JP3113725B2 - Method for preparing polyester polyol composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester polyol composition and a method for preparing the same, and a method for producing a polyurethane using the polyester polyol composition. In addition, it is possible to suppress an excessive urethanization reaction at the time of polyurethane formation and to make the reaction proceed smoothly.

[0002]

2. Description of the Related Art In producing polyurethane, various polyester polyols are used. Polyester polyols are usually produced by directly reacting polycarboxylic acids or their esters or anhydrides with polyols by polycondensation or transesterification, or by ring-opening polymerization of lactones. As a catalyst for producing a polyester polyol, a titanium compound, a tin compound and the like are used. Among them, a titanium compound is widely used because a polyester polyol can be produced in a small amount.

[0003] On the other hand, polyisocyanates such as diphenylmethane diisocyanate and naphthalene diisocyanate, which are widely used in the production of polyurethane, have extremely high reactivity and react quickly with polyester polyol to form polyurethane. The titanium-based catalyst used in the above also acts as a catalyst for the urethane-forming reaction. Therefore, when polyurethane is produced using a polyester polyol produced using a titanium-based catalyst, the titanium-based catalyst contained in the polyester polyol further promotes the urethanization reaction, and it becomes difficult to control the reaction, There are drawbacks such as gelation during the reaction.

In order to improve the above drawbacks, it has been proposed to add an organic acid or an inorganic acid as a reaction regulator or to deactivate a titanium-based catalyst by adding a phosphite or a phosphate after the production of a polyester polyol. (JP-A-63-128017). However, even in the case of such a method, the progress of the urethanization reaction is not sufficiently suppressed, and the reaction is difficult to control.Moreover, when a large amount of a phosphite or a phosphate is added to control the reaction. Has the disadvantage that the hydrolysis resistance of polyester polyols and polyurethanes produced therefrom is reduced.

[0005] A method of purifying a polyester polyol using water and / or n-hexane has been proposed (JP-A-2-284915). However, this method uses low-temperature water of 50 ° C. or lower and / or n-hexane to extract and remove low-molecular-weight substances in the polyester polyol to prevent the low-molecular-weight substances from seeping out to the surface (bleed-out). Prevention) and antifungal properties, and are not intended to deactivate the titanium-based catalyst. In addition, this method has a drawback that when the polyester polyol after the extraction treatment is heated to a high temperature, the catalytic activity of the titanium-based catalyst or the like is restored.

[0006]

In view of the above, the present inventors have found that when they are used in the production of polyurethane, they have a stable reactivity without inducing excessive reaction promotion, and are excellent in hydrolysis resistance and quality. Research has been continued for the purpose of obtaining a polyester polyol capable of providing a good polyurethane. As a result, the inventors have found that the above object can be achieved by adding a specific phosphorus compound after deactivating the titanium-based catalyst by adding water to the polyester polyol and heating it, thereby completing the present invention.

That is, according to the present invention, after water is added to a polyester polyol produced using a titanium-based catalyst and heated, the following formula (I): (RO) _n P (O) _m (OH) _{3 -n} (I) (wherein m is 0 or 1, n is 0, 1 or 2, and R represents a hydrocarbon group) Preparation of polyester polyol composition characterized by adding And a polyester polyol composition prepared by the method. Furthermore, the present invention includes a method for producing a polyurethane using the polyester polyol prepared by the above method.

The polyester polyol in the present invention is not particularly limited as long as it is a polyester polyol produced using a titanium-based catalyst. Among them, polyester polyols having an average molecular weight of about 300 to 10,000 are generally desirable. The polyester polyol in the present invention can be obtained by directly esterifying or transesterifying a polycarboxylic acid, an anhydride or an ester thereof with a polyol using a titanium-based catalyst, or by opening a lactone. It can be produced by ring polymerization.

Polycarboxylic acid, anhydride or ester thereof (hereinafter the three are collectively referred to as "polycarboxylic acid, etc.")
As the divalent carboxylic acid, a trivalent or higher carboxylic acid, or an anhydride or ester thereof can be used. Preferred examples of the polycarboxylic acid and the like include
Saturated or unsaturated aliphatics such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glutaric acid, malonic acid, dodecanedicarboxylic acid, hydrogenated dimer acid, fumaric acid, maleic acid, and dimer acid Examples thereof include aromatic dicarboxylic acids such as dicarboxylic acid, phthalic acid, terephthalic acid, and isophthalic acid, and esters and anhydrides thereof. As the polycarboxylic acid or the like, only one kind may be used, or a plurality of kinds may be used in combination. For example, a plurality of kinds of dicarboxylic acids may be used in combination, or a dicarboxylic acid and a tricarboxylic acid may be used in combination.

[0010] As the polyol, a low molecular weight polyol having two or more hydroxyl groups can be used. Examples of polyols include ethylene glycol,
Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4
-, 1,3- or 2,3-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-
Hexanediol, 3-methyl-1,5-pentaneddiol, 2-ethyl-1,3-hexanediol, 2,
2,4-trimethyl-1,3-pentanediol, 1,
Aliphatic diols such as 8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; meta-xylene Examples thereof include aromatic diols such as glycol, para-xylene glycol, bishydroxyethoxybenzene, and bishydroxyethyl terephthalate; and aliphatic triols such as trimethylolethane, trimethylolpropane, and glycerin. The polyol may be used alone or in combination of two or more. For example, a plurality of diols may be used in combination, or a diol and a triol may be used in combination.

In the case of a polyester polyol used for the production of a thermoplastic polyurethane, it is preferred to use an aliphatic dicarboxylic acid as a polycarboxylic acid or the like and a low molecular diol as a polyol to react the two. When used for thermosetting polyurethanes, any of divalent and / or trivalent or more polycarboxylic acids and the like, and divalent and / or trivalent or more polyols can be used.

The proportion of the polycarboxylic acid or the like and the polyol to be used is not particularly limited. For example, in order to produce a polyester polyol in which all of the terminal groups are substantially hydroxyl groups, the hydroxyl groups of the polyol are converted to the polycarboxylic acid. An excess in a stoichiometric amount with respect to a carboxyl group such as an acid or a group corresponding thereto is preferably 0.5 to 30 mol%, particularly preferably 1 to 15 mol%. Good to use.

When a polyester polyol is produced from a lactone, it is preferable to use a lactone having a 6-membered ring or more as a lactone, for example, ε-caprolactone,
δ-valerolactone and the like.

As the titanium-based catalyst for producing the polyester polyol, any titanium-based catalyst known to be usable for producing this kind of polyester polyol can be used. Examples of preferred titanium-based catalysts include titanic acid, tetraalkoxytitanium compounds, titanium acylate compounds and titanium chelate compounds, and specifically, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2 -Ethylhexyl titanate, tetrastearyl titanate, polyhydroxytitanium stearate, polyisopropoxytitanium stearate, titanium acetylacetonate, triethanolamine titanate, titanium ammonium lactate, titanium ethyl lactate, titanium octylene glycolate and the like.

The amount of the titanium-based catalyst to be used is preferably a ratio suitable for each polyester polyol, and is not particularly limited. Usually, a raw material for the polyester polyol (the total amount of the polycarboxylic acid or the like and the polyol, or Lactone amount), about 0.1 to 50 ppm, preferably about 0.1 ppm.
The content is preferably 5 to 30 ppm. If the amount of the titanium-based catalyst is too small, it takes an extremely long time to form the polyester polyol, and the product is colored. On the other hand, if the amount of the titanium-based catalyst is too large, it does not act favorably on the polyester polyol forming reaction, and it is necessary to add a large amount of a phosphorus compound to reduce the excessive reaction promoting effect on the urethane-forming reaction of the titanium-based catalyst. Become.

The reaction conditions for producing the polyester polyol are not particularly limited, and any known reaction conditions for producing each polyester polyol can be employed. Obtaining polyester polyol by removing unreacted raw materials (polyol, lactone, etc.) at the stage when polyester polyol is formed by reaction of polycarboxylic acid or the like with polyol or ring-opening polymerization of lactone. Can be.

Since the removal of the titanium-based catalyst from the polyester polyol product usually involves complicated steps, the produced polyester polyol is generally used directly in the production of polyurethane without separating the titanium-based catalyst. Many. Therefore, the "polyester polyol produced using a titanium-based catalyst" in the present invention
The term generally refers to a polyester polyol that contains the titanium catalyst used in the reaction as it is without being separated and removed, but a polyester in which the content of the titanium catalyst used in the reaction is reduced by performing purification or the like. The polyol is also included in the polyester polyol of the present invention.

Therefore, in the present invention, water is added to the polyester polyol containing the titanium catalyst produced as described above and heated to deactivate the titanium catalyst contained in the polyester polyol. . This deactivation treatment may be performed immediately after the polyester polyol forming reaction, or may be performed after a predetermined period of time for the previously produced polyester polyol.

The amount of water to be added at this time can vary depending on the type of the produced polyester polyol, the type and amount of the titanium-based catalyst used, and the like, but is usually about 0.1% based on the weight of the polyester polyol product. The content is 5% by weight, preferably 1% by weight or more. The amount of water added
If the amount is less than 0.5% by weight, it is difficult to suppress and reduce the excessive reaction during the urethanization reaction. On the other hand, the upper limit of the amount of water added is not particularly limited, and even when a large amount of water is added, excess reactivity with the isocyanate group of the polyester polyol can be suppressed. However, when it is necessary to remove the added water, the content is preferably 5% by weight or less from the viewpoint of economical efficiency of water removal.

In some cases, the polyester polyol may contain a trace amount of water generated during the production step as it is.
The term does not mean a trace amount of water contained in the polyester polyol generated by such a polyester polyol production reaction, but means heating by adding new water from the outside.

The heating with the addition of water can be carried out by appropriately selecting the temperature, but is generally carried out at a temperature of 70 to 130 ° C., particularly preferably at a temperature of 90 to 120 ° C. When the heating temperature is lower than 70 ° C., it is often difficult to reduce the excess reactivity of the polyester polyol produced using a titanium-based catalyst with an isocyanate group. On the other hand, when the temperature is higher than 130 ° C., decomposition of the polyester polyol often occurs. When heating at 100 ° C. or higher, the heating may be performed under pressure or water may be added in the form of steam. This heat treatment time is not particularly limited,
Usually, it is good to perform for about 1 to 3 hours.

Then, after adding water and performing a heat treatment, the following formula (I); (RO) _n P (O) _m (OH) _3-n (I) (m, n And R are the same as described above) to prepare the polyester polyol composition of the present invention.

The hydrocarbon group represented by R in the above formula (I) is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group. Preferred examples of the phosphorus compound represented by the formula (I), that is, phosphorous acid or phosphoric acid, or a mono- or diester thereof include phosphorous acid, phosphoric acid, dimethyl phosphite, diethyl phosphite, phosphorus phosphite, Diisopropyl acid, di-n-butyl phosphite, diisobutyl phosphite,
Di-n-ethylhexyl phosphite, dilauryl phosphite, dioleyl phosphite, distearyl phosphite, diphenyl phosphite, monomethyl phosphite, monoethyl phosphite, monoethyl phosphite, monoisopropyl phosphite, monophosphite -N-
Butyl, monoisobutyl phosphite, mono-n-phosphite
Ethylhexyl, monolauryl phosphite, monooleyl phosphite, monostearyl phosphite, monophenyl phosphite, dimethyl phosphate, diethyl phosphate, diisopropyl phosphate, di-n-butyl phosphate, diisobutyl phosphate, phosphorus Di-n-ethylhexyl acid, dilauryl phosphate, dioleyl phosphate, distearyl phosphate, diphenyl phosphate, monomethyl phosphate, monoethyl phosphate, monoisopropyl phosphate, mono-n-butyl phosphate, monoisobutyl phosphate, Examples thereof include mono-n-ethylhexyl phosphate, monolauryl phosphate, monooleyl phosphate, monostearyl phosphate, and monophenyl phosphate. Among the above phosphorus compounds, phosphorous acid, diphenyl phosphite, distearyl phosphite, diphenyl phosphate and the like are particularly preferred.

The amount of the phosphorus compound to be added depends on the amount of the titanium-based catalyst contained in the polyester polyol (that is, when the titanium-based compound used as the catalyst is contained in the polyester polyol product as it is, the production amount of the polyester polyol is reduced. It is preferable that the molar ratio of titanium atoms in the titanium-based catalyst to phosphorus atoms in the phosphorus compound = 1: 0.01 to 2 with respect to the amount of the used titanium-based catalyst). When the ratio of the phosphorus atom in the phosphorus compound is less than 0.01 mol per 1 mol of the titanium atom in the titanium-based catalyst, the activity of the titanium-based catalyst is restored when heated to a high temperature (normally 150 ° C. or higher) As a result, it is not possible to achieve a reduction in the excess reactivity of the polyester polyol to the urethanization reaction, while if it exceeds 2 mol, the hydrolysis resistance of the polyester polyol is reduced.

The polyester polyol composition of the present invention prepared as described above can be used as a polyester polyol component in producing a polyurethane.
In the case where the intended polyurethane may contain water in a raw material such as a polyurethane foam,
The polyester polyol composition containing water can be used as it is in the production of polyurethane without removing the water added during the heat treatment from the polyester polyol.

When the above-prepared polyester polyol composition is used as a raw material of a polyurethane (for example, a polyurethane elastomer or polyurethane fiber) in which the presence of water is not desired, the polyester polyol composition prepared above is treated with water. It is good to use after removing. The removal of water is desirably performed after the addition of the phosphorus compound, but is not limited thereto, and may be performed before the phosphorus compound is added after the heat treatment with the addition of water. The removal of water can be performed by any method such as heating and drying under reduced pressure.

Although not limited, for example, when the polyester polyol composition of the present invention is produced using an organic dicarboxylic acid and a low molecular weight diol, a series of the above-described steps of the present invention will be described. Is described as follows. First, an organic dicarboxylic acid and a low molecular weight diol are usually added at about 170 to 240 ° C., preferably 190 to 220 ° C.
C., while distilling off water generated by the reaction,
When the distillation of water almost disappeared, a titanium-based catalyst was added, and the reaction was continued under reduced pressure. When the acid value of the reaction product became 0.8 or less, the reaction was stopped and excess low molecular diol was added. Is distilled off. Then, 0.5 to 5% by weight of water is added to the reaction product, and the mixture is heated at 70 to 130 ° C for 1 to 3 hours. Then, after adding the above-mentioned phosphorus compound, 70-
The polyester polyol composition of the present invention is obtained by dehydration at 130 ° C. under reduced pressure.

Using the polyester polyol composition prepared above, a thermoplastic polyurethane,
Various polyurethanes such as thermosetting polyurethanes, polyurethane foams, paints, adhesives, and sealing agents can be produced. In the production of the polyurethane, the type and amount of the polyisocyanate and other components, the production conditions, and the like, as well as the type of the polyester polyol constituting the polyester polyol composition, may be appropriately selected depending on the content of the intended polyurethane. For example, as polyisocyanates, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,5-
Conventional polyisocyanates, such as naphthalene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, can optionally be used with chain extenders such as low molecular polyols and polyamines. Hereinafter, the present invention will be described specifically with reference to Examples and the like, but the present invention is not limited thereto.

[0029]

EXAMPLES In the following Examples and Comparative Examples, the reactivity of polyester polyol compositions to isocyanate groups and hydrolysis resistance were measured by the following methods.

Isocyan of Polyester Polyol Composition
Measurement of reactivity with nate groups : Measurement of the reactivity with isocyanate groups of a polyester polyol composition obtained by adding a phosphorus compound and dehydrating under reduced pressure, and a composition obtained by heating the composition at 180 ° C. for 1 hour. did. A polyester polyol composition and 4,4′-diphenylmethane diisocyanate are charged into a reaction vessel at a molar ratio of 3: 1.
The temperature was kept at 90 ° C. while stirring, and a part of the reaction product was collected at regular intervals. To this, a fixed amount of a 0.01N di-n-butylamine solution in dimethylformamide was added and dissolved, and a neutralization titration was performed with a 0.01N hydrochloric acid methanol solution using bromophenol blue as an indicator. To determine the remaining amount of isocyanate groups of
From this remaining amount, the urethane bond [NHCO
O] was calculated. Since the urethanization reaction rate is linearly proportional to the respective concentrations of the hydroxyl group and the isocyanate group, the concentration of the urethane bond [NHCOO] obtained above is substituted into the following equation 1 to obtain a reaction rate constant k (second order) Reaction rate constant) (liter / mol · min) was calculated.

[0031]

## EQU1 ## {1 / (ab)} ln {b (ax) / a (bx)} = kt wherein k: reaction rate constant t: reaction time (reaction product collection time ) (Min) a: initial concentration of hydroxyl group [OH] (mol / liter) b: initial concentration of isocyanate group [NCO] (mol / liter) x: [NHCOO] concentration at t (mol / liter)]

Water resistance of polyester polyol composition
Measurement of dissolvability : 0.5 of each polyester polyol composition
g was precisely weighed, 10 ml of acetone was added thereto, and neutralization titration was performed using potassium hydroxide to determine the acid value (A ₀ ) (KOH mg / g) of the polyester polyol composition. In addition, 0.5% of each polyester polyol composition
g was precisely weighed in a test tube, 10 ml of distilled water was added thereto, and the tube was sealed and allowed to stand at 100 ° C. for 4 days. The mixture of the heat-treated polyester polyol composition and water was formed into an aqueous layer and an organic layer. Separate, the aqueous layer is subjected to neutralization titration with potassium hydroxide as it is, while the organic layer is subjected to neutralization titration after addition of acetone in the same manner as above, and the total titer of both is added to the polyester polyol composition after heating. Acid value (A _h ) (KOHmg /
g), and the acid value increase value (△
A) (KOHmg / g) was determined.

[0033]

△ A (KOHmg / g) = A _h −A ₀

<< Reference Example 1 >> [Production of Polyester Polyol] 3000 g of 3-methyl-1,5-pentanediol and 2920 g of adipic acid were added under nitrogen at normal pressure while passing through 20 g.
The mixture was heated to 0 ° C. to conduct a condensation reaction while distilling off water produced by the reaction. When the acid value of the product became 20 or less, 0.14 g (30 ppm based on the product) of tetraisopropyl titanate was added, and the reaction was carried out by gradually increasing the degree of vacuum with a vacuum pump to obtain an average molecular weight of 2,000. 4820 g of polymethylpentylene adipate diol was obtained.

Example 1 1000 g of the polymethylpentylene adipate diol obtained in Reference Example 1 was heated to 100 ° C., and 20 g of water (2 g
(% By weight) and heated with stirring for 2 hours to deactivate the titanium-based catalyst. Then, a 1% aqueous solution of phosphorous acid 0.1%
After 1 g (0.11 mol per 1 mol of titanium-based catalyst) was added, water was distilled off under reduced pressure to obtain a polymethylpentylene adipate diol composition. When the reaction rate constant of this composition was examined by the above method, it was 0.080 liter / mol · min. The reaction rate constant after heating this composition at 180 ° C. for 1 hour was 0.07.
It was 6 liter / mol · min, and the deactivated state of the titanium-based catalyst was maintained as it was even after heating. Further, when the hydrolysis resistance of this composition was measured by the above-described method, the acid value increase value (ΔA) (KOH mg / g) was 1.7.

Examples 2 to 5 A polymethylpentylene adipate diol composition was prepared in the same manner as in Example 1 except that the types of phosphorus compounds and the amounts added were as shown in Table 1 below. The reaction rate constant and the increase in acid value (ΔA) of the obtained composition were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 1000 g of the polymethylpentylene adipate diol obtained in Reference Example 1 was heated to 100 ° C., 20 g of water was added thereto, and the mixture was heated with stirring for 2 hours to deactivate the titanium catalyst. After that, water was distilled off under reduced pressure to obtain polymethylpentylene adipate diol. When the reaction rate constant of this polymethylpentylene adipate diol was examined in the same manner as in Example 1, it was 0.09 liter / mol · min. The reaction rate constant after heating it at 180 ° C. for 1 hour was 0.21 liter / mol · min. Furthermore, when the hydrolysis resistance of this polymethylpentylene adipate diol was measured by the above-mentioned method, the acid value increase (ΔA) (KOHmg / g) was 1.3.

Comparative Examples 2 to 3 To 1000 g of the polymethylpentylene adipate diol obtained in Reference Example 1, water was added, and the phosphorus compounds of the types and amounts shown in Table 1 were directly added without heat treatment. A polymethylpentylene adipate diol composition was prepared in the same manner as in Example 1 except that the reaction rate constant and the increase in acid value (ΔA) were examined. there were.

Comparative Example 4 A polymethylpentylene adipate diol composition was prepared in the same manner as in Example 1 except that the phosphorus compound was changed to triphenyl phosphite 50 ppm, and the reaction rate constant and acid value of the polymethylpentylene adipate diol were measured. When the rise value (ΔA) was examined, it was as shown in Table 1.

[0040]

[Table 1]

From the results in Table 1 above, it is found that Example 1 of the present invention in which water is added to a polyester polyol, heat treatment is performed, and then a specific phosphorus compound represented by the formula (I) is added.
Polyester polyol compositions of No. 5 to No. 5 are excellent in hydrolysis resistance, and despite the small amount of the phosphorus compound added, the titanium-based catalyst used for producing the polyester polyol is deactivated. Can be achieved enough,
When it is used in the production of polyurethane, it does not cause an excessive urethane-promoting reaction, indicating that such excellent properties are not lost even when the polyester polyol composition of the present invention is heated at a high temperature.

On the other hand, in Comparative Example 1 in which only a heat treatment was performed in the presence of water and no phosphorus compound was added, when the polyester polyol was heated at a high temperature, the activity of the deactivated titanium-based catalyst was restored again. It can be seen that an excessive urethane-promoting reaction occurs. Furthermore, in Comparative Examples 2 and 3 in which only the addition of the phosphorus compound was performed without performing the heat treatment in the presence of water, the titanium catalyst could not be deactivated at all if the addition amount of the phosphorus compound was small. It can be seen that when the phosphorus compound is added in a large amount, the hydrolysis resistance of the polyester polyol is greatly reduced. In Comparative Example 4, in which another phosphorus compound not included in the above formula (I) is used, the activity of the titanium-based catalyst is restored again by heating at a high temperature, and the hydrolysis resistance of the polyester polyol is reduced. You can see that

Further, polyurethanes were produced using the polymethylpentylene adipate diol compositions obtained in the above Examples and Comparative Examples, and various performances were compared. The logarithmic viscosity of the obtained polyurethane was measured according to the following method. The mechanical performance and hydrolysis resistance of the polyurethane were evaluated according to the following methods.

Logarithmic viscosity : polyurethane at a concentration of 0.5 g /
Dissolve in dimethylformamide to make dl
Measured in ° C.

Mechanical performance : Evaluated according to the method specified in JIS K7311. That is, a thickness of 100 μm
Using a dumbbell-shaped test piece made of the polyurethane film of No. 1, the breaking strength and the breaking elongation were measured at a tensile speed of 30 cm / min, and the mechanical performance was evaluated based on the measured values.

Hydrolysis resistance : A polyurethane film having a thickness of 100 μm was allowed to stand at 70 ° C. and 95% relative humidity for 28 days, and the retention of the breaking strength of the film before and after that was determined and evaluated.

Example 6 40 g of the polymethylpentylene adipate diol composition obtained in Example 1 (corresponding to 0.02 mol of polymethylpentylene adipate diol) and 5.4 g of 1,4-butanediol (0 .6 mol) in a three-necked flask, kept at 80 ° C., added with 4,4′-diphenylmethane diisocyanate (20 g, 0.08 mol), and stirred for 1 minute. The obtained mixture retaining the fluidity is heated to 230 ° C.
And transferred for 15 minutes.
Thereafter, the mixture was aged at 80 ° C. for 12 hours to obtain a polyurethane. The polyurethane thus obtained was hot-pressed at 240 ° C. to obtain a 100 μm-thick polyurethane film, which was subjected to various physical property tests. The results are shown in Table 2 below.

Example 7 A polyurethane was obtained in the same manner as in Example 6, except that the polymethylpentylene adipate diol composition obtained in Example 3 was used. Table 2 shows the results of various physical property tests of the obtained polyurethane.

Comparative Example 5 40 g of the polymethylpentylene adipate diol composition obtained in Comparative Example 2 (corresponding to 0.02 mol of polymethylpentylene adipate diol) and 5.4 g of 1,4-butanediol (0 .6 mol) was placed in a three-necked flask, kept at 80 ° C., added with 20 g (0.08 mol) of 4,4′-diphenylmethane diisocyanate, and stirred. The stirring became impossible in about 45 seconds. The resulting mixture was transferred to a Labo Plastomill maintained at 230 ° C. and mixed for 15 minutes. Thereafter, the mixture was aged at 80 ° C. for 12 hours to obtain a polyurethane. Table 2 shows the results of various physical property tests of the obtained polyurethane.

Comparative Example 6 A polyurethane was obtained in the same manner as in Example 6, except that the polymethylpentylene adipate diol composition obtained in Comparative Example 3 was used. Table 2 shows the results of various physical property tests of the obtained polyurethane.

[0051]

[Table 2]

[0052]

According to the present invention, the titanium catalyst contained in the polyester polyol can be completely deactivated by a very simple operation of heating with adding water,
Such deactivation of the titanium-based catalyst can be maintained as it is even after heating the polyester polyol composition of the present invention to a high temperature. Therefore, when the polyester polyol composition of the present invention is used for the production of polyurethane, an excessive urethane formation accelerating reaction does not occur at the time of polyurethane formation, the reaction is extremely easy to control, and an undesirable gel is formed during the polyurethane formation reaction. Does not occur. Furthermore, the polyester polyol composition of the present invention has excellent hydrolysis resistance by itself, and therefore, the polyurethane produced using the polyester polyol composition of the present invention also has excellent hydrolysis resistance. .

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/42-18/44 C08G 63/00-63/91 C08L 67/00-67/04

Claims (3)

(57) [Claims] 1. Polyester polyol produced using a titanium-based catalyst is heated by adding water thereto, and then the following formula (I): (RO) _n P (O) _m (OH) _3-n (I (Wherein m is 0 or 1, n is 0, 1 or 2, and R represents a hydrocarbon group). A method for preparing a polyester polyol composition, characterized by adding: 2. A polyester polyol composition prepared by the method according to claim 1. 3. A method for producing a polyurethane using the polyester polyol composition prepared by the method according to claim 1.