JP3888936B2 - Bisphenol A production method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a solid catalyst for producing bisphenol A, and more particularly to a method for producing bisphenol A by dehydration condensation of acetone and phenol in the presence of a solid catalyst having both a sulfonic acid group and a mercapto group.
[0002]
[Prior art]
Bisphenol A [2,2-bis (4-hydroxyphenyl) propane] is usually continuous in the form of a so-called fixed bed flow reaction in which an excess phenol of 8 to 15 times in molar ratio with acetone is passed through a solid catalyst. Are manufactured.
[0003]
Conventionally, as these solid catalysts, a cation exchange resin or a mercapto-modified cation exchange resin in which a mercapto group is immobilized by partially neutralizing with a nitrogen-containing compound having a mercapto group (Japanese Patent Laid-Open No. 57-035533, Techniques using Japanese Patent Application Laid-Open Nos. 08-038910, 08-071433, 08-187436, and 10-212433 are known.
[0004]
In modified ion exchange resin catalysts, it is known that the catalyst life is greatly extended by adding a small amount of water to the raw material as described in JP-A-6-172241.
[0005]
However, in the case of a cation exchange resin, since the basic skeleton is polystyrene, it has a series of application technical limitations due to physical and chemical characteristics due to its organic properties. Specific examples include a relatively low temperature stability of 100 to 130 ° C. and a tendency to cause physical destruction due to strong swelling.
[0006]
In contrast, in the case of an inorganic matrix, most of these drawbacks can be avoided. For example, aluminum oxide, silica gel, titanium oxide and the like have a strong structure, non-swellability, and high temperature stability. In particular, organic polymer siloxanes having sulfonic acid groups (JP 59-20325, JP 61-272237, JP 6-207021) have the advantage of an inorganic polymer skeleton, and have high heat resistance, It has high physical strength and high surface area. Therefore, a modified organic polymer siloxane catalyst in which an organic polymer siloxane having a sulfonic acid group is partially neutralized with a mercaptoalkylamine instead of a cation exchange resin is promising as a catalyst for producing bisphenol A.
[0007]
However, in general known mercaptoalkylamines such as cysteamine, the catalyst life is drastically decreased as the reaction temperature is increased, so that it is difficult to make use of the high heat resistance of the organic polymer siloxane catalyst.
[0008]
[Problems to be solved by the invention]
The present invention provides a method for producing bisphenol A by dehydration condensation of acetone and phenol in the presence of a solid catalyst having both sulfonic acid groups and mercapto groups. In particular, a method for producing bisphenol A by dehydration condensation of acetone and phenol in the presence of an organic polymer siloxane catalyst having a sulfonic acid group in which a pyridine compound having a mercaptoalkyl group is added to 3 to 70% of the sulfonic acid group. It is to provide.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve these problems, the present inventors have found that a sulfone group in which a pyridine compound is added to an ammonium cation moiety in which a mercaptoalkylamine compound is ionically bonded to a sulfonic acid group of a sulfonic acid group-containing organic polymer siloxane. It became clear that the catalyst life was greatly improved by using an acid, and the present invention was completed.
[0010]
That is, the present invention produces bisphenol A by dehydration condensation of acetone and phenol in the presence of an organic polymer siloxane catalyst having a sulfonic acid group obtained by adding a part of a sulfonic acid group with a pyridine compound having a mercaptoalkyl group. Is the method.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The organic polymer siloxane catalyst having a sulfonic acid group used in the present invention is a silica having a siloxane bond described in JP-A-59-20325, JP-A-61-272237, and JP-A-6-207021. This is an organic polymer siloxane having a structure in which a sulfonic acid group-containing hydrocarbon group is partially bonded directly to a silicon atom in a silica matrix by a carbon-silicon bond in the matrix.
[0012]
As the hydrocarbon group having a sulfonic acid group, any hydrocarbon group having at least one sulfonic acid group (—SO ₃ H) can be used in the present invention.
[0013]
The hydrocarbon group having a sulfonic acid group is preferably a hydrocarbon group having 1 to 20 carbon atoms having at least one sulfonic acid group. More preferably a substituted or unsubstituted aromatic hydrocarbon group having at least one sulfonic acid group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms (the sulfonic acid group is directly substituted on the aromatic group) Or a hydrocarbon group substituted with an aromatic group may be a group in which a sulfonic acid group is substituted), or a group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, having at least one sulfonic acid group. And at least one hydrocarbon group selected from the group consisting of substituted or unsubstituted aliphatic and alicyclic hydrocarbon groups.
[0014]
Examples of the hydrocarbon group having a sulfonic acid group include an aromatic hydrocarbon group such as a phenyl group, a tolyl group, a naphthyl group, and a methylnaphthyl group that are nucleus-substituted by at least one sulfonic acid group, a benzyl group Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group substituted with at least one sulfonic acid group such as aromatic substituted alkyl group such as naphthylmethyl group A saturated aliphatic hydrocarbon group such as a t-butyl group, a linear or branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, Examples thereof include alicyclic hydrocarbon groups such as a cyclohexyl group, a methylcyclohexyl group, and an ethylcyclohexyl group. Further, these aromatic or saturated aliphatic or alicyclic hydrocarbon groups may be a hydrocarbon group having a substituent such as a halogen atom, an alkoxy group, a nitro group, or a hydroxy group in addition to the sulfonic acid group. .
[0015]
Such an organic polymer siloxane catalyst can be prepared, for example, by the following method. However, the organic polymer siloxane catalyst used in the present invention is not limited to these preparation methods. For example, (1) a preparation method in which alkoxysilane having a sulfonic acid group-containing hydrocarbon group and tetraalkoxysilane are mixed at an arbitrary ratio, hydrolyzed, and co-condensed. (2) A so-called sol-gel method of alkoxysilane, such as a preparation method in which a hydrolyzate of alkoxysilane having a water-soluble sulfonic acid group-containing hydrocarbon group and tetraalkoxysilane are mixed in an arbitrary ratio and hydrolyzed to co-condense. In addition to the preparation methods (1) and (2) according to (3), (3) silylating alkoxysilane having a sulfonic acid group-containing hydrocarbon group into silanol group present in the organic polymer siloxane, and fixing the sulfonic acid group, A preparation method by so-called silylation is known. These organic polymer siloxane catalysts are porous materials having high catalytic activity.
[0016]
The pyridine compound having a mercaptoalkyl group used in the present invention is a nitrogen-containing compound in which a mercaptoalkyl group is bonded to the pyridine ring. Specific examples of such nitrogen-containing compounds include 4-pyridylmethanethiol, 3-pyridylmethanethiol, 2-pyridylmethanethiol, 2- (4-pyridyl) ethanethiol, and 2- (3-pyridyl). Examples include ethanethiol, 2- (2-pyridyl) ethanethiol, 3- (4-pyridyl) propanethiol, 3- (3-pyridyl) propanethiol, and 3- (2-pyridyl) propanethiol.
[0017]
Modification of the organic polymer siloxane having a sulfonic acid group with a mercaptoalkyl group-containing pyridine compound can be performed by mixing the resin with a mercaptoalkyl group-containing pyridine compound in water or an organic solvent. The organic solvent is not particularly limited as long as it dissolves the pyridine compound. As the reaction temperature, normal temperature or warming is adopted, and the reaction time does not require a long time, and a few minutes is sufficient. However, the reaction mixture is preferably stirred for uniform reaction. In this reaction, a part of the sulfonic acid group contained in the unmodified resin, usually 3 to 70%, preferably 10 to 60%, is preferably converted to a mercapto group.
[0018]
When bisphenol A is produced using a fixed bed flow reactor filled with a sulfonic acid group-containing organopolymer siloxane catalyst modified with a mercapto group, the raw material acetone and phenol are in the range of 1: 3 to 15 in molar ratio. The reaction is carried out under general conditions in the range of 70 ° C to 130 ° C. The acid amount of the solid catalyst is determined by treating with an excess aqueous sodium chloride solution and quantifying the liberated hydrochloric acid. The amount of mercapto can be determined by oxidation-reduction titration with iodine or by producing silver mercaptide using an aqueous silver nitrate solution.
[0019]
【Example】
Next, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited only to these examples.
[0020]
Comparative Example 1
(1) Synthesis of sulfonic acid group-containing siloxane raw material 100 ml of methylene chloride was placed in a two-necked 500 ml round-bottom flask equipped with a dropping funnel, and 130.0 g (0.62 mol) of phenyltrichlorosilane was added thereto, followed by ice cooling. . To this was added dropwise 20 ml of a methylene chloride solution of 50.0 g (0.62 mol) of anhydrous sulfuric acid over 2 hours. After dropping, the ice bath was removed and the mixture was further stirred at room temperature for 1 hour. Subsequently, it heated with the oil bath of 100 degreeC, and the methylene chloride was distilled off.
[0021]
Further, after attaching a cooling pipe, 111.0 g of ethanol was dropped over 2.5 hours while removing hydrogen chloride under a nitrogen stream, and the mixture was further refluxed for 2 hours to carry out an ethoxylation reaction. 214.0 g of the obtained phenylsulfonic acid group-containing triethoxysilane in ethanol was used as a raw material for the sulfonic acid component in the sol-gel preparation of the organic polymer siloxane catalyst having the following sulfonic acid group-containing hydrocarbon groups.
[0022]
(2) Preparation of organic polymer siloxane catalyst 42.0 g of an ethanol solution of phenylsulfonic acid group-containing triethoxysilane obtained above in a three-necked 500 ml round bottom flask equipped with a stirring rod, 150.0 g of tetraethoxysilane ( 0.72 mol) and 150 ml of ethanol were mixed. 30.0 g of water was added dropwise thereto over 5 minutes, and the mixture was stirred at 60 ° C. for 3 hours.
[0023]
After standing to cool, 140.0 g of water was added dropwise over 5 minutes, and further 15 ml of 28% aqueous ammonia was added dropwise to rapidly solidify the reaction solution. This was allowed to stand at room temperature for 4 hours and then aged at 60 ° C. for 3 days. After aging, the solvent was distilled off at 100 ° C. under a reduced pressure of 10 mmHg to obtain a dry solid.
[0024]
The dried solid was transferred to a 500 ml beaker, 200 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes and then filtered off twice to convert the sulfonic acid group into the H + form. After the acid treatment, it was washed with 500 ml of ion-exchanged water and dried at 100 ° C. for 5 hours under a reduced pressure of 10 mmHg to obtain 62.0 g of an organic polymer siloxane catalyst having a sulfonic acid group. The amount of the solid acid was measured by the method described above, and was 0.87 mmol / g.
[0025]
(3) Modification of organopolymer siloxane catalyst with cysteamine 17.7 g of the organopolymer siloxane catalyst obtained above and 200 ml of water are added and stirred and suspended with a stirrer equipped with a stir bar. An aqueous solution in which 3.8 mmol of cysteamine was dissolved in 100 ml of water was added dropwise thereto over 30 minutes using a dropping funnel. After stirring at room temperature for 30 minutes, the mixture was filtered and washed with 100 ml of water. Furthermore, it dried at 100 degreeC under pressure reduction of 10 mmHg for 4 hours, and obtained 17.8 g of ammonium modification type | mold organic polymer siloxane catalysts.
[0026]
When the solid acid amount and the solid mercapto amount were measured by the method described above, the solid acid amount was 0.65 mmol / g and the solid mercapto amount was 0.20 mmol / g. That is, 24% of the sulfonic acid groups are ion exchanged.
[0027]
(4) Bisphenol A synthesis reaction 8.2 g (11 cc) of the ammonium-modified organopolymer siloxane catalyst obtained above was charged into a cylindrical reactor (diameter 1.50 cm, length 15 cm). From the bottom of the reactor, a 5: 1 molar ratio phenol / acetone mixture was passed through the catalyst at a rate of 10.50 g / hr. The reaction temperature was 100 ° C. and the reaction product obtained after 5 hours was analyzed by liquid chromatography. As a result, the conversion of acetone was 55% and the selectivity for bisphenol A was 91%.
[0028]
The reaction was continued and the reaction product obtained after 300 hours was analyzed in the same manner. As a result, the conversion rate of acetone was 44% and the selectivity of bisphenol A was 91%. It declined greatly.
[0029]
Example 1
(1) Modification of organopolymer siloxane catalyst with mercaptoalkyl group-containing pyridine compound Into a 500 ml beaker, 17.7 g of the organopolymer siloxane catalyst obtained above and 200 ml of water were placed and stirred and suspended with a stirrer equipped with a stir bar. . An aqueous solution prepared by dissolving 3.8 mmol of 2- (4-pyridyl) ethanethiol in 100 ml of water was dropped over 30 minutes using a dropping funnel. After stirring at room temperature for 30 minutes, the mixture was filtered and washed with 100 ml of water. Furthermore, it dried at 100 degreeC under pressure reduction of 10 mmHg for 4 hours, and obtained 18.0 g of ammonium modification type | mold organic polymer siloxane catalysts.
[0030]
When the solid acid amount and the solid mercapto amount were measured by the method described above, the solid acid amount was 0.60 mmol / g and the solid mercapto amount was 0.23 mmol / g. That is, 27% of the sulfonic acid groups are ion-exchanged.
[0031]
(2) Bisphenol A synthesis reaction 8.2 g (11 cc) of the pyridine compound-modified organopolymer siloxane catalyst obtained above was charged into a cylindrical reactor (diameter 1.50 cm, length 15 cm). From the bottom of the reactor, a 5: 1 molar ratio phenol / acetone mixture was passed through the catalyst at a rate of 10.50 g / hr. The reaction temperature was 100 ° C., and the reaction product obtained after 5 hours was analyzed by liquid chromatography. As a result, the conversion of acetone was 67% and the selectivity for bisphenol A was 92%.
[0032]
The reaction was continued and the reaction product obtained after 300 hours was analyzed in the same manner. As a result, the conversion of acetone was 65% and the selectivity for bisphenol A was 92%. 2%.
[0033]
Compared to 11% decrease in acetone conversion when using Comparative Example 1 for 300 hours, the decrease in acetone conversion in Example 1 is 2%, indicating that the decrease in activity is largely suppressed.
[0034]
Example 2
(1) Synthesis of sulfonic acid group-containing siloxane raw material 100 ml of methylene chloride was placed in a two-necked 500 ml round bottom flask equipped with a dropping funnel, and 42.0 g (0.20 mol) of phenyltrichlorosilane was added thereto, and the mixture was ice-cooled. . To this was added dropwise 20 ml of a methylene chloride solution of 39.3 g (0.49 mol) of anhydrous sulfuric acid over 1 hour. After the dropwise addition, the ice bath was removed and refluxed for 10 hours. Under reflux, 51.0 g (1.11 mol) of ethanol was added dropwise over 1 hour, and then methylene chloride was distilled off.
[0035]
Further, after adding 51.0 g of ethanol, the mixture was refluxed for 2 hours to carry out an ethoxylation reaction. 150.0 g of the obtained phenylsulfonic acid group-containing triethoxysilane in ethanol was used as a raw material for the sulfonic acid component in the sol-gel preparation of the following organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group.
[0036]
(2) Preparation of organopolymer siloxane catalyst In a three-necked 500 ml round bottom flask equipped with a stirrer, 135.0 g of a phenylsulfonic acid group-containing triethoxysilane ethanol solution obtained above and 119.0 g of tetraethoxysilane ( 0.57 mol) and 100 ml of ethanol were mixed. To this, 24.0 g of water was added dropwise over 15 minutes, followed by stirring at 60 ° C. for 3 hours. After allowing to cool, 120.0 g of water was added dropwise over 5 minutes, and when 35 ml of 28% aqueous ammonia was added dropwise, the reaction solution rapidly solidified.
[0037]
This was allowed to stand at room temperature for 4 hours and then aged at 60 ° C. for 3 days. After aging, the solvent was distilled off at 100 ° C. under a reduced pressure of 10 mmHg to obtain a dry solid. The dried solid was transferred to a 500 ml beaker, 300 ml of 2N hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes and then filtered off twice, so that the sulfonic acid group was changed to H + type. After the acid treatment, it was washed with 500 ml of ion-exchanged water, and further dried under reduced pressure of 10 mmHg at 100 ° C. for 16 hours to obtain 57.0 g of an organic polymer siloxane catalyst having a sulfonic acid group. This solid acid amount was 1.46 mmol / g as measured by the method described above.
[0038]
(3) Modification of organic polymer siloxane catalyst with nitrogen-containing mercapto compound In a 500 ml beaker, 17.7 g of the organic polymer siloxane catalyst obtained above and 200 ml of water were placed and stirred and suspended with a stirrer equipped with a stir bar. An aqueous solution in which 11.6 mmol of 2- (4-pyridyl) ethanethiol hydrochloride was dissolved in 100 ml of water was added dropwise thereto using a dropping funnel over 30 minutes. After stirring at room temperature for 30 minutes, the mixture was filtered and washed with 100 ml of water.
[0039]
Furthermore, it dried at 100 degreeC under pressure reduction of 10 mmHg for 4 hours, and obtained 18.0 g of modified organic polymer siloxane catalysts. When the solid acid amount and the solid mercapto amount were measured by the method described above, the solid acid amount was 0.80 mmol / g, and the solid mercapto amount was 0.65 mmol / g. That is, it is calculated that 45% of the sulfonic acid groups are ion-exchanged.
[0040]
(4) Bisphenol A synthesis reaction 8.2 g (11 cc) of the modified organopolymer siloxane catalyst obtained above was charged into a cylindrical reactor (diameter 1.50 cm, length 15 cm). From the lower side of the reactor, a phenol / acetone / water mixture having a molar ratio of 5/1 / 0.4 was passed through the catalyst at a rate of 10.50 g / hr. The reaction temperature was 100 ° C., and the reaction product obtained after 5 hours was analyzed by liquid chromatography. As a result, the conversion of acetone was 63.1% and the selectivity for bisphenol A was 92%.
[0041]
The reaction was continued and the reaction product obtained after 300 hours was analyzed in the same manner. As a result, the conversion rate of acetone was 62.9%, the selectivity of bisphenol A was 92%, and the catalytic activity decreased after 300 hours. I did not.
[0042]
Comparative Example 2
(1) Modification of organopolymer siloxane catalyst with nitrogen-containing mercapto compound To 50 g of Amberlyst 31 (Rohm & Haas, exchange capacity 1.80 meq / wet-g) suspended in 150 ml of ion exchange water in a 1000 ml beaker An aqueous solution prepared by dissolving 19 mmol of 2- (4-pyridyl) ethanethiol hydrochloride in 100 ml of ion-exchanged water was dropped over 30 minutes using a dropping funnel. After stirring at room temperature for 30 minutes, it was filtered and washed with 500 ml of ion exchange water to obtain 52 g of a modified ion exchange resin.
When this solid acid amount was measured by the above-mentioned method, the solid acid amount was 1.40 meq / wet-g.
[0043]
(2) Bisphenol A synthesis reaction 18.0 g (22 cc) of this modified ion exchange resin was charged into a cylindrical reactor (diameter 1.50 cm, length 15 cm). Phenol was passed from the lower side of the reactor at 70 ° C. at LHSV = 5 hr ⁻¹ for 24 hours. Separately, using a glass column, it was confirmed that 22 cc of the above water-swollen modified ion exchange resin catalyst was dried by phenol flow treatment and contracted to 11 cc.
[0044]
Next, a mixed solution having a phenol / acetone / water molar ratio of 5/1 / 0.4 was passed through the catalyst at a rate of 10.50 g / hr. As a result of analyzing the reaction product obtained after 5 hours by liquid chromatography at a reaction temperature of 100 ° C., the conversion of acetone was 54.0%, and the selectivity for bisphenol A was 90%.
[0045]
【The invention's effect】
In the method of the present invention, since a part of the sulfonic acid group of the sulfonic acid group-containing organic polymer siloxane catalyst is added with a pyridine compound having a mercaptoalkyl group, the catalytic activity is high and the catalyst life is also improved. . As a safe and economical catalyst for producing bisphenol A, the production of bisphenol A, which is industrially important, can be carried out with significant advantages in terms of process and economy.

Claims (1)

A method for producing bisphenol A by dehydration condensation of acetone and phenol in the presence of an organic polymer siloxane having a sulfonic acid group to which 3 to 70% of the sulfonic acid group is added by a pyridine compound having a mercaptoalkyl group.