CN1980981A - Process for producing polyether polyol - Google Patents

Abstract

The present invention provides a process for producing a polyether polyol which is less colored by dehydrating condensation of a polyol with high efficiency and high selectivity. In the production of a polyether polyol by a dehydration condensation reaction of a polyol, a solid acid catalyst is used, and the solid acid catalyst satisfies at least one of the following conditions (1) to (3): (1) acidity function H determined by Hammett indicator adsorption method₀Greater than-3; (2) in a temperature rising desorption analysis (TPD) of ammonia, the ammonia desorption amount in a region of 100 to 350 ℃ is more than 60% of the total ammonia desorption amount (in a region of 25 to 700 ℃); (3) in thermogravimetric analysis (TG), the amount of water released is 3 wt% or more based on the weight in the region of 32-250 ℃.

Description

Manufacturing method of polyether polyol

technical field

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

Background technique

Polyether polyols are polymers that have a wide range of uses, for example, uses as raw materials for soft segments such as elastic fibers or plastic elastomers. As typical polyether polyols, polyethylene glycol, poly(1,2-propylene glycol), polytetramethylene ether glycol, and the like are known. Among these, poly(1,2-propylene glycol) is liquid at room temperature, is easy to handle, and is inexpensive, so it is widely used. However, since poly(1,2-propylene glycol) has primary and secondary hydroxyl groups, the difference in the physical properties of these hydroxyl groups is a problem depending on the application. In contrast, polytrimethylene ether glycol which is a dehydration condensate of 1,3-propanediol has attracted attention in recent years because it has only primary hydroxyl groups and has a low melting point.

Polyether polyols can generally be produced by dehydration condensation reactions of corresponding polyols. However, when ethylene glycol, 1,4-butanediol, and 1,5-pentanediol are dehydrated and condensed, cyclic ethers with 5-membered rings or 6-membered rings are formed, that is, 1,4-dioxane, respectively. , tetrahydrofuran and tetrahydropyran. Therefore, polyether polyols corresponding to polymers of ethylene glycol and 1,4-butanediol can be produced by ring-opening polymerization of corresponding cyclic ethers, ie, ethylene oxide and tetrahydrofuran. In addition, since tetrahydropyran as a cyclic ether is thermodynamically favorable, it is difficult to produce a polyether polyol corresponding to a polymer of 1,5-pentanediol.

Production of polyether polyols using dehydration condensation reactions of polyols is usually performed using acid catalysts. As catalysts, inorganic acids such as iodine, hydroiodic acid, or sulfuric acid, and organic acids such as p-toluenesulfonic acid have been proposed (see Patent Document 1); resins having perfluoroalkylsulfonic acid groups in their side chains (see Patent Document 2) Combination of sulfuric acid and cuprous chloride, activated clay, zeolite, organic sulfonic acid, heteropolyacid (refer to Patent Document 3) and the like.

In addition, as a reaction method, a method of first performing a dehydration condensation reaction under a nitrogen atmosphere and then performing a dehydration condensation reaction under reduced pressure has also been proposed (see Patent Document 4).

Among these, inorganic acids such as iodine, hydroiodic acid, or sulfuric acid, organic acids such as p-toluenesulfonic acid, organic sulfonic acids, heteropolyacids, etc. are acid catalysts of a uniform system, but when using an acid catalyst of a uniform system, due to acid The catalyst exhibits strong acid properties, and the reactor used for the polymerization reaction is corroded. Due to the corrosion of the reactor, the metal component is eluted, and there is a problem of polyether polyol coloring of products containing the eluted metal component in the polyether polyol. In addition, in order to prevent corrosion, it is necessary to use glass or glass-lined reactors, or to use reactors made of high-grade materials such as Hastelloy corrosion-resistant high-nickel alloy (Hasterloy), which will increase the size of the equipment or the construction cost. It is big problem. In addition, when a homogeneous catalyst is used, the end of the polyether polyol of the product contains an ester of an acid derived from the catalyst, and hydrolysis of the ester may be necessary, resulting in a large number of steps and a problem of waste water treatment. In addition, since polyether polyols contain uniform acid catalysts, these acid catalysts must be removed by neutralization, water washing, etc., and there is a problem that a purification process of polyether polyols must be performed for this purpose.

When a solid catalyst is used as a catalyst, these problems can be completely solved, which is a particularly advantageous method.

As solid acid catalysts that can be used in the dehydration condensation reaction of polyols, resins, activated clays, and zeolites having perfluoroalkylsulfonic acid groups in the side chains are listed in the above-mentioned references, but they are used for polyols. During the dehydration condensation reaction, there are many side reaction products such as alkanol, the selectivity of polyether polyol is very low, and the coloring of polyether polyol itself is serious, which is not at a practical level.

Patent Document 1: Specification of US Patent No. 2520733

Patent Document 2: International Publication No. 92/09647 Pamphlet

Patent Document 3: Specification of US Patent No. 5,659,089

Patent Document 4: Specification of US Patent Application Publication No. 2002/0007043

Contents of the invention

The problem to be solved by the invention

The present invention provides a method for producing polyether polyol with low coloration with good selectivity and high yield by dehydrating and condensing polyol using a solid catalyst.

Solution to the problem

As stated above, since strong acids are active with homogeneous catalysts, it is believed that solid acid catalysts having strong acidic properties are preferred for this reaction in the case of heterogeneous catalysts. However, surprisingly, studies by the present inventors have shown that too strong acidic sites (acid sites) promote side reactions such as intramolecular dehydration, and catalysts with strong acidic properties are not suitable. Therefore, the inventors of the present invention found that the above object can be achieved by using a solid acid catalyst that does not have a strong acid site, and completed the present invention.

That is, the gist of the present invention is a kind of manufacturing method of polyether polyol, it is characterized in that, when polyether polyol is manufactured by the dehydration condensation reaction of polyol, use solid acid catalyst, this solid acid catalyst satisfies following (1 )～(3) at least one condition,

(1) The acidity function _H measured by the Hammett indicator adsorption method is greater than -3;

(2) In the temperature rise desorption analysis (TPD) of ammonia, the amount of ammonia desorption in the region of 100-350°C is more than 60% of the total amount of ammonia desorption (in the region of 25°C-700°C);

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

The second point is the above-mentioned method for producing polyether polyol, wherein the solid acid catalyst contains 0.01 to 2.5 equivalents of a metal element and/or an organic base relative to the acid.

The third point is the above-mentioned method for producing polyether polyol, wherein the metal element is an alkali metal.

The fourth point is the above-mentioned method for producing polyether polyol, wherein the organic base has a pyridine skeleton.

The fifth point is the method for producing polyether polyol described above, wherein a solid acid catalyst, a metal element-containing compound, and/or an organic base are used together.

The sixth point is the above-mentioned method for producing polyether polyol, wherein the solid acid catalyst is selected from interlayer compounds, zeolites, interstitial porous substances, metal composite oxides, oxides or composite oxides containing sulfonic acid groups , at least one of a carbon material containing a sulfonic acid group, and a resin having a perfluoroalkylsulfonic acid group in a side chain.

The seventh point is the above-mentioned method for producing polyether polyol, wherein the polyol is a dihydric alcohol having 3 to 10 carbon atoms having two primary hydroxyl groups (however, a 5-membered ring or a 6-membered ring is formed by dehydration) Except the dihydric alcohol of the cyclic ether), or the mixture of above-mentioned dibasic alcohol and other polyhydric alcohol, the ratio of other polyhydric alcohol is lower than 50 mol%.

The eighth point is the method for producing the polyether polyol described above, wherein the reaction is performed at 120°C to 250°C.

The effect of the invention

According to the production method of the present invention, polyether polyol with little coloring can be efficiently produced under mild conditions.

Detailed ways

<Solid acid catalyst>

The solid acid catalyst used in the production method of the present invention satisfies at least one of the conditions described in (1) to (3) shown below. Among these conditions, two conditions are more preferably satisfied, specifically, a solid acid catalyst satisfying the conditions (1) and (2), (1) and (3), or (2) and (3) is more preferable. In addition, a solid acid catalyst satisfying all the conditions of (1), (2) and (3) is particularly preferable.

(1) Hammett indicator adsorption method

The acid strength of the solid acid catalyst used in the present invention must not be too strong in this reaction, and the acidity function H measured by the Hammett indicator adsorption method is greater than _-3 , more preferably greater than +1.5, particularly preferably more than +2. The smaller the value of the acidity function _H0 determined by the Hammett indicator adsorption method, the stronger the acidic site. Therefore, the so-called acidity function H ₀ greater than -3 refers to the weak acidity of the Hammett indicator with pKa=-3 without the coloration of acidic color.

The Hammett acidity function mentioned here can be obtained by measuring the acid strength of a solid acid catalyst treated at 25°C for 2 days in saturated water vapor with a Hammett indicator in a commercially available benzene solution. .

In the Hammett indicator method, when showing acidity, the indicator used to measure the acidity can be easily measured by the Hammett indicator turning acidic color on the solid acid catalyst. When the solid acid catalyst is originally colored, it is difficult to visually confirm the color change of the indicator. Therefore, the change of the indicator can be analyzed by, for example, a spectroscopic method.

(2) Temperature rising desorption analysis method of ammonia (TPD)

The amount of acid and the acid strength of the solid acid catalyst used in the present invention are preferably not many strong acidic sites, and the amount of ammonia desorption in the region of 100 to 350°C measured by the temperature-rising desorption analysis method (TPD: Temperature programmed desorption) of ammonia is preferred. It is 60% or more of the total ammonia desorption amount (in the range of 25°C to 700°C). Among them, 70% or more is more preferable.

In addition, the amount of ammonia desorption in the range of 100°C to 300°C is preferably 50% or more of the total amount of ammonia desorption (in the range of 25°C to 700°C), more preferably 60% or more.

In addition, the amount of ammonia desorption in the range of 100°C to 250°C is preferably 40% or more of the total amount of ammonia desorption (in the range of 25°C to 700°C), more preferably 50% or more.

In addition, the amount of ammonia desorption in the range of 300 to 450°C is 0.6 times or less, preferably 0.5 times or less, more preferably 0.3 times or less, and particularly preferably 0.2 times or less the amount of ammonia desorption in the range of 100 to 300°C. In addition, the amount of ammonia desorption in the region of 400-700°C is 2 mmol/g or less, preferably 1 mmol/g or less, more preferably 0.5 mmol/g or less, particularly preferably 0.4 mmol/g or less. In addition, the amount of ammonia desorption in the region of 100 to 300° C. is 0.1 mmol/g or more, preferably 0.2 mmol/g or more, more preferably 0.3 mmol/g or more.

(3) Thermogravimetry (TG)

The solid acid catalyst used in this reaction preferably has more than 3% of basis weight between 32～250 ℃ when thermogravimetric analysis (TG), more preferably the solid acid catalyst that more than 5% of water is detached, more preferably at 50～250 ℃. A solid acid catalyst that desorbs more than 5% of water by weight at 200°C. The TG analysis method and the reference weight at this time are the TG analysis method and the reference weight according to the method of the Examples described later.

The solid acid catalyst used in this reaction can be selected using the measurement of acid strength by Hammett indicator, or the temperature-intensive desorption analysis of ammonia, or thermogravimetric analysis, so that it can be obtained with a high polyether polyol selectivity. Less coloring of polyether polyols.

In addition, a material obtained by further substituting a metal element for the acid of a solid acid catalyst that partially satisfies at least one of the above conditions, a material obtained by modifying a metal element or an organic base, or a reaction system in addition to the above solid catalyst When a compound containing a metal element or an organic base component is added in a coexistent form, the effect is increased.

The reason why the acid strength of the solid acid catalyst, the amount of strongly acidic sites, and the dehydration behavior of water affect the dehydration condensation reaction of polyol is not clear, but the reason is considered as follows.

Specifically, in the case of a solid acid catalyst, there are sites with various acid properties, and the acid properties of the catalyst are not uniform. In addition, since strong acids are active in the case of a homogeneous catalyst, it is considered that a catalyst having strong acidic properties is preferred for this reaction in the case of a heterogeneous catalyst. However, studies by the inventors of the present invention have revealed that excessively strong acidic sites promote side reactions such as intramolecular dehydration, and ZSM-5 and the like having strong acidic properties are not suitable.

When using a solid acid catalyst that destroys such strongly acidic sites and consists of effective acidic sites for this reaction, polyether polyol can be obtained with high selectivity, and as a result of fewer side reactions, the coloring of polyether polyol itself is also reduced. lighten.

Such solid acid catalyst refers to: the acidity function H measured by the Hammett indicator adsorption method of the present invention is greater than the catalyst of -3, or in the temperature-raising desorption measurement of ammonia, the amount of ammonia desorption in the 100～350 ℃ area is all ( 25°C to 700°C region) 60% or more of the ammonia desorption amount, or a solid acid catalyst that desorbs 3% or more of the basis weight of water in the thermogravimetric analysis between 32°C and 250°C.

In addition, these solid acid catalysts desorb 3% or more of water based on the basis weight in the temperature range of 32 to 250° C., which is considered to mean the following.

In this reaction, water is produced by a dehydration condensation reaction. In addition, the reaction temperature is 120 to 250°C. In thermogravimetric analysis (TG), the detachment of water in the temperature range of 32-250°C means nothing more than the release and retention of water near the reaction temperature. On the contrary, no detachment of water in this temperature range means that there is no water that can participate in the reaction around the catalyst. It can be considered that since water has the effect of poisoning the acidic sites of the solid catalyst, if the catalyst maintains water in the reaction temperature region, the excessively strong acidic sites will be destroyed and only good acidic sites will participate in the reaction. Increased selectivity.

In addition, it can be considered that substituting and modifying metal elements or bases in these solid acid catalysts, or adding these components in the reaction system, destroys the finer strong acid sites on the solid acid catalysts, and then removes side reaction sites.

It is not particularly limited as long as it is a solid acid catalyst that satisfies at least one of the conditions (1) to (3) above, but intercalation compounds such as activated clay, zeolite, interstitial porous substances, silica-alumina, etc. can be preferably used. Or metal composite oxides such as silica-zirconia, oxides or composite oxides containing sulfonic acid groups, organic compounds such as carbon materials containing sulfonic acid groups or ion exchange resins, and perfluoroalkylsulfonic acid in the side chain Acid-based resins, etc. Among these, from the viewpoint of being stable under the reaction conditions, interlayer compounds such as activated clay, zeolites, interstitial porous substances, metal composite oxides such as silica-alumina or silica-zirconia, and metal composite oxides containing Oxides or composite oxides of sulfonic acid groups, carbon materials containing sulfonic acid groups, in terms of high activity and low cost, interlayer compounds such as activated clay, zeolites, interstitial porous materials, and oxides containing sulfonic acid groups are more preferable. Or a composite oxide or a carbon material containing a sulfonic acid group, particularly preferably an oxide containing a sulfonic acid group or a composite oxide or a carbon material containing a sulfonic acid group.

In addition, when synthesizing these solid acid catalysts, it can synthesize|combine by a well-known method.

<metal element>

As the metal element that can be replaced with the proton of the acidic site of the solid acid catalyst or the metal element that can be modified, alkali metals, alkaline earth metals, transition metals from groups 3 to 12, and group 13 elements are preferred, and alkali metals and alkaline earth metals are more preferred. Alkali metals are particularly preferred. As the alkali metal, Li, Na, K, and Cs are preferable, and Na is particularly preferable.

Relative to the acid amount of the solid acid catalyst, the content of the metal element in terms of the metal element may be preferably 0.01 equivalent or less, more preferably 0.05 equivalent or more, and preferably 2.5 equivalent or less, more preferably 1 equivalent or less, and even more preferably 0.5 equivalent or less.

The acid amount mentioned here refers to the theoretical acid amount or the acid amount obtained by the neutral salt decomposition method. In the case of a zeolite containing Al and silicon, it refers to the theoretical acid amount calculated from the amount of Al. In the case of elemental zeolites, interstitial porous substances, solid catalysts containing sulfonic acid, or interlayer compounds such as oxides, composite oxides, and activated clays, it refers to the amount of acid obtained by the neutral salt decomposition method.

The neutral salt decomposition method mentioned here is to ion-exchange the solid acid catalyst with a saturated sodium chloride aqueous solution for 15 minutes at 20-25 ° C, and titrate the H ion-exchanged with Na ⁺ by titrating an aqueous sodium hydroxide solution with a known concentration. ⁺ to get it.

In addition, in the case of a solid acid catalyst, it is sometimes possible to obtain a catalyst in which acidic sites are replaced with metals in advance. The content of the metal element refers to the equivalent of the metal element to the original acid amount in the case of not replacing the acidic sites of the solid acid.

That is, if the acid amount when not metal-substituted is 1 mmol/g, and the acid amount when metal-substituted is 0.7 mmol/g, the metal element content of the metal-substituted solid acid is 0.3 equivalent to the acid amount. In addition, the substitution amount of metal can be obtained by elemental analysis.

As the source of metal elements, compounds containing metal elements can be used, and specific examples include salts of inorganic acids such as metal sulfates, hydrogen sulfates, nitrates, halides, phosphates, hydrogen phosphates, and borates. Or trifluoromethanesulfonate, p-toluenesulfonate, methanesulfonate and other organic sulfonates, formate, acetate and other carboxylates and other metal salts, metal hydroxides, metal alkoxides, metal of acetylacetonate etc.

As a method of substituting or modifying a metal element in a solid acid catalyst, a method of ion-exchanging a solid acid catalyst in a solution of a desired metal compound, a method of impregnating a forced load, or filling a hole with a solution of a metal compound and drying methods, etc., and these catalysts can also be washed with water, dried, and calcined as necessary.

<Organic base>

As the organic base, nitrogen-containing organic bases are preferred, especially nitrogen-containing organic bases having tertiary or quaternary nitrogen atoms. If you want to list a few of them, nitrogen-containing heterocyclic compounds with pyridine skeletons such as pyridine, picoline, quinoline, 2,6-lutidine, N-methylimidazole, 1,5 -Nitrogen-containing heterocyclic compounds with N-C=N bonds, such as diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, etc. Trialkylamines such as triethylamine and tributylamine, quaternary ammonium salts such as 1-picoline chloride, and the like. Among these, bases having a pyridine skeleton and bases having an N-C=N bond are preferable, and bases having a pyridine skeleton are particularly preferable.

The organic base can be preferably used in an amount of 0.01 equivalent or more, more preferably 0.05 equivalent or more, and preferably 2.5 equivalent or less with respect to the acid amount of the solid acid catalyst (at this time, as in the case of the metal element, the acid amount in the case of no replacement) , more preferably less than 1 equivalent, particularly preferably less than 1 equivalent.

As a method of substituting or modifying an organic base in a solid acid catalyst, a method of mixing a solid acid catalyst in a solution containing a desired base, a method of impregnating a forced load, or a method of filling pores with a solution containing a base and drying and other known methods. In addition, these catalysts can also be washed with water and dried if necessary.

<Simultaneous use of solid acid catalyst and metal element and/or organic base>

In the present invention, in addition to satisfying above-mentioned (1) solid acid catalyst whose acidity function _H0 measured by the Hammett indicator adsorption method is greater than -3; A catalyst whose ammonia desorption amount is more than 60% of the total (25°C to 700°C region) ammonia desorption amount; or (3) in thermogravimetric analysis, between 32°C and 250°C, more than 3% of the basis weight of water In addition to at least one conditional solid acid catalyst among the detached catalysts, metal elements and/or organic bases may also be used together. Specifically, these compounds may be added to the reaction system separately, or these compounds may be mixed and used for the reaction. At this time, the sum of the amounts of all metal elements and organic bases present in the reaction system is within the above-mentioned range.

The above-mentioned solid acid catalyst and metal element or organic base may exist separately in the reaction system, and a salt may also be formed from the solid acid catalyst and metal element or organic base.

As the metal elements and organic bases that can be used at this time, the same ones as above can be used.

<Raw material polyol>

As the polyhydric alcohol of the reaction raw material, it is preferable to use 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol and other diols with 2 primary hydroxyl groups, More preferred is 1,3-propanediol. However, even with diols having two primary hydroxyl groups, as described above, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, etc. produce cyclic ethers through dehydration condensation reactions, so , is not preferred as a raw material for the method of the present invention. Although these diols are usually used alone, they can also be used as a mixture of two or more diols, if necessary. However, in this case, it is preferable that the main diol accounts for 50 mol% or more. In addition, 2- to 9-mer oligomers obtained by dehydration condensation reaction of main diols among these diols may be used together. In addition, trihydric or higher polyols such as trimethylolethane, trimethylolpropane, and pentaerythritol, or oligomers of these polyols can also be used together. However, in this case, it is preferable that the main diol accounts for 50 mol% or more. Generally, the carbon atoms with 2 primary hydroxyl groups, except diols such as 1,4-butanediol and 1,5-pentanediol, which form cyclic ethers with 5-membered rings or 6-membered rings through dehydration condensation reactions The dihydric alcohol of the number 3-10, or the mixture of the said dihydric alcohol and other polyhydric alcohol whose ratio of other polyhydric alcohol is less than 50 mol% is supplied to reaction. Preferably, the proportion of dihydric alcohols selected from 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, or other polyhydric alcohols is lower than 50 A mixture of the above-mentioned diols and other polyols in mole % is supplied to the reaction, particularly preferably 1,3-propanediol or other polyols in a ratio of less than 50 mole % of 1,3-propanediol and other polyols The mixture is supplied to the reaction.

<Manufacturing method of polyether polyol>

In the present invention, the production of polyether polyol by the dehydration condensation reaction of polyol can be performed batchwise or continuously. In the case of a batch method, the raw material polyhydric alcohol and solid acid catalyst, as well as metal elements or organic bases added as needed can be charged into the reactor, and the reaction can be carried out under stirring. In this case, the solid acid catalyst is usually used in the range of 0.01 to 1 weight ratio with respect to the polyhydric alcohol of the raw material.

In the case of a continuous reaction, for example, a method in which a solid acid catalyst is retained in a reactor or a flow-through reactor in which a plurality of stirred tanks are arranged in series, and the polyol as a raw material is continuously supplied to the reactor can be used. , and continuously draw out only the reaction solution that does not contain the solid acid catalyst from the other end. At this time, either a suspended bed or a fixed bed reaction can be used.

Usually, the lower limit is usually 0.01 weight times or more, preferably 0.1 weight times or more, and the upper limit is usually 10,000 weight times or less, preferably 1,000 weight times or less of the raw material polyol per hour. . In addition, at this time, since the equivalent ratio of the base to the solid acid catalyst in the reaction device decreases with time, the solid acid catalyst can be extracted a small amount at a time and replaced with a new catalyst, or supplied together with the raw material polyol. base, so that the equivalent ratio of organic base to acid is maintained at the desired value.

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 or lower, preferably 200°C or lower. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The reaction pressure may be any pressure as long as the reaction system maintains the liquid phase, and it is usually performed under normal pressure. If necessary, in order to promote the detachment of water produced by the reaction from the reaction system, the reaction may also be carried out under reduced pressure, or an inert gas may be circulated in the reaction system.

The reaction time varies depending on the amount of catalyst used, the reaction temperature, and the desired yield or physical properties of the resulting dehydration condensate, but the lower limit is usually 0.5 hours or more, preferably 1 hour or more, and the upper limit is usually 50 hours or less, preferably 50 hours or less. for less than 20 hours. In addition, the reaction is usually carried out without a solvent, but a solvent can also be used if necessary. The solvent can be appropriately selected from organic solvents commonly used in organic synthesis reactions in consideration of vapor pressure under reaction conditions, stability, solubility of raw materials and products, and the like.

Separation/recovery of the produced polyether polyol from the reaction system can be carried out according to a usual method.

In the case of a suspended bed, first, the suspended solid acid catalyst is removed from the reaction liquid by filtration or centrifugation. When the metal compound is added to the reaction system, it can be removed by washing with water, or a method of forming a poorly soluble salt and then removing it by filtration can be used. In the case of an organic base, if distillation is possible, it can be removed by distillation, and the taken-out organic base can be returned to the reaction system. When it cannot be distilled, it can be removed by washing with water.

In addition, if necessary, low-boiling oligomers are removed by distillation or extraction with water to obtain the target polyether polyol.

In the case of a fixed bed reaction, if necessary, low-boiling (simmering) components and low-boiling oligomers are removed from the taken-out reaction liquid by distillation or washing with water to obtain the target polyether polyol.

If necessary, these polyether polyols can be further processed into products through a drying process.

<polyether polyol>

The color of the polyether polyols obtained by the process according to the invention is preferably non-pigmented. The degree of coloring was in the order of black>brown>yellow>colorless (white) by visual observation.

In addition, the number average molecular weight of the polyether polyol of the present invention can be adjusted by the type and amount of catalyst used, the lower limit is usually 80 or more, preferably 600 or more, more preferably 1000 or more, the upper limit is usually 10000 or less, preferably 7000 or less, more preferably 5000 or less.

The molecular weight distribution (weight average molecular weight/number average molecular weight) is preferably closer to 1, and the upper limit is usually 3 or less, preferably 2.5 or less.

The polyether polyol of the present invention can be used for elastic fibers, thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, coating materials and the like.

Example

Hereinafter, the present invention will be described more specifically by way of examples.

<Measuring method of acid amount by neutral salt decomposition method>

The measurement of the amount of acid by the neutral salt decomposition method is performed as follows. Accurately weigh 10 mg of the sample to the first decimal place, add 30 ml of saturated aqueous sodium chloride solution (prepared from special grade sodium chloride and desalted water produced by Junzheng Chemical), and stir with a stirring bar for 15 minutes at room temperature.

Then, the solid acid catalyst was separated by filtration, washed with desalted water, and the filtrate was titrated with a 0.025M aqueous sodium hydroxide solution to obtain the amount of ion-exchanged protons and obtain the amount of acid per unit weight.

<Hammett's acid strength function measurement method>

Keep 0.1 g of solid acid catalyst under saturated water vapor at room temperature (25°C±3°C) for 2 days to allow saturated water vapor to be adsorbed. Add 2ml of special-grade benzene produced by domestic chemical industry therein, then add dropwise 2 drops of Hammett indicator of 0.1wt% solution, and observe the color change on the catalyst.

Hammett indicator is anthraquinone (pKa-8.2) → benzaldehyde ketone (pKa-5.6) → dicinnamylidene acetone (pKa-3.0) → 4-phenylazodiphenylamine (pKa+1.5) → Sequential drop of p-dimethylaminoazobenzene (pKa+3.3)→4-phenylazo-1-naphthylamine (pKa+4.0)→methyl red (pKa+4.8)→neutral red (pKa+6.8) add.

The so-called "acidity function _H0 measured by the Hammett indicator method is greater than -3" means, for example, anthraquinone (pKa-8.2), benzaldehyde ketone (pKa-5.6), until dicinnamylidene acetone (pKa-3.0) There is no discoloration to acidic colors, and 4-phenylazodiphenylamine (pKa+1.5), p-dimethylaminoazobenzene (pKa+3.3), 4-phenylazo- The indicators of 1-naphthylamine (pKa+4.0), methyl red (pKa+4.8), and neutral red (pKa+6.8) show the coloring of acidic colors, or use any indicator that does not show the coloring of acidic colors. Color for coloring.

Conversely, the so-called acidity function H ₀ is less than -3, which is indicated by an indication that the pKa of e.g. anthraquinone (pKa-8.2) or benzaldehyde ketal (pKa-5.6) is smaller than that of dicinnamylidene acetone (pKa-3.0) Agents show discoloration to acidic colors.

In Table-1, for example, when 4-phenylazodiphenylamine (pKa+1.5) does not cause discoloration to acid color, but when p-dimethylaminoazobenzene (pKa+3.3) has coloring, it means It is "+1.5<H ₀ ≤+3.3". When there is no discoloration to the acid color even at pKa+6.8, the acid strength is expressed as H ₀ >+6.8. The H ₀ of each catalyst is shown in Table-1.

<Ammonia Temperature Rising Desorption Analysis Method (TPD)>

The temperature-rising desorption analysis of ammonia was performed in the following manner.

Measuring device: ANELBA Co., Ltd. AGS-7000 EI method 70eV

Method: TPD-MS (Temperature Programmed Desorption Mass-Spectrometry)

Determination conditions:

Sample size: Accurately weigh about 30mg

Sample pretreatment conditions: He 80ml/min, after heating from room temperature to 250°C at 30°C/min, keep at 250°C for 30 minutes

Ammonia adsorption conditions: "Use a rotary pump to vacuum exhaust the sample at 100°C, inject 90 torr ammonia gas (purity 100%) into the sample at the same temperature, and keep it for 15 minutes" → "Vacuum exhaust at 100°C × 30 minutes" → "He 200ml/min, 100°C × 30 minutes" → "After returning to room temperature, start TPD measurement after 5 minutes".

TPD measurement gas: He 80ml/min

TPD measurement temperature range: room temperature to 700°C (heating at 10°C/min)

Quantification of detached ammonia: Different from the measurement of each sample, a certain amount of ammonia was injected, and a standard curve was prepared from the area of the amount (number of moles) and the ionic strength (m/z=16) at this time. The area of the ionic strength in this temperature range was obtained, and the amount of ammonia desorbed from each sample was calculated and quantified from the previously obtained calibration curve.

In addition, when there is a possible sample of m/z=16 derived from another compound (representative example: water) having a non-negligible amount with respect to m/z=16 derived from ammonia, it is necessary to calculate The ionic strength of m/z = 16 is determined, and its contributing part is subtracted from the quantitative value of ammonia.

The ionic strength of m/z=16 of the compound can be calculated from the ratio of the original "ionic strength of m/z other than m/z=16" and "ionic strength of m/z=16" of the compound in the TPD measurement data The ionic strength of m/z=16 from this compound.

<Thermogravimetry (TG)>

Thermogravimetric analysis was performed by the following method.

Sample: After performing a pretreatment of holding in saturated water vapor for 2 days, it was sampled at room temperature and in the air.

Measuring device: TG-DTA 6300 from Esairiai Nanotechnorohichi Co., Ltd.

Temperature correction: use In, Pb, Sn three metals for correction

Calibration of weight: Calibrate with weights at room temperature. Calibration was performed with calcium oxalate.

Sample amount: about 10mg

Sample container: made of Al, 5mmφ×2.5mm

Measuring method: Circulate dry nitrogen gas (purity above 99.999%, dew point -60°C) at 200ml/min, keep at 30°C for 30 minutes, then keep at room temperature, then raise the temperature at 10°C/min to 500°C.

Reference weight: The weight obtained by subtracting the amount of decrease to 32° C. from the weight of the sample to be weighed was used as the reference weight.

Amount of desorption of water: the ratio (%) of the amount of decrease in a predetermined temperature range to the reference weight.

The results of thermogravimetric analysis (TG) are shown in Table-1.

<Elemental Analysis>

The amounts of Al, Na, and Si contained in the zeolite catalyst are numerical values quantified by the following method unless otherwise specified.

XRF method: dry the sample at 120°C for 2 hours, after natural cooling, take 500mg and mix it with 5.00g LiB ₄ O ₇ , melt and cool, and after the glass steel traveler (ビ一ド) is formed, use fluorescent X-ray (XRF (fundamental parameter method: FP method)) quantification.

In addition, ZSM-5 (Silicalite) used in Example 4 was quantified by the following method because the content of Al and Na was small.

Chemical analysis method: dry the sample at 120°C for 2 hours, divide it after natural cooling, decompose the whole amount by wet decomposition method, and make a solution, use ICP-AES (Al, standard curve method), AAS (Na, standard curve method) for quantification.

The amount of Na and K in silica containing sulfonic acid groups and Nafion was analyzed by the following method.

Chemical analysis method (2): Dry the sample at 120°C for 2 hours, separate it after natural cooling, decompose the whole amount by dry ashing method, make a solution, and quantify it by AAS and standard curve method.

<Measurement of Number Average Molecular Weight (Mn)>

The measurement of the number-average molecular weight (Mn) of polyether polyol was carried out by gel permeation chromatography under the following conditions, using polytetrahydrofuran as a reference.

column:

TSK-GEL GMHXL-N (7.8mmID×30.0cmL) (Tosoh Corporation)

Mass correction:

POLYTRTRAHYDROFURAN CALIBRATION KIT(Polymer Laboratories)

(Mp=547000, 283000, 99900, 67500, 35500, 15000, 6000, 2170, 1600, 1300)

Solvent: THF

<GC Analysis Conditions>

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

Column: HR-20M film thickness 0.25μm, 0.25mmID×30m

Carrier: nitrogen about 1.5ml/min, split ratio about 40

Oven temperature: 50°C-(10°C/min heating)-230°C (hold for 10 minutes)

Injection port and detector temperature: 240°C

Internal standard: n-tetradecane

In the following examples, the catalysts used in Examples 1, 2, and 8 and Comparative Examples 1 and 3 were dried at 300° C. for 12 hours before use.

Example 1

<Distillation and purification of 1,3-propanediol>

Under a nitrogen atmosphere, add 250 g of 1,3-propanediol (a reagent made by Aldrich Company, a purity of 98%) in a 500 ml four-necked flask manufactured by Pyrex (registered trademark) with a reflux condenser, a nitrogen inlet pipe, a thermometer, and a stirrer. , Batch #10508AB) and 1.75 g potassium hydroxide. Put the flask into an oil bath and heat it. After the liquid temperature reaches 162°C, keep the temperature at 162-168°C. After 2 hours, the flask was removed from the oil bath and left to cool to room temperature. Then, simple distillation was performed at about 90° C. under reduced pressure. 11 g of the first fraction were removed and about 230 g of distillate were recovered.

<Dehydration Condensation Reaction of 1,3-Propanediol>

While supplying nitrogen gas at 40 Nml/min, 20 g of 1,3-propanediol distilled and purified by the above method was added to a 100 ml four-neck flask manufactured by Pyrex (registered trademark) equipped with a distillation tube, a nitrogen gas introduction tube, a thermometer and a mechanical stirrer. The flask was placed in an oil bath at 25° C., and 10 g of HY zeolite (HSZ-320HOA, SiO ₂ /Al ₂ O ₃ (molar ratio)=5.3, lot. ).

After adding the solid acid catalyst, it was stirred at room temperature for 10 minutes to sufficiently remove oxygen in the reactor, and then the temperature of the oil bath was set to 200° C., and heating was started. The temperature of the reaction solution was adjusted to 185° C.±3° C., and kept for 6 hours to allow the reaction, and then the flask was taken out from the oil bath, and left to cool to room temperature. The water formed during the reaction flowed out accompanied by nitrogen, and the above water formed and by-product 1,3-propanediol were collected using a trap around which was cooled by a dry ice-ethanol solution. These were used as low-boiling point components, and the amount of 1,3-propanediol contained was separately analyzed by gas chromatography.

50 g of tetrahydrofuran was added to the reaction liquid cooled to room temperature, and after stirring for 1 hour, the solid acid catalyst was filtered through a filter made of 1 μm PTFE. The inside of the reactor and the inside of the filter were washed with 30 ml of tetrahydrofuran (containing 0.03 wt% of BHT (butyl hydroxytoluene)), and mixed with the above-mentioned filtrate. After repeating this operation twice, tetrahydrofuran was distilled off from the collected organic layer under reduced pressure. The obtained oil layer was heated to 50° C., and vacuum-dried at 2 to 3 mmHg for 3 hours. The oil layer was measured by gel permeation chromatography to determine the number average molecular weight (Mn). In addition, the amount of 1,3-propanediol contained in the oil layer was analyzed and quantified by gas chromatography.

The amounts of unreacted 1,3-propanediol in the low-boiling point components and the components in the oil layer were obtained, and their total values were obtained, and the conversion rate of 1,3-propanediol was obtained according to the following formula. The selectivity of polyether polyol was obtained by subtracting the amount of 1,3-propanediol from the obtained oil layer, and using the remaining amount as polyether polyol, to obtain it from the following formula.

<Conversion ratio of raw material 1,3-propanediol>

(Conversion rate of 1,3-propanediol) (%)={(the mole number of 1,3-propanediol added)-(the mole number of remaining 1,3-propanediol)}×100/(1,3 - moles of propylene glycol)

<Selectivity of polyether polyol>

(Selectivity of polyether polyol) (%)=[{(the weight of oil layer (g)/Mn)*(Mn-18)/58}-(the molar number of 1,3-propanediol in oil layer)]* 100/(moles of converted 1,3-propanediol)

The results are shown in Table-1.

Example 2

In addition to using USY zeolite manufactured by Tosoh Corporation (HSZ-330HUA, Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio) = 0.02/6/1 (manufacturer's nominal value) lot. C2-0719), and In Example 1, polytrimethylene ether glycol was obtained in exactly the same manner. The results are shown in Table-1.

Example 3

<Preparation method of metal element replacement solid acid>

After adding 11 g of special grade sodium nitrate manufactured by Kishida Chemical Co., Ltd. to a four-neck flask manufactured by Pyrex (registered trademark) with a mechanical stirrer, add 100 g of desalted water and dissolve while stirring to prepare about 100 ml of a 1.3 mol/l sodium nitrate aqueous solution , and then add 20 g of USY zeolite (HSZ-330HUA) manufactured by Tosoh, which is the same as that used in Example 2, while stirring, keep the liquid temperature at 80°C for 2 hours, filter and separate the zeolite, and use 80°C desalination Wash with water. After air-drying, it was dried in a desiccator at 120° C. for 12 hours, and then calcined at 500° C. in air for 2 hours to obtain USY zeolite partially substituted with Na. As a result of elemental analysis, Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio) = 0.07/6.4/1.

<Dehydration Condensation Reaction of 1,3-Propanediol>

Except having used the said catalyst as a solid acid catalyst, polytrimethylene ether glycol was obtained by the same method as Example 1. The results are shown in Table-1.

Example 4

<Preparation method of metal element replacement solid acid>

After adding 7.8 g of special grade ammonium nitrate manufactured by Kishida Chemical Co., Ltd. to a four-neck flask made by Pyrex (registered trademark) with a mechanical stirrer, add 100 g of desalted water and dissolve it while stirring to prepare about 100 ml of 0.95 mol/l ammonium nitrate Aqueous solution, and 13g of ZSM-5 (Silicarite) (K-MCM-04, Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio)=21/1640/1 (manufactured (or analytical value)), after maintaining the liquid temperature at 80°C for 2 hours, the zeolite was separated by filtration and washed with desalted water at 80°C. After air-drying, it was dried in a desiccator at 120° C. for 12 hours, and then calcined at 500° C. in air for 2 hours to obtain silicarite partially substituted with Na. As a result of elemental analysis, Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio) = 0.14/1446/1.

<Dehydration Condensation Reaction of 1,3-Propanediol>

Except having used the said catalyst as a solid acid catalyst, polytrimethylene ether glycol was obtained by the same method as Example 1. The results are shown in Table-1.

Comparative example 1

In addition to adding 40.5g of 1,3-propanediol, 16.6g of ZSM-5 zeolite (K-MCM-02-2, Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio) =0/47/1), except that nitrogen was supplied at 100 Nml/min, polytrimethylene ether glycol was obtained in exactly the same manner as in Example 1. The results are shown in Table-1.

In addition, when the TPD of this catalyst was measured, the amount of ammonia desorption at 100 to 250°C was 0.19 mmol/g, which was 33% of the total (25°C to 700°C region) ammonia desorption amount. The ammonia desorption amount is 0.25mmol/g, which is 43% of the total (25°C-700°C region) ammonia desorption amount. area) of 57% of the amount of ammonia desorption.

In addition, the amount of ammonia desorption in the region of 300 to 450°C was 0.24 mmol/g. At this time, the amount of ammonia desorption in the region of 300 to 450°C was 0.96 times the amount of ammonia desorption in the region of 100 to 300°C. The desorption amount of NH ₃ desorbed in the region of 400°C to 700°C was 0.15mmol/g.

Comparative example 2

<Preparation method of metal element replacement solid acid>

Except using 25g of sodium nitrate, 280g of desalted water, and 30g of the ZSM-5 zeolite used in Comparative Example 1 as a solid acid catalyst, the method for preparing the metal element-substituted solid acid of Example 3 was the same as that of the ZSM-5 zeolite that was partially substituted with Na. 5 zeolites.

As a result of elemental analysis, Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio) = 0.26/49/1.

<Dehydration Condensation Reaction of 1,3-Propanediol>

Except having used the said catalyst as a solid acid catalyst, polytrimethylene ether glycol was obtained by the same method as Example 1. The results are shown in Table-1.

Example 5

<Preparation method of metal element replacement solid acid>

10 g of desalted water was added to 4 g of reagent Nafion NR-50 (Beads7-9 mesh) manufactured by Aldrich Co., and a 1N-NaOH aqueous solution was added dropwise at room temperature using a 3.3 ml graduated pipette. After stirring for 2 hours, it was washed with 100 ml of desalinated water, Dry, and dry under reduced pressure at 50°C and 2mmHg. The acid content by the neutral salt decomposition method was 0.11 mmol/g. Since the acid amount of Nafion used in Example 5 was 0.90 mmol/g, 88% of H ⁺ was replaced by Na ⁺ .

<Dehydration Condensation Reaction of 1,3-Propanediol>

Exactly the same as in Example 1 except that 2.5 g of the above-mentioned catalyst was used as the solid acid catalyst, 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. Polytrimethylene ether glycol was obtained.

The results are shown in Table-1.

Example 6

<Preparation method of solid acid>

20 g of mercaptopropyltrimethoxysilane oligomer (X-41-1805, lot305006) manufactured by Shin-Etsu Chemical Co., Ltd. and 39 g of special-grade ethanol manufactured by Junzheng Chemical Co. , Added 1.7 g of desalted water while stirring, and stirred at room temperature for 30 minutes. Then, the temperature in the flask was kept at 70° C. for 20 hours while stirring to perform hydrolysis, followed by gelation. After temporarily returning to room temperature, the product was taken out into a 100 ml eggplant-shaped flask, the solvent was distilled off, dried, pulverized, powdered in a mortar, and dried at 70° C. for 3 hours at 2 mmHg.

13 g of this powder was added to a 100 ml three-necked flask, and 36 g of 30% hydrogen peroxide water was added dropwise over 4 hours while stirring with a mechanical stirrer. Since heat was generated during the dropwise addition, SH groups were oxidized to SO ₃ H groups while cooling in a water bath.

After leaving to stand at room temperature for 12 hours, it stirred at 70 degreeC for 4 hours, and aged it. After cooling to room temperature, 1M sulfuric acid aqueous solution was added to make the solid acid concentration 1% by weight. After ion exchange, water was washed, dried, and dried under reduced pressure at 16 mmHg for 3 hours to obtain silica containing sulfonic acid groups. The acid content by the neutral salt decomposition method was 1.3 mmol/g. In addition, elemental analysis revealed that the sum of the Na ⁺ and K ⁺ substitution amounts was 0.002 equivalent to the acid amount. In addition, when the TPD of this catalyst was measured, the amount of ammonia desorption at 100 to 250°C was 0.83 mmol/g, which was 53% of the total amount (in the region of 25°C to 700°C). The ammonia desorption amount is 1.1mmol/g, which is 69% of the total (25°C-700°C region) ammonia desorption amount. area) of 76% of the ammonia desorption amount.

In addition, the amount of ammonia desorption in the region of 300 to 450°C was 0.15 mmol/g. At this time, the amount of ammonia desorption in the region of 300 to 450°C was 0.14 times the amount of ammonia desorption in the region of 100 to 300°C.

The desorption amount of NH ₃ desorbed in the region of 400°C to 700°C was 0.34mmol/g.

<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-mentioned catalyst was used as a solid acid catalyst and the reaction temperature was adjusted to 189°C±3°C. The results are shown in Table-1.

Example 7

<Preparation method of metal element replacement solid acid>

10 g of desalted water was added to 6 g of the catalyst used in Example 7, and 0.66 ml of 1N-NaOH was added dropwise at room temperature while stirring at room temperature, followed by stirring for 2 hours, and then the catalyst was separated by filtration and washed with 100 ml of desalinated water. After repeating this twice, use 1.46ml of 1N-NaOH to perform the same operation, wash with desalted water in the same way, dry, and dry under reduced pressure at room temperature at 16mmHg to obtain Na-substituted carbon dioxide containing sulfonic acid groups. silicon. The acid content by neutral salt decomposition method is 0.70mmol/g. Therefore, the amount of Na ⁺ substitution was 0.45 equivalent to the original acid amount.

<Dehydration Condensation Reaction of 1,3-Propanediol>

In addition to adding 20 g of 1,3-propanediol to the four-necked flask, add 0.0514 g (0.65 mmol) of pure chemically produced special-grade pyridine and stir well, put the flask in an oil bath at 25°C, and add Polytrimethylene ether glycol was obtained in the same manner as in Example 6 except for 5.06 g of the above catalyst as a solid acid catalyst. The total amount of Na ⁺ and pyridine was 0.55 equivalents to the original acid amount. The results are shown in Table-1.

Example 8

In addition to adding 0.34g of pyridine (0.14 times equivalent to the theoretical acid amount), and slowly adding 10g of USY zeolite (HSZ-350HUA, Na ₂ O/SiO ₂ /Al ₂ O ₃ ) manufactured by Tosoh as a solid acid catalyst (Molar ratio)=0.01/9.2/1, lot.C2-1X05), and make reaction temperature be 185 ℃ ± 3 ℃, obtain polytrimethylene ether glycol with the method similar to embodiment 7. The results are shown in Table-1.

Comparative example 3

In addition to using 0.26g pyridine (0.5 times the equivalent relative to the theoretical acid amount), and using 10g of the same ZSM-5 zeolite used in Comparative Example 1 as a solid acid catalyst, polytrimethylene was obtained in the same manner as in Example 8. base ether glycol. The results are shown in Table-1.

Example 9

Except for the use of 0.18 g of pyridine (one equivalent to the amount of acid by the neutral salt decomposition method), 2.5 g of the same Aldrich Co., Ltd. Reagent NafionNR-50 is used as a solid acid catalyst, and the temperature of the oil bath is heated to 182°C, the reaction temperature is adjusted to 169°C ± 3°C, and the catalyst is separated by decantation, obtained in the same manner as in Example 7 Polytrimethylene ether glycol. The results are shown in Table-1.

Example 10

In addition to using 40g of 1,3-propanediol, 13g of Nafion Powder (manufactured by Dupont, XR-500 Powder, 13S49-8055-K ⁺ 1200EW, the acid content by neutral salt decomposition method is 0.04mmol/g. In addition, it can be known by elemental analysis , the total of Na+, K+ replacement amounts is 0.95 equivalents relative to the original acid amount) as a solid acid catalyst, and except that nitrogen is supplied at 100 Nml/min, polytrimethylene ether glycol is obtained in the same manner as in Example 6. The results are shown in Table-1.

Example 11

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

Example 12

<Preparation method of metal element replacement solid acid>

After adding 48.8 g of special-grade ammonium nitrate manufactured by Kishida Chemical Co., Ltd. to a four-necked flask manufactured by Pyrex with a mechanical stirrer, 600 g of desalted water was added and dissolved while stirring to prepare about 600 ml of a 1 mol/l ammonium nitrate aqueous solution. 30.3 g of Ferrierite (HSZ-720KOA (K ₂ O/Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio)=0.23/0.70/17.7/13( Nominal value), lot.5001), after maintaining the liquid temperature at 80°C for 2 hours, filter and separate the zeolite, and wash it with desalted water at 80°C. Repeat this twice. After air-drying, dry it with a drier at 120°C After 12 hours, it was calcined at 500° C. in air for 2 hours to obtain H ⁺ type ferrierite.

<Dehydration Condensation Reaction of 1,3-Propanediol>

Except having used the said catalyst as a solid acid catalyst, polytrimethylene ether glycol was obtained by the same method as Example 1. The results are shown in Table-1.

Comparative example 4

<Preparation method of metal element replacement solid acid>

In addition to using 8.5g sodium nitrate, desalted water is 1mol/l sodium nitrate aqueous solution of 100g, and using ZSM-5 zeolite used in 20g comparative example 1 as solid acid catalyst, and the metal element replacement solid acid of embodiment 3 The preparation method is the same to obtain Na partially substituted ZSM-5 zeolite.

As a result of elemental analysis, Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio) = 0.23/51/1

<Dehydration Condensation Reaction of 1,3-Propanediol>

Except having used the said catalyst as a solid acid catalyst, polytrimethylene ether glycol was obtained by the same method as Example 1. The results are shown in Table-1.

Example 13

<Preparation method of metal element replacement solid acid>

In addition to using 5.36g sodium nitrate, 50ml desalted water, 1.3mol/l sodium nitrate aqueous solution, and using 15g USY zeolite (HSZ-35OHUA lot.C2-1X05, Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio) = 0.01/9.2/1), Na-substituted USY zeolite (Na ₂ O/SiO ₂ /Al ₂ O ₃ (molar ratio) = 0.12/10/1) was obtained in the same manner as in Example 3. .

<Dehydration Condensation Reaction of 1,3-Propanediol>

Except having used the said catalyst as a solid acid catalyst, polytrimethylene ether glycol was obtained by the same method as Example 1. The results are shown in Table-1.

Table 1

catalyst [Na+K]/H+* Pyridine/H+* mn 1,3-PO conversion rate (%) Polymer selectivity (%) polymer color Hammett acid strength function Ho Water detachment of catalyst (32-250°C)/% Water detachment of catalyst (50-200°C)/% Example 1 HY(5.3) 0.24 0 113 61 87 Colorless and transparent   +1.5＜Ho≤+3.3 12 10 Example 2 USY(6) 0.02 0 222 98 58 yellow -3＜Ho≤+1.5 8.8 7.7 Example 3 Na replacement USY (6.4) 0.07 0 146 81 78 Colorless and transparent -3＜Ho≤+1.5 7.8 6.7 Example 4 ZSM-5(1446) 0.14 0 184 90 72 light brown 8.8＜Ho - - Comparative example 1 ZSM-5(47) 0 0 314 86 37 Brown -5.6＜Ho≤-3 2.4 2.1 Comparative example 2 Na substitution ZSM-5(49) 0.26 0 314 69 33 Brown -5.6＜Ho≤-3 - - Example 5 Na replacement Nafion NR50 0.88 0 143 81 99 White   +1.5＜Ho≤+3.3 - - Example 6   Silica containing sulfonic acid groups 0.002 0 365 95 68 Brown -3＜Ho≤+1.5 9.7 8.6 Example 7   Silica containing Na-substituted sulfonic acid groups 0.45 0.1 109 66 84 Colorless and transparent   +1.5＜Ho≤+3.3 - - Example 8 USY(9.2) 0.01 0.14 107 58 79 Colorless and transparent -3＜Ho≤+1.5 9.0 7.7 Comparative example 3 ZSM-5(47) 0 0.5 287 99 47 Brown -5.6＜Ho≤-3 2.4 2.1 Example 9 Nafion NR50 0.01 1 181 92 98 White -3＜Ho≤+1.5 - - Example 10 Nafion Powder 0.95 0 281 77 79 Brown   +1.5＜Ho≤+3.3 - - Example 11 Nafion Powder 0.95 0.12 87 35 84 Colorless and transparent   +1.5＜Ho≤+3.3 - - Example 12 FER(18) ≤0.93 0 85 36 72 Pale yellow - 6.2 5.5 Comparative example 4 Na substitution ZSM-5(51) 0.23 0 380 75 30 Brown - 2.3 1.9 Example 13 Na substitution ZSM-5(51) 0.12 0 183 88 75 Colorless and transparent - 7.6 6.4

The inside of parentheses is the molar ratio of SiO ₂ /Al ₂ O ₃ , * the molar ratio relative to the amount of acid.

Although the present invention was described in detail using specific embodiments, it is clear to those skilled in the art that various changes and modifications can be made without departing from the intention and scope of the present invention.

In addition, this application is based on Japanese Patent Application (Japanese Patent Application No. 2004-191567) filed on June 29, 2004, Japanese Patent Application (Japanese Patent Application No. 2004-191568) filed on June 29, 2004, and Japanese Patent Application (Japanese Patent Application No. 2004-191568) filed on August 23, 2004. Japanese Patent Application (Japanese Patent Application No. 2004-242744) and Japanese Patent Application (Japanese Patent Application No. 2004-242745) filed on August 23, 2004, the entire contents of which are incorporated by reference.

Industrial Applicability

According to the present invention, it is possible to provide a method for producing a polyether polyol with little coloring at a high yield, selectively, and in high yield by dehydrating and condensing a polyol using a solid catalyst.

Claims (8)

1. A method for producing polyether polyols, characterized in that, when polyether polyols are produced through the dehydration condensation reaction of polyols, a solid acid catalyst is used, and the solid acid catalyst satisfies the following (1) to (3) At least one of the conditions, (1) The acidity function _H measured by the Hammett indicator adsorption method is greater than -3; (2) In the temperature rise desorption analysis (TPD) of ammonia, the amount of ammonia desorption in the region of 100-350°C is more than 60% of the total amount of ammonia desorption (in the region of 25°C-700°C); (3) In the thermogravimetry (TG), the desorption amount of water is 3% by weight or more of the basis weight in the region of 32 to 250°C. 2. The method for producing polyether polyol according to claim 1, wherein the solid acid catalyst contains 0.01 to 2.5 equivalents of a metal element and/or an organic base relative to the acid. 3. The method for producing polyether polyol according to claim 2, wherein the metal element is an alkali metal. 4. The method for producing polyether polyol according to claim 2, wherein the organic base has a pyridine skeleton. 5. The method for producing polyether polyol according to claim 1, wherein a solid acid catalyst, a metal element-containing compound, and/or an organic base are used simultaneously. 6. The method for producing polyether polyol according to any one of claims 1 to 5, wherein the solid acid catalyst is selected from interlayer compounds, zeolites, interstitial porous substances, metal composite oxides, sulfonic acid group-containing At least one of an oxide or composite oxide, a carbon material containing a sulfonic acid group, and a resin having a perfluoroalkylsulfonic acid group in a side chain. 7. The manufacture method of the polyether polyol according to any one of claims 1 to 6, wherein the polyol is a dibasic alcohol having 2 primary hydroxyl groups with 3 to 10 carbon atoms (however, by dehydration to form 5 1-member ring or 6-member ring cyclic ether diols), or a mixture of the above-mentioned diols and other polyols, the ratio of other polyols is less than 50 mol%. 8. The method for producing polyether polyol according to any one of claims 1 to 7, wherein the dehydration condensation reaction is performed at 120°C to 250°C.