WO2006001482A1

WO2006001482A1 - Process for producing polyether polyol

Info

Publication number: WO2006001482A1
Application number: PCT/JP2005/011980
Authority: WO
Inventors: Naoko Fujita
Original assignee: Mitsubishi Chemical Corporation
Priority date: 2004-06-29
Filing date: 2005-06-29
Publication date: 2006-01-05
Also published as: KR20070032725A

Abstract

A process for producing at a high efficiency with high selectivity a polyether polyol reduced in coloration through the dehydrating condensation of a polyol. In producing a polyether polyol through the dehydrating condensation of a polyol, a solid acid catalyst satisfying at least one of the following (1) to (3) is used: (1) the acidity function H0 as measured by Hammett's indicator adsorption method is larger than -3; (2) in analysis by temperature programmed ammonia desorption (TPD), the amount of ammonia desorbed in the region of 100-350°C is at least 60% of the amount of ammonia desorbed in the whole test region (25-700°C region); and (3) in a thermogravimetric (TG) analysis, the amount of water desorbed in the region of 32-250°C is 3 wt.% or larger based on the basis weight.

Description

Specification

Method for producing polyether polyol

Technical field

The present invention relates to a method for producing a polyether polyol by a dehydration condensation reaction of a polyol. Specifically, the present invention relates to a method for efficiently producing a polyether polyol with little coloration by carrying out this reaction in the presence of a catalyst having specific acid properties. Background art

[0002] Polyether polyol is a polymer having a wide range of uses, including raw materials for soft segments such as elastic fibers and plastic elastomers. Typical examples of polyether polyols include polyethylene glycol, poly (1,2-propanediol), and polytetramethylene ether glycol. Among these, poly (1,2-propandiol) is widely used because it is liquid at room temperature, easy to handle, and inexpensive. However, since poly (1,2-propanediol) has a primary hydroxyl group and a secondary hydroxyl group, the physical properties of these hydroxyl groups may be problematic depending on the application. On the other hand, polytrimethylene ether glycol, which is a dehydration condensate of 1,3-propanediol, has recently attracted attention because it has only primary hydroxyl groups and has a low melting point.

[0003] Generally, polyether polyols can be produced by a dehydration condensation reaction of corresponding polyols. However, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, and the like produce 5- or 6-membered cyclic ethers, that is, 1,4-dioxane, tetrahydrofuran, and tetrahydropyran, respectively, during dehydration condensation. . Therefore, a polyether polyol corresponding to a polymer of ethylene glycol and 1,4-butanediol is produced by ring-opening polymerization of a corresponding cyclic ether, that is, ethylene oxide and tetrahydrofuran. Polyether polyols corresponding to 1,5-pentanediol polymers are difficult to produce because tetrahydropyran, a cyclic ether, is thermodynamically advantageous.

[0004] The production of a polyether polyol by a dehydration condensation reaction of a polyol is generally performed using an acid catalyst. Catalysts include iodine, inorganic acids such as hydrogen iodide and sulfuric acid, and And organic acids such as para-toluene sulfonic acid (see Patent Document 1), perfluoroalkyl sulfonic acid groups having a side chain (see Patent Document 2), a combination of sulfuric acid and cuprous chloride, activity White clay, zeolite, organic sulfonic acid, heteropoly acid (see Patent Document 3) and the like have been proposed.

[0005] Further, as a reaction method, a method in which a dehydration condensation reaction is first performed under a nitrogen atmosphere and then a dehydration condensation reaction is performed under reduced pressure (see Patent Document 4) is also proposed.

Among these, inorganic acids such as iodine, hydrogen iodide and sulfuric acid, and organic acids such as para-toluenesulfonic acid, organic sulfonic acids and heteropolyacids are homogeneous acid catalysts. When an acid catalyst is used, since the acid catalyst exhibits strong acid properties, the reactor used for the polymerization reaction corrodes, and the reactor corrodes, so that the metal component is eluted and the product polyether polyol There is a problem that the eluted polyol is contained in the polyether polyol. In order to prevent corrosion, it is necessary to use a reactor that uses glass or glass-lined reactors and high-grade materials such as hastelloy. Met. Furthermore, when a homogeneous catalyst is used, an ester derived from the catalyst acid may be contained at the end of the polyether polyol of the product, and the hydrolysis of the ester may be required, resulting in a large number of steps. The problem of wastewater treatment also arises. In addition, since a uniform acid catalyst is contained in the polyether polyol, it is necessary to remove these acid catalysts by methods such as neutralization and washing with water, and there is a problem that a purification step of the polyether polyol is required for that purpose. To the eye.

[0007] If a solid catalyst can be used as the catalyst, all of these problems can be solved, and this is a particularly advantageous method.

[0008] As solid acid catalysts that can be used in the dehydration condensation reaction of polyols, from the above-mentioned references, the ability to include rosin, activated clay, and zeolite having a perfluoroalkylsulfonic acid group in the side chain. When these are used in the dehydration condensation reaction of polyols, there are many side reaction products such as aryl alcohol, and the polyether polyol selectivity is very low. It was not at a practical level. Patent Document 1: US Pat. No. 2,520,733

Patent Document 2: Pamphlet of International Publication No. 92Z09647

Patent Document 3: U.S. Patent No. 5659089

Patent Document 4: US Patent Application Publication No. 2002Z0007043

Disclosure of the invention

Problems to be solved by the invention

The present invention intends to provide a method for producing a polyether polyol with high selectivity and low coloration in high yield by dehydrating condensation of a polyol using a solid catalyst.

Means for solving the problem

[0010] In the present reaction, since a strong acid is active in the case of a homogeneous catalyst as described above, it has been considered that a solid acid catalyst having a strong acid property even in the case of a heterogeneous catalyst is preferable. Surprisingly, however, it is clear from the study of the present inventor that an acid point that is too strong promotes side reactions such as intramolecular dehydration, and that a catalyst having a strong acid property is unsuitable. became. Therefore, the present inventors have found that the above object can be achieved by using a solid acid catalyst having no strong acid point, and have completed the present invention.

That is, the gist of the present invention is that a solid acid catalyst satisfying at least one of the following conditions (1) to (3) is used when producing a polyether polyol by a dehydration condensation reaction of a polyol. A method for producing a polyether polyol.

• Acidity function H measured by Hammett's indicator adsorption method is greater than -3

0

• For temperature-programmed desorption analysis (TPD) of ammonia, the ammonia desorption amount in the region of 100 to 350 ° C is 60% of the total ammonia desorption amount (region of 25 ° C to 700 ° C). • In thermogravimetric analysis (TG), the desorption amount of water is 3% by weight or more of the reference weight in the region of 32 to 250 ° C.

The second gist is a method for producing a polyether polyol as described above, wherein the solid acid catalyst contains 0.01 to 2.5 equivalents of a metal element and Z or an organic base with respect to the acid. Exist.

The third gist is the polyether polyol as described above, wherein the metal element is an alkali metal. The manufacturing method.

[0012] The fourth gist lies in the method for producing a polyether polyol as described above, wherein the organic base has a pyridine skeleton.

The fifth gist lies in the method for producing a polyether polyol as described above, wherein the solid acid catalyst, the metal element-containing compound and Z or an organic base are used in combination.

[0013] The sixth gist is that the solid acid catalyst is an intercalation compound, zeolite, mesoporous material, metal composite oxide, oxide or composite oxide containing a sulfonic acid group, a carbon material containing a sulfonic acid group, And a method for producing a polyether polyol as described above, which is at least one member selected from the group consisting of a resin having a perfluoroalkylsulfonic acid group in the side chain.

The seventh gist is a polyol having 3 or more and 10 or less carbon atoms having two primary hydroxyl groups (excluding those forming a 5- or 6-membered cyclic ether by dehydration), or This is a mixture of this with other polyols, and the ratio of the other polyols is less than 50 mol%.

[0014] An eighth aspect resides in the above-described method for producing a polyether polyol, wherein the reaction is performed at 120 ° C or higher and 250 ° C or lower.

The invention's effect

[0015] According to the production method of the present invention, it is possible to efficiently produce a polyether polyol with little coloration under mild conditions.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] <Solid acid catalyst>

The solid acid catalyst used in the production method of the present invention shall satisfy at least one of the conditions described in (1) to (3) below. Among these conditions, those satisfying the two conditions are more preferable. Specifically, (1) and (2), (1) and (3), or (2) and (

A solid acid catalyst satisfying the condition 3) is more preferable. Furthermore, a solid acid catalyst that satisfies all the conditions (1), (2), and (3) is particularly preferred.

(1) Hammett's indicator adsorption method

The solid acid catalyst used in the present invention must have an acid strength that is not too strong for this reaction. Yes, with acidity function H measured by Hammett's indicator adsorption method greater than -3, + 1.

0

It is particularly preferable that a value larger than 5 is more preferable +2 or more. The acidity function H measured by Hammett's indicator adsorption method has a stronger acid point as the value is smaller. Therefore

0

An acidity function H greater than -3 means that a Hammett indicator with pKa = -3 will not be colored acidic.

0

V weak, it means that it is acid nature.

Hammett's acid strength function here is obtained by measuring acid strength in a commercially available benzene solution with Hammett's indicator after treating a solid acid catalyst in saturated steam at 25 ° C for 2 days. .

[0017] In Hammett's indicator method, an indicator for measuring acidity can be conveniently measured by changing the acidity of Hammett's indicator to an acidic color on a solid acid catalyst when it shows acidity. If the solid acid catalyst power is originally colored, it is difficult to recognize a change in the color of the indicator visually, so the change in the indicator may be analyzed by, for example, a spectroscopic technique.

(2) Ammonia temperature programmed desorption analysis method (TPD)

The acid amount and strength of the solid acid catalyst used in this reaction is strong, and the amount of acid sites is preferably large. The temperature range is 100 to 350 ° C by temperature programmed desorption analysis (TPD) of ammonia. It is preferable that the ammonia desorption amount at 60% is 60% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C). Among these, 70% or more is more preferable.

[0018] The ammonia desorption amount in the region of 100 to 300 ° C is preferably 50% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C). 60% or more Is more preferable.

[0019] Further, the ammonia desorption amount in the region of 100 to 250 ° C is preferably 40% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C). Is more preferable.

[0020] Further, the ammonia desorption amount in the region of 300 to 450 ° C is 0.6 times or less, preferably 0.5 times or less, more preferably the ammonia desorption amount in the region of 100 to 300 ° C. It is preferably 0.3 times or less, particularly 0.2 times or less. Among them, the range of 400 to 700 ° C It is particularly preferable that the amount of ammonia desorbed at 2 mmolZg or less, preferably ImmolZg or less, more preferably 0.5 mmolZg or less, even more preferably 0.4 mmolZg or less. Further, it is further preferable that the ammonia desorption amount in the region of 100 to 300 ° C. is 0.1 ImmolZg or more, preferably 0.2 mmolZg, more preferably 0.3 mmolZg or more.

[0021] (3) Thermogravimetric analysis method (TG)

The solid acid catalyst used in this reaction is 3% or more, more preferably 5% or more, more preferably 50 to 200 ° C of the reference weight between 32 and 250 ° C in thermogravimetric analysis (TG). A solid acid catalyst from which 5% or more of the standard weight of water is eliminated is preferable. In this case, the TG analysis method and the reference weight are based on the method in Examples described later.

The solid acid catalyst used in this reaction can be selected using acid strength measurement with Hammett's indicator, temperature-programmed desorption analysis of ammonia, or thermogravimetric analysis. A polyether polyol with little coloration can be obtained.

[0022] Further, a solid acid catalyst that satisfies at least one of the above conditions, a part of the acid substituted with a metal element, a metal element or an organic base modified, or the solid In addition to the acid catalyst, if the metal element-containing compound or organic base component is added in the form of coexistence in the reaction system, the effect increases.

The reason why the acid strength of the solid acid catalyst, the amount of the strong acid point, and the desorption behavior of water have an influence on the dehydration condensation reaction of the polyol is not clear, but is considered as follows.

[0023] Specifically, in the case of a solid acid catalyst, there are sites having various acid properties, and the acid properties of the catalyst are not uniform. Furthermore, since a strong acid is active in this reaction in the case of a homogeneous catalyst, it has been considered that a catalyst having a strong acid property even in the case of a heterogeneous catalyst is preferable. However, from the study by the present inventor, it is clear that an acid point that is too strong promotes side reactions such as intramolecular dehydration, and ZSM-5 having strong acid properties is unsuitable. became.

[0024] If a solid acid catalyst composed of acid points effective for this reaction is crushed by using such a strong acid point, a polyether polyol having a high selectivity can be obtained, resulting in less side reaction. The coloring of the ether polyol itself is also reduced. [0025] Such a solid acid catalyst is a catalyst having an acidity function H measured by Hammett's indicator adsorption method of the present invention of greater than -3, or 100 to 350 in the temperature programmed desorption measurement of ammonia.

0

A catalyst whose ammonia desorption amount in the region of ° C is 60% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C), or between 30 and 250 ° C in thermogravimetric analysis This is a solid acid catalyst from which 3% or more of the reference weight is eliminated.

In addition, when these solid acid catalysts release water of 3% or more of the reference weight in the temperature range of 32 to 250 ° C., it is considered that the following meanings are obtained.

[0026] In this reaction, water is generated by a dehydration condensation reaction. The reaction temperature is 120-250 ° C. In thermogravimetric analysis (TG), the desorption of water in the temperature range of 32 to 250 ° C means that water is released and retained near the reaction temperature. Conversely, the fact that water is not desorbed in this temperature range means that there is no water that can participate in the reaction around the catalyst. Since water has the action of poisoning the acid sites of the solid acid catalyst, if the catalyst retains water in the reaction temperature range, the acid sites that are too strong are crushed and only good acid sites are involved in the reaction. Selectivity is thought to improve.

Furthermore, substitution and modification of metal elements and bases in these solid acid catalysts, and addition of these components to the reaction system will crush even more minute strong acid spots on the solid acid catalyst and further eliminate side reaction sites. It is thought that.

Any solid acid catalyst that satisfies at least one of the above conditions (1) to (3) is not particularly limited, but is preferably an intercalation compound such as activated clay, zeolite, mesoporous material, silica-alumina, silica-zircoua, etc. Metal complex oxides, oxides or complex oxides containing sulfonic acid groups, carbon compounds containing sulfonic acid groups, organic compounds such as ion-exchange resins, and perfluoroalkylsulfonic acid groups in the side chain Can be used. Among these, in terms of being stable under reaction conditions, intercalation compounds such as activated clay, zeolite, mesoporous materials, metal composite oxides such as silica-alumina and silica-zirconia, oxides containing sulfonic acid groups Or, considering the fact that composite oxides and carbon materials containing sulfonic acid groups are more preferable and have high activity and low cost, intercalation compounds such as activated clay, zeolite, mesoporous materials, oxidation containing sulfonic acid groups Sulfur and composite oxides, and carbon materials containing sulfonic acid groups are more preferred. Particularly preferred are oxides or composite oxides containing phonic acid groups, and carbon materials containing sulfonic acid groups.

[0027] Further, when these solid acid catalysts are synthesized, they can be synthesized by using a known method.

[0028] <Metal element>

Preferable metal elements that can be replaced with protons at the acid sites of solid acid catalysts or metal elements that can be modified are alkali metals, alkaline earth metals, group 3-12 transition metals, and group 13 elements. Alkali metals are particularly preferred, with alkali metals and alkaline earth metals being more preferred. As the alkali metal, Li, Na, K, and Cs are preferable. Na is particularly preferable.

[0029] The content of the metal element is preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, and preferably 2.5 equivalents or less, as the metal element with respect to the acid amount of the solid acid catalyst. Preferably, it is used so that it is 1 equivalent or less, more preferably 0.5 equivalent or less.

Here, the acid amount refers to a theoretical acid amount or an acid amount obtained by a neutral salt decomposition method. In the case of zeolite composed of A1 and silicon, the theoretical acid amount for which the amount of A1 is calculated, zeolite containing elements other than A1, mesoporous materials, sulfonic acid-containing solid catalysts, oxides, complex oxides, activated clay In the case of intercalation compounds such as the above, it means the acid amount determined by the neutral salt decomposition method.

[0031] Here, the neutral salt decomposition method means that a solid acid catalyst is washed with a saturated sodium chloride aqueous solution at 20 to 25 ° C.

After ion exchange for 15 minutes, the H + ion exchanged with Na + is determined by titration with an aqueous solution of sodium hydroxide and sodium hydroxide of known concentration.

[0032] In the case of a solid acid catalyst, a catalyst having an acid point substituted with a metal may be obtained in advance. The content of the metal element is equivalent to the original acid amount when the metal element is not substituted with the acid point of the solid acid.

[0033] That is, the acid amount when the metal is not substituted is 1 mmolZg, and the acid amount when the metal is substituted is 0.

If it is 7mmolZg, the metal element content of the metal-substituted solid acid is 0.3 equivalent to the acid amount. The amount of metal substitution can also be determined by elemental analysis.

[0034] As the metal element source, a compound containing a metal element can be used, and metal sulfate, hydrogen sulfate, nitrate, halide, phosphate, hydrogen phosphate, borate, etc. Mineral acid salt And metal salts such as organic sulfonates such as trifluoromethanesulfonate, paratoluenesulfonate, methanesulfonate, carboxylates such as formate and acetate, metal hydroxide, metal alkoxide, metal Specific examples include acetylylacetonate.

[0035] As a method of substituting or modifying a metal element in the solid acid catalyst, a method of ion exchange of a solid acid catalyst in a solution of a desired metal compound, a method of forcibly supporting impregnation, a pore filling of a solution of a metal compound, These catalysts can be obtained by a known method such as a drying method, and these catalysts can be subjected to water washing, drying and calcination treatments as necessary.

[0036] <Organic base>

The organic base is preferably a nitrogen-containing organic base, particularly a nitrogen-containing organic base having a tertiary or quaternary nitrogen atom. Some examples are nitrogen-containing heterocyclic compounds having a pyridine skeleton such as pyridine, picoline, quinoline, 2,6-lutidine, N-methylimidazole, 1,5-diazabicyclo [4. ]-5-Nonene, 1,8-diazabicyclo [5. 4. 0]-Nitrogen-containing heterocyclic compounds having _N- C = N bond such as 7-undecene, and triethylamine and triptyluamine Examples include quaternary ammonium salts such as alkylamines and 1-methylpyridicum chloride. Of these, those having a pyridine skeleton and those having a NC = N bond are preferred, and those having a pyridine skeleton are particularly preferred.

[0037] The organic base is preferably 0.01 equivalents or more, more preferably 0.05 relative to the acid amount of the solid acid catalyst (in this case, the acid amount in the case of unsubstituted as in the case of the metal element). It should be used so that it is at least equivalent, preferably 2.5 equivalent or less, more preferably 1 equivalent or less, and particularly preferably less than 1 equivalent.

[0038] As a method for modifying an organic base to a solid acid catalyst, a method in which a solid acid catalyst is mixed in a solution containing a desired base, a method in which impregnation is forcibly supported, a base-containing solution is pore-filled, and then dried. The catalyst can be obtained by a known method such as a method, and these catalysts can be washed and dried as necessary.

[0039] <Combination of solid acid catalyst with metal element and Z or organic base>

In the present invention, (1) a solid acid catalyst having an acidity function H measured by Hammett's indicator adsorption method of greater than −3, or (2) temperature-programmed desorption measurement of ammonia, A catalyst whose ammonia desorption amount in the range of 0 to 350 ° C is 60% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C), or (3) For thermogravimetric analysis! In addition to the solid acid catalyst that satisfies at least one of the conditions of 3% or more of the standard weight of water desorbing between 32 and 250 ° C, a metal element and Z or an organic base are used in combination. May be. Specifically, these may be added separately to the reaction system, or these compounds may be mixed and then used in the reaction. In this case, the sum of the amounts of all metal elements and organic bases present in the reaction system should be within the above range.

[0040] The solid acid catalyst and the metal element or organic base may exist separately in the reaction system, or a salt may be formed between the solid acid catalyst and the metal element or organic base. Good.

[0041] As the metal element and the organic base that can be used in this case, the same elements as described above can be used.

[0042] <Raw material polyol>

Reaction polyols include 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,7- It is preferable to use a diol having two primary hydroxyl groups such as heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decandiol, 1,4-cyclohexanedimethanol. 1,3-propanediol is more preferred. However, even if it is a diol having two primary hydroxyl groups, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, etc. generate cyclic ether ethers by the dehydration condensation reaction as described above. Therefore, it is not preferable as a raw material for the method of the present invention. Usually, the ability to use these diols alone can be used as a mixture of two or more diols if desired. However, even in this case, it is preferable that the main diol accounts for 50 mol% or more. Moreover, the oligomer of the 2-9 mer obtained by the dehydration condensation reaction of the main diol can be used together with these diols. Furthermore, polyols of triol or higher such as trimethylolethane, trimethylolpropane, pentaerythritol, or oligomers of these polyols can be used in combination. Even in these cases, it is preferable that the main diol occupies 50 mol% or more. Usually 1,4-butanediol Diols having 3 to 10 carbon atoms with two primary hydroxyl groups, or those other than those that produce 5- or 6-membered cyclic ethers by dehydration condensation reactions such as 1, 5-pentanediol, etc. A mixture of polyols with a ratio of other polyols of less than 50 mol% is used for the reaction. Preferably, a diol selected from the group consisting of 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, or another polyol and this Mixtures with a proportion of other polyols of less than 50 mol%, particularly preferably 1,3-propanediol or a mixture of this with other polyols with a proportion of other polyols of less than 50 mol% Subject to reaction.

In the present invention, the production of the polyether polyol by the dehydration condensation reaction of the polyol can be carried out either batchwise or continuously. In the case of a batch system, a raw material polyol and a solid acid catalyst and, if necessary, a metal element or an organic base may be charged and reacted with stirring. In this case, the solid acid catalyst is usually used in the range of 0.01 to 1 times by weight with respect to the starting polyol.

[0044] In the case of continuous reaction, for example, a solid acid catalyst is retained in a reaction apparatus or a flow reaction apparatus in which a large number of stirring tanks are connected in series, and the raw material polyol is continuously supplied to the reactor. In addition, a method can be used in which only the reaction solution containing no solid acid catalyst is continuously extracted from the other end. In this case, either a suspension bed or a fixed bed reaction can be employed.

[0045] The lower limit is usually 0.01 times by weight or more, preferably 0.1 times by weight or more, and the upper limit is usually 10,000 times by weight or less, with respect to the solid acid catalyst usually staying in the reactor. Preferably, a raw material polyol of 1000 times by weight or less is fed in one hour. In this case, the equivalent ratio of the base to the solid acid catalyst in the reaction apparatus may decrease with time. Therefore, if necessary, the solid acid catalyst may be withdrawn little by little to charge a new catalyst, The base is supplied together with the solvent so that the equivalent ratio of organic base to acid maintains the desired value.

[0046] The lower limit of the temperature of the dehydration condensation reaction is usually 120 ° C or higher, preferably 140 ° C or higher, and the upper limit is usually 250 ° C, preferably 200 ° C or lower. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen nitrogen. The reaction pressure is maintained in the liquid phase of the reaction system. As long as it is within the range, it is optional and is usually carried out under normal pressure. If desired, the reaction can be carried out under reduced pressure or an inert gas can be circulated through the reaction system to promote the elimination of water produced by the reaction from the reaction system.

[0047] The reaction time varies depending on the amount of catalyst used, the reaction temperature, and the desired yield and physical properties of the dehydration condensate to be produced, but the lower limit is usually 0.5 hours or more, preferably 1 hour or more. Is usually 50 hours or less, preferably 20 hours or less. The reaction is usually carried out in a non-solvent, but a solvent can be used if desired. The solvent should be selected as appropriate according to the organic solvent power used in conventional organic synthesis reactions, taking into consideration the vapor pressure, stability, and solubility of raw materials and products under the reaction conditions.

[0048] Separation / recovery of the produced polyether polyol can be carried out by a conventional method.

[0049] In the case of a suspended bed, first, the suspended solid acid catalyst is removed from the reaction solution by filtration or centrifugation. When a metal compound is added to the reaction system, it can be removed by washing with water or a hardly soluble salt can be formed and removed by filtration. In the case of an organic base, it can be removed by distillation if it can be distilled, and the extracted organic base can be returned to the reaction system. If it cannot be distilled, it can be removed by washing with water.

[0050] If necessary, the low-boiling oligomers are removed by distillation or extraction with water to obtain the desired polyether polyol.

[0051] In the case of a fixed bed reaction, a light-boiling component or a low-boiling oligomer is removed from the taken-out reaction solution by distillation or water washing as necessary to obtain the desired polyether polyol.

[0052] These polyether polyols can be made into products through a drying step if necessary.

[0053] <Polyether polyol>

The color of the polyether polyol obtained by the method of the present invention is so preferable that it is not colored.

V ,. The degree of coloring is visually in the order of black> brown> yellow> colorless (white).

[0054] The number average molecular weight of the polyether polyol of the present invention depends on the type of catalyst used and The lower limit is usually 80 or more, preferably 600 or more, more preferably 1000 or more, and the upper limit is usually 10000 or less, preferably 7000 or less, more preferably 5000 or less.

[0055] As the molecular weight distribution (weight average molecular weight Z number average molecular weight) is closer to 1, the preferred upper limit is usually 3 or less, preferably 2.5 or less.

[0056] The polyether polyol of the present invention can be used for applications such as elastic fibers, thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, and coating materials. Example 1

[0057] The present invention will be described more specifically with reference to the following examples.

[0058] <Method for measuring acid amount by neutral salt decomposition method>

The acid amount was measured by the neutral salt decomposition method as follows. A sample lOmg was precisely weighed to the first decimal place, 30 ml of a saturated aqueous sodium chloride solution (prepared with Pure Chemical's special grade sodium chloride and demineralized water) was added, and the mixture was stirred for 15 minutes at room temperature.

[0059] Thereafter, the solid acid catalyst was filtered off, washed with demineralized water, and the filtrate was titrated with 0.025 M aqueous solution of sodium hydroxide and sodium to obtain the amount of protons ion-exchanged. The amount was determined.

[0060] <Method of measuring Hammett's acid strength function>

Hold solid acid catalyst 0. lg at room temperature (25 ° C ± 3 ° C) under saturated steam for 2 days to adsorb saturated steam. To this was added 2 ml of a 0.1 wt% solution of Hammett's indicator after observing 2 ml of special grade benzene produced by Kokusan Kagaku, and the color change on the catalyst was observed.

[0061] Hammett indicator is anthraquinone (pKa-8. 2) → benzalacetophenone (pKa-5.

6) → Dicinnamalacetone (pKa-3.0) → 4-Benzazodiphenylamine (pKa + 1.5) → p-dimethylaminoazobenzene (pKa + 3.3) → 4-Benzazol-1-naphthylamine The solution was dropped in the order of (pKa + 4.0) → methyl red (pKa + 4.8) → neutral red (pKa + 6.8).

[0062] “Acidity function H measured by Hammett's indicator adsorption method is greater than −3

0, "for example

, Anthraquinone (pKa-8.2), benzalacetophenone (pKa-5.6), and disinnamalaceton (pKa-3.0) have no discoloration to acidic color. -Benze Nazodiphenylamine (pKa + 1.5), p-dimethylaminoazobenzene (pKa + 3.3), 4-benzeneazo-1-naphthylamine (pKa + 4.0), methyl red (pKa + 4.8), new This means that the indicator of Tral Red (pKa + 6.8) shows acid coloration, or none of the indicators show acid coloration.

[0063] On the other hand, the acidity function H is smaller than −3, for example, anthraquinone (pKa-8.2) or ben

0

It shows that there is a color change to an acidic color with an indicator of V and pKa smaller than dicinnamalacetone (pKa-3. 0) as in zalacetophenone (pKa-5. 6).

[0064] In Table 1, for example, when 4-benzeneazodiamine (pKa + 1.5) does not have an acidic color, P-dimethylaminoazobenzene (pKa + 3.3) has a color. , “+ 1.5 <H ≤ + 3.3”. If pKa + 6.8 does not change to acidic color, acid strength

0

Represents H> +6.8. Table 1 shows the H of each catalyst.

0 0

Ammonia Thermal Desorption Analysis Method (TPD)>

The temperature programmed desorption analysis of ammonia was performed by the following method.

[0065] Measuring device: Anelva AGS-7000 EI method 70eV

Method: TPD—MS, 丄, emperature Programmed Desorption Mass—Spe ctrometry)

Measurement condition:

Sample volume; approx. 30 mg precisely weighed

Sample pretreatment conditions: He 80ml / min, raised from room temperature to 250 ° C at 30 ° CZmin, then kept at 250 ° C for 30 minutes.

[0066] Ammonia adsorption condition: “After evacuating the sample with a rotary pump at 100 ° C, inject ammonia gas (purity 100%) for 90 torr at the same temperature and hold for 15 minutes” → “Vacuum exhaustion” 100 ° CX 30 minutes ”→“ He 200ml / min, 100 ° CX 30 minutes ”→“ TPD measurement starts 5 minutes after returning to room temperature. ”

TPD measurement gas; He 80ml / min

TPD measurement temperature range; room temperature to 700 ° C (temperature rise at 10 ° C Zmin)

Quantification of the amount of desorbed ammonia: Separately from the measurement of each sample, a fixed amount of ammonia was injected, and a calibration curve was calculated from the area of the amount (mole number) and the ionic strength (m / z = 16) at that time. Created. The amount of ammonia desorbed from each sample was determined by calculating the area of the ionic strength in the corresponding temperature range, calculating the calibration curve force obtained earlier, and quantifying it.

[0067] In addition, in the case of a sample that may have a non-negligible amount of mZz = 16 derived from another compound (typical example: water) in contrast to mZz = 16 derived from ammonia, mZz = 16 derived from that compound. It is necessary to calculate the ionic strength and remove the contribution from the quantitative ammonia value.

[0068] The ionic strength of the compound at mZz = 16 is calculated from the ratio of the original ionic strength of mZz other than mZz = 16 to the ionic strength of mZz = 16. The ionic strength of the derived mZz = 16 can be calculated.

Thermogravimetric analysis was performed by the following method.

[0069] Sample: Sampling in air at room temperature after pretreatment for 2 days in saturated steam.

[0070] Measuring device: SII Nanotechnology Co., Ltd. TG-DTA 6300

Temperature calibration; calibration with three metals: In, Pb, and Sn

Calibration of weight; calibration with weight at room temperature. Calibration with calcium oxalate.

[0071] Sample amount: about 10 mg

Sample container: A1, 5mm X 2.5mm

Measurement method: Dry nitrogen gas (purity 99.999% or more, dew point-60 ° C) Flow through 200mlZmin, hold at 30 ° C for 30 minutes at room temperature, then heat up at 10 ° C Zmin, then heat up to 500 ° C.

[0072] Reference weight: The weight obtained by subtracting the weight loss to 32 ° C from the weight of the measured sample shall be the reference weight.

[0073] Desorption amount of water; ratio (%) of the weight loss in a predetermined temperature range to the reference weight.

[0074] Table 1 shows the results of thermogravimetric analysis (TG).

[0075] <Elemental analysis>

Unless otherwise specified, the amounts quantified by the following method were used for the amounts of Al, Na, and Si contained in the zeolite catalyst.

[0076] XRF method: The sample was dried at 120 ° C for 2 h, allowed to cool, and 500 mg was taken and mixed with LiB O 5. OOg

4 7

The sample was melted, cooled, glass-beaded, and then quantified by fluorescent X-ray (XRF (fundamental parameter method: FP method)). [0077] ZSM-5 (silicalite) used in Example 4 was quantified by the following method because the content of Al and Na was small.

[0078] Chemical analysis method: The sample was dried at 120 ° C for 2 h, collected after standing to cool, and decomposed by the wet decomposition method to make a solution, and then ICP-AES (A1, calibration curve method), AAS (Na Quantitative analysis using a calibration curve method).

[0079] The amount of Na and K in the sulfonic acid group-containing silica and Nafion was analyzed by the following method.

[0080] Chemical analysis method (2): The sample was dried at 120 ° C for 2 hours, allowed to cool, and collected, and the total amount was resolved by dry ashing to obtain a solution, which was quantified by AAS and calibration curve method.

[0081] <Measurement of number average molecular weight (Mn)>

The number average molecular weight (Mn) of the polyether polyol was measured by gel permeation chromatography under the following conditions and calculated based on polytetrahydrofuran. Column:

TSK-GEL GMHXL- N (7.8 mm ID X 30. OcmL) (Tosohichi Corporation)

Mass calibration:

POLYTRTRAHYDROFURAN CALIBRATION KIT (Polymer Laboratorie s)

(Mp = 547000, 283000, 99900, 67500, 35500, 15000, 6000, 2170, 160 0, 1300)

Solvent: Tetrahydrofuran

The light boiling components and 1,3-propanediol contained in the obtained oil layer were analyzed by gas chromatography (GC).

Column: HR-20M film thickness 0.25 ^ m, 0.25mmID X 30m

Carrier: Nitrogen approx. 1.5mlZmin, split ratio approx. 40

Oven temperature: 50 ° C- (10 ° C, min temperature rise) -230 ° C (10 minutes hold)

Inlet and detector temperature: 240 ° C

Internal standard; n-tetradecane

In the following examples, the catalysts used in Examples 2 and 8 and Comparative Examples 1 and 3 were used after being previously dried at 300 ° C. for 12 hours. [0082] Example 1

In a Pyrex (registered trademark) 500 ml four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer and stirrer, 250 g of 1,3-propanediol (Aldrich reagent, purity 98%) in a nitrogen atmosphere , Batch # 10508AB) and 1.75 g of potassium hydroxide. The flask was placed in an oil bath and heated. When the liquid temperature reached 162 ° C, the temperature was maintained at 162-168 ° C. After 2 hours, the flask was removed from the oil nose and allowed to cool to room temperature. Subsequently, simple distillation was performed at about 90 ° C. under reduced pressure. About 230 g of distillate was recovered by draining the first distillate.

[0083] <Dehydration condensation reaction of 1,3-propanediol>

20 g of 1,3-propanediol purified by distillation using the above method was added to a Pyrex (registered trademark) 100 ml four-necked flask equipped with a distillation tube, a nitrogen inlet tube, a thermometer and a mechano-cal stirrer. It was charged while supplying at. While stirring this flask in an oil bath at 25 ° C., 10 g of Tosoh HY zeolite (HSZ-320HOA, SiO ZA1 O (molar ratio) = 5.3, lot. 2001) was slowly added.

2 2 3

[0084] After adding the solid acid catalyst, the mixture was stirred at room temperature for 10 minutes, and after sufficiently removing oxygen in the reactor, the oil bath temperature was set to 200 ° C and heating was started. The temperature of the reaction solution was adjusted to 185 ° C. ± 3 ° C. and held for 6 hours for reaction, and then the flask was removed from the oil bath and allowed to cool to room temperature. The water generated during the reaction was allowed to flow out with nitrogen, and a trap that had been cooled with dry ice-ethanol solution along with the by-product 1,3-propanediol was used.

Used to collect. These were light-boiling components, and the amount of 1,3-propanediol contained separately was analyzed by gas chromatography.

[0085] 50 g of tetrahydrofuran was added to the reaction solution cooled to room temperature and stirred for 1 hour, and then the solid acid catalyst was filtered through a 1-m PTFE filter. The inside of the reactor and the inside of the filter were washed with 30 ml of tetrahydrofuran (containing 0.03 wt% BHT (butylhydroxyl toluene)) and mixed with the above filtrate. After repeating this operation twice, tetrahydrofuran was distilled off from the collected organic layer under reduced pressure. Heat the resulting oil layer to 50 ° C for 3 hours 2-3 Vacuum dried at mmHg. The oil layer was measured with a gel permeation chromatography and the number average molecular weight (Mn) was determined. In addition, the amount of 1,3-propanepandiol contained in this oil layer was analyzed and quantitatively analyzed by gas chromatography.

[0086] The amount of unreacted 1,3-propanediol is determined for each of the light boiling component and the component in the oil reservoir.

Therefore, the total value was obtained, and the conversion rate of 1,3-propanediol was obtained from the following formula. The selectivity for the polyether polyol was determined from the following formula, subtracting the amount of 1,3-propanediol from the obtained oil layer and using the remainder as the polyether polyol.

[0087] <Conversion rate of raw material 1,3-propanediol>

(1, conversion rate of 3-propanediol) (%) = {(number of moles of 1,3-propanediol charged)-(number of moles of 1,3-propanediol remaining)} X 100Z (1 of charge , 3-Pole diol in moles)

(Polyether polyol selectivity) _(0/0) = [{(weight of oil layer (g) ZMn) X (Mn -18) / 5 8} - (1 in the oil layer, the number of moles of 3-propanediol) X 100Z (number of moles of 1,3-propanediol converted)

The results are shown in Table 1.

[0088] Example 2

USY zeolite (HSZ-330HUA, Na 2 O / SiO 2 / Al) as a solid acid catalyst

2 2 2

O (molar ratio) = 0.02Z6Z1 (manufacturer nominal value) lot.C2- 0719)

Three

Polytrimethylene ether glycol was obtained in the same manner as in 1. The results are shown in Table-1.

[0089] Example 3

Pyrex (registered trademark) four-necked flask equipped with mecha-car stirrer was charged with Kishida Chemical's sodium nitrate special grade l lg, and 100 g of demineralized water was added and dissolved with stirring. 1. 3 mol Zl of nitric acid About 100 ml of an aqueous sodium solution was prepared. While further stirring, 20 g of the same Tosoh USY zeolite (HSZ-330HUA) used in Example 2 was added here, and the liquid temperature was maintained at 80 ° C. for 2 hours. C Washed with demineralized water. After air drying, it was dried in an oven at 120 ° C for 12 hours and then calcined in air at 500 ° C for 2 hours to obtain Na partially substituted USY zeolite. As a result of elemental analysis, NaO / SiO 2 / Al 2 O (molar ratio) = 0.07 / 6.

2 2 3 4Zl.

2

[0090] <Dehydration condensation reaction of 1,3-propanediol>

Polytrimethyl ether glycol was obtained in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. The results are shown in Table-1.

[0091] Example 4

Pyrex (registered trademark) four-necked flask equipped with mecha-car stirrer was charged with 8 g of ammonium nitrate ammonium special grade 7.8 by Kishidai Chemical, 100 g of demineralized water was added and dissolved while stirring, 0 About 100 ml of 95 mol Zl aqueous ammonium nitrate solution was prepared. While further stirring, NE Chemcat ZSM-5 (silicalite), (K-MCM-04, Na O / Si

2

O / Al O (mol

2 2 3 ratio) = 2lZl640Zl (Manufacturer analysis value) 13 g was added and the liquid temperature was kept at 80 ° C. for 2 hours, and then the zeolite was filtered off and washed with 80 ° C. demineralized water. After air drying, it was dried in a dryer at 120 ° C. for 12 hours and then calcined in air at 500 ° C. for 2 hours to obtain Na partially substituted silicalite. As a result of elemental analysis, Na 2 O / SiO 2 / Al 2 O (molar ratio) = 0.14 / 144

2 2 2 3

It was 6Z1.

[0092] <Dehydration condensation reaction of 1,3-propanediol>

Polytriethylene ether glycol was obtained in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. The results are shown in Table 1.

[0093] Comparative Example 1

40.5 g of 1,3-propanediol, as a solid acid catalyst, ZSM-5 Zeolite manufactured by NE Chemcat (K-MCM-02-2, Na OZSiO / Al 2 O (molar ratio) = 16.6 g of 0Z47ZD,

2 2 2 3

A polytrimethylene ether glycol was obtained in exactly the same manner as in Example 1 except that nitrogen was supplied in an amount of lOONmlZ. The results are shown in Table 1.

Further, when the TPD of this catalyst was measured, the ammonia desorption amount at 100 to 250 ° C was 0.19 mmolZg, and the total ammonia desorption amount (region of 25 ° C to 700 ° C) was 33 %Met. In addition, the ammonia desorption amount at 100-300 ° C is 0.25 mmolZg, The ammonia desorption amount at 100-350 ° C is 0.33 mmolZg, with 43% of the ammonia desorption amount (region of 25 ° C-700 ° C), and the total (25 ° C- It was 57% of the amount of ammonia desorbed in the 700 ° C region).

[0094] The ammonia desorption amount in the region of 300 to 450 ° C was 0.24 mmol Zg. At this time, the ammonia desorption amount in the region of 300-450 ° C was 0.96 times the ammonia desorption amount in the region of 100-300 ° C. Desorption of NH desorbing in the region of 400 to 700 ° C

3 strait was 0.15 mmol, g te.

[0095] Comparative Example 2

Similar to the method for preparing a metal element-substituted solid acid in Example 3, except that 25 g of sodium nitrate, 280 g of demineralized water, and 30 g of ZSM-5zelite used in Comparative Example 1 were used as the solid acid catalyst. Obtained 5 zeolite.

As a result of elemental analysis,

Na O / SiO

2 2 ZA1 O (mol

2 3 ratio) = 0.26Z49Z1

Example 5

Add 10g of demineralized water to 4g of Aldrich reagent Nafion NR-50 (Beads 7-9mesh), add ΙΝ-NaOH aqueous solution dropwise at room temperature using 3.3ml measuring pipette, stir for 2 hours, then 100ml Washed with water, dried, and dried under reduced pressure at 50 ° C. and 2 mmHg. The acid amount by the neutral salt decomposition method was 0.1 lmmolZg. Since the acid amount of Nafion used in Example 5 was 0.9 OmmmolZg, 88% of H + was replaced with Na +.

[0096] <Dehydration condensation reaction of 1,3-propanediol>

As the solid acid catalyst, 2.5 g of the above catalyst was used, the temperature of the oil bath was heated to 182 ° C, the reaction temperature was adjusted to 169 ° C ± 3 ° C, and the catalyst was separated by decantation. Except for this, polytrimethylene ether glycol was obtained in exactly the same manner as in Example 1. [0097] The results are shown in Table 1.

[0098] Example 6

Pyrex (registered trademark) 100 ml three-necked flask equipped with mecha-car stirrer was charged with 20 g of Shin-Etsu Chemical mercaptopropyltrimethoxysilane oligomer (X-41-1805, lot305006) and 39 g of pure chemical special grade ethanol While stirring, 1.7 g of demineralized water was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the temperature in the flask was maintained at 70 ° C. for 20 hours with stirring to allow hydrolysis to proceed and gradually gelled. -After returning to room temperature, the product was taken out into a 100 ml eggplant flask, the solvent was distilled off, dried, pulverized, powdered in a mortar, and then dried at 70 ° C for 3 hours at 2 mmHg.

[0099] 13 g of this product was charged into a 100 ml three-necked flask, and 36 g of 30% peroxy hydrogen peroxide solution was added dropwise over 4 hours while stirring with a mechano-car stirrer. Since heat was generated during the dropping, the SH group was oxidized to the SO H group while cooling in a water bath.

Three

[0100] After standing at room temperature for 12 hours, the mixture was aged by stirring at 70 ° C for 4 hours. After cooling to room temperature, a 1M sulfuric acid aqueous solution was added so that the solid acid concentration would be lwt%, and after ion exchange, it was washed with water, dried, and dried under reduced pressure at 16 mmHg for 3 hours. I got Rika. The acid amount by the neutral salt decomposition method was 1.3 mmolZg. Elemental analysis revealed that the total amount of Na + and K + substitution was 0.002 equivalents with respect to the acid amount. When the TPD of this catalyst was measured, the ammonia desorption amount at 100 to 250 ° C was 0.83 mmolZg, and the total ammonia desorption amount (25 ° C to 700 ° C region) 53%. In addition, the ammonia desorption amount at 100-300 ° C is 1. ImmolZg, 69% of the total ammonia desorption amount (25 ° C-700 ° C region), at 100-350 ° C The amount of ammonia desorbed was 1.2 mmolZg, which was 76% of the total amount of ammonia desorbed (range from 25 ° C to 700 ° C).

[0101] The ammonia desorption amount in the region of 300 to 450 ° C was 0.15 mmolZg. At this time, the ammonia desorption amount in the region of 300 to 450 ° C was 0.14 times the ammonia desorption amount in the region of 100 to 300 ° C.

[0102] The amount of NH desorbed in the region of 400 to 700 ° C was 0.34 mmol Zg. [0103] <Dehydration condensation reaction of 1,3-propanediol>

Polytrimethylene ether glycol was obtained in the same manner as in Example 1 except that 5 g of the above catalyst was used as the solid acid catalyst and the reaction temperature was 189 ± 3 ° C. The results are shown in Table-1.

[0104] Example 7

6 g of the catalyst used in Example 7 was charged with 10 g of demineralized water, and 66 ml of lN-NaOHO. Was added dropwise at room temperature while stirring at room temperature. Washed. After repeating this twice, the same operation was performed using 1.46 ml of ΙΝ-NaOH aqueous solution, washed with demineralized water in the same manner, dried, dried under reduced pressure at 16 mmHg at room temperature, and Na-substituted sulfonic acid group Containing silica was obtained. The acid amount by the neutral salt decomposition method was 0.70 mmol Zg. Therefore, the substitution amount of Na + is 0.45 equivalent to the original acid amount.

[0105] <Dehydration condensation reaction of 1,3-propanediol>

Add 20 g of 1,3-propanediol to a four-necked flask, add 0.0514 g (0.665 mmol) of pure chemical special grade pyridine, stir well, and then add the flask to an oil nose at 25 ° C. The polytrimethylene ether glycol was obtained in the same manner as in Example 6 except that 5.06 g of the above catalyst was added as a solid acid catalyst while stirring. The combined amount of Na + and pyridine is 0.55 equivalents of the original acid amount. The results are shown in Table 1.

[0106] Example 8

0.34g of pyridine (0.14 times equivalent to the theoretical amount of acid), USY Zelite (HSZ-350HUA, Na 2 O 3 / SiO 2 / Al 2 O (molar ratio) = 0. 01 / 9.2 as a solid acid catalyst / 1, lot

2 2 2 3

C2-1—X05)) Polytrimethylene ether glycol was obtained in the same manner as in Example 7 except that lOg was slowly added and the reaction temperature was 185 ± 3 ° C. The results are shown in Table-1.

[0107] Comparative Example 3

Polytrimethylene was prepared in the same manner as in Example 8, except that 0.26 g of pyridine (0.5 times the theoretical amount of acid) and 10 g of the same ZSM-5 zeolite used in Comparative Example 1 were used as the solid acid catalyst. Ether glycol was obtained. The results are shown in Table 1.

[0108] Example 9

0.18 g of pyridine (1 equivalent to the acid amount obtained by the neutral salt decomposition method) was used as a solid acid catalyst. Preparation method of metal element-substituted solid acid in Example 5 Using the same Aldrich reagent Nafion NR50 2.5 used in the above, heat the oil bath to 182 ° C and the reaction temperature to 169 ° C ± Polytrimethylene glycol was obtained in the same manner as in Example 7 except that the temperature was adjusted to 3 ° C. and the catalyst was separated by decantation. The results are shown in Table-1.

[0109] Example 10

1,3 Propanediol 40g, Nafion Powder (Dupont, XR-500 Powder, 13S49-8055-K + 1200EW as solid acid catalyst, acid amount by neutral salt decomposition method is 0.04mmol / g _o Elemental analysis The result showed that the total amount of Na + and K + substituted was 0.95 equivalent to the original acid amount.) The same method as in Example 6 except that 13 g was used and nitrogen was supplied in lOONmlZ. To obtain polytrimethylene ether glycol. The results are shown in Table 1.

[0110] Example 11

Polytrimethylene ether diol was obtained in the same manner as in Example 7, except that 0.036 g (0.46 mmol) of pyridine and 5 g of the same Nafion powder used in Example 10 were used as the solid acid catalyst. The total amount of metal element and base is 1.1 times equivalent to the original acid amount. The results are shown in Table 1.

Example 12

Pyrex 4-neck flask equipped with mecha-car stirrer was charged with 48.8 g of ammonium nitrate humic grade made by Kishida Chemical Co., and then dissolved with stirring with 600 ml of demineralized water. About 600 ml of aqueous solution was prepared. While stirring further, fermented by Tosoh (HSZ—720KOA (K O / Na O / SiO / Al O (mol

2 2 2 2 3 ratio) = 0. 23/0. 70/17. 7Z13 (nominal value), lot. 5001), 30.3 g are added, and the liquid temperature is 80

After maintaining at ° C for 2 hours, the zeolite was filtered off and washed with 80 ° C demineralized water. This was repeated twice. After air drying, it was dried in an oven at 120 ° C for 12 hours and then calcined in air at 500 ° C for 2 hours to obtain H + type fluorite.

[0111] <Dehydration condensation reaction of 1, 3 propanediol>

A polytrimethyl compound was prepared in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. Ren ether glycol was obtained. The results are shown in Table 1.

[0112] Comparative Example 4

8.5 g of sodium nitrate, lOOg of demineralized water, ImolZl of sodium nitrate aqueous solution V, and ZSM-5 Zeolite 20 g used in Comparative Example 1 as a solid acid catalyst In the same manner as in the preparation method, Na partially substituted ZSM-5 zeolite was obtained.

As a result of elemental analysis, Na 2 O / SiO 2 / Al 2 O 3 (molar ratio) = 0.23Z51Z1.

2 2 2 3

[0114] <Dehydration condensation reaction of 1, 3 propanediol>

Example 13

Using sodium nitrate 5.36g, demineralized water 50ml, 1. 3molZl sodium nitrate aqueous solution, Tosoh USY zeolite (HSZ—350HUA lot. C2—1X05, Na OZSi

2

O 2 / Al 2 O (molar ratio) = 0.01 / 9. 2/1) The same method as in Example 3 except that 15 g was used.

2 2 3

Thus, Na-substituted USY zeolite was obtained. (Na OZSiO ZAl O (molar ratio) = 0 · 12/10 /

2 2 2 3

1)

<1, 3 Dehydration condensation reaction of propanediol>

[0115] [Table 1] Table 1

() Si0 ₂ / Al ₂ 0 ₃ molar ratio, * molar ratio relative to acid position

[0116] Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.

[0117] This application is based on a Japanese patent application filed on June 29, 2004 (Japanese Patent Application No. 2004-191567), and a Japanese patent application filed on June 29, 2004 (Japanese Patent Application No. 2004-). 19156 8), Japanese patent applications filed on August 23, 2004 (Japanese Patent Application No. 2004-242744), and Japanese patent applications filed on August 23, 2004 (Japanese Patent Application No. 2004-242745). And is incorporated by reference in its entirety.

Industrial applicability

[0118] According to the present invention, it is possible to provide a method for producing a polyether polyol with high selectivity and low coloration in high yield by dehydrating and condensing a polyol using a solid catalyst.

Claims

The scope of the claims

[1] Manufacture of a polyether polyol, wherein a solid acid catalyst satisfying at least one of the following conditions (1) to (3) is used when producing a polyether polyol by a dehydration condensation reaction of the polyol: Method.

0

• Ammonia temperature programmed desorption analysis (TPD) in the range of 100 to 350 ° C

Ammonia desorption amount at 60% or more of the total ammonia desorption amount (25 ° C to 700 ° C region)

• In thermogravimetric analysis (TG), the amount of water desorption is 3% by weight or more of the reference weight in the region of 32 to 250 ° C.

[2] The method for producing a polyether polyol according to claim 1, wherein the solid acid catalyst contains 0.01 to 2.5 equivalents of a metal element and Z or an organic base with respect to the acid.

[3] The method for producing a polyether polyol according to claim 2, wherein the metal element is an alkali metal.

[4] The method for producing a polyether polyol according to claim 2, wherein the organic base has a pyridine skeleton.

5. The method for producing a polyether polyol according to claim 1, wherein the solid acid catalyst is used in combination with the metal element-containing compound and Z or an organic base.

[6] The solid acid catalyst is an intercalation compound, zeolite, mesoporous material, metal composite oxide, oxide or composite oxide containing a sulfonic acid group, a carbon material containing a sulfonic acid group, and a perfluoroalkyl. The method for producing a polyether polyol according to any one of claims 1 to 5, which is at least one selected from the group consisting of a resin having a sulfonic acid group in the side chain.

[7] Diol having 2 or more primary hydroxyl groups and 3 to 10 carbon atoms (excluding those that form a 5- or 6-membered cyclic ether by dehydration), or other polyols The method for producing a polyether polyol according to any one of claims 1 to 6, wherein the ratio of the other polyol is less than 50 mol%. [8] The method for producing a polyether polyol according to any one of claims 1 to 7, wherein the dehydration condensation reaction is performed at 120 ° C or higher and 250 ° C or lower.