WO2002085830A1

WO2002085830A1 - Process for producing bisphenol a

Info

Publication number: WO2002085830A1
Application number: PCT/JP2002/003540
Authority: WO
Inventors: Masahiro Iwahara
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 2001-04-17
Filing date: 2002-04-09
Publication date: 2002-10-31
Also published as: JP2002316962A; MY139605A; TWI238818B

Abstract

A process for producing bisphenol A which comprises condensing phenol with acetone using as a catalyst an acid-form ion-exchange resin partially modified with a sulfurized amine compound, characterized in that when the acetone has a methanol concentration of 400 to 7,000 weight ppm, then the modified acid-form ion-exchange resin is one having a degree of modification of 15 to 50 mol% and a mercaptan compound (preferably ethyl mercaptan) is added. Due to the addition of the mercaptan compound, the catalytic activity can be inhibited from being reduced by the methanol contained as an impurity in the acetone. Thus, bisphenol A can be produced with a high conversion and high selectivity.

Description

Description Bisphenol A Production Method

Technical field

The present invention relates to bisphenol A [2,2-bis (4-hydroxyphenol)]. More specifically, in the production of bisphenol A by condensing phenol and acetone using an acid-type ion-exchange resin catalyst partially modified with an iodamine compound, the mercaptan compound The present invention relates to a method for stably producing bisphenol A at a high conversion by suppressing a decrease in catalytic activity due to methanol, which is an impurity in acetone, by adding the compound. Background art

Bisphenol A is known to be an important compound as a raw material for engineering plastics such as polycarbonate resin and polyarylate resin, or as a raw material for epoxy resins, and the demand for bisphenol A has been increasing in recent years.

This bisphenol A is produced by condensing excess phenol and acetone in the presence of an acidic catalyst and optionally a cocatalyst such as a sulfur compound. As the acid catalyst used in this reaction, inorganic mineral acids such as sulfuric acid and hydrogen chloride have been used in the past, but cation exchange resins have recently attracted attention (UK Patent No. 842209). No. 8,495,655 and No. 8,339,91), which have been used industrially.

On the other hand, as the sulfur compound used as a cocatalyst, alkyl mercaptans having or not having a substituent such as methyl mercaptan, ethyl mercaptan, and thiodaricholic acid are known to be effective (US Patent No. 235 No. 242, specification No. 2,775,620). These mercaptans have the effect of increasing the reaction rate and increasing the selectivity. For example, in the production of bisphenol A, 2- (2-hydroxyphenyl) -12- (4-hydroxyphenyl) propane (o, ρ'-isomer) is mainly produced as a reaction by-product, and other trisphenols are produced. And polyphenols are generated. In particular, raw materials such as polycarbonate resin and polyarylate resin When used, bisphenol / A with high purity and low content of these by-products is required. For this reason, mercaptans are used as a co-catalyst to increase the reaction rate, suppress the generation of the by-products, and increase the selectivity.

In recent years, instead of using the above-mentioned cation exchange resin and mercaptans in combination, various modified acid-type ion-exchange resins obtained by introducing an i-containing group into a part of the sulfonic acid groups of the acid-type ion-exchange resin are used as a catalyst. That is being done.

As one of the modified acid-type ion exchange resins, an acid-type ion exchange resin partially modified with an iodiamine-containing compound is known. However, when bisphenol A is produced by condensing phenol and acetone with this modified acid-type ion-exchange resin as a catalyst, there is a problem that the activity of the catalyst is reduced by methanol, which is an impurity in acetone. Occurs. Therefore, in order to solve such a problem, a method has been proposed in which a small amount of water is present in the reaction raw material to suppress the decrease in the catalyst activity (Japanese Patent Application Laid-Open No. HEI 6-172722). Japanese Patent Application Laid-Open No. H10-175898, Japanese Patent Application Laid-Open No. H10-251,179, Japanese Patent Application Laid-Open No. H10-210,180). However, in this method, since the catalytic activity is newly decreased by water, the effect of suppressing the catalytic activity is not sufficiently exhibited, and it cannot be said that the method is necessarily satisfactory.

On the other hand, the reaction raw material is purified in advance, and the impurities in the raw material, R—X (R is an alkyl group, a ^^ enyl group, a cycloalkyl group or a cycloalkenyl group, and X is Ο, a halogen atom, A method for reducing the content of the compound represented by the formula (1), a sulfate group or a sulfonate group to less than 0.1% by weight has been proposed (JP-A-6-25047).

However, in this method, phenol and acetone as raw materials must be purified in advance, and the number of steps for purifying the raw materials increases, which is not always a satisfactory method.

Disclosure of the invention

Under such circumstances, the present invention provides a method for producing bisphenol by condensing phenol and acetone using an acid-type ion-exchange resin catalyst partially modified with an iodiamine-containing compound. It is an object of the present invention to provide a method for stably producing bisphenol A at a high conversion rate while suppressing a decrease in catalytic activity due to methanol, Things.

Other objects of the present invention will be apparent from the following description of the specification.

The present inventor has conducted intensive studies to achieve the above object, and as a result, using a catalyst in which the modification rate of an acid-type ion exchange resin partially modified with an iodiamin compound is in a specific range, a mercaptan compound is prepared. It has been found that the purpose can be achieved by the addition. The present invention has been completed based on such findings.

That is, in the present invention, when an acid-type ion exchange resin partially modified with an iodiamine-containing compound is used as a catalyst, and phenol and acetone are condensed to produce bisphenol A, the methanol concentration in acetone is 4%. In the case of 0 to 700 ppm by weight, the modified acid-type ion exchange resin having a modification ratio of 15 to 50 mol% is used, and a mercaptan compound is added. Is provided. The modification rate in the present invention means a molar modification rate of an acid-type ion-exchange resin with a sulfonic acid group-containing diamine compound. BEST MODE FOR CARRYING OUT THE INVENTION

The method of the present invention is a method for producing bisphenol A by condensing phenol and acetone with an acid-type ion-exchange resin partially modified with an iodiamine-containing compound as a catalyst, The base acid-type ion exchange resin used in the modified acid-type ion-exchange resin is not particularly limited, and those conventionally used as a catalyst for bisphenol A can be used. Accordingly, a strongly acidic sulfonic acid type ion exchange resin is preferred.

The sulfonic acid type ion exchange resin is not particularly limited as long as it is a strongly acidic ion exchange resin having a sulfonic acid group. Examples thereof include a sulfonated styrene-dibutylbenzene copolymer, a sulfonated crosslinked styrene polymer, and phenol formaldehyde sulfone. Acid resins, benzene formaldehyde sulfonic acid resins and the like can be mentioned. On the other hand, the iodiamine-containing compound used for the partial modification of the acid-type ion-exchange resin is not particularly limited, and any one of conventionally known compounds that can be used for the modification of the acid-type ion-exchange resin is used. Can be appropriately selected and used.

Examples of the diamine compound include 3-mercaptomethyl pyridine, 3- (2 Mercaptoalkylpyridines such as 1-mercaptoethyl) pyridine, 4- (2-mercaptoethyl) pyridine, and mercaptoalkylamines such as 2-mercaptoethylamine, 3-mercaptopropylamine, and 4-mercaptobutylamine Thiazolidine, 2,2-dimethylthiazolidine, thiazolidines such as 2-methyl-2-phenylthiazolidine, 3-methylthiazolidine, and aminothiophenols such as 4-aminothiophenol, and the like. Among them, 4- (2-mercaptoethyl) pyridine, 2-mercaptoethylamine and 2,2-dimethylthiazolidine are preferred.

These iodiamine-containing compounds may be in a free form, or may be in the form of an addition salt of an acidic substance such as hydrochloric acid or a quaternary ammonium salt.

There is no particular limitation on the method for partially modifying the above-mentioned base acid-type ion-exchange resin using these iodiamine-containing compounds, and a conventionally known method can be used. For example, it can be modified by reacting an acid-type ion exchange resin with an iodamine compound in a suitable solvent, preferably an aqueous solvent such as water, so as to obtain a desired modification rate. The reaction may be carried out at room temperature or, if necessary, with heating. By this reaction, a sulfonic acid group as an ion exchange group reacts with an amino group in the ioamine compound, and an io group is introduced into a part of the ion exchange group to be modified. In the method of the present invention, a modified acid-type ion exchange resin having a modification ratio of 15 to 50 mol% is used when the methanol concentration in the raw material acetone is 400 to 700,000 weight ppin. .

The present inventors have used an acid-type ion-exchange resin partially modified with an iodamine-containing compound as a catalyst for condensation of phenol and acetone! The sulfonic acid group acts as a catalyst, and methanol, which is an impurity in acetone, reacts with the mercapto group of the iodiamine-containing compound in the modified acid-type ion-exchange resin to form methyl sulfide. Was found to decrease.

That is, a small amount of a mercaptan compound is added to the reaction system, and the mercaptan compound is reacted with methanol, which is an impurity in acetone, to react the mercapto group of the thiopamine-containing compound in the modified acid-type ion exchange resin with methanol. By suppressing it, the catalyst life can be prolonged. Examples of the mercaptan compound include methyl mercaptan, ethyl mercaptan, n-cap pinolemercaptan, i-propinolemenolecaptan, n-ptinolemenorecaptan, sec-butyl mercaptan, t-butyltinolemenorecaptan, Alkyl mercaptans having 1 to 10 carbon atoms, such as pentinoremercaptan, hexyl menolecaptan, heptylmercaptan, octylmenolecaptan, nonolemenolecaptan, and decylmercaptan, are among these. Alkyl mercaptans having 1 to 3 carbon atoms are preferred.

The amount of the mercaptan compound to be added is preferably 1/20 to 1Z500 (molar ratio), preferably 1 to 50 to 1/400 (molar ratio) based on acetone.

The addition amount can be arbitrarily changed according to the methanol concentration in the raw material acetone, the reaction state of acetone and phenol, and the degree of deterioration of the modified acid-type ion exchange resin catalyst. When the methanol concentration is high or the degree of deterioration of the catalyst is severe, the added amount of the mercaptan compound increases.

The addition of the mercaptan compound of the present invention not only has the effect of extending the catalyst life, but also promotes the reaction of forming bisphenol A by the cocatalytic effect of the mercaptan compound, thereby improving the overall catalytic activity.

In the present invention, it is possible to use a raw material containing water at a ratio of about 500 to 500,000 weight ppm.

By the way, the water content of phenol as a raw material is generally 500 to 100 ppm in a reagent or an industrial product. Similarly, the water content of the raw material acetone is also included in the range of 100 to 300 ppm.

In process, excess phenol and unreacted acetone are collected and recycled, but the above-mentioned water requires considerable purification. In this reaction of bisphenol A, water is produced in an equimolar amount with the product bisphenol A. For example, under the condition of acetone phenol = 1/10 (molar ratio) as a raw material, about 4.0 ppm of acetone at a conversion of 20%, about 900 ppm at a conversion of 50%, At a conversion of 70%, the water concentration is about 1300 ppm. In other words, when the amount of water in the raw material is about 500 to 2000 ppm, the amount of water generated by the reaction is larger as described above, and the reaction result is hardly affected.

In fact, with the addition of 0.05 to 0.2% water, the effect of methanol No. However, water suppresses the production of the target substance, bisphenol A, and if it is present in the raw material in an amount of about 0.4% or more, the activity is greatly reduced.

In the process for producing bisphenol A / re A according to the present invention, the use ratio of phenol and acetone is not particularly limited, but the amount of unreacted acetone is reduced from the viewpoint of easy purification and economical efficiency of the produced bisphenol A. It is desirable to have as little as possible, and it is therefore advantageous to use the phenol in excess of the stoichiometric amount.

Usually, 3 to 30 moles, preferably 5 to 20 moles, of phenol are used per mole of acetone.

In the production of bisphenol A, the reaction solvent is generally not required, except that the reaction liquid is reacted at a low temperature at which the viscosity of the reaction liquid is too high or the solidification hardens the operation.

The condensation reaction between phenol and acetone in the present invention is carried out by continuously supplying phenol and acetone to a reactor filled with an acid-type ion-exchange resin partially modified with the above-described iodamine-containing compound. A fixed bed continuous reaction system can be used. In this case, one reactor may be used, or two or more reactors may be arranged in series or in parallel.

Industrially, it is particularly advantageous to employ a fixed-bed multistage continuous reaction system in which two or more reactors filled with the modified acid-type ion exchange resin are connected in series.

The reaction conditions in this fixed bed continuous reaction system will be described.

First, the acetone / phenol molar ratio is usually selected in the range of 1/30 to 1Z3, preferably 1/20 to 1/5. If the molar ratio is less than 1/30, the reaction rate may be too slow. If the molar ratio is more than 1 Z3, the generation of impurities may increase, and the selectivity of bisphenol A tends to decrease.

In the present invention, the method of supplying the phenol, acetone and mercaptan compound to the reactor is not particularly limited, but it is preferable to separately supply the acetone and mercaptan compound to each reactor.

The reaction temperature is selected in the range of usually 40 to 150 ° C, preferably 55 to 100 ° C. If the temperature is lower than 40 ° C, the reaction rate is low, and the viscosity of the reaction solution is extremely high. In some cases, the reaction solution may be solidified.If the temperature exceeds 150 ° C, the reaction control becomes difficult, and bisphenol The selectivity of A (ρ, 'one) decreases, and the modified acid-type ion-exchange The fat may decompose or deteriorate.

Further, the LHSV (liquid hourly space velocity) of the raw material mixture is usually selected in the range of 0.2 to 30 hr—preferably 0.5 to 20 hr— ¹ .

In the method of the present invention, the reaction mixture coming out of the reactor is subjected to a post-treatment by a known method, and bisphenol A is taken out. Next, an example of this post-treatment will be described. First, concentration is performed prior to crystallization. The concentration conditions are not particularly limited, but the concentration is usually performed at a temperature of 130 to 170 ° C and a pressure of 13 to 53 kPa. If the temperature is lower than 130 ° C, a high vacuum is required. If the temperature is higher than 1Ί0 ° C, impurities may increase or coloring may occur. The concentration of bisphenol A in the concentrated residual liquid is advantageously in the range of 25 to 40 weight ^_0/0. If the concentration is less than 25% by weight, the recovery of bisphenol A is low, and if it exceeds 40% by weight, it becomes difficult to transfer the slurry after crystallization.

Crystallization of the adduct of bisphenol A and phenol from the concentrated residue is usually carried out by vacuum cooling crystallization, which utilizes the latent heat of water evaporation under reduced pressure. In this vacuum cooling crystallization method, about 3 to 20% by weight of water is added to the concentrated residue, and crystallization is performed at a normal temperature of 40 to 70 ° C and a pressure of 3 to 13 kPa. Processing is performed. If the amount of water added is less than 3% by weight, the heat removal ability is not sufficient, and the weight is 20%. If the ratio exceeds / ₀ , the dissolution opening of bisphenol A becomes large, which is not preferable. If the crystallization temperature is lower than 40 ° C, the viscosity of the crystallized liquid may increase or solidify. If it exceeds 70 ° C, the dissolution loss of bisphenol A increases, which is not preferable.

Next, the thus-crystallized adduct of bisphenol A and phenol is separated by a known method, and is usually washed with phenol. Next, the washed adduct is separated into bisphenol A and phenol. In this case, the temperature is usually selected in the range of 130 to 200 ° C, preferably in the range of 150 to 180 ° C. Orientation pressure is usually selected in the range of 3 to 20 kPa.

Bisphenol A obtained by this separation treatment is substantially completely removed by a method such as steam stripping to remove residual phenol therein, thereby obtaining high-quality bisphenol A.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1

In a packed bed reactor with an inner diameter of 12 m: m and a height of 1200 mm, a sulfonic acid type ion-exchange resin denatured with 20 mol% of 2-mercaptoethylamine as a catalyst [Mitsubishi Chemical Corporation Product name: DIAION SK-104H] 69.3 Milliliter (swelled with water) was filled. The two reactors were connected in series.

The first-stage reactor was charged with 277 milliliters of phenol and the first and second stages were charged with 500 ppm by weight of methanol and 1/400 ppm of ethyl mercaptan (vs. The reaction was carried out while maintaining the reaction temperature at 75 ° C. by dividing and passing acetonitrile containing 15.6 tons / mole ratio (15.6 torr / mol).

The reaction mixture was analyzed over time to determine the conversion of phenol. The results are shown in Table 1.

Example 2

In Example 1, a sulfonic acid type ion-exchange resin (described above) modified with 2,2-dimethylthiazolidine at 25 mol% was used as a catalyst, and methanol (1000 ppm by weight) and ethyl mercaptan (1/20) were used. The procedure was performed in the same manner as in Example 1 except that the acetone was changed to 0 (molar ratio to acetone).

Table 1 shows the results.

Example 3

In Example 1, a sulfonic acid-type ion-exchange resin (described above) modified with 2,2-dimethylthiazolidine at 25 mol% was used as a catalyst, and methanol 5,000 weight 111 and ethyl mercaptan 1/1 were used. The procedure was performed in the same manner as in Example 1 except that the acetone was changed to include acetone (molar ratio to acetone).

Table 1 shows the results.

Example 4

In Example 1, a sulfonic acid type ion-exchange resin (described above) modified with 45 mol% of 2,2-dimethylthiazolidine was used as a catalyst, and methanol 5,000 weight 111 and ethyl mercaptan 1/50 were used. (Mole ratio to acetone) The procedure was performed in the same manner as in Example 1 except that the acetone was changed to include acetone.

Table 1 shows the results. Example 5

In Example 1, a sulfonic acid type ion-exchange resin (described above) denatured by 30 mol% with 4 _ (2-mercaptoethyl) pyridine was used as a catalyst. The procedure was carried out in the same manner as in Example 1 except that the acetone was changed to contain ethyl mercaptan 1/200 (molar ratio to acetone).

Table 1 shows the results.

In Examples 1 to 5, the selectivity of bisphenol A was 93% or more, and good results were obtained.

Comparative Example 1

In Example 1, a sulfonic acid-type ion-exchange resin (described above) modified with 2-mercaptoethylamine by 10 mol% was used as a catalyst, and was changed to acetone containing 1,000,000 ppm by weight of methanol. Except for the above, the procedure was the same as in Example 1.

Table 1 shows the results.

Comparative Example 2

Example 1 was carried out in the same manner as in Example 1 except that acetone containing 5,000 weight ppm of methanol was used.

Table 1 shows the results.

Comparative Example 3

In Example 1, a sulfonic acid-type ion-exchange resin (described above) modified with 2,2-dimethylthiazolidine at 25 mol% was used as the catalyst, and the catalyst was changed to acetone containing 100,000 weight-methanol. Was carried out in the same manner as in Example 1.

Table 1 shows the results.

Comparative Example 4

In Example 1, using 4 i (2 Merukaputechiru) pyridine 7 mole ^_0/0 denatured sulphonic acid type ion-exchange resin (supra) as a catalyst, the Aseton containing methanol 4, 0 0 0 weight m Except having changed, it carried out similarly to Example 1.

Table 1 shows the results.

Comparative Example 5

In Example 1, 2 as the catalyst, 1 6 mole at 2-dimethyl-thiazolidine ^_0/0 denatured Example 2 except that the sulfonic acid type ion-exchange resin (described above) was used, and the acetone was changed to contain 200,000 wt.% Methanol and ethyl mercaptan 1Z400 (molar ratio to acetone). This was performed in the same manner as in 1.

Table 1 shows the results.

In Comparative Examples 1 to 4, the selectivity of bisphenol A decreased with a decrease in the conversion, and became less than 90% after 800 hours.

Table 1 _ 1 in acetone. Tan Modified H «Ion exchange grease

Of methanol "^

(Acetone conversion I rate, direct S PHU molar ratio) Iodiamine-containing compounds

(\ Module / »%)

2-Strength Putethylamine 20 500 1/400 Example 2 2,2 Membrane; Pin 25 1,000 1,000 1/200 Row 3 2, 2—Mesh Membrane 25 5,000 1 / 100 雞 Example 4 2, 2-'Min., 'Risin' 45 5 000 1/50 雞 Example 5 4-1 (2-detethyl) pylicin 30 1, 000 1/200 Comparative example 1 2-Mf Toethylamine 10 1, 000 0 Specific glue 2 2 -Me; Yu, Toethylamine 20 5,000 000 0 Comparative example 3 2,2-Si "Methi;Aso" Risin 25 25 000 0 Comparative example 4 4— (2-Yuputethyl) pyricin 7 4 000 0 Comparative Example 5 2,2-Si 2 Table 1 I 2

Industrial applicability

According to the present invention, when bisphenol A is produced by condensing phenol and acetone using an acid-type ion exchange resin catalyst partially modified with an iodiamine-containing compound, by adding a mercaptan compound, Bisphenol A can be stably produced at a high conversion rate by suppressing a decrease in catalytic activity due to methanol, which is an impurity of phenol.

Claims

The scope of the claims

(1) When bisphenol A is produced by condensing phenol and acetone using an acid-type ion exchange resin partially modified with an iodiamine-containing compound as a catalyst, the methanol concentration in the acetone is 400 to 700% by weight. In the case of ppm, a process for producing bisphenol A, characterized in that a modified acid type ion exchange resin having a modification ratio of 15 to 50 mol% is used, and a mercaptan compound is added.

2. The method for producing bisphenol A according to claim 1, wherein the mercaptan compound is an alkyl mercaptan having 1 to 3 carbon atoms, and the amount of the added mercaptan is from 120 to 500 (molar ratio) with respect to acetone.

3. The process for producing bisphenol A according to claim 2, wherein the alkyl mercaptan is ethyl mercaptan, and the amount thereof is 150 to 140 (molar ratio) to acetone.

4. The method for producing bisphenol A according to claim 1, wherein the acid-type ion exchange resin is a strongly acidic sulfonic acid-type ion exchange resin.

5. The process for producing bisphenol A according to claim 1, wherein the diamine-containing compound is at least one member selected from the group consisting of mercaptoalkylpyridines, mercaptoalkylamines, thiazolidines, and aminothiophenols.

6. The process for producing bisphenol A according to claim 1, wherein a condensation reaction is performed by using a device in which two or more reactors are connected in series as a reaction device and adding acetone and a mercaptan compound to each of the reaction groups in a divided manner.

7. The process for producing bisphenol A according to claim 6, wherein the condensation reaction is carried out under the condition that the molar ratio of acetone Z phenol is 1/30 to 1Z 3 and the reaction temperature is 40 to 150 ° C.