JPH11217431A - Method for producing phenolic polyol, and method for producing polyurethane resin and polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a phenolic polyol which does not require complicated post-reaction treatment and has a high terminal primary hydroxylation rate, and a method for producing a polyurethane resin and a polyurethane foam using the same. I will provide a. A method for producing a phenolic polyol for adding an alkylene oxide to a phenolic compound, comprising the steps of:
The phenolic compound is reacted with 5 to 50% by weight of an alkylene oxide containing at least 50% by weight of an alkylene oxide having 3 or more carbon atoms, and then ethylene oxide is added in an amount of 1 mol per mole of hydroxyl group of the obtained reaction product. A method for producing a phenolic polyol characterized by reacting 3 to 10 moles, and a method for producing a polyurethane resin and a polyurethane foam using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a phenolic polyol, and a method for producing a polyurethane resin and a polyurethane foam using the method for producing a phenolic polyol. Specifically, in the presence of a basic catalyst,
At a relatively low temperature of 80 to 150 ° C., first, an alkylene oxide having 3 or more carbon atoms such as propylene oxide is added to a phenolic compound such as bisphenol A, and then ethylene oxide is added to the obtained reaction product. Method for producing a phenolic polyol having a simple alkylene oxide addition polymerization operation and having a high terminal primary hydroxylation rate, and methods for producing a polyurethane resin and a polyurethane foam using the method for producing a phenolic polyol About.

[0002]

2. Description of the Related Art As a method for producing a phenolic polyol by adding an alkylene oxide to a phenolic compound, generally, a method of reacting at a temperature higher than the melting point of the phenolic compound, or a method of dissolving or using a solvent. Methods performed in a dispersed system are known. As the solvent, an inert solvent having low reactivity with the alkylene oxide is used.

[0003] Phenolic compounds such as bisphenol A are easily decomposed at high temperatures above their melting points. As an improved method of these oxyalkylation, for example, Japanese Patent Publication No.
No. 29308 discloses a method of adding an alkylene oxide to a molten phenolic compound at a high temperature of 160 to 185 ° C. using a lithium catalyst such as lithium hydroxide or lithium acetate. Although the decomposition of the phenolic compound can be suppressed to some extent by using a lithium catalyst, by-products are easily generated because the reaction conditions are severe at high temperatures.

On the other hand, there is a method of adding an alkylene oxide to a phenolic compound in a solvent-free or inert solvent using a basic catalyst, but the reaction between the basic catalyst and the phenolic hydroxyl group is difficult to proceed. To
The reaction speed becomes slow. Therefore, it is necessary to react at a high temperature equal to or higher than the melting point of the phenolic compound or to increase the amount of the catalyst. However, the reaction conditions become relatively severe, the reaction selectivity between the phenolic hydroxyl group and the alcoholic hydroxyl group decreases, the addition molar distribution width of the alkylene oxide increases, and the residual phenolic hydroxyl group increases. have.

As a method of adding an alkylene oxide to a phenolic compound under mild conditions at the expense of a decrease in the reaction rate, a method of usually dissolving the phenolic compound in a solvent and reacting the alkylene oxide in the presence of a catalyst is known. It has been known. As the solvent, a solvent capable of dissolving the phenolic compound, for example, an organic solvent such as toluene is used, but the solvent is flammable, the recovery of the solvent is complicated, and the recovery of the solvent is sufficiently performed. It is difficult to achieve sufficient economic efficiency and quality due to the fact that some of them remain in the polyol.

Further, a method has been reported in which water is used as a dispersing solvent to react with a specific amount of alkylene oxide in the presence of a catalyst (Japanese Patent Application Laid-Open No. Sho 60-48942 and Japanese Patent No. 2543522). However, since water undergoes an addition reaction with the alkylene oxide, it must be removed by vacuum removal or the like after completion of the reaction, which not only consumes a large amount of heat source but also requires a long time. In addition, urethane foam having sufficient mechanical strength cannot be obtained due to the influence of by-produced propylene glycol and the like. When an organic solvent is used as a reaction medium, not only a large amount of heat source is consumed due to removal under reduced pressure, but also a long time is required for production.

[0007]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a reaction at a relatively low temperature without using a special catalyst and a solvent, thereby eliminating the need for a complicated alkylene oxide addition polymerization step. Another object of the present invention is to provide a method for producing a phenolic polyol having a high terminal primary hydroxylation rate. It is another object of the present invention to provide a method for producing a polyurethane resin and a polyurethane foam using the method for producing a phenolic polyol.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, in the presence of a basic catalyst,
The phenolic compound is first reacted with a specific amount of an alkylene oxide having an alkylene oxide having 3 or more carbon atoms as a main component, and then the obtained reactant is reacted with a specific amount of ethylene oxide to obtain the above-mentioned product. The inventor found that the object could be achieved and reached the invention.

That is, the first invention of the present invention is a method for producing a phenolic polyol in which an alkylene oxide is added to a phenolic compound, the method comprising the steps of: producing a phenolic polyol at 80 to 150 ° C. in the presence of a basic catalyst; 5 to 50 alkylene oxides containing at least 50% by weight of an alkylene oxide having 3 or more carbon atoms.
% By weight, and then reacting 1.3 to 10 moles of ethylene oxide per mole of hydroxyl group of the obtained reaction product.

[0010] The second invention of the present invention is a method for producing a polyurethane resin in which a phenolic polyol is produced by the above-mentioned method and then the obtained phenolic polyol is reacted with polyisocyanate. Further, the third invention of the present invention provides a method for producing a phenolic polyol by the above method, and then reacting the obtained phenolic polyol with a polyisocyanate in the presence of a catalyst, a foaming agent and a foam stabilizer. It is a manufacturing method.

A feature of the first invention of the present invention is that, when an alkylene oxide is added to a phenolic compound, firstly, an alkylene oxide mainly containing an alkylene oxide having 3 or more carbon atoms such as propylene oxide is added, Then, the ethylene oxide is added. Further, the reaction temperature is lower than the melting point of the phenolic compound, and is relatively low. Further, there is no use of a reaction solvent.

The phenolic polyol obtained by the first invention of the present invention does not contain a decomposition product of a phenolic compound. The terminal primary hydroxylation rate is 90% or more, which is extremely high. When adding an alkylene oxide, it is not necessary to use a reaction solvent in order to add an alkylene oxide having an alkylene oxide having three or more carbon atoms as a main component such as propylene oxide. It is highly safe and does not require complicated post-treatment after the reaction. Further, the polyurethane resin and the polyurethane foam obtained by the other invention of the present invention have excellent mechanical properties such as dimensional stability and compressive strength.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the method for producing the phenolic polyol of the present invention will be described. The outline of the method for producing the phenolic polyol of the present invention is as follows.In the presence of a basic catalyst, at a specific temperature, first, a phenolic compound is prepared by adding a specific amount of an alkylene oxide having an alkylene oxide having 3 or more carbon atoms as a main component. After the reaction, the obtained reactant is reacted with a specific amount of ethylene oxide.

The phenolic compounds used in the present invention include bisphenol A, bisphenol F, 2,2-bis (4-hydroxyphenyl) butane, bisphenol S, novolak, resole, hydroquinone, resorcinol, halogenated bisphenol (for example, Bromobisphenol A, tetrachlorobisphenol A, tetrabromobisphenol S) and the like. These may be used in combination of two or more. Among them, bisphenol A, bisphenol F, 2,2-bis (4-hydroxyphenyl) butane, bisphenol S (hereinafter, these are referred to as bisphenols) and the like are preferable. More preferably, bisphenol A is used. Commercially available products include Bisphenol A and the like, manufactured by Mitsui Chemicals, Inc.

The alkylene oxide having 3 or more carbon atoms used in the present invention includes propylene 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, styrene oxide and the like are preferable.

The basic catalyst used for the reaction between the phenolic compound and the alkylene oxide includes alkali metals, alkaline earth metals and amine compounds. Examples of the alkali metals and alkaline earth metals include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide. Are alkali metal or alkaline earth metal hydroxides of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate,
It is a carbonate of an alkali metal or an alkaline earth metal such as magnesium carbonate, calcium carbonate or barium carbonate, and a hydrogen carbonate such as potassium hydrogen carbonate, sodium hydrogen carbonate and cesium hydrogen carbonate.

Examples of the amine compound include triethylamine, dimethylethanolamine, pyridine, methyldimethylamine, tri-n-propylamine, dimethylpalmitylamine, and dimethyloctylamine. These catalysts can be used alone or in combination of two or more. The amount of the basic catalyst used is 0.01 to 10 parts by weight based on 100 parts by weight of the phenolic compound.

In the present invention, first, in the presence of the above-mentioned basic catalyst, an alkylene oxide mainly containing an alkylene oxide having 3 or more carbon atoms is reacted with the phenolic compound. The amount of the alkylene oxide containing an alkylene oxide having 3 or more carbon atoms as a main component is 5 to 50% by weight based on the phenolic compound. If it is less than 5% by weight, the stirring load of the reactor becomes large, which is not practical. On the other hand, if it exceeds 50% by weight, mechanical properties such as dimensional stability and compressive strength of the polyurethane resin and polyurethane foam obtained from the phenolic polyol of the present invention tend to decrease.

The alkylene oxide having 3 or more carbon atoms may be mixed with ethylene oxide. The mixing amount of ethylene oxide is preferably 50% by weight or less. If it exceeds 50% by weight, the synthesis time of the phenol-based polyol becomes long, which is not preferable.

Next, the obtained reaction product is reacted with ethylene oxide. The amount of the ethylene oxide to be used is preferably 1.3 to 10 mol per 1 mol of a hydroxyl group of a reaction product obtained by adding an alkylene oxide containing an alkylene oxide having 3 or more carbon atoms as a main component.
If it is less than 1.3 mol, the terminal primary hydroxylation rate will be less than 90%, and the urethane-forming reaction will be slow. When it exceeds 10 moles, the polyurethane resin obtained from the phenolic polyol of the present invention, the dimensional stability of the polyurethane foam,
It tends to decrease mechanical properties such as compressive strength.

Alkylene oxa to phenolic compound
The addition reaction of the id is carried out in a temperature range of 80 to 150 ° C.
It is. Preferably, the temperature range is 90 to 130 ° C. Anti
When the reaction temperature falls below 80 ° C, the reaction of alkylene oxide
Response time becomes longer. If the reaction temperature exceeds 150 ° C,
The product is increased. Maximum reaction pressure is 10kgf / cm ^Two
(980 kPa). More preferably, 7 kgf / c
m^Two(686 kPa), most preferably 6 kgf / cm^Two
(588 kPa). Reaction pressure is 10kgf / cm
^Two(980 kPa), the by-products increase.
You.

In the method for producing a phenolic polyol of the present invention, a known post-treatment is preferably carried out in order to remove the remaining basic catalyst after the above reaction. As a post-treatment method for removing the basic catalyst, the following method may be mentioned.

A method of treating with at least one neutralizing agent selected from inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid, organic acids such as formic acid, acetic acid, oxalic acid, succinic acid, phthalic acid and maleic acid, and carbon dioxide. . Levatit MP500, Levatit M500, Levatit M504, Levatit MP6
00, Levatit MP500A (manufactured by Bayer), DIAION PA406, DIAION PA408, DIAION PA412 (manufactured by Mitsubishi Chemical Corporation), Amberlite I
A method of treating with an ion exchange resin commercially available under various trade names such as RA430, Amberlite IRA458, Amberlite IRA900 (manufactured by Rohm and Haas).

Tomix AD series, for example, Tomix AD-600, Tomix AD-700 (manufactured by Tomita Pharmaceutical), Kyoward series, for example, Kyoward 30
0, Kyoward 400, Kyoward 500, Kyoward 600, Kyoward 700, Kyoward 2000 (manufactured by Kyowa Chemical Industry), MAGNESOL (manufactured by DALLAS)
A method of treating with a commercially available adsorbent under various trade names. Alternatively, a method using the above-described neutralization treatment and an adsorbent in combination. Purification method using a solvent inert to water and polyol, or a mixture thereof, and the like.

For the purpose of stabilizing the quality of the polyol,
After the above purification treatment, an antioxidant such as t-butylhydroxytoluene (BHT) may be added. The antioxidant is usually added to 10 parts by weight of the polyol.
Use 0 to 5000 ppm.

The phenolic polyol produced by the present invention has a hydroxyl value (hereinafter abbreviated as OHV) of 60 to 60.
620 mg KOH / g, preferably 150-500 mg
KOH / g, most preferably 200-400 mg KOH
/ G. If the OHV exceeds 620 mgKOH / g, the viscosity of the polyol increases, and, for example, when polyurethane is produced, the miscibility with the polyisocyanate compound decreases. The terminal primary hydroxylation rate of the phenolic polyol produced by the present invention is 90 to 100%, preferably 95 to 100%. 90% primary hydroxylation rate
If it is less than 1, the urethanization reaction rate is significantly reduced.
The phenolic polyol produced according to the present invention is of high quality without such adverse effects.

Usually, a polyurethane resin is produced by reacting an active hydrogen compound with a polyisocyanate. Further, a polyurethane foam is produced by reacting an active hydrogen compound with a polyisocyanate in the presence of a catalyst, a foaming agent and a foam stabilizer.

A phenolic polyol is produced by the method of the present invention, and a polyurethane foam and a polyurethane resin can be produced by using the obtained phenolic polyol as an active hydrogen compound.

That is, a phenolic polyol is produced by the above method, and then a polyisocyanate is reacted with the obtained phenolic polyol in the presence of a catalyst, a foaming agent and a foam stabilizer to produce a polyurethane foam. can do. Further, a polyurethane resin can be produced by reacting the obtained phenolic polyol with a polyisocyanate.

In producing the polyurethane foam and the polyurethane resin, the phenolic polyol produced by the above method may be used in combination with another polyol. Examples of the polyols that may be used in combination include polyoxyarylene polyols in which an alkylene oxide has been added to a compound such as a polyhydric alcohol, an aromatic amine, a polyamine, or an alkanolamine by the method described above, and a mixture of two or more thereof. Can be Furthermore, polyols such as polymer-dispersed polyols, polyester polyols, polytetramethylene glycol, polycarbonate polyols, and polybutadiene-based polyols that may be used in combination are also included.

The hydroxyl value of the other polyols which may be used in combination is preferably from 10 to 700 mgKOH / g. More preferably, 15 to 600 mgKOH / g
It is. Although a method for producing a polyurethane foam will be described later, when a rigid polyurethane foam is produced, a hydroxyl value is in a high range in the above range, and when a flexible polyurethane foam is produced, a hydroxyl value is in the above range. Are preferably used. The mixing amount of other polyols that may be used in combination may be such that they account for 98% by weight of the total polyols. Preferably, it is 50% by weight or less in the total polyol. That is, the proportion of the phenolic polyol obtained in the present invention is preferably 50 to 100% by weight. Hereinafter, the phenol-based polyol obtained by the method of the present invention and a mixture of the phenol-based polyol and another polyol are collectively referred to as an active hydrogen compound.

A method for producing a polyurethane foam will be described. The active hydrogen compound obtained as described above is mixed with a predetermined amount of a catalyst, a foaming agent, a foam stabilizer, and an auxiliary agent such as a crosslinking agent according to the purpose, and mixed to form a mixture (hereinafter abbreviated as resin solution) Is prepared and adjusted to a predetermined temperature, for example, 20 to 30 ° C. A polyisocyanate is mixed with the obtained resin solution. At that time, the NCO group of the polyisocyanate and the active hydrogen in the resin solution were measured according to a predetermined equivalent ratio,
The temperature is adjusted to a predetermined temperature, for example, 20 to 30C. As a molding method, a method of rapidly mixing a resin solution and a polyisocyanate and injecting the mixture into a mold whose temperature is controlled to a predetermined temperature, for example, 20 to 70 ° C., and a method of directly mixing a resin solution and a polyisocyanate compound with each other are used. And a method of spraying and shaping the material (spray method).

Examples of the polyisocyanate used for producing the polyurethane foam include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
80/20 weight ratio of these organic polyisocyanates (T
DI-80 / 20), 65/35 weight ratio (TDI-65
/ 35), any isomers of crude tolylene diisocyanate containing polyfunctional tar, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, diphenylmethane diisocyanate Mixture, crude MDI (polymeric MDI) containing tri- or higher polyfunctional tar, toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and carbodiimide-modified, burette-modified products of these organic polyisocyanates,
Alternatively, prepolymers and the like, which are modified with a polyol or a monol alone or in combination, may be mentioned. The above polyisocyanates can be used in a mixture at an arbitrary ratio.

The equivalent ratio between the polyisocyanate and the active hydrogen compound is not particularly limited, but is based on the NCO group in the polyisocyanate and the active hydrogen compound, and active hydrogen such as water as a blowing agent. NCO / H (active hydrogen) is preferably in the range of 0.50 to 4.0 (hereinafter, referred to as NCO / H (active hydrogen)).
NCO index).

The foaming agent used for producing a polyurethane foam is slightly different between a flexible polyurethane foam and a rigid polyurethane foam. When producing a flexible polyurethane foam, water may be used alone as the foaming agent, but when producing a rigid polyurethane foam,
Depending on the required thermal insulation performance of the foam, water, low-boiling hydrocarbon compounds, hydrochlorofluorocarbons (hereinafter, referred to as
HCFCs), hydrofluorocarbons (hereinafter abbreviated as HFCs), fluorocarbons (hereinafter abbreviated as F
C), or at least one compound of fluorinated ethers.

The amount of the foaming agent used is 1 to 9 parts by weight based on 100 parts by weight of the active hydrogen compound when the foaming agent is water alone. Low boiling point hydrocarbon compounds, HCFCs,
When at least one selected from HFCs, FCs, and fluorinated ethers is used, 1 to 40 parts by weight is used per 100 parts by weight of the active hydrogen compound.

The low-boiling hydrocarbon compounds include cyclopentane, n-pentane, isopentane and the like. As HCFCs, HCFC-141b is HF
For Class C, HFC-134a, HFC-356 or H
FC-245fa and the like, and FCs such as C5F12. Examples of the fluorinated ethers include JP-A-4-2
No. 8729 can be used.

Examples of the catalyst include amine catalysts such as triethylamine, tripropylamine, tributylamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, Dimethylcyclohexylamine, bis [2
[(Dimethylamino) ethyl] ether, triethylenediamine, triethylenediamine salts, etc., as organometallic catalysts, tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyl Examples include tin dichloride, lead octanoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate. These catalysts can be arbitrarily mixed and used. The amount used is 0.0001 to 10.0 parts by weight based on 100 parts by weight of the active hydrogen compound.

As the foam stabilizer, conventionally known organic silicon-based surfactants are preferably used. For example, trade names made by Nippon Unicar: L-501, L-532, L-540, L-5
44, L-544, L-550, L-3550, L-5
302, L-5305, L-5320, L-5340,
L-5410, L-5420, L-5421, L-57
10, SZ-1642, SZ-1627, SZ-192
3 etc., trade name: SH-190, manufactured by Toray Silicone Co., Ltd.
SH-192, SH-193, SH-194, SH-1
95, SH-200, SPX-253, etc., manufactured by Shin-Etsu Silicone Co., Ltd .: F-114, F-121, F-12
2, F-220, F-230, F-258, F-260
B, F-317, F-341, F-343, F-34
5, F-347, F-348, F-350S, etc., trade names made by Toshiba Silicone Co., Ltd .: TFA-4200, TFA-4
202 and the like. These foam stabilizers can be arbitrarily mixed and used. The used amount is 0.1 to 10 parts by weight based on 100 parts by weight of the active hydrogen compound.

Depending on the purpose, the following crosslinking agents, flame retardants and the like can be used. Examples of the crosslinking agent include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol,
Polyols such as 4-butanediol, alkanolamines such as triethanolamine and diethanolamine,
Aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine, aniline, 2,4
Aromatic polyamines such as -tolylenediamine and 2,6-tolylenediamine, and compounds having a hydroxyl value of 200 mgKOH / g or more obtained by adding ethylene oxide, propylene oxide or the like to these compounds. The amount used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the active hydrogen compound.

A flame retardant may be used depending on the purpose of use of the polyurethane foam. Examples of the flame retardant include tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, tris (2,2-chloroethyl) phosphate, hexabromocyclododecane, and a product manufactured by Daihachi Chemical Co., Ltd. Name: CR-505 and CR-507, trade names manufactured by Monsanto Chemical Co., Ltd .: Phosgard2XC-20 and C-22-R, trade names manufactured by Stoffer Chemical Co., Ltd .: Fyro
11-6 and the like. The amount used is 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the active hydrogen compound.

Next, a method for producing a polyurethane resin will be described. Representative methods for producing a polyurethane resin include the following two methods (a) and (b).
(A) A method in which an active hydrogen compound, a polyisocyanate and a chain extender are simultaneously mixed and molded (hereinafter, abbreviated as a one-shot method). (B) A method in which an active hydrogen compound is reacted with a polyisocyanate to synthesize a prepolymer having an isocyanate group at a molecular terminal, and a chain extender is reacted with the prepolymer to form a prepolymer (hereinafter, abbreviated as prepolymer method). Do).

When the OHV of the phenolic polyol obtained according to the present invention is high in the above-mentioned range, specifically,
When it is 200 mgKOH / g or more, the method (a) is preferable. When the OHV is low in the above-mentioned range, specifically, when the OHV is 300 mgKOH / g or less, the method (b) is preferable.

The polyisocyanate used for producing the polyurethane resin is the same as the polyisocyanate used for producing the polyurethane foam. The amount used will be described later. Examples of the chain extender include the same as the above-mentioned cross-linking agent. The amount used is the active hydrogen compound 10
0.1 to 20 parts by weight with respect to 0 parts by weight.

(A) In the case of the one-shot method, the polyol that may be used in combination with the phenolic polyol is the same as the polyol described above. However, for example, since the polyester polyol and polytetramethylene glycol are incompatible depending on the mixing ratio, the appearance of the mixture may become cloudy.
Conduct after understanding the physical properties. The molding temperature is -2
A temperature range from 0 to 150C is preferred.

(B) In the case of the prepolymer method, the polyol which may be used in combination with the phenolic polyol is the same as the polyol described above. In the case of the prepolymer method, when producing a prepolymer (hereinafter referred to as an isocyanate group-terminated prepolymer), the NCO index is 1.3 to 20.0, preferably 1.4 to 12.0,
More preferably, the polyisocyanate is used in such an amount that it becomes 1.5 to 9.0. Free isocyanate group content of the isocyanate group-terminated prepolymer (hereinafter referred to as NC
O%) is 0.1 to 40.0% by weight, preferably 0.3 to 25.0% by weight, more preferably 0.4 to 4% by weight.
It is preferably 18.0% by weight.

In the isocyanate group-terminated prepolymer used in the one-pack type curable composition obtained by using moisture in the air as a curing agent, the NCO% is preferably in the low range of the above range. Further, it is used for a two-part curable composition using a curing agent containing glycols such as 1,4-butanediol and polyoxyalkylene polyol, and polyamine compounds such as 3,3′-dichloro-4,4′-diaminodiphenylmethane. In the isocyanate group-terminated prepolymer to be obtained, the NCO% is preferably designed to be higher within the above range as compared with the one-pack type.

The temperature for 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. Under nitrogen atmosphere 2
The reaction is carried out with stirring for ２０20 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, an organometallic catalyst is particularly preferable. The amount used is 0.0001 to 2.0 parts by weight, preferably 0.01 to 1.0 part by weight, based on 100 parts by weight of the active hydrogen compound.

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

[0050]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. “Parts” in the examples represent parts by weight.
Each characteristic value shown in the examples was measured by the following method. (1) Viscosity of polyol (cps) It is measured with a B-type viscometer according to the polyurethane polyether test method specified in JIS K-1557. (2) Primary hydroxylation rate of terminal (%) The polyol is acetylated and measured by 90 MHz proton nuclear magnetic resonance (NMR) speckle. (3) Reactivity (sec.) When producing a polyurethane foam in the same manner as in Example 2 described later and Comparative Examples 4 to 6, a reaction in a container is observed, and a time at which foaming is started. The cream time (CT), the time when the resin becomes a gel and the resin is stretched to draw a thread, the gel time (GT), and the time when the resin surface becomes non-sticky and the tack free time (TFT) are measured. .

(4) Low temperature dimensional stability (%) The polyurethane foams obtained in Example 2 and Comparative Examples 4 to 6 described below were cured at room temperature for 24 hours, and then 10 cm
A sample is cut out into a shape of × 10 cm × 5 cm, the apparent density is measured, and the volume change rate after standing at −30 ° C. for 24 hours is measured to evaluate the low-temperature dimensional stability.
The physical property test method is as follows. (5) Density (kg / m ³ ) After curing the polyurethane foams obtained in Example 2 and Comparative Examples 4 to 6 described below at room temperature for 24 hours, 10 cm
A test piece is prepared in a shape of × 10 cm × 5 cm. The test piece is measured by a method specified in ASTM D-16259T. (6) Compressive strength (kg / cm ² ) ASTM-162 for the same test specimen as in (5) above
It is measured by the method specified in 159T.

Example 1 563.7 parts of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) and 2.0 parts of potassium hydroxide were placed in an autoclave equipped with a stirrer, and propylene oxide was added. Add 84.6 parts and stir with 10
The reaction was performed at 0 ° C. Further, the reaction temperature is maintained and the reaction is continued for 4 hours. Subsequently, 351.7 parts of ethylene oxide are introduced over a period of 4 hours. Further, the reaction temperature is maintained and the reaction is continued for 2 hours. After completion of the polymerization, post-treatment A (neutralization, dehydration, filtration) was performed for purification. The obtained phenolic polyol had a hydroxyl value of 277 mgKOH / g, a viscosity of 14,
000 cps / 25 ° C., the primary hydroxylation rate at the molecular end was 95% (EO content: 81% by weight). Total reaction time: 10 hours, time required for post-treatment A: 5 hours, total production time: 15 hours. The reaction was allowed to proceed easily, and the post-treatment after the completion of the polymerization was extremely simple.

Comparative Example 1 Bisphenol A 563.8 parts, sodium acetate 1.6
7 parts and 422.8 parts of water are placed in an autoclave equipped with a stirrer, the mixture is heated to 90 ° C., and 64.4 parts of ethylene oxide are introduced over 3 hours. Further, the reaction temperature is maintained and the reaction is continued for 2 hours. After polymerization, post-treatment B
(Washing, dehydration under reduced pressure) was performed to obtain an ethylene oxide reactant. The obtained ethylene oxide reactant 231.
2 parts and 3.0 parts of potassium hydroxide are placed in an autoclave equipped with a stirrer, the mixture is heated to 120 ° C., and 371.8 parts of ethylene oxide are introduced over 4 hours. Further, the reaction temperature is maintained and the reaction is continued for 2 hours. After completion of the polymerization, post-treatment A (neutralization, dehydration, filtration) was performed for purification. The obtained phenolic polyol had a hydroxyl value of 273 mg.
The KOH / g, the viscosity was 11,000 cps / 25 ° C., and the primary hydroxylation rate at the molecular terminals was 100% (EO content: 100% by weight). Total reaction time: 11 hours, time required for post-treatment A: 5 hours, time required for post-treatment B: 10 hours, total production time:
26 hours. After the completion of the first ethylene oxide addition reaction, post-treatment B was required, the process was complicated, and it took about 10 hours. The post-treatment B is performed by adding 500 ml of water and stirring for 90 minutes.
Heated to 30 ° C. (time required: 30 minutes) and stirring was continued for 30 minutes. Then, it cooled to 30 degreeC (time required: 30 minutes). The reaction product was solidified, and the upper aqueous phase was removed from the system (required time: 30 minutes). This operation was repeated three times.
Next, the mixture was heated to 90 ° C., decompressed and degassed for 2 hours to 10 mmHg, and further reduced to 2 mm at 10 mmHg.
The degassing was continued for a time to degas.

Comparative Example 2 Bisphenol A 200.0 parts, potassium hydroxide 0.6
9 parts are placed in an autoclave equipped with a stirrer, the mixture is heated to 100 ° C., and 145.1 parts of propylene oxide are introduced over 3 hours. Further, the reaction temperature is maintained and the reaction is continued for 3 hours. After completion of the polymerization, post-treatment A (neutralization, dehydration, filtration) was performed for purification. The obtained phenolic polyol had a hydroxyl value of 280 mgKOH / g, a viscosity of 90,
000 cps / 25 ° C., lower than the detection limit of primary hydroxylation rate at molecular terminals (EO content: 0% by weight). Total reaction time: 6 hours, time required for post-treatment A: 5 hours,
Total production time: 11 hours. The post-treatment after the polymerization was simple, but a phenolic polyol having a high primary hydroxylation rate at the molecular terminals could not be obtained.

Comparative Example 3 Bisphenol A 563.7 parts, potassium hydroxide 2.0
The mixture was placed in an autoclave equipped with a stirrer, 165.1 parts of propylene oxide was added, and the mixture was added at 100 ° C. with stirring. Further, the reaction temperature is maintained and the reaction is continued for 4 hours. Subsequently, 271.2 parts of ethylene oxide are introduced over a period of 4 hours. Further, the reaction temperature is maintained and the reaction is continued for 2 hours. After completion of the polymerization, post-treatment A (neutralization, dehydration, filtration) was performed for purification. The obtained phenol resin polyol had a hydroxyl value of 276 mgKOH / g and a viscosity of 21,000 cps.
/ 25 ° C., the primary hydroxylation rate at the molecular end was 88% (EO
Content 62% by weight). Total reaction time: 10 hours, time required for post-treatment A: 5 hours, total production time: 15 hours. The post-treatment after the polymerization was simple, but a phenolic polyol having a high primary hydroxylation rate at the molecular terminals could not be obtained.

Example 2, Comparative Examples 4 to 6 The phenolic polyol obtained in Example 1, the polyol obtained in Comparative Examples 1 to 3, and the commercially available polyol [Mitsui, at the weight ratios shown in Table 1] Product name: Chemical Co., Ltd.
SU-460, hydroxyl value: 450 mg KOH / g], foam stabilizer (manufactured by Nippon Unicar, trade name: SZ-1642, silicone), flame retardant [manufactured by Daihachi Chemical Co., Ltd., trade name:
Tris (2-chloropropyl) phosphate], water,
Catalyst (manufactured by Active Materials Chemical, trade name: Minico ™)
HD) and a foaming agent (trade name: manufactured by Daikin Industries, Ltd.)
HCFC-141b] was mixed to prepare a resin solution.
Obtained resin solution and polyisocyanate [M-200 (Polymeric MD, manufactured by Mitsui Chemicals, Inc.)
I)] was adjusted to 20 ° C. The resin solution and the polyisocyanate were mixed at a liquid ratio at which the NCO index was 1.0, stirred vigorously for 6 seconds, and poured into a box-shaped container having an open upper end. The container was left under the conditions of 22 ° C. and 40% relative humidity for 24 hours to produce a polyurethane foam.
The reactivity, density, low-temperature dimensional stability, and compressive strength of the obtained polyurethane foam were measured by the above methods. The results obtained are shown in [Table 1].

[0057]

[Table 1]

Example 3 100 g of the phenolic polyol obtained in Example 1 was weighed into a 500 ml polycup, and a polyisocyanate (trade name: M-200 (polymeric MDI) manufactured by Mitsui Chemicals, Inc.) was added to the NCO. The amount at which the index becomes 1.0, and triethylenediamine (concentration 1)
6.5% by weight dipropylene glycol solution) 0.03
After stirring for 3 minutes (300 rpm), the mixture was defoamed under reduced pressure of 10 mmHg for 15 minutes. The mixed solution was molded into an aluminum mold (200 mm x 200 mm x 1
mm) at 100 ° C. under a nitrogen atmosphere.
After curing for 4 hours, the mold was removed to obtain a polyurethane resin.

[0059]

According to the present invention, the hydroxyl value is from 60 to 620.
A phenolic polyol having a mgKOH / g and a terminal primary hydroxylation rate of 90% or more can be produced without complicated post-treatment operations. Further, by producing a phenolic polyol according to the present invention, and further producing a polyurethane foam using the same, the reactivity is good, excellent compressive strength,
And a polyurethane foam having low-temperature dimensional stability can be produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 101: 00) C08L 75:04 (72) Inventor Saku Izukawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Chemicals, Inc. In company

Claims (6)

[Claims] 1. A method for producing a phenolic polyol for adding an alkylene oxide to a phenolic compound, the method comprising the steps of:
The phenolic compound is reacted with 5 to 50% by weight of an alkylene oxide containing at least 50% by weight of an alkylene oxide having 3 or more carbon atoms, and then ethylene oxide is added in an amount of 1 mol per mole of hydroxyl group of the obtained reaction product. A method for producing a phenolic polyol, comprising reacting 3 to 10 moles. 2. The method for producing a phenolic polyol according to claim 1, wherein the phenolic compound is a bisphenol. 3. The phenolic compound according to claim 1, wherein the alkylene oxide having 3 or more carbon atoms is at least one compound selected from the group consisting of propylene oxide, butylene oxide and styrene oxide. A method for producing a polyol. 4. The polyol has a hydroxyl value of from 60 to 620 m.
The method for producing a phenolic polyol according to any one of claims 1 to 3, wherein gKOH / g and a terminal primary hydroxylation rate are at least 90%. 5. A method for producing a polyurethane resin in which an active hydrogen compound is reacted with a polyisocyanate, wherein the phenolic polyol is produced by the method according to any one of claims 1 to 4, wherein the phenolic polyol is produced. A method for producing a polyurethane resin, comprising using as an active hydrogen compound. 6. A method for producing a polyurethane foam, comprising reacting an active hydrogen compound with a polyisocyanate in the presence of a catalyst, a foaming agent and a foam stabilizer, wherein the method according to claim 1 is carried out. A method for producing a polyurethane foam, comprising producing a phenolic polyol by using the phenolic polyol as an active hydrogen compound.