JP2008120791A - Method for producing bisphenols - Google Patents

Abstract

Bisphenols such as bisphenol A are produced with high selectivity and high yield by reaction of carbonyl compounds such as acetone with phenols such as phenol.
A bisphenol is produced by reacting a carbonyl compound with a phenol in the presence of a heteropolyacid modified with a nitrogen-containing compound having a mercapto group and / or a heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group. To do. As the catalyst, phosphotungstic acid or silicotungstic acid or a cesium salt thereof modified with a nitrogen-containing compound having a mercapto group is preferable. As the nitrogen-containing compound having a mercapto group, mercaptopyridines or mercaptoamines are preferable. By the reaction of acetone and phenol, 2,2-bis (4-hydroxyphenyl) propane can be produced with high selectivity and high yield.
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Description

  The present invention relates to a method for producing bisphenols by reacting a carbonyl compound and a phenol, and a heteropoly acid modified with a nitrogen-containing compound having a mercapto group and / or a heteropoly acid salt modified with a nitrogen-containing compound having a mercapto group The present invention relates to a method for producing bisphenols, which produces bisphenols with high selectivity and high yield by using as a catalyst.

  Bisphenols such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”) are useful as intermediate materials for polycarbonate, polyester, epoxy resin and thermal paper developer. A compound.

  Bisphenol A is usually synthesized by reacting phenol and acetone in the presence of a catalyst (acid condensing agent), and a sulfur compound such as methyl mercaptan may be added as a co-catalyst. As an acidic catalyst, hydrogen chloride is usually used, but hydrogen chloride is highly corrosive, so a reactor using an expensive material is necessary for actual production, and the catalyst is removed from the reaction mixture. There are problems such as the need for a purification step to achieve this.

  In addition, the method of using an acidic ion exchange resin as a catalyst (Patent Document 1) has a drawback that the activity is reduced by water produced by the reaction, and a method of performing the reaction while removing water (Patent Document 2) has also been studied. However, the ion exchange resin has a problem that the life of the resin is short and the cost is high.

  Patent Document 3 proposes a method using a modified strongly acidic sulfonic acid type ion exchange resin in which mercaptoamines are ion-bonded. However, in this method, it is necessary to perform the reaction after the water contained in the modified resin is replaced with phenol by treating with phenol before use, and the operation is complicated. In addition, since ion exchange resins swell with water and phenol, the reactor becomes large and difficult to downsize on an industrial scale. In addition, there is a problem that the heat resistance of the ion exchange resin itself is low and easily deteriorates.

  On the other hand, Patent Document 4 discloses a process for producing bisphenol A in which acetone and phenol are reacted in the presence of a heteropolyacid or heteropolyacid salt and an organic compound having a mercapto group as a promoter. "Specific examples of the organic compound having a mercapto group include alkyl mercaptans such as ethyl mercaptan, propyl mercaptan and butyl mercaptan; mercaptocarboxylic acids such as mercaptopropionic acid and mercaptoacetic acid; mercaptoethanol such as mercaptoethanol and mercaptobutanol. Alcohols; mercaptopyridines such as mercaptopyridine, mercaptonicotinic acid, mercaptopyridinooxide, and mercaptopyridinol; thiophenols such as thiophenol and thiocresol It is, but it is described that alkyl mercaptans and mercapto carboxylic acids are particularly preferred. "In the embodiment only butyl mercaptan is used in combination with the cesium salt of heteropoly acid or heteropoly acid.

Patent Document 5 discloses a method for producing bisphenols using a heteropolyacid or a salt thereof as a catalyst. “A heteropolyacid salt in which a part of protons of a heteropolyacid is substituted with an alkali metal, an alkaline earth metal element, or the like. Substitution elements are not limited to these, and those widely substituted with transition metal elements, etc. can also be used. It is also possible to use those obtained by substituting a part of the protons in the above formula. "However, in Patent Document 5, the proton-substituted products of the heteropolyacid actually used are cesium salts, sodium salts and calcium. Only salt.
Japanese Patent Publication No. 36-23334 Japanese Patent Application Laid-Open No. 61-78741 JP-A-62-298454 Japanese Patent No. 3003294 JP-A-2-45439

  However, in the method of Patent Document 5, for example, when there is a large amount of water of crystallization in the heteropolyacid in the reaction between phenol and acetone, the acetone conversion is 2.5% and the yield is 2.0% at 60 ° C. for 4 hours. There was a drawback that the reaction was very slow.

  Further, the method of Patent Document 4 has a drawback that it is necessary to use a cocatalyst together and it is difficult to separate the product bisphenol A and the cocatalyst.

  The present invention solves the above-mentioned problems of the prior art and provides a method for producing bisphenols such as bisphenol A with high selectivity and high yield by reaction of a carbonyl compound such as acetone and a phenol such as phenol. For the purpose.

  The method for producing bisphenols according to the present invention (Claim 1) is a method for producing bisphenols by reacting a carbonyl compound with phenols, and a heteropolyacid and / or a mercapto group modified with a nitrogen-containing compound having a mercapto group. The reaction is carried out in the presence of a heteropolyacid salt modified with a nitrogen-containing compound having

  The method for producing bisphenols according to claim 2 is characterized in that the nitrogen-containing compound having a mercapto group is at least one compound selected from the group consisting of mercaptopyridines and mercaptoamines.

  The method for producing bisphenols according to claim 3 is characterized in that the heteropolyacid salt is an alkali metal salt of a heteropolyacid.

  According to the present invention, by using a heteropolyacid modified with a nitrogen-containing compound having a mercapto group and / or a heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group as a catalyst, bisphenols such as bisphenol A are increased. It can be produced with high selectivity and high yield. The catalyst used in the present invention is easy to prepare, easy to handle, easy to separate and recover the catalyst after reaction, has excellent heat resistance compared to conventional ion exchange resins, and has few problems of swelling. Since bisphenols can be produced with a high selectivity and a high yield, the reactor can be miniaturized, and the present invention is an industrially excellent method even in the superiority of such a catalyst.

  Hereinafter, embodiments of the method for producing bisphenols of the present invention will be described in detail.

  First, the catalyst used in the present invention will be described.

  The catalyst used in the present invention is a heteropolyacid modified with a nitrogen-containing compound having a mercapto group and / or a heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group.

  The heteropolyacid used in the present invention has a structure in which at least one oxide selected from the group consisting of molybdenum, tungsten, and vanadium and an oxyacid selected from the group consisting of phosphorus, silicon, arsenic, and germanium are condensed. Usually, those having an atomic ratio of 2.5 to 12 with respect to the latter are easily available and preferably used. These heteropolyacids include, for example, phosphotungstic acid, phosphomolybdic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, phosphomolybdotungstovanadic acid, phosphotungstovanadic acid, phosphomolybdniobic acid, silicotungstic acid, Examples thereof include silicomolybdic acid, silicomolybdotungstic acid, silicomolybdo-tungstovanadic acid, germanium tungstic acid, arsenic molybdic acid, and arsenic tungstic acid.

  Among these, heteropolyacids are preferred because they are particularly high in selectivity and yield for the intended reaction of phosphotungstic acid or silicotungstic acid. That is, the catalyst used in the present invention is preferably phosphotungstic acid or silicotungstic acid modified with a nitrogen-containing compound having a mercapto group.

The heteropolyacid modified with a nitrogen-containing compound having a mercapto group used in the present invention is obtained by substituting a part or all of hydrogen in such a heteropolyacid with a nitrogen-containing compound having a mercapto group. That is, since the nitrogen-containing compound having a mercapto group has basicity in the nitrogen-containing part, an acid-base reaction is caused by mixing this with a heteropolyacid, thereby having an acidic part of the heteropolyacid and a mercapto group. The basic moiety of the nitrogen-containing compound is bound by an ionic bond. By such an action, the hydrogen of the heteropolyacid is replaced with a nitrogen-containing compound having a mercapto group.
The substitution ratio (ratio of hydrogen substituted with a nitrogen-containing compound having a mercapto group with respect to hydrogen in the heteropolyacid before substitution with a nitrogen-containing compound having a mercapto group) varies depending on the structure of the heteropolyacid. It is preferably at least mol%, particularly preferably at least 75 mol% and not more than 95 mol%. When this substitution ratio is less than 60 mol% or higher than 95 mol%, the yield and selectivity may be remarkably lowered.

  On the other hand, examples of the heteropolyacid salt used in the present invention include alkali metal salts of heteropolyacids as described above, preferably phosphotungstic acid or silicotungstic acid, particularly preferably cesium salts of these heteropolyacids. Is mentioned.

  This heteropolyacid salt is a salt in which part or all of the hydrogen in the heteropolyacid has been replaced with a metal, and among them, one in which a part of hydrogen has been replaced is preferable. The substitution rate (ratio of hydrogen substituted with metal to hydrogen in heteropolyacid before substitution with metal) is usually 30 mol% or more, preferably 40 to 80 mol%, more preferably 50 to 70 mol%. If the substitution rate is less than 30 mol%, the yield and selectivity may be significantly reduced.

  The heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group used in the present invention is obtained by substituting part or all of the remaining hydrogen in such a heteropolyacid salt with a nitrogen-containing compound having a mercapto group, The substitution ratio varies depending on the structure of the heteropolyacid, but the hydrogen remaining without being replaced with a metal or with a nitrogen-containing compound is converted into the original heteropolyacid (a nitrogen-containing compound having a mercapto group and a metal). It is preferable that it is less than 30 mol% of hydrogen of the heteropoly acid before being substituted with, and particularly preferably 5 to 20 mol%. When the ratio of the remaining hydrogen is less than 5 mol% or higher than 20 mol%, the yield and selectivity may be remarkably lowered. Hereinafter, the ratio of the remaining hydrogen is referred to as a hydrogen remaining ratio.

  The advantage of using a heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group as a catalyst is that the heteropolyacid is a heteropolyacid salt, thereby controlling hydrogen (Bronsted acid point) and having hydrogen and a mercapto group. As a result of improving the balance with the nitrogen-containing compound, the active point of the catalyst is increased to increase the catalytic activity and selectivity.

  The nitrogen-containing compound having a mercapto group used for the modification is, for example, mercaptoalkylamine (or amino) such as 2-mercaptoethylamine, 3-mercaptobutylamine, 3-n-propylamino-1-propylmercaptan, 2-diethylaminoethylmercaptan. Alkyl mercaptans); mercaptoalkylpyridines such as 3-mercaptomethylpyridine, 3-mercaptoethylpyridine, 4-mercaptoethylpyridine; thiazolidine, 2,2-dimethylthiazolidine, cycloalkylthiazolidine, 2-methyl-2-phenylthiazolidine, 3 -Thiazolidine such as methylthiazolidine; aminothiophenol such as 1,4-aminothiophenol; Particularly preferably, mercaptoamines such as mercaptoalkylamine (the carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3) and mercaptoalkylpyridine (the carbon number of the alkyl group is Preferred are mercaptopyridines such as 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3).

  The aforementioned nitrogen-containing compound having a mercapto group can be an addition salt of an acidic substance such as hydrochloric acid or a quaternary ammonium salt. Moreover, it can also be a compound which produces a mercapto group under the treatment conditions in modification.

  The heteropolyacid modified with a nitrogen-containing compound having a mercapto group and / or the heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group may be used alone or in combination of two or more.

The method for producing a heteropolyacid modified with a nitrogen-containing compound having a mercapto group and a heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group used as a catalyst in the present invention is not particularly limited and should be prepared according to a conventional method. Can do.
For example, in the case of a heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group, a commercially available heteropolyacid is dissolved in a solvent such as water, alcohols or ethers at a concentration of about 0.01 to 10 mol / L. Nitrogen-containing compounds having a mercapto group, and addition salts or quaternary ammonium salts of acidic substances such as hydrochloric acid dissolved directly or in water, alcohols, ethers, etc. at a concentration of about 0.01 to 10 mol / L. The method of adding and mixing as a solution is mentioned.
In addition, the heteropoly acid salt modified with a nitrogen-containing compound having a mercapto group may be prepared by adding a nitrate or chloride of the corresponding metal (alkali metal such as cesium) directly or as a solution of water, alcohols, ethers, etc. And a method of adding and mixing to the above solution.
The heteropolyacid or heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group precipitated in the mixed solution is recovered by centrifugation or filtration, and then washed with a solvent such as water, alcohols or ethers. A heteropolyacid or heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group can be obtained by recovering from the solvent used for washing by centrifugation or filtration and further drying. The mixing time is preferably about 30 minutes to 3 days after addition, the drying temperature is 50 to 100 ° C., and the drying time is preferably about 1 hour to 3 days.

  In the present invention, two or more kinds of heteropolyacids modified with nitrogen-containing compounds having different mercapto groups and / or heteropolyacid salts modified with nitrogen-containing compounds having mercapto groups may be used, and they have mercapto groups. You may use 2 or more types of the heteropoly acid and / or heteropoly acid salt from which a nitrogen-containing compound and its substitution ratio differ. In addition, these heteropolyacids modified with a nitrogen-containing compound having a mercapto group can be used as they are, but they may be used by supporting them on a carrier such as activated carbon, alumina, silica-alumina, diatomaceous earth, or the like.

In the present invention, the carbonyl compound to be subjected to the reaction may be a carbonyl compound belonging to a ketone or an aldehyde, and is not particularly limited. Specifically, a compound represented by the general formula R ¹ COR ² may be mentioned. it can. Here, R ¹ and R ² may be the same or different from each other, and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or 6 to 6 carbon atoms. A carbonyl compound having 14 aryl groups or an alkylaryl group having 7 to 20 carbon atoms is suitable as the carbonyl compound used in the present invention. A cyclic ketone (cycloalkanone derivative) in which R ¹ and R ² are bonded to each other to form a ring is also suitable as the carbonyl compound used in the present invention. In this case, the ring may further have a substituent.

More specifically, preferred carbonyl compounds include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and R ¹ and R ² such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, and methyl isobutyl ketone each having 12 or less carbon atoms. Saturated fatty acid ketones preferably having 6 or less alkyl groups, aromatic ketones such as phenyl methyl ketone, unsaturated ketones such as mesityl oxide, cyclohexanone, and cyclohexanone having 1 to 10 carbon atoms as substituents Examples thereof include alicyclic ketones (for example, 4-n-propylcyclohexanone).

  On the other hand, specific examples of phenols include compounds represented by the following general formula.

（式中、Ｒ^３〜Ｒ^６は互いに同一であっても相違していても良く、水素原子、炭素数１〜４のアルキル基、又はハロゲン原子を表す。）

(In formula, R < ³ > -R < ⁶ > may mutually be same or different, and represents a hydrogen atom, a C1-C4 alkyl group, or a halogen atom.)

  In the present invention, it is particularly preferable to use a phenol derivative in which the para-position or ortho-position is unsubstituted (hydrogen atom) from the orientation of the substitution reaction in the aromatic ring of the phenol. Specific examples of phenols used in the present invention include phenols, orthocresols, metacresols, 2,6-dimethylphenols, tetramethylphenols, 2,6-ditertiary butylphenols, alkylphenols, orthochlorophenols, and metachlorophenols. And halogenated phenols such as 2,6-dichlorophenol.

  The carbonyl compounds and phenols may be used alone or in combination of two or more.

  In the reaction between the carbonyl compound and the phenol, the amount of the phenol used is usually 3 to 50 mol, preferably 5 to 20 mol, relative to 1 mol of the carbonyl compound. If the amount of phenol used is less than 3 mol, in addition to the desired bisphenol A such as bisphenol A, for example, the reaction of acetone with phenol increases the amount of by-products such as chromans, which is not preferable. If it is used in excess, the recovered amount of unreacted phenols will increase and the productivity will be lowered, which is not practical.

  In the reaction between the carbonyl compound and the phenol, the amount of the catalyst used is usually 0.01 to 0.5 mol, particularly 0.05 to 0.005, based on 1 mol of the carbonyl compound subjected to the reaction, from the viewpoint of reactivity and economy. It is preferable to use in the range of 3 mol.

  The reaction temperature is usually 30 to 250 ° C, preferably 40 to 180 ° C. Although the reaction time depends on the amount of catalyst and the reaction temperature, it is usually 2 to 12 hours. If the reaction temperature is too low or the reaction time is too short, the reaction will be inadequate because of the slow progress of the reaction. Conversely, if the reaction temperature is excessively high, for example, the crystal structure of the catalyst at a temperature of 500 ° C. or higher. This is not preferable because the loss of water is unfavorable, and if the reaction time is excessively long, industrial productivity is hindered.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In the following, the yield and selectivity of bisphenol A were calculated from the measured values by gas chromatography (manufactured by Shimadzu Corporation, GC-2010, column used: Rtx-5 (manufactured by RESTEK)) by the following formula.
Yield of bisphenol A (%) = (generated bisphenol A (mol) ÷ amount of acetone charged (mol)) × 100
Bisphenol A selectivity (%) = (bisphenol A yield (%) ÷ acetone conversion (%)) × 100

The conversion rate of acetone is calculated by the following formula.
Acetone conversion (%) = (reacted acetone amount (mol) ÷ added acetone amount (mol)) × 100

  In addition, the heteropolyacid modified with a nitrogen-containing compound having a mercapto group as a catalyst is obtained by using an aqueous solution of a heteropolyacid (0.3 mol / L) and a corresponding aqueous solution of a nitrogen-containing compound having a mercapto group (0.75 mol / L). Then, after dropping and stirring and mixing so that the amount of the nitrogen-containing compound having a mercapto group is a predetermined substitution amount, the resulting precipitate is centrifuged, washed with water, centrifuged and collected, and then at 80 ° C. overnight. The solid obtained by drying was used as it was.

  Moreover, the heteropoly acid salt modified with a nitrogen-containing compound having a mercapto group as a catalyst is obtained by using an aqueous solution of a heteropoly acid (0.3 mol / L) and a corresponding aqueous solution of metal chloride or metal nitrate (0.6 mol / L). After mixing so that the amount of introduced ions is a predetermined ion exchange rate, an aqueous solution (0.15 mol / L) of a nitrogen-containing compound having a corresponding mercapto group is replaced with a predetermined substitution amount of the nitrogen-containing compound having a mercapto group. Then, the resulting precipitate was centrifuged, washed with water, centrifuged and collected, and the solid obtained by drying at 60 ° C. overnight was used as it was.

Example 1
In a reactor equipped with a reflux condenser and a stirrer, 1.88 g (20 mmol) of phenol, 2-diethylaminoethyl mercaptan hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ / 28H ₂ O, 0.1 g (0.03 mmol) of phosphotungstic acid modified with 2.5 equivalent of 2-diethylaminoethyl mercaptan prepared from Nippon Inorganic Chemical Industry Co., Ltd. (substitution rate is 3 equivalents of acid equivalent of phosphotungstic acid) Therefore, 2.5 / 3 = 83.3 mol% is calculated.), 0.12 g (2.0 mmol) of acetone was added, and the mixture was reacted at 80 ° C. for 6 hours.
The yield and selectivity of bisphenol A at this time were as shown in Table 1.

Comparative Example 1
Instead of phosphotungstic acid modified with 2.5 equivalents of 2-diethylaminoethyl mercaptan of Example 1, 0.1 g (0 of phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ / 28H ₂ O, manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) 0.03 mmol), and 2.5 equivalents of 2-diethylaminoethyl mercaptan hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.013 g, 0.075 mmol) was added, and the reaction was conducted in the same manner as in Example 1.
The yield and selectivity of bisphenol A at this time were as shown in Table 1.

Comparative Example 2
Instead of phosphotungstic acid modified with 2.5 equivalents of 2-diethylaminoethyl mercaptan of Example 1, 0.1 g (0 of phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ / 28H ₂ O, manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) 0.03 mmol) was used in the same manner as in Example 1.
The yield and selectivity of bisphenol A at this time were as shown in Table 1.

Example 2
In a reactor equipped with a reflux condenser and a stirrer, 1.88 g (20 mmol) of phenol, cesium nitrate, 2-diethylaminoethyl mercaptan hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ / 28H) _{And 2} -diethylaminoethyl mercaptan 1.0 equivalent (substitution rate with 2-diethylaminoethyl mercaptan is equivalent to 1.0 / 3 = 33.3 mol%) prepared from ₂ O, manufactured by Nippon Inorganic Chemical Co., Ltd. Phosphotungstic acid cesium salt (substitution ratio (cesium substitution ratio) by cesium is 1.5 / 3.0 = 50 mol%, and therefore the hydrogen remaining ratio is 100− (33.3 + 50) = 16.7 mol%). 1 g (0.03 mmol) was charged, 0.12 g (2.0 mmol) of acetone was added, and the mixture was reacted at 80 ° C. for 3 hours.
The yield and selectivity of bisphenol A at this time were as shown in Table 2.

Comparative Example 3
Instead of the cesium phosphotungstic salt modified with 1.0 equivalent of 2-diethylaminoethyl mercaptan in Example 2, the cesium phosphotungstic salt (substitution ratio (cesium substitution ratio) with cesium is 1.5 / 3.0 = 50) Example 2 except that 0.1 g (0.03 mmol) of 0.1 mol (0.0 mol%) and 0.005 g (0.03 mmol) of 2-diethylaminoethyl mercaptan hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. It was made to react similarly.
The yield and selectivity of bisphenol A at this time were as shown in Table 2.

Comparative Example 4
Instead of the cesium phosphotungstic salt modified with 1.0 equivalent of 2-diethylaminoethyl mercaptan in Example 2, the cesium phosphotungstic salt (substitution ratio (cesium substitution ratio) with cesium is 1.5 / 3.0 = 50) The reaction was conducted in the same manner as in Example 2 except that 0.1 g (0.03 mmol) was used.
The yield and selectivity of bisphenol A at this time were as shown in Table 2.

  From Tables 1 and 2, bisphenol A was obtained in high yield and high by using a heteropolyacid modified with a nitrogen-containing compound having a mercapto group or a heteropolyacid salt modified with a nitrogen-containing compound having a mercapto group according to the present invention as a catalyst. It turns out that it can manufacture with a selectivity.

Claims (3)

  In the method of producing bisphenols by reacting a carbonyl compound and a phenol, in the presence of a heteropoly acid modified with a nitrogen-containing compound having a mercapto group and / or a heteropoly acid salt modified with a nitrogen-containing compound having a mercapto group A process for producing bisphenols, characterized by carrying out a reaction.   The method for producing bisphenols according to claim 1, wherein the nitrogen-containing compound having a mercapto group is at least one compound selected from the group consisting of mercaptopyridines and mercaptoamines.   The method for producing bisphenols according to claim 1 or 2, wherein the heteropolyacid salt is an alkali metal salt of a heteropolyacid.