JPH0565497B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing 2,2-bis(4-hydroxyphenyl)propane, and more specifically, the present invention relates to a method for producing 2,2-bis(4-hydroxyphenyl)propane. The present invention relates to a method for producing bis(4-hydroxyphenyl)propane (commonly known as bisphenol A). [Prior art and problems to be solved by the invention] _{Conventionally} , phenol and an unsaturated hydrocarbon represented by the general formula _C3H4 are reacted to produce bisphenol A,
That is, as a method for producing 2,2-bis(4-hydroxyphenyl)propane, a method using an ion exchange resin as a catalyst (West German Patent No.
1161284), or a method using a Lewis acid such as boron trifluoride or aluminum trichloride as a catalyst (US Pat. No. 2,884,462). However, the method using the ion exchange resin described above has problems such as significant deterioration of the ion exchange resin as a catalyst.On the other hand, the method using the aforementioned Lewis acid such as boron trifluoride or aluminum trichloride This method had problems such as low selectivity to bisphenol A and the need to decompose and remove the Lewis acid used after the reaction, making it impossible to reuse the catalyst. On the other hand, the applicant has previously proposed a method for producing alkylphenols such as p-tert-butylphenol by reacting an alkene such as isobutene with a phenol using a halide of a lanthanide element as a Lewis acid catalyst. (Unexamined Japanese Patent Publication 1986-
No. 107747). However, there is no known example of using a halide of a lanthanide element as a catalyst for a reaction between an alkyne or a diene and a phenol. The object of the present invention is to solve the above-mentioned problems, to provide high selectivity to bisphenol A, that is, 2,2-bis(4-hydroxyphenyl)propane, and to easily recover it for reuse. The reaction between phenol and an unsaturated hydrocarbon represented by the general formula C ₃ H ₄ efficiently produces
An object of the present invention is to provide a practically advantageous method for producing 2,2-bis(4-hydroxyphenyl)propane, which is capable of producing -bis(4-hydroxyphenyl)propane. [Means for Solving the Problems] In order to solve the above problems, the present inventors first,
An attempt was made to develop a new catalyst effective for the synthesis of 2,2-bis(4-hydroxyphenyl)propane by the reaction of phenol with propane (methylacetylene) or 1,2-propadiene (arene). In developing such a catalyst, the present inventors discovered that halides of specific elements among the lanthanide series elements, particularly halides of trivalent elements, have properties as Lewis acids and react with water. Noting that it does not undergo hydrolysis and can be easily recovered for reuse, it has been used as a catalyst for the synthesis reaction of 2,2-bis(4-hydroxyphenyl)propane, which is one of the lanthanide series elements. When halides of specific elements were used, these halides alone were not effective as catalysts. However, surprisingly, when these halides are used in the presence of hydrogen halide,
It becomes an effective catalyst showing high selectivity for the above reaction, and even after being used in the above reaction, the halide does not react with water and is hydrolyzed, and is easily recovered. We discovered new and interesting findings, such as the fact that it can be reused as a catalyst. Based on these findings, the present inventors have completed the present invention. That is, the present invention deals with phenol and general formula C ₃ H ₄
2,2-, which is characterized by reacting an unsaturated hydrocarbon represented by
This is a method for producing bis(4-hydroxyphenyl)propane. In the present invention, the phenol used as a raw material for the reaction is usually preferably pure, but it may contain impurities as long as it does not interfere with the purpose of the present invention. Further, it is usually desirable to use this phenol in the above-mentioned reaction in an anhydrous or sufficiently dehydrated state. In the present invention, the unsaturated hydrocarbons represented by the general formula C ₃ H ₄ used as other raw materials in the reaction include propyne (i.e., methyl, acetylene), 1,2-propadiene (i.e., allene), , or a mixture of these in any proportion. It is generally preferable that the propyne and 1,2-propadiene used be pure, but they may contain impurities such as other hydrocarbons as long as they do not interfere with the purpose of the present invention. Note that these unsaturated hydrocarbons represented by the general formula C ₃ H ₄ are usually desirably used in the above reaction in an anhydrous or sufficiently dehydrated state. In the present invention, the halide of the trivalent lanthanide series element used as a component of the catalyst in the reaction is a fluoride, chloride, bromide, or iodide of the trivalent lanthanide series element, or any composition thereof. Examples include mixtures of halides and complex halides. That is, in the present invention, the halides of the trivalent lanthanide series elements include one or more elements selected from the various trivalent lanthanide series elements, and fluorine, chlorine, bromine, and iodine. Examples include various halides or composite halides comprising one or more elements selected from the following, or mixtures thereof in arbitrary proportions. Furthermore, these halides may contain other elements as cationic and/or anionic components within the range that does not impede the purpose of the present invention, and if desired, may also contain other elements as carriers. It may be used by being supported on the hydroxide, or it may be used in combination with other components or in combination. Note that among these halides, chlorides are usually preferably used. In the method of the present invention, among the halides of trivalent lanthanide series elements, trihalides of trivalent lanthanide series elements are preferably used,
Particularly preferred are trichlorides of trivalent lanthanide series elements. Specific examples of trihalides of these trivalent lanthanide series elements include terbium trifluoride, dysprosium trifluoride, holmium trifluoride, erbium trifluoride, thulium trifluoride, and ytterbium trifluoride. , lutetium trifluoride, terbium trichloride, dysprosium trichloride,
Holmium trichloride, erbium trichloride, thulium trichloride, ytterbium trichloride, lutetium trichloride, terbium tribromide, dysprosium tribromide,
Holmium tribromide, erbium tribromide, thulium tribromide, yzterbium tribromide, lutetium tribromide, terbium triiodide, dysprosium triiodide, holmium triiodide, erbium triiodide,
Examples include thulium triiodide, ytterbium triiodide, and lutetium triiodide. Among these, for example, terbium trichloride, dysprosium trichloride, holmium trichloride,
Erbium trichloride, thulium trichloride, ytterbium trichloride, lutetium trichloride, and the like are preferred in terms of chemical stability, and ytterbium trichloride, erbium trichloride, dysprosium trichloride, and the like are particularly preferred. Note that these trihalides may be used alone or in combination of two or more, or may be used in combination with other rare earth elements such as yttrium,
Lanthanum, cerium, praseodymium, neodymium,
It may be used as a mixture with halides such as samarium, europium, and gadolinium, and furthermore, it may be used as a mixture with other compounds as long as it does not interfere with the purpose of the present invention. In the method of the present invention, the halide of the trivalent lanthanide series element or the catalyst component containing the same is usually used as a catalyst component in the reaction after being sufficiently dehydrated by anhydride or heat treatment. is desirable. The hydrogen halide in the present invention includes:
Mention may be made of hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide. These hydrogen halides may be used alone or in combination of two or more. Note that it is usually desirable to use these hydrogen halides in an anhydrous form or in a sufficiently dehydrated state. In the method of the present invention, phenol and the general formula
By reacting an unsaturated hydrocarbon represented by C ₃ H ₄ in the presence of a halide of the trivalent lanthanide series element and hydrogen halide, 2,
Synthesize 2-bis(4-hydroxyphenyl)propane. In the above reaction, the proportion of the unsaturated hydrocarbon represented by the general formula C ₃ H ₄ and phenol is not particularly limited as long as it is a stoichiometric amount, but in reality, it is It is appropriate that the proportion of the unsaturated hydrocarbon is in the range of 0.05 to 0.5 mol, preferably 0.1 to 0.25 mol. If the ratio of unsaturated hydrocarbons to phenol is too small, the amount of unreacted phenol will increase, while if it is too large, reactions between unsaturated hydrocarbons may occur, or the amount of unreacted unsaturated hydrocarbons may increase. The amount may be large. The ratio of hydrogen halide and unsaturated hydrocarbon represented by the general formula C ₃ H ₄ used in the above reaction is:
The ratio of the phenol to the unsaturated hydrocarbon used, the type and amount of the trivalent lanthanide-series element halide used, the reaction temperature, the reaction method used, and other conditions must be defined. However, the hydrogen halide is usually
A suitable proportion is within the range of 0.1 to 10 mol, preferably 0.8 to 1.5 mol. If the proportion of hydrogen halide used is too small, sufficient reaction results may not be obtained; on the other hand, if it is too large, the excess amount of hydrogen halide used will no longer contribute to improving the reaction results and will be wasted. On the contrary, the efficiency of the post-processing process such as the hydrogen halide recovery process may be reduced. In the present invention, the hydrogen halide is considered to act as one of the catalytic components of the reaction, but the purpose of the present invention can be achieved with a small amount of the hydrogen halide used as described above. In the present invention, there is no particular restriction on the reaction method used for the reaction, and the reaction can be performed by any method such as a batch method, continuous flow method, semi-continuous method, or semi-batch method. . Further, the reaction may be a gas phase catalytic reaction, or
The reaction can be carried out in any state such as gas-liquid phase contact reaction, but usually, for example, phenol as a reaction raw material is used in a liquid state, and the reaction is carried out in the presence of a halide of the trivalent lanthanide series element. ,
A gas-liquid phase catalytic reaction in which the unsaturated hydrocarbon and hydrogen halide are introduced into the reaction system in a gaseous state is suitable. The above reaction can usually be carried out without using any particular solvent, but if desired, it can also be carried out using an appropriate solvent that does not interfere with the above reaction. Further, the reaction can be carried out, if desired, in the presence of an inert gas such as nitrogen, argon, helium, etc. that does not interfere with the reaction. When the reaction is carried out by a gas-liquid phase contact reaction as described above, it is preferable to carry out the reaction by stirring the reaction system appropriately, for example by using a stirrer or bubbling the introduced gas into the liquid. Adopted. At that time, part or all of the gas such as unsaturated hydrocarbon or hydrogen halide introduced into the reaction system may be supplied continuously, intermittently, or , or may be introduced into the reactor in advance. The ratio of the halide of the trivalent lanthanide series element used as a catalyst component in the reaction and the unsaturated hydrocarbon represented by the general formula C ₃ H ₄ is:
the type of the trivalent lanthanide series element used;
It varies depending on other conditions such as the ratio of the phenol used and the unsaturated hydrocarbon used, the type and amount of hydrogen halide used, the reaction temperature, etc., and also depends on the reaction method used, so it is not generally specified. However, when the reaction is carried out by a batch method or a semi-batch method, the amount of the halide of the trivalent lanthanide series element used per mol of the unsaturated hydrocarbon used is usually 0.01
It is appropriate that the proportion be within the range of ~0.1 mol, preferably 0.02-0.03 mol. When the above reaction is carried out by a batch method or a semi-batch method, the reaction time cannot be uniformly specified because it varies depending on the type of catalyst component used, the ratio to other components, and other conditions such as the reaction temperature. Usually, it is appropriate to keep the heating time within the range of 1 to 4 hours, preferably 2 to 3 hours. When the reaction is carried out by a continuous flow method, the reaction is usually carried out by controlling the ratio of the amount of the halide of the trivalent lanthanide series element to the feed rate of the reaction raw material supplied to the reaction system, that is, the contact time.
This can be suitably carried out by setting the contact time within the range corresponding to the reaction time in the batch method. The reaction temperature for the above reaction cannot be unconditionally defined because it varies depending on other conditions such as the type of catalyst component used and the ratio to other components, but it is usually 50 to 100 °C, preferably 50 to 100 °C.
It is appropriate to keep the temperature within the range of about 50 to 70°C. If this reaction temperature is too low, the reaction rate may not be sufficient; on the other hand, if it is too high, side reactions such as product decomposition reactions cannot be ignored, and as a result, selectivity tends to decrease. be. The reaction pressure for the above reaction is not particularly limited and may be reduced pressure, normal pressure, or increased pressure, but is usually normal pressure 0 to 1 Kg/cm ² (gauge pressure), preferably normal pressure. It is appropriate to set the pressure within a range of about 0 to 0.5 kg/cm ² (gauge pressure). In the manner described above, the desired 2,2-bis(4-hydroxyphenyl)propane, that is, bisphenol A, can be synthesized. The synthesized 2,2-bis(4-hydroxyphenyl)propane is separated from the resulting reaction mixture by appropriately performing post-treatment methods such as known separation and purification methods, and is purified as a product of desired purity. It can be recovered. As a step of this post-treatment method, in the method of the present invention, water is added to the reaction system or reaction mixture after the reaction is completed. By adding this water, the promoter function of the halide of the trivalent lanthanide series element used as the catalyst or catalyst component is deactivated, and the halide and remaining water-soluble components such as hydrogen halide are dissolved and Extract to form an aqueous phase. A simple method of appropriately separating this aqueous phase and the obtained oil phase consisting of 2,2-bis(4-hydroxyphenyl)propane or the like by phase separation or the like is preferably employed. As mentioned above, even if water is used to deactivate and separate the catalyst component, the halide of the trivalent lanthanide series element used as the catalyst component in the reaction in the method of the present invention cannot be used as a catalyst or catalyst component in the conventional method. Unlike Lewis acids such as aluminum chloride and boron fluoride, which are used as aluminum fluoride, they are not irreversibly hydrolyzed, and the recovered aqueous solution of the trivalent lanthanide series element halide is subjected to heating or reduced pressure treatment. By removing moisture in the halides, trivalent lanthanide series elements can be easily recovered as halides, and the recovered halides can be used again as catalyst components for reactions. Further, the used hydrogen halide and unreacted reaction raw materials can be appropriately separated and recovered and used again in the reaction. 2,2-bis(4-
Hydroxyphenyl)propane can be suitably used for various purposes including, for example, as a raw material for polymers such as polycarbonate. [Example] (Example 1) 100 g of dehydrated phenol and 1 g of itterbium chloride hexahydrate (YbCl ₃ 6H ₂ O) were placed in a 300 ml three-necked flask, and heated for 30 minutes while introducing hydrogen chloride gas.
The inside of the flask was replaced with methylacetylene every minute and stirred. The reaction was carried out at a temperature of 90°C for 3 hours, and the resulting reaction solution was analyzed by liquid chromatography. The results are shown in Table 1. (Example 2) Yzterbium chloride hexahydrate (YbCl ₃ 6H ₂ O)
Put 1g into a 3-necked flask with a volume of 300ml, and add 1mm
It was heated to 150°C under Hg or less to dehydrate it. The reaction was carried out in the same manner as in Example 1, except that 100 g of dehydrated phenol was added after cooling. The results are shown in Table 1. (Example 3) Ytterbium chloride hexahydrate (ErCl ₃ 6H ₂ O) as a halide of trivalent lanthanide series elements
The reaction was carried out under the same conditions as in Example 2, except that 1 g was used. The results are shown in Table 1. (Example 4) Dysprosium chloride hexahydrate (DyCl ₃ 6H ₂ O) as a halide of trivalent lanthanide series elements
The reaction was carried out under the same conditions as in Example 2, except that . The results are shown in Table 1. Example 5 Same as Example 2 except that a hydrate of a heavy rare earth chloride mixture having a rare earth metal composition corresponding to the composition (1) shown in Table 2 was used as the halide of the trivalent lanthanide series element. The reaction was carried out under the following conditions. The results are shown in Table 1. (Example 6) Example 6 except that a hydrate of a heavy rare earth chloride mixture having a rare earth metal composition corresponding to composition (2) shown in Table 2 was used as the halide of the trivalent lanthanide series element. The reaction was carried out under the same conditions as in 2. The results are shown in Table 1.

[Table] (Comparative Example 1) 100 g of dehydrated phenol was placed in a three-necked flask with a volume of 300 ml, and while hydrogen chloride gas was introduced, the inside of the flask was replaced with methyl acetylene every 30 minutes and stirred. The reaction was carried out at a temperature of 90°C for 3 hours, and the reaction solution was analyzed by liquid chromatography. The results are shown in Table 1. (Comparative Example 2) Example 2 except that a hydrate of light rare earth chloride mixture (LnCl ₃ .nH ₂ O) having the composition (3) shown in Table 3 was used.
The reaction was carried out under the same conditions. The results are shown in Table 1.

[Table] (Comparative Example 3) Put 100 g of dehydrated phenol into a 300 ml three-necked flask, add 670 mg of boron trifluoride ethyl ether chain (BF ₃ O (C ₂ H ₅ ) ₂ ), and add methyl ether every 30 minutes. The mixture was replaced with acetylene and stirred. The reaction was carried out at a temperature of 90° C. for 1 hour, and the resulting reaction solution was analyzed by liquid chromatography. The results are shown in Table 1. (Comparative Example 4) 100g of dehydrated phenol and 1g of ZnCl ₂ in a volume of 300ml
The mixture was placed in a three-necked flask, and while hydrogen chloride gas was introduced, the inside of the flask was replaced with methylacetylene every 30 minutes and stirred. The reaction was carried out at a temperature of 90° C. for 3 hours, and the reaction solution was analyzed by liquid chromatography. The results are shown in Table 1. From the results shown in Table 1, it can be seen that the method of the present invention has the following advantages and features. In Example 1 (when hydrogen chloride and yzterbium chloride hexahydrate were used as catalysts), the conversion rate of phenol was 14.4% and the selectivity of bisphenol A was 71.8%, whereas in Comparative Example 1 (when hydrogen chloride is used as a catalyst), the conversion rate of phenol is 5.6% and the selectivity of bisphenol A is 62.7%, which is higher than when hydrogen chloride and yzterbium chloride hexahydrate are used. The reaction results are better when In Example 2 (when hydrogen chloride and yzterbium chloride anhydrous salt were used as catalysts), the conversion rate of phenol was 26.1% and the selectivity of bisphenol A was 71.8%, and the reaction results were even better than in Example 1. is good. Example 2 (when hydrogen chloride and ytterbium chloride anhydrous salt are used as a catalyst), Example 3 (when hydrogen chloride and erbium chloride anhydrous salt are used as a catalyst), and Example 4 (when hydrogen chloride and erbium chloride anhydrous salt are used as a catalyst). When comparing the results (when dysprosium chloride anhydrous salt is used), it can be seen that the heavier the rare earth, the greater the catalytic effect. (Y
When the rare earths are arranged in order from heavy rare earths, they are Lu, Yb,
(Tm, Er, Ho, Dy, Tb) In Examples 5 and 6 (when using hydrogen chloride and a heavy rare earth chloride mixture as a catalyst), the higher the proportion of heavy rare earth contained, the better the reaction results. . In Comparative Example 2 (in which a mixture of hydrogen chloride and light rare earth chloride is used as a catalyst), the conversion rate of phenol is low and no catalytic action is observed. In Comparative Example 3, the catalyst concentration is the same as in Example 2, and although the reaction time is one-third of that, one hour, the conversion rate of phenol is the same. This indicates that the boron trifluoride ethyl ether chain is more active than the catalyst consisting of ytterbium chloride and hydrogen chloride. However, the selectivity of bisphenol A was 46.0%.
This is significantly inferior to 71.8% of Example 2. That is, the boron trifluoride ethyl ether chain can be used as a catalyst for producing bisphenol A.
Inferior to catalysts consisting of ytterbium chloride and hydrogen chloride. In Comparative Example 4, the catalyst concentration was about 3
Although it is twice as large, the conversion rate of phenol is inferior to that of Example 2, and the selectivity of bisphenol A is also inferior. In other words, a catalyst consisting of zinc chloride and hydrogen chloride can be used as a catalyst for producing bisphenol A.
Inferior to catalysts consisting of ytterbium chloride and hydrogen chloride. [Comparison of a catalyst consisting of ytterbium chloride and hydrogen chloride and a conventional Lewis acid catalyst] Conventional Lewis acid catalysts include boron trifluoride ethyl ether chains, zinc chloride, and aluminum chloride. As mentioned above, the boron trifluoride ethyl ether chain and zinc chloride are inferior to the catalyst consisting of ytterbium chloride and hydrogen chloride in selectively and efficiently synthesizing bisphenol A. Aluminum chloride reacts with phenol and decomposes, which cannot be recovered and reused. From these facts, it can be said that the catalyst consisting of ytterbium chloride and hydrogen chloride is more useful than the conventional Lewis acid catalyst.

【table】

【table】

[Table] [Effects _of the Invention] According to _the present invention, 2,2-
Since a specific catalyst component is used as a catalyst system for the synthesis of bis(4-hydroxyphenyl)propane, i.e., bisphenol A, the catalyst or catalyst component can be easily recovered and reused, and the desired 2,2 -bis(4-hydroxyphenyl)
Practically advantageous 2,2-
A method for producing bis(4-hydroxyphenyl)propane can be provided.

Claims (1)

[Claims] 1. A method characterized by reacting a phenol with an unsaturated hydrocarbon represented by the general formula C ₃ H ₄ in the presence of a halide of a trivalent lanthanide series element and a hydrogen halide. A method for producing 2,2-bis(4-hydroxyphenyl)propane. 2 The halide of the trivalent lanthanide series element is terbium, dysprosium, holmium,
2,2-bis(4-hydroxyphenyl)propane according to claim 1, which is a halide of one or more rare earth metals selected from the group consisting of erbium, thulium, ytterbium, and lutetium. manufacturing method.