JPH07149883A - Method for producing lactone type polyester polyether polyol and polyurethane resin using the same - Google Patents

Abstract

(57) [Summary] [Structure] A lactone compound is subjected to a ring-opening addition polymerization reaction in the presence of a catalyst with a compound having two or more active hydrogens, and then alkylene oxide is added in the presence of the catalyst to react. A method for producing a lactone-based polyester polyether polyol, which is characterized. [Effect] The stabilized lactone-based polyester ether polyol obtained by the present invention exhibits an extremely high degree of thermal stability, and this polyol provides a polyurethane resin having excellent hydrolysis resistance and heat resistance. It is used in various fields and is extremely useful in industry.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a lactone-based polyester polyether polyol having a hydroxyl group at the terminal, which is suitable for economically producing a high-quality polyurethane, and a method for producing the same. Heat resistance used
The present invention relates to a novel polyurethane resin having excellent hydrolysis resistance.

[0002]

2. Description of the Related Art Polyurethane resin compositions comprising a high molecular weight linear dihydroxy compound, an organic diisocyanate and a low molecular weight compound having at least two hydrogen atoms which react with an isocyanate group as necessary are well known.
As the high molecular weight linear dihydroxy compound, a dicarboxylic acid polyester mainly having a hydroxyl group, generally an adipic acid polyester is used. Polyurethane resins obtained from adipic acid polyester generally have excellent mechanical properties, but have the drawback of being inferior in hydrolysis resistance, although there are some differences depending on the polyol component present in the adipic acid polyester. As a polyol having higher hydrolysis resistance than adipic acid polyester, there is a lactone-based polyester obtained by ring-opening polymerization of a lactone with a polyhydroxy compound. Typical examples of lactone-based polyesters include polycaprolactone obtained by ring-opening polymerization of ε-caprolactone with ethylene glycol, diethylene glycol, trimethylolpropane, etc. I am not completely satisfied. On the other hand, among the same lactones, lactone-based polyesters obtained by ring-opening polymerization of β-methyl-δ-valerolactone and the like have been reported to show excellent hydrolysis resistance (JP-A-60-26019).
However, ring-opening polymerization of β-methyl-δ-valerolactone and the like generally has a problem that the reaction does not proceed with a titanium- or tin-based catalyst used for ring-opening polymerization of ε-caprolactone, and the thermal stability of polyol is high. Bad, for example, 1
When it is left under the temperature condition of 20 ° C., it has a defect that it rapidly depolymerizes. Therefore, a method of stabilizing a lactone polyol by prepolymerizing it with polyisocyanate has been reported (Japanese Patent Laid-Open No. 60-199017), but the present situation is that the use and the manufacturing method are very limited.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to improve the method for producing such a defect and to produce a novel lactone type polyester polyether polyol having excellent thermal stability. It is to obtain a novel polyurethane resin having excellent properties such as heat resistance and hydrolysis resistance.

[0004]

In view of the above-mentioned problems, the present inventors have earnestly studied a method for obtaining a lactone type polyester polyol having improved thermal stability and suppressed dissociation due to heat, and as a result, the present invention has been completed. Came to.

That is, according to the present invention, a lactone compound is subjected to a ring-opening addition polymerization reaction with a compound having two or more active hydrogens in the presence of a catalyst, and then an alkylene oxide is added and reacted in the presence of the catalyst. Provided is a method for producing a characteristic lactone polyester polyether polyol. Further, preferably the catalyst is an alkali metal hydroxide and / or an alkali metal alcoholate, preferably the lactone compound is β-methyl-δ-valerolactone and / or ε-caprolactone, the polyol To provide a polyurethane resin using.

(Structure) Specific examples of the lactone compound used in the present invention include, for example, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, α-
Methyl-ε-caprolactone. β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, β, δ-dimethyl-ε-caprolactone, 3,3,5-trimethyl-ε-
Caprolactone, enanthlactone (7-heptanolide), dodecanolactone (12-dodecanolide, DL)
And most preferably β-methyl-δ-valerolactone, and these can be used alone or in combination of two or more kinds.

Examples of the compound having two or more active hydrogen atoms include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, butanediol, 3-methyl-1,5-pentanediol, 1,
5-pentanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, neopentyl glycol, and other polyols, ethylenediamine, hexaethylenediamine, and other low-molecular-weight polyamines,
Further, low molecular weight alkanolamines such as ethanolamine may be mentioned, and they may be used alone or in combination of two or more kinds.

Examples of the catalyst used in the present invention include alkali metals such as lithium, sodium and potassium, or their hydroxides and alcoholates, including the use alone or in combination of two or more, It also includes adding in the form of the raw material. It is preferably used in the form of alcoholate. This alcoholate may be prepared in the same reaction vessel or may be prepared separately and collected.
The catalyst amount is 1 ppm to 5 with respect to the polyester polyol.
It is desirable to use it within the range of 0000 ppm.

The alkylene oxide used in the present invention includes, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin and the like, and they may be used alone or in combination of two or more kinds.

The reaction is carried out in an atmosphere of an inert gas such as nitrogen, helium or argon. Prior to carrying out this reaction, it is desirable to reduce the water content of the lactones as much as possible. The reaction is usually performed at a temperature of 0 to 250 ° C., but for β-methyl-δ-valerolactone, it is 12
Temperature conditions not exceeding 0 ° C are preferred. The reaction time is in the range of about 10 minutes to 50 hours. The reaction is usually carried out in the absence of a solvent, but a solvent inert to the reaction can be used. The progress of the reaction is
Determine by the viscosity of the reaction product.

After the reaction between the compound having two or more active hydrogens and the lactone compound is almost completed (the completion of this reaction is confirmed by the fact that the viscosity of the reaction product becomes a constant value below 10,000 poise). ), A predetermined amount of alkylene oxide is continuously charged and further reacted. At this time, in the ring-opening polymerization of lactones, the catalyst of the alkali metal hydroxide used is active, and the alkylene oxide is easily added to the terminal of the lactone polymer to obtain the polymer polyol used in the present invention. The addition reaction temperature is generally in the range of 50 to 180 ° C., but β-methyl-
In the case of addition reaction to δ-valerolactone polymer or the like, it is desirable to carry out at a temperature of 120 ° C or lower.

As the amount of alkylene oxide increases, the thermal stability improves, but the physical properties such as strength of the polyurethane decrease. Therefore, when synthesizing a polyol, the number of moles of alkylene oxide added to the lactone polyester polyol is preferably in the range of 1.0 to 3.0 moles relative to the hydroxyl group.

The thermal stability of the lactone type polyester polyether polyol obtained in the present invention may be hindered by the low boiling point component present in the system and the catalyst used for producing the lactone polymer, or Undesirable side reactions during polyurethane formation may occur due to its presence, so the lactone-based polyester polyether polyol obtained has the low boiling point present in the system after removal of the catalyst by washing extraction, neutralization filtration, adsorption treatment, etc. It is desirable to remove the components under reduced pressure.

The number average molecular weight of the polyol obtained according to the present invention is usually 300 to 10,000. The physical properties of the urethane resin are preferably 600 to 4,000.

Examples of the organic polyisocyanate used in the present invention include diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate and 1,5-
Naphthylene diisocyanate, 3,3'-dichloro-4,4'-
Aromatic diisocyanates such as iphenylmethane diisocyanate, xylylene diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate,
Aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, 4,4′-dichlorohexylmethane diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated phenylene diisocyanate can be mentioned. The polyisocyanates may be used alone or as a mixture.

In the synthesis of polyurethane resin,
Although a low molecular weight compound having two or more active hydrogen atoms is usually used as a chain extender, these active hydrogen atom compounds can also be used in the method of the present invention.

As typical examples of these active hydrogen atom-containing compounds, for example, ethylene glycol, butanediol, propylene glycol, 1,6-hexanediol,
1,4-bis (β-hydroxyethoxy) benzene, 1,4-
Cyclohexanediol, bis (β-hydroxyethyl) terephthalate, diols such as xylene glycol, water, hydrazine, ethylenediamine, isophoronediamine, piperazine, phenylenediamine, tolylenediamine, adipic acid dihydrazide, isophthalic acid dihydrazide, and the like, You may use these compounds individually or in mixture. Furthermore, if necessary, a monohydric low molecular weight alcohol, a low molecular weight diamine or the like can be used as a modifier.

Regarding the production method for obtaining polyurethane, a known urethanization reaction technique is used. For example, a ratio of the number of active hydrogen atoms and the NCO group of these compounds is about 1: 1 after mixing a high molecular weight polyol and a low molecular weight compound having an active hydrogen atom and preheating to about 40 to 100 ° C. It is obtained by adding the polyisocyanate compound in an amount of, stirring vigorously for a short time, and then leaving it at about 50 to 150 ° C. Furthermore, it can also be carried out via a polyurethane prepolymer. Because it is usually affected by moisture,
The polyisocyanate compound is used in only a slight excess. These reactions are carried out using 1-form of dimethylformamide, diethylformamide, dimethylsulfoxide, dimethylacetamide, tetrahydrofuran, isopropanol, benzene, toluene, ethylcellosolve, trichlene, etc.
It can also be carried out in a solvent of one kind or two or more kinds.
In this case, if the concentration is in the range of 10 to 40% by weight, it is convenient to obtain a high molecular weight product.

The polyurethane obtained by the method of the present invention is remarkably excellent in hydrolysis resistance and can be used for various purposes. Several examples of the production method and application of the polyurethane obtained in the present invention will be given below.

(1) A substantially granular thermoplastic polyurethane pellet is prepared, and the pellet is heated and melted to prepare an elastomer product by a method such as injection molding or extrusion molding calendering.

(2) A polymer polyol, an organic polyisocyanate and a chain extender are mixed together, or a polymer polyol and an organic polyisocyanate are previously reacted to prepare a prepolymer having a terminal isocyanate group or a terminal hydroxyl group. It is mixed with a chain extender or polyisocyanate and used for casting elastomers, paints, adhesives and the like.

(3) Polyurethane obtained by solution polymerization or polyurethane obtained by melt polymerization is dissolved in a solvent to prepare a coating agent and impregnating agent for synthetic leather, artificial leather fiber, etc.,
Used as a texture modifier.

(4) Dissolving the terminal isocyanate prepolymer in a solvent, adding a chain extender and the like to prepare a stable spinning dope, and producing elastic fibers by a wet or dry method.

(5) Various additives such as a foaming agent are blended with the polymer polyol, and an organic polyisocyanate or a prepolymer having a terminal isocyanate group is added to the mixture to foam at a high speed to obtain a heat-welding polyelter. Produce foamed polyurethane products.

More specifically, the polyurethane obtained in the present invention is used for the sheet, film, roll gear, solid tire, belt, hose, tube, vibration isolator, backing material, shoe sole (microcellular, etc.), It is useful for artificial leather, fiber treatment agents, cushioning materials, paints, adhesives, sealing materials, waterproof materials, flooring materials, elastic fibers and the like.

[0026]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples, Comparative Examples and Reference Examples. However, the invention is not limited to only these examples.

Example 1 Content 5 with stirrer, dropping funnel and gas inlet / outlet
After thoroughly replacing a 00 ml separable flask with dry nitrogen gas, 450 g of ethylene glycol was added to the flask.
Then, 30.2 g of potassium hydroxide was charged, and the mixture was treated with stirring at a bath temperature of 100 ° C. under a reduced pressure of 20 mmHg for 1 hour to prepare an alcoholate.

An autoclave kettle having a content of 1000 ml equipped with a stirrer, a dropping funnel and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and then 26.4 g of the alcoholate prepared above was charged in the kettle and the temperature was raised to 50 while stirring. 728.8 g of β-methyl-δ-valerolactone was added all at once from the dropping funnel while maintaining the temperature at ℃ and stirring vigorously. Immediately with heat generation, the viscosity of the solution increased. After stirring for 2 hours at 50 ° C., 46.4 g of propylene oxide was added, the temperature was raised to 110 ° C., and the reaction was continued. After 2 hours, stirring was stopped and the contents of the kettle were taken out. Next, the polyol was transferred to a vacuum distillation apparatus, and the bath temperature was 60 ° C under a reduced pressure of 1 mmHg.
Degassing for 1 hour, the residual propylene oxide is distilled off, the catalyst is removed by adsorption and filtration, and OHv57.
A liquid polyester polyol having a molecular weight of 1,960 was obtained. The thermal stability of the polyol is 80 ° C for the polyol.
It was allowed to stand in a dryer and evaluated by the viscosity retention rate after 8 hours.

Example 2 Content 5 with stirrer, dropping funnel and gas inlet / outlet
After thoroughly replacing a 00 ml separable flask with dry nitrogen gas, 450 g of ethylene glycol was added to the flask.
Then, 30.2 g of potassium hydroxide was charged, and the mixture was treated with stirring at a bath temperature of 100 ° C. under a reduced pressure of 20 mmHg for 1 hour to prepare an alcoholate.

An autoclave kettle having a content of 1000 ml equipped with a stirrer, a dropping funnel and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and then 26.4 g of the alcoholate prepared above was charged in the kettle and the temperature was raised to 50 while stirring. While maintaining vigorous stirring at 68 ° C, 682.4 g of β-methyl-δ-valerolactone was added all at once from the dropping funnel. Immediately with heat generation, the viscosity of the solution increased. After stirring at 50 ° C. for 2 hours, 92.8 g of propylene oxide was added, the temperature was raised to 110 ° C., and the reaction was further continued. After 2 hours, stirring was stopped and the contents of the kettle were taken out. Next, the polyol was transferred to a vacuum distillation apparatus and degassed under a reduced pressure of 1 mmHg at a bath temperature of 60 ° C. for 1 hour to remove the residual propylene oxide by distillation, adsorption and filtration to remove the catalyst, and OHv58.
A liquid polyester polyol having a molecular weight of 0 and a molecular weight of 1,930 was obtained. The thermal stability of the polyol was evaluated by the viscosity retention rate after the polyol was allowed to stand in a dryer at 80 ° C. for 8 hours.

Example 3 Content 5 with stirrer, dropping funnel and gas inlet / outlet
After thoroughly replacing a 00 ml separable flask with dry nitrogen gas, 450 g of ethylene glycol was added to the flask.
Then, 30.2 g of sodium hydroxide was charged, and the mixture was treated under a reduced pressure of 20 mmHg for 1 hour while keeping the bath temperature at 100 ° C. with stirring to prepare an alcoholate.

A 1000 ml autoclave kettle equipped with a stirrer, a dropping funnel and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and then 26.4 g of the alcoholate prepared above was charged into the kettle and the temperature was raised to 50 while stirring. 728.8 g of β-methyl-δ-valerolactone was added all at once from the dropping funnel while maintaining the temperature at ℃ and stirring vigorously. Immediately with heat generation, the viscosity of the solution increased. After 2 hours, 46.4 g of propylene oxide was added and the temperature was changed to 110 ° C.
The reaction was continued. After 2 hours, stirring was stopped and the contents of the kettle were taken out. Next, the polyol was transferred to a vacuum distillation apparatus and degassed under a reduced pressure of 1 mmHg at a bath temperature of 60 ° C. for 1 hour to remove the residual propylene oxide by distillation, adsorption, and filtration to remove the catalyst, OHv57.6, molecular weight 1 , 950 liquid polyester polyols were obtained. The thermal stability of the polyol was evaluated by the viscosity retention rate after the polyol was allowed to stand in a dryer at 80 ° C. for 8 hours.

Comparative Example 1 Content 5 equipped with a stirrer, dropping funnel and gas inlet / outlet port
After thoroughly replacing a 00 ml separable flask with dry nitrogen gas, 450 g of ethylene glycol was added to the flask.
Then, 30.2 g of potassium hydroxide was charged, and the mixture was treated under a reduced pressure of 1 mmHg for 1 hour while the bath temperature was kept at 100 ° C. with stirring to prepare an alcoholate.

A 1000 ml separable flask equipped with a stirrer, a dropping funnel, and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and 26.4 g of the alcoholate prepared above was charged in the flask, and the temperature was maintained while stirring. 775.2 g of β-methyl-δ-valerolactone was added all at once from a dropping funnel while maintaining the temperature at 50 ° C. and stirring vigorously. Immediately the viscosity of the solution increased. Next, the polyol was transferred to a vacuum distillation apparatus and the bath temperature was 60 ° C under a reduced pressure of 1 mmHg.
Was degassed for 1 hour, and the catalyst was removed by adsorption and filtration to obtain a liquid polyester polyol having OHv of 59.0 and a molecular weight of 1900. The thermal stability of the polyol was evaluated by the viscosity retention rate after the polyol was allowed to stand in a dryer at 80 ° C. for 8 hours.

Comparative Example 2 Content 1 equipped with stirrer, dropping funnel and gas inlet / outlet
After thoroughly replacing a 000 ml separable flask with dry nitrogen gas, 24.8 g of ethylene glycol and 0.04 g of tetrabutyl titanate were charged in the flask in advance, and the temperature was kept at 180 ° C. while stirring and vigorously stirred. 775.2 g of β-methyl-δ-valerolactone was added at once through the dropping funnel.

After 5 hours, no thickening was observed and no polymer was formed.

Comparative Example 3 Content 1 equipped with a stirrer, dropping funnel and gas inlet / outlet port
After thoroughly replacing a 000 ml separable flask with dry nitrogen gas, 24.8 g of ethylene glycol and 0.04 g of stannous chloride were charged in the flask in advance, and the temperature was kept at 180 ° C while stirring and vigorously stirred. Meanwhile, 775.2 g of β-methyl-δ-valerolactone was added at once through the dropping funnel.

After 5 hours, no thickening was observed and no polymer was formed.

Comparative Example 4 Content 5 equipped with a stirrer, dropping funnel and gas inlet / outlet port
After thoroughly replacing a 00 ml separable flask with dry nitrogen gas, 450 g of ethylene glycol was added to the flask.
Then, 30.2 g of potassium hydroxide was charged, and the mixture was treated under a reduced pressure of 1 mmHg for 1 hour while the bath temperature was kept at 100 ° C. with stirring to prepare an alcoholate.

A 1000 ml separable flask equipped with a stirrer, a dropping funnel and a gas inlet / outlet was sufficiently replaced with dry nitrogen gas, and then 26.4 g of the alcoholate prepared above was charged into the flask and the temperature was maintained while stirring. 728.8 g of β-methyl-δ-valerolactone and propylene oxide 46.
4 g was added all at once from the dropping funnel. Since thickening was observed, the polyol was then transferred to a vacuum distillation apparatus, degassed under a reduced pressure of 1 mmHg at a bath temperature of 60 ° C for 1 hour, and the catalyst was removed by adsorption and filtration.
50 liquid polyester polyols were obtained. The thermal stability of the polyol is 8 after leaving the polyol in the dryer at 80 ° C.
The viscosity retention rate after time was evaluated.

Example 4 Five times the molar amount of 4, based on the polyol synthesized in Example 1,
4'-diphenylmethane diisocyanate under nitrogen 60
The reaction was carried out at ° C. The obtained prepolymer was dissolved in dimethylformamide to a concentration of 25% by weight. Next, a 4-fold molar amount of 1,4-butanediol with respect to the polyol was added to the above-mentioned prepolymer solution and stirred at 70 ° C. for 10 hours to cause a reaction to obtain a dimethylformamide solution of polyurethane. After adjusting the polyurethane concentration of this solution to 10% by weight, this solution was cast on a glass plate and dried to obtain a dry film having a film thickness of 100 μm. The hydrolysis resistance of polyurethane was evaluated by the jungle test described below. That is, the above-mentioned polyurethane film 70
The hydrolysis resistance was evaluated by the retention of the tensile strength of the film before and after the jungle test after leaving it for 28 days at 95 ° C and a relative humidity of 95%. Regarding the evaluation of heat resistance, the polyurethane film was left at a constant temperature of 120 ° C. for 28 days, and the heat resistance was evaluated by the film tensile strength retention rate before and after the jungle test.

COMPARATIVE EXAMPLE 5 5 times the molar amount of 4, based on the polyol synthesized in Comparative Example 1,
4'-diphenylmethane diisocyanate under nitrogen 60
The reaction was carried out at ° C. The obtained prepolymer was dissolved in dimethylformamide to a concentration of 25% by weight. Next, a 4-fold molar amount of 1,4-butanediol with respect to the polyol was added to the above-mentioned prepolymer solution and stirred at 70 ° C. for 10 hours to cause a reaction to obtain a dimethylformamide solution of polyurethane. After adjusting the polyurethane concentration of this solution to 10% by weight, this solution was cast on a glass plate and dried to obtain a dry film having a film thickness of 100 μm. The hydrolysis resistance of polyurethane was evaluated by the jungle test described below. That is, the above-mentioned polyurethane film 70
The hydrolysis resistance was evaluated by the retention of the tensile strength of the film before and after the jungle test after leaving it for 28 days at 95 ° C and a relative humidity of 95%. Regarding the evaluation of heat resistance, the polyurethane film was left at a constant temperature of 120 ° C. for 28 days, and the heat resistance was evaluated by the film tensile strength retention rate before and after the jungle test.

Comparative Example 6 A 5 times molar amount of 4,4 'with respect to a polycaprolactone polymer (Mw 2,000) using ethylene glycol as an initiator was used.
-Diphenylmethane diisocyanate was reacted at 60 ° C under nitrogen. The obtained prepolymer was dissolved in dimethylformamide to a concentration of 25% by weight. Next, a 4-fold molar amount of 1,4-butanediol with respect to the polyol was added to the above-mentioned prepolymer solution and stirred at 70 ° C. for 10 hours to cause a reaction to obtain a dimethylformamide solution of polyurethane. After adjusting the polyurethane concentration of this solution to 10% by weight, this solution was cast on a glass plate and dried to obtain a dry film having a film thickness of 100 μm. The hydrolysis resistance of polyurethane was examined by the jungle test described below. That is, the above-mentioned polyurethane film at 70 ° C,
The sample was left under a relative humidity of 95% for 28 days, and the hydrolysis resistance was evaluated by the film tensile strength retention rate before and after the jungle test. Regarding the evaluation of heat resistance, the polyurethane film was left at a constant temperature of 120 ° C. for 28 days, and the heat resistance was evaluated by the film tensile strength retention rate before and after the jungle test.

Table 1 shows the evaluation results of the thermal stability of the polyol obtained in the present invention. Table 2 shows the evaluation of the urethane resin using the same.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

The stabilized lactone type polyester ether polyol obtained by the present invention exhibits a very high degree of thermal stability, and this polyol gives a polyurethane resin having excellent hydrolysis resistance and heat resistance. Therefore, it is used in various fields and is extremely useful in industry.

Claims (4)

[Claims] 1. A ring-opening addition polymerization reaction of a lactone compound with a compound having two or more active hydrogens in the presence of a catalyst,
Next, a method for producing a lactone-based polyester polyether polyol, which comprises reacting by adding alkylene oxide in the presence of the catalyst. 2. The method for producing a lactone polyester polyether polyol according to claim 1, wherein the catalyst is an alkali metal hydroxide and / or an alkali metal alcoholate. 3. The lactone compound is β-methyl-δ-
The method for producing a lactone-based polyester polyether polyol according to claim 1, which is valerolactone and / or ε-caprolactone. 4. A polyurethane resin comprising the lactone-based polyester polyether polyol according to claim 1.