or less, most preferably CPR is 0. If the CPR of the polyoxyalkylene polyol is greater than 5, the storage stability of the isocyanate group-terminated prepolymer reacted with the polyisocyanate compound will decrease.

The peroxide concentration in the polyoxyalkylene polyol obtained by the above operation is 0.28 mm
ol / kg or less, preferably 0.20 mmol / kg
Below, most preferably, it is 0.15 mmol / kg or less. When the peroxide concentration exceeds 0.28 mmol / kg, when the tin-based catalyst is used in the reaction with the polyisocyanate compound, the activity of the tin-based catalyst is reduced by the peroxide, so that the moldability and mechanical properties of the polyurethane are reduced. Physical properties decrease.

When the peroxide concentration is 0.28 mmol /
If a polyoxyalkylene polyol exceeding kg is left in the air, the peroxide becomes an acidic compound and the acid value in the polyoxyalkylene polyol increases. When the acid value increases, the reactivity with the polyisocyanate compound decreases, and the physical properties of the obtained polyurethane deteriorate or the odor increases. In order to improve the storage stability of the polyoxyalkylene polyol, the peroxide concentration is 0.28 m
mol / kg or less, and the concentration of the antioxidant in the polyol is preferably 100 to 4000 ppm. The acid value of the polyoxyalkylene polyol obtained by such an operation is preferably 0.05 mgKOH / g or less.

Next, the isocyanate group-terminated prepolymer of the present invention will be described. The isocyanate group-terminated prepolymer is produced by reacting a polyol component with a polyisocyanate compound.

The residual amount of the catalyst for producing a polyoxyalkylene polyol in the isocyanate group-terminated prepolymer is 1
20 ppm or less. Preferably it is 90 ppm or less, most preferably 30 ppm or less. When the concentration of the compound in the prepolymer exceeds 120 ppm, the storage stability of the prepolymer decreases.

The polyol component used as a raw material of the isocyanate group-terminated prepolymer of the present invention is preferably a polyol containing at least 30% by weight of a polyoxyalkylene polyol obtained by using a phosphazenium compound as a catalyst according to the present invention. More preferably, the content is 50% by weight or more.

Examples of the polyol other than the polyoxyalkylene polyol obtained by using a phosphazenium compound as a catalyst include polyoxyalkylene polyols, polymer-dispersed polyols, polytetramethylene glycol, polyester polyols, polybutadiene-based polyols produced by conventionally known methods. Polycarbonate-based polyols and the like can be mentioned. When these conventionally known polyols are used, the concentration of the trace metal component in the polyol is 1%.
Less than 0 ppm is preferred.

As the polyisocyanate compound used as a raw material of the isocyanate group-terminated prepolymer, known polyisocyanate compounds used in the production of aromatic, aliphatic, alicyclic and other polyurethanes having two or more isocyanate groups in one molecule. Can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
An 80/20 weight ratio (hereinafter abbreviated as TDI-80 / 20), a 65/35 weight ratio (hereinafter abbreviated as TDI-65 / 35) isomer mixture, and a polyfunctional tar of these polyisocyanate compounds are used. Crude tolylene diisocyanate (polyfunctional tar is a mixture of tar-like substances that are by-produced during the production of isocyanate and contain two or more isocyanate groups in the molecule; the same applies hereinafter);
4,4′-diphenylmethane diisocyanate, 2,
4'-diphenylmethane diisocyanate, 2,2'-
Diphenylmethane diisocyanate, polymethylene polyphenylisocyanate described in Japanese Patent Application Laid-Open No. Hei 8-188637 previously filed by the present applicant, any isomer mixture of diphenylmethane diisocyanate, crude diphenylmethane diisocyanate containing a trifunctional or higher polyfunctional tar (Hereinafter abbreviated as polymeric MDI), toluidine diisocyanate, xylylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, norbornene diisocyanate and carbodiimide modified, buret modified, allophanate modified of these polyisocyanate compounds,
Examples include urea-modified products, isocyanurate-modified products, oxazolidone-group-containing modified products, uretoimine-modified products, and prepolymers obtained by modifying these alone or in combination with a monohydroxy compound.

The above-mentioned polyisocyanate compounds can be used in a mixture at any ratio. Of these, TDI-80 / 20, TDI-65 / 35, polymeric MDI alone, these TDI and polymeric M
DI or a prepolymer modified product of these polyisocyanate compounds, isophorone diisocyanate and norbornene diisocyanate.

As the prepolymerization reaction catalyst, a conventionally known catalyst for producing a polyurethane such as an amine compound or an organometallic compound can be used. When the molecular weight of the polyoxyalkylene polyol is large, that is, when the OHV is low, it may not be necessary to use a catalyst.

As the amine compound, for example, triethylamine, tripropylamine, tributylamine,
N, N, N ′, N′-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine,
Examples thereof include dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether, triethylenediamine, and salts of triethylenediamine.

Examples of the organometallic compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate, lead naphthenate, nickel naphthenate and naphthenate. Cobalt acid and the like. These catalysts can be used alone or in combination of two or more.

The temperature at the time of producing the isocyanate group-terminated prepolymer is preferably from 50 to 120 ° C. Particularly preferably, it is 70 to 105 ° C. At the time of the reaction, it is desirable to carry out the reaction in the presence of an inert gas in order to avoid contact with moisture in the air. Examples of the inert gas include nitrogen and helium, and nitrogen is preferable. The reaction is carried out with stirring under a nitrogen atmosphere for 2 to 20 hours. A catalyst may not be used, but when it is used, the above-mentioned amine compound or organometallic compound can be used. These catalysts can be arbitrarily mixed and used. Among these catalysts,
Organometallic catalysts are preferable, and the amount of the catalyst is the polyol component 10 containing the polyoxyalkylene polyol of the present invention.
0.0001 to 2.0 parts by weight, preferably 0.01 to 1.0 part by weight, based on 0 parts by weight.

When producing the prepolymer, the ratio of the isocyanate group concentration in the polyisocyanate compound to the active hydrogen group concentration in the polyol component (hereinafter, abbreviated as isocyanate index) is in the range of 1.3 to 20.0. Is preferred. More preferably, it is from 1.4 to 12.0, most preferably from 1.5 to 9.0.

The isocyanate group content (hereinafter abbreviated as NCO%) of the isocyanate group-terminated prepolymer is as follows:
0.3-30.0% by weight, preferably 0.5-25.0
% By weight, more preferably 0.7 to 18.0% by weight.

The isocyanate group-terminated prepolymer used for the moisture-curable polyurethane elastomer obtained by using water in the air as a curing agent has a low NCO%,
An isocyanate group-terminated prepolymer used in a two-pack curable polyurethane elastomer having a curing agent of glycols such as butanediol and polyoxyalkylene polyol, and polyamine compounds such as 3,3'-dichloro-4,4'-diaminodiphenylmethane. For polymers, NCO% is designed to be higher than that of one-pack type.

The remaining amount of the catalyst in the polyoxyalkylene polyol and the isocyanate group-terminated prepolymer of the present invention is preferably determined by capillary electrophoresis. When no phosphoric acid compound was used to remove the catalyst in the polyoxyalkylene polyol, the amount of phosphorus in the phosphazenium compound was determined by inductively coupled plasma emission spectrometry (hereinafter abbreviated as ICP).
The phosphazenium compound concentration can also be back calculated.

When the isocyanate group-terminated prepolymer is analyzed by capillary electrophoresis, it is reacted with a lower monoalcohol, such as methanol, in order to make the isocyanate group at the molecular end inert to water. Is preferred.

In preparing the isocyanate group-terminated prepolymer of the present invention, an organic solvent which is inert to the polyisocyanate compound or the polyol before or after the reaction can be used. The amount of the organic solvent is 40% by weight based on the total weight of the polyol and the polyisocyanate compound.
Or less, preferably 20% by weight or less. like this,
As the solvent, aromatic, aliphatic, alicyclic, ketone, ester and ester ether solvents can be used.
For example, toluene, xylenes, hexanes, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and the like. At this time, a curing catalyst, a filler, a plasticizer, a dye / pigment, a reinforcing agent, a flame retardant, a stabilizer and the like can be used according to the purpose.

According to the above method, the obtained isocyanate group-terminated prepolymer is reacted with an active hydrogen compound having an isocyanate index in the range of 0.5 to 2.0 and a functional group number of more than 1 to obtain a polyurethane elastomer. The isocyanate index is preferably from 0.7 to 1.8. Most preferably, it is in the range of 0.8 to 1.4.
If the isocyanate index is less than 0.5, the tack (stickiness) of the polyurethane elastomer increases. If it exceeds 2.0, the mechanical properties of the polyurethane elastomer will decrease.

The active hydrogen compound having more than one functional group is a compound having at least one active hydrogen group in one molecule capable of reacting with an isocyanate group. At least one of a polyol compound and a polyamine compound is used. Can be As the polyol compound, for example,
Dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol; trivalent alcohols such as glycerin and trimethylolpropane Including alcohols, cyclohexylene such as cyclohexanediol and spirohexanediol, including spiro ring and methylene chain, including various bonds such as ether bond and ester bond as those connecting them, and including various substituents as derivatives thereof Things can be used.

The polyamine compounds include tolylenediamine, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene,
Diphenylmethanediamine, m-phenylenediamine,
Aromatic diamines such as 3,3'-dichloro-4,4'-diaminodiphenylmethane and diethyltoluenediamine, aliphatic and alicyclic diamines such as isophorone diamine and norbornene diamine, linear aliphatic diamines, carbodihydrazide and adipic acid A conventionally known polyamine compound such as an alkyl dihydrazide such as dihydrazide or a derivative thereof can be used. Further, polyols obtained by adding an epoxide compound to these active hydrogen compounds by a conventionally known method can also be used.

The isocyanate group-terminated prepolymer of the present invention and the above compound are rapidly mixed, deaerated under reduced pressure, and poured into a mold heated to a predetermined temperature, for example, 40 to 130 ° C., to prepare a polyurethane elastomer.

NC of the isocyanate group-terminated prepolymer of the present invention used for moisture-curable polyurethane elastomer
O% is 0.3-3% by weight. If the NCO% exceeds 3% by weight, the curing time becomes longer, and the workability is reduced. When preparing the moisture-curable polyurethane elastomer, the organic solvent described above in the isocyanate group-terminated prepolymer,
A curing catalyst, a filler, a plasticizer, a dye / pigment, a reinforcing agent, a flame retardant, a stabilizer and the like may be used.

The polyurethane elastomer using the isocyanate group-terminated prepolymer of the present invention is excellent in a wide range of fields such as paints, adhesives, flooring materials, waterproof materials, sealing agents, shoe soles, elastic reinforcing agents, rollers and timing belts. It has mechanical properties, thermal stability and weather resistance.

[0084]

EXAMPLES Examples of the present invention will be shown below to clarify the present invention, but the present invention is not limited to these examples. The hydroxyl value, total unsaturation, CPR, residual amount of catalyst, isocyanate group concentration, viscosity, hardness, tensile properties, weather resistance, thermal stability, and storage stability shown in the examples were measured by the following methods. . (1) hydroxyl value (hereinafter abbreviated as OHV; unit: mgKOH / g), total unsaturation (hereinafter abbreviated as C = C, unit: meq./g) of polyoxyalkylene polyol,
And CPR (without unit) were determined by the method described in JIS K-1557. (2) Residual amount of phosphazenium compound catalyst in polyoxyalkylene polyol and isocyanate group-terminated prepolymer (unit: ppm) This was carried out by capillary electrophoresis using a fully automatic CIA system manufactured by Waters. A hydrochloric acid aqueous solution was added to the sample, and a shaker [manufactured by Tokyo Rika Kikai Co., Ltd., type: E
YELA SHAKER] to extract a phosphazenium compound into an aqueous hydrochloric acid solution. Thereafter, liquid separation was performed by standing, the aqueous layer was separated, and the remaining amount of the catalyst was quantified using a capillary electrophoresis analyzer. The isocyanate group-terminated prepolymer was quantified by the above method after the following pretreatment. After reacting the free isocyanate groups in the prepolymer with methanol (special grade reagent), 8
The mixture was heated to 0 ° C., and the pressure was reduced to 1330 Pa (10 mmHg) or less to remove residual methanol.

(3) Storage stability of isocyanate group-terminated prepolymer Based on the viscosity immediately after production, the rate of increase in the viscosity of the prepolymer after storage in an oven at 60 ° C. for 14 days is shown. Those having a viscosity increase rate of 20% or less are judged to be excellent in storage stability (）), and those exceeding 20% are judged to be poor in storage stability (X). (4) Isocyanate group concentration in the prepolymer (hereinafter, referred to as
NCO concentration, unit:%), and viscosity (unit: mPa · s)
/ 25 ° C) It was measured by the method specified in JIS K-7301. (5) Hardness of polyurethane elastomer (shore)
A, unit: none) Tensile physical property unit: MPa or%) Measured by a method specified in JIS K-7312 and JIS A-6021. (6) Weathering resistance and thermal stability of polyurethane elastomer An accelerated exposure test was conducted according to the method specified in JIS A-6021. ).

Preparation Example 1 <Synthesis of phosphazenium compound (hereinafter abbreviated as P5NMe2OH)> 30 equipped with a thermometer and a dropping funnel
In a 00 ml three-necked flask, 60.20 g of phosphorus pentachloride (manufactured by Junsei Chemical Co., Ltd.) is weighed, and 525 ml of orthodichlorobenzene [hereinafter abbreviated to ODCB]. Mitsui Chemicals, Inc.] to obtain a suspension. This was heated to 30 ° C., and in a 900 ml ODCB, Reinhard Schwezinger et al., “Angevante Himika International Edition English”, 32 volumes, 1361
1363, 1993 (ReinhardSchwesinger, et al. A
Engl., 1993, 32, 1361-1363), and a solution in which 439.27 g of tris (dimethylamino) phosphazene ｛(Me ₂ N) ₃ P = NH｝ is dissolved. Was added dropwise over 1 hour. After stirring at the same temperature for 30 minutes, the temperature was raised to 160 ° C. over about 30 minutes, and further stirred for 20 hours. The generated insolubles were filtered, ion-exchanged water was added to the filtrate, and water washing was performed three times. 1091.2 g of a water-insoluble layer (hereinafter abbreviated as an organic layer) after the water washing treatment
To the solution, 619.26 g of ion-exchanged water and 289.5 ml of 1N hydrochloric acid were added, and the aqueous layer was separated, and tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride {[(Me ₂ N) ₃ P = N]
₄ P ⁺ Cl ^- was obtained}.

Further, ion-exchanged water was added to prepare a 2.5% by weight aqueous solution. Next, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium was placed in a polycarbonate cylindrical column filled with ion exchange resin Levatit MP-500 (manufactured by Bayer) whose exchange group was changed to a hydroxyl group with a 1N aqueous sodium hydroxide solution. A 2.5% by weight aqueous solution of chloride was added at 23 ° C to an SV (Sp
ace Velocity) 0.5 (1 / hr), the solution was passed through the column from the bottom in an ascending flow, and ion exchange was performed with tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide.

Further, ion-exchanged water was passed through the column filled with the ion-exchange resin, and the phosphazenium compound remaining in the column was recovered. Thereafter, an aqueous solution of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide was added at 80 ° C. under a reduced pressure of 7,980 Pa for 2 hours, and further at 80 ° C., 133
By performing dehydration under reduced pressure for 7 hours under the condition of Pa, powdered tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me
₂ N) ₃ P = N] ₄ P ⁺ OH ⁻ ｝ (P5NMe ² OH) was obtained. The yield determined from the weight measurement of the compound after drying was 98.
%Met. The chemical shift of ¹ H-NMR (400 MHz NMR manufactured by JEOL) using tetramethylsilane as an internal standard in a deuterated dimethylformamide solution is 2.6 p.
pm (d, J = 9.9 Hz, 72H). Elemental analysis: C; 38.28; H; 9.82; N; 29.4.
3, P; 19.94 (theoretical, C; 38.09, H;
9.72, N; 29.61, P; 20.46). In the chemical formula (2), the phosphazenium compound is (1,1,1,1) in the order of a, b, c, and d, R is a methyl group, and Q ⁻ is a hydroxy anion of OH ⁻ .

Hereinafter, the synthesis of the polyoxyalkylene polyol will be described. An apparatus for synthesizing and purifying a polyoxyalkylene polyol has an internal volume of 2.5 L, 6 L equipped with a stirrer, a thermometer, a pressure gauge, a nitrogen inlet, a line for measuring oxygen in a gas phase, and an epoxide compound inlet as a monomer. A 9 L pressure-resistant autoclave (Nitto Koatsu) was used. Hereinafter, the synthesis device is abbreviated as an autoclave. At the time of synthesis and purification of the polyoxyalkylene polyol, the number of rotations is 100 to 350 r.
p. m. The stirring was performed under the following conditions.

Example 1 <Polyoxyalkylene polyol A> 0.01 mol per mol of dipropylene glycol was placed in a 500 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer.
2 mol of P5NMe2OH and 0.06 mol of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) were added, nitrogen was introduced through a capillary tube, and dehydration under reduced pressure and removal of toluene were performed at 105 ° C. and 1330 Pa or less for 5 hours. Was done. afterwards,
The contents of the flask were charged into an autoclave under a nitrogen atmosphere, and after nitrogen replacement, the reaction temperature was changed from atmospheric pressure to 70 ° C., and the OHV was increased to 14.5 mgKOH / g under the condition that the maximum pressure during the reaction was 392 kPa. The multi-stage addition polymerization of propylene oxide was performed until the polymerization was completed. When the internal pressure of the autoclave stops changing, 665 Pa, 30
Vacuum treatment was performed for a minute to obtain a crude polyoxyalkylene polyol containing a phosphazenium compound. Hereinafter, the crude polyoxyalkylene polyol is referred to as crude polyol A.

The crude polyol A was charged into an autoclave under a nitrogen atmosphere, and after the temperature was raised to 80 ° C., the pressure inside the autoclave was reduced to 2660 Pa at the same temperature.
Hold for 8 minutes. Next, after pressurizing to 392 kPa with nitrogen, the pressure was released to atmospheric pressure. Next, 35 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyol A, and then 4 mol of hydrochloric acid (in the form of a 0.1 N aqueous solution) is added to 1 mol of the phosphazenium compound in the crude polyol A. The mixture was quickly charged, and a neutralization reaction was performed at 80 ° C. for 2 hours. After the neutralization reaction, 1200 ppm of pentaerythrityl-tetrakis [3- (3,5-di-tert-) was added to 100 parts by weight of the crude polyol A.
Butyl-4-hydroxyphenyl) propionate]
(Product name: IRGANOX101, manufactured by Ciba-Geigy)
After charging 0), dehydration was performed under reduced pressure, and the pressure was 13.3 k.
At the time of Pa, relative to 100 parts by weight of the crude polyol A,
1.0 part by weight of adsorbent AD-600 [Yoshitomi Pharmaceutical Co., Ltd.
Made quickly. Finally, vacuum nitrogen bubbling was performed at 105 ° C. and 2660 Pa for 4 hours while passing nitrogen through the liquid phase. 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. packed with Celite to purify the polyoxyalkylene polyol. The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification operation was 15.0 mgKOH / g, and the total unsaturation (C = C) was 0.019 meq. / G, CPR is 0.
6. The residual amount of the catalyst in the polyol was 20 ppm.

Example 2 <Polyoxyalkylene polyol B> In a 500 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 0.005 mol of P5 was added per mol of glycerin.
NMe2OH and 0.09 mol of toluene [special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.] were added, nitrogen was introduced through a capillary tube, and dehydration under reduced pressure and toluene removal operations were performed at 105 ° C. and 1330 Pa or less for 5 hours. . Thereafter, the contents of the flask were charged into an autoclave under a nitrogen atmosphere, and after purging with nitrogen, the reaction temperature was reduced from the atmospheric pressure to 8 ° C.
5 ° C. and the maximum pressure during the reaction was 392 kPa.
Multistage addition polymerization of propylene oxide was performed until the HV became 27 mgKOH / g. When the internal pressure of the autoclave was no longer changed, the pressure was reduced at 665 Pa for 30 minutes to obtain a crude polyoxyalkylene polyol containing a phosphazenium compound. Hereinafter, the crude polyoxyalkylene polyol is referred to as crude polyol B.

The crude polyol B was charged into an autoclave under a nitrogen atmosphere, and after the temperature was raised to 80 ° C., the pressure inside the autoclave was reduced to 2660 Pa at the same temperature.
Hold for 8 minutes. Next, after pressurizing to 392 kPa with nitrogen, the pressure was released to atmospheric pressure. Next, 35 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyol B, and then 4 mol of hydrochloric acid (in the form of a 0.1 N aqueous solution) is added to 1 mol of the phosphazenium compound in the crude polyol A. The mixture was quickly charged, and a neutralization reaction was performed at 80 ° C. for 2 hours. After completion of the neutralization reaction, 1000 ppm of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (trade name: IRGANOX1076, manufactured by Ciba Geigy) is added to 100 parts by weight of the crude polyol B. After charging, dehydration was performed under reduced pressure, and at a pressure of 13.3 kPa, 1.8 parts by weight of an adsorbent AD-600 [manufactured by Yoshitomi Pharmaceutical Co., Ltd.] was quickly charged to 100 parts by weight of crude polyol B. Entered. Finally, while bubbling nitrogen through the liquid phase, 105
Vacuum nitrogen bubbling was performed at 2660 Pa for 4 hours. After the pressure was reduced from atmospheric pressure to atmospheric pressure by nitrogen, Celite was reduced to 5
Filtration under reduced pressure was performed using a C filter paper (retained particle size: 1 μm) to purify the polyoxyalkylene polyol. The hydroxyl value (OH) of the polyoxyalkylene polyol after the refining operation
V) is 27.8 mgKOH / g, total unsaturation (C = C)
0.019 meq. / G, CPR was 0.2, and the residual amount of the catalyst in the polyol was 12 ppm.

Example 3 <Polyoxyalkylene polyol C> In a 500 ml four-necked flask equipped with a stirrer, a nitrogen introducing tube and a thermometer, 0.01 mol per mol of dipropylene glycol was added.
2 mol of P5NMe2OH and 0.06 mol of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) were added, nitrogen was introduced through a capillary tube, and dehydration under reduced pressure and removal of toluene were performed at 105 ° C. and 1330 Pa or less for 5 hours. Was done. afterwards,
The contents of the flask were charged into an autoclave under a nitrogen atmosphere, and after nitrogen replacement, the reaction temperature was increased from atmospheric pressure to 75 ° C., and the OHV was increased to 27.6 mgKOH / g under the condition that the maximum pressure during the reaction was 392 kPa. The multi-stage addition polymerization of propylene oxide was performed until the polymerization was completed. When the internal pressure of the autoclave stops changing, 665 Pa, 30
Vacuum treatment was performed for a minute to obtain a crude polyoxyalkylene polyol containing a phosphazenium compound. Hereinafter, the crude polyoxyalkylene polyol is referred to as crude polyol C.

The crude polyol C was charged into an autoclave under a nitrogen atmosphere, and after the temperature was raised to 80 ° C., the pressure inside the autoclave was reduced to 2660 Pa at the same temperature.
Hold for 8 minutes. Next, after pressurizing to 392 kPa with nitrogen, the pressure was released to atmospheric pressure. Next, 30 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyol C, and then 4.5 mol of phosphoric acid (7 mol) is added to 1 mol of the phosphazenium compound in the crude polyol C.
5.1% by weight aqueous solution) at 80 ° C.
For 2 hours. After the neutralization reaction was completed, 1000 ppm of BHT was added to 100 parts by weight of the crude polyol C, and then dehydration was performed under reduced pressure.
At the time of kPa, 1.8 parts by weight of the adsorbent AD-600 [manufactured by Yoshitomi Pharmaceutical Co., Ltd.] was quickly charged to 100 parts by weight of the crude polyol C. Finally, vacuum nitrogen bubbling was performed at 105 ° C. and 2660 Pa for 4 hours while passing nitrogen through the liquid phase. 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. packed with Celite to purify the polyoxyalkylene polyol. The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification operation is 28.3 mgKOH / g,
Total unsaturation (C = C) 0.012 meq. / G, CPR
Was 0.5, and the residual amount of the catalyst in the polyol was 11 ppm.

Example 4 <Polyoxyalkylene polyol D> In a 500 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, was added 0.00 to 1 mol of dipropylene glycol.
8 mol of P5NMe2OH and 0.08 mol of toluene (special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.) were added, nitrogen was introduced through a capillary tube, and dehydration under reduced pressure and removal of toluene were performed at 105 ° C. and 1330 Pa or less for 5 hours. Was done. afterwards,
The contents of the flask were charged into an autoclave under a nitrogen atmosphere, and after purging with nitrogen, the reaction temperature was changed from atmospheric pressure to 75 ° C., and the maximum pressure during the reaction was 392 kPa until the OHV became 55 mgKOH / g. Multistage addition polymerization of propylene oxide was performed. When the internal pressure of the autoclave was no longer changed, the pressure was reduced at 665 Pa for 30 minutes to obtain a crude polyoxyalkylene polyol containing a phosphazenium compound. Less than,
The crude polyoxyalkylene polyol is referred to as crude polyol D.

The crude polyol D was charged into an autoclave under a nitrogen atmosphere, and after the temperature was raised to 80 ° C., the pressure inside the autoclave was reduced to 2660 Pa at the same temperature.
Hold for 8 minutes. Next, after pressurizing to 392 kPa with nitrogen, the pressure was released to atmospheric pressure. Next, 30 parts by weight of ion-exchanged water was added to 100 parts by weight of the crude polyol D, and 50 parts by weight of Levatit S-100BG (manufactured by Bayer KK), which had been ion-exchanged to a hydrogen form, was added under nitrogen atmosphere. Stirring was performed at 60 ° C. for 5 hours. Thereafter, 100 parts by weight of the crude polyol D was added to 100 parts by weight.
After charging 0 ppm of BHT, dehydration was performed under reduced pressure.
Vacuum nitrogen bubbling was performed at 0 Pa for 4 hours.
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. packed with Celite to purify the polyoxyalkylene polyol. The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification operation is 55.
2 mg KOH / g, total unsaturation (C = C) 0.008 m
eq. / G, CPR was 2.3, and the residual amount of the catalyst in the polyol was 43 ppm.

Comparative Example 1 <Polyoxyalkylene polyol E> The crude polyol A obtained in Example 1 was charged into an autoclave under a nitrogen atmosphere, heated to 80 ° C., and the inside of the autoclave was evacuated to 2660 Pa at the same temperature. , And kept for 8 minutes under the same conditions. Next, after pressurizing to 392 kPa with nitrogen, the pressure was released to atmospheric pressure. Next, 5 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyol A, and then 0.4 mol of phosphoric acid (an aqueous solution of 75.1% by weight is added to 1 mol of the phosphazenium compound in the crude polyol A). Was quickly charged and a neutralization reaction was performed at 80 ° C. for 2 hours. After completion of the neutralization reaction, 1200 ppm of IRGAN based on 100 parts by weight of the crude polyol A
After loading OX1010, dehydration was performed under reduced pressure.
At 3.3 kPa, 0.05 parts by weight of the adsorbent AD-600 [manufactured by Yoshitomi Pharmaceutical Co., Ltd.] was quickly charged to 100 parts by weight of the crude polyol A. Finally, at a temperature of 105 ° C. and 2660 Pa, while nitrogen gas is passed through the liquid phase,
Vacuum nitrogen bubbling was performed for a time. After the pressure was reduced from nitrogen to atmospheric pressure by nitrogen, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol. The hydroxyl value (O) of the polyoxyalkylene polyol after the refining operation
HV) is 15.0 mgKOH / g, total unsaturation (C =
C) 0.022 meq. / G, CPR was 8.0, and the residual amount of the catalyst in the polyol was 175 ppm.

Comparative Example 2 <Polyoxyalkylene Polyol F> The crude polyol A obtained in Example 1 was charged into an autoclave under a nitrogen atmosphere, heated to 80 ° C., and the inside of the autoclave was depressurized to 2660 Pa at the same temperature. , And kept for 8 minutes under the same conditions. Next, after pressurizing to 392 kPa with nitrogen, the pressure was released to atmospheric pressure. Next, 2 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyol A, and then 0.1 mol of phosphoric acid (an aqueous solution of 75.1% by weight is added to 1 mol of the phosphazenium compound in the crude polyol A). Was quickly charged and a neutralization reaction was performed at 80 ° C. for 2 hours. After completion of the neutralization reaction, 1200 ppm of IRGAN based on 100 parts by weight of the crude polyol A
After loading OX1010, dehydration was performed under reduced pressure.
At 3.3 kPa, 0.02 parts by weight of the adsorbent AD-600 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was quickly charged to 100 parts by weight of the crude polyol A. Finally, at a temperature of 105 ° C. and 2660 Pa, while nitrogen gas is passed through the liquid phase,
Vacuum nitrogen bubbling was performed for a time. After the pressure was reduced from nitrogen to atmospheric pressure by nitrogen, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol. The hydroxyl value (O) of the polyoxyalkylene polyol after the refining operation
HV) is 15.1 mg KOH / g, total unsaturation (C =
C) 0.022 meq. / G, CPR was 9.2, and the residual amount of the catalyst in the polyol was 294 ppm.

Comparative Example 3 <Polyoxyalkylene Polyol G> The crude polyol B obtained in Example 2 was charged into an autoclave under a nitrogen atmosphere, heated to 80 ° C., and the inside of the autoclave was evacuated to 2660 Pa at the same temperature. , And kept for 8 minutes under the same conditions. Next, after pressurizing to 392 kPa with nitrogen, the pressure was released to atmospheric pressure. Next, 4 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyol B, and then 0.4 mol of phosphoric acid (75.1% by weight aqueous solution) is added to 1 mol of the phosphazenium compound in the crude polyol B. Was quickly charged and a neutralization reaction was performed at 80 ° C. for 2 hours. After completion of the neutralization reaction, 1200 ppm of IRGAN based on 100 parts by weight of the crude polyol B
After loading OX1076, dehydration was performed under reduced pressure.
At 3.3 kPa, 0.02 parts by weight of the adsorbent AD-600 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was quickly charged to 100 parts by weight of the crude polyol B. Finally, at a temperature of 105 ° C. and 2660 Pa, while nitrogen gas is passed through the liquid phase,
Vacuum nitrogen bubbling was performed for a time. After the pressure was reduced from nitrogen to atmospheric pressure by nitrogen, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol. The hydroxyl value (O) of the polyoxyalkylene polyol after the refining operation
HV) is 27.8 mg KOH / g, total unsaturation (C =
C) 0.020 meq. / G, CPR was 6.5, and the residual amount of the catalyst in the polyol was 160 ppm.

Comparative Example 4 <Polyoxyalkylene polyol H> The crude polyol B obtained in Example 2 was charged into an autoclave under a nitrogen atmosphere, heated to 80 ° C., and then the autoclave was evacuated to 2660 Pa at the same temperature. , And kept for 8 minutes under the same conditions. Next, after pressurizing to 392 kPa with nitrogen, the pressure was released to atmospheric pressure. Next, 20 parts by weight of ion-exchanged water is added to 100 parts by weight of the crude polyol B, and then 0.4 mol of oxalic acid (0.5 N aqueous solution is added to 1 mol of the phosphazenium compound in the crude polyol B). Was quickly charged and a neutralization reaction was performed at 80 ° C. for 2 hours. After completion of the neutralization reaction, 1200 ppm of IRGAN based on 100 parts by weight of the crude polyol B
After loading OX1076, dehydration was performed under reduced pressure.
At 3.3 kPa, 0.02 parts by weight of the adsorbent AD-600 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was quickly charged to 100 parts by weight of the crude polyol B. Finally, at a temperature of 105 ° C. and 2660 Pa, while nitrogen gas is passed through the liquid phase,
Vacuum nitrogen bubbling was performed for a time. After the pressure was reduced from nitrogen to atmospheric pressure by nitrogen, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol. The hydroxyl value (O) of the polyoxyalkylene polyol after the refining operation
HV) is 27.9 mg KOH / g, total unsaturation (C =
C) 0.020 meq. / G, CPR was 10.2, and the residual amount of the catalyst in the polyol was 350 ppm.

The results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1. <Explanation of Symbols in Table> The polyol in Table 1 is an abbreviation of polyoxyalkylene polyol, OHV is a hydroxyl value, and C = C is an abbreviation of total unsaturation. The remaining amount of the catalyst for producing the polyoxyalkylene polyol was defined as the amount of the remaining catalyst in the polyol.

[0103]

[Table 1] Next, isocyanate group-terminated prepolymers were synthesized using the polyoxyalkylene polyols (hereinafter abbreviated as polyols) obtained in Examples 1 to 4 and Comparative Examples 1 to 4.

Example 5 <Isocyanate-terminated prepolymer a and polyurethane elastomer> The polyol A610 obtained in Example 1 was placed in a 2000 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer under a nitrogen atmosphere. 0.4 g and 301.6 g of the polyol B obtained in Example 2,
Next, 88.1 g of 4,4'-diphenylmethane diisocyanate [manufactured by Mitsui Chemicals, Inc., trade name: Cosmonate PH, the same applies hereinafter], which was previously heated to 42 ° C., was charged and stirred, and then 1% by weight with dioctyl phthalate. Octob Zr [Hope Pharmaceutical Co., Ltd .; Was added thereto and reacted at 80 ° C. for 3 hours under a nitrogen atmosphere. Then, the mixture was stirred at 90 ° C. for 3 hours.
The reaction was continued at ℃ for 22 hours. After the reaction, the content of the flask was cooled to room temperature, 10.0 g of xylene was added, and the mixture was stirred. N of the obtained isocyanate group-terminated prepolymer
CO% is 1.22% and viscosity is 24,200 mPa · s /
25 ° C. and the residual amount of the catalyst in the prepolymer was 14 pp.
m. After defoaming the isocyanate group-terminated prepolymer under reduced pressure, it was poured into a Teflon-coated 2 mm thick mold and allowed to stand at room temperature for one day. Next, the resulting polyurethane elastomer was allowed to stand in an oven at 50 ° C. and a relative humidity of 70% for 5 days, cured at room temperature for 1 day, and then measured for physical properties of the obtained polyurethane elastomer. The measurement results of physical properties are shown in [Table 2].

Example 6 <Isocyanate group-terminated prepolymer b and polyurethane elastomer> The polyol A742. Obtained in Example 1 was placed in a 2000 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer under a nitrogen atmosphere. 7 g and 172.1 g of the polyol B obtained in Example 2 were charged,
Next, 85.2 g of 4,4'-diphenylmethane diisocyanate, which had been heated to 42 ° C. in advance, was charged and stirred, and 1.0 g of a catalyst solution was added, followed by a reaction at 80 ° C. for 3 hours under a nitrogen atmosphere. Then, the mixture was stirred at 90 ° C. for 3 hours.
The reaction was continued at ℃ for 22 hours. After the reaction, the content of the flask was cooled to room temperature, 10.0 g of xylene was added, and the mixture was stirred. N of the obtained isocyanate group-terminated prepolymer
CO% is 1.21% and viscosity is 18,500 mPa · s /
25 ° C. and the remaining amount of catalyst in the prepolymer was 15 pp.
m. After defoaming the isocyanate group-terminated prepolymer under reduced pressure, it was poured into a Teflon-coated 2 mm thick mold and allowed to stand at room temperature for one day. Next, the polyurethane elastomer was allowed to stand in an oven at 50 ° C. and a relative humidity of 70% for 5 days. After curing at room temperature for 1 day, physical properties of the polyurethane elastomer were measured. The measurement results of physical properties are shown in [Table 2].

Example 7 <Isocyanate group-terminated prepolymer c and polyurethane elastomer> The polyol C540. Obtained in Example 1 was placed in a 1000 ml four-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer under a nitrogen atmosphere. 2 g and 217.6 g of the polyol D obtained in Example 2 were charged,
Next, 242.2 g of 4,4′-diphenylmethane diisocyanate previously heated to 42 ° C. was charged and reacted at 80 ° C. for 6 hours under a nitrogen atmosphere. Further, at 60 ° C
For 18 hours. After the reaction, the contents of the flask were cooled to room temperature. The obtained isocyanate group-terminated prepolymer has an NCO% of 5.90% and a viscosity of 5,920 m
Pa · s / 25 ° C., and the residual amount of the catalyst in the prepolymer was 15 ppm. After heating the isocyanate group-terminated prepolymer to 65 ° C. and defoaming under reduced pressure, an amount of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) having an isocyanate index of 1.05 was charged, and then dioctyl phthalate was added. Then, 0.4 part by weight of a dibutyltin dilaurate solution diluted to 1% by weight was added to 100 parts by weight of the isocyanate group-terminated prepolymer, and the mixture was stirred for 1 minute. It was poured into a mold having a thickness of 2 mm, which had been heated to 100 ° C. in advance, and allowed to stand in an oven at 100 ° C. for 24 hours. Next, after curing at room temperature for 3 days, physical properties of the polyurethane elastomer were measured. The measurement results of physical properties are shown in [Table 2].

Comparative Example 5 <Isocyanate group-terminated prepolymer d and polyurethane elastomer> Using the same apparatus as in Example 5, the polyol E obtained in Comparative Example 1 was used instead of the polyol A,
The polyol G obtained in Comparative Example 3 was used in place of the polyol B, and an isocyanate group-terminated prepolymer was synthesized under the same charging amount and operating conditions as in Example 5. The NCO% of the obtained isocyanate group-terminated prepolymer was 1.
The viscosity was 20%, the viscosity was 45,500 mPa · s / 25 ° C., and the residual amount of the catalyst in the prepolymer was 147 ppm. After defoaming the isocyanate group-terminated prepolymer under reduced pressure,
The mixture was poured into a Teflon-coated 2 mm thick mold and allowed to stand at room temperature for one day. Then, at 50 ° C. and 70% relative humidity
R. H. In an oven for 5 days and then at room temperature for 1 day.
After curing, the physical properties of the polyurethane elastomer were measured. The measurement results of physical properties are shown in [Table 2].

Comparative Example 6 <Isocyanate group-terminated prepolymer e> Using the same apparatus as in Example 5, polyol F obtained in Comparative Example 2 was used instead of polyol A, and Comparative Example 4 was used instead of polyol B. Using the obtained polyol H, an isocyanate group-terminated prepolymer was synthesized under the same charging amount and operating conditions as in Example 5. Although the residual amount of the catalyst in the isocyanate group-terminated prepolymer was 259 ppm, the viscosity of the contents of the flask rapidly increased in the latter stage of the reaction and gelled, so that the NCO% and the viscosity could not be measured. Therefore, no elastomer was prepared.

Comparative Example 7 <Isocyanate Group-Ended Prepolymer f and Polyurethane Elastomer> Using the same apparatus as in Example 5, the polyol obtained in Comparative Example 4 was replaced with the polyol A and Polyol B obtained in Example 1. Using H, an isocyanate group-terminated prepolymer was synthesized under the same charging amount and operating conditions as in Example 5. The obtained isocyanate group-terminated prepolymer has an NCO% of 1.19% and a viscosity of 39,80.
It was 0 mPa · s / 25 ° C., and the residual amount of the catalyst in the prepolymer was 95 ppm. After defoaming the isocyanate group-terminated prepolymer under reduced pressure, Teflon-coated 2 mm thick
And left to stand at room temperature for one day. Then 5
After standing in an oven at 0 ° C. and a relative humidity of 70% for 5 days, and curing at room temperature for 1 day, physical properties of the polyurethane elastomer were measured. The measurement results of physical properties are shown in [Table 2].

<Explanation of Symbols in Table> The prepolymer in Table 2 is an abbreviation of an isocyanate group-terminated prepolymer. The remaining amount of the catalyst for producing a polyoxyalkylene polyol in the isocyanate group-terminated prepolymer was defined as the remaining amount of the catalyst in the prepolymer. The curing mode in the table is
In the case of being prepared by moisture curing, in the notation of moisture, when prepared by reacting with an active hydrogen compound having a number of functional groups greater than 1, 1,4-BD which is an abbreviation of 1,4-butanediol used as a curing agent is used. did. 1,4-BD is a glycol having two functional groups.

Next, the isocyanate group-terminated prepolymers obtained in the examples and the comparative examples were mixed with a metal 1
The container was sealed in an L container and left in an oven at 60 ° C. for 14 days to perform a storage stability test. After the storage stability test, the prepolymer was cooled to room temperature, and the viscosity of the prepolymer and the NCO% were measured. The viscosity before the test was subtracted from the viscosity after the storage stability test, and the value obtained by dividing the value by the viscosity before the test and multiplying by 100 was used as the viscosity increase rate (unit%) of the prepolymer to evaluate the storage stability. . The case where the prepolymer viscosity increase rate was 20% or less was evaluated as ○, and the case where it was larger than 20% was evaluated as ×.
Furthermore, a polyurethane elastomer was prepared using the prepolymer after the storage stability test, and the physical properties were measured. The results obtained are shown in [Table 2].

[0112]

[Table 2]

<Consideration 1 of Examples> [Table 2] shows that the remaining amount of the catalyst in the polyoxyalkylene polyol (in the table,
It is the notation of the amount of catalyst remaining in the prepolymer. In the isocyanate group-terminated prepolymer using a polyol having a large content of ()), the viscosity of the prepolymer is high (Example 5 and Comparative Examples 5 and 7). Further, in the case of a polyurethane elastomer using a prepolymer having a residual amount of catalyst exceeding 120 ppm, the weather resistance and thermal stability are reduced. This gives a polyurethane elastomer with excellent properties.

Examples 8 to 10, Comparative Examples 8 to 9 Using the isocyanate group-terminated prepolymer after the storage stability test, polyurethane elastomers were prepared in the same manner as described above. The physical properties of the obtained polyurethane elastomer were measured by the above methods, and the results are shown in [Table 3].

[0115]

[Table 3]

<Consideration 2 of Example> The remaining amount of the catalyst is 120 p.
When the prepolymer is less than pm, the rate of increase in the viscosity of the prepolymer after 14 days at 60 ° C. is low and the storage stability is excellent. Furthermore, when the prepolymer is used, a polyurethane elastomer having a small difference from the initial physical properties and excellent mechanical properties can be obtained.

[0117]

According to the present invention, the residual amount of the phosphazenium compound catalyst is 150 ppm or less, and the total unsaturation, which indicates the monool content in the polyol, is 0.07 me.
q. / G or less, and the CPR of the polyol is 5 or less. By using the polyoxyalkylene polyol having the above properties provided by the present invention, an isocyanate group-terminated prepolymer having excellent storage stability can be obtained when the isocyanate group content is in the range of 0.3 to 30% by weight. . Further, by reacting the isocyanate group-terminated prepolymer with an active hydrogen compound having a functional group number greater than 1 in an isocyanate index of 0.5 to 2.0, a polyurethane elastomer having excellent mechanical properties and heat stability can be obtained. In addition to being obtained, the isocyanate group-terminated prepolymer of the present invention having an isocyanate group content of 0.3 to 3% by weight is used as a curing component, and is reacted with moisture in the air to obtain mechanical properties, heat stability, and weather resistance. The present invention can provide a moisture-curable polyurethane elastomer having excellent properties and the like. The isocyanate group-terminated prepolymer of the present invention can be used in a wide range of fields such as paints, adhesives, flooring waterproofing materials, sealing agents, shoe soles, elastic reinforcing agents and rollers and timing belts.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Sanji Takagi, 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside of Mitsui Chemicals Co., Ltd. Within Chemical Co., Ltd. (72) Inventor Saku Izukawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Chemicals, Inc.

Claims (7)

[Claims] An isocyanate group-terminated prepolymer obtained by reacting a polyol component with a polyisocyanate compound, wherein at least one of the polyol components is prepared by adding an epoxide compound to an active hydrogen compound in the presence of a phosphazenium compound catalyst. A polyoxyalkylene polyol produced by addition polymerization, wherein the residual amount of the phosphazenium compound catalyst in the prepolymer is 120 pp.
m or less, and isocyanate group-terminated prepolymer. 2. The polyoxyalkylene polyol has a phosphazenium compound catalyst having a remaining amount of 150 pp.
m or less, and the total degree of unsaturation is 0.07 meq. / G or less, and CPR is 5 or less, The isocyanate group-terminated prepolymer according to claim 1, characterized in that: 3. The isocyanate group-terminated prepolymer according to claim 1, wherein the polyol component contains at least 30% by weight of the polyoxyalkylene polyol. 4. The isocyanate group-terminated prepolymer according to claim 1, wherein the content of the isocyanate group in the prepolymer is 0.3 to 30% by weight. 5. A polyoxyalkylene polyol produced by addition polymerization of an epoxide compound to an active hydrogen compound in the presence of a phosphazenium compound catalyst, wherein the remaining amount of the phosphazenium compound catalyst is 150 pp.
m or less, and the total degree of unsaturation is 0.07 meq. / G and CPR of 5 or less. 6. The reaction of the isocyanate group-terminated prepolymer according to claim 1 with an active hydrogen compound having an isocyanate index of 0.5 to 2.0 and a functional group number of more than 1 Polyurethane elastomer obtained by 7. An isocyanate group content of 0.3 to 3
A moisture-curable polyurethane elastomer comprising the isocyanate group-terminated prepolymer according to any one of claims 1 to 3 as a curing component.