JP2008063391A - Method for producing polyether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyether by performing the ring-opening polymerization of a cyclic ether in the presence of a catalyst, capable of controlling the average molecular weight of the polyether easily and efficiently as a desired value. <P>SOLUTION: This method for producing the polyether by performing the ring-opening polymerization of the cyclic ether is provided by using a catalyst obtained by incorporating 1 kind or ≥2 kinds of metal elements selected from the groups 3, 5, 10 and 11 of the Periodic table, that are not included in a solid acid catalyst, to the solid acid catalyst containing 1 kind or ≥2 kinds of elements selected from the groups 1, 2, 4, 6, 8, 9, 12, 13, 14, 15, 16 and 17 of the Periodic table and capable of performing the ring-opening polymerization of the cyclic ether by itself. As the solid acid catalyst, a metal oxide carrying catalyst, a composite metal oxide catalyst, a clay catalyst and a zeolite catalyst are preferable, and as the metal element, copper and nickel are preferable. As the catalyst, it is preferable to use those prepared by loading the metal hydroxides and/or metal oxides in the pores of the carrier by a uniform precipitation method in the carrier pores. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a polyether, and more particularly to a method for producing a polyether by ring-opening polymerization of a cyclic ether in the presence of a specific solid acid catalyst, and the molecular weight of the resulting polyether can be controlled. The present invention relates to a method for producing a polyether.

  Polyether is a polymer having a wide range of uses, including raw materials for soft segments such as elastic fibers and thermoplastic elastomers, raw materials such as polyurethane, urethane urea, and polyester.

  As typical polyethers, polyethylene glycol, poly (1,2-propanediol), polytetramethylene ether glycol and the like are known. Among them, polytetramethylene ether glycol synthesized by ring-opening polymerization of tetrahydrofuran (THF) is attracting attention because it is excellent in terms of stretchability and elasticity.

  In Patent Documents 1 and 2, a metal oxide is supported on an oxide carrier such as zeolite or silica as a catalyst used for producing a polyether such as polytetramethylene ether glycol by ring-opening polymerization such as THF. A solid acid catalyst is disclosed.

  The polyethers thus produced have different average molecular weights depending on their use, and therefore, it is required to produce various average molecular weight polyethers even with the same composition. ing.

Conventionally, in the production of a polyether, as a method for controlling the average molecular weight of the obtained polyether, a method of changing reaction conditions, that is, a method of changing a reaction temperature, a conversion rate, or the like has been adopted.
JP-A-9-241374 JP 2000-327770 A

When the average molecular weight of the obtained polyether is changed depending on the reaction conditions, for example, when it is desired to increase the average molecular weight, it is possible to obtain a polyether having a large average molecular weight by lowering the reaction temperature, but the reaction temperature is lowered. As a result, reaction activity decreases and productivity decreases. Further, it is possible to obtain a polyether having a large average molecular weight by lowering the conversion rate, but also in this case, the productivity is lowered.
It is possible to increase the average molecular weight of the resulting polyether by lowering the concentration of initiator / stopper such as acetic anhydride, but in this case also the productivity decreases due to the decrease in the reaction initiation rate. Will be.

Conversely, when trying to produce a polyether having a small average molecular weight, it is possible to increase the reaction temperature, but in this case, the molecular weight distribution increases (deteriorates) and the viscosity of the polyether increases. , It will be easy to color.
It is also possible to reduce the average molecular weight of the resulting polyether by increasing the concentration of initiator / stopper such as acetic anhydride, but in this case, acetic anhydride remaining in the reaction solution Due to the large amount, there will be a disadvantage in the subsequent separation step.

  For this reason, there is a need for a method for controlling the average molecular weight of the obtained polyether to a desired value without adversely affecting other performance such as reaction activity, characteristics of the polyether, and processing operation.

  The present invention relates to a method for producing a polyether by ring-opening polymerization of a cyclic ether in the presence of a catalyst, without adversely affecting other properties such as reaction activity, properties of the polyether, and processing operations. An object of the present invention is to provide a method for producing a polyether capable of easily and efficiently controlling the average molecular weight of the ether to a desired value.

  As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention used a cyclic ether as a catalyst in the method of producing a polyether by ring-opening polymerization in the presence of a catalyst. Comprising one or more elements selected from the group consisting of groups 4, 6, 8, 9, 12, 13, 14, 15, 16, 17 and ring-opening polymerization of the cyclic ether by itself By producing a polyether using a possible solid acid catalyst, the average molecular weight of the obtained polyether can be easily and efficiently controlled to a desired value without adversely affecting other performances. As a result, the present invention has been completed.

  That is, the gist of the present invention is that in the method for producing a polyether by ring-opening polymerization of a cyclic ether in the presence of a catalyst, the periodic table Nos. 1, 2, 4, 6, 8, 9, 12, 13 A solid acid catalyst containing one or more elements selected from the group consisting of Group 14, 15, 16, 17 and capable of ring-opening polymerization of a cyclic ether by itself. A polyether production method characterized by using a catalyst containing one or more metal elements selected from the group consisting of Groups 3, 5, 10, and 11 of the periodic table not included.

  The second gist of the present invention is a solid acid catalyst capable of ring-opening polymerization of a cyclic ether by itself, from the group consisting of a metal oxide-supported catalyst, a composite metal oxide catalyst, a clay catalyst, and a zeolite catalyst. The method for producing a polyether according to claim 1, wherein one or two or more selected solid acid catalysts are used.

  The third gist of the present invention is characterized in that copper and / or nickel is used as a metal element selected from the group consisting of Groups 3, 5, 10, and 11 of the periodic table not included in the solid acid catalyst. It exists in the manufacturing method of the polyether of claim | item 1 or 2.

  The fourth gist of the present invention is one or two selected from the group consisting of a clay catalyst, silica-alumina, silica-titania, and silica-zirconia as a solid acid catalyst capable of ring-opening polymerization of a cyclic ether. The method for producing a polyether according to any one of claims 1 to 3, wherein at least one kind of solid acid catalyst is used.

  The fifth aspect of the present invention is that the catalyst is produced by supporting a metal hydroxide and / or metal oxide in the pores of the support by a uniform precipitation method in the support pores. Item 5. A method for producing a polyether according to any one of Items 1 to 4.

According to the method for producing a polyether of the present invention, the average molecular weight of the obtained polyether can be obtained only by changing the components of the catalyst used and the composition thereof without adversely affecting the performance other than the average molecular weight without changing the reaction conditions. Can be changed.
Therefore, according to the present invention, it is possible to easily and efficiently produce a polyether having a desired average molecular weight according to the use of the polyether.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to the gist of the present invention. The content of is not specified.

  The present invention relates to a process for producing a polyether by ring-opening polymerization of a cyclic ether in the presence of a catalyst, and as the catalyst, the periodic tables Nos. 1, 2, 4, 6, 8, 9, 12, 13, 14, A solid acid catalyst containing one or more elements selected from the group consisting of groups 15, 16, and 17 and capable of ring-opening polymerization of a cyclic ether by itself is not included in the solid acid catalyst Use of a catalyst containing one or more metal elements selected from the group consisting of Groups 3, 5, 10, and 11 of the periodic table (hereinafter sometimes referred to as “specific metal elements”). It is a feature.

[catalyst]
First, the catalyst used in the present invention will be described. The catalyst used in the present invention is a solid acid catalyst containing a specific (Group 3, 5, 10, 11) metal element.

<Solid acid catalyst>
In the present invention, examples of the solid acid catalyst include zeolites having a crystal structure such as MFI, X, and Y; metal oxides such as silica, alumina, titania, zirconia; silica-titania, silica-alumina, silica- Composite metal oxides combining multiple metal oxides such as zirconia and alumina-titania; supported type that supports metal oxide, clay, and zeolite as a carrier, and a metal oxide or a compound having acid properties different from this carrier Acid catalysts; clays such as layered silicates; and the like.
Among these, when using composite metal oxides and supported acid catalysts, silica-zirconia, silica-alumina, zirconia-supported silica, and alumina-supported silica are particularly preferable. When clays such as layered silicates are used, kaolinite, smectite and the like are usually mentioned, and among the smectites, montmorillonite is preferably used. The clays are preferably used as activated clay washed with an acid, and it is particularly preferred to use activated clay obtained by washing montmorillonite with an acid.

<Method for producing solid acid catalyst>
As a method for producing the solid acid catalyst, a known technique can be used and is not particularly limited. Specifically, the production methods described in Patent Document 1, Patent Document 2, and the like can be employed.

  The catalyst used in the present invention is preferably a catalyst in which a metal hydroxide and / or a metal oxide is supported in the pores of the support by a uniform precipitation method in the support pores.

<Method of containing a specific metal element>
As a method of including a specific metal element in the solid acid catalyst,
(1) A method in which a specific metal element is preliminarily contained in a support to be used when preparing a solid acid catalyst
(2) A method of containing a specific metal element at the same time when preparing a solid acid catalyst
(3) Any method of adding a specific metal element after preparing a solid acid catalyst can be taken, but (2) a method of adding a specific metal element at the same time when preparing a solid acid catalyst. preferable.

<Production of catalyst by homogeneous precipitation method>
The present invention exemplifies a method for producing a catalyst according to the present invention by preparing a solid acid catalyst and simultaneously containing a specific metal element when producing a catalyst by a uniform precipitation method in the support pores. The catalyst according to the above will be described.
When the catalyst according to the present invention is a supported acid catalyst, the total metal loading on the carrier, the metal loading as the solid acid catalyst, and the specific metal element loading are preferably a metal salt or metal oxide described later. This is an amount obtained by conversion from the supported amount.

  The homogeneous precipitation method according to the present invention includes, for example, impregnating a carrier with a metal salt and a precipitant precursor that generates a precipitant by a chemical reaction such as hydrolysis in a solution, and then heat-treating the impregnated carrier. It carries out by performing the process which produces | generates a precipitant from a precipitant precursor. Since it is a uniform precipitation method, it is important that the metal salt and the precipitant precursor are in a liquid phase, that is, a solution. That is, the carrier is impregnated with an impregnation solution containing a metal salt and a precipitant precursor, and then a precipitant is generated from the precipitant precursor.

  In the present invention, as the metal salt dissolved in the impregnation solvent, a metal salt for generating a solid acid catalyst (hereinafter sometimes referred to as “acid-generating metal salt”) and a metal for generating a specific metal element. A salt (hereinafter sometimes referred to as “specific metal salt”) is used in combination.

(1) Carrier The carrier used in the present invention is not particularly limited, but metal oxides, composite metal oxides, zeolites, and clays are preferable, and silica, alumina, zirconia, titania, silica-alumina, Silica-zirconia, silica-titania, and clays are more preferable, and silica, alumina, zirconia, and clays are particularly preferable.

  These carriers may be used alone or in combination of two or more.

(2) Metal salt dissolved in impregnation solution (2-1) Acid-generating metal salt The metal elements of the metal salt supported on the carrier and expressing the solid acid include the first, second, fourth, sixth and eighth periodic tables. One or more of Group 9, 12, 13, 14, 15, 16, and 17 metal elements are used. Preferably, metal elements of Group 4, Group 13, and Group 14 of the periodic table are used, Ti, Zr, Hf, Al, and Si metal elements are more preferable, and Ti, Zr, and Al are particularly preferable.

  Although there is no restriction | limiting in particular as a kind of salt, Nitrate, acetate, sulfate, oxynitrate, a chloride, and an oxychloride are preferable, and an oxynitrate, an oxychloride, and a sulfate are more preferable.

  That is, the acid-generating metal salt includes nitrates, acetates, sulfates, oxynitrates, chlorides of Groups 1, 2, 4, 6, 8, 9, 12, 13, 14, 15, 16, and 17 of the periodic table. Oxychloride is preferable, and zirconium oxynitrate, zirconium oxychloride, zirconium sulfate, titanium chloride, and aluminum sulfate are more preferable.

  These acid-generating metal salts may be used alone or in combination of two or more.

(2-2) Specific Metal Salt On the other hand, the specific metal element added to the solid acid catalyst is a metal element of Group 3, Group 5, Group 10, or Group 11 of the periodic table, and Ni, Cu , Ce metal elements are preferable, and Ni and Cu are particularly preferable.

  There are no particular limitations on the salts of these specific metal elements, but nitrates, acetates, sulfates, oxynitrates, chlorides, and oxychlorides are preferred, and oxynitrates, oxychlorides, and sulfates are more preferred.

  That is, as the specific metal salt, nitrates, acetates, sulfates, oxynitrates, chlorides, and oxychlorides of Group 3, Group 5, Group 10, and Group 11 metals of the periodic table are preferable, nickel nitrate, Nickel chloride, copper nitrate, and copper chloride are more preferable.

  These specific metal salts may be used individually by 1 type, and may use 2 or more types together.

(3) Precipitating agent precursor The precipitating agent precursor according to the present invention is a substance that causes a hydrolysis or other chemical reaction by a treatment such as heating in an impregnating solution to generate a precipitating agent. The precipitating agent reacts with the metal salt in the impregnation solution to cause precipitation of the metal hydroxide. Precipitating agent precursors that generate a base as a precipitating agent, that is, a base is generated by hydrolysis or other chemical reaction in the impregnation solution, and the pH of the solution is raised to convert the metal salt into a hydroxide or oxide. What is precipitated as is called “base precursor”.

  The precipitant precursor for carrying out the uniform precipitation method is not particularly limited, but a base precursor is generally used.

  As the base precursor, urea, cyanuric acid, alkyl-substituted urea, thiourea, alkyl-substituted thiourea, an amide compound composed of an amine and a carboxylic acid, or the like is used. Preferably, urea, cyanuric acid, and alkyl-substituted urea are used, and the use of urea and cyanuric acid is particularly preferable in terms of availability and cost. These base precursors may be used alone or in combination of two or more.

(4) Basic substance In addition to the above-mentioned base precursor, a predetermined amount of a basic substance may be added to the impregnating solution in advance in order to raise the pH within a range not causing precipitation. By using a basic substance, it is possible to reduce the amount of base precursor used and the time required for precipitation.

  The basic substance is not particularly limited, and examples thereof include alkali metal, alkaline earth metal, and ammonium hydroxides, carbonates, hydrogen carbonates, phosphates, acetates, ammonia, and organic amines. Ammonia, organic amines, ammonium carbonate, hydrogen carbonate, and phosphate are preferable, and ammonium carbonate and ammonium hydrogen carbonate are more preferable.

  These basic substances may be used individually by 1 type, and may use 2 or more types together.

(5) Impregnation solution The impregnation solution is usually prepared by dissolving the above-mentioned acid-generating metal salt, a specific metal salt, a precipitant precursor, and a basic substance used as necessary in water.

  The concentration of the metal salt and the precipitating agent precursor in the impregnation solution is not particularly limited as long as it is a concentration that can maintain a dissolved state and can realize a suitable loading amount on the carrier described later. The salt concentration is 0.01 to 50% by weight, preferably 0.1 to 40% by weight, particularly preferably 0.5 to 30% by weight in terms of the total concentration of the acid-generating metal salt and the specific metal salt. As will be described later, the body is 0.1 to 10 times, preferably 0.2 to 8 times, particularly preferably 0.3 to 5 times the theoretical amount sufficient to precipitate all of the metal salt.

  The basic substance is appropriately used so that necessary pH conditions can be obtained. That is, since the pH conditions necessary for the formation of the precipitate vary depending on the type and concentration of the metal salt and the precipitant used, the necessary amount of the basic substance is used according to these conditions.

  In the present invention, in order to carry out the uniform precipitation method in the support, before performing the treatment for converting the precipitant precursor into the precipitant, at least the acid-generating metal salt and the specific metal salt in the impregnation solution are used. It is necessary that the two metal salts and the precipitant precursor are in a liquid phase, that is, a dissolved state, but the substances other than the at least two metal salts and the precipitant precursor are in any state in the impregnation solution. It does not matter if it exists.

(6) Uniform precipitation method (6-1) Method of impregnating carrier with impregnating solution There is no particular limitation on the method of impregnating the carrier with the above impregnating solution, but the acid-generating metal salt and the specific metal salt are uniformly on the carrier. It is preferable to carry out by a pore filling method in order to carry | support to. In this case, the volume of the impregnation solution impregnated in the support is preferably 60 to 120% of the support pore volume, more preferably 70 to 110%, and particularly preferably 80 to 105%. preferable. If the amount of the liquid is too small, the impregnating solution does not uniformly enter the carrier pores and becomes non-uniform. On the other hand, if the amount is too large, the impregnating liquid adheres to the outer surface of the carrier, which also makes it nonuniform.

  The amount of the metal salt supported on the support by impregnation can be selected in any amount, but is usually 0.01 to 50% by weight in total of the acid-generating metal salt and the specific metal salt with respect to the weight of the support, Preferably it is 0.05 to 40 weight%, More preferably, it is 0.1 to 30 weight%. Regarding the loading amount of the precipitating agent precursor, a molar ratio of 0.1 to 10 is usually used, preferably 1 to 0.2, assuming that the theoretical amount sufficient to precipitate all the metal salt supported on the carrier is 1. It is in the range of 8, more preferably in the range of 0.3-5.

(6-2) Precipitation generation and post-treatment method In the present invention, the impregnating solution is impregnated in the support, so that the metal salt and the precipitant precursor supported on the support maintain the state of the solution in the support pores. The precipitating agent precursor is converted into the precipitating agent, such as heating, and the metal salt is converted into the corresponding metal hydroxide by the precipitating agent that is uniformly generated inside the carrier.

  In general, a base precursor is used as the precipitant precursor, and hydrolysis of the base precursor by heating is used for the conversion of the base precursor into a base.

  As described above, in order to carry out the uniform precipitation method in the support pores, at least two kinds of metal salts and the precipitating agent precursor are in solution before the treatment for converting the precipitating agent precursor into the precipitating agent. Although it is required to be in a state, that is, a liquid phase, substances other than at least two kinds of metal salts and precipitant precursors may be in any state.

  When the base precursor is converted to a base by a hydrolysis reaction caused by heating, the heating temperature is usually 50 to 300 ° C, preferably 60 to 200 ° C. The heating temperature can be changed with time. If the heating temperature is too low, the precipitant formation reaction may not take place from the precipitant precursor, or it may take a very long time. If the heating temperature is too high, precipitation may occur from the precipitant precursor. There is a possibility that all the water necessary for the hydrolysis is removed before the formation reaction of the agent is completed. In order to carry out a good and stable uniform precipitation method, it is preferable that 5% or more of the moisture in the impregnating solution impregnated on the carrier remains at the time when the precipitation reaction is completed, and 10% or more More preferably, it remains.

  Heating of the carrier impregnated with the impregnation solution may be performed in a state where the supported carrier does not move as in the case of a fixed bed heating apparatus. However, particularly when a large amount of catalyst is prepared, the supported carrier flows. It is more preferable to use a floor device, a rotary heating device, or the like. In the case where moisture evaporates during heating, it is considered that the flow of the carrier does not change the amount of water evaporated for each particle of the carrier, and the homogeneity increases.

  Also, if the evaporation of moisture during heating is too fast, all of the moisture will be removed before the hydrolysis of the base precursor is completed, and the precipitating agent may not be sufficiently supplied, Normally, it is desirable to complete the removal of water by taking 1 hour or more, preferably 3 hours or more, more preferably 6 hours or more from the start of heating to the completion of precipitation reaction until the complete removal of water.

  Thereafter, the obtained catalyst is washed with water, an alkaline aqueous solution, an acid aqueous solution, an organic solvent, or the like, if necessary, and then an inert gas atmosphere such as nitrogen or argon, or an oxidation such as air or diluted oxygen gas. The catalyst of desired performance can be obtained by calcination in a reactive gas atmosphere. In this case, the heating and firing temperature is usually 100 to 1200 ° C, preferably 300 to 1100 ° C, and more preferably 500 to 1000 ° C. By performing such heating and firing, the catalytic activity and stability of the resulting catalyst, that is, the solid acid catalyst to which a specific metal element is added, can be improved.

  However, the above-mentioned steps are not all essential steps, and any step can be used as long as a catalyst obtained by adding a specific metal element to a solid acid catalyst is obtained, and the production process is not particularly limited.

<Metal loading>
The catalyst obtained by the method as described above is usually obtained by adding a specific metal element in the form of an oxide to a solid acid catalyst.

  When the catalyst used in the present invention is a solid acid catalyst in which a metal oxide such as zirconia is supported on a support such as silica, a specific metal element such as Ni, Cu, or Ce is added. The amount of metal supported as the acid catalyst is preferably 0.1 to 15 mol%, particularly preferably 0.5 to 10 mol%. If the loading amount is larger than this range, it becomes difficult to carry the metal in a uniformly and highly dispersed state, and if it is less, a sufficient acid amount is not generated. Further, the supported amount of the specific metal element with respect to the support is 0.01 to 10 mol%, particularly 0.05 to 5 mol%, and the specific metal element / solid acid catalyst metal molar ratio is 0.01 to 5, particularly It is preferable that it is 0.05-3.

  If the specific metal element loading is larger than this range, the catalyst performance other than the average molecular weight may be adversely affected, and if it is less, the effect of varying the average molecular weight cannot be obtained sufficiently.

  When the catalyst used in the present invention is a catalyst obtained by adding a specific metal element to a clay catalyst as a solid acid catalyst, the amount of the specific metal element added to the clay catalyst is 0.01 to 20% by weight, particularly It is preferable that it is 0.05 to 15 weight%. If the specific metal element loading is larger than this range, the catalyst performance other than the average molecular weight may be adversely affected, and if it is less, the effect of varying the average molecular weight cannot be obtained sufficiently.

[Method for producing polyether]
Below, the manufacturing method of the polyether of this invention which uses the solid acid catalyst containing the specific metal element manufactured as mentioned above as a polymerization catalyst is demonstrated.

  The method for producing the polyether of the present invention is carried out by ring-opening polymerization reaction of cyclic ethers, that is, by subjecting cyclic ethers as reaction raw materials to ring-opening polymerization reaction.

  In the case of producing a polyether by a ring-opening polymerization reaction of a cyclic ether, examples of the cyclic ether used as a reaction raw material include those having 3 to 10 carbon atoms constituting the ring, and an alkyl group, a halogen group, A cyclic ether substituted with an acyl group or the like can also be used. Specifically, tetrahydrofuran, oxetane, oxepane, 1,4-dioxane, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran and the like are used. In addition, both homopolymerization using only one kind of cyclic ether and copolymerization using two or more kinds of cyclic ethers can be performed.

  As the catalyst, one or more solid acid catalysts containing a specific metal element as described above are used.

  The ring-opening polymerization reaction of the cyclic ether is preferably performed in the presence of a carboxylic acid anhydride and / or carboxylic acid from the viewpoint of molecular weight control. As the carboxylic acid anhydride and / or carboxylic acid, those having 2 to 12 carbon atoms which are aliphatic or aromatic are generally used, and those having 2 to 8 carbon atoms are preferably used. These carboxylic acid anhydrides and / or carboxylic acids may be used alone or in combination of two or more. Carboxylic anhydride and / or carboxylic acid is usually added in a range of 0.01 to 1.0 (molar ratio) with respect to the cyclic ether.

  In the polymerization reaction, a solvent inert to the reaction can also be used. As the solvent, one or more of aliphatic hydrocarbons, aromatic hydrocarbons and the like which are inert to the ring-opening polymerization reaction are generally used.

  As the reaction format, those generally used such as a tank type and a tower type are used, and either a batch system or a continuous system may be used. For example, a method in which a cyclic ether, a catalyst, a carboxylic acid anhydride and / or a carboxylic acid are charged and polymerized with stirring (batch method), and a cyclic ether, a carboxylic acid anhydride and / or a carboxylic acid are continuously added to a reactor containing the catalyst. There is a method (continuous method) in which the reaction solution is continuously supplied and the reaction solution is withdrawn. From the viewpoint of productivity, the continuous method is preferable.

  The amount of catalyst used is determined by the type and is not particularly limited. For example, in a batch reactor, if the amount of catalyst is too small, the polymerization rate is slow, and conversely, if it is too large, the heat of polymerization is removed. It becomes difficult. Further, since the slurry concentration in the reaction system becomes high, stirring becomes difficult, and a problem is likely to occur in the separation of the catalyst and the reaction liquid after the completion of the polymerization reaction. Therefore, the amount of the catalyst used is usually selected from the range of 0.001 to 50 times by weight, preferably 0.01 to 20 times by weight with respect to the liquid phase, in consideration of the reaction form of batch reaction and flow reaction. However, in the case of flow reaction, the amount of catalyst used represents the amount of catalyst relative to the amount of liquid phase supplied per unit time.

The reaction temperature is usually 0 to 200 ° C., preferably 10 to 80 ° C.
The reaction pressure may be a pressure that allows the reaction system to maintain a liquid phase, and is usually selected from the range of normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
The reaction time is not particularly limited, but it is preferably in the range of 0.1 to 20 hours, preferably in the range of 0.5 to 15 hours in consideration of both the amount of catalyst and the yield and economy. The reaction time here means the time from the time when the reaction temperature rises to the reaction temperature in the batch system to the time when the reaction ends and the cooling starts, and in the continuous system, the reaction composition liquid stays in the reactor. It refers to time.

  The molecular weight distribution of the produced polyether depends on the kind of raw material compound, but when ring-opening polymerization reaction of tetrahydrofuran (THF) is performed, the number average molecular weight (Mn) is 200 to 80,000, particularly 200 to 40, A low to medium molecular weight polyether of about 000 can be obtained. Furthermore, one of the features is that a polyether having a narrow molecular weight distribution can be easily produced. In other words, industrially demanding polyethers have Mw / Mn of 1.3 to 2.5, but by using the solid acid catalyst according to the present invention, Mw / Mn is less than 3, for example 1. By selecting a polyether of 1 to 3.0, particularly preferable conditions of the present invention, a polyether having a very narrow molecular weight distribution with Mw / Mn of about 1.3 to 2.0 can be obtained.

  It should be noted that the relationship between the amount of the specific metal element added to the solid acid catalyst of the catalyst used and the average molecular weight of the resulting polyether cannot be generally stated, and various average molecular weights depending on the type of the specific metal element. Polyether can be obtained, but generally, when the same specific metal element is added to the same solid acid catalyst, the larger the specific metal element addition amount, the higher the average molecular weight of the polyether tends to be obtained. is there.

  The polyether produced according to the present invention can be used for applications such as elastic fibers, thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, and coating materials.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the following examples do not limit the scope of the present invention.

In the following, the conversion rate of tetrahydrofuran (THF), the number average molecular weight (Mn) of polytetramethylene ether glycol acetate (PTME), and the molecular weight distribution (Mw / Mn) are the following GPC (gel permeation chromatography). ).
GPC device: GPC 8220 manufactured by Tosoh Corporation
Column: TSK-GEL H (30 cm) x 2 Detection method: RI
Column temperature: 40 ° C
Moving bed: THF
Flow rate: 1 ml / min
Sample injection volume: 500 μl
Sample concentration: Adjusted so that the concentration of polyether is about 0.1% by weight

[Comparative Example 1]
<Preparation of solid acid catalyst>
2.84 g of ZrO (NO ₃ ) ₂ .2H ₂ O and 0.957 g of urea were dissolved in demineralized water to obtain a 12.1 ml homogeneous solution. To this impregnating solution, 10.0 g of silica support (manufactured by Fuji Silysia, Carrier Mito Q30, particle size 75 to 500 μm, average particle size 200 μm, pore volume 1.21 ml / g, average pore size 30 nm) was added at room temperature. It was left to impregnate for 1 hour with occasional shaking. The impregnated carrier was placed in a 100 ml Erlenmeyer flask, capped, and treated in a dryer at 110 ° C. for 6 hours. Six hours later, the lid of the flask was opened, and it was dried in a dryer at 110 ° C. for 16 hours. This was further dried at 140 ° C. for 4 hours and then allowed to cool. The product thus obtained was added to a solution of 7.2 g of ammonium hydrogen carbonate (containing 20% by weight of ammonia) in 72 ml of demineralized water at room temperature, stirred for 1 hour, filtered, and further 84 ml of demineralized water. After being suspended and washed three times, the catalyst was dried at 120 ° C. and calcined at 900 ° C. under air flow to obtain a catalyst.

<Polymerization reaction>
Under nitrogen, 133.5 g of THF and 6.85 g of acetic anhydride were added to a 500 ml four-necked flask and mixed with stirring. 4.68 g of the catalyst was weighed under nitrogen and added to the mixture with stirring, and then reacted at 40 ° C. for 5 hours. The reaction solution was analyzed by GPC, and the conversion of THF, the average molecular weight (Mn) of PTME, and the molecular weight distribution (Mw / Mn) were measured. The conversion was 32%, Mn was 3002, and Mw / Mn was 1.84. Met.

[Example 1]
ZrO (NO ₃ ) ₂ · 2H ₂ O 2.86 g, Ce (NO ₃ ) ₃ · 6H ₂ O 0.464 g and urea 1.108 g were dissolved in demineralized water to prepare an impregnation solution as a 12.1 ml homogeneous solution. A specific metal element-containing solid acid catalyst was prepared in the same manner as in Comparative Example 1 except that the polymerization reaction was similarly carried out using this catalyst.
As a result, the conversion ratio was 28%, Mn was 2664, and Mw / Mn was 1.84.

[Example 2]
ZrO (NO ₃ ) ₂ · 2H ₂ O 2.86 g, Fe (NO ₃ ) ₃ · 9H ₂ O 0.432 g and urea 1.108 g were dissolved in demineralized water to prepare an impregnating solution as a 12.1 ml homogeneous solution. A specific metal element-containing solid acid catalyst was prepared in the same manner as in Comparative Example 1 except that the polymerization reaction was similarly carried out using this catalyst.
As a result, the conversion was 36%, Mn was 3241, and Mw / Mn was 1.82.

[Example 3]
ZrO (NO ₃ ) ₂ · 2H ₂ O 2.86 g, Ni (NO ₃ ) ₂ · 6H ₂ O 0.311 g and urea 1.06 g were dissolved in demineralized water to prepare an impregnating solution as a 12.1 ml homogeneous solution. A specific metal element-containing solid acid catalyst was prepared in the same manner as in Comparative Example 1 except that the polymerization reaction was similarly carried out using this catalyst.
As a result, the conversion was 34%, Mn was 4137, and Mw / Mn was 1.83.

[Example 4]
ZrO (NO ₃ ) ₂ · 2H ₂ O 2.86 g, Cu (NO ₃ ) ₂ · 3H ₂ O 0.258 g and urea 1.059 g were dissolved in demineralized water to prepare an impregnating solution as a 12.1 ml homogeneous solution. A specific metal element-containing solid acid catalyst was prepared in the same manner as in Comparative Example 1 except that the polymerization reaction was similarly carried out using this catalyst.
As a result, the conversion was 30%, Mn was 4059, and Mw / Mn was 1.76.

[Comparative Example 2]
<Preparation of solid acid catalyst>
22.35 g of demineralized water was added to 88.01 g of a zirconium oxynitrate solution (18.46 wt% as ZrO ₂ ) manufactured by Shin Nippon Metal Chemical Co., and mixed uniformly. To this, 11.89 g of urea was added and mixed uniformly to prepare an impregnation solution. To this solution, 80 g of silica support (manufactured by Fuji Silysia, Carrieract Q15, particle size 75 to 500 μm, average particle size 200 μm, pore volume 1.16 ml / g, average pore size 15 nm) is added and shaken for about 1 hour. However, it was impregnated with pore filling (the amount of the impregnating solution was 100% of the carrier pore volume).

  This was put into a 500 ml pear-shaped flask, and a bent tube filled with a joint and glass wool was connected to the top of the flask. Then, the flask was fixed to the rotating shaft of the rotary dryer with a clamp. The rotating shaft was rotated at a speed of 10 rpm, the dryer temperature was set to 105 ° C., and heating was performed for 2 hours. Then, after removing the bent tube filled with the upper glass wool, the dryer temperature was set to 120 ° C. and heating was performed for 16 hours. Then, after removing the upper joint, the dryer temperature was set to 140 ° C. and heating was performed for 4 hours. After 4 hours, heating and rotation were stopped, and the catalyst was taken out. Transfer the catalyst to a 500 ml beaker and let it cool to room temperature, add about 300 ml of demineralized water, repeat suspension washing for about 10 minutes 3 times, air dry and dry overnight in a 120 ° C. dryer, then air flow The catalyst was calcined at 900 ° C. below.

<Polymerization reaction>
When the polymerization reaction was carried out in the same manner as in Comparative Example 1 using the solid acid catalyst obtained above as a catalyst, the conversion was 43%, Mn was 2116, and Mw / Mn was 1.75.

[Example 5]
23.22 g of demineralized water was added to and mixed uniformly with 77.52 g of a zirconium oxynitrate solution (18.46 wt% as ZrO ₂ ) manufactured by Shin Nippon Metal Chemical Co., Ltd. To this, 1.03 g of Ca (NO ₃ ) ₂ .4H ₂ O was added and mixed uniformly. Furthermore, a specific metal element-containing solid acid catalyst was prepared in the same manner as in Comparative Example 2 except that 10.92 g of urea was added and mixed uniformly to prepare an impregnation solution, and a polymerization reaction was similarly performed using this catalyst. Carried out.
As a result, the conversion was 46%, Mn was 2279, and Mw / Mn was 1.75.

[Example 6]
Deionized water (20.31 g) was added to 77.69 g of a zirconium oxynitrate solution (18.46 wt% as ZrO ₂ ) manufactured by Shin Nippon Metal Chemical Co., and mixed uniformly. To this, 2.12 g of Ni (NO ₃ ) ₂ .6H ₂ O was added and mixed uniformly. Furthermore, a specific metal element-containing solid acid catalyst was prepared in the same manner as in Comparative Example 2 except that 11.81 g of urea was added and mixed uniformly to prepare an impregnation solution, and a polymerization reaction was similarly performed using this catalyst. Carried out.
As a result, the conversion was 47%, Mn was 2687, and Mw / Mn was 1.76.

[Example 7]
23.22 g of demineralized water was added to and mixed uniformly with 77.52 g of a zirconium oxynitrate solution (18.46 wt% as ZrO ₂ ) manufactured by Shin Nippon Metal Chemical Co., Ltd. To this, 1.05 g of Cu (NO ₃ ) ₂ .3H ₂ O was added and mixed uniformly. Furthermore, a specific metal element-containing solid acid catalyst was prepared in the same manner as in Comparative Example 2 except that 10.92 g of urea was added and mixed uniformly to prepare an impregnation solution, and a polymerization reaction was similarly performed using this catalyst. Carried out.
As a result, the conversion was 47%, Mn was 2983, and Mw / Mn was 1.74.

[Example 8]
20.95 g of demineralized water was added to 77.56 g of a zirconium oxynitrate solution (18.46 wt% as ZrO ₂ ) manufactured by Shin Nippon Metal Chemical Co., and mixed uniformly. This was mixed Cu a _{(NO 3) 2 · 3H 2} O 0.35g, Ni (NO 3) 2 · 6H 2 O and 1.70g added uniformly. Furthermore, a specific metal element-containing solid acid catalyst was prepared in the same manner as in Comparative Example 2 except that 11.13 g of urea was added and mixed uniformly to prepare an impregnation solution, and a polymerization reaction was similarly conducted using this catalyst. Carried out.
As a result, the conversion was 46%, Mn was 2667, and Mw / Mn was 1.74.

[Comparative Example 3]
Polymerization reaction in the same manner as in Comparative Example 1 except that 20 g of Todsil OptimFF, Sued Chemie Co., Ltd., which is a clay (active clay) catalyst, was baked at 400 ° C. for 1 hour under air flow. Carried out.
As a result, the conversion was 42%, Mn was 3497, and Mw / Mn was 2.01.

[Example 9]
0.35 g of Cu (NO ₃ ) ₂ .3H ₂ O was dissolved in 10 g of demineralized water and mixed uniformly. This was impregnated with 20 g of Tonsil OptimFF (Sued Chemie), which is a clay catalyst, and left for 1 hour. Thereafter, as in Comparative Example 3, a specific metal element-containing solid acid catalyst was prepared by calcining at 400 ° C. for 1 hour under air flow, and a polymerization reaction was similarly carried out using this catalyst.
As a result, the conversion was 42%, Mn was 4002, and Mw / Mn was 2.00.

[Example 10]
0.78 g of Ni (NO ₃ ) ₂ .6H ₂ O was dissolved in 10 g of demineralized water and mixed uniformly. This was impregnated with 20 g of Tonsil OptimFF (Sued Chemie), which is a clay catalyst, and left for 1 hour. Thereafter, as in Comparative Example 3, a specific metal element-containing solid acid catalyst was prepared by calcining at 400 ° C. for 1 hour under air flow, and a polymerization reaction was similarly carried out using this catalyst.
As a result, the conversion was 39%, Mn was 4380, and Mw / Mn was 2.01.

  The results of the above Examples and Comparative Examples are summarized in Tables 1-3.

As can be seen from Comparative Example 1 and Examples 1 to 4, by incorporating a specific metal element of Group 3, 5, 8, 10, 11 of the periodic table into the solid acid catalyst, other performance is adversely affected under the same reaction conditions. It is possible to change only the average molecular weight without giving.
Further, as can be seen from Comparative Example 2 and Examples 5 to 8, the same can be said even when two or more metal elements are added when the production conditions of the solid acid catalyst are changed.
Further, as can be seen from Comparative Example 3 and Examples 9 and 10, the same applies to the case where a metal element is added to the solid acid catalyst later.

Claims (5)

In a method for producing a polyether by ring-opening polymerization of a cyclic ether in the presence of a catalyst,
The catalyst contains one or more elements selected from the group consisting of Groups 1, 2, 4, 6, 8, 9, 12, 13, 14, 15, 16, 17 of the periodic table, A solid acid catalyst capable of ring-opening polymerization of a cyclic ether, one or more metal elements selected from the group consisting of Groups 3, 5, 10, and 11 of the periodic table not included in the solid acid catalyst A method for producing a polyether, which comprises using a catalyst containing.   As a solid acid catalyst capable of ring-opening polymerization of a cyclic ether by itself, one or more selected from the group consisting of a metal oxide-supported catalyst, a composite metal oxide catalyst, a clay catalyst, and a zeolite catalyst The method for producing a polyether according to claim 1, wherein a solid acid catalyst is used.   The polyether according to claim 1 or 2, wherein copper and / or nickel is used as a metal element selected from the group consisting of Groups 3, 5, 10, and 11 of the periodic table not included in the solid acid catalyst. Manufacturing method.   As a solid acid catalyst capable of ring-opening polymerization of a cyclic ether, one or more solid acid catalysts selected from the group consisting of clay catalysts, silica-alumina, silica-titania, and silica-zirconia are used. The method for producing a polyether according to any one of claims 1 to 3, wherein:   5. The catalyst according to claim 1, wherein the catalyst is produced by supporting a metal hydroxide and / or metal oxide in the pores of the support by a uniform precipitation method in the support pores. A method for producing the polyether according to 1.