KR20070032725A - Process for producing polyether polyol - Google Patents

Abstract

By dehydration condensation of a polyol, there is provided a method of producing a highly efficient polyether polyol having high selectivity and low coloring.

When manufacturing a polyether polyol by the dehydration condensation reaction of a polyol, the solid acid catalyst which satisfy | fills at least 1 among following (1)-(3) is used.

(1) The acidity function (H ₀ ) measured by Hammett's indicator adsorption method is larger than -3.

(2) In the temperature-desorption analysis (TPD) of ammonia, the ammonia removal amount in the 100-350 degreeC area | region is 60% or more of the ammonia removal amount of the whole (25 degreeC-700 degreeC area).

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

Description

Production method of polyether polyol {PROCESS FOR PRODUCING POLYETHER POLYOL}

The present invention relates to a process for producing polyetherpolyols by dehydration condensation reaction of polyols. Specifically, the present invention relates to a method for efficiently producing polyether polyols with low coloring by carrying out the reaction in the presence of a catalyst having specific acid properties.

Polyether polyols are polymers having a wide range of uses, including raw materials of soft segments such as elastic fibers and plastic elastomers. As typical examples of the polyether polyol, polyethylene glycol, poly (1,2-propanediol), polytetramethylene ether glycol, and the like are known. Among them, poly (1,2-propanediol) 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 difference in the physical properties of these hydroxyl groups becomes a problem depending on a use. On the other hand, polytrimethylene ether glycol which is a dehydration condensate of 1,3-propanediol has attracted attention recently because it has only a primary hydroxyl group and a low melting point.

Polyetherpolyols can generally be produced by dehydration condensation of the corresponding polyols. However, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, and the like are cyclic ethers of 5- or 6-membered rings, that is, 1,4-dioxane, tetrahydrofuran and tetrahydro, respectively, in dehydration condensation. Generates pyran. For this reason, the polyether polyol corresponding to the polymer of ethylene glycol and 1, 4- butanediol is manufactured by ring-opening polymerization of the corresponding cyclic ether, ie, ethylene oxide and tetrahydrofuran. In addition, the polyether polyol corresponding to the polymer of 1,5-pentanediol is difficult to manufacture because tetrahydropyran, which is a cyclic ether, is thermodynamically advantageous.

The production of polyether polyols by dehydration condensation reaction of polyols is generally performed using an acid catalyst. Examples of the catalyst include iodine, inorganic acids such as hydrogen iodide and sulfuric acid, organic acids such as paratoluenesulfonic acid (see Patent Document 1), resins having perfluoroalkylsulfonic acid groups in the side chain (see Patent Document 2), sulfuric acid and cuprous chloride. Combinations, activated clay, zeolite, organic sulfonic acid, heteropoly acid (see Patent Document 3), and the like have been proposed.

Moreover, as a reaction method, the method (refer patent document 4) which performs dehydration condensation reaction first in nitrogen atmosphere, and then performs dehydration condensation reaction under reduced pressure is also proposed.

Among these, inorganic acids such as iodine, hydrogen iodide and sulfuric acid, organic acids such as paratoluenesulfonic acid, organic sulfonic acids and heteropolyacids are homogeneous acid catalysts, but when a homogeneous acid catalyst is used, the acid catalyst is a strong acid. Because of its properties, the reactor used for the polymerization reaction is corroded, the reactor is corroded, the metal component is eluted, the polyether polyol of the product is colored, and the eluted metal component is contained in the polyether polyol. There was. Moreover, in order to prevent corrosion, it is necessary to employ the reactor of glass or glass lining, or to use the reactor using high quality materials, such as Hastelloy, and it was a big problem at the time of enlargement of a facility and a construction cost. In addition, when a homogeneous catalyst is used, the ester derived from the acid of the catalyst may be contained at the terminal of the polyether polyol of the product, so that hydrolysis of the ester may be necessary. Occurs. Moreover, since a uniform acid catalyst is contained in a polyether polyol, these acid catalysts must be removed by methods, such as neutralization and water washing, and there existed a problem that the purification process of the polyether polyol for this is required.

If a solid catalyst can be used as the catalyst, all of these problems can be solved, which is a very advantageous method.

Examples of the solid acid catalyst which can be used for the dehydration condensation reaction of the polyol include resins, activated clays and zeolites having a perfluoroalkylsulfonic acid group in the side chain from the above-mentioned references, which are used in the dehydration condensation reaction of the polyols. In this case, there are many side reaction products such as allyl alcohol, the selectivity of polyether polyol is very low, and the coloring of the polyether polyol itself is severe, which is not a practical level.

Patent Document 1: US Patent No. 2520733

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

Patent Document 3: US Patent No. 55908989

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

Disclosure of the Invention

Problems to be Solved by the Invention

The present invention aims to provide a method for producing a high yield of polyether polyol having good selectivity and low coloring by dehydrating polyol using a solid catalyst.

Means to solve the problem

Since the strong acid is active in the case of the homogeneous catalyst as described above, the solid acid catalyst having the strong acid property has been considered to be preferable even in the case of the heterogeneous catalyst. Surprisingly, however, from the inventor's review, it became clear that the side reactions such as excessively strong acid point dehydration and the like were promoted, and that the catalyst having strong acid properties was unsuitable. 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 characterized by using a solid acid catalyst which satisfies at least one of the following conditions (1) to (3) when the polyether polyol is produced by the dehydration condensation reaction of the polyol. It is in the manufacturing method of a polyether polyol.

The acidity function (H ₀ ) measured by the Hammett indicator adsorption method is greater than -3.

In the elevated temperature desorption analysis (TPD) of ammonia, the ammonia removal amount in the region of 100 to 350 ° C. is 60% or more of the ammonia removal amount of the whole (a region of 25 ° C. to 700 ° C.).

In the thermogravimetric analysis (TG), the amount of water leaving is at least 3% by weight of the reference weight in the region of 32 to 250 ° C.

A 2nd summary is the manufacturing method of the polyether polyol as described above whose solid acid catalyst contains 0.01 equivalent or more and 2.5 equivalent or less of metal elements and / or organic base with respect to an acid.

A third aspect is a method for producing the polyether polyol as described above, wherein the metal element is an alkali metal.

A fourth aspect is the production method of the polyether polyol as described above, wherein the organic base has a pyridine skeleton.

5th summary is the manufacturing method of the polyether polyol mentioned above using a solid acid catalyst and a metal element containing compound and / or an organic base together.

The sixth aspect is a resin in which a solid acid catalyst has an interlayer compound, a zeolite, a mesoporous material, a metal complex oxide, an oxide or complex oxide containing a sulfonic acid group, a carbon material containing a sulfonic acid group, and a perfluoroalkylsulfonic acid group on the side chain thereof. It is in the manufacturing method of the polyether polyol as described above which is at least 1 sort (s) chosen from the group which consists of.

The seventh aspect is that a polyol has 3 to 10 carbon atoms having two primary hydroxyl groups, except that dehydration forms a 5- or 6-membered cyclic ether by dehydration, or other As a mixture of polyols, wherein the proportion of the other polyols is less than 50 mol%.

8th point is the manufacturing method of the above-mentioned polyether polyol which performs dehydration condensation reaction at 120 degreeC or more and 250 degrees C or less.

Effects of the Invention

According to the manufacturing method of this invention, polyether polyol with few coloring can be manufactured efficiently under mild conditions.

To practice the invention  Best form for

<Solid Acid Catalysts>

The solid acid catalyst used by the manufacturing method of this invention shall satisfy at least 1 of the conditions as described in (1)-(3) shown below. Among these conditions, it is more preferable to satisfy two conditions, and specifically, the solid acid which satisfies the conditions of (1) and (2), (1) and (3), or (2) and (3). More preferred are catalysts. In addition, solid acid catalysts which satisfy all the conditions of (1), (2) and (3) are particularly preferred.

(1) Hammett's indicator adsorption method

The solid acid catalyst used in the present invention requires that the acid strength is not too strong in the present reaction, and the acidity function (H ₀ ) measured by Hammett's indicator adsorption method is more preferably greater than -3 and greater than +1.5. It is especially preferable that it is +2 or more. The acidity function (H ₀ ) measured by Hammett's indicator adsorption method has a strong acid point. Thus, an acidity function (H ₀ ) greater than -3 means that the Hammett indicator with pKa = -3 is a weak acidic property with no acidic coloration.

Hammett's acid strength function here is calculated | required by measuring acid intensity | strength with Hammett's indicator in the commercially available benzene solution which processed the solid acid catalyst for 2 days at 25 degreeC in saturated steam.

In Hammett's indicator method, the indicator for measuring acidity can be easily measured by changing the indicator of Hammett's acid into an acidic color on a solid acid catalyst when acidic is indicated. When the solid acid catalyst is originally colored, it is difficult to recognize the color change of the indicator by the naked eye, so that the change of the indicator may be analyzed by, for example, spectroscopic method.

(2) Method of elevated temperature desorption analysis of ammonia (TPD)

It is preferable that the acid amount and acid strength of the solid acid catalyst used in this reaction do not have a large amount of strong acid point, and the amount of ammonia leaving in the region of 100 to 350 ° C. by a temperature programmed desorption (TPD) of ammonia. It is preferable that it is 60% or more of the ammonia removal amount of the whole (25 degreeC-700 degreeC area | region). Especially, it is more preferable that it is 70% or more.

Moreover, it is preferable that it is 50% or more, and it is more preferable that it is 60% or more of the ammonia removal amount in the area | region of 100-300 degreeC of the whole (region of 25 degreeC-700 degreeC).

Moreover, it is preferable that it is 40% or more of the ammonia removal amount of the whole (region of 25 degreeC-700 degreeC) in 100-250 degreeC area | region, and it is more preferable that it is 50% or more.

The amount of ammonia released in the region of 300 to 450 ° C. is 0.6 times or less, preferably 0.5 times or less, more preferably 0.3 times or less, particularly 0.2 times or less with respect to the amount of ammonia released in the region of 100 to 300 ° C. desirable. Among them, the ammonia release amount in the region of 400 to 700 ° C is preferably 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. It is more preferable if it is. Moreover, even if it is 0.1 mmol / g or more, Preferably it is 0.2 mmol / g, More preferably, it is 0.3 mmol / g or more.

(3) Thermogravimetric Analysis Method (TG)

The solid acid catalyst used in this reaction is 3% or more of the reference weight, more preferably 5% or more, and still more preferably 50 to 200 ° C between 32 to 250 ° C in thermogravimetric analysis (TG). Preferably, at least 5% of the reference weight of water is a solid acid catalyst which is desorbed. The analysis method and reference weight of TG at this time shall be based on the method in the Example mentioned later.

The solid acid catalyst used in this reaction can be selected using measurement of acid strength by Hammett's indicator, elevated temperature desorption analysis of ammonia, or thermogravimetric analysis, polyether polyol with high polyether polyol selectivity and low coloration. Can be obtained.

In addition, a part of the acid of the solid acid catalyst that satisfies at least one of the above conditions is replaced with a metal element, or a metal element or an organic base modified or used in addition to the solid acid catalyst. When the element-containing compound or the component of the organic base is added in the form of coexistence in the reaction system, the effect is increased.

It is not clear why the acid strength of the solid acid catalyst, the amount of strong acid point, and the desorption behavior of water affect the dehydration condensation reaction of the polyol.

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. In addition, since the strong acid is active in the case of the homogeneous catalyst, this reaction has been considered to be preferable in the case of heterogeneous catalysts. However, according to the inventor's study, it became clear that excessively strong acid sites promote side reactions such as intramolecular dehydration, and that ZSM-5 and the like having strong acid properties are unsuitable.

If such a strong acid point is damaged and a solid acid catalyst composed of an acid point effective in the present reaction is used, the selectivity is high, a polyether polyol can be obtained, and the coloring of the polyether polyol itself is reduced as a result of less side reactions.

Such solid acid catalyst is a catalyst having an acidity function (H ₀ ) greater than -3 measured by the indicator adsorption method of Hammett of the present invention, or ammonia desorption amount in the region of 100 to 350 ° C. in the measurement of elevated temperature desorption of ammonia. It is a catalyst which is 60% or more of the ammonia desorption amount of the area | region (25 degreeC-700 degreeC), or a solid acid catalyst by which 3% or more of reference weights are desorbed between 30-250 degreeC in thermogravimetric analysis.

In addition, it is thought that these solid acid catalysts desorb | release 3% or more of water of a reference weight in the temperature range of 32-250 degreeC, as follows.

In this reaction, water is produced by the dehydration condensation reaction. Moreover, reaction temperature is 120-250 degreeC. The fact that water is desorbed in the temperature range of 32-250 degreeC by thermogravimetric analysis (TG) is clear that there exists water release and water retention in the vicinity of reaction temperature. On the contrary, the absence of water desorption in this temperature range means that there is no water that can be involved in the reaction around the catalyst. Since water has a function of poisoning the acid point of the solid acid catalyst, if the catalyst maintains water in the reaction temperature range, excessively strong acid point is damaged and only a good acid point is involved in the reaction. I think it improves.

In addition, the substitution or modification of metal elements or bases with these solid acid catalysts, or the addition of these components to the reaction system is thought to damage the more minute strong acid point on the solid acid catalyst and to eliminate side reaction sites.

Although it will not specifically limit, if it is a solid acid catalyst which satisfy | fills at least 1 condition of the above (1)-(3), Preferably it is an interlayer compound, such as activated clay, a zeolite, a mesoporous substance, silica-alumina, silica-zirconia, etc. Metal composite oxides, oxides or sulfides containing sulfonic acid groups, organic compounds such as carbonaceous materials and ion exchange resins containing sulfonic acid groups, resins having perfluoroalkylsulfonic acid groups in the side chain, and the like can be used. Among these, in terms of being stable under the reaction conditions, interlayer compounds such as activated clay, zeolites, mesoporous materials, metal complex oxides such as silica-alumina and silica-zirconia, oxides containing sulfonic acid groups or complex oxides, containing sulfonic acid groups Considering that the carbon material is more preferable, the activity is high and inexpensive, it is more preferable that the interlayer compound such as activated clay, zeolite, mesoporous material, oxide or complex oxide containing sulfonic acid group, carbon material containing sulfonic acid group, Particularly preferred are oxides or complex oxides containing sulfonic acid groups and carbon materials containing sulfonic acid groups.

Moreover, when synthesize | combining these solid acid catalysts, it can synthesize | combine by using a well-known method.

<Metal element>

As a proton of the acid point of a solid acid catalyst, and a metal element which can be substituted, or a metal element which can be modified, alkali metal, alkaline-earth metal, the transition metal of group 3-12, the element of group 13 are preferable, and alkali metal, alkali Earth metals are more preferred, and alkali metals are particularly preferred. As alkali metal, Li, Na, K, Cs is preferable and Na is especially preferable.

The content of the metal element is, as a metal element, preferably 0.01 equivalent or more, more preferably 0.05 equivalent or more, preferably 2.5 equivalents or less, more preferably 1 equivalent or less, further preferably, relative to the acid amount of the solid acid catalyst. Preferably it is used so that it is 0.5 equivalent or less.

Here, the acid amount refers to the theoretical acid amount or the acid amount determined by the neutral salt decomposition method. In the case of zeolites composed of Al and silicon, the theoretical acid amount calculated from the amount of Al, zeolites containing elements other than Al, mesoporous materials, sulfonic acid-containing solid catalysts, or interlayer compounds such as oxides, complex oxides and activated clays Means the amount of acid determined by the neutral salt decomposition method.

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

In addition, in the case of a solid acid catalyst, the catalyst in which the acid point is substituted by the metal may be obtained previously. The content of the metal element refers to the equivalent to the original acid amount when the metal element is not substituted with the acid point of the solid acid.

That is, when the acid amount in the case of unsubstituted metal is 1 mmol / g and the acid amount in the case of metal substitution is 0.7 mmol / g, the content of the metal element of the metal-substituted solid acid is 0.3 equivalent to the acid amount. In addition, the substitution amount of a metal can also be calculated | required by elemental analysis.

As the metal element source, a metal element-containing compound can be used, and salts of mines such as sulfates, hydrogen sulfates, nitrates, halides, phosphates, hydrogen phosphates, and borate salts of metals, trifluoromethane sulfonates, and paratoluene sulfonic acid Examples thereof include metal salts such as salts and organic sulfonates such as methane sulfonate, carboxylates such as formate and acetate, metal hydroxides, metal alkoxides and acetylacetonates of metals.

As a method of substituting or modifying a metal element in a 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 impregnating a solution, pore-filing a solution of a metal compound, It can obtain by well-known methods, such as a method of drying, and these catalysts can also employ | adopt the process of water washing, drying, and baking as needed.

<Organic base>

The organic base is preferably a nitrogen-containing organic base, in particular a nitrogen-containing organic base having tertiary or quaternary nitrogen atoms. Some of them are exemplified by nitrogen-containing heterocyclic compounds having a pyridine skeleton such as pyridine, picoline, quinoline, 2,6-lutidine, N-methylimidazole, 1,5-diazabicyclo [4.3. Nitrogen-containing heterocyclic compounds having an NC = N bond, such as 0] -5-nonene and 1,8-diazabicyclo [5.4.0] -7-undecene, and trialkylamines such as triethylamine and tributylamine And quaternary ammonium salts such as 1-methylpyridinium chloride and the like. Among these, those having a pyridine skeleton, those having an N-C = N bond are preferred, and those having a pyridine skeleton are particularly preferred.

The organic base is preferably 0.01 equivalent or more, more preferably 0.05 equivalent or more with respect to the acid amount of the solid acid catalyst (also in this case, the acid amount in the case of unsubstituted as in the case of metal elements). It is good to use so that it may be 2.5 equivalent or less, More preferably, it is 1 equivalent or less, Especially preferably, it is less than 1 equivalent.

As a method of modifying an organic base in a solid acid catalyst, a known method such as a method of mixing the solid acid catalyst in a solution containing a desired base, a method of forcibly impregnating an impregnation, a method of fore-pilling a base-containing solution, and drying the method It can obtain by the method, and these catalysts can also employ | adopt the process of water washing and drying as needed.

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

In the present invention, the solid acid catalyst having an acidity function (H ₀ ) measured by the indicator adsorption method of (1) Hammett described above is greater than -3, or (2) an elevated temperature desorption measurement of ammonia in a region of 100 to 350 ° C. Catalyst having 60% or more of the total amount of ammonia released in the range of 25 ° C to 700 ° C, or (3) at least 3% of the reference weight of water desorbed during 32 to 250 ° C in thermogravimetric analysis. In addition to the solid acid catalyst which satisfies at least one of the conditions of the catalyst, a metal element and / or an organic base may be used in combination. Specifically, you may add these to a reaction system separately, and after mixing these compounds, you may use for reaction. In this case, the sum of the amounts of all metal elements and organic bases present in the reaction system is in the above range.

Said solid acid catalyst and a metal element or an organic base may exist separately in a reaction system, and may form the salt with a solid acid catalyst, a metal element, or an organic base.

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

<Raw material polyol>

Examples of the polyol of the reaction raw material include 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, and 1,7-heptanediol It is preferable to use diols having two primary hydroxyl groups, such as 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,4-cyclohexanedimethanol, and 1,3 More preferred is propanediol. However, even in the case of diol having two primary hydroxyl groups, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, and the like generate cyclic ethers by dehydration condensation reaction as described above. It is not preferable as a raw material of the method of the invention. Normally these diols are used alone, but may be used as a mixture of two or more diols, if desired. However, even in this case, it is preferable to make the main diol occupy 50 mol% or more. Moreover, the dimer oligomer obtained by the dehydration condensation reaction of main diol can be used together in these diols. Moreover, you may use together the polyol more than triol, such as trimethylol ethane, a trimethylol propane, pentaerythritol, or the oligomer of these polyols. However, even in these cases, it is preferable to make the main diol occupy 50 mol% or more. Normally 3 to 10 carbon atoms having two primary hydroxyl groups, except that 5- or 6-membered cyclic ethers are produced by dehydration condensation reactions such as 1,4-butanediol and 1,5-pentanediol The reaction is provided with a diol of, or a mixture with other polyols, of less than 50 mol% of other polyols. Preferably, a diol selected from the group consisting of 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, or a mixture with other polyols The reaction is provided with a proportion of polyol of less than 50 mol%, particularly preferably of 1,3-propanediol, or a mixture of other polyols with a proportion of other polyol of less than 50 mol%.

<Method for producing polyether polyol>

In the present invention, the production of the polyether polyol by the dehydration condensation reaction of the polyol can be carried out in a batch method or in a continuous mode. In the case of a batch system, what is necessary is just to inject a polyol and a solid acid catalyst which are raw materials, and a metal element or an organic base as needed in a reactor, and to react under stirring. In this case, the solid acid catalyst is usually used in the range of 0.01 to 1 times by weight based on the polyol of the raw material.

In the case of a continuous reaction, for example, the solid acid catalyst is kept in a reaction apparatus or a flow-type reaction apparatus in which a large number of stirring tanks are in series, and the polyol which is a raw material is continuously supplied to the reactor, and the solid acid is fed from another stage. The method of continuously removing only the reaction liquid containing no catalyst can be used. In this case, it can employ | adopt also in a suspended phase or a stationary phase reaction.

The lower limit is usually 0.01 weight times or more, preferably 0.1 weight times or more, and the upper limit is usually 10000 weight times or less, preferably 1000 weight times or less with respect to the solid acid catalyst remaining in the reaction apparatus. The polyol is fed in 1 hour. In this case, since the equivalence ratio of the base to the solid acid catalyst in the reaction apparatus may decrease over time, a small amount of the solid acid catalyst may be taken out as needed to charge the new catalyst. Alternatively, the base may be fed together with the raw material polyol so that the equivalent ratio of organic base to acid is maintained at a desired value.

As for the temperature of a dehydration condensation reaction, a minimum is 120 degreeC or more normally, Preferably it is 140 degreeC or more, and an upper limit is good to carry out reaction at 250 degreeC normally, Preferably it is 200 degrees C or less. It is preferable to perform reaction in inert gas atmosphere, such as nitrogen and argon. The reaction pressure is arbitrary as long as the reaction system is maintained in the liquid phase, and is usually performed under normal pressure. If desired, the reaction may be carried out under reduced pressure or an inert gas may be passed through the reaction system in order to promote the desorption of the water generated by the reaction from 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 it is 20 hours or less. The reaction is usually carried out without solvent, but a solvent may be used if desired. The solvent may be appropriately selected and used from an organic solvent used in a commercial organic synthesis reaction in consideration of vapor pressure, stability, solubility of raw materials and products under reaction conditions, and the like.

Separation and recovery of the resulting polyether polyol from the reaction system can be carried out by a conventional method.

In the case of a suspended phase, suspended solid acid catalyst is first removed from the reaction liquid by filtration or centrifugation. When a metal compound is added to the reaction system, a method of removing by water washing, forming a poorly soluble salt and removing by filtration can be adopted. In the case of an organic base, when it can distill, it can remove by distillation operation, and the taken out organic base can be returned to a reaction system again. If distillation is not possible, it can remove by water washing.

Moreover, the oligomer of low boiling point is removed by distillation or extraction of water etc. as needed, and the target polyether polyol is obtained.

In the case of the fixed-phase reaction, the nasal component and the low boiling point oligomer are removed from the reaction liquid taken out by distillation or water washing as needed, and the target polyether polyol is obtained.

These polyether polyols can be made into a product through a drying process further as needed.

<Polyether polyol>

The color of the polyether polyol obtained by the method of the present invention is preferred as there is no coloring. The degree of coloring is visually black> brown> yellow> colorless (white).

Moreover, the number average molecular weight of the polyether polyol of this invention can be adjusted with the kind and catalyst amount of the catalyst to be used, and a minimum is 80 or more normally, Preferably it is 600 or more, More preferably, it is 1000 or more, and an upper limit is Usually, it is 10000 or less, Preferably it is 7000 or less, More preferably, it is 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 applications such as elastic fibers, thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, and coating materials.

Example 1

The present invention will be described in more detail with reference to the following Examples.

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

The acid amount by the neutral salt decomposition method was measured as follows. 10 mg of the sample was quantified to the first decimal place, and 30 ml of saturated aqueous sodium chloride solution (prepared by Kosei Chemical Co., Ltd., special grade sodium chloride and demineralized water) was added and stirred at room temperature with a stirrer for 15 minutes.

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

<Measurement of Hammett's Acid Strength Function>

0.1 g of the solid acid catalyst is kept at room temperature (25 ° C. ± 3 ° C.) for 2 days under saturated steam to adsorb saturated steam. After adding 2 ml of high-grade benzene manufactured by Kokusan Chemical Co., Ltd., 2 drops of a Hammett indicator in a 0.1 wt% solution was added dropwise to observe a change in color on the catalyst.

Hammett indicators are anthraquinone (pKa-8.2) → benzalacetophenone (pKa-5.6) → discinnamalacetone (pKa-3.0) → 4-benzeneazodiphenylamine (pKa + 1.5) → p-dimethylaminoazobenzene (pKa +3.3)-4-benzeneazo-1-naphthylamine (pKa + 4.0)-methyl red (pKa + 4.8)-neutral red (pKa + 6.8) was dripped in this order.

`` The acidity function (H ₀ ) measured by the Hammett's indicator adsorption method is greater than -3 '' means, for example, anthraquinone (pKa-8.2), benzalacetophenone (pKa-5.6), and dicinnamalacetone (pKa). 4-benzene azodiphenylamine (pKa + 1.5), p-dimethylaminoazobenzene (pKa + 3.3), 4-benzeneazo-1- having no discoloration to an acidic color and having a pKa greater than -3.0 up to -3.0) The indicators of naphthylamine (pKa + 4.0), methyl red (pKa + 4.8) and neutral red (pKa + 6.8) show coloration in acidic color, or no indicator indicates coloration in acidic color.

Conversely, the acidity function (H ₀ ) is less than -3, for example, smaller than dicinnamalacetone (pKa-3.0), such as anthraquinone (pKa-8.2) or benzalacetophenone (pKa-5.6). An indicator of pKa indicates discoloration to an acidic color.

In Table-1, when 4-benzene- azodiphenylamine (pKa + 1.5) does not have coloring with an acidic color, but has coloring with p-dimethylamino azobenzene (pKa + 3.3), it is "+1.5 < H ₀ ≦ + 3.3 ”. Even in pKa + 6.8, when there is no change to an acidic color, the acid intensity is represented by H ₀ > +6.8. H ₀ of each catalyst is shown in Table-1.

<Ammonia Tally Analysis Method>

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

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

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

Measuring conditions :

Sample amount; About 30mg

Sample pretreatment conditions; He 80 ml / min, the temperature was raised to 30 degreeC / min from room temperature to 250 degreeC, and 250 degreeC * 30 minutes hold | maintain.

Ammonia adsorption condition; `` After evacuating the sample with a rotary pump at 100 ° C, inject 90ml of ammonia gas (100% purity) into the sample at the same temperature and hold it for 15 minutes '' → `` Vacuum exhaust 100 ° C x 30 minutes '' 200 mL / min, 100 ° C. × 30 min. &Quot; Return to room temperature and start TPD measurement after 5 min. '

TPD measuring gas; He 80ml / min

TPD measurement temperature range; Room temperature to 700 ° C (heating at 10 ° C / min)

Determination of the amount of desorbed ammonia; Apart from the measurement of each sample, a fixed amount of ammonia was injected, and a calibration curve was prepared from the amount (molar number) and the area of ionic strength (m / z = 16) at that time. The amount of ammonia desorbed in each sample was calculated and quantified by calculating the area of the ionic strength in the corresponding temperature range, and from the obtained calibration curve.

Moreover, when m / z = 16 derived from ammonia, the sample which may have m / z = 16 derived from the non-negligible amount of another compound (representative example: water), m / z derived from the compound It is necessary to calculate the ionic strength of = 16 and exclude the contribution from the ammonia quantitative value.

The ionic strength of m / z = 16 of the compound is TPD measurement data from the ratio of the original “m / z ionic strength other than m / z = 16” and “ionic strength of m / z = 16”. The ionic strength of m / z = 16 derived from the compound in it can be calculated.

Thermogravimetric Analysis (TG)

Thermogravimetric analysis was performed by the following method.

sample ; Sampling in air at room temperature after pretreatment to hold for 2 days in saturated water vapor.

Measuring device; SII Nanotechnology Co., Ltd. TG-DTA 6300

Calibration of temperature; Calibrated with In, Pb, Sn 3 types of metals

Calibration of weight; Calibrate with weights at room temperature. Calibrated with calcium oxalate.

Sample amount; About 10mg

Sample container; Al, 5 mm diameter x 2.5 mm

How to measure ; Dry nitrogen gas (purity 99.999% or more, dew point -60 degreeC) After 200 mL / min flow and holding at 30 degreeC for 30 minutes at room temperature, it heated up at 10 degreeC / min and heated up to 500 degreeC.

Reference weight; The weight loss up to 32 ° C is taken as the reference weight based on the weight obtained by subtracting the weight of the measured sample.

Release of water; Percentage of weight loss relative to reference weight in a given temperature range.

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

Element Analysis

About the quantity of Al, Na, and Si contained in a zeolite catalyst, the numerical value quantified by the following method was employ | adopted, unless there is particular notice.

XRF method: The sample was dried at 120 ° C for 2h, cooled to 500 mg, collected, mixed with 5.00 g of LiB ₄ O ₇ , melted and cooled to form glass beads, followed by fluorescent X-ray (XRF (Basic Parameter Method ( Fundamental Parameter): FP method)).

In addition, since ZSM-5 (silica light) used in Example 4 had little content of Al and Na, it quantified by the following method.

Chemical analysis method: The sample was dried for 2h at 120 degreeC, cooled, separated and collected, the whole amount was decomposed by the wet decomposition method, it was made into a solution, and quantified by ICP-AES (Al, calibration curve method), AAS (Na, calibration curve method).

The amounts of Na and K in the sulfonic acid group-containing silica and Nafion were analyzed by the following method.

Chemical analysis method (2): The sample was dried for 2 h at 120 ° C, cooled, separated and collected, and the total amount was decomposed by a dry incineration method to make a solution, and quantified by AAS and calibration curve method.

<Measurement of Number Average Molecular Weight (Mn)>

The measurement of the number average molecular weight (Mn) of polyether polyol was performed on the following conditions by gel permeation chromatography, and was computed based on polytetrahydrofuran.

column :

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

Mass calibration:

POLYTETRAHYDROFURAN CALIBRATION KIT (Polymer Laboratories)

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

Solvent: Tetrahydrofuran

<GC analysis condition>

1,3-propanediol contained in the nasal component and the obtained oil layer was analyzed by gas chromatography (GC).

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

Carrier: Nitrogen 1.5 ml / min, Split ratio 40

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

Inlet, Detector Temperature: 240 ℃

Internal standard; n-tetradecane

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

Example 1

<Distillation purification of 1,3-propanediol>

In a Pyrex® 500 ml four-necked flask equipped with a reflux condenser, nitrogen inlet tube, thermometer and stirrer under a nitrogen atmosphere, 250 g of 1,3-propanediol (Reagent manufactured by Aldrich, Purity 98%, Batch # 10508AB) and 1.75 g of potassium hydroxide were injected. The flask was placed in an oil bath and heated to maintain the temperature at 162 ° C. to 168 ° C. if the liquid temperature reached 162 ° C. After 2 hours, the flask was removed from the oil bath and left to cool to room temperature. Subsequently, monostillation was carried out at about 90 degreeC under reduced pressure. 11 g of the initial distillation was discarded and about 230 g of distillate was recovered.

<Dehydration condensation reaction of 1,3-propanediol>

20 g of 1,3-propanediol distilled and purified by the above method was added to a Pyrex (registered trademark) 100 ml four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a thermometer, and a mechanical stirrer. It was injected while feeding. This flask was attached to an oil bath at 25 ° C. and stirred with HY zeolite (HSZ-320HOA, SiO ₂ / Al ₂ O ₃ manufactured by Tosoh) (Molar ratio) = 5.3, lot. 10 g) was added slowly.

After the solid acid catalyst was added, the mixture 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. After adjusting the temperature of the reaction liquid to 185 degreeC +/- 3 degreeC, it hold | maintained for 6 hours and made it react, and the flask was taken out of the oil bath, it was left to room temperature, and cooled. The water produced during the reaction was entrained with nitrogen and was collected and collected using a by-product trap, which was cooled with a dry ice-ethanol solution along with byproduct, 1,3-propanediol. These were analyzed as the nasal component and the amount of 1,3-propanediol contained in separate gas chromatography.

After adding 50 g of tetrahydrofuran to the reaction liquid cooled to room temperature and stirring for 1 hour, the solid acid catalyst was filtered through the 1 micrometer PTFE filter. 30 mL of tetrahydrofuran (containing 0.03 wt% BHT (butylhydroxytoluene)) was used to wash the inside of the reactor and the inside of the filter, and mixed with the filtrate. After repeating this operation twice, tetrahydrofuran was distilled off under reduced pressure from the combined organic layers. The obtained oil layer was heated to 50 degreeC, and it vacuum-dried at 2-3 mmHg for 3 hours. This oil layer was measured by gel permeation chromatography to obtain a number average molecular weight (Mn). The amount of 1,3-propanediol contained in this oil layer was analyzed by gas chromatography and quantified.

The amount of unreacted 1,3-propanediol was calculated for each of the nasal components and the components in the oil layer to obtain a total value, and the conversion ratio of 1,3-propanediol was obtained from the following equation. The selectivity of the polyether polyol was obtained by subtracting the amount of 1,3-propanediol from the oil layer thus obtained and using the remainder as the polyether polyol from the following formula.

<Conversion of raw 1,3-propanediol>

(Conversion ratio of 1,3-propanediol) (%) = {(moles of 1,3-propanediol injected)-(moles of 1,3-propanediol remaining)} × 100 / (1,3 injected -Moles of propanediol)

<Polyether Polyol Selectivity>

(Polyetherpolyol Selectivity) (%) = [{(weight of oil layer (g) / Mn) × (Mn-18) / 58}-(mole number of 1,3-propanediol in oil layer)] × 100 / (Moles of converted 1,3-propanediol)

The results are shown in Table-1.

Example 2

As a solid acid catalyst, USY zeolite manufactured by Tosoh (HSZ-330HUA, Na ₂ O / SiO ₂ / Al ₂ O ₃ (Molar ratio) = 0.02 / 6/1 (manufacturer's nominal value) lot. Polytrimethylene ether glycol was obtained in the same manner as in Example 1 except that C2-0719) was used. The results are shown in Table-1.

Example 3

<Method of preparing a metal element-substituted solid acid>

Into a Pyrex (trademark) fourth-neck flask equipped with a mechanical stirrer, 11 g of sodium nitrate express manufactured by Kishida Chemical Co., Ltd. was injected, followed by dissolving with 100 g of demineralized water, followed by stirring, and about 100 mol / l sodium nitrate aqueous solution. ML was prepared. While further stirring, 20 g of the same Toso-made USY zeolite (HSZ-330HUA) used in Example 2 was added thereto, the liquid temperature was kept at 80 ° C for 2 hours, and the zeolite was separated by filtration to 80 ° C demineralized water. Washed. After air drying, the resultant was dried in a dryer at 120 ° C. for 12 hours, and then calcined at 500 ° C. for 2 hours in air to obtain a Na-substituted USY zeolite. 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>

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

Example 4

<Method of preparing a metal element-substituted solid acid>

Into a Pyrex (trademark) fourth-neck flask equipped with a mechanical stirrer, 7.8 g of ammonium nitrate express manufactured by Kishida Chemical Co., Ltd. was injected, followed by dissolving with 100 g of demineralized water, followed by stirring to dissolve it, and an aqueous solution of 0.95 mol / L ammonium nitrate About 100 ml was prepared. While further stirring, ZSM-5 (silicalite) manufactured by NE ChemCAT, (K-MCM-04, Na ₂ O / SiO ₂ / Al ₂ O ₃ (molar ratio) = 21/1640/1 (manufacturer analyzed value)) 13 g was added to maintain the temperature of the liquid at 80 ° C. for 2 hours, and then the zeolite was separated by filtration and washed with demineralized water at 80 ° C. After air drying, drying was carried out at 120 ° C. for 12 hours with a dryer, followed by air at 500 ° C. for 2 hours. It was calcined in to give Na partially substituted silicalite, and 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>

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

Comparative Example 1

40.5 g of 1,3-propanediol, as a solid acid catalyst, manufactured by NE Kamkyato ZSM-5 zeolite (K-MCM-02-2, Na ₂ O / SiO ₂ / Al ₂ O ₃ Polytrimethylene ether glycol was obtained in the same manner as in Example 1 except that 16.6 g of (molar ratio) = 0/47/1) and nitrogen were supplied at 100 Nml / min. The results are shown in Table-1.

Moreover, as a result of measuring TPD of this catalyst, the ammonia removal amount in 100-250 degreeC was 0.19 mmol / g, and was 33% of the ammonia removal amount of the whole (25 degreeC-700 degreeC region). In addition, the ammonia removal amount at 100-300 degreeC is 0.25 mmol / g, 43% of the ammonia removal amount of the whole (25 degreeC-700 degreeC area), and the ammonia removal amount at 100-350 degreeC is 0.33. As mmol / g, it was 57% of the ammonia removal amount of the whole (region of 25 degreeC-700 degreeC).

Moreover, the ammonia removal amount in the 300-450 degreeC area | region was 0.24 mmol / g. At this time, the ammonia removal amount in the 300-450 degreeC area | region was 0.96 times with respect to the ammonia removal amount in the 100-300 degreeC area | region. The amount of NH ₃ released in the region of 400 to 700 ° C. was 0.15 mmol / g.

Comparative Example 2

<Method of preparing a metal element-substituted solid acid>

Except for using 25 g of sodium nitrate, 280 g of demineralized water, and 30 g of ZSM-5 zeolite used in Comparative Example 1 as the solid acid catalyst, Na partially substituted ZSM-5 was used in the same manner as in the preparation method of the metal element-substituted solid acid of Example 3. Zeolite was obtained.

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>

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

Example 5

<Method of preparing a metal element-substituted solid acid>

10 g of demineralized water was added to 4 g of reagent Nafion NR-50 (Beads 7-9mesh) manufactured by Aldrich Inc., and a 1N-NaOH aqueous solution was added dropwise at room temperature using a 3.3 ml mesopite, stirred for 2 hours, and then water was washed with 100 ml demineralized water. Washed, dried and dried under reduced pressure at 50 ° C., 2 mmHg. The acid amount according to 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 substituted with Na +.

<Dehydration condensation reaction of 1,3-propanediol>

As the solid acid catalyst, 2.5 g of the 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 separation of the catalyst was carried out by decantation. Polytrimethylene ether glycol was obtained in the same manner as 1.

The results are shown in Table-1.

Example 6

<Method of preparing a solid acid>

In a Pyrex (trademark) 100 ml three-necked flask equipped with a mechanical stirrer, 20 g of mercaptopropyltrimethoxysilane oligomer (X-41-1805, lot. 305006) manufactured by Shin-Etsu Chemical Co., Ltd. and premium ethanol manufactured by Junsei Chemical 39 g was added, 1.7 g of demineralized water was added with stirring, and it stirred at room temperature for 30 minutes. Thereafter, the temperature in the flask was maintained at 70 ° C. for 20 hours with stirring, followed by hydrolysis to gradually gel. After returning to room temperature once, the product was taken out in a 100 ml eggplant flask, the solvent was distilled off, dried and pulverized to make a powder in a mortar and then dried at 70 ° C. for 2 hours at 2 mmHg.

This was poured into a 13 g, 100 ml three-necked flask, and 36 g of 30% hydrogen peroxide solution was added dropwise over 4 hours while stirring with a mechanical stirrer. Since exotherm occurs during the dropping, the SH group is oxidized to SO ₃ H group while cooling in a water bath.

After standing at room temperature for 12 hours, the mixture was stirred at 70 ° C for 4 hours to mature. After cooling to room temperature, 1M sulfuric acid aqueous solution was injected so as to have a concentration of solid acid of 1wt%, ion exchange was performed, followed by water washing and drying, and drying under reduced pressure at 16mmHg for 3 hours to obtain a sulfonic acid group-containing silica. The acid amount according to the neutral salt decomposition method was 1.3 mmol / g. In addition, it was found by elemental analysis that the sum of the substitution amounts of Na + and K + was 0.002 equivalents to the amount of acid. Moreover, as a result of measuring TPD of this catalyst, the ammonia removal amount in 100-250 degreeC was 0.83 mmol / g, and it was 53% of the ammonia removal amount of the whole (25 degreeC-700 degreeC region). In addition, the ammonia removal amount at 100-300 degreeC is 1.1 mmol / g, 69% of the ammonia removal amount of the whole (25 degreeC-700 degreeC area), and the ammonia removal amount at 100-350 degreeC is 1.2 mmol As / g, it was 76% of the ammonia removal amount of the whole (region of 25 degreeC-700 degreeC).

Moreover, the ammonia removal amount in the 300-450 degreeC area | region was 0.15 mmol / g. At this time, the ammonia removal amount in the 300-450 degreeC area | region was 0.14 times with respect to the ammonia removal amount in the 100-300 degreeC area | region.

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

<Dehydration condensation reaction of 1,3-propanediol>

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

Example 7

<Method of preparing a metal element-substituted solid acid>

10 g of demineralized 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 demineralized water. . After repeating this twice, the same operation was performed using 1.46 ml of 1N-NaOH aqueous solution, and then washed with demineralized water and dried, and dried under reduced pressure at 16 mmHg at room temperature to obtain a Na-substituted sulfonic acid group-containing silica. The acid amount according to the neutral salt decomposition method was 0.70 mmol / g. Therefore, Na + substitution amount is 0.45 equivalent with respect to original acid amount.

<Dehydration condensation reaction of 1,3-propanediol>

20 g of 1,3-propanediol was poured into a four-necked flask, and 0.0514 g (0.65 mmol) of Pysei's premium pyridine was added thereto, followed by sufficient stirring, followed by stirring the flask into a 25 ° C oil bath. Polytrimethylene ether glycol was obtained in the same manner as in Example 6 except that 5.06 g of the catalyst was added as the solid acid catalyst. The total amount of Na + and pyridine is 0.55 equivalents to the original acid amount. The results are shown in Table-1.

Example 8

0.34 g of pyridine (0.14 times equivalent to theoretical acid), USY zeolite manufactured by Tosso as a solid acid catalyst (HSZ-350HUA, Na ₂ O / SiO ₂ / Al ₂ O ₃ (Molar ratio) = 0.01 / 9.2 / 1, lot. C2-1 X05)) 10g was added slowly, and the polytrimethylene ether glycol was obtained by the same method as Example 7 except having made reaction temperature into 185 +/- 3 degreeC. The results are shown in Table-1.

Comparative Example 3

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

Example 9

0.18 g of pyridine (1 equivalent to acid amount by neutral salt decomposition) and 2.5 g of Aldrich's reagent Nafion NR50 manufactured by Aldrich Co., Ltd., the same as that used in <Method for producing metal-substituted solid acid> of Example 5, was used as a solid acid catalyst. , Polytrimethylene glycol was obtained in the same manner as in Example 7 except that 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. The results are shown in Table-1.

Example 10

40 g of 1,3-propanediol, Nafion Powder (manufactured by Dupont, XR-500 Powder, 13S49-8055-K + 1200EW as a solid acid catalyst, the acid amount according to the neutral salt decomposition method is 0.04 mmol / g. It was found that the sum of the substitution amounts of Na + and K + was 0.95 equivalent to the original acid amount.) Polytrimethylene ether in the same manner as in Example 6 except that 13 g was used and nitrogen was supplied at 100 Nml / min. Glycol was obtained. 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 and 5 g of the same Nafion powder as used in Example 10 were used as the solid acid catalyst. The total amount of the metal element and the base is 1.1 times the amount of the original acid. The results are shown in Table-1.

Example 12

<Method of preparing a metal element-substituted solid acid>

Into a Pyrex four-necked flask equipped with a mechanical stirrer, 48.8 g of ammonium nitrate express manufactured by Kishida Chemical Co., Ltd. was charged, followed by addition of 600 ml of demineralized water, followed by stirring to dissolve, to prepare about 600 ml of an aqueous 1 mol / L ammonium nitrate solution. It was. While further stirring, the 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) and 30.3g were added, the liquid temperature was hold | maintained at 80 degreeC for 2 hours, zeolite was isolate | separated by filtration and washed with 80 degreeC demineralized water. This was repeated twice. After air drying, the resultant was dried with a drier at 120 ° C for 12 hours, and then calcined at 500 ° C for 2 hours in air to obtain an H + type ferrierite.

<Dehydration condensation reaction of 1,3-propanediol>

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

Comparative Example 4

<Method of preparing a metal element-substituted solid acid>

A 1 mol / L aqueous sodium nitrate solution was used as 8.5 g of sodium nitrate and 100 g of demineralized water, and 20 g of the ZSM-5 zeolite used in Comparative Example 1 was used as the solid acid catalyst. In the same manner as in the preparation method, a Na partially substituted ZSM-5 zeolite was obtained.

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

<Dehydration condensation reaction of 1,3-propanediol>

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

Example 13

<Method of preparing a metal element-substituted solid acid>

5.36 g of sodium nitrate and 50 ml of demineralized water were used, and 1.3 mol / L sodium nitrate aqueous solution was used, and USY zeolite (HSZ-350HUA lot. C2-1X05, Na ₂ O / SiO ₂ / Al ₂ manufactured by Tosoh) was used. Na-substituted USY zeolite was obtained in the same manner as in Example 3 except that 15 g of O ₃ (molar ratio) = 0.01 / 9.2 / 1) was used. Na ₂ O / SiO ₂ / Al ₂ O ₃ (Molar ratio) = 0.12 / 10/1)

<Dehydration condensation reaction of 1,3-propanediol>

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

Although this invention was demonstrated in detail using the specific aspect, it is clear for those skilled in the art for various changes and modification to be possible, without leaving | separating the intent and range of this invention.

In addition, this application is a Japanese patent application filed on June 29, 2004 (Japanese Patent Application 2004-191567), a Japanese patent application filed on June 29, 2004 (Japanese Patent Application 2004-191568), 8 2004 It is based on the Japanese patent application (Japanese Patent Application 2004-242744) filed on May 23, and the Japanese patent application (Japanese Patent Application 2004-242745) filed on August 23, 2004, which is incorporated by reference in its entirety. .

According to the present invention, by dehydrating and condensing a polyol using a solid catalyst, it is possible to provide a method for producing a high yield of polyether polyol having good selectivity and low coloring.

Claims (8)

When manufacturing a polyether polyol by the dehydration condensation reaction of a polyol, the manufacturing method of the polyether polyol characterized by using the solid-acid catalyst which satisfy | fills at least 1 among the conditions of following (1)-(3). The acidity function (H ₀ ) measured by the Hammett indicator adsorption method is greater than -3. In the elevated temperature desorption analysis (TPD) of ammonia, the ammonia removal amount in the region of 100 to 350 ° C. is 60% or more of the ammonia removal amount of the whole (a region of 25 ° C. to 700 ° C.). In the thermogravimetric analysis (TG), the amount of water leaving is at least 3% by weight of the reference weight in the region of 32 to 250 ° C. The method of claim 1, A method for producing a polyether polyol, wherein the solid acid catalyst contains 0.01 to 2.5 equivalents of metal elements and / or organic bases relative to the acid. The method of claim 2, The manufacturing method of the polyether polyol whose metal element is an alkali metal. The method of claim 2, A process for producing a polyetherpolyol, wherein the organic base has a pyridine skeleton. The method of claim 1, The manufacturing method of the polyether polyol which uses a solid acid catalyst and a metal element containing compound and / or an organic base together. The method according to any one of claims 1 to 5, The solid acid catalyst consists of an interlayer compound, a zeolite, a mesoporous material, a metal complex oxide, an oxide or complex oxide containing a sulfonic acid group, a carbon material containing a sulfonic acid group, and a resin having a perfluoroalkylsulfonic acid group in the side chain. A method for producing a polyether polyol, which is at least one member selected from the group. The method according to any one of claims 1 to 6, As a polyol having from 3 to 10 carbon atoms having two primary hydroxyl groups, except that dehydration forms a 5- or 6-membered cyclic ether by dehydration, or a mixture of these and other polyols, A process for producing a polyetherpolyol, wherein the proportion of the other polyol is less than 50 mol%. The method according to any one of claims 1 to 7, The manufacturing method of the polyether polyol which performs dehydration condensation reaction at 120 degreeC or more and 250 degrees C or less.